JPS62104818A - Styrene polymer - Google Patents

Abstract

PURPOSE:To provide the titled novel polymer with the stereochemical structure of the side chain to the main chain being syndiotactic one, having such regular molecular structure as having never been found, outstanding in high heat and chemical resistances, also usable as a functional polymer. CONSTITUTION:A styrene derivative monomer as the raw material is polymerized in the presence of a catalyst consisting of, for example, a combination of a titanium compound such as titanium halide and alkylamino acid to obtain the objective polymer with a polymerization degree >=5 having recurring unit of formula (R is H, halogen or substituent containing C, O or N; n is integer 1-3) with its stereoregularity being of syndiotactic structure.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a styrenic polymer having a novel steric structure, and more specifically to a styrene polymer in which the stereochemical structure of the side chain with respect to the main chain of the polymer is mainly a syndiotactic structure. Related to polymers.

[Prior art and problems to be solved by the invention] Generally, it is known that styrenic polymers such as polystyrene and polyparamethylstyrene can be produced by radical polymerization, anionic polymerization, cationic polymerization, or polymerization using a Ziegler type catalyst. It is being The structure of the styrenic polymer thus obtained is theoretically classified into isotactic structure, diotactic structure, and actic structure depending on the configuration of the molecular chains.

So far, we have used conventional radical polymerization, anionic polymerization,
It is known that cationic polymerization mainly yields styrene polymers with an active structure, and polymerization using a Ziegler type catalyst yields styrene polymers mainly with an isotactic structure.

In this way, until now there have been many studies on styrenic polymers (
Although there have been reports on the manufacturing method and its structure,
Styrenic polymers with a highly syndiotactic structure are
There are no examples of it being manufactured except for model materials equivalent to 3 to 5 star bodies using organic synthetic chemical methods.

[Means for solving problems]

Therefore, the present inventors conducted repeated research in order to produce a styrenic polymer having a highly syndiotactic structure, which has never been produced before. As a result, when styrenic monomers are polymerized using a catalyst that combines a certain type of transition metal compound and an organometallic compound, a styrenic polymer with a structure that has never been obtained before is surprisingly obtained. It was found that it has a highly syndiotactic structure, and the present invention was completed.

That is, the present invention is based on the general formula (1) [wherein R represents a hydrogen atom, a halogen atom, or a substituent containing carbon, oxygen, nitrogen, sulfur, phosphorus or a silicon atom, and n represents an integer of 1 to 3] . ] This object provides a styrenic polymer having a polymerization degree of 5 or more and having a repeating unit represented by the following, and whose stereoregularity is mainly a syndiotactic structure.

The styrenic polymer in the present invention has a structural unit (repeat unit) represented by the above general formula (1), and includes polystyrene and various nuclear-substituted polystyrenes such as polyalkylstyrene and polyhalogenated styrene. .

R and n in the above general formula (1) are as described above. That is, the nuclear substituent (R) is a substituent containing a hydrogen atom, a halogen atom such as chlorine, bromine, or iodine, or a carbon, oxygen, nitrogen, sulfur, phosphorus, or silicon atom. here,
Specific examples of substituents containing carbon atoms include those having 1 to 2 carbon atoms;
0 alkyl group (for example, methyl group, ethyl group, isopropyl group, tertiary-butyl group, etc.) or a halogen-substituted alkyl group having 1 to 20 carbon atoms (for example, chloromethyl group, bromomethyl group, chloroethyl group, etc.), Specific examples of substituents containing carbon atoms and oxygen atoms include:
Alkoxy group having 1 to 10 carbon atoms (e.g. methoxy group, ethoxy group, isopropoxy group, etc.) or having 1 to 10 carbon atoms
There are 10 carboxyester groups (e.g. carboxymethyl ester group, carboxyethyl ester group, etc.), and specific examples of substituents containing carbon atoms and silicon atoms include:
There are alkylsilyl groups having 1 to 20 carbon atoms (trimethylsilyl group, etc.), and specific examples of substituents containing carbon atoms and nitrogen atoms include alkylamino groups having 1 to 20 carbon atoms (dimethylamino group, etc.) and cyano groups. be. Further, specific examples of substituents containing a sulfur atom include a sulfonyl group, a sulfonic acid alkyl ester group, an alkylthio group, or a mercap I-5 group, and specific examples of substituents containing a phosphorus atom include a phosphoric acid ester group, It has a phosphite group or an alkylphosphinyl group.

