JPH01143A - 3-Methylbutene-1 polymer composition and method for producing the same - Google Patents

Abstract

(57) [Summary] 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 provides a 3-methylbutene-/
The present invention relates to a polymer composition and a method for producing the same.

[Conventional technology]

In recent years, resins with excellent heat resistance, mechanical strength, electrical properties, chemical resistance, moisture absorption resistance, etc. have become increasingly important as various molding materials or stretched/unstretched film materials.

3-Methylbutene/polymer has been known as a crystalline polyolefin having a high melting point. For example, JP-A No. 17-18230j, same! ;7-/9j70u publication, same! No. 1-1701 and the like disclose a method of polymerizing 3-methylbutene-7 using titanium trichloride with a low aluminum content and an organic aluminum compound. Furthermore, in JP-A-4/-7311, two components are disclosed: a polymer having a 3-methylbutene content of 90% by weight or more, and a polymer having a 3-methylbutene content of 90% by weight or more. The present inventors have proposed a composition comprising: and a method for producing the same.

However, although the 3-methylbutene-1 polymers obtained by these conventional methods exhibit a high melting point, they have poor mechanical strength such as tear strength and impact strength of molded products, heat resistance as expressed by Vicat softening point, and However, their properties, especially in terms of their balance, are still insufficient, and they are not necessarily satisfactory as various molding materials or stretched/unstretched film materials.

[Problem that the invention seeks to solve]

The present inventors have conducted intensive studies to improve the balance of the above-mentioned drawbacks of 3-methylbutene-1 polymer, namely heat resistance expressed by Vicat softening point, stretchability, mechanical strength, etc., and as a result, The present invention has been achieved, and conventionally such 3
-Methylbutene-1 polymer compositions and methods for producing the same were not known.

[Means for solving problems]

That is, the gist of the present invention is as follows: (a) 3-methylbutene-1 homopolymer, or 3-methylbutene-7 and carbon having a heat of fusion measured by a differential scanning calorimeter (DSC) of 7 cal/or more. Number 2~
(b) a heat of fusion measured by differential scanning calorimetry (DSC) of greater than /cal/P and less than 7 cal/P; 3-methylbutene-/ and other α having 2 to 1 carbon atoms
- copolymer with olefin IO-♂ 5% by weight and (c) rubbery 3-methylbutene-1 with no melting peak observed in differential scanning calorimetry (DSC) and other copolymers with 2 to 18 carbon atoms. A 3-methylbutene/polymer composition comprising a copolymer with an α-olefin or a copolymer of two or more other α-olefins having a carbon number of 3 to ψO. and its manufacturing method.

A film with excellent heat resistance and tear strength can be obtained from the 3-methylbutene-7 polymer composition obtained by the method of the present invention, and since it has good stretchability, a stretched film can be easily obtained. Furthermore, a molded article with excellent rigidity, impact resistance, and elongation can be obtained. In addition to these properties, it has excellent electrical properties, chemical resistance, moisture absorption resistance, and transparency, so this film, molded product, or laminate can be used as a variety of packaging materials, insulating materials, printed circuit board materials, magnetic recording pastes, etc. It is useful for films, heat-resistant containers, planar antenna materials, etc.

Next, the present invention will be explained in more detail.

The first component (hereinafter referred to as (a) component 2) in the polymer composition of the present invention has a heat of fusion of 7 c as measured by a differential scanning calorimeter (DSC").
al/g or higher, a 3-methylbutene-1 homopolymer or a copolymer of 3-methylbutene-7 and another α-olefin having 2 to 11 carbon atoms.

Other α-olefins having 2 to 18 carbon atoms in the copolymer include ethylene, propylene, butene, hexene, Hiro-methylpentene-11 octene, decene, dodecene,
Examples include tetradecene, styrene, vinylcyclohexane, and the like.

