JPS6291530A - Production of aromatic polyketone - Google Patents

Abstract

PURPOSE:To obtain the titled crystalline compound excellent in heat resistance and chemical resistance, by polycondensing 4-hydroxythiophenol and/or p- dimercaptobenzene and a dihaloaromatic compound in a specified solvent. CONSTITUTION:100pts.wt. mixture of 4-hydroxythiophenol and/or p- dimercaptobenzene (A) with 1mol, per mol of component A, of a dihaloaromatic compound which is 4,4'-dihaloterephthalophenone and/or 4,4'-dihalobenzophenone is polycondensed at 200-400 deg.C in the presence of an alkali (e.g., K2CO3) in 10-1,000pts.wt. solvent which is a benzophenone compound of formula I (wherein R and R' are each H, a 1-3C alkyl or phenyl) to obtain a crystalline polyketone of an intrinsic viscosity >=1.5, having a linear polymer structure in which structural units of formulas II and/or III and structural units of formulas IV and/or V are alternately bonded.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to an improved process for producing crystalline aromatic polyketones. More specifically, the present invention uses a specific reaction solvent to produce a highly crystalline aromatic polyketone containing a high molecular weight thioether group that has excellent heat resistance, chemical resistance, flame retardance, mechanical strength, etc. This invention relates to an industrially advantageous manufacturing method.

BACKGROUND OF THE INVENTION In recent years, crystalline aromatic polyetherketones, in which phenylene groups are linked via ether groups and ketone groups, have been found to have excellent heat resistance, chemical resistance, mechanical strength, etc.
It is attracting attention as a molding material in various fields.

Such crystalline aromatic polyetherketones have traditionally been
It has been produced by a polycondensation method using highly polar sulfonic solvents such as diphenylsulfone and sulfolane. For example, a method in which a dialkali metal salt of bisphenol containing a keto/group and a dihalogeno compound containing a ketone group is heated to a temperature of 250 to 400°C in the presence of an aromatic sulfone (Japanese Patent Publication No. 57-22938), Containing 10 phenols along with alkali metal carbonates,
Producing crystalline aromatic polyetherketone by heating to a temperature of 200 to 400°C in N-methylelepyrrolidone, aliphatic sulfone, or aromatic sulfone compound (U.S. Pat. No. 4,113,699), etc. It is known that it can be done.

By the way, the present inventors focused on the excellent properties of crystalline aromatic polyether ketone, and first created 4.4' from 4゜4'-dihaloterephthalophenone and 4-hydroxythiophenol. -dihalobenzophenone and 4-hydroxythiophenol, 4゜4'-dihaloterephthalophenone and p-dimercaptobenzene tocara, 4.4'
- from dihalobenzophenone and p-dimercaptobenzene, or from 4°4'-dihaloterephthalophenone and 4,4'-dino)lopenzophenone, 4-hydroxythiophenol and p-dimercaptobenzene,
We have developed a method for producing crystalline aromatic polyketones having a chemical structure in which phenylene groups are linked via ether groups, thioether groups, and ketone groups.

So far, sulfo/based solvents, xanthone compounds, and thioxanthone compound solvents have been used as reaction solvents for producing crystalline aromatic polyketones containing these thioether groups and ether groups, but sulfone-based solvents However, it has insufficient solubility in polymers and thermal stability at high temperatures, and is not necessarily satisfactory as a solvent for producing a high molecular weight thioether group-containing crystalline aromatic polyketone.

On the other hand, xanthone compounds and thioxanthone compounds are
The solubility of the polymer as a solvent and its thermal stability at high temperatures are good, but it remains solid at room temperature (xanthone: mp 17
3-174℃, thioxanthone: m9207-209℃
), therefore, when these are used as solvents, product separation, solvent recovery, purification, etc. are inevitably complicated.

Therefore, in order to industrially advantageously produce a high molecular weight crystalline aromatic polyketone containing thioether groups, the resulting polymer must have excellent solubility and be stable even at high temperatures.
It has been desired to select a compound that has appropriate polarity and can be treated as a liquid at room temperature and use it as a polymerization solvent.