Further, specific examples of the styrenic polymer of the present invention include:
Polystyrene, poly(p-methylstyrene), poly
(m-methylstyrene), poly (0-methylstyrene), poly (2,4-dimethylstyrene), poly (2
, 5-dimethylstyrene), poly(3,4-dimethylstyrene), poly(3,5-dimethylstyrene), poly(p-tert-butylstyrene), etc.
(alkyl styrene), poly (p-chlorostyrene)
, poly(m-chlorostyrene), poly(0-chlorostyrene), poly(p-bromostyrene), poly(m-chlorostyrene)
-bromostyrene), poly(0-bromostyrene), poly(p-fluorostyrene), poly(m-fluorostyrene), poly(0-fluorostyrene), poly(
Poly(halogenated styrene) such as 0-methyl-p-fluorostyrene), poly(p-chloromethylstyrene), poly(m-chloromethylstyrene), poly(
Poly(halogen-substituted alkylstyrene) such as (0-chloromethylstyrene), poly(p-methoxystyrene)
, poly (alkoxystyrene) such as poly (m-methoxystyrene), poly (0-methoxystyrene), poly (p-methoxystyrene), poly (m-ethoxystyrene), poly (0-ethoxystyrene), poly (p-carboxymethylstyrene), poly(m-carboxymethylstyrene)2poly(carboxyester styrene) such as (0-carboxymethylstyrene), poly(p-vinylbenzylpropyl ether), etc. alkyl ether styrene), poly
Examples include poly(alkylsilylstyrene) such as (p-trimethylsilylstyrene), poly(ethyl vinylbenzenesulfonate), and poly(vinylhensyldimethoxyphosphide).

The styrenic polymer of the present invention mainly has a steric structure, that is, a three-dimensional structure in which phenyl groups or substituted phenyl groups, which are side chains, are alternately located in opposite directions with respect to the main chain formed from carbon-carbon bonds. It has
Its toughness is determined by nuclear magnetic resonance method (NMR method)
It is quantified by

Specifically, the C1 carbon signal of the aromatic ring, the methine/methylene carbon signal, or the 'H-NM
Based on the analysis of the prone signal of R.

Toughness measured by NMR refers to the proportion of a plurality of consecutive structural units, for example, a diad if there are two units, and a triazodate if there are three units.

In the case of 5 pieces, it can be represented by a pentad, but
The term "polymer mainly having a syndiotactic structure" as used in the present invention means a polymer having a syndiotactic structure of 85% or more in terms of diad or 50% or more in pentad.

However, depending on the presence or absence and type of substituents, the degree of syndiotacticity achieved conventionally differs slightly, and even if the above-mentioned value is not necessarily satisfied, the syndiotacticity referred to in the present invention is mainly a styrene-based polymer with a structure. This corresponds to merging. More specifically, for example, for polystyrene, it is 75% or more diad or 30% or more pentad, and for poly(p-methylstyrene), it is 75% or more diad or 30% or more pentad. For poly(m-methylstyrene), 75% or more for diad or 35% or more for pentad; for poly(0-methylstyrene), 85% or more for diad or 30% or more for pentad; Poly(0-methoxystyrene) containing 80% or more diad or 40% or more pentad, and poly(p-methoxystyrene) containing 75% or more diad or 30% or more pentad are also included in the present invention. It is mainly included in styrenic polymers having a syndiotactic structure.

The styrenic polymer mainly having a syndiotactic structure as used in the present invention does not necessarily have to be a single compound. As long as the syndiotacticity is within the above range, it may be a mixture with a styrene polymer having an isotactic or actic structure, or it may be incorporated into a copolymer chain. The styrenic polymers of the present invention may be a mixture of different molecular weights, and the degree of polymerization is at least 5 or more, preferably 10 or more.