Two or more of these other α-olefins may be used, and a small amount of polyenes such as butadiene and isoprene may also be included. The copolymerization method is preferably a so-called random copolymerization method. The 3-methylbutene-l content in the copolymer varies depending on the other α-olefins to be copolymerized, but it is usually 2
It exceeds 0% by weight, and when particularly high heat resistance is required, the content is 5% by weight or more. In this case, the heat of fusion is ric
It becomes more than al/g. The heat of fusion of component (a) is 7 cal/
If it is less than , the crystallinity of the entire composition is insufficient or the melting point is lowered, which impairs the high heat resistance and solvent resistance characteristics of poly-3-methylbutene-7, which is not preferable.

The proportion of component (a) in the composition is 10-IJ'% by weight, preferably 30 to 70% by weight, and more preferably 30 to 70% by weight.
Weight%.

The second component (hereinafter referred to as component (b)) consists of 3-methylbutene-l whose heat of fusion measured by a differential scanning calorimeter (DSC) is greater than /cal18 and less than 7cal/P, and which has a carbon number of 2 to 1 It is a copolymer with other α-olefins.

Other α-olefins are selected from those used in component (a). Two or more of these other α-olefins may be used, and a small amount of polyenes such as butadiene and isoprene may also be included. The copolymerization method is preferably a so-called random copolymerization method.

(b) The heat of fusion of the component is /cal18 and 7ca
The copolymerization amount of other α-olefins varies depending on the type of α-olefin, but the content of 3-methylbutene-7 is less than 60% by weight and less than 5% by weight. It is. If the heat of fusion is above the above range, the effect of improving stretchability and impact resistance will be insufficient, and if it is below the above range, the heat resistance will be insufficient.

Is the ratio of component (b) in the composition 10-? j weight%
, preferably /j-10% by weight, more preferably 20 to
Selected from the range ≠j% by weight.

If the proportion of component (b) is too small, improvements in stretchability, impact strength, etc. will be insufficient.

The third component (hereinafter referred to as component (c)) is a mixture of rubbery 3-methylbutene-/ and other α-olefins having 2 to 18 carbon atoms, in which no melting peak is observed in a differential scanning calorimeter (DSC). Copolymer or two or more carbon atoms 2~/
It is a copolymer of lr and other α-olefins. other α
- The olefin is selected from those used in component (a). Furthermore, a small amount of polyene such as butadiene and isoprene may be contained. The copolymerization method is preferably a so-called random copolymerization method. This component (c) is 3
Copolymers of two or more α-olefins other than -methylbutene-/, e.g. 1
%≠-Memethipente7-/~decene, goo-methylpentene-/~dodecene, Hiro-methylhente/-/~decene~
Component (c) may be a copolymer such as tetradecene with a content of about 30 to 70% by weight of each comonomer, but preferably component (c) is a copolymer of 3-methylbutene-1 and α-olefin. be. The content of 3-methylbutene-l in the copolymer is less than 60% by weight, preferably less than 50% by weight, and more preferably 5 to 5% by weight of SO. Outside this range, the stretchability, tear strength, and impact resistance of the molded product will be affected. Strength improvement is insufficient.

The proportion of component (c) in the composition is 3 to μO% by weight,
It is preferably selected from the range of 3 to 30% by weight, more preferably from the range of j-2 weight it%. If the proportion of component (c) is too small, improvements in drawability, elongation, and tear strength will not be sufficient, and if it is too large, heat resistance, solvent resistance, etc. will deteriorate, which is undesirable.

The degree of crystallinity of a polymer, or the amount of crystalline components, is reflected in the heat of fusion of the polymer as measured by differential scanning calorimetry. The heat of fusion of 3-methylbutene-/homopolymer is also influenced by stereoregularity and molecular weight, but usually /b
The value is approximately cal/', and substantially no heat of fusion is observed in the rubbery copolymer.

In this composition, component (a) is 3-methylbutene-
(c)
The ingredients are for improving impact resistance and stretchability.