Problems to be Solved by the Invention Under these circumstances, the purpose of the present invention is to provide a polymer that can be practically handled as a liquid, has excellent solubility in the resulting polymer, and is stable even at high temperatures. By using a polymerization solvent with appropriate polarity, a highly crystalline aromatic polyketone containing a high molecular weight thioether group with excellent heat resistance, chemical resistance, flame retardance, mechanical strength, etc. The object of the present invention is to provide an industrially advantageous manufacturing method.

Means for Solving the Problems The inventors of the present invention have conducted extensive research to achieve the above object, and as a result, the object has been achieved by using a benzophenone compound as a polymerization solvent when producing a crystalline aromatic polyketone. We have found that it is possible to achieve the following, and based on this knowledge, we have accomplished the present invention.

That is, the present invention provides 4,4'-dihaloterephthalophenone, id4,4'-dihalobenzophenone, or both, and 4-hydroxythiophenol, p-dimercaptobenzene, or both in a solvent. Polycondensation is performed to form a structural unit represented by formula (Ia) or both, and formula (1a)
When producing a crystalline aromatic polyketone that has a linear polymer structure in which the structural units represented by (nb) or both of them are alternately bonded and has an intrinsic viscosity of 0.15 or more, the solvent is , general formula (in the formula, R and R' are each a hydrogen atom, carbon number 1-3
The present invention provides a method for producing a crystalline aromatic polyketone, which is characterized by using a penzophenone compound represented by an alkyl group or a phenyl group, which may be the same or different.

The condensation polymerization reaction in the method of the present invention can be carried out, for example, with 4-hydroxythiophenol or p-dimercaptobenzene or both with 4,4'-dihaloterephthalopheno7
or using substantially equimolar amounts of 4,4'-dihalobenzophenone or both and heating in the presence of an alkali in a predetermined solvent, or 4-hydroxythiophenol or p-dimercaptobenzene or both alkali metal salts thereof and substantially equimolar amounts of 4.
This can be accomplished by heating 4'-dihaloterephthalophenone, 4,4-dihalopenzophenone, or both in a predetermined solvent.

Among these methods, 4-hydroxytheophenol having a free hydroxyl group and a mercapto group and p-dimercabutobenzene having a free mercapto group are more stable than their alkali metal salts. The former method using an alkali is preferable because of the simplicity of the polymerization operation.

The raw material monomers used in the method of the present invention include 4-hydroxythiophenol, p-dimercaptobenzene or an alkali metal salt thereof, and the general formula (in the formula, x1 and x2 are... rogen atoms, They may be the same or different)
．． 4'-Dino\Loterephthalophenone is a 4,4'-dihalopenzophenone represented by the general formula (x1 and x2 in the formula have the same meanings as above).

The alkali metal salt of 4-hydroxythiophenol or p-dimercaptobenzene can be obtained by a known method, for example, by reacting 4-hydroxythiophenol or p-dimercaptobenzene with an alkali metal hydroxide.

In addition, specific examples of 4.4'-dihaloterephthalophenone include 4.4'-dichloroterephthalophenone,
Examples include 4.4'-cyfluoroterephthalophenone, 4-chloro4'-7loloterophthalo7eno7, and the like. These monomers may be used alone or in combination of two or more.

On the other hand* Specific examples of 4.4'-dihalobenzophenone include 4.4'-dichlorobenzophenone, 4.4'-
Examples include difluoropenzophenone and 4-chloro-4'-fluoropenzophenone. These monomers may be used alone or in combination of two or more.

In this way, in the present invention, it is not necessary to use fluorine compounds that are difficult to obtain as raw materials, and xl and
Even if an easily available compound in which both of 2 and 2 are chlorine atoms is used, a high molecular weight polymer can be obtained in the same polymerization time as when a fluorine compound is used.

In the method of the present invention, it is necessary to use an aromatic ketone compound represented by the general formula (in which R and R' have the same meanings as above) as a polymerization solvent. Further, when R is a phenyl group, the compound may be condensed with a benzene ring of the be/siphenone skeleton.

Examples of such compounds include benzophenone, 4
-/Tylbenzophenone, 4-phenylbenzophenone, naphthyl phenyl ketone, 4,4'-dimethylbenzophenone, etc. Of these, be/Tylbenzophenone is particularly preferred because it is thermally stable and easily available.