The styrenic polymer of the present invention as described above can be produced by polymerizing the corresponding monomers or using the obtained polymer as a raw material.
By applying fractionation, blending or organic synthesis techniques, embodiments with desired stereoregularity and substituents can be produced.

In order to produce the styrenic polymer of the present invention, a combination of a titanium compound such as a titanium halide, an alkoxydichne, and an alkylaluminoxane is used, using styrene, an alkyl styrene, or a styrene BH>5 monomer such as a halogenated styrene as a raw material. By carrying out polymerization in the presence of a catalyst consisting of a combination of the following compounds, the styrenic polymer referred to in the present invention can be obtained in a wide variety of ways, as shown in the Examples below. The polymer obtained by the darning polymerization method has an unprecedentedly high syndiotoughness even without any treatment such as fractionation, but if an appropriate fractionation method such as a solvent is used, A polymer with syndiotacticity close to 100% can be obtained, and by blending this high tacticity polymer again with an active or isotactic styrenic polymer using known and conventional means, the desired result can be obtained. It is also possible to obtain a styrenic polymer according to the present invention having toughness.

Furthermore, it is well known that various substituents can be introduced into polystyrene by organic synthetic methods such as chloromethylation on the aromatic rings of polystyrene, and by such means, the styrenic polymer of the present invention can be used as a base material to create a wood-tough material. The styrenic polymer according to the present invention having various aromatic substituents can be produced while maintaining its properties.

〔Effect of the invention〕

As described above, the styrenic polymer of the present invention has an unprecedented regular molecular structure, and among those that crystallize, it has significantly better heat resistance than the commonly used atactic polystyrene. It also has excellent chemical resistance and can be used as a molding material in various fields where these are required. Side chain Hensen I again! Those in which a functional substituent is introduced into 2 are effectively and widely used as functional polymers.

〔Example〕

Next, Examples of the present invention will be shown, and it will be confirmed that the obtained styrenic polymer mainly shows a syndiotactic structure.

Example 1 (1) Preparation of catalyst components 41.4 ml (492 mmol) of trimethylaluminum was added to 200 mJ of toluene solvent, and 35.5 g of copper sulfate pentahydrate (Cu S 04 ・51-120) was added thereto. (142 mmol) plus 2 at 20°C
The reaction was allowed to proceed for 4 hours. After the reaction, the solvent toluene was removed by filtration to obtain 12.4 g of methylaluminoxane.
I got it.

(2) Polystyrene manufacturing capacity 500m4! 100 mj of toluene in a glass container with a stirrer! and 40 mmol JJI+ of the methylaluminoxane obtained in (1) above as aluminum atoms.
Then, 0.05 mmol of cyclopentadienyl titanium trichloride was added thereto.

Subsequently, 180 ml of styrene was added at 20°C to carry out a polymerization reaction for 1 hour, and then methanol was injected to stop the reaction. Next, a mixture of hydrochloric acid and methanol was added to decompose the catalyst components.

The yield of the polystyrene obtained here was 16.5 g, and the interlayer average molecular weight was 280,000 and the number average molecular weight was 57,000. Furthermore, when this polystyrene was extracted using a Soxhlet extraction apparatus for 4 hours using methyl ethyl ketone as a solvent, 97%
It was accommodating. Further, the melting point of this methyl ethyl ketone-insoluble polystyrene was 260°C, and the specific gravity was 1.043.

In addition, this methyl-ethyl ketone? Figure 1 shows the aromatic ring C3 carbon signal of CNMR of polystyrene.
The ``C-NMR methine/methylene carbon signal is shown in Figure 2 (・1), the ``H-NMR (proton nuclear magnetic resonance spectrum) is shown in Figure 3 (a), and the X-ray diffraction pattern is shown in Figure 4.
The infrared absorption spectrum is shown in Figure (al) and Figure 5 (al), respectively.

Comparative Example 1 Actic polystyrene obtained by radical polymerizing styrene at 0° C. using organic peroxide was extracted with methyl ethyl ketone in the same manner as in Example 1 (2), and the entire amount was extracted. Further, this polystyrene had a glass transition temperature of 100° C. and a specific gravity of 1.05.

