JP2012201821A - Method for producing graft copolymer, and thermoplastic resin composition including graft copolymer obtained by the production method - Google Patents

Abstract

The present invention provides a method for producing a graft copolymer that provides a highly productive and highly uniform graft copolymer.
SOLUTION: Reactive polyolefin satisfying specific requirements 20 to 100% by mass, 100 parts by mass of a combination of polyolefins other than reactive polyolefins 0 to 80% by mass, and monomer mixture 0.2 to 300% by mass Part of the radical copolymer in the presence of 0.001 to 10 parts by mass of a radical initiator, wherein the monomer (a) and the monomer (b) are different from each other. A graft copolymer which is a monomer and contacts the monomer (b) with the monomer (a) and the reactive polyolefin in a state where the monomer (a) and the reactive polyolefin are in contact with each other Manufacturing method.
[Selection figure] None

Description

  The present invention relates to a method for producing a graft copolymer and a thermoplastic resin composition containing the graft copolymer obtained by the production method.

Conventionally, an olefin polymer (graft copolymer) obtained by graft-modifying a polyolefin such as polyethylene or polypropylene with an unsaturated carboxylic acid or an acid anhydride thereof is used as a modifier for various resins or as an adhesion promoter. It's being used.
These modifiers are expected to further improve performances such as adhesion and compatibilization by improving the graft modification amount and enhancing the controllability of the graft structure.

  For polyolefins used in the production of graft copolymers, low-ordered polyolefins obtained using metallocene-based catalysts have low stereoregularity and are therefore excellent in flexibility and miscibility with olefin-based resins. By further adding a group, it is expected to expand its application to adhesiveness and composite with different resins.

Several proposals have been made regarding the method for producing the graft copolymer.
In Patent Document 1, graft copolymerization is performed in a molten state using a polyolefin, a monomer, and a radical polymerization initiator that satisfy specific requirements. There was a problem with sex.
Patent Document 2 discloses a method of producing a maleic anhydride copolymer by radical polymerization of maleic anhydride and a vinyl monomer. However, since the reaction rate is poor and a large amount of unreacted monomer remains, a separation and purification process that reduces productivity is indispensable. Further, the obtained copolymer is also a low-branched graft, and there are problems in adhesiveness, dispersibility, and compatibilizing performance.

WO2008 / 066168A JP-A-01-204911

  An object of the present invention is to provide a method for producing a graft copolymer, which can provide a highly productive and highly uniform graft copolymer.

According to the present invention, the following method for producing a graft copolymer and the like are provided.
1. 100 parts by mass of a combination of 20 to 100% by mass of a reactive polyolefin satisfying the following (1) to (5) and 0 to 80% by mass of a polyolefin other than the reactive polyolefin,
A monomer comprising at least one monomer (a) selected from the following [V] to [VIII] and at least one monomer (b) selected from the following [I] to [V] and [VIII]: A method for producing a graft copolymer in which 0.2 to 300 parts by mass of a body mixture is graft-polymerized in the presence of 0.001 to 10 parts by mass of a radical initiator,
The monomer (a) and the monomer (b) are mutually different monomers,
A method for producing a graft copolymer, wherein the monomer (b) is brought into contact with the monomer (a) and the reactive polyolefin in a state where the monomer (a) and the reactive polyolefin are in contact with each other.
[Reactive polyolefin]
(1) One homopolymer or two or more copolymers selected from α-olefins having 3 to 28 carbon atoms, or one or more monomers selected from α-olefins having 3 to 28 carbon atoms Copolymer of 90% by mass or more and 10% by mass or less of ethylene (2) Mesopentad fraction [mmmm] is 30 to 80 mol% (3) 0.5 to 1.0 terminal unsaturated group per molecule (4) The molecular weight distribution Mw / Mn is 4 or less. (5) In decalin, the intrinsic viscosity ([η]) measured at 135 ° C. is 0.01 to 2.5 dl / g [monomer ( a)]
[V] Maleic anhydride and substituted products thereof [VI] Maleic acid and esters thereof [VII] Vinylalkoxysilanes [VIII] α-olefin [monomer (b)]
[I] Acrylic acid and its derivative [II] Methacrylic acid and its derivative [III] Vinyl ester and its derivative [IV] Styrene and its derivative [V] Maleic anhydride and its substitute [VIII] α-olefin The reactive polyolefin contains a vinylidene group as a terminal unsaturated group,
2. The method for producing a graft copolymer according to 1, wherein a ratio of the vinylidene group to all terminal unsaturated groups is 50 to 100 mol%.
3. The graft term polymer according to 1 or 2, wherein a temperature at the time of contact of the reactive polyolefin, the monomer (a) and the monomer (b) is 40 to 260 ° C.
4). 100 parts by mass of a combination of 20 to 100% by mass of a reactive polyolefin satisfying the following (1) to (5) and 0 to 80% by mass of a polyolefin other than the reactive polyolefin,
In the method for producing a graft copolymer, one or more monomers selected from the following [I] to [IV] are graft-polymerized in the presence of 0.001 to 10 parts by mass of a radical initiator in the amount of 0.2 to 300 parts by mass. There,
A method for producing a graft copolymer, wherein the graft polymerization is carried out at a temperature of 140 to 260 ° C.
(1) One type of homopolymer or two or more copolymers selected from α-olefins having 3 to 28 carbon atoms, or 90 masses of one or more monomers selected from α-olefins having 3 to 28 carbon atoms (2) Mesopentad fraction [mmmm] is 30 to 80 mol% (3) 0.5 to 1.0 terminal unsaturated groups per molecule (4) The molecular weight distribution (Mw / Mn) is 4 or less. (5) The intrinsic viscosity ([η]) measured at 135 ° C. in decalin is 0.01 to 2.5 dl / g. [I] Acrylic acid And derivatives thereof [II] Methacrylic acids and derivatives thereof [III] Vinyl esters and derivatives thereof [IV] Styrene and derivatives thereof 100 parts by mass of a combination of 20 to 100% by mass of a reactive polyolefin satisfying the following (1) to (5) and 0 to 80% by mass of a polyolefin other than the reactive polyolefin,
0.2 to 300 parts by mass of one or more monomers selected from the following [I] to [IV] including at least a monomer selected from the following [I ′] to [III ′] 5. The method for producing a graft copolymer according to 4, wherein graft polymerization is performed at 140 to 260 ° C. in the presence of 001 to 10 parts by mass.
(1) One type of homopolymer or two or more copolymers selected from α-olefins having 3 to 28 carbon atoms, or 90 masses of one or more monomers selected from α-olefins having 3 to 28 carbon atoms (2) Mesopentad fraction [mmmm] is 30 to 80 mol% (3) 0.5 to 1.0 terminal unsaturated groups per molecule (4) The molecular weight distribution (Mw / Mn) is 4 or less. (5) The intrinsic viscosity ([η]) measured at 135 ° C. in decalin is 0.01 to 2.5 dl / g. [I] Acrylic acid And derivatives thereof [II] Methacrylic acids and derivatives thereof [III] Vinyl esters and derivatives thereof [IV] Styrene and derivatives thereof [I ′] Acrylic esters containing a hydrocarbon group having 4 to 20 carbon atoms in the ester residue and the derivatives thereof Derivative [I I ′] Methacrylic acid ester having 4 to 20 carbon atoms in the ester residue and derivatives thereof [III ′] Vinyl ester having 4 to 20 carbon atoms in the residue and derivatives thereof6. 100 parts by mass of a combination of 20 to 100% by mass of a reactive polyolefin satisfying the following (1) to (5) and 0 to 80% by mass of a polyolefin other than the reactive polyolefin,
In the presence of 0.001 to 10 parts by mass of a radical initiator, at least one monomer selected from the following [I] to [IV] is used in the presence of 0.001 to 10 parts by mass of an aliphatic hydrocarbon, alicyclic hydrocarbon or cyclic ether. The graft according to 4, wherein the graft polymerization is carried out in a solvent consisting of an organic carboxylic acid ester and an aliphatic hydrocarbon, or in a mixed solvent consisting of an organic carboxylic acid ester, an aliphatic hydrocarbon and an alicyclic hydrocarbon. A method for producing a copolymer.
(1) One type of homopolymer or two or more copolymers selected from α-olefins having 3 to 28 carbon atoms, or 90 masses of one or more monomers selected from α-olefins having 3 to 28 carbon atoms (2) Mesopentad fraction [mmmm] is 30 to 80 mol% (3) 0.5 to 1.0 terminal unsaturated groups per molecule (4) The molecular weight distribution (Mw / Mn) is 4 or less. (5) The intrinsic viscosity ([η]) measured at 135 ° C. in decalin is 0.01 to 2.5 dl / g. [I] Acrylic acid And derivatives thereof [II] Methacrylic acids and derivatives thereof [III] Vinyl esters and derivatives thereof [IV] Graft copolymer obtained by the method for producing a graft copolymer according to any one of styrene and derivatives 7.1 to 6 Including coalescence The thermoplastic resin composition.

  ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the graft copolymer from which the productivity and the highly uniform graft copolymer can be obtained can be provided.

It is a figure which shows the result of carrying out ruthenium dyeing | staining of the polycarbonate composition obtained in Example 6, and observing with a transmission electron microscope. It is a figure which shows the result of carrying out ruthenium dyeing | staining of the polycarbonate composition obtained by the comparative example 2, and observing with a transmission electron microscope.

[Method for producing first graft copolymer]
The manufacturing method of the 1st graft copolymer of this invention is the combination 100 of 20-100 mass% of reactive polyolefins which satisfy | fill (1)-(5), and 0-80 mass% of polyolefins other than reactive polyolefin. And 1 part or more of a monomer (a) selected from [V] to [VIII] and one or more monomers (b) selected from [I] to [V] and [VIII]. This is a method for producing a graft copolymer in which 0.2 to 300 parts by mass of the monomer mixture is graft-polymerized in the presence of 0.001 to 10 parts by mass of a radical initiator.
However, monomer (a) and monomer (b) are mutually different monomers.
[Reactive polyolefin]
(1) One homopolymer or two or more copolymers selected from α-olefins having 3 to 28 carbon atoms, or one or more monomers selected from α-olefins having 3 to 28 carbon atoms Copolymer of 90% by mass or more and 10% by mass or less of ethylene (2) Mesopentad fraction [mmmm] is 30 to 80 mol% (3) 0.5 to 1.0 terminal unsaturated group per molecule (4) The molecular weight distribution Mw / Mn is 4 or less. (5) In decalin, the intrinsic viscosity ([η]) measured at 135 ° C. is 0.01 to 2.5 dl / g [monomer ( a)]
[V] Maleic anhydride and substituted products thereof [VI] Maleic acid and esters thereof [VII] Vinylalkoxysilanes [VIII] α-olefin [monomer (b)]
[I] Acrylic acid and its derivative [II] Methacrylic acid and its derivative [III] Vinyl ester and its derivative [IV] Styrene and its derivative [V] Maleic anhydride and its substitute [VIII] α-olefin

In the first method for producing a graft copolymer of the present invention, in the state where the monomer (a) and the reactive polyolefin are in contact, the monomer (b) is replaced with the monomer (a) and the reactive polyolefin. Contact with. The monomer (a) that is less reactive than the monomer (b) is first reacted with the reactive polyolefin, and the monomer (b) that is more reactive than the monomer (a) By reacting with the reactive polyolefin, the total reaction amount can be improved.
By improving the reaction amount, the separation step of the unreacted monomer can be omitted, and yellowing of the graft copolymer due to the residual monomer can be avoided.

  Moreover, a highly uniform graft copolymer can be obtained by using the first method for producing a graft copolymer of the present invention. A highly uniform graft copolymer refers to a graft copolymer having a narrow molecular weight distribution and a stereoregular distribution, a small amount of infusible and insoluble components such as gels, and a small amount of low molecular weight components that are soluble in polar solvents. The first method for producing a graft copolymer according to the present invention has a high conversion ratio of monomers to a graft copolymer, and at the end of the reaction, the unreacted monomer is greatly reduced, so that The purity of the polymer can be greatly improved.

[Reactive polyolefin]
The reactive polyolefin is a polyolefin that can be radically copolymerized via a specific monomer and a terminal functional group, and is a polyolefin that satisfies the following (1) to (5).
(1) One homopolymer or two or more copolymers selected from α-olefins having 3 to 28 carbon atoms, or one or more monomers selected from α-olefins having 3 to 28 carbon atoms Copolymer of 90% by mass or more and 10% by mass or less of ethylene (2) Mesopentad fraction [mmmm] is 30 to 80 mol% (3) 0.5 to 1.0 terminal unsaturated group per molecule (4) The molecular weight distribution Mw / Mn is 4 or less. (5) The intrinsic viscosity ([η]) measured at 135 ° C. in decalin is 0.01 to 2.5 dl / g.

The reactive polyolefin is one homopolymer selected from α-olefins having 3 to 28 carbon atoms, two or more copolymers selected from α-olefins having 3 to 28 carbon atoms, or 3 to 28 carbon atoms. It is a copolymer of 90% by mass or more of one or more monomers selected from α-olefins and 10% by mass or less of ethylene.
The α-olefin having 3 to 28 carbon atoms is preferably an α-olefin having 3 to 20 carbon atoms. For example, propylene, 1-butene, 1-pentene, 4-methylpentene-1, 1-hexene, 1-octene. 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene and the like.

  The copolymer of 90% by mass or more of one or more monomers selected from α-olefins having 3 to 28 carbon atoms and 10% by mass or less of ethylene is preferably selected from α-olefins having 3 to 28 carbon atoms. And a copolymer of 92% by mass or more and 8% by mass or less of ethylene, more preferably 95% by mass of one or more monomers selected from α-olefins having 3 to 28 carbon atoms. % Or more and 5% by mass or less of ethylene.

The reactive polyolefin satisfying (1) is a propylene homopolymer; a propylene copolymer of 90% by mass or more of propylene and 1 or more and 10% by mass or less selected from ethylene and an α-olefin having 4 to 28 carbon atoms. Butene homopolymer; 1-butene 90% by mass or more, butene-based copolymer of 1 to 10% by mass selected from ethylene, propylene, and an α-olefin having 5 to 28 carbon atoms; 12 to 12 carbon atoms; Homopolymer comprising one kind of 28 α-olefins; Copolymer comprising two or more kinds of α-olefins having 12 to 28 carbon atoms; 90% by mass or more of one kind of α-olefin having 12 to 28 carbon atoms and ethylene And a copolymer with 10% by mass or less of an α-olefin having 3 to 10 carbon atoms is preferable.
The propylene-based copolymer is more preferably a propylene-based copolymer of 92% by mass or more of propylene and 1 or more and 8% by mass or less selected from ethylene and an α-olefin having 4 to 28 carbon atoms, and more preferably. Is a propylene-based copolymer of 95% by mass or more of propylene and 1 or more and 5% by mass or less selected from ethylene and an α-olefin having 4 to 28 carbon atoms.