These solvents may be used alone or in combination of two or more. Furthermore, if desired, other solvents such as diphenylsulfone, xanthone, etc. can be used in combination within a range that does not impair the purpose of the present invention.

Examples of the alkali used in the method of the present invention include alkali metal hydroxides, carbonates, bicarbonates, fluorides, hydrides, alkoxides, and alkylated products. Among these, preferred are alkali metal carbonates and alkali metal bicarbonates, and specific examples thereof include sodium carbonate, potassium carbonate, rubidium carbonate, cesium carbonate, potassium hydrogen carbonate, and potassium hydrogen carbonate. ,
Examples include rubidium hydrogen carbonate and cesium hydrogen carbonate.

Particularly suitable are sodium carbonate, potassium carbonate, sodium hydrogen carbonate, and potassium hydrogen carbonate. Further, these alkalis may be used alone or in combination of two or more.

Next, a preferred embodiment of the production method of the present invention will be described. First, in a solvent such as benzophenone, a required amount of alkali metal carbonate or alkali metal bicarbonate %
4-Hydroxythiophenol, p-dimercaptobenzene and dihaloaromatic compounds? (4,4'-dihaloterephthalophenone or 4,4'-dihalobenzophenone) is added. In this case, the solvent is usually used in an amount of 10 to 1000 parts by weight per 00 parts by weight of the total of 4-hydroxythiophenol, p-dimercaptobenzene, and dihaloaromatic compound. In addition, in the alkali metal salt, only a few of the alkali metal atoms are 4-hydroxythiophenol,
-') used in proportions such that the amount is 50.5 to 2 gram atoms, preferably 0.7 to 1.2 gram atoms per μmol of mercaftobenzene. If the alkali metal salt is used in excess, the reaction will be too vigorous, causing harmful side reactions and also being disadvantageous in terms of cost, so it is desirable to use as little amount as possible. However, when the amount of alkali metal atoms is less than 0.5 gram atoms, it is necessary to lengthen the polymerization time, and it becomes difficult to obtain a polymer with a desired high molecular weight.

The alkali metal salt is preferably anhydrous, but if it is a hydrated salt, it can be used by distilling off the water together with the azeotropic solvent from the single reaction system.

Also, 4.4′-dihaloterephthalophenone and 4.4
The proportions of '-dihalobenzophenone and 4-hydroxythiophenol or p-dimercaptobenzene need to be substantially equimolar, with the former being 1 mole per mole and the latter being 0.95 to 1 mole. The amount is selected within a range of 20 moles, and if it deviates from this range, a high molecular weight polymer cannot be obtained.

In addition, in order to make the polymer terminal a stable aromatic halide unit, 1.00 to 1.05 mol of the dihaloaromatic compound should be used per 1 mol of 4-hydroxythiophenol or p-dimercaptobenzene. is particularly preferred.

Next, the mixture of the solvent, alkali metal salt, and monomer is heated to 200 to 400°C, preferably 250 to 350°C, under an inert gas atmosphere such as nitrogen or argon.
The polymerization reaction is carried out in the temperature range of . If this temperature is less than 200°C, the polymer will precipitate during polymerization and a high molecular weight polymer will not be obtained, while if it exceeds 400°C, the resulting polymer will deteriorate and become seriously discolored. In addition, a rapid temperature rise is undesirable because it causes side reactions and causes coloring and gelation of the polymer. Therefore, it is necessary to raise the temperature in one step or gradually so that the temperature of the polymerization system is kept as uniform as possible.

To obtain a high molecular weight polymer with an intrinsic viscosity of 0.15 or more,
Although it is necessary that the final polymerization temperature be 200° C. or higher, it is advantageous to carry out the prepolymerization at a temperature lower than that. In addition, it is preferable to remove water Fi generated during polymerization to the outside of the system, but methods for removing it include simply replacing the gas phase of the polymerization system with a dry inert gas, or removing water Fi from the polymerization solvent. A method is used in which a low boiling point solvent is introduced into the system and distilled out of the system along with the solvent.

The polymerization reaction is carried out using a suitable terminal capping agent, such as a monochamber, functional or polyfunctional halide, specifically methyl chloride, tθr.
t-Butyl chloride, 4.4'-dichlorodiphenyl sulfone, 4.4'-difluorobenzophenone, 4.4
'-difluoroterephthalophenone, 4-fluorobenzophenone, etc. are added to the reaction system at the polymerization temperature,
It can be stopped by reacting. Also,
This makes it possible to obtain a polymer having a thermally stable alkyl group or halogen group at the end.