In addition, this polystyrene's "C-NMR yt=ring C,
The carbon signal is shown in Figure 1 (bl), the methine/methylene carbon signal of '3C-NMR is shown in Figure 2 (bl), and the infrared absorption spectrum is shown in Figure 5 (bl).

Comparative Example 2 Magnesium Jetoxide 10. Og to titanium tetrachloride 5
Using a combination of 1.0 mmol of a titanium catalyst component supporting a titanium compound and 10 mmol of triethylaluminum as a catalyst, a polymerization reaction of 100 ml of styrene was carried out at 70°C for 2 hours in a heptane solvent, and the weight Average molecular weight 1. 48.7 g of isotactic polystyrene of OOO, OOO was obtained. When this polystyrene was extracted with methyl ethyl ketone in the same manner as in Example 1 (2), 964% of the polystyrene was found to be non-volatile.

In addition, this methyl ethyl ketone-insoluble polystyrene
The C-NMR aromatic ring CI carbon signal is shown in Figure 1 fcl, and the C-NMR methine/methylene carbon signal is shown in Figure 2.
Figure (C) shows the 'H-NMR, Figure 3 (bl) shows the X-ray diffraction pattern, Figure 4 (bl) shows the infrared absorption spectrum, and Figure 5 (C) shows the infrared absorption spectrum.

Next, it was confirmed that the polystyrene obtained in Example 1 (2) had a syndiotactic structure based on the analysis results of this polystyrene, the atactic polystyrene obtained in Comparative Example 1, and the atactic polystyrene obtained in Comparative Example 2. 61 while comparing the analysis results of isotactic polystyrene! I approve.

(1) Result of 13C-NMR) Aromatic ring C1 signal It is well known that the splitting of the aromatic 15 ring C1 carbon signal corresponds to the microstructure of a polymer. Literature values and actual measured values of polystyrene, actinocboristyrene, and isotactic polystyrene obtained in Example 1 (Figure 1 (a)
+, (bl, (C1)) are organized and shown in Table 1.

From Table 1, the polystyrene of Example 1 has a syndiotactic structure, and as calculated from the peak area in FIG.
It had a toughness close to 0.00%.

*l:m is -CII CI'l z CHG H
Structural unit of z-, *2: Il, 5ato, Y, Tanaka
, J. Polym, Sci.

Polym, Phys, Hd, 21. 1667
~1674 (1983).

(11) Methine/methylene carbon signal It is well known that methine/methylene carbon signal splitting corresponds to the microstructure of polymers, and in the case of polystyrene, there are many literatures reporting the attribution of this splitting. Literature values and actual measured values of polystyrene, active polystyrene, and isotactic polystyrene obtained in Example 1 (
Figures 2 (a), (b), and (C)) are summarized and shown in Table 2.

Note that the units of numbers in the table are ppm (TMS standard). As is clear from Table 2, the polystyrene obtained in Example 1 is syndioctic polystyrene and has a single peak, so it has a syndiotacticity close to 100%. I understand that there is something.

+21 'Results of H-NMR' It is well known that H-NMR can provide information about the microstructure in the same way as C-NMR (
S, Brownstein, S, Bywater
, D.T., Worsfol J., Phys., Ch.
Em, 66, 2067 (1962)).

The polystyrene obtained in Example 1 is shown in FIG. 3(a).

(Comparing bl, the methine proton signal of the isotactic polystyrene appears in a higher magnetic field than the methine proton of the polystyrene of Example 1, and is clearly different from isotactic polystyrene. Furthermore, the polystyrene obtained in Example 1 shows a microstructure, and atactic polystyrene (F, A, Bovey,
F, P, Hood III, J, Chem.

Phys, 38.1026 (1963)), only one type of methine and notylene protons in the molecular chain are observed, so
% syndiotactic structure.

