JPS5871903A - Polymer composition and manufacture - 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 The present invention relates to ring-containing polymers, processes for their preparation, and polymer compositions comprising such polymers.

1.4-cyclohegizadiene homopolymer, and 1,
Copolymers of 4-cyclohegizadiene and 1'W sulfur are known. 1,2-dihydroxy-cyclohexa-
6,5-Diene can be polymerized by free radical or ion Higashi method.1. However, we hereby present certain derivatives of 1,2-disubstituted cyclohexa-6,5-dienes, as well as certain homologs (6) and analogs (analogs) of the derivatives. ) under appropriate conditions.

By homopolymerizing or copolymerizing with an appropriate polymerizable comonomer, you can create polymers with useful properties! @ Discover Dekikok! , 1. Known polymers having an aromatic ring in the main chain are often difficult to mold or shape due to their difficulty in handling. In some cases, they often contain rogen impurities because of the way they are manufactured.

We have shown that certain of the above-mentioned BoIJ (1,2-disubstituted cyclohexyl-15-dienes) can be easily shaped or striped and then converted into polyphenylenes. It has been discovered that such polyphenylenes often contain less or no nitrogen impurities than conventional polyphenylenes.

Therefore, according to the first feature of the present invention, a polymerizable composition comprising a 1,2-disubstituted cyclohegycer 3,5-diene or a homolobe or analog thereof is treated under polymerization conditions for the composition (7). 1. A method for producing a polymer composition comprising:
, 2-substituents may be the same or different and are not hydroxy groups and do not significantly interfere with the polymerization of the polymerizable composition.

According to a second aspect of the invention, the low tr According to a sixth aspect of the present invention, there is provided a polymer composition comprising a polymer which can be prepared by a method comprising: A method for producing a polymer having an aromatic ring in the main chain, the method comprising: producing a polymer having a 1.2-disubstituted cyclohexenylene ring in the main chain; 1.2-1ff from xenylene ring
The above-mentioned production method is provided, which comprises treating under conditions such that the substituent is eliminated.

According to a fourth aspect of the present invention, there is provided a composition comprising a polymer (8) consisting of a polymer having a structure represented by the following general formula (T).

1 → A r )---+ X To-In
m [In the above formula (■), the residues A, r and X (if x exists) may be different at every 111th position in one polymer,
Ar represents a divalent aromatic or substituted aromatic group; 1. or the residue of one or more polymerizable comonomers as defined below, where n and m are defined below, with the proviso that 1-. When Ar represents a ))-phenylene group and m is zero, n is greater than 120 and the polymer has a crystallinity of at least 40%, more preferably at least 60%, and
represents an I'll-phenylene group, and X is -5O2-
When the polymer composition is! -,000J:1].

Herein, "polymerizable comonomer 1" means 1.2 as defined above.
-if substituent to 1,2-disubstituted cyclo, xa-3
,5-',' refers to a compound that reacts with ene under polymerization conditions to form a covalent polymer with it.

As an example of a suitable comonomer that can be used in the present invention, (9) is a vinyl instanter such as olefinic hydrocarbon (e.g.
There are compounds such as styrene (styrene and styrene), methacrylate, vinyl halides, vinyl esters, acrylonitrile and tetrafluoroethylene; and carbon monoxide, carbon dioxide and sulfur dioxide.

Offshore monoderma is 1. It is preferred to generate a "stable" radical when it is used in the present invention.

Stable radical refers to a chain-propagating radical stabilized with L to an electron-withdrawing group such as phenyl, cyryno, ryosyl, and the reason for this is that 1,2-disubstituted - a polymerizable composition containing such a polymeric symbiotic dispersion in addition to cyclohex"ly-3.5-diene, or a polymerizable composition containing a polymerizable comonomer that generates active radicals. This is because it has been found that the molecular weight of the polymer composition is 4 to 2. Examples of polymerizable co-111 decomposition and t7 are examples of methyl methacrylate, egg, etc. 1/N, J- and acrylonitrile (a).

(lO) In the polymerizable composition used in the process according to the first aspect of the invention, the 1,2-substituted cyclohexa-3,5-diene or its homolobes or analogs have mutually different 1,2-substituents. It is preferable to have a cis-related compound because such a compound is disclosed in our English Patent Application No. 81301.
1, which is derived from cis-1,2-dihydroxy-cyclohexa-6,5-diene, which is easily prepared by the biochemical method described in No. 16.
However, in the present invention, the 1,2-substituents may be in a cis-relationship with each other.

Examples of the 1,2-substituents mentioned above and [2] include, inter alia, acyloxy, carbonate, alkoxy. Amide 9゜halide, thioester, urethane and xanthate substituents may be mentioned 1゜1,2-disubstituted cyclohexa-3゜ which forms the polymerizable composition used in the method according to the first paragraph of the present invention 5-')ene has a structure represented by the following general formula ('m).

(n) [Here, each R1 is the same, but may have a different peak C.

acyl (e.g. aroyloyl) L <+alkanoyl) or R20CO- (R2 is aryol or alkyl with less than 10 carbon atoms, ll1-), and Y is hydrogen, halogen or It is an alkyl group having a carbon atom].

The polymer phase 1jEi according to the second experiment of the present invention is represented by the formula (1) in Section 11-1'i, and preferably has a t'l skeleton structure 1゜(I2) [Here , the cyclohexenylene ring and the residue X (if present) may vary from unit to unit along the polymer chain; each R3 may be the same or different and may be hydrogen or R1 (R1 is Jm as defined above): X and Y are as defined in @, n and m are integers, and the ratio of n:m is within the range of 1:O to 1:100. be〕.

The polymer constituting the polymer composition used in the sixth aspect of the present invention preferably has a structure represented by general formula (1v) in F.

[wherein the cyclohexenylene ring and the residue X (if present) may vary from unit to unit along the polymer chain: each R'' (identical or different), X, n and m is as defined above].

R1 in general formula II. and R3 in the general formulas In and ■ is preferably (a) an aroyl group, (b) 8
(13) an alkanoyl group having less than 1 carbon atoms and lacking one hydrogen atom on the carbon atom adjacent to its carboxy group, or (c) R" OCO- (R" is as defined above),
More preferably CI-T, 0CO- group 1, Y in the general formulas IF and lil is preferably hydrogen, chlorine, methyl or ethyl, even more preferably hydrogen (if Y is hydrogen) In some polymers, it is small (because some rings can be easily aromatized).

In virtually all rings in the polymers of formulas 1 and 1v, each bond linking the ring to the polymer backbone is attached to a carbon atom adjacent to an olefinic double bond in the ring. (ie, the ring is preferably attached to the polymer backbone in the 3,6-position).

Ar in the polymer of general formula I is preferably a phenylene ring, and more preferably, the phenylene ring is bonded to the main chain of the polymer in a -q/pyl relationship position 1aV
be.