It is believed that component (b) acts as a compatibilizer to promote uniform dispersion of component (c) in component (a) and reduction in particle size.

In the usual mixing method, the rubbery component is insufficiently dispersed in the 3-methylbutene-7 homopolymer, and the expected effects of improving impact resistance and stretchability are hardly observed.

When the amount of other α-olefins copolymerized with 3-methylbutene// is increased and the crystallinity of the copolymer is lowered, the dispersion of the rubbery component is promoted and impact resistance and stretchability are improved.

However, in this case, at the same time, the heat resistance of the copolymer with an increased amount of copolymerization also decreases, so the improvement from the viewpoint of the balance between heat resistance, impact resistance, and stretchability is slight.

Therefore, highly crystalline, which originally has poor compatibility with rubbery components,
By combining a high heat resistant component and a rubbery component, and incorporating a component with an intermediate degree of crystallinity in order to make the two compatibilized, a 3. -Methylbutene-1 polymer composition was obtained, and the present invention was achieved.

In order to obtain a composition from components (a), (b) and (c), the powders or pellets of both components may be simply mixed together, a suitable solution may be mixed, a single screw or λ-shaft extruder or A method such as kneading with a Banbury mixer is used, and although there is no particular restriction, a three-stage polymerization method is preferred.

To explain the three-stage polymerization method, in an aliphatic, alicyclic or aromatic hydrocarbon such as butane, hexane, heptane, cyclohexane, benzene, etc., in a liquid olefin,
Alternatively, in the absence of a solvent, a transition metal compound and the periodic table 1
Polymerizing 3-methylbutene-/-i or 3-methylbutene-/ and an α-olefin in the presence of an organometallic compound of a Group to Group 3 metal to produce components (a) and (b); Then, component (e) is generated. It is preferable to form component (a) first, then component (b), and finally component (c) in this order, in order to prevent component (e) from eluting into the solvent in the catalyst removal step.

There are no particular limitations on the transition metal compound and the organometallic compound of Group 1 to Group 3 metals of the periodic table, which are catalysts, and those commonly used in the polymerization of olefins can be used.

Preferably, it is a combination of a solid catalyst component containing Mg, Ti, halogen, and an electron-donating compound such as an ether or ester, an organoaluminium compound, and, if necessary, an electron-donating compound such as an ether or ester. Such solid catalyst components are disclosed in JP-A-52-1R076, J3-2≠371, J3-ZA-JF77, and JP-A-1989! It is described in J.T.3-//7013, J.T.H.620, J.T.//306 and the like. Moreover, the aluminum content is 0.0 in terms of the atomic ratio of aluminum to titanium. / r or less, and a combination of a solid titanium trichloride catalyst component containing a gas complexing agent and an organoaluminum compound, especially an aluminum dialkyl monohalide, and optionally an electron-donating compound such as an ether, ester, etc., is also suitable. used for. Such solid titanium trichloride catalyst components are disclosed in Japanese Patent Publication No. Showa RZ-RVSI, Japanese Patent Publication No. 5S-R Kou No. 52, SS-ZA No. 003,
Same as J'l-2717/publication, same as J-3ri No. 166, same! ! -1uOju Publication, No. 53 Suri No. 52, etc.

The superposition temperature is 0 to iso°C. Further, a molecular weight regulator such as hydrogen may be used if necessary.

The melting point of the polymer composition thus obtained is 2170°C or higher, preferably 260°C or higher.

After adding stabilizers, metal damage inhibitors, flame retardants, inorganic or organic fillers, etc. as necessary, this polymer composition can be used as a base polymer for film or other molding processes, or as a base polymer for grafting reactions. It is offered.

〔Example〕

Examples will be shown below, but the present invention is not limited to the following examples unless the gist of the invention is exceeded.

Physical property values in the following examples were measured according to the following methods.

