JPH02110104A - Manufacture of polyolefin resin composition - Google Patents

Abstract

(57) [Abstract] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a method for producing a modified polyolefin resin composition by reacting a copolymer of alkenylsilane and olefin with a compound containing an unsaturated bond. .

``Prior art'' Olefin polymers are used for a variety of purposes because they are inexpensive and have a relatively good balance of physical properties.In addition, various methods have been developed for random or block copolymerization of olefins to improve the balance of physical properties. Improvements have been made.

[Problem to be solved by the invention]

However, due to their nature, olefin polymers have characteristics such as poor adhesion to polymers containing polar groups, metals, etc., and poor adhesion to paints, which will further expand the uses of polyolefins. Therefore, attempts have been made to introduce polar groups into polyolefins to improve their physical properties.

However, in ethylene, it is possible to copolymerize with monomers containing polar groups by radical polymerization by high-pressure polymerization, or in other polyolefins, it is possible to radically graft polar group-containing monomers onto polyolefins. It's just that the particular method I mentioned has been successful. In addition, the present inventors previously attempted to modify polyolefins by treating a copolymer of alkenylsilane and olefin with a compound that reacts with 5i-H bonds (Japanese patent application No. 6
3-26528, etc.), in this method, when trying to increase the amount of the compound that reacts with the Si-It bond introduced, in some cases, when the resulting composition is used for molding, the flowability may be poor and molding may not be possible. It has been difficult to modify polyolefins with good reproducibility, such as the inability to mix them with other olefins.

(Means for Solving the Problems) The present inventors have conducted extensive studies on a method for solving the above problems and producing a modified polyolefin resin composition, and have arrived at the present invention.

In the present invention, a copolymer obtained by copolymerizing an olefin and an alkenylsilane using a catalyst consisting of a transition metal catalyst and an organometallic compound is dissolved under heating in a solvent that dissolves a cough copolymer, and then the copolymer is This is a method for producing a polyolefin resin composition, which is characterized by carrying out a contact treatment with a compound containing an unsaturated bond in the presence of a hydrosilylation catalyst at a temperature lower than the temperature at which the polymer is dissolved.

In the production of the composition of the present invention, a copolymer of an alkenylsilane and an olefin is first produced. This can be achieved by polymerizing alkenylsilanes and olefins, and the production of copolymers of alkenylsilanes and α-olefins by polymerizing alkenylsilanes and olefins in the presence of transition metal compounds and organometallic compounds has been reported in the United States. It is disclosed in Patent No. 3,223,686.

Here, the alkenylsilane is vinylsilane, allylsilane, butenylsilane, pentenylsilane, or a compound in which 1 to 2 Si-II bonds of these monomers are substituted with an alkyl group, or 1 to 3 S
Examples include compounds in which the i-It bond is substituted with chloro.

In the present invention, α-olefins include ethylene, propylene, butene-11pentene-1, hexene-1,2
-Methylpentene-1 or their combinations, and mixtures of these with small amounts of olefins having a larger number of carbon atoms are exemplified.

The catalyst comprising a transition metal compound and an organometallic compound used to produce the copolymer of the present invention includes not only those described in the above-mentioned U.S. patent, but also many α-olefin catalysts with improved performance that have been disclosed since then. Polymerization catalysts can be used without problems.

The most suitable polymerization method is a solvent method using an inert solvent, but bulk polymerization and gas phase polymerization can also be used. Here, as a catalyst consisting of a transition metal compound and an organometallic compound, the transition metal compound is titanium halide,
Alternatively, vanadium halide is preferably used, and an organoaluminum compound is preferably used as the organometallic compound. For example, titanium trichloride obtained by reducing titanium tetrachloride with metallic aluminum, hydrogen, or organoaluminum, or titanium trichloride obtained by modifying these with an electron-donating compound, an organoaluminum compound, and, if necessary, an electron-donating compound such as an oxygen-containing organic compound. Catalyst system consisting of chemical compounds, vanadium halides,
Alternatively, a catalyst system consisting of vanadium oxyhalide and organic aluminum, or a carrier such as magnesium halide, or a titanium halide, vanadium halide, or vanadium oxyhalide after being treated with an electron donating compound, is used. A catalyst system consisting of a transition metal compound catalyst obtained by
Alternatively, the reaction product of magnesium chloride and alcohol is dissolved in a hydrocarbon solvent, and then treated with a precipitant such as titanium tetrachloride to make it insoluble in the hydrocarbon solvent. Examples include a catalyst system consisting of a transition metal compound catalyst obtained by a method of treating with a compound and then a titanium halide, an organoaluminium compound, and if necessary an electron-donating compound such as an oxygen-containing organic compound (for example, , various examples are described in the following documents: Ziegler-Nat
Catalysts and Polymeri
zation by John Boor Jr.
ade＋＊ic Press), Journal o
f Macromorecular 5ience
Reviews in Macromolec
ular Chemistry and Physics
s, C24(3) 355385 (1984), same C
25(1) 57B-597 (1985)).