The reactive polyolefin has a mesopentad fraction [mmmm] of 30 to 80 mol%, preferably 30 to 75 mol%, more preferably 32 to 70 mol%.
When the mesopentad fraction of the reactive polyolefin is 30 mol% or more, the reactive polyolefin is a crystalline polyolefin and can exhibit heat resistance. Further, when the mesopentad fraction of the reactive polyolefin is 80 mol% or less, the reactive polyolefin is moderately soft and has good solubility in a solvent, so that solution reaction and the like can be widely applied.

When the reactive polyolefin is a polyolefin mainly composed of polypropylene (propylene 90% by mass or more), the mesopentad fraction [mmmm] can be measured by the following method.
The mesopentad fraction [mmmm], the racemic pentad fraction [rrrr], and the racemic mesoracemi meso fraction [rmrm] of the reactive polyolefin were measured by A. Zambelli et al., “Macromolecules, 6,925 (1973 The meso fraction, the racemic fraction, and the racemic meso-racemic meso fraction in pentad units in the polypropylene molecule measured by the methyl group signal of the ¹³ C-NMR spectrum in accordance with the method proposed in “)”. As the mesopentad fraction [mmmm] increases, the stereoregularity increases.
The measurement of ¹³ C-NMR spectrum can be carried out with the following apparatus and conditions in accordance with the attribution of the peak proposed by “Ama Zambelli” in “Macromolecules, 8, 687 (1975)”. it can.

Apparatus: JNM-EX400 type ¹³ C-NMR apparatus manufactured by JEOL Ltd. Method: Proton complete decoupling method Concentration: 220 mg / ml
Solvent: 90:10 (volume ratio) mixed solvent of 1,2,4-trichlorobenzene and heavy benzene Temperature: 130 ° C
Pulse width: 45 °
Pulse repetition time: 4 seconds Integration: 10,000 times

The method for calculating the mesopentad fraction M is as follows.
M = (m / S) × 100
R = (γ / S) × 100
S = Pββ + Pαβ + Pαγ
S: Signal intensity of side chain methyl carbon atoms of all propylene units Pββ: 19.8 to 22.5 ppm
Pαβ: 18.0 to 17.5 ppm
Pαγ: 17.5 to 17.1 ppm
γ: Racemic pentad chain: 20.7 to 20.3 ppm
m: Mesopentad chain: 21.7-22.5 ppm

When the reactive polyolefin is a polyolefin containing polybutene as a main component (butene 90% by mass or more), the mesopentad fraction [mmmm] can be measured by the following method.
Mesopentad fraction [mmmm] is reported in “Polymer Journal, 16, 717 (1984)”, J. Asakura et al.
“Macromol. Chem. Phys., C29, 201 (1989)” reported by Randall et al. It can be measured according to the method proposed in “Macromol. Chem. Phys., 198, 1257 (1997)” reported by Busico et al.
That is, the mesopentad fraction in the poly (1-butene) molecule can be determined by measuring signals of methylene group and methine group using ¹³ C nuclear magnetic resonance spectrum.
^{The 13} C nuclear magnetic resonance spectrum can be measured using the above apparatus and conditions.

The stereoregularity index {(mmmm) / (mmrr + rmmr)} of the reactive polyolefin can be calculated from the values obtained by measuring (mmmm), (mmmr) and (rmmr) by the above method. The racemic triad fraction (rr) can also be calculated by the above method.
The 1-butene homopolymer and the copolymer have a stereoregularity index {(mmmm) / (mmrr + rmmr)} of, for example, 20 or less, preferably 18 or less, more preferably 15 or less.
When the stereoregularity index exceeds 20, there is a possibility that the flexibility is lowered.

When the reactive polyolefin is a polymer containing an α-olefin having 5 or more carbon atoms as a main component (the α-olefin having 5 or more carbon atoms is 90% by mass or more), the stereoregularity can be evaluated by the following method.
The mesopentad fraction is determined by T.W. Asakura, M .; Demura, Y .; It can be determined in accordance with the method proposed in “Macromolecules, 24, 2334 (1991)” reported by Nishiyama.
That is, the mesopentad fraction is obtained by utilizing the fact that CH ₂ carbon at the side chain α-position derived from the higher α-olefin is split and observed in the ¹³ CNMR spectrum, reflecting the difference in stereoregularity. Can do.
The ¹³ C nuclear magnetic resonance spectrum measuring apparatus and conditions are the same as described above.

The reactive polyolefin has 0.5 to 1.0 terminal unsaturated groups per molecule.
The number of terminal unsaturated groups per molecule is 0.6 to 1.0, 0.7 to 1.0, 0.8 to 1.0, 0.82 to 1.0, 0 .85 to 1.0 and 0.9 to 1.0 in order (preferably 0.9 to 1.0).
When the number of terminal unsaturated groups per molecule of the reactive polyolefin is 0.5 or more (by increasing the concentration of unsaturated groups), the production efficiency of the graft copolymer can be increased.

Examples of the terminal unsaturated group of the reactive polyolefin include a vinyl group, a vinylidene group, and a trans (vinylene) group. Among them, a vinylidene group is preferable, and a ratio of the vinylidene group to all terminal unsaturated groups is preferably 50 to 100. It is mol%, More preferably, it is 60-100 mol%, More preferably, it is 70-100 mol%, Most preferably, it is 80-100 mol%.
The reactive polyolefin of the present invention does not contain a component having two or more unsaturated groups per molecule, for example, a component having unsaturated groups at both ends. A component having two or more unsaturated groups per molecule acts as a so-called cross-linking agent, and thus forms a cross-linked structure (H-type) during graft polymerization and by-produces a gel component.
For this reason, as the reactive polyolefin, for example, an unsaturated polyolefin produced by thermal decomposition, the structure and production conditions of the reactive polyolefin that can be used are not clear at present and are not preferable.

In general, nuclear magnetic resonance spectroscopy can be used for measurement of the terminal unsaturated group of the reactive polyolefin.

When measuring the terminal unsaturated group of a reactive polyolefin by nuclear magnetic resonance spectroscopy, for example, when the terminal unsaturated group to be measured is a vinylidene group, the number of terminal vinylidene groups per molecule is determined by ¹ H-NMR measurement. be able to. Based on the terminal vinylidene group appearing in δ 4.8 to 4.6 (2H) obtained from ¹ H-NMR measurement, the content (C) (mol%) of the terminal vinylidene group can be calculated. Furthermore, the number per terminal vinylidene group per molecule can be calculated from the number average molecular weight (Mn) and monomer molecular weight (M) determined from gel permeation chromatography (GPC) by the following formula.
Number of terminal vinylidene groups per molecule (pieces) = (Mn / M) × (C / 100)

In addition to the above method, the number of terminal vinylidene groups can also be determined using ¹³ C-NMR. In this method, all end group species are determined, and their abundance is measured.
The number of terminal vinylidene groups per molecule can be determined from the proportion of terminal vinylidene groups relative to the total amount of terminal groups, and the selectivity of terminal vinylidene groups can be determined from the proportion of terminal vinylidene groups relative to all unsaturated groups.
The measurement of the number of terminal vinylidene groups using ¹ H-NMR and ¹³ C-NMR will be described below using a propylene polymer as an example.

[Measurement of the number of terminal vinylidene groups using ¹ H-NMR]
In the propylene polymer, a methylene group (4.8 to 4.6 ppm) of <2> terminal vinylidene group and a methylene group (5.10 to 4.90 ppm) of <1> terminal vinyl group were observed, and the ratio to the total propylene Can be calculated by the following equation. <3> corresponds to the peak intensity corresponding to the methine, methylene, and methyl groups of the propylene chain (0.6 to 2.3 ppm).
Terminal vinylidene group amount (A) = (<2> / 2) / [(<3> + 4 × <1> / 2 + 3 × <2> / 2) / 6] × 100 Unit: mol%
Terminal vinyl group amount (B) = (<1> / 2) / [(<3> + 4 × <1> / 2 + 3 × <2> / 2) / 6] × 100 Unit: mol%

[Measurement of the number of terminal vinylidene groups using ¹³ C-NMR]
In the propylene polymer, <5> terminal methyl group (near 14.5 ppm) of n-propyl terminal, <6> terminal methyl group (near 14.0 ppm) of n-butyl group, <4> iso-butyl terminal A methine group (around 25.9 ppm) and a <7> terminal vinylidene group methylene group (around 111.7 ppm) are observed.

The peak intensity of the amount of terminal vinyl groups in ¹³ C-NMR is calculated as follows using (A) and (B) obtained by ¹ H-NMR spectrum.
¹³ C-NMR terminal vinyl group content peak intensity = (B) / (A) × <7>
Here, the total concentration (T) of the end groups is expressed as follows.
T = (B) / (A) × <7> + <4> + <5> + <6> + <7>
Therefore, the ratio of each terminal is as follows.
(C) Terminal vinylidene group = <7> / T × 100 Unit: mol%
(D) Terminal vinyl group = (B) / (A) × <7> × 100
(E) n-propyl terminal = <5> / T × 100
(F) n-butyl group terminal = <6> / T × 100
(G) iso-butyl end = <4> / T × 100
The number of terminal vinylidene groups per molecule is 2 × (C) / 100 units: pieces / molecule.

The reactive polyolefin has a molecular weight distribution Mw / Mn of 4.0 or less, preferably 3.5 or less, more preferably 3.0 or less, and further preferably 2.5 or less.
The molecular weight distribution of the reactive polyolefin is preferably as narrow as possible. This is because the reactive polyolefin forms a chain, and the narrower the molecular weight distribution of the reactive polyolefin, the smaller the side chain length (chain length) and the more controlled the graft copolymer can be obtained. .

The molecular weight distribution Mw / Mn can be determined by measuring the weight average molecular weight (Mw) and the number average molecular weight (Mn) by the GPC method.
The weight average molecular weight (Mw) and the number average molecular weight (Mn) are determined by the Universal Calibration method using the constants K and a of the Mark-Houwink-Sakurada formula in order to convert the polystyrene equivalent molecular weight into the molecular weight of the corresponding polymer. Can do.
Specifically, it can be determined by the method described in ““ Size Exclusion Chromatography ”” by Sadao Mori, P67-69, 1992, Kyoritsu Shuppan. K and α are “Polymer Handbook” John Wiley & Sons, Inc. "It is described in. Moreover, it can also determine by a conventional method from the relationship of the intrinsic viscosity with respect to the newly calculated absolute molecular weight.

The measuring apparatus and measurement conditions of GPC are as follows, for example.
Detector: RI detector for liquid chromatography Waters 150C
Column: TOSO GMHHR-H (S) HT
Solvent: 1,2,4-trichlorobenzene Measurement temperature: 145 ° C
Flow rate: 1.0 ml / min Sample concentration: 0.3% by mass

The reactive polyolefin has an intrinsic viscosity ([η]) measured at 135 ° C. in decalin of 0.01 to 2.5 dl / g, preferably 0.05 to 2.5 dl / g, more preferably It is 0.05-2.0 dl / g, More preferably, it is 0.1-2.0 dl / g, Most preferably, it is 0.15-1.8 dl / g.
When the intrinsic viscosity of the reactive polyolefin is in the above range, the graft copolymer obtained has a sufficient polyolefin side chain length (chain length), and functions such as compatibilization can be sufficiently exhibited. In addition, since the reactive polyolefin has a high concentration of terminal unsaturated groups during the graft polymerization, the reactive polyolefin having an intrinsic viscosity in the above range can increase radical polymerizability.

The intrinsic viscosity ([η]) is calculated by measuring the reduced viscosity (η _SP / c) with a Ubbelohde viscometer in decalin at 135 ° C. and using the following formula (Huggins formula).
η _SP / c = [η] + K [η] ² c
η _SP / c (dl / g): Reduced viscosity [η] (dl / g): Intrinsic viscosity c (g / dl): Polymer viscosity K = 0.35 (Haggins constant)

The reactive polyolefin preferably further satisfies the following (6) and / or (7).
(6) Racemic meso racemic meso fraction [rmrm]> 2.5 mol%
(7) The melting point (Tm, unit: ° C.) observed by a differential scanning calorimeter (DSC) and [mmmm] satisfy the following relationship.
1.76 [mmmm] -25.0 ≦ Tm ≦ 1.76 [mmmm] +5.0

  When the racemic meso racemic meso fraction [rmrm] of the reactive polyolefin is 2.5 mol%, the randomness increases and the transparency of the resulting graft copolymer can be improved.

The relational expression (7) represents the uniformity of the mesopentad fraction of the reactive polyolefin.
When the stereoregularity of the reactive polyolefin is high, that is, when the stereoregularity distribution is narrow, it means that the uniformity of the side chain of the obtained graft copolymer is high, and with the polypropylene resin etc. Compatibility can be improved. On the other hand, when a reactive polyolefin having a high mesopentad fraction and a reactive polyolefin having a low mesopentad fraction are mixed or they are block-bonded, that is, when the stereoregularity distribution is wide, the obtained graft copolymer The coalescence may decrease the compatibility with the polypropylene resin or the like.
In addition, [mmmm] in the formula (7) is measured as an average value, and it cannot be clearly distinguished between a case where the stereoregularity distribution is wide and a case where it is narrow, but the relationship with the melting point (Tm) is within the above range. By limiting, a highly uniform reactive polyolefin can be defined.

In the formula (7), when the melting point Tm exceeds (1.76 [mmmm] +5.0), it means that the reactive polyolefin has a part having a high stereoregularity part and a part having no stereoregulation. To do. Moreover, when melting | fusing point Tm is less than (1.76 [mmmm] -25.0), there exists a possibility that the heat resistance of reactive polyolefin may not be enough.
Formula (7) is preferably:
1.76 [mmmm] -20.0 ≦ Tm ≦ 1.76 [mmmm] +3.0
More preferably, it is the following.
1.76 [mmmm] -15.0 ≦ Tm ≦ 1.76 [mmmm] +2.0

Melting | fusing point Tm can be calculated | required by DSC measurement, for example, can be measured with the following method.
10 mg of a sample is heated to 25 ° C. to 220 ° C. at 320 ° C./min in a nitrogen atmosphere, held at 220 ° C. for 5 minutes, then cooled to 25 ° C. at 320 ° C./min, and held at 25 ° C. for 50 minutes. The temperature is raised from 25 ° C. to 220 ° C. at 10 ° C./min, and the peak top of the endothermic peak observed on the highest temperature side of the melting heat absorption curve detected in the temperature raising process is defined as melting point Tm.

The reactive polyolefin preferably satisfies any one or more of the following (11) to (13).
(11) [rrrr] / (1- [mmmm]) ≦ 0.1
(12) [mm] × [rr] / [mr] ² ≦ 2.0
(13) The component amount W25 eluting at 25 ° C. or lower in the temperature programmed chromatography is 20 to 100% by mass.

  When the reactive polyolefin satisfies (11), stickiness can be suppressed.

With respect to the formula (12), when [mm] × [rr] / [mr] ² is 2.0 or less, a decrease in transparency of the obtained graft copolymer can be suppressed, and the balance between flexibility and elastic recovery can be achieved. Can be good.
[Mm] × [rr] / [mr] ² is preferably 0.5 to 1.8, and more preferably 0.5 to 1.5.