The polymer of the present invention thus obtained has a structure
or (Ib) c or both, and the structural unit (n), i.e. (Ila) -〇shaS-
or (ub)-srs- or both are alternately linked.

Among these structural units, the structural unit (■a) is a structural unit corresponding to the formula (where m and m are ' is O or l), but the copolymer of the present invention may contain any one of these structural units, or both may be randomly arranged It may be included regularly or regularly.

Among these, polymers having a structure with a high crystal melting point are preferred because they have a high degree of crystallinity.

Without particular control, there is no regularity in the connection format, and random structures are thought to be preferentially generated. However, at low temperatures, mercapto groups are much more reactive than hydroxyl groups, so if prepolymerization is performed at a low temperature and then polymerized at a high temperature, structural units in the linked form represented by formula (4) are preferentially formed. Also, add 0 to 1 mole of 4-hydroxythiophenol in advance.
．． After reacting 5 moles of the dihaloaromatic compound,
When the remaining 0.5 mol of the dihaloaromatic compound is reacted, the structural unit of the connected type represented by the above-mentioned (2) is preferentially produced.

Further, when the structural unit (1) is composed of (Ia) and (Ib), there are distribution states of the structural units (Ia) and (Ib), such as random, alternating, and block states.

Such a state of distribution can be controlled by the method of adding 4,4'-dihaloterephthalophenone and 4,42-dihalobenzophenone. For example, if equimolar amounts of 4-hydroxythiophenol or p-dimercaptobenzene and a mixture of the aromatic dino-ride are simultaneously charged into the reaction system and polymerized, the structural unit (la) and the structural unit (I
A copolymer in which t:+) is randomly distributed is obtained.

On the other hand, b equimolar 4-hydroxythiophenol or p
- After reacting dimercaptobenzene and 4,4'-dino-10-terephthalophenone, further adding and reacting equimolar amounts of p-dimercaptobenzene or 4-hydroxythiophenol and 4,4'-dino-10-benzophenol. In this way, a copolymer in which the structural units (Ia) and (Ib) are substantially distributed blockwise is obtained, and also when 2 mol of 4-hydroxythiophenol or p-dimercaptobenzene and 1 mol of 4 ,4'-dino-10 terephthalophenone, and then 1 mol of 4,4'-dino-1
By adding zero benzophenone and reacting, a highly alternating copolymer in which structural units (Ia) and (It:+) are alternately contained can be obtained.

Furthermore, when the structural unit (It) is composed of (Da) and (ub), there are similarly distribution states of the structural units (H&) and (nb), such as random, alternating, and block states.

The state of such distribution can be controlled by the method of adding p-dimercaptobenzene and 4-hydroxythiophenol. For example, a mixture of p-dimercaptobenzene and 4-hydroxythiophenol,
On the other hand, if equimolar amounts of 4,4'-dihaloterephthalophenone, 4,4'-dihalobenzophenone, or both are simultaneously charged into the reaction system and polymerized, the structural unit (D
A copolymer in which a) and (nb) are randomly distributed is obtained.

-10,000, equimole of p-dimercaptobenzene 4゜4'-
After reacting with dihaloterephthalophenone or 4.4'-dihalobenzophenone or both, an equimolar amount of 4-hydroxythiophenone/I/4.4
By adding and reacting '-dihaloterephthalophenone, 1d4,4'-dihalobenzophenone, or both, a copolymer in which the structural units (Ila) and (Ilb) are substantially distributed in a block manner can be obtained. You can get it and also
2 moles of 4.4'-dino rotylephthalophenone or Ha4
．． 4'-dino lobenzophenone or both and 1
After reacting with moles of p-dimercaptobenzene,
By further adding 1 mol of 4-hydroxythiophenol and reacting, a highly alternating copolymer in which the structural units Cl1a) and (Ilb) are alternately contained is obtained.

In general, when monomers that yield crystalline polymers are copolymerized, they become amorphous within a certain composition range; Regardless of whether the structural unit is contained in any state, such as in which the structural unit (la) and (I
It was unexpected that b) or the structural units (Ila) and (IIb) were crystalline in any distribution state, such as random, alternating, or block-like distribution.