As the electron-donating compound, oxygen-containing compounds such as ethers, esters, orthoesters, and alkoxy silicon compounds are generally preferred, and alcohols, aldehydes, water, and the like can also be used.

As the 47N aluminum compound, trialkylaluminum, dialkylaluminum halide, alkylaluminum sesquihalide, alkyl aluminum civalide can be used, and examples of the alkyl group include methyl group, ethyl group, propyl group, butyl group, hexyl group, etc. /'%Ride is exemplified by chlorine, bromine, and iodine.

There is no particular restriction on the polymerization ratio of alkenylsilane and α-olefin, but usually alkenylsilane is
The content is preferably about 0 mol% to 0.01 mol% for the purpose of catalyst activity during polymerization, or the reaction between the copolymer and the unsaturated compound and its utilization, particularly 10 mol% to 0.05 mol%. It is preferable that the amount is within a certain range.

There is no particular limit to the molecular weight of the polymer, but it is preferable that the molecular weight is extremely high, for example, the intrinsic viscosity measured in a tetralin solution at 135°C is 3 or more.
More preferably, the intrinsic viscosity is about 0.1 to 2.

In the present invention, the copolymer obtained by the above reaction is first dissolved in a solvent. The solvent used here is preferably a hydrocarbon compound having 6 to 12 carbon atoms, or a part of hydrogen thereof. ~A halogenated hydrocarbon compound in which all Hp are halogen atoms is preferably used, and usually 10
It is dissolved by heating to 0'C to 200C.

The solution is cooled after or prior to the addition of the unsaturated compound described below. The temperature after cooling is usually 50°C.
The following is preferable in terms of preventing the crosslinking reaction from proceeding due to side reactions. Next, after adding the unsaturated compound, a hydrosilylation catalyst is added in a cooled state and the reaction is carried out. During the reaction, the temperature should be maintained at 50°C or lower, usually -70°C or higher, and generally 0°C to 40°C. The reaction takes place. Here, the unsaturated compound is C-C1 or C
Examples include compounds containing a =C bond, preferably a compound containing a C=C bond, and the group bonded to this unsaturated group is not particularly limited. For example, various compounds known as vinyl compounds and vinylidene compounds, various compounds known as aldehydes, and ketones can be preferably exemplified. Vinyl compounds and vinylidene compounds include those containing polar groups such as carboxylic acid, carboxylic acid ester, nitro, and sulfonic acid directly on the double bond or with -(C1+,) groups in between, or those containing various polar groups on the phenyl group. In addition to vinyl compounds, general polar groups in which the above polar groups are bonded, polyalkylene oxides such as polyethylene oxide, polyethylene oxide, polypropylene oxide, silicones having -5iO- bonds, etc. A so-called macromer, in which the vinyl group is bonded directly or indirectly to a vinyl group, can also be used.

Examples of oxygen-containing compounds include aldehydes and ketones, and specifically, aldehydes such as formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, valeraldehyde, caproaldehyde, and henzaldehyde, acetone, methyl ethyl ketone, and methyl propyl ketone. , diethylkene, 2-hegisanone,
Examples include 3-hexanone, cyclohexanone, biacetyl, acetophenone, hensifhenone, and those in which some of the hydrogens are replaced with the above polar groups.

When contacting with the above compound, use known hydrosilylation catalysts, such as triphenylphosphine 13 of rhodium, metal catalysts from Group I of the periodic table such as chloroplatinic acid or its salts (Chemistry of Organosilicon Compounds, Bear 1). Makoto et al., published by Kagaku Doujin, p. 165), it is necessary to have a radical initiator such as an Ab compound, and an amine such as triethylamine present. Since the hydrosilylation reaction is relatively fast, the reaction proceeds sufficiently at temperatures around room temperature, but if necessary, such as to avoid crosslinking reactions, the reaction rate or side reactions can be controlled by cooling or heating.

Unreacted unsaturated compounds after contact treatment are usually i! ! However, depending on the use of the composition, it may not be necessary to completely remove unreacted compounds, and in some cases, some unreacted compounds may remain as they are. It can also be a composition.

〔Example〕

The present invention will be further explained with reference to Examples below.