In the formula (13), W25 is an index indicating whether or not the reactive polyolefin is soft, and when this value is small, a component having a high elastic modulus is increased or nonuniformity of [mmmm] is widened. Means that.
W25 is preferably 30 to 100% by mass, and more preferably 50 to 100% by mass. When the W25 is 20% by mass or more, the flexibility of the reactive polyolefin can be maintained.

  W25 is the amount (% by mass) of the component that elutes without being adsorbed by the packing material at a column temperature of 25 ° C. of TREF (temperature rising elution fractionation) in the elution curve determined by temperature rising chromatography.

W25 can be measured, for example, by the following operation method.
The sample solution is introduced into a TREF column adjusted to a temperature of 135 ° C., then gradually cooled to 0 ° C. at a temperature decrease rate of 5 ° C./hour, held for 30 minutes, and the sample is crystallized on the surface of the filler. Thereafter, the column is heated to 135 ° C. at a temperature increase rate of 40 ° C./hour to obtain an elution curve.

An example of devices and conditions that can be used for W25 measurement is shown below.
TREF column: silica gel column (4.6φ × 150 mm) manufactured by GL Science
Flow cell: GL Science optical path length 1 mm KBr cell Liquid feed pump: Senshu Scientific SSC-3100 pump Valve oven: GL Science model 554 oven (high temperature type)
TREF oven: GL Sciences 2 series temperature controller: Rigaku Kogyo REX-C100 temperature controller Detector: Infrared detector for liquid chromatography FOXBORO MIRAN 1A CVF
10-way valve: Barco Electric valve Loop: Barco 500 μl loop Solvent: o-dichlorobenzene Sample concentration: 7.5 g / L
Injection volume: 500 μl
Pump flow rate: 2.0 ml / min Detection wave number: 3.41 μm
Column filler: Chromosolv P (30-60 mesh)
Column temperature distribution: within ± 0.2 ° C

[Method for producing reactive polyolefin]
Reactive polyolefin can be manufactured by using a metallocene catalyst.
As said metallocene catalyst, it is a catalyst containing following (A) and (B), Comprising: The catalyst which can produce | generate a terminal unsaturated group is mentioned.
(A) Transition metal compound containing a metal element belonging to Groups 3 to 10 of the periodic table having cyclopentadienyl group substitution, cyclopentadienyl group, indenyl group, and substituted indenyl group. (B) Reacts with transition metal compound. Compounds that can form ionic complexes

  Examples of the transition metal compound include compounds composed of biscyclopentadienyl ligands such as zirconocene chloride and pentamethylcyclopentadienyldiconium dichloride; ethylenebisindenylzirconium dichloride, dimethylsilylene-bis- [2-methyl- 4-phenylindenyl] zirconium dichloride, a compound comprising a bridged indenyl ligand such as dimethylsilylene-bis- [2-methyl-4,5-benzoindenyl] zirconium dichloride; pentamethylcyclopentadienyltrimethoxytitanium, Compound consisting of monocyclopentadienyl ligand such as pentamethylcyclopentadienyl trichlorotitanium; dichloro [dimethylsilylene (cyclopentadienyl) (2,4-dimethyl-4H-1-azurenyl)] Hough , Dichloro [dimethylgermylene (cyclopentadienyl) (2,4-dimethyl-4H-1-azulenyl)] hafnium, dichloro [dimethylsilylene (2-methyl-1-indenyl) (2,4-dimethyl-4H -1-Azulenyl)] A compound composed of an azulenyl ligand such as hafnium.

Examples of the transition metal compound include bi-bridged complexes represented by the following formula (I).
The reactive polyolefin is one homopolymer or two or more copolymers selected from α-olefins having 3 to 28 carbon atoms using a catalyst containing a di-crosslinked complex represented by the formula (I); carbon Copolymer of 90% by mass or more of one or more monomers selected from α-olefins of several 3 to 28 and 10% by mass or less of ethylene; propylene homopolymer; or 90% by mass or more of propylene, ethylene and carbon number A propylene-based copolymer of 1 to 10% by mass selected from 4 to 28 α-olefins is preferred.

In formula (I), M represents a metal element belonging to Groups 3 to 10 of the periodic table, and specific examples include titanium, zirconium, hafnium, yttrium, vanadium, chromium, manganese, nickel, cobalt, palladium, and lanthanoid metals. Is mentioned. Among these, the fourth metal element is preferable from the viewpoint of olefin polymerization activity and the like, titanium, zirconium and hafnium are preferable, and zirconium is most preferable from the viewpoint of the yield of the terminal vinylidene group and the catalytic activity.
E ¹ and E ² are respectively substituted cyclopentadienyl group, indenyl group, substituted indenyl group, heterocyclopentadienyl group, substituted heterocyclopentadienyl group, amide group (—N <), phosphine group (—P <), Hydrocarbon group [>CR-,> C <] and silicon-containing group [>SiR-,> Si <] (where R is hydrogen, a hydrocarbon group having 1 to 20 carbon atoms, or a heteroatom-containing group) A ligand selected from among (A) is shown, and a crosslinked structure is formed through A ¹ and A ² . E ¹ and E ² may be the same as or different from each other. As E ¹ and E ² , a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group and a substituted indenyl group are preferable, and at least one of E ¹ and E ² is a cyclopentadienyl group, A substituted cyclopentadienyl group, an indenyl group or a substituted indenyl group;
X represents a σ-bonding ligand, and when there are a plurality of X, the plurality of X may be the same or different, and may be cross-linked with other X, E ¹ , E ² or Y. Specific examples of X include a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an amide group having 1 to 20 carbon atoms, and carbon. Examples thereof include a silicon-containing group having 1 to 20 carbon atoms, a phosphide group having 1 to 20 carbon atoms, a sulfide group having 1 to 20 carbon atoms, and an acyl group having 1 to 20 carbon atoms.

  Examples of the halogen atom for X include a chlorine atom, a fluorine atom, a bromine atom, and an iodine atom. Specific examples of the hydrocarbon group having 1 to 20 carbon atoms include methyl groups, ethyl groups, propyl groups, butyl groups, hexyl groups, cyclohexyl groups, octyl groups and other alkyl groups; vinyl groups, propenyl groups, cyclohexenyl groups, etc. An arylalkyl group such as benzyl group, phenylethyl group, phenylpropyl group; phenyl group, tolyl group, dimethylphenyl group, trimethylphenyl group, ethylphenyl group, propylphenyl group, biphenyl group, naphthyl group, methylnaphthyl group Group, anthracenyl group, aryl group such as phenanthonyl group, and the like. Of these, alkyl groups such as methyl group, ethyl group, and propyl group, and aryl groups such as phenyl group are preferable.

  Examples of the alkoxy group having 1 to 20 carbon atoms of X include an alkoxy group such as a methoxy group, an ethoxy group, a propoxy group, and a butoxy group, a phenylmethoxy group, and a phenylethoxy group. Examples of the aryloxy group having 6 to 20 carbon atoms include a phenoxy group, a methylphenoxy group, and a dimethylphenoxy group. Examples of the amide group having 1 to 20 carbon atoms include a dimethylamide group, a diethylamide group, a dipropylamide group, a dibutylamide group, a dicyclohexylamide group, and a methylethylamide group, a divinylamide group, and a dipropenylamide group. Alkenylamide groups such as dicyclohexenylamide group; arylalkylamide groups such as dibenzylamide group, phenylethylamide group and phenylpropylamide group; arylamide groups such as diphenylamide group and dinaphthylamide group.

  Examples of the silicon-containing group having 1 to 20 carbon atoms of X include a monohydrocarbon-substituted silyl group such as a methylsilyl group and a phenylsilyl group; a dihydrocarbon-substituted silyl group such as a dimethylsilyl group and a diphenylsilyl group; a trimethylsilyl group and a triethylsilyl group Groups, tripropylsilyl groups, tricyclohexylsilyl groups, triphenylsilyl groups, dimethylphenylsilyl groups, methyldiphenylsilyl groups, tritolylsilyl groups, trinaphthylsilyl groups, and other trihydrocarbon-substituted silyl groups; trimethylsilyl ether groups, etc. Examples include hydrocarbon-substituted silyl ether groups; silicon-substituted alkyl groups such as trimethylsilylmethyl group; silicon-substituted aryl groups such as trimethylsilylphenyl group. Of these, a trimethylsilylmethyl group, a phenyldimethylsilylethyl group, and the like are preferable.

  Examples of the phosphide group having 1 to 20 carbon atoms of X include a methyl sulfide group, an ethyl sulfide group, a propyl sulfide group, a butyl sulfide group, a hexyl sulfide group, a cyclohexyl sulfide group, and an alkyl sulfide group such as an octyl sulfide group; a vinyl sulfide group, Alkenyl sulfide groups such as propenyl sulfide group and cyclohexenyl sulfide group; arylalkyl sulfide groups such as benzyl sulfide group, phenylethyl sulfide group and phenylpropyl sulfide group; phenyl sulfide group, tolyl sulfide group, dimethylphenyl sulfide group, trimethylphenyl sulfide Group, ethylphenyl sulfide group, propylphenyl sulfide group, biphenyl sulfide group, naphthyl sulfide group, methyl naphthyl sulfide group Anthracenyl Nils sulfide group, an aryl sulfide groups such as a phenanthridine Nils sulfide group.

  Examples of the sulfide group having 1 to 20 carbon atoms of X include a methyl sulfide group, an ethyl sulfide group, a propyl sulfide group, a butyl sulfide group, a hexyl sulfide group, a cyclohexyl sulfide group, and an octyl sulfide group; a vinyl sulfide group, Alkenyl sulfide groups such as propenyl sulfide group and cyclohexenyl sulfide group; arylalkyl sulfide groups such as benzyl sulfide group, phenylethyl sulfide group and phenylpropyl sulfide group; phenyl sulfide group, tolyl sulfide group, dimethylphenyl sulfide group, trimethylphenyl sulfide Group, ethylphenyl sulfide group, propylphenyl sulfide group, biphenyl sulfide group, naphthyl sulfide group, methyl naphthyl sulfide group Anthracenyl Nils sulfide group, an aryl sulfide groups such as a phenanthridine Nils sulfide group.

  Examples of the acyl group having 1 to 20 carbon atoms of X include formyl group, acetyl group, propionyl group, butyryl group, valeryl group, palmitoyl group, thearoyl group, oleoyl group and other alkyl acyl groups, benzoyl group, toluoyl group, salicyloyl Groups, cinnamoyl groups, naphthoyl groups, phthaloyl groups and other arylacyl groups, and oxalyl groups, malonyl groups, succinyl groups and the like derived from dicarboxylic acids such as oxalic acid, malonic acid, and succinic acid.

On the other hand, Y represents a Lewis base, and when there are a plurality of Y, the plurality of Y may be the same or different, and may be cross-linked with other Y, E ¹ , E ² or X. Specific examples of the Lewis base of Y include amines, ethers, phosphines, thioethers and the like.

  Examples of the amines of Y include amines having 1 to 20 carbon atoms, specifically, methylamine, ethylamine, propylamine, butylamine, cyclohexylamine, methylethylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine. Alkylamines such as vinylamine, propenylamine, cyclohexenylamine, alkenylamines such as divinylamine, dipropenylamine, dicyclohexenylamine; arylalkylamines such as phenylamine, phenylethylamine, and phenylpropylamine; Examples include arylamines such as diphenylamine and dinaphthylamine.

  Examples of ethers of Y include aliphatic single ether compounds such as methyl ether, ethyl ether, propyl ether, isopropyl ether, butyl ether, isobutyl ether, n-amyl ether, isoamyl ether; methyl ethyl ether, methyl propyl ether, methyl isopropyl Aliphatic hybrid ether compounds such as ether, methyl-n-amyl ether, methyl isoamyl ether, ethyl propyl ether, ethyl isopropyl ether, ethyl butyl ether, ethyl isobutyl ether, ethyl n-amyl ether, ethyl isoamyl ether; vinyl ether, allyl ether Aliphatic unsaturated ether compounds such as methyl vinyl ether, methyl allyl ether, ethyl vinyl ether, ethyl allyl ether; , Aromatic ether compounds such as phenetol, phenyl ether, benzyl ether, phenyl benzyl ether, α-naphthyl ether, β-naphthyl ether, cyclic ethers such as ethylene oxide, propylene oxide, trimethylene oxide, tetrahydrofuran, tetrahydropyran, dioxane Compounds.

Examples of phosphines of Y include phosphines having 1 to 20 carbon atoms. Specific examples include monohydrocarbon-substituted phosphines such as methylphosphine, ethylphosphine, propylphosphine, butylphosphine, hexylphosphine, cyclohexylphosphine, and octylphosphine; dimethylphosphine, diethylphosphine, dipropylphosphine, dibutylphosphine, dihexylphosphine, dicyclohexyl Dihydrocarbon-substituted phosphines such as phosphine and dioctylphosphine; alkyl phosphines such as trihydrocarbon-substituted phosphines such as trimethylphosphine, triethylphosphine, tripropylphosphine, tributylphosphine, trihexylphosphine, tricyclohexylphosphine, and trioctylphosphine; vinyl Monoalkenes such as phosphine, propenylphosphine, cyclohexenylphosphine, etc. Dialkenylphosphine in which two alkenyls are substituted for phosphine and phosphine hydrogen atoms; Trialkenylphosphine in which three alkenyls are substituted for phosphine hydrogens; Arylalkylphosphine such as benzylphosphine, phenylethylphosphine, phenylpropylphosphine; Diarylalkylphosphine or aryldialkylphosphine having three hydrogen atoms substituted with aryl or alkenyl; phenylphosphine, tolylphosphine, dimethylphenylphosphine, trimethylphenylphosphine, ethylphenylphosphine, propylphenylphosphine, biphenylphosphine, naphthylphosphine, methylnaphthyl Phosphine, anthracenyl phosphine, phenanthenyl phosphine; phosphine water Atom alkyl aryl two substituted di (alkylaryl) phosphine; arylphosphine such as a hydrogen atom of phosphine alkylaryl three substituted with tri (alkylaryl) phosphine.
Examples of the thioether of Y include the above sulfides.

A ¹ and A ² are divalent bridging groups that bind two ligands, each having a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, Germanium-containing group, tin-containing group, —O—, —CO—, —S—, —SO ₂ —, —Se—, —NR ¹ —, —PR ¹ —, —P (O) R ¹ —, —BR ¹ - or -AlR ¹ - indicates, ^{R 1} represents a hydrogen atom, a halogen atom, a hydrocarbon group or a halogen-containing hydrocarbon group having 1 to 20 carbon atoms having 1 to 20 carbon atoms and are identical or different from each other May be. q represents an integer of 1 to 5 and represents [(M valence) -2], and r represents an integer of 0 to 3.
Among such crosslinking groups, at least one is preferably a crosslinking group composed of a hydrocarbon group having 1 or more carbon atoms. Examples of such a crosslinking group include those represented by the general formula (a), and specific examples thereof include a methylene group, an ethylene group, an ethylidene group, a propylidene group, an isopropylidene group, a cyclohexylidene group, 1,2-cyclohexylene group, vinylidene group (CH ₂ = C =), dimethylsilylene group, diphenylsilylene group, methylphenylsilylene group, dimethylgermylene group, dimethylstannylene group, tetramethyldisiylene group, diphenyldisiylene group Groups and the like. Among these, an ethylene group, an isopropylidene group, and a dimethylsilylene group are preferable.

