JPH04332744A - Crystalline syndiotactic polystyrene composition - Google Patents

Abstract

PURPOSE:To obtain a crystalline syndiotactic polystyrene composition having high rate of crystallization and high crystallization temperature by adding a polymer of a specific compound. CONSTITUTION:The objective composition is produced by compounding a syndiotactic polystyrene with a polymer of a compound of formula (n is 0-10; R is cyclic hydrocarbon group) (e.g. vinylcyclohexane) in an amount of 0.05-10,000wt.ppm (preferably 500-1,000wt.ppm) in terms of the monomer unit of the compound.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a crystalline syndiotactic polystyrene composition having a fast crystallization rate and a high crystallization temperature.

0002

BACKGROUND OF THE INVENTION Syndiotactic polystyrene is a crystalline polymer with a higher melting point than isotactic polystyrene. However, its crystallization rate is slow, it does not show a clear X-ray diffraction pattern unless it is annealed at 230° C. or higher, and its heat resistance is also poor considering its high melting point.

0003

SUMMARY OF THE INVENTION In view of the conventional situation, it is an object of the present invention to provide a crystalline syndiotactic polystyrene composition which has a faster crystallization rate and a higher crystallization temperature.

0004

[Means to solve the problem]

The present invention is based on the general formula, CH2=CH(CH2
)n R (I) (in the formula, n is 0 to 1
The integer of 0 and R each represent a cyclic hydrocarbon group. ) is contained in a monomer unit of the compound represented by general formula (I) in an amount of 0.05 to 10,000 wtppm based on syndiotactic polystyrene. The present invention relates to otakutic polystyrene compositions.

The present invention will be explained in detail below. General formula, CH2=CH(CH2)n R
(I) (wherein n is an integer of 0 to 10,
Each R represents a cyclic hydrocarbon group. ) Examples include compounds having a saturated cyclic hydrocarbon group such as vinylcyclohexane, vinyl-2-methylcyclohexane, vinyl-3-methylcyclohexane, allylcyclohexane, and 4-vinylcyclohexene-1,4- Vinyl-2-methylcyclohexene-1, styrene, α-
Examples include compounds having a cyclic hydrocarbon group having a double bond such as methylstyrene. Among these compounds,
Preferred is vinylcyclohexane and its derivatives. These compounds are used as the polymer (A) when forming a composition with syndiotactic polystyrene, and the polymer (A) is a homopolymer of the compound represented by the general formula (I), a compound represented by the general formula It is a copolymer of mutually different compounds represented by formula (I) or a copolymer of a compound represented by general formula (I) and 1-olefin such as ethylene or propylene, and a certain amount of the compound represented by general formula (I). Any polymer may be used as long as it contains monomer units of the compound. Furthermore, in the case of compounds with cyclic hydrocarbon groups having double bonds, such as styrene and α-methylstyrene, it is also effective to generate saturated cyclic hydrocarbon groups such as cyclohexane rings by nuclear hydrogenation of the polymer. It is.

General formula, CH2=CH(CH2)n R
(I) (wherein n is an integer of 0 to 10,
Each R represents a cyclic hydrocarbon group. ) The polymer (A) of the compound represented by is prepared using a Ziegler-Natta catalyst that gives an isotactic polymer using a solvent such as butane, hexane, heptane, benzene, toluene, etc. at 20°C to 1°C.
Although it is preferable to obtain the polymer by polymerizing at 00° C. and normal pressure to 100 kg/cm 2 , it may also be obtained by anionic polymerization, cationic polymerization, or radical polymerization.

[0007] As the Ziegler-Natta catalyst that provides the isotactic polymer used in the production of the polymer (A), specifically, trichloride commercially available from Toyo Stouffer, Toho Titanium, Marubeni Solvay, etc. Titanium catalyst, JP-A No. 57-59916, No. 55-
Catalysts made of organoaluminum and solid catalyst components containing halogen, magnesium, and titanium, which are described in JP 133408, JP 62-238184, JP 63-142003, etc., are preferably used. The organic aluminum compound is AlXa R3-a (X: halogen atom, alkoxy group, or hydrogen atom, R: carbon number 1
-18 alkyl groups, a: the number 0≦a≦3) is preferable, and specific examples include Al(CH3)3, Al(CH3)
2 Cl, Al(CH3)2 Br, Al(CH3
)2 (OC2 H5 ), Al(C2 H5 )3
, Al(C2 H5 )2 Cl, Al(C2 H5
)2 Br, Al(C2 H5 )2 (OC2 H5
), Al(C2 H5 )2 (OC4 H9 ),
Al(C2H5)(OC4H9)2, Al(
C2H5)Cl2, Al(C4H9)3,
Al(C4 H9)2 Cl, Al(C5 H13)
3, Al(C6H13)2Cl, and mixtures thereof. Furthermore, in order to improve the stereoregularity of the polymer during polymerization, it is also possible to add an electron donor such as a carboxylic acid ester, a phosphoric acid ester, or a silicate ester to obtain the polymer (A).