Example 1 A vibratory mill equipped with four crushing bots each having an internal volume of 41 and containing 9 kg of steel balls each having a diameter of 12 mm was prepared. 20 h of magnesium chloride in each pot under nitrogen atmosphere.

Di-n-butyl phthalate 75-1 40 d of titanium tetrachloride was added and pulverized for 40 hours. 100g of co-pulverized material thus obtained
into a 512 flask and add 2. Add OP 1
Treat at 15'C for 2 hours, then remove toluene at 90°C and repeat 4I once! The titanium catalyst was obtained by irradiation with heptane (7 times). According to analysis, it contained 1.9 wt% titanium.

Toluene under nitrogen atmosphere in an autoclave with an internal volume of 51
0d, the above transition metal catalyst 50m5. Add 0.05d of methylcyclohexyldimethoxysilane and 0.50d of triethylaluminum, then charge 30g of vinylsilane, 1200g of propylene, and 4jJp of hydrogen, and heat to 70°C.
Polymerization was carried out for 4 hours. Next, unreacted propylene and vinylsilane were purged, the powder was taken out and dried, and then weighed and its physical properties were measured.The intrinsic viscosity (hereinafter abbreviated as η) measured in a tetralin solution of 480 g of powder at 135 ° C. is 1.35, and the vinyl silane content is 1.35. ]wt%, 2150c11 in infrared absorption spectrum
A strong absorption was observed at -'. Put 10g of this polymer into a 200d flask and add 100d of toluene.
Melted by heating under nitrogen atmosphere to 5°C and then 30'C.
Polyethylene glycol monoallyl ether (Unionox PKA-5001 manufactured by NOF)
After adding 0 mfl and stirring, 0.05 g of triphenylphosphine complex of rhodium chloride was added and the mixture was heated at 30°C for 2 hours.
Stir for hours. After the reaction, the slurry was taken out and filtered, and the polymer was thoroughly washed with toluene. According to the infrared absorption spectrum, the absorption of ethylene glycol was observed at 11l100c', and the absorption of 5i11 at 2150cm-' was decreased. The ratio of polypropylene and polyethylene glycol monomethacrylate-1 calculated by elemental analysis is 1:
It was 0.18. This polymer can be thermoformed by hot pressing at 230°C, and the η obtained by separately polymerizing propylene with the above catalyst is 1.62, and the boiling point Il! Extracted with rhohebutane for 6 hours, the extraction residue ratio is 96.8% polypropylene 1:1
When mixed at a ratio of 0 to 1 and heated and molded, a uniform sheet was formed. Even when this film was stretched at 150'c, no unevenness occurred.

Comparative Example 1 Using the copolymer obtained in Example 1, 10 g of the polymer was added to 100 mff1 of toluene and polyethylene glycol mononucleic acid 50 db of triphenylphosphine tu4 of 80 ml of triphenylphosphine tu4 using the copolymer obtained in Example 1.
The mixture was stirred at °C for 2 hours. Similar analysis revealed that the ratio of polypropylene to polyethylene glycol molylether was 1:0.08, but a uniform sheet could not be obtained even after hot pressing at 230°C, and the mixture was mixed with polypropylene as in Example 1. When I made a notebook out of it, it was uneven and when I stretched it out, the sheet broke.

Example 2 A tetrahydrofuran solution of chloroplatinic acid (0.05 g as chloroplatinic acid) was prepared using allylsilane instead of vinylsilane, phthyl acrylate (AB-6 manufactured by Toagosei Chemical Co., Ltd.) instead of polyethylene glycol monoallyl ether, and a solution of chloroplatinic acid in tetrahydrofuran (0.05 g as chloroplatinic acid).
) was used, except that the polysilicon macromer ratio was 0.17, and the resulting composition was moldable in the same manner as in Example 1.

Example 3 The same procedure as in Example 1 was carried out except that acetophenone was used instead of polyethylene glycol monomethacrylate, the reaction temperature was 10°C, and the reaction was carried out for 10 hours.The amount of acetophenone added was 0.07, and the obtained composition was was moldable.

〔Effect of the invention〕

By carrying out the method of the present invention, a composition containing a polar group can be easily obtained and is extremely valuable industrially.

Patent applicant: Mitsui Toatsu Chemical Co., Ltd.

Claims (1)

[Claims] A copolymer obtained by copolymerizing an olefin and an alkenylsilane using a catalyst consisting of a transition metal catalyst and an organometallic compound is dissolved under heating in a solvent that dissolves the copolymer, and then the copolymer is dissolved. 1. A method for producing a polyolefin resin composition, which comprises carrying out a contact treatment with a compound containing an unsaturated bond in the presence of a hydrosilylation catalyst at a temperature lower than the above temperature.