(D is a group 14 element of the periodic table, and examples thereof include carbon, silicon, germanium and tin. R ² and R ³ are each a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and they are the same as each other. However, they may be different from each other, and may be bonded to each other to form a ring structure.

  Specific examples of the transition metal compound represented by the formula (I) include specific examples described in WO2008 / 066168, preferably a transition metal compound of Group 4 of the periodic table, and a zirconium compound is particularly preferable. .

Among the transition metal compounds represented by the above formula (I), compounds represented by the following formula (II) are preferable.

In the general formula (II), M represents a metal element belonging to Groups 3 to 10 of the periodic table, and A ^1a and A ^2a are each a cross-linking group represented by the general formula (a) in the general formula (I). CH ₂ , CH ₂ CH ₂ , (CH ₃ ) ₂ C, (CH ₃ ) ₂ C (CH ₃ ) ₂ C, (CH ₃ ) ₂ Si and (C ₆ H _{5) 2} Si are preferred.
A ^1a and A ^2a may be the same as or different from each other.
R ^{4 to} R ¹³ each represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, or a heteroatom-containing group.
Examples of the halogen atom, the hydrocarbon group having 1 to 20 carbon atoms, and the silicon-containing group are the same as those described in the general formula (I).
Examples of the halogen-containing hydrocarbon group having 1 to 20 carbon atoms include p-fluorophenyl group, 3,5-difluorophenyl group, 3,4,5-trifluorophenyl group, pentafluorophenyl group, 3,5-bis ( (Trifluoro) phenyl group, fluorobutyl group and the like.
Examples of the heteroatom-containing group include C1-C20 heteroatom-containing groups. Specifically, nitrogen-containing groups such as a dimethylamino group, a diethylamino group, and a diphenylamino group; a phenylsulfide group, a methylsulfide group, and the like Sulfur-containing groups of: phosphorus-containing groups such as dimethylphosphino groups and diphenylphosphino groups; oxygen-containing groups such as methoxy groups, ethoxy groups, and phenoxy groups. Among these, as R ⁴ and R ⁵ , a group containing a hetero atom such as halogen, oxygen, or silicon is preferable because of high polymerization activity. As R < ⁶ > -R < ¹³ >, a hydrogen atom or a C1-C20 hydrocarbon group is preferable. X and Y are the same as in general formula (I). q represents an integer of 1 to 5 and represents [(M valence) -2], and r represents an integer of 0 to 3.

  Among the transition metal compounds represented by the above general formula (II), when both indenyl groups are the same, examples of the transition metal compounds in Group 4 of the periodic table include specific examples described in WO2008 / 066168. Preferably, it is a transition metal compound of Group 4 of the periodic table, and among them, a zirconium compound is preferred.

On the other hand, among the transition metal compounds represented by the above formula (II), when R ⁵ is a hydrogen atom and R ⁴ is not a hydrogen atom, the transition metal compound of Group 4 of the periodic table is described in WO2008 / 066168 Specific examples thereof are preferable, and a transition metal compound belonging to Group 4 of the periodic table is preferable, and a zirconium compound is particularly preferable.

(B) As a compound capable of forming an ionic complex by reacting with a transition metal compound, a borate compound in that a high purity terminal unsaturated olefin polymer having a relatively low molecular weight can be obtained and a catalyst having high activity. Is preferred.
Examples of borate compounds include triethylammonium tetraphenylborate, tri-n-butylammonium tetraphenylborate, trimethylammonium tetraphenylborate, tetraethylammonium tetraphenylborate, and methyl (tri-n-butyl) ammonium tetraphenylborate. , Benzyl (tri-n-butyl) ammonium tetraphenylborate, dimethyldiphenylammonium tetraphenylborate, triphenyl (methyl) ammonium tetraphenylborate, trimethylanilinium tetraphenylborate, methylpyridinium tetraphenylborate, tetra Benzylpyridinium phenylborate, methyl tetraphenylborate (2-cyanopyridinium), tetrakis (pentafluorophenyl) borate trie Ruammonium, tetrakis (pentafluorophenyl) borate tri-n-butylammonium, tetrakis (pentafluorophenyl) borate triphenylammonium, tetrakis (pentafluorophenyl) borate tetra-n-butylammonium, tetrakis (pentafluorophenyl) ) Tetraethylammonium borate, benzyl (tri-n-butyl) ammonium tetrakis (pentafluorophenyl) borate, methyldiphenylammonium tetrakis (pentafluorophenyl) borate, triphenyl (methyl) ammonium tetrakis (pentafluorophenyl) borate , Tetrakis (pentafluorophenyl) methylanilinium borate, tetrakis (pentafluorophenyl) dimethylanilinium borate, tetra (Pentafluorophenyl) trimethylanilinium borate, tetrakis (pentafluorophenyl) methylpyridinium borate, tetrakis (pentafluorophenyl) benzylpyridinium borate, tetrakis (pentafluorophenyl) methylborate (2-cyanopyridinium), Benzyl tetrakis (pentafluorophenyl) borate (2-cyanopyridinium), methyl tetrakis (pentafluorophenyl) borate (4-cyanopyridinium)
, Tetrakis (pentafluorophenyl) triphenylphosphonium borate, tetrakis [bis (3,5-ditrifluoromethyl) phenyl] dimethylanilinium borate, ferrocenium tetraphenylborate, silver tetraphenylborate, trityl tetraphenylborate , Tetraphenylporphyrin manganese tetraphenylborate, triphenylcarbenium tetrakis (pentafluorophenyl) borate, methylanilinium tetrakis (perfluorophenyl) borate, ferrocenium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) ) Boric acid (1,1'-dimethylferrocenium), tetrakis (pentafluorophenyl) borate decamethylferrocenium, tetrakis (pentafluoropheny) ) Silver borate, tetrakis (pentafluorophenyl) trityl borate, tetrakis (pentafluorophenyl) lithium borate, tetrakis (pentafluorophenyl) sodium borate, tetrakis (pentafluorophenyl) tetraphenylporphyrin manganese borate, tetrafluoro Examples thereof include silver borate. These can be used individually by 1 type or in combination of 2 or more types. When the molar ratio of hydrogen and transition metal compound (hydrogen / transition metal compound) described later is 0, dimethylanilinium tetrakis (pentafluorophenyl) borate, triphenylcarbenium tetrakis (pentafluorophenyl) borate, and tetrakis (Perfluorophenyl) methylanilinium borate and the like are preferable.

The catalyst used for the production of the reactive polyolefin may be a combination of the component (A) and the component (B), and an organoaluminum compound is used as the component (C) in addition to the component (A) and the component (B). Also good.
As the organoaluminum compound of component (C), trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trinormal hexylaluminum, trinormaloctylaluminum, dimethylaluminum chloride, diethylaluminum chloride, methylaluminum dichloride, ethylaluminum dichloride. Dimethylaluminum fluoride, diisobutylaluminum hydride, diethylaluminum hydride and ethylaluminum sesquichloride. These organoaluminum compounds may be used alone or in combination of two or more.
Of these, trialkylaluminum such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trinormalhexylaluminum, and trinormaloctylaluminum is preferable, and triisobutylaluminum, trinormalhexylaluminum, and trinormaloctylaluminum are more preferable. preferable.

The amount of component (A) used is usually 0.1 × 10 ^{−6 to} 1.5 × 10 ⁻⁵ mol / L, preferably 0.15 × 10 ^{−6 to} 1.3 × 10 ⁻⁵ mol / L, more preferably ^{0.2 × 10 -6 ~1.2 × 10 -5} mol / L, particularly preferably ^{0.3 × 10 -6 ~1.0 × 10 -5} mol / L. When the amount of component (A) used is 0.1 × 10 ⁻⁶ mol / L or more, the catalytic activity is sufficiently expressed, and when it is 1.5 × 10 ⁻⁵ mol / L or less, the heat of polymerization is easy. Can be removed.
The use ratio (A) / (B) of the component (A) and the component (B) is preferably 10/1 to 1/100, more preferably 2/1 to 1/10 in terms of molar ratio. When (A) / (B) is in the range of 10/1 to 1/100, an effect as a catalyst can be obtained and the catalyst cost per unit mass polymer can be suppressed. Further, there is no fear that a large amount of boron exists in the target terminal unsaturated olefin polymer.
The use ratio (A) / (C) of the component (A) and the component (C) is preferably 1/1 to 1/10000, more preferably 1/5 to 1/2000, and further preferably 1 in terms of molar ratio. / 10 to 1/1000. By using the component (C), the polymerization activity per transition metal can be improved. When (A) / (C) is in the range of 1/1 to 1/10000, the balance between the effect of addition of component (C) and economy is good, and the intended terminal unsaturated olefin polymer There is no fear that a large amount of aluminum is present inside.
Preliminary contact can also be performed using the above-described components (A) and (B), or components (A), (B), and (C). The preliminary contact can be performed by bringing the component (A) into contact with, for example, the component (B). However, the method is not particularly limited, and a known method can be used. Such preliminary contact is effective in reducing the catalyst cost, such as improving the catalytic activity and reducing the proportion of the (B) component used as the promoter.

The reactive polyolefin is preferably a reactive polyolefin having a small amount of the catalyst residue, particularly preferably a transition metal content of 5 mass ppm or less, an aluminum content of 300 mass ppm or less, and a boron content of 5 mass ppm or less. .
The transition metal content of 5 mass ppm or less means that the total amount of transition metals such as titanium, zirconium and hafnium is 5 mass ppm or less.
The aluminum content is preferably 280 mass ppm or less.
These metal components can be measured by an ICP (High Frequency Inductively Coupled Plasma Spectroscopy) measuring device.
A graft copolymer obtained by using a reactive polyolefin having a small amount of catalyst residue is preferable because it is now pure and can be applied to the electric and electronic fields.

[Polyolefins other than reactive polyolefins]
Examples of polyolefins other than reactive polyolefins include polyolefins substantially free of terminal unsaturated groups obtained using Ziegler catalysts, metallocene catalysts, and the like.
For example, a polyolefin containing no unsaturated group obtained by hydrogenation of a reactive polyolefin having an unsaturated group, or a polyolefin containing no unsaturated group produced without using a polyene component. More specifically, The polyolefin of 1)-(3) is mentioned, Preferably it is polyolefin comprised by the same olefin seed | species as reactive polyolefin.
(1) Polyethylene resins such as high density polyethylene (HDPE), low density (LDPE), L-LDPE (2) isotactic polypropylene, syndiotactic polypropylene, atactic polypropylene, propylene and ethylene, 4 to 12 carbon atoms Copolymer composed of one or more α-olefins, polypropylene resin such as block polypropylene (3) Polymer composed of one or more olefins having 6 to 28 carbon atoms

  Combinations of reactive polyolefins and polyolefins other than reactive polyolefins include molten mixtures of reactive polyolefins and polyolefins other than reactive polyolefins, powder blends, dry blend mixtures such as pellets, solutions dissolved in hydrocarbon solvents, or after dissolution And a mixture in a suspended state produced by cooling or reprecipitation.

The mixing ratio of the reactive polyolefin to the polyolefin other than the reactive polyolefin is 20 to 100% by mass of the reactive polyolefin and 0 to 80% by mass of the polyolefin other than the reactive polyolefin, preferably 30 to 100% by mass of the reactive polyolefin. 0 to 70% by mass of polyolefin other than reactive polyolefin, more preferably 40 to 100% by mass of reactive polyolefin and 0 to 60% by mass of polyolefin other than reactive polyolefin, more preferably 50 to 100% by mass of reactive polyolefin and reactive polyolefin The other polyolefin is 0 to 50% by mass.
When the content of the reactive polyolefin is 20% by mass or more, the amount of the graft copolymer produced after the graft polymerization reaction is preferably increased. Since the production amount of the graft copolymer increases as the content of the reactive polyolefin increases, the content of the reactive polyolefin is preferably 100% by mass.
From another point of view, when the graft copolymer of the present invention is added to the same type of thermoplastic resin as the polyolefin other than the reactive polyolefin, the graft copolymer is sufficient in the polyolefin other than the reactive polyolefin. If the amount is present and is in a good dispersion state, the graft copolymer is easily dispersed throughout the resulting composition, which is preferable. Therefore, when the polyolefin other than the reactive polyolefin is 80% by mass or less, the polyolefin becomes an appropriate amount, which is preferable from the viewpoint of dispersibility.

[Monomer (a) and Monomer (b)]
The monomer (a) is at least one selected from the following [V], [VI], [VII] and [VIII], and is a monomer having poor single radical polymerizability.
[V] Maleic anhydride and substituted products thereof [VI] Maleic acid and esters thereof [VII] Vinylalkoxysilanes [VIII] α-olefins

[V] Examples of maleic anhydride and substituted products thereof include maleic anhydride such as maleic anhydride, methyl maleic anhydride, dimethyl maleic anhydride, phenyl maleic anhydride, diphenyl maleic anhydride, and substituted products thereof.
[VI] Examples of maleic acid and esters thereof include maleic acid such as maleic acid, methylmaleic acid, dimethyl maleate, diethyl maleate, dibutyl maleate and monomethyl maleate, and esters thereof.
[VII] Examples of vinylalkoxysilanes include vinyltrimethoxysilane and vinyltriethoxysilane.
[VIII] α-olefins include ethylene, propylene, 1-butene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, Examples include 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-nonacene, 1-eicosene and other α-olefins having 2 to 28 carbon atoms; and branched olefins such as isobutene.

The monomer (b) is at least one selected from the following [I], [II], [III], [IV], [V] and [VIII], and the monomer (a) It is a monomer that can be radically copolymerized.
In the case where the monomer (a) is two or more monomers selected from [V], [VI], [VII] and [VIII], at least one monomer (b) is selected. It is sufficient that the monomer can be copolymerized with any one monomer of the monomer (a).
[I] Acrylic acid and its derivative [II] Methacrylic acid and its derivative [III] Vinyl ester and its derivative [IV] Styrene and its derivative [V] Maleic anhydride and its substitute [VIII] α-olefin

Monomer (a) and monomer (b) are mutually different monomers.
For example, when the monomer (a) is two or more monomers selected from [V], [VI], [VII] and [VIII], the monomer (b) It does not overlap with any of a).