Judging comprehensively from the results of (1) and (21) above, the polystyrene obtained in Example 1 is a polymer with a syndiotactic structure in which the steric structure is 96% or more in pentad structure and is close to 100%. It was confirmed.

d, +31 X-ray diffraction pattern The polystyrene obtained in Example 1 shows crystallinity, but the X-ray diffraction pattern of the crystallized product (Figure 4 (a)) and the X-ray diffraction pattern of isotactic polystyrene (Figure 4 Figure (b
l) (G, Natta, P, Corradi
ni.

Nuovo Cimento 15, 5upp1. 40 (1960)), the two are markedly different. Therefore, it can be seen that the polystyrene of Example 1 has a different crystal structure from isotactic polystyrene.

Furthermore, from the results in Figure 4 (al), the fiber period of the polystyrene of Example 1 was 5.04. In addition to the NMR results, the polystyrene of Example 1 further supports a syndiotactic structure.

(4) When the peaks of the infrared absorption spectrum in Figure 5 + a), (b), and (cl) are organized, they are as shown in Table 3.

Further, the polystyrene of Example 1 has a unique absorption peak at 122Qcs-' that is not present in polystyrene having an isotactic structure or an actic structure.

(5) Melting point The melting point of the polystyrene obtained in Example 1 is 260-27
0°C, the melting point of isotactic polystyrene (
(220°C to 230°C).

(6) Toughness of extracts of methyl ethyl ketone--When determining stereoregularity in polystyrene for S, Soxhlet extraction is performed using methyl ethyl ketone as a solvent, and if it is insoluble, it is treated as isotactic polystyrene. In some cases, it has been determined that it is active polystyrene. (Tadashi Nakata, Yasuo Kinoshita, Takayuki Otsu, Minoru Imoto.

Industrial Chemistry, ■, 858-864 (1965)).

The methyl ethyl ketone insoluble portion of the polystyrene obtained in Example 1 had a syndiotactic structure, but the methyl ethyl ketone soluble portion also had a syndiotactic structure of 82% or more.

Example 2 Using 1 mmol of titanium tetrachloride and 40 mmol of methylaluminoxane as a catalyst, 100 mj2 of styrene was
Polymerization was carried out at 0° C. for 8 hours, and polystyrene O, Ig was obtained in the same manner as in Example I (2).

The gingioctality of the obtained polystyrene is:
"C-NMR pentad is 36%, weight average molecular weight (MW) 544,000° number average molecular i (Mn
) was 223,000.

When this polystyrene was extracted with methyl ethyl ketone, 79-t% was extracted, and the syndiotacticity of the extracted residue was 86% by C-NMR pentad.
The weight average molecular weight (MW) was 678,000, and the number average molecular weight (Mn) was 272.000. The syndiotacticity of the extracted product was 23% as determined by '3c-NMR pentad, which was the same as that of ordinary radical polymers.

Example 3 Example 2 except that the amount of titanium tetrachloride used as a catalyst component was 0.05 mmol, the amount of styrene used was 180 ml, and the polymerization time was 2 hours.
In the same manner as above, 6.7 g of polystyrene was obtained.

When this polystyrene was extracted with methyl ethyl ketone, 8% was extracted. The syndiotacticity of the extracted polystyrene was 99% or more, the weight average molecular weight (MW) was 348,000, and the number average molecular weight (Mn) was 156,000.

Example 4 0.4 g of polystyrene was obtained in the same manner as in Example 2, except that 1 mmol of isopropoxytitanium trichloride was used instead of titanium tetrachloride as a catalyst component and the polymerization time was 2 hours. The syndiotacticity of this polystyrene is 96% in C-NMR pentad, and the weight average molecular weight (MW) is 92,000.
0, and the number average molecular weight (Mn) was 31,000.

When this polystyrene was extracted with methyl ethyl ketone, 58 wL% was extracted. The syndiotacticity of the extracted polystyrene was 96% in pentads of C-NMI, and the weight average molecular weight (MW) was 100.0.
00, and the number average molecular weight (Mn) was 36.000. The syndiotacticity of the extract is 2 pentads.
It was 3%.