[0008] Polymer (A) can be produced using the above-mentioned catalysts, etc., but specifically, it can be produced by the following various methods. Using a Ziegler-Natta catalyst,
(1) Obtain a homopolymer of the compound represented by general formula (I). (2) Obtaining a copolymer of mutually different compounds represented by general formula (I). (3) In the first step, the compound represented by general formula (I) is polymerized, and in the second step, copolymerization with 1-olefin is performed. In addition, for example, (4) polystyrene obtained by emulsion, suspension, bulk polymerization, etc. may be used, or the polystyrene obtained in this manner may be treated with a catalyst such as Raney nickel, palladium, ruthenium, platinum, etc. Dissolved in a solvent such as cyclohexane to a concentration of about 5 wt% and heated at 50 to 300°C and under hydrogen pressure of normal pressure to 200 kg/cm2.
It can also be hydrogenated under these conditions to have a cyclohexane ring.

The syndiotactic polystyrene used in the present invention is a styrenic polymer in which the syndiotactic diad has a syndiotacticity of 85% or more based on the aromatic C1 carbon or the methylene carbon signal in the main chain in the 13C NMR spectrum. . A styrenic polymer having such syndiotacticity can be obtained as follows. The catalyst is T as a transition metal complex.
i(O-iso-Pr)4 , TiCp2 Cl2 (
Cp: cyclopentadienyl), TiCpCl3, T
i(bz)4 (bz: benzyl), Zr(bz)4
, Cp2 Ti(ph)2 (ph: phenyl), or chemical formula 1

0010

Transition metal complexes represented by (X: methylene or sulfur, R1, R2: hydrogen atom, alkyl group, aryl group, or halogen atom) are preferably used.

[0011] As the organoaluminum compound, chemical formula 2

[
An aluminoxane compound having a repeating unit represented by (n is an integer of 4 or more) is preferable.

Specific examples of styrenic monomers used in the production of styrenic polymers having a syndiotactic structure include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o,p-dimethylstyrene, o-ethylstyrene, m-ethylstyrene, p-
Examples include ethylstyrene, o-chlorostyrene, p-chlorostyrene, α-methylstyrene, and these monomers may be used alone or in a mixture. The polymerization method is not particularly limited either, but for example, the solvent may be an aliphatic hydrocarbon solvent such as butane, pentane, hexane, heptane, or octane, an aromatic hydrocarbon solvent such as benzene or toluene, or a halogen such as methylene chloride. A carbonized hydrocarbon solvent or a monomer aromatic vinyl compound can be used as the solvent.

The content of the polymer (A) contained in the crystalline syndiotactic polystyrene composition is determined by the general formula (I
) 0.05 to 1 in the amount of monomer units of the compound represented by
0000wtppm, preferably 500wtppm~1
0000wtppm. If it is less than 0.05wtppm, no crystallinity improvement effect can be obtained;
If it is larger than pm, the further improvement effect is small. The composition of crystalline syndiotactic polystyrene and polymer (A) can be prepared by mixing the two polymers together using a mixing method that is commonly used for mixing 1-olefin polymers, such as mixing the two polymer powders together, granulating pellets together, This is carried out by melt-kneading the polymer powder and granulated pellets using a Henschel mixer, Banbury mixer, roll or granulator, or by mixing solutions of both polymers. The crystalline syndiotactic polystyrene composition of the present invention contains all kinds of heat and light stabilizers, antistatic agents, antioxidants, carbon black, pigments, flame retardants, etc. that are normally added to 1-olefin polymers. Additives and fillers such as mica and talc can be blended and mixed for use. The crystalline syndiotactic polystyrene of the present invention can be made into various products such as sheets, films, containers, fibers, etc. by well-known techniques such as injection molding, pressure forming, vacuum forming, extrusion molding, blow molding, and stretching.