When the monomer (a) is [V] maleic anhydride and its substitution or [VI] maleic acid and its ester, the monomer (b) excludes, for example, [V] maleic anhydride and its substitution The following can be used.
[I] As acrylic acid and derivatives thereof, acrylic acid; acrylic acid such as methyl acrylate, ethyl acrylate, butyl acrylate (also referred to as normal butyl acrylate), normal octyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, etc. Esters: Polyethylene glycol monoacrylate, polyethylene glycol polypropylene glycol acrylate, poly (ethylene glycol-n-tetramethylene glycol) monoacrylate, propylene glycol polybutylene glycol monoacrylate, polypropylene glycol monoacrylate, etc. Type glycols: sodium acrylate, potassium acrylate, magnesium acrylate, calcium acrylate Acrylic acid metal salt composed of acrylic acid and typical metal elements such as acrylates; acrylic acid esters containing oxygen, nitrogen, sulfur and silicon atoms in the ester residue (for example, glycidyl acrylate, 2-hydroxyethyl acrylate, acrylic acid 2-hydroxypropyl, 2-hydroxy-3-phenoxypropyl acrylate, 4-hydroxybutyl acrylate, acryloyloxyethyl isocyanate, methacryloyloxyethyl isocyanate, 3-acryloxypropyltrimethoxysilane (also referred to as methacryloxypropyltrimethoxysilane), Acrylic acid esters having functional groups such as 3-acryloxypropyltriethoxysilane; polyethylene glycol monoacrylate, polyethylene glycol polypropylene glycol acrylate Poly (ethylene glycol-n-tetramethylene glycol) monoacrylate, propylene glycol polybutylene glycol monoacrylate, long-chain polyalkylene glycols having a molecular weight of 30000 or less, such as polypropylene glycol monoacrylate); acrylamide; oxygen as a substituent, N-substituted acrylamide containing nitrogen, sulfur and silicon atoms (for example, N-methylacrylamide, N-ethylacrylamide, N-isopropylacrylamide, N-cyclohexylacrylamide, N, N-dimethylacrylamide, N, N-diethylacrylamide) N, N-dibutylacrylamide, N, N-dicyclohexylacrylamide, N- (2-hydroxyethyl) -acrylamide, N- (2-hydroxypropyl) -N-substituted acrylamides such as acrylamide, N, N-dimethylaminoethyl acrylamide, N-methylol acrylamide); acrylonitrile.
[II] Methacrylic acids (methacrylic acid and α-alkyl substituted products of acrylic acid) and derivatives thereof include alkyl groups such as a methyl group (preferably carbon at the α-position of the above [I] acrylic acid and derivatives thereof) And a monomer having an alkyl group of 6 or less.
[III] Vinyl esters and derivatives thereof include vinyl esters such as vinyl acetate, vinyl propionate, vinyl isolacrate, vinyl pivalate, vinyl undecanoate, vinyl palmitate, vinyl caproate, vinyl laurate, and derivatives thereof. It is done.
[IV] Styrene and derivatives thereof include α-methyl styrene, p-methyl styrene, p-ethyl styrene, p-propyl styrene, p-isopropyl styrene, p-butyl styrene, p-tert-butyl styrene, p-phenyl. Styrene, o-methyl styrene, o-ethyl styrene, o-propyl styrene, o-isopropyl styrene, m-methyl styrene, m-ethyl styrene, m-isopropyl styrene, m-butyl styrene, mesityl styrene, 2,4- Alkyl styrenes such as dimethyl styrene, 2,5-dimethyl styrene and 3,5-dimethyl styrene; alkoxy styrenes such as p-methoxy styrene, o-methoxy styrene and m-methoxy styrene; p-chloro styrene, m-chloro Styrene, o-bromostyrene, p-full Halogenated styrenes such as orostyrene, m-fluorostyrene, o-fluorostyrene, o-methyl-p-fluorostyrene; styrene such as trimethylsilylstyrene and vinylbenzoic acid and derivatives thereof.
[VIII] The α-olefin includes the α-olefins exemplified for the monomer (a).

  When the monomer (a) is [VIII] α-olefin, the monomer (b) can use, for example, [V] maleic anhydride and its substitution product. As a specific example of the combination of the body (b), the above-mentioned monomer (a) is [V] maleic anhydride and a substituted product thereof, and the monomer (b) is a [VIII] α-olefin. It is the same.

  When the monomer (a) is [VII] vinyl alkoxysilane, the monomer (b) may be, for example, [I] acrylic acid and derivatives thereof, and [IV] styrene and derivatives thereof.

Preferred combinations of the monomer (a) and the monomer (b) include the following.
Monomer (a) is [V] maleic anhydride and its substitution product, and monomer (b) is a combination of [VIII] α-olefin, more preferably monomer (a) is anhydrous. Maleic acid or a combination of maleic acid and monomer (b) being an α-olefin having 4 to 28 carbon atoms, more preferably monomer (a) is maleic anhydride and monomer ( A combination in which b) is an α-olefin having 6 to 18 carbon atoms.
The monomer (a) is [V] maleic anhydride and a substituted product thereof, and the monomer (b) is a combination of [I] acrylic acid and a derivative thereof, more preferably the monomer (a). Is maleic anhydride or maleic anhydride, and monomer (b) is acrylic acid or a combination of acrylic esters, more preferably monomer (a) is maleic anhydride, monomer ( b) is a combination of acrylic acid or acrylic acid esters.
The monomer (a) is [V] maleic anhydride and a substituted product thereof, and the monomer (b) is a combination of [III] vinyl ester and a derivative thereof, more preferably the monomer (a). Is maleic anhydride and the monomer (b) is vinyl acetate.
The monomer (a) is a vinyl alkoxysilane, and the monomer (b) is a combination of [I] acrylic acids and derivatives thereof, more preferably the monomer (a) is vinyltrimethoxysilane or It is vinyltriethoxysilane, and the monomer (b) is a combination of acrylic acid esters or acrylonitrile.

As a compounding ratio of the monomer (a) and the monomer (b) in the monomer mixture, for example, the monomer (a) / monomer (b) is 0.01 to 0.5 [mol / mol. ], Preferably 0.02-0.4 [mol / mol], more preferably 0.03-0.35 [mol / mol].
When the monomer (a) / monomer (b) is less than 0.01, the content of the monomer (a) in the graft copolymer is lowered, and the performance such as adhesion may be lowered. There is. On the other hand, when the monomer (a) / monomer (b) exceeds 0.5, the monomer (a) may remain as an unreacted product, which may cause problems such as coloring and an increase in production cost. is there.

The amount of the monomer mixture comprising the monomer (a) and the monomer (b) is 0.2 to 300 parts by mass with respect to 100 parts by mass of the reactive polyolefin and the polyolefin other than the reactive polyolefin. Preferably, it is 1-250 mass parts, More preferably, it is 5-200 mass parts, More preferably, it is 10-180 mass parts.
The amount of monomer in the graft copolymer obtained by setting the amount of the monomer mixture to be 0.2 parts by mass or more with respect to 100 parts by mass of the combination of reactive polyolefin and polyolefin other than reactive polyolefin is It raises and functions, such as compatibilization, become easy to express. Moreover, the amount of the monomer mixture used is preferably 300 parts by mass or less, so that a polymer that does not participate in the graft reaction does not occur as a by-product.

[Radical initiator]
The radical initiator is not particularly limited and can be appropriately selected from conventionally known radical initiators, for example, various organic peroxides, azo compounds, and the like. Both compounds are suitable radical initiators. It is an agent.
Examples of the organic peroxide include dibenzoyl peroxide, di-8,5,5-trimethylhexanoyl peroxide, dilauroyl peroxide, didecanoyl peroxide, and di (2,4-dichlorobenzoyl) peroxide. Diacyl peroxides, t-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, hydroperoxides such as 2,5-dimethylhexane-2,5-dihydroperoxide, di-t-butyl Peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3, Dialkyl pars such as α, α'bis (t-butylperoxy) diisopropylbenzene Peroxyketals such as xoxides, 1,1-bis-t-butylperoxy-3,3,5-trimethylcyclohexane, 2,2-bis (t-butylperoxy) butane, t-butylperoxyoct , Alkyl peresters such as t-butyl peroxypivalate, t-butyl peroxyneodecanoate, t-butyl peroxybenzoate, di-2-ethylhexyl peroxydicarbonate, diisopropyl peroxydicarbonate, di Examples include peroxycarbonates such as -sec-butylperoxydicarbonate and t-butylperoxyisopropylcarbonate, and among these, dialkyl peroxides are preferable. Examples of the azo compound include azobisisobutyronitrile and azobisisovaleronitrile.
A radical initiator may be used individually by 1 type, and may be used in combination of 2 or more type.

There is no restriction | limiting in particular as the usage-amount of a radical initiator, According to the desired physical property of a graft copolymer, it selects suitably.
A radical initiator is used in 0.001-10 mass parts with respect to 100 mass parts of combinations of reactive polyolefin and polyolefins other than reactive polyolefin, Preferably it is used in 0.005-5 mass parts.

In the first method for producing a graft copolymer of the present invention, for example, the monomer (b) is continuously supplied to a mixture obtained by contacting a reactive polyolefin containing a radical initiator and the monomer (a); Or it can implement by supplying a monomer (b) continuously to the mixture which contacted the combination of the reactive polyolefin containing a radical initiator, and polyolefin other than reactive polyolefin, and the monomer (a).
In addition, the monomer (b) and the radical initiator are continuously supplied to the mixture in which the reactive polyolefin and the monomer (a) are contacted; It can also be carried out by continuously supplying the monomer (b) and the radical initiator to the mixture in contact with the monomer (a).

The above-mentioned “continuous supply” means supply in which the supply amount per unit time is always constant; supply in which the supply amount per unit time changes with time but without interruption; and monomer or radical initiation The total amount of the agent is divided into about 2 to 10 times, and each of them is sequentially supplied at an arbitrary time.
The supply time may be set between 10 minutes and 12 hours from the start to the end of supply.

  When carrying out the method for producing the first graft copolymer of the present invention, the reactive polyolefin or the combination of the reactive polyolefin and the polyolefin other than the reactive polyolefin may be dissolved in a solvent, without using a solvent. It may be melted.

When a reactive polyolefin or a combination of a reactive polyolefin and a polyolefin other than the reactive polyolefin is dissolved in a solvent and the first graft copolymer is produced, the solvent includes benzene, toluene, xylene, Aromatic hydrocarbons such as mixed xylene; Aliphatic hydrocarbons such as hexane, heptane, octane, nonane, decane and dodecane; Alicyclic hydrocarbons such as cyclohexane and methylcyclohexane; Methyl acetate, ethyl acetate, propyl acetate Organic carboxylic esters such as butyl acetate, propyl acetate, hexyl acetate and octyl acetate; ketones such as acetone and methyl ethyl ketone; cyclic ethers such as tetrahydrofuran and tetrahydropyran; and halogenated hydrocarbons such as chlorobenzene Can do.
These solvents may be used alone or as a mixed solvent of two or more.

  Among the above solvents, when one kind of solvent is used, aliphatic hydrocarbons such as heptane, octane and decane, aromatic hydrocarbons such as toluene and xylene, and cyclic ethers such as tetrahydrofuran are preferable.

When the above solvent is used as a mixed solvent, it is preferable to use a solvent that dissolves the monomer (a), the monomer (b), the reactive polyolefin, and the polyolefin other than the reactive polyolefin, and these are uniformly dissolved. It is preferable to adjust the mixing ratio in advance.
Examples of the mixed solvent include one or more selected from aliphatic hydrocarbons and alicyclic hydrocarbons, and one or more mixed solvents selected from carboxylic esters and ketones. Specifically, Examples include hexane / ethyl acetate, hexane / butyl acetate, hexane / methyl ethyl ketone, and mixed solvents in which hexane is replaced with heptane, decane, cyclohexane, or methylcyclohexane.
In addition, a mixed solvent in which two or more of the above-mentioned single solvents are combined, or a mixed solvent in which the above-mentioned single solvent and a carboxylic acid ester ketone are combined can be used.
In the composition of the mixed solvent composed of two or more solvents, the ratio of the specific one solvent to the total solvent weight is, for example, 25 to 75% by weight, preferably 30 to 70% by weight, and more preferably 35 -65% by weight. In the mixed solvent, when the content ratio of one specific solvent is less than 25% by weight or more than 75% by weight, an insoluble component may be generated.

  The concentration of the reactive polyolefin in the solvent or the combination of the reactive polyolefin and the polyolefin other than the reactive polyolefin is usually 10 to 80% by weight.

When the reactive polyolefin or the combination of the reactive polyolefin and the polyolefin other than the reactive polyolefin is melted without using a solvent to carry out the first graft copolymer production method, the reactive polyolefin, or the reactive polyolefin and It is preferable that the monomer (a) can be dissolved in a mixture of polyolefins other than the reactive polyolefin.
Examples of such a monomer (a) include [VIII] α-olefin and [VII] vinyl alkoxysilanes.

The reaction temperature during graft polymerization in the method for producing the first graft copolymer is, for example, in the range of 40 to 260 ° C, preferably 70 to 260 ° C, more preferably 80 to 250 ° C, and most preferably 90 to 240. It is in the range of ° C. If the reaction temperature is less than 40 ° C., the melt fluidity may be inferior, or the graft reaction rate may be reduced. On the other hand, when the reaction temperature exceeds 260 ° C., there is a high possibility that the reactive polyolefin or a mixture of the reactive polyolefin and the polyolefin other than the reactive polyolefin is thermally decomposed, which may cause deterioration, coloring, and the like.
When the graft polymerization is carried out using a solvent, the substantial upper limit of the reaction temperature corresponds to the temperature at which the solvent boils under atmospheric pressure conditions, preferably 40 to 180 ° C, more preferably 40 to 160 ° C. Most preferably, it is in the range of 50 to 150 ° C. On the other hand, when the graft polymerization is carried out in a molten state, there is no restriction in the case of using a solvent, and it can be carried out in the range of 40 to 260 ° C. It is sufficient if the temperature is higher than the temperature at which the melt flows.

The reaction time can be set, for example, in the range of 10 minutes to 12 hours, preferably 20 minutes to 11 hours, and more preferably 30 minutes to 10 hours.
If the reaction time is less than 10 minutes, the graft reaction may not be sufficiently completed if less than 10 minutes, and unreacted monomers and the like may remain. On the other hand, when the reaction time exceeds 12 hours, yellowing may occur when the reaction temperature is high.
The “reaction time” is the time after the total amount of the reactive polyolefin, the monomers (a) and (b), and the radical initiator is in contact, and does not include the time required for supply. .

Graft polymerization may be carried out in the presence of a Lewis acid.
Examples of the Lewis acid that can be used in the first method for producing a graft copolymer of the present invention include the following compounds.
(1) Halides of group 2 to group 4 elements (chlorine, bromine, fluorine, iodine), alkylates (hydrocarbon groups having 1 to 20 carbon atoms), alkyl halides (2) aluminum, boron, Lewis acid consisting of zinc, tin, magnesium and calcium atoms

  Specific examples of Lewis acids include magnesium chloride, calcium chloride, zinc chloride, boron trichloride, aluminum trichloride, gallium trichloride, silicon tetrachloride, silicon tetrachloride, and compounds in which chlorine atoms are converted to bromine and fluorine atoms. , Butylethylmagnesium, diethylzinc, trimethylaluminum, triethylaluminum, triisobutylaluminum, trinormal hexylaluminum, trimethylboron, triethylboron, triethylgallium, trimethylgallium, diethylaluminum monochloride, ethylaluminum dichloride, ethylaluminum sesquichloride Of these, zinc compounds, aluminum compounds, and boron compounds are preferred.