Tensile test ASTM D 6.31r (measures tensile modulus, tensile stress at yield point, and elongation at break) Vicat softening point ASTM D /! ;2; Melt index (MI) ASTM D t23t
r (320℃, 2.16 cod) Elmendorf tear test JIS P ♂/1
The melting point and heat of fusion of the 6 copolymer are Tata 0 manufactured by DupOnt.
It was measured using a type 0 differential scanning calorimeter. In Table 1, the heat of fusion of the -stage polymer is the measured value, but the heat of fusion of the second stage polymer is based on the measured value of the copolymer component in Figure 1. This was determined from the relationship between heat of fusion.

The content of each component of the copolymer is JEOL FX200 type NM.
C at 310℃ using R device (equipped with high temperature variable device)
It was determined by measuring a high-resolution NMR spectrum.

The sample of the poly 3-methylbutene-l resin composition used in the measurement was molded into a press sheet of approximately ≠00 μm and then heated at 200°C.
/hr heat treatment, and commercially available C-
The PET containers were measured as they were.

The measuring device is a Rheometrics drop tester.
Falling weight height! Measurements were made at 0.2 ilm, falling weight 3, weight 7-9, and falling weight speed 3.3337 M/S. The measurement temperature is room temperature.

The measured value was expressed by dividing the amount of energy required for fracture by the sample thickness.

The sample piece was fixed to a clamp with an inner diameter of 1.5 inches and used for measurement.

Catalyst Production Example At room temperature, purified toluene stsml was placed in an autoclave with a volume of /l that was sufficiently purged with nitrogen, and under stirring, n-butyl ether 6 mol/t (0,! mol) s titanium tetrachloride ψ, ri? (Oi mol) and diethylaluminum chloride 2♂, 11 (0.2 hmol)
) was added to obtain a brown homogeneous solution. Then, the temperature is raised to 30°C. After 30 minutes, the temperature was raised to ≠0°C and kept at μO°C for 2 hours. Then 32? Titanium tetrachloride (0,/7 mol) and tridecyl methacrylate (o, oss: mol) of /j,jr were added.
The temperature was raised to ℃.

After holding at ♂°C for 2 hours, a granular purple solid was separated and washed with toluene to obtain solid titanium trichloride.

Example: Diethylaluminum monochloride was placed in a 5 t capacity induction stirring autoclave that had been thoroughly dried and replaced with argon.
00 mmol and 3-methylbutene-73,000
, 1 was prepared. After raising the internal temperature to ♂O℃, the solid titanium trichloride catalyst component obtained in the catalyst production example! , 07 Ir■ was pressurized with argon gas to start the seventh stage polymerization. 3 at 10℃ while simultaneously supplying octene-/ and hydrogen continuously.
-Methylbutene-/ and octene-1 were copolymerized for 90 minutes. The total amount of octene supplied to the 7th stage is 27
The total amount of f1 hydrogen was /-2,/mmol.

Next, the supply of hydrogen was stopped, and at the same time the amount of octene// was increased, and the second stage copolymerization of 3-methylbutene// was carried out for 2 minutes at 10°C.

The total amount of octene/supply in the second stage was defined as Jf.

Then, the temperature was immediately lowered to aO°C, and at the same time, octene/610ru1% Hiro-methylpentene/310.
1 was pressurized with argon, and the third stage polymerization was carried out at 110° C. for ≠j minutes.

300.1 l of isobutanol was pressurized with argon to stop the polymerization, and at the same time unreacted monomers were expelled, n-hexane 180.1 l was charged, and the mixture was stirred at po°C for 60 minutes, then the temperature was lowered to room temperature and the supernatant liquid was extracted. . After repeating this operation six times to wash and remove the catalyst component in the polymer, it is dried to form a white powdery 3-methylbutene/polymer composition.
Obtained 37t.

The proportions of each component determined by catalyst analysis in a small amount of the polymer sampled at the end of the first, second, and third stages are as follows: 57% by weight of the /stage polymer (component (a)); The octene-l content in component (a) is 100% by weight, the second stage polymer (component (b)) is 26% by weight, and the octene-l content in component (b) is /jwt%. t%, the third-stage polymer (component (c)) was 77% by weight, the content of octene-1 in the component (c) was 10% by weight, and the content of Hiromethylpentene was 71% by weight.

