JPH0320130B2 - - Google Patents

Description

[Detailed description of the invention]

Industrial Application Field The present invention relates to a novel crosslinkable polymer and a method for producing the same.
More specifically, crosslinking is characterized by obtaining a polyarylene ether crosslinkable polymer in which a cyano group is arranged as a crosslinking group at the ortho position of an aromatic ring, reacting with heat or the like to give a three-dimensional crosslinked product, and then crosslinking. This invention relates to a method for producing polymers. BACKGROUND ART AND PROBLEMS TO BE SOLVED Thermosetting resins such as epoxy resins and phenol resins have been known as polymers that provide three-dimensional crosslinking. These are generally low molecular weight,
Since it immediately liquefies at a relatively low temperature, methods such as casting are generally used for curing. On the other hand, for thermoplastic resins, a so-called injection molding method is used, in which a relatively high molecular weight resin is made to flow under conditions of high temperature and high pressure, and then filled into a mold. This method is widely used because it increases productivity, but because it uses thermoplastic resin, it does not have sufficient heat resistance and has relatively low mechanical properties. In recent years, the performance requirements for polymeric materials have increased, and high-performance polymeric materials have been developed accordingly. Examples include polyarylene ethers or polyarylene sulfides such as poly-(2,6-dimethylphenylene oxide), polyphenylene sulfide. These are high-crystalline, high-melting-point materials, and are increasingly being used in recent years for applications such as casing materials for high-temperature electronic devices and mechanical parts. However, they are thermoplastic resins and essentially have no heat resistance. It is insufficient and its uses are limited. Therefore, there has been a long-awaited development of a polymeric material that can be injection molded and has heat resistance equal to or higher than that of thermosetting resins and good mechanical properties at high temperatures. In response, a reaction injection molding method (so-called RIM) or a liquid injection molding method has been proposed. However, these methods require control of reaction conditions,
The reality is that the field of application is limited due to pot life, etc. By the way, polymers with cyano groups as crosslinking groups are
For example, SAMPE Quarterly Vol. 12, No. 4, p. 1 (1981), Journal of Polymer Science Polymer Chemistry Edition, Vol. 12,
1301 (1974) etc. Among these publicly known ones, SAMPE Quarterly Vol. 12 No. 4 1
The example disclosed by Page (1981) is an example of crosslinking of an oligomer having a terminal cyano group, and because the functional group is located at the end of the molecule, the average molecular weight between crosslinking points becomes large, and the crosslinking density is limited. , examples of the latter include polyphenylene ether and polyphenylene polyester having cyano groups, where the cyano groups are located meta to each other with respect to the main chain bonding position, so the molecular chain is It is greatly bent due to the aromatic ring bonded to the cyano group, which serves as a crosslinking point. A polymer having such a structure is essentially an amorphous polymer, and its heat resistance is also limited. Means for Solving the Problems The present invention has been made in view of the above circumstances, and it is an object of the present invention to provide a method for producing a polymeric material that has heat resistance, good mechanical properties at high temperatures, and can be injection molded. The purpose is to The present inventor has conducted repeated studies to obtain a polymer material that can be injection molded, has heat resistance equal to or higher than that of thermosetting resins, and has excellent mechanical properties at high temperatures. As a result of considering the steric environment of the crosslinkable polymer,
The present invention was achieved by discovering that a polymeric material having a repeating unit consisting of a specific arylene ether having a cyano group as a crosslinking group at the ortho position of an aromatic ring satisfies the above object. That is, the present invention provides an aromatic dihalogen compound having at least one cyano group represented by the general formula ()

[Formula] is reacted with an alkali metal salt of a difunctional phenol () MO-Ar-Z-Ar'-OM represented by the general formula () to produce a crosslinkable polymer containing a repeating structure of the general formula (I'). A method for producing a crosslinked polymer, which comprises obtaining [However, X, X', Y, and Y' are selected from hydrogen, halogen, and cyano group, at least one of them is an acyno group, W, W' are halogen, and Ar and Ar' are non- a substituted or substituted arylene group, Z is O, S, SO, SO ₂ or
CRR' (R and R' are hydrogen or an alkyl group having 1 to 3 carbon atoms). ] General formula () An aromatic ether compound represented by is reacted with a halogenated sulfur compound represented by the general formula () or (') using an iron compound as a catalyst, () ZX″ ₂ , (′) S ₂ X″ ₂ General formula ( This invention relates to a method for producing a crosslinked polymer, which comprises obtaining a crosslinkable polymer containing a repeating structure of ``), and then crosslinking it. [However, X, X', Y, and Y' are selected from hydrogen, halogen, and cyano group, at least one of which is a cyano group, and Ar and Ar' are unsubstituted or substituted arylene groups. Yes, Z′ is S, SO,
SO ₂ and X″ is a halogen.] In the present invention, polyarylene ether,
It is essential that the basic skeleton of polyarylene ether sulfide, polyarylene ether sulfoxide, and polyarylene ether sulfone contains a unit having a cyano group directly connected to an aromatic ring, and this cyano group is subjected to a crosslinking reaction. . Various advantages arise from the selection of cyano groups. The cyano group can form a crosslinking point with a single type of functional group because it trimerizes by cleavage of the triple bond alone or in the presence of a catalyst to form a triazine ring or an azomethine bond. In general, crosslinking reactions utilize reactions between two different functional groups, so a two-component type reaction is inevitable. However, polymers having such different functional groups are generally incompatible, and this tendency becomes more pronounced as the molecular weight increases. On the other hand, the use of polymers having dual reactive functional groups at the same time poses problems in stability as well as difficulty in synthesis. It is suitable to use a cyano group as a crosslinkable functional group for this purpose. The reaction of the cyano group mainly involves a trimerization reaction, resulting in essentially a one-component curing type. The cyano group itself is extremely stable at room temperature, and in addition, no leaving group is generated in the trimerization reaction. This is important in bulk crosslinking reactions; for example, in reactions such as condensation, water produced by the reaction cannot be removed from the system, so it is impossible to increase the degree of crosslinking beyond a certain level by an equilibrium reaction. By using a cyano group as a crosslinkable functional group, high-density crosslinking is possible in a closed space, for example, within a mold of an injection molding machine. As described above, the cyano group has many advantages as a crosslinkable functional group, but in order to increase the heat resistance of the resulting crosslinked polymer, the cyano group must be directly connected to the aromatic ring contained in the polymer chain. , This gives rise to various constraints. In particular, during crosslinking, triazine ring formation mainly occurs through trimerization, so stereochemical considerations are necessary. In known examples of conventional crosslinking reactions using cyano groups, the cyano group is selected in an environment where the steric configuration of the cyano group is not crowded, such as at the end of the molecule or at the meta position. This is because the reaction of cyano groups is mainly a trimerization reaction, and especially in the case of cyano groups directly connected to aromatic rings, the triphenyl-S-triazine ring produced after crosslinking is itself a rigid and bulky atomic group, so the crosslinking environment is limited. In the present invention, cyano groups are placed as crosslinking groups at the ortho and meta positions of the aromatic rings bonded via ether bonds in polyarylene ether, polyarylene ether sulfide, polyarylene ether sulfoxide, and polyarylene ether sulfone. By doing this, it is possible to place cyano groups that can serve as crosslinking points in the polymer without introducing many bending points in the main chain. is achieved. At this time, polyarylene ether, polyarylene ether sulfide, polyarylene ether sulfoxide, and polyarylene sulfone have a zigzag structure due to the presence of ether bonds, so the three polymer chains mutually interact at the crosslinking point.
Triphenyl formed at the crosslinking point at an angle of 120
A specific crosslinked structure is formed in which the S-triazine is used as a common plane, and each cross-links the common plane at an angle of 55 degrees. These relationships are shown in FIG. 1, where white circles represent enzyme atoms and black circles represent nitrogen atoms. The S-triazine ring in the center is a crosslinking point created by trimerization of the nitrile group, and the three benzene rings bonded to this triazine ring are each attached to a polymer chain to which a cyano group was bonded before crosslinking. They are aromatic rings, and they all lie on the same plane. The three polymer chains, each containing one aromatic ring in the main chain, form a common plane and protrude in the vertical direction of this plane in a manner that intersects with each other, and between the molecular chain axis and the common plane. The angle is 55° for both polymer chains. In the crosslinkable polymer of the present invention, the above-mentioned crosslinked structure can be achieved stereochemically without difficulty. For example, an acetylene group is used as a similar crosslinking group, and a benzene ring formation reaction is performed by trimerization of the acetylene group. When this happens, the crosslinking reaction cannot be achieved without distortion such as twisting of the polymer chain due to steric hindrance at the points shown in FIG. 1, which becomes a factor that inhibits the crosslinking reaction itself. In the crosslinkable polymer of the present invention, as described above, a conjugated π-bonded electron system is formed by triphenyl-S-triazine having a common plane at the crosslinking point in three polymer chains, so that The fact that it can be expected that energy transfer (thermal energy, electrical energy, etc.) is carried out efficiently by the crosslinking points can also be said to enhance the usefulness of the present invention. In addition, as the molecular weight range of the crosslinkable polymer according to the present invention, the number of repeating units n is 1000>n≦3,
Desirably 300>n≦5 (molecular weight approximately 1000 to
300000). If n is more than 1000, the fluidity at high temperatures will be poor and processability will tend to be problematic, and n
This is because heat resistance is not sufficient if it is <3. Specific examples of the crosslinkable polymer of the present invention include poly[p-phenyleneoxy-p-(2,5
-dicyano)phenyleneoxy-p-phenylene sulfide], poly[p-phenyleneoxy-p
-(2-cyano)phenyleneoxy-p-phenylene sulfide], poly[p-phenyleneoxy-p-(2,5-dicyano)phenyleneoxy-
p-phenylenesulfone], poly[p-phenyleneoxy-P-(2-cyano)phenyleneoxy-p-phenylenesulfone], poly[p-phenyleneoxy-p-(2,5-dicyano)phenyleneoxy-p-phenylene ether], poly[p
-phenyleneoxy-p-(2-cyano)phenyleneoxy-p-phenylene ether] and the like. The method for producing the crosslinkable polymer according to the present invention is as follows. The first method is to obtain an aromatic dihalogen compound containing at least one cyano group represented by the general formula () shown above and an alkali metal salt of a difunctional phenol represented by the general formula () shown above. It is a nuclear substitution reaction. Examples of the aromatic dihalogen compound having a cyano group of the general formula () are 2,5-dibromocyanobenzene, 2,5-dichlorocyanobenzene, 2,5-
Dibromo terephthalonitrile, 2,5-dichloroterephthalonitrile, 2,6-dicyano-1,4
-dichlorobenzene, 2,5-(p-bromophenyloxy)terephthalonitrile, etc.
These compounds are described, for example, by DEPearson et al., Journal of Organic Chemistry, 28
Vol., page 3147 (1963), it is synthesized by halogenation reaction of cyanobenzene, or by converting dihalogenated aromatic carboxylic acids and dihalogenated aromatic aldehydes into dihalogenated aromatic cyano compounds by known methods. sell. In particular, the latter gives more desirable results for compounds having two or more cyano groups. Examples of the bifunctional phenol compound of general formula () are bisphenol A, bisphenol S, tetrabromobisphenol A, tetrabromobisphenol-S, 2,2'-bis(4-hydroxyphenyl)butane, 4 , 4'-dihydroxydiphenyl ether and other difunctional phenols are easily available. The alkali metal salt of a difunctional phenol can be obtained by reacting the above-mentioned difunctional phenols with an alkali metal hydroxide such as sodium hydroxide, potassium hydroxide, lithium hydroxide, or the like.
In addition, it is preferable to use these alkali metal salts of difunctional phenols that are sufficiently dried before use. Also, sodium amide,
A compound that does not produce water upon reaction with phenol, such as sodium hydride, can also be used, and in this case, the alkali metal salt of the difunctional phenol compound can be produced directly in the reaction flask. The polymer of the present invention can be obtained by heating approximately equimolar amounts of the alkali metal salt of the difunctional phenol compound and the dihalogenated aromatic cyano compound together with a solvent. Polar aprotic solvents are particularly preferred as reaction solvents. Examples include N,N-dimethylformaldehyde, N,N-dimethylacetamide, dimethylsulfoxide, etc., which are used alone or in the form of a mixed solvent with xylene, toluene, etc. A suitable reaction temperature is 70°C to 200°C. In addition, as a second production method, an electrophilic substitution reaction catalyzed by an iron compound between an aromatic ether compound having a cyano group of the above general formula () and a halogenated sulfur compound of the general formula () or (') is carried out. For example, 2,5-diphenoxycyanobenzene, 2,5-diphenoxy-1,4
-dicyanobenzene, 2,5-diphenoxy-
1,3-dicyanobenzene, 2,5-diphenoxy-1,6-dicyanobenzene, 2,5-bis(3,5-dibromophenyloxy)-1,4-dicyanobenzene, 2,5-bis(3 , 5-dibromophenyloxy)cyanobenzene, 3,6-diphenoxy-1,2,4,5-tetracyanobenzene, etc. per mol of an aromatic ether compound having a cyano group of general formula (), iron content, Using iron compounds such as iron chloride (ferrous chloride, ferric chloride), ferrous bromide, ferric bromide, ferrous sulfate, ferric sulfate, iron oxide, iron sulfide as a catalyst, approximately It is obtained by reacting moles of a halogenated sulfur compound as an electrophilic reagent. Examples of the halogenated sulfur compound of general formula () or (') include sulfur monochloride, sulfur dichloride, sulfuryl chloride, thionyl chloride, and sulfur bromide. In this case, iron compounds are good catalysts for polymer production, and the reason for this is explained by Fujisawa et al., Polymer Letters Vol. 8, 19.
(1970). At this time, it is preferable to use a reaction solvent. It is necessary to select a reaction solvent that is inert to electrophilic reactions, for example, o
-dichlorobenzene, p-dichlorobenzene, etc. When crosslinking the crosslinkable polymer of the present invention,
Although the trimerization reaction can occur without a catalyst, it is preferable to use a catalyst. Conventionally used catalysts are used, such as hydrochloric acid, sulfuric acid,
Acids such as p-trienesulfonic acid, methanesulfonic acid, trichloromethanesulfonic acid, tolylfluoromethanesulfonic acid, anhydrous aluminum chloride,
Lewis acids such as anhydrous aluminum bromide, anhydrous ferric chloride, and zinc chloride, phosphorus compounds such as phosphorus pentachloride and phosphorus pentoxide, metal salts such as silver salts, copper salts, and antimony salts, or complex compounds thereof, triphenyltin , tertiary amines, amine oxides, etc. are used. One or more types of these can be used. Although attempts have been made to measure the molecular weight of the crosslinkable polymer of the present invention, it has not been possible to find a good solvent that completely dissolves the polymer, and a molecular weight measurement method based on a solution method, such as gel permeability, has been used. It was impossible to measure by John chromatography method or reduced viscosity method. Strong acid solvents (concentrated sulfuric acid, methanesulfonic acid, trifluoromethanesulfonic acid, etc.) commonly used in such cases can be used in the crosslinkable polymer of the present invention because these strong acid solvents act as catalysts for the crosslinking reaction. is impossible. Further, the solvent viscosity method also has a problem because the crosslinkable polymer of the present invention gradually undergoes a crosslinking reaction at its melting temperature. When using the crosslinkable polymer of the present invention,
Depending on the purpose, various additives such as antioxidants, surfactants, pigments, dyes, and fillers may be added. Further, other polymers such as polystyrene may be added for the purpose of improving moldability. EXAMPLES The present invention will now be explained in more detail with reference to Examples. A. Synthesis of raw materials and monomers Monomers were synthesized according to the procedure shown below. (A-1) Synthesis of 2,5-dichloroterephthalic acid 2,5-dichloro-p-xylene 21.88g
(0.125 mol), potassium permanganate 124.5 g
(0.75 mol) and 1.5 mol of water into the reaction flask,
Refluxed for 12 hours. After the reaction product was filtered hot to remove manganese dioxide, the system was acidified with hydrochloric acid to isolate precipitated 2,5-dichloroterephthalic acid (8.15 g, yield 28%).
The purity was confirmed to be 98% or more by measuring the acid value. The infrared absorption spectrum (hereinafter abbreviated as IR spectrum) is shown in Figure 2. (A-2) Synthesis of 2,5-dichloroterephthalamide 2,5-dichloroterephthalic acid (A-1)
5.0 g was refluxed with a large excess of thionyl chloride (approximately 10 ml) for a day and night, and when a homogeneous solution was obtained, the excess thionyl chloride was distilled off. The residue was poured into ice-ammonia water, and the precipitated 2,5-
Dichloroterephthalamide (A-2) was isolated. (4.96g, yield 100%). Amide formation was confirmed from the IR spectrum (Figure 3). (A-3) Synthesis of 2,5-dichloroterephthalonitrile (raw material of the present invention) 4.9 g of 2,5-dichloroterephthalamide (A-2) and 12.0 phosphorus pentachloride were placed in a reaction flask.
After adding g, tightly stopper and shake, place on oil bath.
Heated at 160°C for 1 hour. After the bath was removed and cooled, 30 ml of dry xylene was added, and the mixture was refluxed overnight. By concentrating the reaction solution,
2,5-dichloroterephthalonitrile (A-
3) Obtained 3.26g (55%). From the IR spectrum (Figure 4), it was confirmed that the absorption due to the amide bond disappeared and the characteristic absorption (2130 cm ^-1 ) of the nitrile group was newly generated. (A-4) Synthesis of 2,5-diphenoxyterephthalonitrile (raw material of the present invention) 0.82 g (0.02 mol) of sodium amide 20
1.88 g of phenol was added to a reaction flask containing ml of dry N,N'-dimethylacetamide.
(0.02 mol) was added and stirred at room temperature for 30 minutes.
Add 1.97 g (0.01 mol) of 2,5-dichloroterephthalonitrile (A-3) under a nitrogen stream,
The reaction was carried out at 120°C for 20 hours. 2.96 g (94.9%) of 2,5-diphenoxyterephthalonitrile (A-4) was obtained by a conventional method. Similarly, 2,5-bis(p-bromophenoxy)terephthalonitrile was obtained by using p-bromophenol. (84%). FIG. 5 shows the IR spectrum of (A-4). (A-5) Synthesis of 2,5-dibromobenzonitrile (raw material of the present invention) Benzonitrile according to the synthesis method of DEPearson et al. (Journal of Organic Chemistry, Vol. 28, p. 3147 (1963)) was brominated in the presence of anhydrous aluminum chloride to obtain 2,5-dibromobenzonitrile (A-5). (A-6) 2,5-diphenoxybenzonitrile (raw material of the present invention) Add sodium amide to a 300 ml reaction flask.
8.24g (0.20mol) freshly distilled N,N
- Add 200 ml of dimethylacetamide, cool with water under nitrogen stream, and add 18.8 g of phenol (0.20 ml).
mol) was added dropwise. Salt precipitated while generating ammonia. After continuing stirring for 30 minutes after the dropwise addition, 2,5-dibromobenzonitrile
23.5g (0.09mol) was added and heated at 120°C. As the salt dissolved, sodium bromide began to precipitate. After heating for 20 hours, the reaction product was poured into a large amount of sodium hydroxide aqueous solution to remove unreacted phenol, extracted with ether, and the extract was concentrated to yield 16.3 g (63%) of 2,5-diphenoxybenzonitrile. ) was obtained. It was found by gel permeation chromatography that this product contained about 5% of a monobrome compound. The above synthesis is shown in Reaction Formula 1 and Reaction Formula 2. B Synthesis of crosslinked polymer Monomers (A-3) to (A-6) obtained in A
The following polymers were synthesized using (B-1) Poly[p-phenyleneoxy-p-(2,
Synthesis of 5-dicyano)phenyleneoxy-p-phenylene sulfide] And in a color reaction flask, 5 ml of o-dichlorobenzene, 1.0 g (3.2 x 10 ^-3 mol) of 2,5-diphenoxyterephthalonitrile (A-4), 0.26 g (1.9 x 10 ^-3 mol) of sulfur monochloride, 200 mg of electrolytic iron powder was added and reacted for 20 hours at 100°C under a nitrogen stream. The reaction product was poured into methanol, and the precipitate precipitated was filtered and washed to obtain 0.62 g of polymer (B-1) (yield: 51%). FIG. 6 shows the IR spectrum of the obtained (B-1). In addition, Figures 7 and 8 show the curves obtained using a differential scanning calorimeter (DSC-1500 manufactured by Shinku Riko Co., Ltd.) for the raw material (A-4) and the product (B-1), respectively. Indicated. As a result, the endothermic curve (230°C) due to the melting point of the raw material compound (A-4) that is clearly seen in Figure 7 disappears in the product (B-1) in Figure 8, indicating that no polymer is produced. You can see that The IR spectrum in Figure 6 (B-1) is
Compared to the IR spectrum of raw material (A-4) shown in the figure, there is no significant change in the main absorption position, and the absorption is broader overall, indicating higher molecular weight. Considering these results and the experimental results of Fujisawa et al., (B-1) is It was confirmed that it is a polymer compound consisting of a repeating structure consisting of. (B-2) Poly[-p-(2,5dicyano)phenyleneoxy-p-phenylenesulfonyl-p-
Synthesis of phenylene ether 0.42 g of sodium amide in the reaction flask
(10.2×10 ^-3 mol), high purity bisphenol
S1.27g (5.08×10 ^-3 mol, NICCA Chemical Industry Co., Ltd.)
20 ml of N,N-dimethylacetamide was added and stirred for 30 minutes at room temperature under a nitrogen atmosphere.
3) Add 1.0g (5.08×10 ^-3 mol) and heat to 120°C.
The reaction was carried out for 20 hours. The reaction product was poured into methanol, filtered and washed to obtain 1.60 g (84%) of polymer (B-2). In the IR spectrum of this product, in addition to the characteristic absorption of the cyano group, there is a new strong ether absorption near 1200 cm ^-1 and characteristic absorption due to the sulfone group near 1330 cm ^-1 and 1130 cm ^-1 .
It was confirmed that this polymer compound had the above-mentioned repeating structure. (B-3) Synthesis of poly[-p-(2,5dicyano)phenyleneoxy-p-phenylene(dimethyl)methylene-p-phenylene ether] In the same manner as in the synthesis of (B-2), high purity bisphenol-S was used instead of bisphenol-S.
By using 1.16 g (5.08 x 10 ^-3 mol) of A, 1.32 g (75%) of polymer (B-3) was obtained. This product was also confirmed from the IR spectrum to be a polymer compound having the above-mentioned repeating unit. (B-4) Synthesis of poly[-p-phenyleneoxy-(2-cyano)phenyleneoxy-p-phenylene sulfide] 2,5-diphenoxybenzonitrile (A
-6) 1.43g (5 x 10 ^-3 mol), o-dichlorobenzene 10ml, freshly distilled sulfur monochloride 0.37g (2.74 x 10 ^-3 mol), electrolytic iron powder 500
mg was added, and the mixture was reacted at 100°C for 20 hours under a nitrogen stream. The reaction product was poured into methanol, filtered and washed to obtain 0.82 g (52 g) of polymer (B-4).
%) was obtained. Similarly, it was confirmed from the IR spectrum that it was a polymer compound having the above-mentioned repeating unit. (B-5) Synthesis of poly[-p-(2-cyano)phenyleneoxy-p-phenylenesulfonyl-p-phenylene ether] 2,5-dibromobenzonitrile (A-
5) 2.61 g (10.0 x 10 ^-3 mol), high purity bisphenol S 2.50 g (10.0 x 10 ^-3 mol, manufactured by NICCA Chemical Co., Ltd.), sodium amide 0.78 g
(20.0×20 ^-3 mol) and 20 ml of N,N-dimethylformaldehyde to form a polymer (B-5) by carrying out the reaction in the same manner as in (B-2).
2.0g (57%) was obtained. Similarly, the IR spectrum confirmed that this compound was a polymer compound having the above-mentioned repeating unit. Crosslinking Reaction Example A curing reaction was carried out using the polymers (B-1) and (B-2) obtained in B. To 1.0 g of (B-1), 0.05 g of anhydrous zinc chloride and 1 ml of methanol were added and thoroughly kneaded on a mortar. This material was dried in a vacuum dryer at 5 mmHg and 120°C for 10 hours, and 10 mg of it was weighed and dried under a nitrogen stream using a differential thermal balance TGD-5000 manufactured by Shinku Riko Co., Ltd. Heating was carried out from room temperature to 280°C at a temperature increase rate of 10°C/min, and the temperature was further maintained at 280°C for 1 hour. An exothermic curve was observed in the temperature range of 220°C to 230°C. During this time and after 1 at 280℃
No weight loss was observed during the temperature hold for hours. After heating, the temperature was lowered to room temperature under a nitrogen stream, the melted and hardened sample was collected, and the sample was transferred to Shimadzu Corporation.
Observation of the infrared absorption spectrum using an infrared spectrophotometer IR-403 revealed that the characteristic absorption (2230 cm ^-1 ) of the nitrile group observed in the polymer (B-1) before heat treatment almost disappeared. I was able to confirm that it was. This is shown in FIG. From the above results, it was concluded that the polymer (B-1) did not undergo thermal decomposition under these heating conditions, but a three-dimensional crosslinking reaction occurred due to the nitrile groups being subjected to the crosslinking reaction. Fill a cylindrical mold with a diameter of 10 mm with 0.5 g of a sample containing polymer (B-2) and adding a catalyst in the same manner, and apply mirror-finished extrusion plates from above and below, while performing vacuum evacuation. 30 minutes at 250℃
Curing was carried out under a load of 70 kg/cm ² . The resulting pellet-like cured product was insoluble in organic solvents such as toluene and chloroform, and showed no weight loss up to 400°C under a nitrogen stream when measured on a differential thermal balance. (Heating rate: 10℃/min). In these reactions, since zinc chloride used as a catalyst is highly endothermic, it is desirable to carry out sufficient preliminary drying before curing. Effects of the Invention The crosslinkable polymer according to the present invention has excellent heat resistance and can be subjected to reaction injection molding. This cured product is expected to be highly heat resistant and have good mechanical properties, and can be expected to have a wide range of uses, including heat-resistant engineering plastics, mechanical parts, semiconductor encapsulation materials, and plasma etching resists.

[Brief explanation of the drawing]

FIG. 1 is an explanatory diagram of the structure at the crosslinking point of the crosslinkable polymer obtained by the present invention. Also, the second
Figures 3, 4, 5 and 6 show compounds (A-1), compound (A-2), compound (A-
3), compound (A-4) and polymer (B-1)
IR spectra, Figures 7 and 8 are differential scanning calorimeter curves of compound (A-4) and polymer (B-1), and Figure 9 is the differential scanning calorimeter curve of compound (A-4) and polymer (B-1). This is an IR spectrum of the cured product.

Claims (1)

[Scope of Claims] 1 An aromatic dihalogen compound having at least one cyano group represented by the general formula () MO-Ar-Z-Ar′-OM 2 A method for producing a crosslinked polymer, which comprises reacting a functional phenol with an alkali metal salt to obtain a crosslinkable polymer containing a repeating structure of general formula ('), and then crosslinking the polymer. [However, X, X', Y, and Y' are selected from hydrogen, halogen, and cyano group, and at least one of them is a cyano group, W and W' are halogen, and Ar and Ar' are non- a substituted or substituted arylene group, Z is O, S, SO, SO ₂ or
CRR' (R and R' are hydrogen or an alkyl group having 1 to 3 carbon atoms). ] 2 General formula () An aromatic ether compound represented by is reacted with a halogenated sulfur compound represented by the general formula () or (′) using an iron compound as a catalyst, () Z′X″ ₂ , (′) S ₂ X″ ₂ General A method for producing a crosslinked polymer, which comprises obtaining a crosslinkable polymer containing a repeating structure of formula ('') and then crosslinking it. [However, X, X', Y, and Y' are selected from hydrogen, halogen, and cyano group, at least one of which is a cyano group, and Ar and Ar' are unsubstituted or substituted arylene groups. Yes, Z′ is S, SO,
or SO ₂ , and X″ is halogen.]