As the amount of Lewis acid used in the graft polymerization reaction, Lewis acid / monomer (mol / mol) is 0.01 to 1, preferably 0.05 to 1, and more preferably 0.1 to 0.5. . Here, the monomer means the total substance amount of the monomer (a) and the monomer (b).
When the Lewis acid / monomer (mole / mole) is 0.01 or more, the graft ratio is high, and when it is 1 or less, the removal of the Lewis acid residue by deashing is unnecessary, so that there is no coloration.
The Lewis acid can be added before the radical initiator is added to carry out a graft polymerization reaction, or the graft polymerization reaction can be carried out by using a monomer and a Lewis acid previously brought into contact with each other.

[Method for producing second graft copolymer]
The manufacturing method of the 2nd graft copolymer of this invention is the combination 100 of 20-100 mass% of reactive polyolefins which satisfy | fill (1)-(5), and 0-80 mass% of polyolefins other than reactive polyolefin. Manufacture of a graft copolymer that is graft-polymerized using 1 part by mass or more, 0.2 to 300 parts by mass of a monomer selected from [I] to [IV], and 0.001 to 10 parts by mass of a radical initiator The method wherein the graft polymerization is carried out in a homogeneous reaction field at a temperature of 140-260 ° C.
(1) One type of homopolymer or two or more copolymers selected from α-olefins having 3 to 28 carbon atoms, or 90 masses of one or more monomers selected from α-olefins having 3 to 28 carbon atoms (2) Mesopentad fraction [mmmm] is 30 to 80 mol% (3) 0.5 to 1.0 terminal unsaturated groups per molecule (4) The molecular weight distribution (Mw / Mn) is 4 or less. (5) The intrinsic viscosity ([η]) measured at 135 ° C. in decalin is 0.01 to 2.5 dl / g. [I] Acrylic acid And derivatives thereof [II] Methacrylic acids and derivatives thereof [III] Vinyl esters and derivatives thereof [IV] Styrene and derivatives thereof

  In the second method for producing a graft copolymer of the present invention, a reactive polyolefin, a polyolefin other than the reactive polyolefin, and one or more monomers selected from [I] to [IV] are graft-polymerized in a uniform reaction field. By carrying out the above, it is possible to suppress the formation of a homopolymer of a monomer that does not participate in graft polymerization, and to improve the uniformity of the resulting graft copolymer. Moreover, since the composition of raw materials such as reactive polyolefin can be made uniform, the conversion efficiency can also be improved.

  The “homogeneous reaction field” in the production method of the second graft copolymer of the present invention is a reactive polyolefin or reactive polyolefin during graft polymerization in a molten state (melt reaction) or during graft polymerization using a solvent. It means a state in which the polyolefin and the monomer other than are melted or dissolved.

When the second graft copolymer production method is carried out in a molten state, the uniformity of the molten reaction field can be ensured by using one or more monomers capable of dissolving the reactive polyolefin.
The monomer capable of dissolving the reactive polyolefin is a monomer selected from [I] to [IV], and among these, preferably bonded to an acrylate ester having an ester group having 4 or more carbon atoms or a carbonyl carbon And vinyl esters having 4 or more carbon atoms in the hydrocarbon group and derivatives thereof.
When implementing the manufacturing method of a 2nd graft copolymer using a solvent, a uniform reaction field is securable by using the solvent of the manufacturing method of a 1st graft copolymer.

The reactive polyolefin that can be used in the method for producing the second graft copolymer, the polyolefin other than the reactive polyolefin, the monomers [I] to [IV], the radical initiator, and the like are the same as those in the first graft copolymer. The same manufacturing method can be used.
The reactive polyolefin used in the method for producing the second graft copolymer, the polyolefin other than the reactive polyolefin, the monomers [I] to [IV], the radical initiator, This is the same as the method for producing the graft copolymer.

The production method of the second graft copolymer is preferably a combination of 20 to 100% by mass of a reactive polyolefin satisfying the following (1) to (5) and 0 to 80% by mass of a polyolefin other than the reactive polyolefin. 100 parts by mass;
0.2 to 300 parts by mass of one or more monomers selected from the following [I] to [IV] including at least a monomer selected from the following [I ′] to [III ′] Graft polymerization is performed at 140 to 260 ° C. in the presence of 001 to 10 parts by mass.
(1) One type of homopolymer or two or more copolymers selected from α-olefins having 3 to 28 carbon atoms, or 90 masses of one or more monomers selected from α-olefins having 3 to 28 carbon atoms (2) Mesopentad fraction [mmmm] is 30 to 80 mol% (3) 0.5 to 1.0 terminal unsaturated groups per molecule (4) The molecular weight distribution (Mw / Mn) is 4 or less. (5) The intrinsic viscosity ([η]) measured at 135 ° C. in decalin is 0.01 to 2.5 dl / g. [I] Acrylic acid And derivatives thereof [II] Methacrylic acids and derivatives thereof [III] Vinyl esters and derivatives thereof [IV] Styrene and derivatives thereof [I ′] Acrylic esters containing a hydrocarbon group having 4 to 20 carbon atoms in the ester residue and the derivatives thereof Derivative [I I ′] Methacrylic acid ester having 4 to 20 carbon atoms in the ester residue and derivatives thereof [III ′] Vinyl ester having 4 to 20 carbon atoms in the residue and derivatives thereof

The monomers [I '], [II'] and [III '] can dissolve both high-polarity monomers and low-polarity reactive polyolefins. This is preferable because it can be present in the system.
[I ′] Examples of the acrylate ester and derivatives thereof containing a hydrocarbon group having 4 to 20 carbon atoms in the ester residue include butyl acrylate, 2-ethylhexyl acrylate, and stearyl acrylate.
[II ′] Examples of methacrylic acid esters and derivatives thereof containing a hydrocarbon group having 4 to 20 carbon atoms in the ester residue include butyl methacrylate, 2-ethylhexyl methacrylate, and metastearyl acrylate.
[III ′] Examples of the vinyl ester containing a hydrocarbon group having 4 to 20 carbon atoms in the residue and derivatives thereof include vinyl undecanoate, vinyl palmitate, vinyl caproate, vinyl laurate, and vinyl stearate.

In addition to the above, the production method of the second graft copolymer is preferably 20 to 100% by mass of a reactive polyolefin satisfying the following (1) to (5), and 0 to 80% by mass of a polyolefin other than the reactive polyolefin. A combination of 100 parts by weight,
In the presence of 0.001 to 10 parts by mass of a radical initiator, at least one monomer selected from the following [I] to [IV] is used in the presence of 0.001 to 10 parts by mass of an aliphatic hydrocarbon, alicyclic hydrocarbon or cyclic ether. In the above solvent, the graft polymerization is carried out in a mixed solvent composed of an organic carboxylic acid ester and an aliphatic hydrocarbon, or in a mixed solvent composed of an organic carboxylic acid ester, an aliphatic hydrocarbon and an alicyclic hydrocarbon.
(1) One type of homopolymer or two or more copolymers selected from α-olefins having 3 to 28 carbon atoms, or 90 masses of one or more monomers selected from α-olefins having 3 to 28 carbon atoms (2) Mesopentad fraction [mmmm] is 30 to 80 mol% (3) 0.5 to 1.0 terminal unsaturated groups per molecule (4) The molecular weight distribution (Mw / Mn) is 4 or less. (5) The intrinsic viscosity ([η]) measured at 135 ° C. in decalin is 0.01 to 2.5 dl / g. [I] Acrylic acid And derivatives thereof [II] Methacrylic acids and derivatives thereof [III] Vinyl esters and derivatives thereof [IV] Styrene and derivatives thereof

  In the method for producing a graft copolymer using a specific solvent, the solvent to be used is a common solvent for the reactive polyolefin and the monomer, and specific examples of the solvent are the methods for producing the first graft copolymer of the present invention. It is the same as that of the solvent.

The method for producing the second graft copolymer includes, for example, continuously supplying the monomer to a solution or molten mixture of a reactive polyolefin containing a radical initiator; or a reactive polyolefin and a reactive polyolefin containing a radical initiator It can carry out by supplying a monomer continuously to the solution or molten mixture of the combination of polyolefin other than.
Also, the monomer and radical initiator are continuously supplied to the reactive polyolefin; or the monomer and radical initiator are continuously supplied to the combination of the polyolefin other than the reactive polyolefin and the reactive polyolefin. Can also be implemented.
The solvent that can be used for the reactive polyolefin or the combination of the reactive polyolefin and the polyolefin other than the reactive polyolefin is the same as the solvent in the method for producing the first graft copolymer.

When the reactive polyolefin or the combination of the reactive polyolefin and the polyolefin other than the reactive polyolefin is dissolved in a solvent and the method for producing the second graft copolymer is carried out, the stirring state does not change depending on the reaction scale. If the reaction field shows a uniform mixing property, the monomer can be supplied in the same continuous supply regardless of the reaction scale.
However, since the uniformity of the reaction field generally decreases as the reaction scale increases, the solvent system contains less than 1 kg of reactive polyolefin or a mixture of reactive polyolefin and polyolefin other than reactive polyolefin. On the scale, the monomer (and radical initiator) supply time is 5 minutes to 5 hours, more than 1 kg to less than 10 kg, 10 minutes to 10 hours, more than 10 kg to less than 100 kg, more than 30 minutes to 20 hours, more than 100 kg. It may be 60 minutes to 30 hours for a scale less than ˜1000 kg, 90 minutes to 40 hours for a scale greater than 1000 kg to less than 10,000 kg, and 120 minutes to 50 hours for a scale greater than 10000 kg to less than 100,000 kg.

When a reactive polyolefin or a combination of a reactive polyolefin and a polyolefin other than the reactive polyolefin is melted and the method for producing the second graft copolymer is carried out, the reaction field has a high viscosity, so that it can be uniformly mixed by stirring. Mixability is reduced compared to the solvent system described above.
In the melt system, when the reactive polyolefin or the mixture of the reactive polyolefin and the polyolefin other than the reactive polyolefin is 1 kg or less, the monomer (and radical initiator) supply time is 10 minutes to 5 hours and exceeds 1 kg. 20 minutes to 15 hours for a scale less than 10 kg, 50 minutes to 30 hours for a scale greater than 10 kg to less than 100 kg, 100 minutes to 40 hours for a scale greater than 100 kg to less than 1000 kg, 120 minutes to 50 hours for a scale less than 1000 kg to less than 10,000 kg, In the scale of more than 10,000 kg to less than 100,000 kg, the time is preferably 180 minutes to 60 hours.

The reaction temperature at the time of graft polymerization in the method for producing the second graft copolymer is 140 to 260 ° C, preferably 140 to 250 ° C, more preferably 142 to 250 ° C, and further preferably 145 to 245 ° C. . When the reaction temperature is 140 to 260 ° C., the polymerization reaction rate of the monomer increases, and the unreacted monomer can be greatly reduced.
In a high temperature reaction of 140 to 260 ° C., a rapid reaction is likely to proceed due to a high reaction rate, and there is a possibility that a monomer homopolymer may be formed or a screen clogging of an extruder may occur. In the method for producing a graft copolymer, these problems can be solved by carrying out polymerization in a uniform reaction field.

  Graft polymerization may be carried out in the presence of a Lewis acid, and usable Lewis acids are the same as in the method for producing the first graft copolymer.

[Graft copolymer]
The graft copolymer of the present invention is obtained by the method for producing the first graft copolymer of the present invention or the method for producing the second graft copolymer.
The first graft copolymer of the present invention obtained by the method for producing the first graft copolymer is, for example, one homopolymer selected from α-olefins having 3 to 28 carbon atoms or two or more types of copolymer A chain end and / or main chain pendant of a reactive polyolefin which is a copolymer or a copolymer of 90% by mass or more of one or more monomers selected from α-olefins having 3 to 28 carbon atoms and 10% by mass or less of ethylene A graft copolymer having a structure in which the unsaturated group is incorporated into a copolymer chain derived from one or more selected from the monomer (a) and one or more selected from the monomer (b) is there.
The graft copolymer of the present invention obtained by the method for producing the second graft copolymer is derived from one or more monomers selected from, for example, [I], [II], [III] and [IV]. One or more homopolymers or two or more copolymers selected from α-olefins having 3 to 28 carbon atoms, or one or more selected from α-olefins having 3 to 28 carbon atoms. It is a graft copolymer having a side chain derived from a reactive polyolefin which is a copolymer of 90% by mass or more of monomers and 10% by mass or less of ethylene.

The graft ratio of the first graft copolymer and the second graft copolymer of the present invention (hereinafter sometimes collectively referred to as the graft copolymer of the present invention) is preferably 1 to 150% by mass. Yes, more preferably 2 to 130% by mass, still more preferably 5 to 100% by mass.
When the graft ratio is 1% by mass or more, the number of side chains is appropriate, and functions such as compatibilization and adhesion can be sufficiently exerted. When the graft rate is 150% by mass or less, the reactive polyolefin component is appropriate and functions sufficiently. Can demonstrate.

The graft ratio can be measured, for example, as follows.
From the mass of the insoluble graft copolymer component (W2) and the mass of the reactive polyolefin used as a raw material (W1) Calculate as follows.
Graft ratio (mass%) = (W2−W1) / W1 × 100
Moreover, it is not limited to the said method, It can determine by a conventional method from the NMR measurement of an insoluble graft copolymer component.

The graft copolymer of the present invention preferably has an intrinsic viscosity [η] measured at 135 ° C. in decalin of 0.01 to 2.5 dl / g, more preferably 0.02 to 2.2, and even more preferably. Is 0.05 to 2.0.
When the intrinsic viscosity [η] is 0.01 dl / g or more, functions such as resin compatibilization are improved, and when it is 2.5 dl / g or less, dispersibility in the resin is improved.

  The weight average molecular weight of the graft copolymer of the present invention is usually 500 to 400,000, preferably 700 to 350,000, more preferably 1000 to 300000, and most preferably 1500 to 250,000.

The molecular weight distribution (Mw / Mn) of the graft copolymer of the present invention is 1.8 to 6, preferably 1.8 to 5, more preferably 1.8 to 4, and most preferably 1.5. ~ 4. In addition, by using appropriate reaction conditions, controlling the reactivity of unsaturated groups, controlling the number of terminal unsaturated groups per molecule of reactive polyolefin, etc., side reactions other than graft polymerization are suppressed, and the molecular weight distribution is further lowered. It is possible.
In addition, evaluation of the weight average molecular weight and molecular weight distribution of a graft copolymer can use the above-mentioned GPC method.

The graft copolymer of the present invention preferably has a gel fraction of 5% by weight or less, and more preferably contains substantially no gel component.
The gel fraction can be evaluated by the following method, for example.