In the polymers of general formulas 1, IT and IV, n is preferably (14) greater than or equal to about 400; m is preferably zero, and when the group X is present, the n:m ratio is 50:1. and 1:50; preferably the ring and the group X (if present) form an alternating conjugate; the group Preferably, it is a comonomeric residue.

H3 -CH2-CHAr-, -(, -'to(2-C-, -C
f-In2-C: H2-t02R4 -CH2-C1i'2-, -GO- and -8o2-(
where Z is a halogen atom or H4) 14 is hydrogen or R2 as defined above).

Group X is more preferably -GH2CHPh-, -CH2-
G M e G 02 M e- or -GH2CHC
N-.

Certain of the 1°2-disubstituted cyclohexadienes for use in the process of the first aspect of the invention are often obtained by microbiological processes.

(15) For example, cis-1,2-:)hydroxy-cyclohexa-
6,5-dienes can be obtained from suitable post-liquid organisms, e.g.
can be produced by a mutant strain of the sp.
(described in detail in the specification), the hydroxyl group can be converted into suitable derivatives (e.g. ester and carbonate derivatives) by well-known methods. ) or acyl anhydride. Ester or carbonate derivatives are preferably used in the first embodiment of the present invention because of ease of polymerization reaction.

Although the 1,2-disubstituted cyclohexadiene derivatives used in the method of the first aspect of the invention are conveniently obtained by biochemical methods, the use of those obtained by conventional organic synthesis methods, The use of 1,2-substituents in the trans relationship is within the scope of this invention. 1+ Sue is y h yH in U.S. Patent No. 6,755,080.
-7-44-7 A microbiological method has been described for converting phthalene compounds into their 1,2-dihydro-90-1,2-tons dihydroxy derivatives using a type of bacteria. -Chernische Beri
c-htel (1959), Vo192. P163
172 and (195/')), VOI ・89. P
2224-2229 IC, Nakajima et al.
A chemical synthesis method for 3,5-diene is described, and r
-8yn tbes is, 1 (1977), Vnl
・7. P449-450 includes Brad etc. Cadrance-1
, 2-diacetoxycyclohexa-6,5-diene is described.

The polymerization process of the first aspect of the invention can be initiated using conventional olefin polymerization catalysts, preferably free radical initiation.

The polymerization method of the first aspect of the present invention involves using a pure (additive-free) polymerizable composition; a solution of the polymerizable composition dissolved in a suitable organic solvent;
e.g. toluene, benzene).

Halogenated hydrocarbons (e.g. 1,1.2-1lichlor(17
) rho1.22-to11fluoroethane), ketones (e.g.
acetone, methyl ethyl ketone)! f, or ester (
1+6: ethyl acetate)]; or for a suspension 1 dispersion or emulsion of a polymerizable composition [as a medium, an aqueous medium (i+IJ: water) or a suitable solvent (a liquid (e.g. Methyl decalinzene is a tetrafluoroethylene tetramer]; Preferably, monopolymerization is carried out using pure (additive-free) 1,2-disubstituted cyclohegiza-3,5-diene or its homolobe or It is carried out in the presence of an analogue or in the presence of a suitable supernatant liquid.

The temperature at which the method of the first aspect of the invention is carried out is:

Among others, it varies depending on the thermal stability of the particular 1,2-disubstituted cyclocyclo5-diene, typically between 10 and 1
It is carried out in the range of 00℃.

The polymerizable composition used in the method of the first aspect of the present invention may consist of one or more of the cyclohexadiene derivatives described in @1. (18) or a mixture of one or more of these and one or more polymerizable comonomers. If one or more polymerizable comonomers are present, the comonomers can represent up to 99 mole percent of the polymer product.

For example, when the polymerizable comonomer is ethylene, we have prepared various copolymers with styrene contents ranging from 1 mol% to 99 mol%. Polymer compositions typically have molecular weights of at least tens of thousands, and often hundreds of thousands.

The polymer composition of the second aspect of the invention comprises organic acids such as ketones (eg acetone), esters (eg ethyl acetate), hydrocarbons (eg toluene).

...logenated hydrocarbons (e.g. chloroform), polar neutral magents (e.g. dinonalformamide, dimethyl sulfoxide), and protic solvents (e.g. nitrifluoroacetic acid,
can be easily dissolved in acetic acid). Films and fibers can be easily produced from such solutions.

The polymer composition according to the second aspect (e) of the present invention is a product example (1).
9) Can be processed by conventional methods, e.g. for the production of fibers and films.

The polymer composition of the second aspect of the invention readily forms polymer blends with suitable polymers.

For example, one polymer composition of the second aspect of the invention.

It can be easily mixed with (eg, dissolved in) a suitable monomer and then polymerized. Alternatively, the polymer composition described above and a suitable solution (the polymer can be dissolved in a common solvent,
Polymer blend 9 can be recovered from the droplets 1, to form such a blend! Examples of suitable polymers for y) include, inter alia, polystyrene.

Mention may be made of polyphenylene oxide 9 and polyethylene terephthalate.

When the group R3 is a water group in the polymer of general formula (2),
Such polymer compositions can be prepared, for example, by hydrolysis of the corresponding esters. , the Ji method for carrying out such hydrolysis is well known.

The method of the sixth aspect of the present invention is carried out by treating (20) a polymer composition consisting of a solution of the polymer of general formula (1) in a suitable solvent (e.g. squalane or sulfuran). In this case, it is often preferable to use a pure polymer composition consisting of the polymer of general formula (2), since it may not be excluded from the present invention.

(21) The method according to the sixth aspect of the present invention can be carried out by treating a polymer composition of general formula 1ν with a suitable agent,
In many cases, subjecting such polymer compositions to appropriate heat treatment is sufficient to cause aromatization. A suitable heat treatment typically consists of heating the polymer composition for several hours to a temperature of, for example, 100 to 300C. It will be appreciated that the precise conditions used will depend on the particular polymer composition used and on the substituent to be eliminated. For example, when removing acetic acid groups, a temperature of 260 to 290 U is often suitable (
, 280 to 320 when removing the benzoate group
A temperature of about 250C is often suitable, and for the removal of the methyl carbonate group, a temperature of about 250C is often suitable.

Since the carbonate group can be eliminated at a lower temperature, it is preferable to eliminate the carbonate group.

When the carbonate group is eliminated, the elimination reaction is preferably carried out in the presence of a suitable agent.

Examples of suitable cross-linking agents include Jinpeng salts (e.g. alkali (22
) and alkali metal bases (e.g., potassium methoxide, potassium hydroxide).

Carrying out the method of the sixth aspect of the invention on a polymer composition in the form that the product of the method is to have, such as a film or fiber.

Often preferred. Furthermore, for shaped and/or shaped cyclohexenylene polymers.

Applying tensile stress during processing under the conditions mentioned above
Often preferred, the reason being that tensile stress causes the product (
This is because the tensile modulus of fibers) tends to increase.

When the process of the third aspect of the invention is carried out on a polymer in the form of fibers, the fibers are prepared by dry spinning the polymer from a suitable solvent such as methylene chloride. is suitable.

The fibers can then be subjected to suitable heat treatments.

For example, the heat treatment may be performed under reduced pressure or in an inert atmosphere (e.g.
(nitrogen).

The resulting polymers are often at least 90% polystyrene as shown by microanalysis and IR absorption (23) photometry.

According to a fifth aspect of the invention, therefore, there is provided a method for producing fibers that are substantially polyphenylene, the method comprising: subjecting fibers of a suitable cyclohexenylene polymer to a suitable heat treatment in a suitable atmosphere; provides a method comprising simultaneously applying tensile stress to the fibers to cause molecular orientation.

Process I of the Sixth Aspect of the Invention It is within the scope of the invention when carried out on polymers having a substantially three-dimensional shape (eg solid cubes). If the elimination reaction is carried out on such a form of polymer, and if the polymer contains suitable volatile substituents or derivatives thereof (which are eliminated during the process), a foam product may be produced. can be generated.

When a foamed product is to be produced, a kashihashi in which the elimination reaction is carried out by induction heating is preferred.

The polymer composition of the fourth aspect of the invention typically has a molecular weight of at least a few Ym, or a decomposition temperature of 25'OC or higher, but with a decomposition temperature of 1 minute (24). It will be clear that when a polymerizable comonomer is used, it depends on the type and amount of the comonomer.

It is clear that as the n:m ratio increases in general formula 1, the modulus of the resulting polymer increases, giving a very high modulus polymer (especially if the polymer buttons are oriented). ).

The polymer compositions of the fourth aspect of the invention readily form polymer blends with suitable polymers, in which the polymers are often molecularly dispersed. Examples of such suitable polymers include, inter alia, polyethylene terephthalate.

Mention may be made of polymethyl methacrylate, nylon, polyethersulfone, polycarbonate, polystyrene and polyphenylene oxide.

The amount of the polymer composition of the fourth aspect of the invention used in such polymer blends is inter alia.

It depends on the properties of the blend and on the particular polymer composition used. Polymer (25) The weight ratio of the composition to a suitable polymer is from 1:2 to 1:
10[]0, preferably 1:4 to 1:20.

Polymer blends comprising the polymer compositions of the fourth aspect of the invention are preferably prepared by mixing a polycyclohexadiene homopolymer or copolymer of general formula 1 into a suitable polymeric precursor or monomer. (dissolution) and polymerization of its precursor or monomer under conditions such that most, preferably substantially all, of the cyclohexyl rings in the polycyclohexadiene homopolymer or copolymer of general formula IV are aromatized. It is better to manufacture it by carrying out. For example, a polycyclohexadiene homopolymer or copolymer is dissolved in a prepolymer of polyethylene terephthalate, and the prepolymer of polyethylene terephthalate is dissolved by a known method, e.g.
Can a polymer blend be made by polymerizing at a temperature of 00t:'?

Alternatively, the first polymer blend is prepared from a polycyclohexadiene homopolymer or copolymer of general formula B and a suitable polymer (26) (e.g., polystyrene, polyethylene oxide), for example, by melt or solution blending. , and the first polymer blender is treated (e.g., by heating) to eliminate at least most of the 1°2-di-substituents in the polycyclohexadiene O homopolymer or copolymer of general formula (2).
A second polymer blend comprising the polymer composition of the fourth aspect of the invention and a suitable polymer can then be obtained.

In the polymer blend comprising the polymer composition of the fourth aspect of the invention, when said polymer composition is polyphenylene, the degree of agglomeration of the polyphenylene polymer can be determined by solid state neutron scanning testing. .

According to a fifth aspect of the invention, monomers of general formula (V) are provided.

[Here, Hl and Y are as defined above.

(27) (When alY is hydrogen, R1 is not C83C〇-.

(When blY is hydrogen and 01 (one group is in a trans relationship with each other, R1 is not C6H3C○-, and (when clY is cti3 and the OR' groups are in a cis relationship with each other, Hl is 0H3CO - Not.] The divine aspects of the invention are further illustrated below by way of illustrative examples.

[Journal of Biological Chemistry J
(1966) Vol, 241, p380[J~
Pseudomonas putida NC;
A mutant strain was prepared from B. No. 11680.

This mutant strain was subjected to the operations described by Kibson et al. in Biochemistry (1970) Vol-9, T) 1626+=1650, and 1 Biochemistry J (1970) Vol-9, 9. p1631-
(28) was used with appropriate aromatic compounds in a procedure published by Gipson et al. in 1665.

“Synthesis J (1977), Vol. 7. p44
Trans-1,2-diacetogycycyclohexane-5-diene was synthesized from 1,4-cyclohexadiene by the method of Pratt et al., No. 9-450.

Using procedure AY of Examples 1-5 below, cis-1,2-
Cis-1,2-diacetoxy6-methyl-cyclohexa-6,5-diene was prepared from dihydroxy-6-methyl-cyclohexa-6,5-diene and acetyl chloride. This has a boiling point of 12 at 0.01asH2
It was 0C.

Using the method of Procedure B of Examples 1-5 below.

cis-1,2-dihydroxy-cyclohexaro, 5(
29) Cis-1,2-diacetoxy-cyclohexa-3,5-sienna was made from monodiene and acetic anhydride.

This product had a boiling point of 83-84C at 0.07 Hg.

Benzoyl peroxide Benzoyl peroxide is diluted with 20tZ' and 0.01 before use.
iaH)/ for 4 hours.

Preparation of polyethylene terephthalate “prepolymer” Dimethylene terephthalate (48,541 + 0.25
mole), ethylene glycol (filtration 4.169, 0.53
mol) and manganese diacetate tetrahydrate 4fJ t (18
, 4LW.Z 5 μmol) under reflux with stirring.

The mixture was heated until almost all methanol (16y·50.25 mol) was generated. Ortho-phosphoric acid (168 μt) in methanol (406 μt) was added via syringe to precipitate the catalyst as manganese phosphate.

Residual traces of methanol were removed under reduced pressure. The mixture was then allowed to cool to obtain a solid polyethylene terephthalate preform.

(30) Examples 1-5 (a) Procedure A A water-cooled surface of the appropriate acyl halide or chloroformate (8 mmol) dissolved in dry toluene (4Ril)
Toluene? #For bath, use the same amount of dry diethyl ether)  , dry pyridine C4nr, l) middle 1.2
) Hydroxy-cyclohexa-6,5-diene (4 mmol) was added dropwise at a rate of 7 to a stirred solution (0~5G) so that the temperature of the mixture did not rise above 8C. .

After stirring for 0.5 hour at 0~5C, remove the cooling tube.

The reaction mixture was stirred for an additional hour with m2oc. The solvent was removed under reduced pressure (with heating in a bath at 0 to 40C), dissolved in chloroform or diethyl ether, and then washed with an aqueous sodium carbonate solution and water.
Dry with Na2SO4 or Mid, SO2. The filtered bath agent was evaporated to recover the crude acyl(31) derivative, which was purified by recrystallization and/or distillation. Purification and product details are shown in Table 1.

(bl Operation B 1,2-dihydroxy- in pyridine (2,5ral)
A stirred solution of cyclohexa-6,5-diene (1,01)
0.5 C), acetic anhydride < 7.5 rnl),
It was added dropwise at such a rate that the temperature of the mixture did not rise above 6C. -Remove the cooling source in the same way as step A in H.1
The reaction mixture was stirred for an additional hour at 20 U and then treated similarly to give the crude diacetate derivative. This was purified by distillation and/or recrystallization. Purification and product details are shown in Table 1.

(112) Example 2 is an example in which poly(1,2-cis-diacetoxy-cyclohexa-3,5-diene) is produced from an additive-free pure molder.

Freshly distilled cis-1,2-diacetoxy-cyclohexa-3,5-diene (2,4 g) in a glass tube.

12.2mM) and benzoyl peroxide (8.5mg,
35 μM) was degassed under reduced pressure, frozen,
The glass tube was then sealed. After 40 hours at 75°C.

The glass tube was opened and the contents in the form of a transparent glass-like polymer were dissolved in chloroform. The chloroform solution was concentrated and methanol was added to precipitate the polymer. The solids were filtered and dried under reduced pressure.

A fluffy white solid of poly(1,2-cis-diacetoxy-
cyclohexa-6,5-diene) was obtained (1.84 g).

774). The infrared spectrum (KBr disc) of this polymer showed a peak at: 2920 cm-
'(C-H);1740cm-1(-COCH3)
;1370c1rL (-UAc):, 1-; and 12
40,104104O'rc-0). The proton magnetic resonance spectrum of the above (34) polymer in deuterochloroform at 29°C showed a signal at the following location: δ 2.05 (61-1, Hiroshi, I, 'l x
(-1-(3α]-); δ2.60 (2H, extremely wide,
>(-'!Mo' (shiH=CHC, f-1 iron;); δ
460-61r4H,, *wide, δ5.2o and 5.6V
C Tsurezorebee 9.2X) CH<) Ac and -C! 1
= e l-1-). The (2 magnetic resonance spectrum) of the above polymer in deuterochloroform at 29°C showed a signal at: δ20.97(dan1(3(-:0-
, sharp); δ39.84 (wide.

"-)-("HC(+=Cr1-): δ68,96
(wide, 〉mi UAc); δ127.32 (wide, -LH4
H-); δ169.97 (flA.

-COCH3). Low angle of scattering V − in ethylene dichloride
Weight average molecular number (absolute) of the above polymer measured with the light beam
was 103,600 (±2 factor) and 1.03×10 when scattered in methyl ethyl ketone. The glass transition temperature and decomposition temperature of the polymer were 209° C. and 260° C., respectively, and its radius of gyration (measured in methyl ethyl ketone) was 26 rrn.

Examples 7-9 These examples are based on poly(1,2-7sudiacetate(35
) shows the production of xy-cyclohexa-6,5-diene) by a solution method.

Cis-1,2-diacetoxy-cyclohexa-6,5-diene (500 mg, 2.6 mM) in a glass tube
and benzoyl peroxide'!?, 57tt
A mixture of M) dissolved in a solvent ('l, Qml) is degassed under reduced pressure, frozen, and the glass tube is sealed. The contents were stirred at 80°C for a specified time (magnetic stirring).

Open the tube and add chloroform to the contents. The solution was concentrated and poly(1,2-cis-diacetoxycyclo-3,5-diene) was precipitated by addition of hexane. Each polymer was then identified by infrared spectroscopy and gel permeation chromatography. Preparation and product details are shown in Table 2.

(36) Table 2 Poly(1,2-cis-diacetoquine cyclohexa-6,
(37) Examples 10 and 11 These examples are (1,2-cis-diacetoxy-
Figure 2 shows the suspension method of manufacturing cyclohexa-3,5-diene. Cis-1,2-diacetoxy-cyclohexa-3,5-diene (500 mg, 2.6 mmol)
, benzoyl peroxide (9 mg, 157 μmol), and organic liquid (2 ml) were placed in a glass tube, which was degassed under reduced pressure, frozen, and the tube was sealed. The contents were stirred vigorously to disperse the [1,2-diacetoxycyclohegiza-3,5-diene] in the organic liquid. 80℃
After 17 hours, the glass tube was opened and its contents were dissolved in chloroform. The chloroform solution was concentrated and the polymer was precipitated by the addition of hexane. The precipitate was filtered through δ1, washed with 2-hexane, dried under reduced pressure, and purified with poly(12
-cis-diacetoxy-cyclohexa-3,5-diene) was obtained.

The organic liquid in Example 10 was perfluoro-1-methyldecalin, and the yield of monopolymer θ) was 67%.

(38) The organic liquid in Example 11Vc was a tetrafluoroethylene tetramer, and the yield of the polymer was 41%.

Example 12 This example demonstrates the preparation of poly(1,2-cis-dibenzoyloxy-cyclohexa-6,5-diene).

cis-1,2-dibenzoyloxy-cyclohexa-6,
5-diene (600 mg, 1.88 mmol) and benzoyl peroxide (3 m, g, 12.4 μmol)
The mixture was placed in a glass tube, degassed under reduced pressure, and frozen.

The glass tube was sealed. After 18 hours at 97-98°C, the tube was opened and the contents consisting of transparent glassy polymer were dissolved in chloroform. This chloroform solution was filtered once,
The polymer was precipitated by concentrating and slowly adding Rohhegetane (150 IBl).

The precipitate was filtered, washed with pentane and dried under reduced pressure to give poly(1,2-cis-dibenzoyloxy-cyclohexane-
6,5-diene) was obtained (4507ig, 75%).

When a film was formed on this polymer fNa C1, the spectrum was analyzed, and a peak (39
) showed: 1720(-(shi0Ar);1600.1
58Q (A, r); 1445.1610.1215 (wide), 1170.1105° 1090.1065.102
0 and 705 sieves. Proton magnetic resonance spectra of the above polymer in (1)-6 dimethyl sulfoxide at 29 DEG C. gave signals at the following positions: :δ4.80~6.4
0(-(kodan=nidan-and 2×〉(Koi0 (,:
OP h ): and δ6.40
~8.40 (believed to be aromatic σ) hydrogen).

Xiang I with a low-angle laser beam scattered in ethylene dichloride
The average molecular strength (absolute) of the polymer determined is 206,
It was 000.

Example 13 This example is poly(1,2-cis-dibenzoyloxy-6
-Methylcyclohexa-5,5-diene).

Cis-1,2-dibenzoyloxy-3-methyl-cyclohexa-3,5-diene (1,50,1?, 4.5 mmol)-#6 and benzoyl peroxide (12 mg, 4
9.6 μmol) of the mixture was placed in a glass tube, degassed under reduced pressure, frozen, and the tube was sealed. Bales for 17 hours at 90-95°C.

(40) The tube was opened and the contents were dissolved in chloroform. The polymer was then precipitated from the solution by addition of methanol.

The precipitate was filtered and dried under reduced pressure to give PolyM, 2-cis-dipenzoyloxy-6-methyl-cyclohexa-6,5-
diene) was obtained (66 mg).

0[)4%). f of this polymer (KBrBrtisf)
The 11° spectrum had peaks at the following positions: 1
750(-Co); 1600, 1580rAr): 14
45:1110゜1270, 1175, 1105, 10
95.1065.1020 and 7[15m-'. 40
Proton magnetic resonance spectra of the above polymer in deuterochloroform at °CIC gave signals at the following positions:
δ0.40-2.0 (3H, extremely broad resonance, δ1.
Peaks at 25 and 1,70, CH3-(a): δ2
．． 20-3.80 (approx. 1.5) 1. very wide signal):
\ δ, L80-8.20 [(Very wide signal, δ5.9
0 (believed to correspond to the integrals about 4H,2
It is believed to correspond to the meta/para and ortho protons of the group, respectively. ) (41) Example 14 This example demonstrates the preparation of poly(6-chloroO-1,2-cis-diacetoxy-cyclohexa-6,5-diene).

3-chloro-1,2-cis-diacetoxycyclohegytha-6,5-diene (400 mg, 1.73 mmol)
and t-butyl perbenzoate (4 mg, 20
．． 6 μmol) of the mixture was placed in a glass tube, degassed under reduced pressure, and the tube was sealed. After 72 hours at 96°C, the tube was opened and the contents washed with methanol/pentane.

The insoluble material w is filtered and dried to give poly('6-chloro1
, 2-cis-diacetoxy-cyclohexa-6,5-diene) (1B+y, 0.05%). The I'L spectrum of the polymer (as a KHr disk) had a peak at the following position: 1750 box-' (-C
O(:1-(3); 1370cIn-' (-OA,
c) = 1235 and 1045CrrL'(('-
〇).

Proton magnetic resonance spectra of the polymer in deuterochloroform at 29°C gave the following signal: δ2.
10(roI(,mu, -IC)C1-1a); δ2
．． 15 (“IH, prefecture.

-CO(:H3); δ2.50-2.32(11-1,
Very spacious.

(42) 〉(dan('I-(,,,,C(); and δ4.90
-6;30 (4H, very wide, 2X>(r tan(J
A, c and -C1 C11-1° Example 15 This example demonstrates the preparation of poly(1,2-cis-dihydroxycyclohegiza-6,5-diene).

Sodium methoxide solution prepared by dissolving 5 g of sodium in 203 m/ml of dry methanol (20 C Jrue)y, hot methanol (250 rnl
A solution of poly(1,2-cis-diacetoxy-cyclohexa-6,5-diene) (600 rng, prepared in Example 6) in a liquid was cooled for 15 minutes.

After approximately 50 me addition, the solution became cloudy and a fluffy white precipitate separated out. Reflux the mixture gently for 20 hours at +7r
It was then cooled and water (5d) was added. The precipitate was collected by filtration, washed sequentially with methanol and ice-cold water, and dried under reduced pressure to yield poly(1,2-cis-dihydroxy-cyclohexa-6,5-diene) (145■, 85 Section)
. I of this product (in the form of a film on a KBr disk)
R spectrum is 2910cnt'(C-[-1);14
The proton magnetic resonance spectrum of the above product polymer in D-6 dimethyl sulfoxide at 70°C showed δ5.40-4 .60 (maximum at δ, 65.3-80 and 4.1) and δ5.20-6.0 (5,
The peak at 50 and the debris at 5.65 are the signals shown: the integrated intensities of each of these two broad signals were in a 2:1 ratio. This polymer product is acetone.

It is insoluble in chloroform, pyridine, nitrobenzene, and dimethylformamide, slightly soluble in dithermal water, and quite soluble in dimethyl sulfoxide.
It was found that it is easily soluble in trifluoroacetic acid.

Examples 16-28 These examples illustrate the preparation of a range of cis-1,2-diacetoxy-cyclohexa-6,5-diene and styrene copolymers.

cis-1,2-diacetoxy-cyclohegiza-6,5-
A mixture of diene, benzoyl peroxide, and lightly distilled styrene was placed in a glass tube, degassed under reduced pressure, frozen, and the tube was sealed. (44) After 40 hours, the tube was opened and the polymer product was collected as in Example 6 and reacted with cis-1,2-diacetoxy-cyclohexa-6,5-diene and styrene. A copolymer was obtained. The IR spectrum of each polymer thus obtained (as a KBr disk) had a peak at the following position (dark-1): 3030.2930(t-t(); 1740(
(COH3CO-); 1600,1495.1455(
Polystyrene): 137Q (-0Ac/PS); 12
45.1225 (waste) (C-0): 1040.105
0(C-C)); 760 and 7QQrA, r). 29
Proton magnetic resonance spectra of the copolymer in deuterochloroform at °C gave signals at the following positions: δ1.
0-2.80 (Uδ1.90, 2.05 and 2.
Peak at 60, polystyrene neutral strength Ar-C tan- (Sitan 2
．． and 2×Cdan3c(J and)(:F(CH=(
'l-IC'H(:δ4.20-5.80(2X〉CH
(JAc.

-(:Month-CH-); δ6.20-7.40(δ6.5
peak at 5, which corresponds to two ortho protons, 71
The peak at 0 corresponds to one para-proton and two meta-protons): the integrated intensity gave the ratio of cyclohexenylene rings to styrene residues in the copolymer.

(45) The results are shown in Table 6.

Table 3 (46) Example 29 This example shows 6-chloro-cis-1,2-diacetoxy-
The production of a copolymer of cyclohexa-3,5-diene and styrene is illustrated.

6-chloro-cis-1,2-diacetoxy-cyclohexa-6,5-diene (500 mm, 2.16 mmol),
A mixture of azobisisobutyronitrile (4 μm, 244 μmol) and freshly distilled styrene (180 μm, 244 μmol) was placed in a glass tube, degassed, frozen, and the tube sealed at 7C.

After 1:56 hours at 60°C, open the tube and pour the contents into methanol.The resulting precipitate was washed with methanol, dried under reduced pressure, and filtered. A copolymer (100/II!?')'Y of cis-diacetoxy-cyclohexa-3,5-diene and styrene was obtained.

The III spectrum of this copolymer (in the form of KBr disks) had a peak at the following position (cN'): 5060.
2950 (C-H); 1750 (-COCI(3)
1600.1495.1455 (polystyrene); (4
1) 1570 (OAc/PS); I240, 1045
(Co)Nio, J:Hi700 (A,r). σ) Proton magnetic resonance spectrum of the above copolymer α) in deuterium chloroform at 40°C gives a signal at the following position: δ1
．． 20-2.60 (wide, δ1.52 and 2.101i
(Peak, Bo 11 Ar'CI-IC in styrene
H2-1 and [2Xδ6.6-7.4 (δ6.7 K
This peak corresponds to two ortho protons. peak at δZ1, which corresponds to one para- and two meta-protons in Bo II styrene), and the intensity in one table is based on the molar ratio of cyclohexenylene ring to styrene residue of 1:4. I begged for something.

Example 50 This example illustrates the preparation of a copolymer of cis-1,2-diacetoxy-6-methylcyclohexa-3,5-diene and styrene. cis-1,2-diacetoxy-6-methylcyclohexa-3,5-diene (500In9.2
, 68 mmol), benzyl(48) chloride (1,511 Ip, 62 μmol) and freshly distilled styrene (4ootv, 6.85 mmol) were placed in a glass tube, degassed, frozen, and the tube sealed. did. 9
After 40 hours at 0°C, the contents of the tube were isolated as in Example 6 and cis-1,2-diacetoxy-cyclohexane
Copolymer of 3,5-diene and styrene 'Y244 (
110~). The IR spectrum of this copolymer (in the form of K'Br disks) shows a peak at the following position (-).
Friend: 3030, 2960 (C-11); 1740 (
-COCI-13): 1600°1495.1455(
polystyrene); 1570(-C)kc/', PS);
1245.1225 (scrap) (C-0) The proton magnetic resonance spectra of the above copolymer in deuterochloroform at 60 and 700 (Ar), 29°C and 50°C give a signal at the following positions: :δ1. O-2.4
0 (broad, peaks at δ 1,55 and 1,90, 2X CHCO-, CH3-Cmi and -C
H=CH-C pillow): 3 δ4.30-5.50 (very wide signal, -CH=CH
−(49) and 2 X〉CHOA c ): δ6.20
-7.4 (There is a peak at δ6.B, which corresponds to two ortho protons in polystyrene, and 'iT is δ7.0.
5 V (There is also a peak. This is two υ in polystyrene.
) meta- and one bala-proton). The integrated intensity indicates that the molar ratio of hexenylene and styrene residues in the copolymer is about 1=5.

Glass transition temperature of copolymer (1) S C't'' measurement)
is 116 degrees Celsius.

Example 61 This example illustrates the preparation of a copolymer of cis-1,2-diacetoxy-6-methylcyclohexa-3,5-diene and methyl methacrylate.

Cis-1,2-diacetoxy-6-methylcyclohexa-6,5-diene (480 mg, 2.29 mmol)
, hendiyl peroxide (1,5 lng, 6.2 x -E
) and freshly distilled methyl methacrylate)
(470 mg, 4.7 mmol) was placed in a glass tube,
Degas, freeze, and seal the tubes. 40:11 at 90℃
1, open the tube, and collect the contents (50) as shown in the middle m91 to extract cis-1,2-diacetoxy-6-methylcyclohexa-6,5-diene and methyl methacrylate. This copolymer (K I
The IR spectrum of -3r f (the shape of the film on the disk) is as follows: 11≦C (■-1).
000.2955 (C-1-1); 1740-17
25 (-COCI-I3 and -COOC11,):
1485.1450.1465.1270 (waste),
1245.1195 and 1150°C and 1150°C in monohydrogen chloroform gave a signal at tt of the following proton resonance spectra: δ0.
50 - 1.40 [peaks at 0,90 and 1.05, -
CH2-C-(CH,)CO2Me]; δ1.40-2
．． 30 (peaks at 1,85 and 2.10, PMMA
-CH2CMeCO2Metx and C of acetate
? 1I3C-5', CH-CH=CH- and 2XC
H3CO-); 65(COzMe);
δ4.5-5.7 < -crt-cn-, t,;
2×Cl-10AC). The integrated intensity indicates that the molar ratio of the butalohexenylene ring to the methyl methacrylate residue in the copolymer is approximately 1=15.

The glass transition temperature of the copolymer was 114°C.

(51) Example 62 This example illustrates the preparation of a complex of benzene-cis-glycol dimethyl carbonate by a dispersion process. Pense glycol dimethyl carbonate (12 g, 52.66 mmol) was added to a 250 ml flask equipped with a paddle stirrer and degassed.

Fill the flask with nitrogen and add 1 part of azobisisobutyronide.
1 l (84#117.0.51 mmol), cyclohexane (84 ml) and dispersant (84#I&, polymethyl methacrylate raw silk with poly-11-12-hydroxystearic acid branches grafted copolymer) )ke added,
The mixture was homogenized at room temperature. Then the mixture was mixed with 6
Heat for 96 hours in a 0 °C bath + rv. Milky product (1
The polymer (0.5 g, 87.5% yield) consisted of spherical particles (average size 0.12 microns) in cyclohexane, dissolved in methylene chloride, then precipitated in hexane and separated. 7. Dry under reduced pressure. The molecular weight data of each rod was violated. Intrinsic viscosity in dichloroethane (1, V,
) was 0.66, and low-angle laser beam scattering in the same m agent gave a Mw value of 456811 (52). In the G, P,, C, molecular weight method, the distance n = 32.074 and the weight W = 25.20840. Illustrate.

Benzene cis-glycol dimethyl carbonate-1 (1
g, 44 mmol) in a quartz glass tube and sealed. The glass '# then Philips MLV
After 92 hours, kept at a distance from a 500 W UV lamp such that the temperature of the tube was maintained at 40° C., the glass tube was opened and the solid product was dissolved in methylene chloride and precipitated with hexane.

Isolated and vacuum dried polymer (0,!M, 50% yield)
has an intrinsic viscosity v of 0.41 in 1,2-dichloroethane
ht, , G, P, C, legal molecular weight is M n = 888
98, Mw=521849.

Example 62 This example demonstrates how cis-1,2(
53) - Bulk polymerization of divibaroki7-7chlorohexa-3,5-diene is illustrated.

Cis-1,2-dibiparoxycyclohexa-65-diene (1,9,6,57 mmol) and benzoyl peroxide (6,6-[1,026 mmol) were degassed in a glass tube; Seal under vacuum. After 24 hours at 80°C, the tube was opened and the solid contents dissolved in methylene dichloride. This polymer was precipitated with methanol, isolated, and dried under vacuum.

The polymer (0,8,9,80qb yield) has Mn = 29940 as G, P, C molecular weight, 'Mw - 7737
5 Beggar k.

ko (7”) jij union (／'I T gba 240℃
Deatsu T-ko.

Example 65 This series illustrates the bulk thermal polymerization of 1,cis-1,2-diacetoxy-cyclohexa-5,5-diene.

Degas cis-1,2-diacetoxy-cyclohex-6,5-diene (1,9,5,1 mmol) in a glass tube and seal with vPj under vacuum. 90τ] after 72 hours,
The blue product was dissolved in methylene chloride and precipitated with hexane. The isolated and vacuum-dried Sada (54) has G, 1), C molecular weight as Mn = 54960.
and Mw=145510° Mw in low angle laser source scattering method in 1.2-dichloroethane is 112500
(55) An example is cis-1,2-diazetoxycyclohexane.
(Example: copolymerization of 3,5-diene and vinyl chloride).

Cis-1,2-diacetoxy-cyclohexa-3゜5-
The diene (2,53,!9.12.9 mmol) and benzoyl peroxide (61° C.g, 0.025 mmol) were degassed in a glass tube. Next, salt bath vinyl (10 m
1, 108 mmol) was distilled into the tube and the tube was sealed under vacuum F. Heat the rice at 90℃ for 42 hours, open the tube, and pour the contents into hexane x7. The isolated and vacuum-dried copolymer (0, isi, p.

1.58% yield) was shown to contain 45 mol% vinyl chloride by microanalysis2, the Tg of this polymer
was 144°C. As G, P, C1 molecular weight, A
4n=2945. Example 7 in which Mw=8369 This is an example of copolymerization of 1>1&yo, di-1,2-diacetoxycyclohexaro, 5-diene and chlorotrifluoroethylene.

Key to cis-1,2-cya7toxycyclo! j--3
．． 5-Diene (1 g, 5.1 mmol) and benzoyl peroxide (4 mg, 0.017 mmol) were placed in a glass tube and degassed, then chlorotrifluoroethylene (1 m
1, 8.6 mmol) was distilled into the tube,
The tube was sealed under vacuum. After 20 hours at 90°C, the tube was opened and the solid contents were dissolved with methylene chloride and precipitated with hexane. Isolated and vacuum-dried copolymer (0.15 mg
, 15% yield) was found to contain 1 in its structure by microanalysis.
It was estimated that it contained 0 mol% of residual chlorotrifluoroethylene. The T,9 of the copolymer was 182°C.

Q, P, C.

The molecular weights were Mn=22969 and Mw=56443.

Example 6B This example illustrates the copolymerization of benzene-cis-glycol dimethyl carbonate and 1,6-butadiene-d. Benzenezosuglycol dimethyl carbonate (29.8.8 mmol) and azobisisobutyronitrile (10 mg, 0.061 (57) mmol) were degassed in a glass tube and then 1. Lofter) en-d' (1,7+m, i9.8 mmol) was introduced with distillation and the tube was sealed under vacuum. 50
After 60 hours at °C, the tube was opened and the contents were dissolved in diphenolic methylene and precipitated with hexane. Isolated and vacuum-dried polymer (1.3 grams, 40.8% 1 Tg of -1
The temperature was 5°C. G, P, C, as molecular plane, Mn=5
0155, Mw=148997 and A.). Proton magnetic resonance of this polymer in deuterated chloroform at 29°C! The A spectrum gave a signal at the position F: 82.6 (2H12111nC and -CH=CH-
) ;83.8 (6H1 sharp, single, CH3(L-)
;S 4.9 3 (2H,24,;CHO)
; and 85.6 (2H, single, -CI-1=CI-
1-).

Example 69 This example demonstrates the preparation of poly-trans-1,2- from pure monomers.
The production of diacetoxy-cyclohexa-3,5-diene is illustrated.

Freshly distilled trans-1,2-diacetoxy-cyclohexa-6,5-diene and diyl peroxide (58) diyl (single body/catalyst ratio -102/1) were added to glass f.
-J was degassed under reduced pressure, frozen, and sealed with glass. After 46 hours at 90°C, the tube was opened and its contents (clear glassy polymer) were dissolved in chloroform. The chloroform solution was concentrated (concentrated) and the polymer was precipitated with hexane. The solid was heated to -Pa and dried under reduced pressure to obtain poly(1,2-1 lance-diacetoxy-cyclohexa-6,5-diene) in the form of a fluffy solid (conversion rate 49%).

Mw=10240, Mn-5770.

Procedure A The matrix polymer and poly(1,2-disubstituted cyclohexane 6,5-diene) were each dissolved in a common solvent and the two baths were mixed together. The d agent was removed under reduced pressure to obtain a crude blend.

Operation B Matrix polymer and poly(1,2-disubstituted (59
) cyclohexa-6,5-diene) were each dissolved in a common solvent and the two solutions were mixed together. A solid blend of the two polymers was then produced by precipitation with a common non-solvent. The solids are filtered and washed,
It was dried under reduced pressure F.

The results are shown in Table 4.

The presence of poly(benzene-cis-glycol dimethyl carbonate) in each blend of Examples 40 and 41
It was easily detected by IR spectrum.

(60) (61) In Example 4 Example C illustrates the production of poly-paraphenylene.

Poly-3,6,-(1,2-cis-diacetoxy-cyclohex-3,5-:)ene) (50~) from a solution in dichloromethane (1 TrLl) was deposited on a microscope slide as a colorless polymer. Soy sauce forming a film. The temperature of the film is increased to 2 in a substantially oxygen-free atmosphere.
The temperature was increased to 320° C. over a period of time and maintained at that temperature for 6 hours, resulting in a light yellow film.

I of this pale yellow film (as KBr Tisf)
The R.sub.S vector did not show a peak corresponding to CH3-Co-. , (CH3-Co- is 148Q.

peaks at 1000 and 810 cIrL-1)
. Also, the students are M, J, Johns, P. Journal of the
Polymer Science, Polymer Chemistry J
(1981), Vol. 19. The spectrum was extremely similar to that of poly(paraphenylene) (62) published in P. 89-109.

Examples 44-49 These examples illustrate the production of aromatic polymers according to the present invention.

General Method A A ~20% solution of poly(cis-1,2-disubstituted cyclohexa-6,5-diene) in chloroform was evaporated under reduced pressure to yield a polymer film.

Add an antioxidant (product name: "ganOX") to the solution as appropriate.
lolo, about 1% w/w of polymer) and/or an elimination catalyst (e.g. potassium bromide, about 1 mol%) were added.

The film was heated to a specific temperature for a specific time. The aromatization reaction rate was determined by isothermal gravimetric analysis (T GA ) and in separate experiments by IR analysis.

The products were analyzed by IR spectroscopy, T, (3A, in-phase proton magnetic resonance SR, and X-ray crystallography. The results of these analyzes were previously published in the 1-journal by J. G. Ito et al.・Opφ Macro (63) Molecular Fist Xience, Reviewus Onomacro Molegyuf ・Chemistry J (1971), Vol.
, C5, P295-686.
Substantial agreement with the data for phenylene was found.

Method B (Example 49) Poly(cis-1,2-disubstituted-cyclohegiza-6,5-
diene) powders (optionally containing antioxidants or elimination reaction catalysts) were treated by specific thermal cycles. When the product was analyzed as per the method described above, it was found that it was substantially poly-
It was confirmed to be pyphenylene.

The results are shown in Table 5.

Example 50 This example illustrates poly(cis-1) in the sixth aspect of the invention.
, 2-disubstituted-cyclohexa-6,5-diene).

A 7F solution prepared by dissolving sodium (4,6 g) in methanol (50 ml) was added to hollybenzene cis-glycol dimethyl carbonate (2,28 ml) in tetrahydrofuran (20 M).
，! It was added dropwise over 5 minutes to the refluxing @ solution of i').

The mixture is cooled, filtered, and the overproduct is
Washed sequentially with water, methanol and vinegar. When the dried product (0.7, l) was analyzed by IR spectroscopy,
The product was shown to be essentially p-phenylene.

Example 51 This example illustrates the preparation of aromatic polymers according to the present invention.

Poly-benzene- in squalane (10[]mff1)
(66) A solution of 7s glycol dipiparate (51) was refluxed under nitrogen for 8.5 hours. During this experiment, a pale yellow precipitate gradually formed. The mixture was cooled, filtered, and The analysis of this product was consistent with the morphology of polyphenylene.[It STR showed approximately 90% aromatization, but ) suggested a crystallinity of about 40%.

Examples 52-54 These examples illustrate the preparation of fibrous aromatic polymers according to the present invention.

A solution of poly(cis-1,2-disubstituted cyclohexa-6,5-diene) in a suitable solvent [optionally with antioxidants (e.g. Irganox 1010 in heavy duty, 01% wl)]
] was dry spun and the solvent was flash evaporated to produce fibers. Its diameter varies as the relevant conditions (e.g. winding speed) change.

The above fiber was held under tension in an oxygen-free atmosphere and its temperature was allowed to rise to a specified value (67) over a specified period of time.

The results are shown in Table 6. Illustrative example.

cis-1,2-diacetoxy-cyclohexa-6,5-
A series of diene/styrene copolymers (from 2.5 to 97.5
mol % styrene content) were aromatized using the method of Examples 44-49. Products containing up to 70 mol% aromatic residues were completely soluble in methylene chloride. 25
The glass softening points of polymers containing ~96 mol% phenylene residues are shown in Table 7.

(70) Table 7 Example 6 This example illustrates the aromatization of poly(1,2-trans-diacetoxycyclohexyl, 5-diene).

PoIJ (1,2-trans(71
A thin film of diacetoxycyclohexyl-6,5-diene) was solution cast from chloroform onto a potassium bromide disk. The disk was placed in a nitrogen-purged furnace in the Ill Mostector spectrometer, with the optical path passing through the window and film. The disc was then heated to 285°C. By regularly monitoring the connection
Release of Acetate Groups and Presence of Polyphenylene were Shown 5, Examples 64-6 These Examples illustrate the preparation of polymer blends comprising androaromatic polymers according to the present invention.

The polymer blends prepared in Examples 40-42 were heated to elevated temperatures in an oxygen-free atmosphere.

The presence of polyphenylene in the blend was demonstrated by IRS throw analysis or by dissolving the matrix polymer in a suitable solvent leaving a residue of insoluble polyphenylene.

The results are shown in Table 8.

For patent purposes, applicant: Real Chemical Industries, Ltd. (74) Continued from page 1 Priority claim (3) October 6, 1981 [phase] United Kingdom (GB) ■ 8130115 @ October 6, 1981 Japan [phase] United Kingdom (GB) ■81
30116

Claims (1)

[Scope of Claims] (11) A method for producing a polymer composition, comprising a polymerizable composition comprising a 1,2-substituted cyclohegycer 6,5-diene or a homolog or analog thereof. and 1,2-diI!-converted cyclohexyl 3.5-
The method for producing the polymer composition described above, wherein the 1,2-substituent of the diene is not a hydroxyl group and does not significantly interfere with the polymerization of the polymerizable composition. (2+1,2-disubstituted cyclohexa-3,5-diene or its homologue or analogue has the following general formula (1) (wherein each R1 may be the same or different, acyl or hydrocarbyloxy Keto; Y is hydrogen, halogen, or an alkyl group having less than 4 carbon atoms. (3) Copolymerizable composition The method according to claim 1 or 2, wherein the product also contains a polymerizable comonomer. (4) The polymerizable comonomer is methyl methacrylate. Claim 6, wherein the polymerizable comonomer is styrene or acrylonitrile. (5) General formula [wherein the above cyclohexenylene ring and the residue X (if X exists) may differ from unit to unit along one polymer chain: each R2 is the same; may be hydrogen, acyl or hydrocarbyloxy (2) keto; X (if present) is the residue of a polymerizable comonomer; both OR" groups are adjacent each bonded to a carbon atom: Y is as described in claim 2; n and m are integers, and the ratio n:m is 1.
:0 to 1:1000. ] A polymer composition comprising a polymer having a structure represented by: (6) The polymer composition according to claim 5, wherein both OR2 groups are in a cis relationship with each other. (The force Composition. (8) A method for producing a polymer having an aromatic ring in the main chain, wherein the polymer having a 1,2-disubstituted cyclohexenylene ring in the main chain has a small number of 1,2-substituents. (3) The above-mentioned production method comprising a treatment such that substantially all of the cyclohexenylene rings are eliminated. (9) A polymer having a 1,2-disubstituted cyclo-\xenylene group in the main chain is , the following general formula [where the cyclohexenyl ring and the residue X (if X is present) differ by units Tσ along the polymeric armor (;
X, n and m are as described in claim 5; and R1 is as described in claim 2. ] The method according to claim 8, having a structure represented by: 00) Hara f! 4-polymer (II+ it' is aroyl, one on the carbon atom adjacent to the carboxy group with less than 8 carbon atoms) or (4) R30CO (where JR3 is aroyl or an alkyl group having less than 10 carbon atoms). 03) A polymer composition comprising a polymer having a structure represented by the following general formula %: Ar and X (if present) may vary from unit to unit along the polymer chain; A is a divalent aromatic or substituted aromatic group; As described in claim 5, provided that when A is a P-phenylene group and m is zero, n is 120 or more; and Ar is a P-phenylene group and X or -
802-, the polymer composition has a number average molecular weight of 5000 or more]. (14) The polymer composition according to claim 13 (5), wherein m is zero. (1F9 The polymer composition according to claim 16 or 14, wherein -A, r- is P-phenylene. (16) Any of claims 13 to 15, which is in the form of fiber or film. 07) A suitable organic polymer and claims 16 to 14.
Polymer friends with aromatic polymers defined in any of the terms.