[0014]

[Examples] The present invention will be specifically explained below using Examples. The crystallization rate was determined by comparing the crystallization temperatures of the composition and syndiotactic polystyrene not containing the polymer (A), and the one with a higher crystallization temperature was judged to have a faster crystallization rate. The crystallization temperature was measured using a differential scanning calorimeter (D
SC) at a cooling rate of 4°C/min from 250°C. Example 1 (I) Polymerization of syndiotactic polystyrene (1) Preparation of catalyst components In a flask with an internal volume of 100 ml equipped with a stirrer, 2,2'
-dihydroxy-3,3'-di-t-butyl-5,5'
- Take 0.9 mmol of dimethyl diphenyl sulfide, replace with argon, and dry n-butyl ether 50
ml was added and stirred to dissolve. This solution contains 0 titanium tetrachloride.
．． 9 mmol was added. The reaction was carried out at 25° C. for 2 hours with stirring. A part of the precipitate was dissolved in toluene, and Ti was 0.
A solution containing 0.001 mmol/ml was prepared. (2) Synthesis of organoaluminum component After purging a flask with an internal volume of 500 ml equipped with a stirrer, a dropping funnel, and a reflux condenser with argon, 44 g
(0.176 mol) of CuSO4 ・5H2 O in 3
00ml of toluene, and while keeping the internal temperature at 5℃ and stirring, add 56ml of trimethylaluminum (
0.58 mol) and 70 ml of toluene.
It dripped over time. After dropping, lower the flask internal temperature to 5°C.
Stir for 40 hours while keeping at room temperature, then stir at room temperature for 2 hours.
Stirring was continued for 0 hours. After removing the precipitate, the solvent was removed under reduced pressure to obtain 13.0 g of methylaluminoxane. For polymerization, it was diluted with toluene to 0.05 g/ml. Note that this methylaluminoxane solution was used in the following examples. (3) Polymerization of styrene After purging a three-neck flask with an internal volume of 100 ml and equipped with a stirrer with argon, add 30 ml of toluene and 20 ml of styrene.
ml was added, and the internal temperature of the flask was maintained at 25°C. (1)
3 ml of the reaction solution synthesized in (2) and 10 ml of the methylaluminoxane solution synthesized in (2) were charged into a flask to start polymerization. After polymerization was carried out at 25° C. for 14 hours with stirring, 10 ml of methanol was added and stirring was continued for 30 minutes. The polymer was filtered off and washed with a 1N HCl/methanol solution, then washed with methanol, and dried under reduced pressure at 60°C for 2 hours. The obtained polystyrene was 3.25
g, which corresponds to 22.6 kg of polymer produced per Ti atom. The obtained polystyrene had a molecular weight of 4.7×10 5 and an [rrrr] fraction of 0.98 or more, and was syndiotactic polystyrene. (II) Polymerization of Polymer (A) 0.157 g of titanium trichloride (manufactured by Marubeni Solvay) and 0.3 g of triethylaluminum were added to a mixed solution of 10 ml of n-hexane and 5 g of vinylcyclohexane, and polymerized at 50°C for 45 minutes. I did it. After the polymerization was completed, the polymerization was stopped with n-butanol, washed with methanol with hydrochloric acid, and
．． 1 g of polyvinylcyclohexane was obtained. (III) Production of crystalline syndiotactic polystyrene composition 0.1 g of the above polymer (A) and 100 g of the syndiotactic polystyrene powder obtained in (3) were dissolved in 300 ml of decahydronaphthalene under refluxing conditions, and dissolved in methanol. It was reprecipitated and mixed uniformly. After filtration, decahydronaphthalene and methanol were removed by drying under reduced pressure. 0.05 parts by weight of calcium stearate and BHT (2,6-
di-t-butylhydroxytoluene) 0.2 parts by weight, tetrakis[methylene 3-(3',5'-di-t-butyl-4-hydroxyphenyl)propionate]methane 0
．． After adding 0.05 parts by weight, roll kneading was performed. The crystallization temperature of this composition was 239°C.

Example 2 A composition of syndiotactic polystyrene and polymer (A) was obtained in the same manner as in Example 1 except that the amount of syndiotactic polystyrene powder was changed to 10 g. . The crystallization temperature of this composition was 240°C.

Comparative Example 1 For comparison, the crystallization temperature of the syndiotactic polystyrene homopolymer in Examples 1 and 2 without the addition of polymer (A) was measured and found to be 231°C.

The results of Examples 1 and 2 and Comparative Example 1 are shown in Table 1.

[0018]

The composition according to the invention can obtain a higher crystallization temperature than syndiotactic polystyrene alone.

Claims (1)

[Claims] [Claim 1] General formula, CH2=CH(CH2)n R
(I) (in the formula, n is an integer of 0 to 10, and R represents a cyclic hydrocarbon group, respectively). 0 in the monomer unit of the compound represented by
．． 1. A crystalline syndiotactic polystyrene composition containing 0.05 to 10000 wtppm.