In addition, in the cleaning process of catalyst components, non-grade and low molecular weight components that are soluble in n-hexane (hereinafter referred to as n-hexane soluble components) are
．． It was % by weight.

After adding 0.2 parts each of Irganox 101O, Irgafos P-EPQ (all manufactured by Nippon Ciba Geigy) and dihydroanthracene to the obtained polymer composition,
Pelletization was carried out using an extruder at °C.

The melting point of this product was 290° C., and the melt index (hereinafter referred to as MI) was 1/10 of O8.

A press sheet is formed from this pellet, heated at 200℃,
After annealing for 7 hours, it was subjected to a tensile test, an Elmendorf tear test, and a Picat softening point measurement.

The polymerization results are shown in Table 1, and the various test results are shown in Table λ.

Example λ ~ In Example 1, (a) component, (b) component, and (c)
The same procedure was carried out except that the composition ratio of the components and the comonomer content were changed as shown in the table.

The polymerization results are shown in Table 7, and the various test results are shown in Table 2.

Comparative Example/-2 Diethylaluminum monochloride 2 was placed in a 2 t capacity induction stirring autoclave that had been thoroughly dried and replaced with argon.
．． u I mmol and 3-methylbuty/-tbooH
I prepared g. After raising the internal temperature to 0.degree. C., 722 cm of the solid titanium trichloride catalyst component obtained in the catalyst production example was introduced under pressure with argon gas to initiate polymerization.

10 while continuously supplying octene-7 and hydrogen at the same time.
℃3-Methylbutene-l and octene-/copolymerization at 12
This was done for 0 minutes.

The total amount of octene-7 supplied is r, tt,
In Comparative Example 1, the total of 4.5f 1 hydrogen is 3.5f in Comparative Example 1. jmmol was set to 2.6 mmol in Comparative Example 2.

Next, inbutanol rOat was pressurized with argon to stop the polymerization, and after expelling unreacted monomers,
n-hexane r00. After stirring at 60°C for 6Q minutes, the temperature was lowered to room temperature, and the supernatant liquid was extracted. This operation was repeated for 5 days to wash and remove the catalyst component in the polymer, and then dried to obtain a white powdery 3-methylbuty/-7 copolymer, each of which was produced as a white powder (comparative example t)/jlit<comparative example 2. ) was obtained. The polymerization results are shown in Table 1.

After adding the stabilizer, the test results were obtained in the same manner as in Example 1 and are shown in Table 2.

Comparative Examples 3 to Hong Example 1, the second stage copolymerization of 3-methylbutene-7 and octene-7 was excluded, and component (a) and (c
) The same procedure was carried out except that the proportions of the components and the comonomer content were changed as shown in Table 7.

The various test results are shown in Table 1.

Further, the relationship between the Vicat softening point and the elongation at break in each of the above Examples and Comparative Examples is shown in FIG.

〔Effect of the invention〕

As described above, according to the present invention, a 3-methylbutene-1 polymer composition can be obtained which is excellent in mechanical strength such as heat resistance and stretchability expressed by Vicat softening point, impact strength, and tear strength.

[Brief explanation of the drawing]

FIG. 1 is a diagram showing the relationship between copolymerization component content and heat of fusion. In the figure, l indicates the copolymer of 3-methylbutene-7 and butene-7, and 2 indicates the relationship between the copolymer content and heat of fusion of the copolymer of 3-methylbutene-7 and octene-7. This is a curve showing the relationship. FIG. 2 is a diagram showing the relationship between Vicat softening point and elongation at break. In the figure, /-jf indicates an example, /-j #, and 7' to Hiro' indicate a comparative example, respectively. Applicant: Mitsubishi Chemical Industries, Ltd. Agent: Patent Attorney Hase - (7 others)