In this way, polymers with various regularities and irregularities can be produced even by combining the same monomers depending on the polymerization temperature and the method of adding monomers. Of these, the regularity is relatively high;
A material with high crystallinity is desirable.

The polymers produced in this way containing structural units with different connection types in various proportions have different crystal melting points (Tm) and glass transition temperatures (Tg).

Since it has a crystallization rate, it is possible to select an appropriate manufacturing method depending on the application.

Further, the intrinsic viscosity of the polymer of the present invention is required to be 0.15 or more, preferably 0.4 to 1.8.

Those having an intrinsic viscosity of less than 0.15 do not exhibit properties as a polymer and are unsuitable.

In the method of the present invention, there is no particular restriction on the amount of the benzophenone compound of the general formula (I It can be selected arbitrarily.Usually, this range is in the range of 100:10 to 100:1000 by weight based on the total amount of raw materials.

When conventionally producing aromatic polyether sulfone and aromatic polyether ketone sulfone copolymers using solvents that only have ketone groups such as TEHA or benzophenone, it is not possible to obtain products with high molecular weight; Although high molecular weight products were obtained only when highly polar solvents such as sulfonic solvents were used (see, for example, Japanese Patent Publication No. 57-22938, Example 2), in the present invention, benzophenone It was completely unexpected that a highly crystalline aromatic polyketone containing an extremely high molecular weight thioether group was obtained using the compound as a solvent.

This is thought to be because the structure of the solvent is similar to the structure of the produced polymer, so the produced polymer chains are well dispersed during polymerization and the reaction is likely to occur.

For example, the temperature at which a polymer with an intrinsic viscosity of 0.96 in which structural units (la) and structural units (Ila) are alternately bonded is uniformly dissolved in a solvent to form a 2 weight solution is when benzophenone is used as a solvent. is 272°C, but when diphenylsulfone solvent is used, it will not dissolve unless the temperature is as high as 282°C.

Effects of the Invention In the method for producing a crystalline aromatic polyketone of the present invention, unlike conventional methods, a benzophenone compound having excellent solubility in the produced polymer is used as a polymerization solvent. Since the polymer is extremely easily obtained and the produced polymer dissolves well in the solvent, stirring of the system is carried out smoothly, and gel formation due to local overheating is suppressed. Compared to the method of
It is characterized by the ability to obtain polymers with similar degrees of polymerization at low reaction temperatures or short reaction times.

Furthermore, since the solvent used in the present invention can be handled as a liquid at around room temperature, it is easy to separate, recover, purify, etc., and the desired aromatic polyketo can be industrially advantageously produced. As is clear from the above, since there is no oxidizing property, there is no risk of oxidizing the monomer phenols, and the product itself is thermally stable and can be used repeatedly. It has the advantage of being less likely to produce heterogeneous structures such as branches.

The high molecular weight thioether group-containing highly crystalline aromatic polyketone obtained by the method of the present invention has excellent heat resistance, chemical resistance, flame retardance, mechanical strength, etc., and can be used alone as a structural material, film, fiber, etc. Polymers with low intrinsic viscosity can be used as coating materials for fibrils, and can also be used as blends with other polymers or as reinforcement materials such as glass fibers, carbon fibers, aramid fibers, calcium carbonate, and calcium silicate. Or it can be used as a composite material mixed with a filler.

EXAMPLES Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples in any way.

The polymer of the present invention is only slightly soluble in concentrated sulfuric acid and is insoluble in general organic solvents, so it is difficult to determine its average molecular weight. Therefore, the intrinsic viscosity is used as a measure of molecular weight.

Further, the physical properties of the monopolymer were measured as follows.

(1) Using concentrated sulfuric acid with an intrinsic viscosity of 84 f/-, prepare a solution containing 0.12 polymer per 100 solution and a solution containing 9 polymer 0.52 per 100 solution. was measured at 25°C, and the formula % formula % [where ηrel is the relative viscosity and C is the concentration (f/100
-) and hC→0 means extrapolating the value of (ηre1-1)/C to the point where the concentration C is 0].