Example 5 Ethoxytitanium trichloride 0.02 as catalyst
Polystyrene was obtained in the same manner as in Example 2, except that mmol and 10 mmol of methylaluminoxane were used and the conditions shown in Table 4 were used. Thereafter, the obtained polystyrene was extracted with methyl ethyl ketone in the same manner as in Example 2. The properties of this polystyrene are shown in Table 4.

Example 6 As a catalyst, 0.2 mmol (as titanium tetrachloride) of titanium tetrachloride supported on magnesium jetoxide (146 μg/g-tF3 body) and 10 mmol of methylaluminoxane were used, and the catalysts shown in Table 4 were used. Polystyrene was obtained in the same manner as in Example 2 except for the following conditions.

Thereafter, the obtained polystyrene was extracted with methyl ethyl ketone in the same manner as in Example 2. The properties of this polystyrene are shown in Table 4.

Example 7 Tetraethoxytitanium was supported on magnesium chloride as a catalyst (80 mg/g/support) and 0.2 mmol (
Polystyrene was obtained in the same manner as in Example 2, except that 10 mmol of tetraethoxytitanium) and methylaluminoxane were used and the conditions shown in Table 4 were used. Thereafter, the obtained polystyrene was extracted with methyl ethyl ketone in the same manner as in Example 2. The properties of this polystyrene are shown in Table 4.

Example 8 Example 8 except that a large excess of titanium tetrachloride was used as a catalyst, 0.02 mmol of titanium supported on magnesium chloride and 10 mmol of methylaluminoxane were used, and the conditions shown in Table 4 were used. Polystyrene was obtained in the same manner as in 2.

Thereafter, the obtained polystyrene was extracted with methyl ethyl ketone in the same manner as in Example 2. The properties of this polystyrene are shown in Table 4.

Example 9 Using titanium tetrachloride and ethyl benzoate as catalysts,
0.0 as titanium supported on magnesium chloride
Polystyrene was obtained in the same manner as in Example 2, except that 2 mmol and 10 mmol of methylaluminoxane were used and the conditions shown in Table 4 were used. Thereafter, the obtained polystyrene was extracted with methyl ethyl ketone in the same manner as in Example 2. The properties of this polystyrene are shown in Table 4.

Example 10 Polystyrene was obtained in the same manner as in Example 2, except that 0.02 mmol of titanium trichloride and 20 mmol of methylaluminoxane were used as catalysts, and the conditions shown in Table 4 were changed. Thereafter, the obtained polystyrene was extracted with methyl ethyl ketone in the same manner as in Example 2. The properties of this polystyrene are shown in Table 4.

Example 11 1 mmol of titanium tetrachloride and 1 mmol of tributoxyhanadyl (VO(0.C4H9):I) as a catalyst
Polystyrene was obtained in the same manner as in Example 2, except that 40 mmol of methylaluminoxane and 40 mmol of methylaluminoxane were used and the conditions shown in Table 4 were used. Thereafter, the obtained polystyrene was extracted with methyl ethyl ketone in the same manner as in Example 2. The properties of this polystyrene are shown in Table 4.

Example 12.13 Polystyrene was obtained in the same manner as in Example 2, except that 1 mmol of isopropoxytitanium chloride, 1 mmol of tributoxyvanadyl, and 40 mmol of methylaluminoxane were used as catalysts, and the conditions shown in Table 4 were used. Ta. Thereafter, the obtained polystyrene was used in Example 2.
Extracted with methyl ethyl ketone in the same manner as above. The properties of this polystyrene are shown in Table 4.

Examples 14 to 16 0.05 mmol of tetraethoxytitanium and 5 mmol of methylaluminoxane were used as catalysts, and a fourth
Polystyrene was obtained in the same manner as in Example 2 except that the conditions shown in the table were used. Thereafter, the obtained polystyrene was extracted with methyl ethyl ketone in the same manner as in Example 2. The properties of this polystyrene are shown in Table 4.

Example 17 Polystyrene was obtained in the same manner as in Example 2, except that 0.05 mmol of tetraethoxytitanium and 10 mmol of methylaluminoxane were used as catalysts, and the conditions shown in Table 4 were used. Thereafter, the obtained polystyrene was extracted with methyl ethyl ketone in the same manner as in Example 2. The properties of this polystyrene are shown in Table 4.