Claims (4)

[Claims] (1) (a) 3-Methylbutene-1 homopolymer, or 3-methylbutene-1 and others having 2 to 18 carbon atoms, having a heat of fusion of 7 cal/g or more as measured by a differential scanning calorimeter (DSC) 10 to 85% by weight of a copolymer with an α-olefin of
10 to 85% by weight of a copolymer of 3-methylbutene-1 and other α-olefin having 2 to 18 carbon atoms, which is greater than cal/g and less than 7 cal/g, and (c) differential scanning calorimeter ( A copolymer of rubber-like 3-methylbutene-1 and another α-olefin having 2 to 18 carbon atoms, or two or more other α-olefins having 2 to 18 carbon atoms, in which no melting peak is observed in DSC). A 3-methylbutene-1 polymer composition comprising 3 to 40% by weight of an olefin copolymer. (2) Transition metal compounds and Groups 1 to 3 of the periodic table
(a) 3-methylbutene-1 or 3-methylbutene-1 in the presence of a catalyst mainly composed of an organometallic compound of group metal;
1 and other α-olefins having 2 to 18 carbon atoms to obtain a polymer or copolymer having a heat of fusion of 7 cal/g or more as measured by a differential scanning calorimeter (DSC). (b) 3-methylbutene-1 and other α having 2 to 18 carbon atoms;
- copolymerizing an olefin with a heat of fusion greater than 1 cal/g and less than 7 cal/g as measured by differential scanning calorimetry (DSC) in an amount of 10 to 85% by weight of the total polymer product; (c) 3-methylbutene-1 and other α having 2 to 18 carbon atoms.
- By copolymerizing an olefin or copolymerizing two or more types of α-olefins having 2 to 18 carbon atoms, a rubber-like 3-methylbutene-1 with no melting peak observed in differential scanning calorimetry (DSC) is obtained. 1. A method for producing a 3-methylbutene-1 polymer composition, which comprises producing 3 to 40% by weight of a copolymer of and another α-olefin having 2 to 18 carbon atoms. (3) (a) 3-methylbutene-1 homopolymer or copolymer of 3-methylbutene-1 with a 3-methylbutene-1 content of more than 90% by weight and other α-olefin having 2 to 18 carbon atoms (b) 3-methylbutene-1 content is 90 to 60% by weight.
10 to 85% by weight of a copolymer of 3-methylbutene-1 and another α-olefin having 2 to 18 carbon atoms, and (c) a 3-methylbutene-1 content of less than 60% by weight. It is characterized by comprising 3 to 40% by weight of a copolymer of methylbutene-1 and another α-olefin having 2 to 18 carbon atoms or a copolymer of two or more α-olefins having 2 to 18 carbon atoms. A 3-methylbutene-1 polymer composition. (4) Transition metal compounds and Groups 1 to 3 of the periodic table
(a) 3-methylbutene-1 or 3-methylbutene-1 in the presence of a catalyst mainly composed of an organometallic compound of group metal;
1 and other α-olefins having 2 to 18 carbon atoms to produce a polymer or copolymer with a 3-methylbutene-1 content of more than 90% by weight, which is 10 to 85% by weight of the total produced polymer. and (b) copolymerizing 3-methylbutene-1 with another α-olefin having 2 to 18 carbon atoms to produce a copolymer with a 3-methylbutene-1 content of 90 to 60% by weight. The step of producing a polymer in an amount of 10 to 85% by weight of the total produced polymer is carried out in any order, and then (c) 3-methylbutene-1 and other α having 2 to 18 carbon atoms are added.
- By copolymerizing olefins or copolymerizing two or more types of α-olefins having 2 to 18 carbon atoms, a copolymer having a 3-methylbutene-1 content of less than 60% by weight is produced as a total polymer. A method for producing a 3-methylbutene-1 polymer composition, characterized in that the composition is produced in a proportion of 3 to 40% by weight.