(2) Crystal melting point (Tm), glass transition temperature (Tg) DS
The temperature was measured using a C (differential scanning calorimeter) at a heating rate of 10° C./min. The powder obtained by polymerization was used as it was for the measurement of Tm.

Example 1 A separable four-bottle flask equipped with a stirrer, a nitrogen inlet pipe, and a condenser was purged with nitrogen, and then 4,4'-
Difluoroterephthalophenone 13.14F (0,0
408 mol), 4-hydroxythiophenol 5.04
t (0,040 mol) and 40 g of benzophenone were added, and heating was started under a nitrogen atmosphere. After adding 5.529 (0,040 mol) of anhydrous potassium carbonate at 120°C, the temperature was raised to 305°C in 1 hour and maintained at that temperature for 3 hours, and the reaction solution became a viscous liquid. The reactions were consistently carried out at normal pressure (atmospheric pressure). At that temperature 4,
Add 4'-difluoroterephthalophenone 4.09 to 3
After holding for 0 minutes, it was cooled, ground, and washed twice with hot acetone, twice with hot water, and once with hot acetone to obtain a polymer with a yield of 96%. The intrinsic viscosity of this product was 1, 1101T was 355°C, and Tg was 152°C.

This polymer has a structure in which structural units (Ia) and structural units (na) are alternately bonded.

After this polymer 'i was formed into a film using a press at 400°C and held at that temperature for 30 minutes, the intrinsic viscosity of the film remained unchanged at 1.10, demonstrating that this polymer is extremely thermally stable. became.

Example 2 4.4'-dichloroterephthalophenone 14.48 F
(0,0408 mol), 4-hydroxythiophenol 5.04 y (0,040 mol), anhydrous potassium carbonate 5.52 f (0,040 mol), benzophenone 4
09 was used, except that anhydrous potassium carbonate was added from the beginning and the reaction was maintained at the final temperature of 300° C. for 4 hours.

A polymer was obtained in the same manner as in Example 1.

The intrinsic viscosity of this polymer is 0.80, Tm 345°C, T
g 151'C. Further, when pressed at 400°C for 5 minutes, a strong film resistant to bending was obtained.

Example 3 4.4'-difluorobenzophenone 8.899 (0,
0408 mol), 4-hydroxythiophenol 5.0
4 f (0,040 mol), anhydrous potassium carbonate 2.7
6 t (0,020 mol), anhydrous sodium carbonate2.
129 (0,020%#), and benzopheno 74
A polymer was obtained in the same manner as in Example 1, except that anhydrous potassium carbonate and anhydrous sodium carbonate were added from the beginning using 02, and the final temperature of the reaction was set to 2801:: and held at that temperature for 3 hours. . The intrinsic viscosity of this polymer is 1.02
, Tm was 276°C, and Tg was 143°C. Also,
When pressed at 400°C for 5 minutes, a strong film resistant to bending was obtained.

This polymer has a structure in which structural units (Ib) and structural units (H&) are alternately bonded.

Example 4 4.4′-dichloroterephthalophenone 14.20 F
(0,040 mol), p-dimercaptobenzene 5.6
8F (0,040 mol), anhydrous potassium carbonate 5.52
F (0,040 mol), using benzophenone 402 L
A polymer was obtained in the same manner as in Example 1, except that the final temperature was maintained at 305° C. for 4 hours.

The intrinsic viscosity of this polymer is 0.85, Tm 367°C, T
g 141 t::. Further, when pressed at 400° C. for 5 minutes, a strong film resistant to bending was obtained.

This polymer had repeating units of a structural unit (la) and a structural unit (nb).

Example 5 4.4'-difluorobenzophenone 8.289 (0
,038 mol), p-dimercaptobenzene 5.689
(0,040 mol), anhydrous sodium carbonate 4.24
F (0,040 mol) and benzophenone 402, anhydrous sodium carbonate was added from the beginning, and the final B
A polymer was obtained in the same manner as in Example 1 except that the temperature was set to 295°C and held for 3 hours.

This polymer has an intrinsic viscosity of 0.68 and a Tm of 304°C.
, Tg was 135°C. Further, when pressed at 360° C. for 5 minutes, a strong film resistant to bending was obtained.