Examples 18 to 20 Polystyrene was obtained in the same manner as in Example 2, except that 0.05 mmol of tetraethoxytitanium and 25 mmol of methylaluminoxane were used as catalysts, and the conditions shown in Table 4 were used. Thereafter, the obtained polystyrene was extracted with methyl ethyl ketone in the same manner as in Example 2. The properties of this polystyrene are shown in Table 4.

Example 21 Polystyrene was obtained in the same manner as in Example 2, except that 1 mmol of tetraisopropoxytitanium, 1 mmol of tributoxyvanadyl, and 40 mmol of methylaluminoxane were used as catalysts, and the conditions shown in Table 4 were used. Thereafter, the obtained polystyrene was extracted with methyl ethyl ketone in the same manner as in Example 2. The properties of this polystyrene are shown in Table 4.

Example 22 0.02 mmol of cyclopentagenyl titanium trichloride and 10 mmol of methylaluminoxane were used as catalysts, styrene and p-methylstyrene were used as starting materials, and the conditions shown in Table 4 were used except that A copolymer of styrene and p-methylstyrene was obtained in the same manner as in Example 2. Thereafter, the obtained copolymer was extracted with methyl ethyl ketone in the same manner as in Example 2. The properties of this copolymer are shown in Table 4.

Example 23 0.025 mmol of cyclopentadienyl titanium trichloride and 40 mmol of methylaluminoxane as catalyst
Except that mmol was used, p-methylstyrene was used as the raw material monomer, and the conditions were as shown in Table 4.
Poly(p-methylstyrene) was obtained in the same manner as in Example 2. After that, the obtained poly(p-methylstyrene)
was extracted with methyl ethyl ketone in the same manner as in Example 2. The properties of this poly(p-methylstyrene) are shown in Table 4.

In addition, the 130-N of this poly(p-methylstyrene)
The MR aromatic ring CI carbon signal is shown in Figure 1fdl as “C
-NMR methine/methylene carbon signals in Figure 2 (d
), 'H-NMR is shown in Figure 3 (C), X-ray diffraction pattern is shown in Figure 4 (C), and infrared absorption spectrum is shown in Figure 5 (
dl respectively.

Example 24 Using 0.05 mmol of cyclopentadienyl titanium chloride as a catalyst and 30 mmol of noxane as a catalyst, m-
Poly(m-methylstyrene) was obtained in the same manner as in Example 2, except that methylstyrene was used and the conditions shown in Table 4 were used. Thereafter, the obtained poly(m-methylstyrene) was extracted with methyl ethyl ketone in the same manner as in Example 2. The properties of this poly(m-methylstyrene) are shown in Table 4.

In addition, 13C-N of this poly(m-methylstyrene)
The MR aromatic ring C and carbon signals are shown in Figure 1(e).

Example 25 The procedure was carried out except that 0.05 mmol of cyclopentadienyl titanium trichloride and 30 mmol of methylaluminoxane were used as the catalyst, pt-butylstyrene was used as the raw material monomer, and the conditions shown in Table 4 were used. Poly(pt-butylstyrene) was obtained in the same manner as in Example 2. Thereafter, the obtained poly(pt-butylstyrene) was extracted with methyl ethyl ketone in the same manner as in Example 2. The properties of this poly (pt-butylstyrene) are shown in Table 4. Incidentally, the aromatic ring C + carbon signal of this poly(pt-butylstyrene) in 13C-NMR is shown in FIG. 1(f).

Example 26 Example 2 except that 0.05 mmol of cyclopentadienyl titanium trichloride and 40 mmol of methylaluminoxane were used as the catalyst, p-chlorostyrene was used as the raw material monomer, and the conditions shown in Table 4 were further set. Poly(p-chlorostyrene) was obtained in the same manner as above. Thereafter, the obtained poly(p-chlorostyrene) was extracted with methyl ethyl ketone in the same manner as in Example 2. The properties of this poly(p-chlorostyrene) are shown in Table 4.