Using a solvent that dissolves both the main chain and side chain components of the graft copolymer, a glass separable flask equipped with a stirrer is made of a 400 mesh stainless steel mesh (opening: 0.034 mm). Add 50 mg of copolymer and fix to a stirring blade.
A solvent containing 0.1% by mass of an antioxidant (BHT) is added and dissolved with stirring at the boiling point for 4 hours. After dissolution, the collected soot is sufficiently dried in vacuum, and the insoluble part is determined by weighing.
The gel component (gel fraction) defined as an insoluble part is calculated by the following formula.
[Remaining amount in mesh (g) / Amount of charged sample (g)] × 100 (unit:%)
Examples of the solvent include paraxylene and toluene.
Usually, in the above formula, it is defined that the gel component is not included with a range of 0 to 1.5 mass%.

The molded body produced by heating and melting and cooling and solidifying the graft copolymer of the present invention has, for example, a sea-island structure and includes at least an island portion having a particle diameter of 10 to 100 nm.
The particle diameter is preferably 10 to 90 nm, more preferably 10 to 80 nm.

The sea-island structure of the graft copolymer can be evaluated by the following method.
A film is formed by hot pressing or solvent casting at a temperature higher than the melting point or glass transition temperature of the graft copolymer, and a ruthenium-stained sample is observed with a transmission electron microscope (TEM), and image analysis or visual inspection is performed. Check the particle size.

[Composition of the present invention and use thereof]
The thermoplastic resin composition of the present invention includes the graft copolymer of the present invention, and may further include a thermoplastic resin, a filler, a pigment, and the like.
Examples of the thermoplastic resin include the following resins.
(1) Polyethylene: high density polyethylene (HDPE), high pressure low density polyethylene (LDPE), etc. (2) ethylene / α-olefin copolymer: ethylene / propylene copolymer, ethylene / propylene / diene copolymer, etc. Polyolefin rubber; linear low density polyethylene (L-LDPE) such as ethylene / butene copolymer, ethylene / hexene copolymer, ethylene / octene copolymer
(3) Ethylene / polar monomer copolymer: ethylene / vinyl acetate copolymer and its ketone product, ethylene / acrylic acid copolymer, ethylene / methyl methacrylate copolymer, ethylene / glycidyl methacrylate copolymer, etc. (4 ) Polypropylene: isotactic polypropylene, syndiotactic polypropylene, atactic polypropylene, low to medium isotactic polypropylene having a mesopentad fraction [mmmm] of 30 to 85 mol%, etc. (5) propylene copolymer: ethylene, butene, Copolymerized polypropylene using hexene, octene or the like as a copolymerization component (6) Polybutene: isotactic polybutene, low to medium isotactic polybutene having a mesopentad fraction [mmmm] of 30 to 90 mol%, etc. (7) 16 carbon atoms ~ 28 α- Higher poly α- olefins obtained from olefin (8) polysiloxane (9) petroleum resin (10) Polystyrene (11) polyamide, of these condensation polymer such as polyester, polypropylene, polybutene are preferred.

Examples of the inorganic filler and / or inorganic pigment include silica, alumina, glass, quartz, carion, mica, talc, clay, hydrated alumina, wollastonite, iron powder, potassium titanate, titanium oxide, zinc oxide, and silicon carbide. Silicon nitride, calcium carbonate, carbon black, barium sulfate, bismuth boron vanadate, iron oxide, fired Fe / Cr, fired Cu / Cr, fired Co, Zn, Al and the like.
Examples of organic pigments include dioxazine, benzimidazolone, anthraquinone, quinacdrine, phthalocyanine, and isoindolinone.
Further, it may contain various resin additives such as antioxidants, ultraviolet absorbers and antifogging agents, process oils and the like.

In the thermoplastic resin composition of the present invention, the content ratio of the thermoplastic resin / the graft copolymer of the present invention (part by mass / part by mass) is usually about 100 / 0.1 to 100/50, preferably Is 100 / 0.5 to 100/45, more preferably 100 / 1.0 to 100/40.
When the graft copolymer is 0.1 part by mass or more, a large modification effect can be obtained, and when the graft copolymer is 50 parts by mass or less, the physical properties of the resin component can be improved.

In the thermoplastic resin composition of the present invention, the content ratio of the inorganic filler and the organic inorganic pigment / graft copolymer (part by mass / part by mass) is usually about 100 / 0.1 to 100/5000, preferably It is 100 / 0.05-100 / 4000, More preferably, it is 100 / 0.08-100 / 3000.
When the mass part of the graft copolymer is 0.01 or more, a large modification effect can be obtained, and when it exceeds 5000 parts by mass, the graft copolymer not involved in the surface treatment of the inorganic filler increases, and the physical properties are increased. May decrease.

Specific examples of the thermoplastic resin composition of the present invention are as follows.
When performing the surface treatment of the inorganic filler, the inorganic filler / graft copolymer (part by mass / part by mass) is usually about 100 / 0.05 to 100/20, preferably 100 / 0.1 to 100 / 1.5, more preferably 100 / 0.5 to 100/10. Furthermore, when producing a masterbatch, it is about 100 / 5-100 / 500 normally, Preferably it is 100 / 10-100 / 450, More preferably, it is 100 / 20-100 / 400.

The inorganic filler surface-treated product and master batch can be diluted and kneaded into a thermoplastic resin or the like by a conventional method and used for production of various molded products.
The thermoplastic resin composition of the present invention can be produced by ordinary melt kneading such as uniaxial or biaxial melt kneading, a melt extruder, batch-type melt kneading or the like.

Production Example 1
[Production of reactive polyolefin]
In a stainless steel reactor with an internal volume of 20 L with a stirrer, n-heptane was 24 L / h, triisobutylaluminum was 15 mmol / h, and dimethylanilinium tetrakispentafluorophenylborate and (1,2'-dimethylsilylene) (2 , 1′-Dimethylsilylene) -bis (3-trimethylsilylmethylindenyl) zirconium dichloride, triisobutylaluminum and propylene in a mass ratio of 1: 2: 20, a catalyst component obtained by converting the catalyst component to 6 μmol / h was fed continuously.
The polymerization temperature was set to 83 ° C., and propylene and hydrogen were continuously supplied so that the hydrogen concentration in the gas phase part of the reactor was maintained at 0.86% and the total pressure in the reactor was maintained at 0.7 MPa · G. A polymerization reaction was performed.
To the resulting polymerization solution, Irganox 1010 (manufactured by Ciba Specialty Chemicals), which is a stabilizer, is added so that its content is 500 ppm by mass, and n-heptane, which is a solvent, is removed to reduce the content. Crystalline polypropylene was obtained. This low crystalline polypropylene was made into resin pellets by underwater cutting.
The obtained low crystalline polypropylene had a mesopentad fraction [mmmm] of 45 mol%, a terminal unsaturated group number of 0.95 / molecule, a weight average molecular weight (Mw) of 45600, and a molecular weight distribution (Mw / Mn The intrinsic viscosity ([η]) measured at 135 ° C. in decalin was 0.41 dl / g. Moreover, the ratio which occupies for all the terminal unsaturated groups of vinylidene group was 98 mol%.
The number of terminal unsaturated groups was determined by the following method. The following manufacturing examples are also the same.
Based on the terminal vinylidene group appearing in δ 4.8 to 4.6 (2H) obtained from ¹ H-NMR measurement, the content (C) (mol%) of the terminal vinylidene group was calculated. Furthermore, from the number average molecular weight (Mn) and monomer molecular weight (M) obtained from gel permeation chromatography (GPC), the number of terminal vinylidene groups per molecule was calculated according to the following formula.
Number of terminal vinylidene groups per molecule (pieces) = (Mn / M) × (C / 100)

Production Example 2
[Production of reactive polyolefin]
In a stainless steel reactor with an internal volume of 20 L with a stirrer, n-heptane was 24 L / h, triisobutylaluminum was 15 mmol / h, and dimethylanilinium tetrakispentafluorophenylborate and (1,2'-dimethylsilylene) (2 , 1′-Dimethylsilylene) -bis (3-trimethylsilylmethylindenyl) zirconium dichloride, triisobutylaluminum and propylene in a mass ratio of 1: 2: 20, a catalyst component obtained by converting the catalyst component to 6 μmol / h was fed continuously. The polymerization temperature was set to 67 ° C., and propylene and hydrogen were continuously fed so that the hydrogen concentration in the gas phase part of the reactor was 0.74% and the total pressure in the reactor was maintained at 0.75 MPa · G. A polymerization reaction was performed.
To the resulting polymerization solution, Irganox 1010 (manufactured by Ciba Specialty Chemicals), which is a stabilizer, is added so that its content is 500 ppm by mass, and n-heptane, which is a solvent, is removed to reduce the content. Crystalline polypropylene was obtained. This low crystalline polypropylene was made into resin pellets by underwater cutting.
The obtained low crystalline polypropylene had a mesopentad fraction [mmmm] of 46 mol%, a terminal unsaturated group number of 0.97 / molecule, a weight average molecular weight (Mw) of 131,000, and a molecular weight distribution (Mw / Mn ) And the intrinsic viscosity ([η]) measured at 135 ° C. in decalin was 0.91 dl / g. Moreover, the ratio which occupies for all the terminal unsaturated groups of vinylidene group was 98 mol%.

Example 1
[Production of graft copolymer]
Into a 300 ml separable flask equipped with a stirrer, a thermometer and an inlet, 80.0 g of the terminal unsaturated polyolefin (reactive polyolefin) produced in Production Example 1 was introduced, and dry nitrogen was circulated to sufficiently replace the nitrogen. The following reactions were all carried out under a nitrogen atmosphere. The separable flask was immersed in a heated oil bath to melt the terminal unsaturated polyolefin, and then the temperature was controlled at 160 ° C. with stirring. A mixed solution of 10.1 g of 2-ethylhexyl acrylate, 3.4 g of methacryloxypropyltrimethoxysilane and 0.22 g of tertiary butyl cumyl peroxide prepared in advance was added at a constant rate for 35 minutes. After completion of the addition, a graft copolymer was produced by reacting for 15 minutes. In order to remove the unreacted product of the produced graft copolymer, the supply of nitrogen was stopped and dried under reduced pressure at about 2 mmHg for 2 hours. The molten bat was collected in a stainless steel vat, cooled, and stored under nitrogen.

The monomer conversion rate in the graft polymerization was measured as follows.
Immediately after completion of the reaction, a small amount of the reaction mixture was collected and dissolved in toluene. Methanol was added thereto to precipitate a polymer component. The methanol toluene mixed solution was centrifuged to separate it into a polymer component and a solution component. The obtained solution component was subjected to gas chromatography analysis, and the monomer conversion rate was calculated by quantifying the amount of unreacted monomer.

It was 4630 mPaS when B viscosity of the obtained graft copolymer was measured.
The B viscosity was measured with a Brookfield viscometer for the graft copolymer melted at 190 ° C. in accordance with JISK-6862. For the viscometer, a TVB-10 type viscometer manufactured by Toki Sangyo Co., Ltd., M2 rotor (No. 21) was used, and an H-2 type small sample adapter was used.

  About the obtained graft copolymer, the uniformity and transparency were evaluated by the following methods. The results are shown in Table 1. As can be seen from Table 1, the obtained graft copolymer had excellent uniformity and was transparent.

10 g of the obtained graft copolymer was put into a 100 ml glass bottle, and further 40 g of normal heptane was added, followed by stirring for 30 minutes while heating with a block heater at 60 ° C. About 1 g of the solution cooled to room temperature (solid content 20% by weight) was applied to an aluminum foil with a bar coater (# 12), dried in an air oven at 180 ° C. for 1 minute, and sufficiently cooled and solidified at room temperature.
When the state of the obtained coating film was observed, the case where there were no cloudiness and the number of gel-like substances that could be visually detected was 10 or less in a visual field of 5 × 5 cm ² was evaluated as “◯”, and white turbidity was observed. The case where the number of gel-like substances that can be detected in 10 exceeds 10 in a 5 × 5 cm ² field of view was evaluated as “×”.
When the graft copolymer contains a polyolefin other than the reactive polyolefin, the uniformity can be evaluated by the following method.
The graft copolymer is melted at 200 ° C., about 1 g of the graft copolymer melt is dropped onto an aluminum substrate on a hot plate heated to 180 ° C., and applied with a bar coater (# 12). The solidified film obtained by cooling is observed.

  The obtained graft copolymer was produced by a hot melt press at 180 ° C. to produce a molten sheet having a thickness of 50 mm square and a thickness of 1 mm, and this molten sheet was cooled for 5 minutes with a cooling press controlled at 25 ° C. to produce a sheet. . This sheet was placed on a black plane and visually observed. The case where no cloudiness was observed was evaluated as “transparent”, and the case where cloudiness was observed was evaluated as “opaque”.

Example 2
Into a 5 liter separable flask equipped with a stirrer, a thermometer and an inlet, 1100 g of the terminal unsaturated polyolefin produced in Production Example 1 was introduced, and dry nitrogen was circulated to sufficiently substitute the nitrogen. The following reactions were all carried out under a nitrogen atmosphere. To this was added 2.4 liters of dehydrated toluene, the temperature was controlled at 80 ° C. and dissolved while stirring, and 77.2 g of maleic anhydride was added as monomer (a) and stirred until dissolved.
200 ml of a toluene solution containing 220 g of normal butyl acrylate as the monomer (b) and 60.6 g of acrylic acid and 10.0 g of azobisisobutyronitrile as the radical initiator was prepared. This toluene solution was added dropwise over 7 hours so that the internal temperature of the reactor did not exceed 82 ° C. After completion of the dropwise addition, the reaction was continued for 3 hours, and the reaction mixture was recovered to remove toluene. In order to remove the unreacted monomer, the graft copolymer was produced by drying under reduced pressure at 120 ° C. for 24 hours.

As a result of quantification of the monomer remaining in the reaction solution by gas chromatography, the content of maleic anhydride, normal butyl acrylate and acrylic acid in the obtained graft copolymer was 5.1% by weight and 15.0% by weight, respectively. It was 4.0% by weight. Moreover, B viscosity of the obtained graft copolymer was 120,000 mPaS.
Further, the uniformity and transparency of the obtained graft copolymer were evaluated in the same manner as in Example 1. The results are shown in Table 1.

Example 3
A glass 0.5 liter separable flask having a stirrer and an inlet was sufficiently dried and then placed in a nitrogen atmosphere. 100 g of the terminal unsaturated polyolefin produced in Production Example 1 and 2.31 g of maleic anhydride were added thereto. To this was added 96.5 g of dehydrated ethyl acetate, and stirring was started at room temperature. To this was added 96.2 g of dehydrated heptane. It heated so that it might be in a boiling state (internal temperature 80.6 degreeC) using the oil bath. A homogeneous solution consisting of 16.1 g of acrylic acid, 1.02 g of azobisisobutyronitrile, and 13.6 g of dehydrated ethyl acetate was charged at a constant rate over 115 minutes. The reaction was continued for an additional 180 minutes after the end of the addition. After completion of the reaction, the unreacted monomer present in the liquid part of the reaction mixture was quantified by gas chromatogram method. As a result, the conversion of maleic anhydride was 95.2%, and the conversion of acrylic acid was 99.0% or more. there were. Further, the liquid portion of the reaction mixture was removed by heating under reduced pressure, and the pressure was reduced at 140 ° C. for 8 hours to recover a white graft copolymer.

When the infrared absorption spectrum of the obtained graft copolymer was measured, since the absorption based on the vinylidene group which exists in 888 cm < ^-1 > was not recognized, it confirmed that the graft reaction advanced efficiently. The obtained graft copolymer had a B viscosity of 33500 mPas.
Further, the uniformity and transparency of the obtained graft copolymer were evaluated in the same manner as in Example 1. The results are shown in Table 1.

Example 4
A white graft copolymer was obtained in the same manner as in Example 3 except that a mixture of 14.0 g of acrylic acid and 5.0 g of 2-ethylhexyl acrylate was used as the monomer (b) instead of 16.1 g of acrylic acid. .
As a result, the conversion of maleic anhydride was 95.55%, the conversion of acrylic acid was 99.0% or more, and the conversion of 2-ethylhexyl acrylate was 99% or more. Moreover, when the infrared absorption spectrum of the obtained graft copolymer was measured, since the absorption based on the vinylidene group which exists in 888 cm < ^-1 > was not recognized, it confirmed that the graft reaction advanced efficiently.
Further, the uniformity and transparency of the obtained graft copolymer were evaluated in the same manner as in Example 1. The results are shown in Table 1.

Example 5
A 0.3 liter separable flask made of glass having a stirrer, a reflux line and a charging port was sufficiently dried and then placed in a nitrogen atmosphere. 90 g of the terminal unsaturated polyolefin produced in Production Example 1 was charged into the flask and melted at 120 ° C. After confirmation of melting, stirring was started, and 3.0 g of vinyltrimethoxysilane (Bp = 123 ° C.) was added and heated to a reaction temperature of 160 ° C. A homogeneous solution containing 10.0 g of 2-ethylhexyl acrylate and 0.90 g of dicumyl peroxide prepared in advance was added at a constant rate over 120 minutes. After completion of the addition, the reaction was continued for an additional 60 minutes to produce a graft copolymer.
After completion of the reaction, the reaction mixture was cooled to room temperature, and a large amount of toluene was added to obtain a homogeneous solution, and then unreacted monomers present in the liquid part were quantified by gas chromatogram method. As a result, the conversion rate of vinyltrimethoxysilane was 85.5%, and the conversion rate of 2-ethylhexyl acrylate was 99.0% or more.
When the infrared absorption spectrum of the obtained graft copolymer was measured, the absorption based on the vinylidene group present at 888 cm ⁻¹ almost disappeared, so that it was confirmed that the graft reaction proceeded efficiently. Further, the uniformity and transparency of the obtained graft copolymer were evaluated in the same manner as in Example 1. The results are shown in Table 1.

Comparative Example 1
A glass 0.5 liter separable flask having a stirrer and an inlet was sufficiently dried and then placed in a nitrogen atmosphere. 100 g of the terminal unsaturated polyolefin produced in Production Example 1 and 2.31 g of maleic anhydride were added. To this were added 96.5 g of dehydrated ethyl acetate and 16.1 g of acrylic acid, and stirring was started at room temperature. Further, 96.2 g of dehydrated heptane was added. It heated so that it might be in a boiling state (internal temperature 80.6 degreeC) using the oil bath. To this was added a homogeneous solution consisting of 1.02 g of azobisisobutyronitrile and 13.6 g of dehydrated ethyl acetate over 115 minutes, and the temperature was adjusted so as not to vigorously boil while cooling or heating the reactor. After completion of the charging, the reaction was carried out for 180 minutes to produce a graft copolymer.
After completion of the reaction, the unreacted monomer present in the liquid part was quantified by gas chromatogram method. As a result, the conversion of maleic anhydride was 35.5% and the conversion of acrylic acid was 98.0%. The graft copolymer was recovered by removing the liquid portion of the reaction mixture by heating and reducing the pressure and reducing the pressure at 130 ° C. for 8 hours, and the graft copolymer turned yellow. Moreover, when the infrared absorption spectrum of the graft copolymer was measured, since the absorption based on the vinylidene group existing at 888 cm ⁻¹ remained, it was confirmed that the efficiency of the graft reaction was low. The uniformity and transparency of the obtained graft copolymer were evaluated in the same manner as in Example 1. The results are shown in Table 1.

Reference Example 100 g of a terminal unsaturated polyolefin produced in Production Example 2 was charged into a glass reactor equipped with a stirring apparatus purged with nitrogen, melted at 170 ° C., and stirred at a rotational speed of 150 rpm. To this, 13.5 g of acrylic acid, 3.5 g of glycidyl methacrylate, 2,5-dimethyl-2,5-di (tertiarybutylperoxy) hexane [trade name: Perhexa 25B] manufactured by NOF Corporation 1.01 g A homogeneous solution consisting of was added dropwise over 20 minutes. The reaction proceeded without dissolving the dropped monomer solution in the molten terminal unsaturated polyolefin.
After the completion of dropping, the reaction mixture was recovered after reacting for 10 minutes. When the obtained reaction mixture was observed with the naked eye, it was recognized that a large amount of a gel-like material that did not dissolve uniformly was produced.
The uniformity and transparency of the obtained graft copolymer were evaluated in the same manner as in Example 1. The results are shown in Table 1.

Example 6
[Production of thermoplastic resin composition and molded article]
(1) Production of Extruded Composition Into a mixer equipped with a nitrogen-substituted stirrer was charged 1.3 kg of terminally unsaturated polyolefin produced in Production Example 2, and stirred at room temperature with 176 g of 2-ethylhexyl acrylate and 45 g of glycidyl methacrylate. Then, a homogeneous solution consisting of 13.1 g of 2,5-dimethyl-2,5-di (tertiarybutylperoxy) hexane [trade name: Perhexa 25B, manufactured by NOF Corporation] was added and stirred. After 6 hours, impregnated pellets having good fluidity without wetting the pellet surface were obtained.
The total amount of the impregnated pellets and 558 g of commercially available polypropylene [Random PP MFR = 1.5 manufactured by J232WA Prime Polymer Co., Ltd.] were dry blended.

(2) Melt reaction extrusion Using the composition of the above (1) under the conditions of a barrel temperature of 170 ° C., a die temperature of 150 ° C., and a rotation speed of 100 rpm using a Toyo Seiki Lab Plast Mill (20 mmφ, L / D = 27). Melt reaction extrusion was performed.
The molten strand was introduced into a water bath at about 25 ° C., and the cooled and solidified strand was cut with a pelletizer to continuously produce graft copolymer composition pellets.

(3) Manufacture of a polycarbonate composition 20 parts by mass of the graft copolymer composition of the above (2) in a lab plast mill (internal volume 50 ml) manufactured by Toyo Seiki, a polycarbonate having terminal hydroxyl groups [manufactured using bisphenol A and phosgene as raw materials. Viscosity average molecular weight (Mv) = 16500, OH group weight 0.92 molecules / molecule] A total amount of 55 g consisting of 80 parts by mass was added and kneaded at 250 ° C. and 100 rpm for 10 minutes to obtain a polycarbonate composition. Manufactured. The resulting composition was excellent in gloss.
The obtained polycarbonate composition was dyed with ruthenium and observed with a transmission electron microscope. The obtained photograph is shown in FIG.
As a result of observation, the observed dispersion state was good.

Comparative Example 2
Other than the graft copolymer composition pellets, a dry blend of 1.3 kg of terminally unsaturated polyolefin produced in Production Example 2 and 558 g of commercially available polypropylene [Random PP MFR = 1.5 manufactured by J232WA Prime Polymer Co., Ltd.] was used. Produced a polycarbonate composition in the same manner as in Example 6 (3).
The obtained polycarbonate composition was not glossy and the surface was rough and fragile.
The obtained polycarbonate composition was dyed with ruthenium and observed with a transmission electron microscope. The obtained photograph is shown in FIG.
As a result of observation, it was confirmed that the dispersibility was greatly reduced as compared with the polycarbonate composition of Example 6.

  The graft copolymer of the present invention or the thermoplastic resin composition containing the graft copolymer is a polyolefin modifier, such as an inorganic filler or dye, as a sealant having high adhesion to plastic materials, paper, wood, etc. As a modifier to obtain polyolefins with improved compatibility properties, mechanical properties and fluidity with polar polymers, polar wax, wood powder, metals, etc., or surface treatment agents, primer treatment agents, coating agents for polyolefins Useful as a component.

Claims (7)

100 parts by mass of a combination of 20 to 100% by mass of a reactive polyolefin satisfying the following (1) to (5) and 0 to 80% by mass of a polyolefin other than the reactive polyolefin,
A monomer comprising at least one monomer (a) selected from the following [V] to [VIII] and at least one monomer (b) selected from the following [I] to [V] and [VIII]: A method for producing a graft copolymer in which 0.2 to 300 parts by mass of a body mixture is graft-polymerized in the presence of 0.001 to 10 parts by mass of a radical initiator,
The monomer (a) and the monomer (b) are mutually different monomers,
A method for producing a graft copolymer, wherein the monomer (b) is brought into contact with the monomer (a) and the reactive polyolefin in a state where the monomer (a) and the reactive polyolefin are in contact with each other.
[Reactive polyolefin]
(1) One homopolymer or two or more copolymers selected from α-olefins having 3 to 28 carbon atoms, or one or more monomers selected from α-olefins having 3 to 28 carbon atoms Copolymer of 90% by mass or more and 10% by mass or less of ethylene (2) Mesopentad fraction [mmmm] is 30 to 80 mol% (3) 0.5 to 1.0 terminal unsaturated group per molecule (4) The molecular weight distribution Mw / Mn is 4 or less. (5) In decalin, the intrinsic viscosity ([η]) measured at 135 ° C. is 0.01 to 2.5 dl / g [monomer ( a)]
[V] Maleic anhydride and substituted products thereof [VI] Maleic acid and esters thereof [VII] Vinylalkoxysilanes [VIII] α-olefin [monomer (b)]
[I] Acrylic acid and its derivative [II] Methacrylic acid and its derivative [III] Vinyl ester and its derivative [IV] Styrene and its derivative [V] Maleic anhydride and its substitute [VIII] α-olefin The reactive polyolefin contains a vinylidene group as a terminal unsaturated group,
The method for producing a graft copolymer according to claim 1, wherein a ratio of the vinylidene group to all terminal unsaturated groups is 50 to 100 mol%.   The graft polymer according to claim 1 or 2, wherein a temperature at the time of contact of the reactive polyolefin, the monomer (a) and the monomer (b) is 40 to 260 ° C. 100 parts by mass of a combination of 20 to 100% by mass of a reactive polyolefin satisfying the following (1) to (5) and 0 to 80% by mass of a polyolefin other than the reactive polyolefin,
In the method for producing a graft copolymer, one or more monomers selected from the following [I] to [IV] are graft-polymerized in the presence of 0.001 to 10 parts by mass of a radical initiator in the amount of 0.2 to 300 parts by mass. There,
A method for producing a graft copolymer, wherein the graft polymerization is carried out at a temperature of 140 to 260 ° C.
(1) One type of homopolymer or two or more copolymers selected from α-olefins having 3 to 28 carbon atoms, or 90 masses of one or more monomers selected from α-olefins having 3 to 28 carbon atoms (2) Mesopentad fraction [mmmm] is 30 to 80 mol% (3) 0.5 to 1.0 terminal unsaturated groups per molecule (4) The molecular weight distribution (Mw / Mn) is 4 or less. (5) The intrinsic viscosity ([η]) measured at 135 ° C. in decalin is 0.01 to 2.5 dl / g. [I] Acrylic acid And derivatives thereof [II] Methacrylic acids and derivatives thereof [III] Vinyl esters and derivatives thereof [IV] Styrene and derivatives thereof 100 parts by mass of a combination of 20 to 100% by mass of a reactive polyolefin satisfying the following (1) to (5) and 0 to 80% by mass of a polyolefin other than the reactive polyolefin,
0.2 to 300 parts by mass of one or more monomers selected from the following [I] to [IV] including at least a monomer selected from the following [I ′] to [III ′] The method for producing a graft copolymer according to claim 4, wherein graft polymerization is carried out at 140 to 260 ° C in the presence of 001 to 10 parts by mass.
(1) One type of homopolymer or two or more copolymers selected from α-olefins having 3 to 28 carbon atoms, or 90 masses of one or more monomers selected from α-olefins having 3 to 28 carbon atoms (2) Mesopentad fraction [mmmm] is 30 to 80 mol% (3) 0.5 to 1.0 terminal unsaturated groups per molecule (4) The molecular weight distribution (Mw / Mn) is 4 or less. (5) The intrinsic viscosity ([η]) measured at 135 ° C. in decalin is 0.01 to 2.5 dl / g. [I] Acrylic acid And derivatives thereof [II] Methacrylic acids and derivatives thereof [III] Vinyl esters and derivatives thereof [IV] Styrene and derivatives thereof [I ′] Acrylic esters containing a hydrocarbon group having 4 to 20 carbon atoms in the ester residue and the derivatives thereof Derivative [I I ′] Methacrylic acid ester having 4 to 20 carbon atoms in the ester residue and derivatives thereof [III ′] Vinyl ester having 4 to 20 carbon atoms in the residue and derivatives thereof 100 parts by mass of a combination of 20 to 100% by mass of a reactive polyolefin satisfying the following (1) to (5) and 0 to 80% by mass of a polyolefin other than the reactive polyolefin,
In the presence of 0.001 to 10 parts by mass of a radical initiator, at least one monomer selected from the following [I] to [IV] is used in the presence of 0.001 to 10 parts by mass of an aliphatic hydrocarbon, alicyclic hydrocarbon or cyclic ether. The graft polymerization is carried out in a solvent consisting of an organic carboxylic acid ester and an aliphatic hydrocarbon, or in a mixed solvent consisting of an organic carboxylic acid ester, an aliphatic hydrocarbon and an alicyclic hydrocarbon. A method for producing a graft copolymer.
(1) One type of homopolymer or two or more copolymers selected from α-olefins having 3 to 28 carbon atoms, or 90 masses of one or more monomers selected from α-olefins having 3 to 28 carbon atoms (2) Mesopentad fraction [mmmm] is 30 to 80 mol% (3) 0.5 to 1.0 terminal unsaturated groups per molecule (4) The molecular weight distribution (Mw / Mn) is 4 or less. (5) The intrinsic viscosity ([η]) measured at 135 ° C. in decalin is 0.01 to 2.5 dl / g. [I] Acrylic acid And derivatives thereof [II] Methacrylic acids and derivatives thereof [III] Vinyl esters and derivatives thereof [IV] Styrene and derivatives thereof The thermoplastic resin composition containing the graft copolymer obtained by the manufacturing method of the graft copolymer in any one of Claims 1-6.