This polymer has -@)-'a -@)-s -@7- in which the structural unit (Ib) and the structural unit (nb) are alternately bonded.
It had an s - repeating unit.

Example 6 4.4′-difluoroterephthalophenone 12.88F
(0,040 mol), 4-hydroxythiophenol 2
．． 52 F (0,020 mol), p-dimercaptopenze/2.84? Example 1 except that anhydrous potassium carbonate (0,020 mol), anhydrous potassium carbonate 4.42 F (0,032 mol), and benzophenone 402 were used, and anhydrous potassium carbonate was added from the beginning and held at a final temperature of 305° C. for 4 hours.
A copolymer was obtained in the same manner as above.

The intrinsic viscosity of this copolymer is 0.78, Tm 338°C,
Tg was 147°C. Further, when pressed at 360° C. for 5 minutes, a strong film resistant to bending was obtained.

The copolymer has the structural unit (Ia) (na) -o8s -s omo/l/4 and the structural unit (
11b)-8*"3)-s-somol) were linked alternately.

Example 7 4.4'-dichloroterephthalophenone 7.249 (0
,0204 mol), 4,4'-dichlorobenzophenone 6.579 (0,0204 mol), 4-hydroxythiophenol 5.04 f (0,040 mol), anhydrous potassium carbonate A 5.52? A copolymer was obtained in the same manner as in Example 1, except that 40 fi of benzophenone (0,040%) was used and the final temperature was maintained at 300° C. for 5 hours. The intrinsic viscosity of the copolymer is 0.76, Tm 311'
C1Tg was 147°C.

Further, when pressed at 380° C. for 5 minutes, a strong film resistant to bending was obtained.

The copolymer has structural unit (I) (constituent unit < ta) (
Ib) -@=gsha 50 moles) and the constituent unit (Il
a) -〇*D-s- were connected alternately.

Example 8 4.4'-dichlorobenzophenone 10.041 (0,
040 mol), 4-hydroxythiophenol 1.51
? (0,012 mol), p-dimercaptobenzene 3
．． 98? (0,028 mol), anhydrous potassium carbonate5.
529 (0,040 mol), benzophenone 40 y
Use shi.

A copolymer was obtained in the same manner as in Example 1, except that anhydrous potassium carbonate i was added at 90°C, the final polymerization temperature was 290°C, and the temperature was maintained for 4 hours.

The intrinsic viscosity of this copolymer is 0.58, Tm 290°C,
Tg was 138°C. Furthermore, the film pressed at 360° C. for 5 minutes was strong and resistant to bending.

The copolymer has a structural unit (1b) and a structural unit (n) (a structural unit (Ila) -o8s -50 molar ratio and a structural degree (IIt+) -s<◇-8-50 molar ratio) alternately. It was connected.

Example 9 4.4'-difluoroterephthalophenone 6.44f (
0,020 mol), 4,4'-difluorobenzophenone 4.369 (0,020 mol), p-dimercaptobenzene 5.68 f (0,040 mol), anhydrous potassium carbonate 4.419 (0,032 mol) ), Benzophenone 402 was used, and a copolymer was obtained in the same manner as in Example 1 except that potassium carbonate was added at 90°C. The intrinsic viscosity of this copolymer is 0.71% Tm 346°C, Tg1
The temperature was 39°C. Further, a strong film resistant to bending was obtained by pressing at 400° C. for 5 minutes.

The copolymer has a structural unit (I) (a structural unit (Ia) (I
t:+)+Kun@-s o molar width) and structural unit (I[b)
-s-@-s- were connected alternately.

Example 1O The same apparatus as in Example 1 was used, but the atmosphere was replaced with nitrogen.4.
4'-difluoroterephthalophenone 6.44F (0
,020 mol), p-dimercaptobenzene 2.52
r (0,020 mol), anhydrous sodium carbonate 2.12
F (0,020 mol) and benzophenone 402 were added, and heating was started under a nitrogen atmosphere. 305℃ in 1 hour
After the temperature was raised to , this temperature was maintained for 2 hours. then 12
After cooling to 0°C, 4.36 F (0, (100 mol)) of 4,4'-difluorobenzophenone, 2.52 F (0,020 mol) of 4-hydroxythiophenol, and 2.76 F (0,020 mol) of anhydrous potassium carbonate were added. 0,020 mol) was added, the temperature was raised to 305°C in 1 hour, and then maintained at this temperature for 3 hours.The reaction was consistently carried out at normal pressure (atmospheric pressure).
I did it. At that temperature 4,4'-difluoroterephthalophenone 4. After adding Of 'i and holding for 30 minutes, J
This was cooled and ground, and then washed twice with hot acetone, twice with hot water, and once with hot acetone to obtain a copolymer.