In addition, “c-NM” of this poly(p-chlorostyrene)
The aromatic ring C2 carbon signal of R is shown in Figure 1 (g), and
As a reference, “C” of Akkuchiku (p-chlorostyrene)
-NMR aromatic ring CI carbon signal is shown in FIG. 1(h).

Example 27 The same procedure as in Example 2 was carried out, except that 0.05 mmol of tetraethoxytitanium and 5 mmol of methylaluminoxane were used as the catalyst, m-chlorostyrene was used as the raw material monomer, and the conditions shown in Table 4 were used. Poly
(m-chlorostyrene) was obtained. Thereafter, the obtained poly(m-chlorostyrene) was extracted with methyl ethyl ketone in the same manner as in Example 2. The properties of this poly(m-chlorostyrene) are shown in Table 4. In addition, this poly (m-
The aromatic ring C1 carbon signal of lffC-NMR of chlorostyrene) is shown in Figure 1 O).

Example 28 Except for using 0.05 mmol of cyclopentagenyl titanium trichloride and 30 mmol of methylaluminoxane as a catalyst, using p-fluorostyrene as a raw material monomer, and using the conditions shown in Table 4,
Poly (p-fluorostyrene) was prepared in the same manner as in Example 2.
I got it. Thereafter, the obtained poly(p-fluorostyrene) was extracted with methyl ethyl ketone in the same manner as in Example 2. The properties of this poly(p-fluorostyrene) are shown in Table 4. The aromatic ring CI carbon signal of IfC-NMR of this poly(p-fluorostyrene) is shown in Figure 10.
Shown in 1.

[Brief explanation of drawings]

Figure 1 (a) to N) are the polystyrene obtained in Example 1, the active polystyrene obtained in Comparative Example 1, the isotactic polystyrene obtained in Comparative Example 2, and the isotactic polystyrene obtained in Example 23, respectively. Poly(p-methylstyrene)
, poly(m-methylstyrene) obtained in Example 24
, poly(p-t-butylstyrene) obtained in Example 25, poly(p-chlorostyrene) obtained in Example 26. Acetic poly(p-chlorostyrene), Example 2
Poly(m-chlorostyrene) obtained in 7. and aromatic ring CI carbon signals of the poly(p-fluorostyrene) obtained in Example 28. C-NMR methine/methylene carbon signals of the active polystyrene obtained in Comparative Example 1, the isotactic polystyrene obtained in Comparative Example 2, and the poly(p-methylstyrene) obtained in Example 23 shows. Figures 3(a) to (c) show the polystyrene obtained in Example 1, the isotactic polystyrene obtained in Comparative Example 2, and the poly(p-methylstyrene) obtained in Example 23, respectively. H-NMR is shown. FIGS. 4(a) to (c) show the polystyrene obtained in Example 1, the isotactic polystyrene obtained in Comparative Example 2, and the The line diffraction pattern is shown. Figures 5 <a> to (d) show the polystyrene obtained in Example 1, the actinic polystyrene obtained in Comparative Example 1, the isotactic polystyrene obtained in Comparative Example 2, and the isotactic polystyrene obtained in Example 23, respectively. The infrared absorption spectrum of the obtained poly(p-methylstyrene) is shown. Note that in FIG. 4, θ indicates the Bragg angle (0). Figure 1 (e) 145, 13 146.0 145.5 145.0
+44.0 tppm 1st figure (fn 143 142 Cppn) ¥1 figure 146.24 147.5 1470 746.5 146.0
145.5 (ppm) Fig. 1 I3θ, 9 Fig. 5 (a) Roma Suho 5 Fig. (b) ! & Satoshi

Claims (1)

[Claims] (1) General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R represents a hydrogen atom, a halogen atom, or a substituent containing a carbon, oxygen, nitrogen, sulfur, phosphorus, or silicon atom, and n represents an integer from 1 to 3. ] A styrenic polymer having a degree of polymerization of 5 or more and having a repeating unit represented by the following, and whose stereoregularity is mainly a syndiotactic structure.