The intrinsic viscosity of this product was 1.23. In addition, the copolymer has a structural unit ([a), a structural unit (11), a structural unit (tla) -o+s-s o molar range, and a structural unit (Il'b) -8O8-50 molar width, The structural units (I[a) and the structural units (nb) seem to be distributed in blocks) were alternately connected.

Example 11 Using the same equipment as in Example 1, after replacing with nitrogen, 4
．． 4'-Dichloroterephthalophenone 14.2Of (
0,040 mol), p-dimercaptobenzene 2.84
P CO 0,020 mol), benzophenone 402 gold were placed, and heating was started under a nitrogen atmosphere. At 120°C, 2.76 f (0,020 mol) of anhydrous potassium carbonate was added, and 1
It was held at 50°C for 3 hours. At that temperature, 2.529 (0,020 mol) of 4-hydroxythiophenol and 2.76 F (0,020 mol) of anhydrous potassium carbonate were added, and then the temperature was raised to 305°C over 1 hour. This temperature was maintained for 5 hours, and then 4.02 g of 4,4'-difluorobenzophenone was added thereto and maintained for 30 minutes.

The reactions were consistently carried out at normal pressure (atmospheric pressure). The reaction mixture was cooled and triturated, then washed twice with hot acetone and twice with hot water.
A copolymer was obtained by washing twice and once with warm acetone.

The intrinsic viscosity of this product was 0.63. In addition, the copolymer has the structural unit (Ia), the structural unit (■) (the structural unit (Ila) -Q+51-50 molar width and the structural unit (nb)
) -s+s -50 molar width, and the structural unit (Ila
) and the structural unit (Ilb) (which seems to have a high degree of alternation) were linked alternately.

Example 12 Using the same equipment as in Example 1, after replacing with nitrogen,
4.4'-difluoro, benzophenone 4.365'
(0,020 mol), 4-hydroxythiophenol 5
．． 04 f (0,040 mol), anhydrous sodium carbonate 4.249 (0,040 mol), benzophenone 40
2 was added, and heating was started under a nitrogen atmosphere. After holding at 170°C for 1 hour, 6.479 (0,0201 mol) of 4,4'-difluoroterephthalophenone was added,
The temperature was raised to 300°C in 30 minutes. The reactions were consistently carried out at normal pressure (atmospheric pressure). After holding at 300℃ for 3 hours,
．． 4'-difluorobenzophenone 4. Added Off and held for an additional 30 minutes. This was cooled, ground, and washed twice with hot acetone, twice with warm water, and once with hot acetone to obtain a copolymer.

The intrinsic viscosity of this product was 0.93.

The polymer has a structural unit (I) (a structural unit (Ia) (It
+) +8 11 structural units (Ia) with 50 molar width
and the structural unit (Ib)) and the structural unit (Ila) are connected alternately, that is, the structure of 4 (XH◎4 (to X) os-@-o- It seems that the unit generates it preferentially.

Example 13 A polymer was obtained in exactly the same manner as in Example 1, except that phenylbenzophenone was used instead of benzophenone in Example 1. The intrinsic viscosity of this polymer was 0.63.

Claims (1)

[Scope of Claims] 1. 4,4'-dihaloterephthalophenone or 4,4'-dihalobenzophenone or both, and 4-hydroxythiophenol or p-dimercaptobenzene or the like in a solvent. By polycondensing both, we have the formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. A crystalline aromatic polyketone that has a linear polymer structure in which the structural units shown by ▼ or ▲ have mathematical formulas, chemical formulas, tables, etc., or both are alternately bonded, and has an intrinsic viscosity of 0.15 or more. In producing the solvent, there are general formulas ▲ mathematical formulas, chemical formulas, tables, etc.
(which may be the same or different) A method for producing a crystalline aromatic polyketone, characterized by using a benzophenone compound represented by: