JP2000256467A - Synthesis of polymer, resin composition, and production of molded article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for synthesizing a polymer which effectively conduct the termination of polymerization reaction and the dissolution of the association of resins with one another, the improvement of the solubility of the resulting polymers, the control of their re-association and the like. SOLUTION: The process for synthesizing a polymer comprises reacting (A) a first monomer having (-CO)2O, -COOH, -OH or -CHOCH2 as the functional group having bonding properties with (B) a second monomer having -NH2, -NCO or -CHOCH2 as the functional group having bonding properties in the respective equivalent amounts to be defined by the target average molecular weight to render the resulting product high molecular weight and then, adding a low-molecular weight compound having a reactive functional group to the reaction solution thereby modifying the remaining active groups to extremely reduce the reactivity and polarity of the polymer and dissolving the once formed association of the polymer to an optional extent to make the re-association difficult.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for synthesizing a polymer, and more particularly, to a method for producing a synthetic polymer such as an adhesive or a fiber material. The present invention relates to a method for synthesizing a polymer, which effectively improves the solubility of the resin and suppresses reassociation.

[0002]

2. Description of the Related Art Generally, in order to obtain a polymer having a desired average molecular weight from a monomer in a polymer synthesis, for example, in the case of a polymerization reaction by heat, a stop point of the polymerization reaction is determined by a reaction solution viscosity or GPC.
The reaction is often stopped in advance by a method such as cooling down the reaction system or precipitating the reaction solution in a solvent when the reaction system is reached. Alternatively, a method of adjusting the charge ratio of the raw materials in advance and setting the polymerization so as to stop the polymerization at a target molecular weight is also used.

[0003] However, when these methods are used, unreacted or reactive functional groups are apt to remain in the product. Therefore, when the reaction solution is directly used as a resin solution for coating or spinning, a solution is used. During storage, the reaction easily proceeded or side reactions were likely to occur due to moisture or oxygen in the air, and the storage life was often extremely short. When the reaction solution is precipitated in a solvent such as water for the purpose of stopping the polymerization reaction or purifying the resin, the physical properties of the resin often change due to the reaction via the solvent.

[0004] In polymer synthesis, the association of the polymer often proceeds simultaneously with the polymerization reaction, and the viscosity of the solution and the molecular weight measured by the GPC method are affected by both the degree of polymer polymerization and the amount of aggregate formed. Therefore, when the reaction end point is determined by using these, a large difference may occur in the average molecular weight between lots, and there is a disadvantage that it is difficult to obtain a polymer having a constant molecular weight. Further, the physical properties of the obtained resin were also affected by the association, and it was often difficult to obtain the essential characteristics of the polymer.

[0005]

SUMMARY OF THE INVENTION The present invention has been made to solve these problems, and suppresses a reaction through a solvent such as water or alcohol, in addition to moisture and oxygen in the air, so that a change in physical properties hardly occurs. In addition, it also significantly improves the solubility of the resin when preparing a resin solution by dissolving it in a solvent. In addition, by eliminating the association generated during the polymer synthesis process to an arbitrary degree and making the association less likely to occur, a product having a uniform molecular weight distribution with little difference between synthesis lots can be obtained, and the essential characteristics of the polymer can be obtained. It provides a method of synthesizing a polymer that facilitates the synthesis.

[0006]

Means for Solving the Problems As a result of diligent studies, the present inventor has found that by modifying the unreacted or reactive functional groups remaining in the polymer with a certain compound, the reactivity of the polymer is improved. It has been found that the polarity of the polymer can be remarkably reduced, and the association between the polymers formed once can be eliminated to an arbitrary degree to make it difficult to associate again, and the present invention has been completed. The present invention is intended to reduce the reactivity and polarity of the polymer by reacting with a low molecular weight compound having a reactive functional group such as an -OH group or an epoxy group to leave unreacted or reactive in the polymer. Characterized in that the functional groups are structurally modified.

That is, the method for synthesizing the polymer of the present invention comprises:
The method is characterized in that a low molecular weight compound having a reactive functional group is added to a reaction solution in which a monomer is polymerized to increase the molecular weight of the polymer to around a target molecular weight, thereby modifying the remaining active group. Further, the method for synthesizing a polymer according to the present invention comprises a first monomer (A) and a second monomer (B) reactive therewith.
Is reacted by an equivalent amount defined by the desired average molecular weight to obtain a high molecular weight, and then the remaining active group is modified by adding a low molecular weight compound having a reactive functional group to the reaction solution. I do. The monomer (A) has (—CO) ₂ O, —COOH, and —O as functional groups having a binding property.
H, or —CHOCH ₂ , and the monomer (B) has —NH ₂ , —NCO or —C
Those having HOCH ₂ are preferred. The resin composition of the present invention includes a reaction solution in which the low-molecular weight compound having a reactive functional group is added to modify the remaining active group. A molded article can be produced by directly using the reaction solution in which the above-mentioned low molecular weight compound having a reactive functional group is added to modify the remaining active groups as a resin solution.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The polymer synthesized in the present invention comprises a monomer (A) mainly having an acid component and a monomer (B) mainly having a base component, optionally added with a catalyst, and optionally in a solvent. By reacting with Examples of the monomer (A) include pyromellitic dianhydride, 3,3 ′, 4,
4'-benzophenonetetracarboxylic dianhydride (BT
DA), 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, hexafluoroisopropylidene dianhydride 2,2-bisphthalate, bis (3,4-dicarboxyphenyl) ether dianhydride, Bis (3,4-dicarboxyphenyl) sulfone dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenylsulfone dianhydride, 2,2-bis [4- (3,4-di Carboxyphenoxy) phenyl] propane dianhydride, ethylene glycol bistrimellitate dianhydride (EBTA),
Tetracarboxylic dianhydrides such as decamethylene glycol bistrimellitate dianhydride (DBTA) and bisphenol A bistrimellitate dianhydride (BABT);
Tricarboxylic anhydrides such as trimellitic anhydride, succinic acid, glutaric acid, adipic acid, speric acid, azelaic acid, aliphatic dicarboxylic acids such as sebacic acid, decanedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, naphthalenedicarboxylic acid And the like. These dicarboxylic acids may be used alone or as a mixture of two or more.

In addition, ethylene glycol, propylene glycol, butanediol, 1,3-butylene glycol, 2-methyl-1,3-propanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, hexanediol , 2,2-diethyl-1,
Aliphatic diols such as 3-propanediol, 2-ethyl-1,3-hexanediol, 3,3-dimethylolheptane, nonanediol, 2-methyl-1,8-octanediol, decanediol, bisphenol A, hydroquinone And aromatic diols such as 4,4'-biphenyldiol and 2,6-naphthalenediol.
These diols may be used alone or as a mixture of two or more.

When a dicarboxylic acid and a diol are reacted and used as a polyester, there is no particular limitation as long as the polyester is formed, but a melting operation eliminates the need for a production operation such as solvent removal. The amounts of the dicarboxylic acid and the diol used in the production of the polyester are appropriately determined depending on the desired terminal group. When a dicarboxylic acid is used in excess, a polyester having carboxyl groups at both terminals is obtained, and when a diol is used excessively, a polyester having hydroxy groups at both terminals is obtained.

When trimellitic acid and a diol are reacted to obtain a tetracarboxylic dianhydride, a product obtained by converting trimellitic acid to trimellitic acid chloride and a diol are reacted in the presence of pyridine or the like, and then the anhydride is added. Recrystallization from acetic acid gives the desired product. As these carboxylic acid compounds, free acids (tetracarboxylic acid, tricarboxylic acid) can be used in addition to anhydrides, and derivatives such as esterified products and chlorides can also be used. These monomers may be used alone or in combination of two or more.

Examples of monomer B include 1,2-diaminopropane, 1,3-diaminopropane, 1,2-diamino-2-methylpropane, 1,4-diaminobutane,
6-diaminohexane, 1,7-diaminoheptane, 1,
Alkylenediamines such as 8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,12-diaminododecane, etc., isophoronediamine, phenylenediamine, toluylenediamine, xylylenediamine, naphthalenediamine, dicyclohexyl Methanediamine, 4,
4'-diaminodiphenylmethane, 4,4'-diaminodiphenylether, 4,4'-diaminodiphenylsulfone, 4,4'-diaminobenzanilide, 3,3 '
-Diaminodiphenylsulfone, 3,3'-diaminobenzophenone, 3,3'-dimethyldiphenyl-4,
4'-diamine, 3,3 ', 5,5'-tetramethyl-
4,4'-diaminodiphenylmethane, 3,3 ', 5
5′-tetraisopropyl-4,4′-diaminodiphenylmethane, 1,4-bis (4-aminocumyl) benzene, 1,3-bis (4-aminocumyl) benzene, 1,
4-bis (4-aminophenoxy) benzene, 1,4-
Bis (3-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 2,2-bis [4
-(4-aminophenoxy) phenyl] propane, 2,
2-bis [4- (3-aminophenoxy) phenyl] propane, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, bis [4- (4 Aromatic diamines such as -aminophenoxy) phenyl] ether and 2,2-bis [4- (4-aminophenoxy) phenyl] biphenyl; siloxane diamines represented by Chemical Formula 1;

[0013]

Embedded image (In the formula, R1 and R2 represent a divalent organic group, R3 and R4 represent a monovalent organic group, and m represents an integer of 1 to 100.)
These may be used in combination of two or more. Also,
Examples of the diisocyanate that can be used include those obtained by replacing “amino” with “isocyanate” in the diamine shown above. These base components may be used alone or in combination of two or more.

One of the monomers A and B may be a monomer having two or more epoxy groups,
For example, polypropylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether,
In addition to 1,2,7,8-diepoxyoctane, ethylene glycol diglycidyl ether and the like, epoxy resins derived from bisphenol A, bisphenol F, bisphenol AD and the like and epichlorohydrin, for example, AER-X8501 (Asahi Kasei Corporation) Product name), YDF-
170 (trade name, manufactured by Toto Kasei Co., Ltd.), R-710 (trade name, manufactured by Mitsui Petrochemical Co., Ltd.), novolak epoxy resin N-73
OS (trade name, manufactured by Dainippon Ink Co., Ltd.), phenol novolak type epoxy resin Quatrex-2010 (trade name, manufactured by Dow Chemical Company), cresol novolak type epoxy resin YDCN-702S (trade name, manufactured by Toto Kasei Co., Ltd.), EO
CN-100 (trade name, manufactured by Nippon Kayaku Co., Ltd.), bisphenol A type epoxy resin R-301, YL-980 (trade name, manufactured by Yuka Shell Epoxy), polyfunctional epoxy resin EPPN
-501 (trade name, manufactured by Nippon Kayaku Co., Ltd.), TACTIX-74
2 (trade name of Daku Chemical Co., Ltd.), VG-3010 (trade name of Mitsui Petrochemical Co., Ltd.), 1032S (trade name of Yuka Shell Epoxy Co., Ltd.), epoxy resin HP-4032 having a naphthalene skeleton (Dainippon) Ink Co., Ltd. trade name, alicyclic epoxy resin EHPE-3150 (Daicel Chemical Co., Ltd. trade name) and the like.

In the present invention, particularly when a polymer having a high molecular weight is obtained, the use of a polyester or polyether and a carboxylic dianhydride or the like with a diamine or a diisocyanate or the like is based on the use of substantially equimolar amounts. , An excess within 30 mol% is preferred.

The organic solvent used in the polymer synthesis reaction is
Aprotic polar solvents such as N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, and sulfolane; and ether solvents such as tetrahydrofuran, dioxane, monoglyme, and diglyme. Further, for dissolving the raw material monomers and the reactants, an appropriate amount of an organic solvent such as benzene, toluene, xylene, methyl ethyl ketone, methyl cellosolve, cellosolve acetate and the like can be used.

When an organic solvent is added to the obtained polymer to form a liquid resin composition such as a varnish, the organic solvent includes N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N -Aprotic polar solvents such as dimethylformamide and sulfolane, ether solvents such as tetrahydrofuran, dioxane, monoglyme, diglyme, benzene, toluene, xylene, methyl ethyl ketone, methyl cellosolve, cellosolve acetate,
Examples thereof include cyclohexanone and the like and a mixed solvent thereof.

Examples of the functional group having a binding property remaining after the polymerization reaction of the polymer include -OH, -COOH, -N
H2, -NCO, (-CO) 2O and the like.
In order to modify them, a low molecular weight compound having a reactive functional group such as an -OH group or an epoxy group may be used. Examples of the low molecular weight compound having a -OH group include anisyl alcohol, isobutyl alcohol, and isopropyl. Alcohol, isopropylbenzyl alcohol, isopentyl alcohol, undecyl alcohol,
Eicosyl alcohol, 2-ethylhexyl alcohol, enanthate alcohol, octadecyl alcohol, octyl alcohol, cumin alcohol, diacetone alcohol, 3,4-dimethoxybenzyl alcohol, stearyl alcohol, decyl alcohol, tetradecyl alcohol, dodecyl alcohol, tridecyl alcohol, Nonyl alcohol, 2-phenylethyl alcohol, phenylpropyl alcohol, phenethyl alcohol, butyl alcohol, propyl alcohol, isopropylbenzyl alcohol, hexadecyl alcohol, hexyl alcohol, heptyl alcohol, benzyl alcohol, pentadecyl alcohol, pentyl alcohol, 3-methylbutyl Alcohol, 1-methylbenzyl alcohol, methoxyben Alcohol, lauryl alcohol, 1-octen-3-ol, alpha-terpineol, N- acetyl-aminoethanol, 2-anilinoethanol, 2- (benzylamino) ethanol, 2-
(4-biphenylyl) -2-propanol, butanol, 2-n-butoxyethanol, 2- (2-n-butoxyethoxy) ethanol, cyclododecanol, cycloheptanol, cyclohexaneethanol, cyclohexanemethanol, cyclohexanol, 2- Cyclohexylethanol, cyclooctanol, cycloheptanol, cyclopropylmethanol, decanol, 1,
3-diethoxy-2-propanol, 2-diethylaminoethanol, 1-dimethylamino-2-propanol, 3-diethylamino-1-propanol, 2,3-
Dimethylcyclohexanol, 2,2-dimethyl-1,
3-dioxolan-4-methanol, diphenylmethanol, docosanol, dodecanol, 1-eicosanol, ethanol, 2-ethoxyethanol, 2- (2-
(Ethoxyethoxy) ethanol, 2-ethoxyaminoethanol, 2-ethyl-1-butanol, 2-ethylhexanol, heptanol, 1-hexadecanol, hexanol, indanol, methanol, 4-methoxy-1-butanol, 2-methoxyethanol , 2- (2
-Methoxyethoxy) ethanol, 2- (methylamino) ethanol, 2-methyl-1-butanol, 2-methyl-2-butanol, 3-methyl-1-butanol,
4-methylcyclohexanol, 3-methyl-3-methoxybutanol, 2-methyl-1-propanol, 2-
Methyl-2-propanol, 2-morpholinoethanol, nonanol, octanol, pentadecanol, pentanol, 2-phenoxyethanol, N-phenyl-2-aminoethanol, phenylethanol, 1-phenyl-1-propanol, 2-phenyl- 1-propanol, 3-phenylpropanol, N-piperidineethanol, propanol, pyridylmethanol, 2-
(2-pyridyl) ethanol, tetradecanol, triphenylmethanol, triphenylsilanol, undecanol and the like can be used.

The low molecular weight compounds having an epoxy group include styrene oxide, epoxycyclooctane,
1,2-epoxy-3-phenoxypropane, 1,2-
Epoxy propane, 2,3-epoxypropyl isopropyl ether, 2,3-epoxypropyl phenyl ether, glycidyl phenyl ether, cyclododecane epoxide, butyl glycidyl ether and the like can be used.

In the method according to the present invention, the active groups remaining in the polymer are modified to suppress further reactions, the polarity is controlled to be low, steric hindrance is introduced, and as a result, The low-molecular-weight compound to be added does not react with other polymers or its raw materials, oligomers in the course of polymerization, or other low-molecular-weight compounds after reacting with the active group in the polymer because the purpose is to reduce the reactivity. Is desirable. For this reason, a low molecular weight compound having a reactive functional group has only one relatively reactive functional group such as an -OH group or an epoxy group in one molecule, and this is the active group in the polymer. It is preferable to react efficiently.
Here, the functional groups remaining in the polymer are -OH, -C
In the case of OOH, -NH2, etc., a new -OH is generated by a reaction with an epoxy group, and this may cause a side reaction or association depending on conditions. For this reason, it is generally desirable to use a low molecular weight compound having an —OH group as a reactive functional group. Especially for polymer synthesis
When the reaction is performed at a high temperature of 0 ° C. or higher, when the polymer is purified by a method such as water washing after the reaction is stopped, or when the polymer is precipitated in a solvent such as water or alcohol to obtain the polymer as a solid, the boiling point is high. High water solubility,
It is convenient to use a benzyl alcohol compound having low toxicity. According to this method, it can be easily treated with only a small amount of a low-boiling compound without using a special apparatus, and the waste liquid can be easily treated, which is industrially advantageous. When using a low-molecular-weight compound having a low boiling point, after lowering the reaction solution to a temperature lower than the boiling point of the low-molecular-weight compound, attach a reflux device to the reaction vessel, add the low-molecular-weight compound to the reaction solution, and stir while refluxing for a while. It can be handled by such methods as doing.

The amount of the low molecular weight compound used for the deactivation treatment is not particularly limited. However, when the low molecular weight compound is added directly to the reaction solution, the functional group having the binding property contained in the raw material for polymer synthesis is used. It is often sufficient to add the low molecular weight compound in an amount corresponding to the total number of moles of the group. In addition, in the polymer synthesis reaction, all the remaining unreacted or reactive functional groups do not necessarily need to be structurally modified, so simply pouring the reaction solution directly into a low molecular weight compound is sufficient. The effect can be improved. In this case, it is desirable to pour the reaction solution into a low molecular weight compound in which the entire reaction solution is sufficiently immersed.

The reaction solution deactivated by the above-described method hardly causes a reaction due to moisture or oxygen in the air, so that the properties of the polymer hardly change for a long time. For this reason, the reaction solution can be stored as a resin solution as it is, and the reaction solution can be applied as it is as a varnish, or can be spun into a fiber. In addition, even when the reaction solution is precipitated in water for the purpose of purifying the resin or obtaining the resin as a solid, it is difficult to cause a reaction via these precipitation solvents, so that the treatment is performed without changing the physical properties of the polymer. Can be. This is for example -NCO in the polymer
If the group remains, a urea bond may be formed by the reaction between the polymers via water to increase the molecular weight. This causes a change in the physical properties of the polymer, and also significantly lowers the solubility of the polymer in a solvent to easily form a gel. Therefore, performing an inactivation treatment at the stage of a reaction solution is an extremely effective method.

The method of the present invention can also be used as a method for resolving once formed polymer association to any extent and preventing re-association. Generally, the polymerization reaction of a polymer often causes an association between the polymers in addition to the polymerization reaction of the polymer itself. The amount of aggregate formed is likely to be affected by synthesis conditions such as the raw material charge ratio, reaction solution concentration, and reaction temperature. In addition, since the viscosity of the reaction solution is easily affected by the amount of aggregates formed, when the viscosity of the reaction solution is used as a criterion for judging the end point of polymerization, when the amount of aggregates formed differs for each synthesis lot, the molecular weight of the polymer itself also increases. You can't get a certain thing. Further, since the data obtained by the measurement by the GPC method is the molecular weight distribution of the polymer including the aggregate, it is difficult to obtain an accurate molecular weight distribution of the polymer itself. Modifying the unreacted or reactive functional groups remaining in the polymer by the method of the present invention,
By reducing reactivity and polarity and causing partial steric hindrance in the polymer chain, even a reaction solution that has reacted almost to a rubbery state can be returned to a solution state and can be used as a resin solution In addition, the precipitation operation in a solvent such as water or alcohol becomes extremely easy. Also,
As the associative properties of the polymer decrease, the ratio (Mw / Mn) between the weight average molecular weight and the number average molecular weight decreases, and the molecular weight of the polymer itself can be easily measured, and at the same time, the properties of the polymer itself can easily appear. The ratio of the weight average molecular weight to the number average molecular weight (Mw / Mn) depends on the molecular structure and processing time of the polymer, but when the resulting polymer is linear and has no crosslinked structure, Mw / Mn = 2.5 to 1 .3 can be adjusted.

Further, if the feed ratio of the raw materials is adjusted so that the desired average molecular weight can be obtained in the polymer synthesis by using the present method, it is sufficient that the polymerization reaction of the polymer itself under the conditions is completed. If the time is measured in advance, a polymer having a constant molecular weight distribution can be always obtained by performing the inactivation treatment after reacting for the time. That is, the polymerization reaction can be handled only by controlling the time without measuring the viscosity of the reaction solution or the change in the molecular weight during the polymerization reaction.

The time required for the inactivation treatment is not particularly defined because it depends on the low-molecular weight compound used, the reaction conditions, and the desired degree of dissociation of the association. About 10 minutes to 2
It is about an hour, preferably one hour or more. In many cases,
Polymer association is likely to occur in a state where polymerization of the polymer itself has progressed to a certain degree or more, and accordingly, the viscosity of the reaction solution rapidly increases from a certain point. However, the reaction solution is several tens.
Even if the viscosity becomes considerably higher than 0 P, the association is relatively easily eliminated by the treatment according to the present invention, so that the solution can be returned to a low-viscosity solution in a very short time.

Polymers that have been structurally modified to reduce reactivity and polarity and at the same time to dissociate to any extent have improved solubility in solvents. For this reason,
When a resin solution is prepared using the obtained polymer, the ratio of the resin component in the resin solution can be increased as compared with the case where a resin solution is not used. Thus, for example, when a resin solution is used as a varnish for coating, the adjustment range of the varnish viscosity and the resin concentration can be widened. This makes it possible to adjust the smoothness of the coated surface and the thickness of the dried film. Since the structurally modified polymer is less likely to reassociate, aggregation is less likely to occur even in a resin solution. For this reason, the stability over time of the resin solution including the change in viscosity is increased, and the storage life can be extended.

When a deactivation treatment is newly performed on a resin already obtained as a solid by another method, the resin is dissolved in a solvent, and then a low molecular weight compound having a reactive functional group is added. If necessary, the mixture can be treated by heating and stirring while refluxing.

The method for synthesizing a polymer according to the present invention can prevent a side reaction occurring when a reaction solution after polymer synthesis is precipitated in a solvent. By performing the treatment after the polymerization reaction, the ratio (Mw / M) of the weight average molecular weight to the number average molecular weight measured by the gel permeation chromatography (GPC) method is obtained.
n) can be reduced. By inactivating the reaction solution after polymerizing for a predetermined time in polymer synthesis, a polymer having a constant molecular weight distribution can be obtained regardless of the synthesis lot. By modifying the structure of an existing polymer with a low molecular weight compound having a reactive functional group, the ratio (Mw / Mn) of the weight average molecular weight to the number average molecular weight of the polymer measured by the gel permeation chromatography (GPC) method is calculated. Can be smaller. By utilizing the polymer obtained according to the present invention, it is possible to improve the resin component ratio in the resin solution,
Further, the storage life of the resin solution can be improved.

[0029]

EXAMPLE 1 A solid content ratio of 23.3% in a reaction solution, a reaction time of 3 hours, precipitation in water and methanol in a 3-liter separable flask, 2452 g of sulfolane and 3-methyl-1-phenyl-3-phospholene in a separable flask. 0.86 g of 1-oxide was weighed out. A cooling tube connected to a 100 ml eggplant flask via a decompression adapter, a nitrogen suction plug, and a stirring blade were attached to a three-port separable cover, and the container was attached to a separable flask and passed through a container in an oil bath while passing nitrogen through the container.
Stirred at ° C. When the solution temperature reaches approximately 200 ° C., hexamethylene diisocyanate (Mw = 168.2) 4
5.98 g and 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride (Mw = 322.2) 70.56
g, polyester having carboxyl groups at both terminals (copolymer of adipic acid and 1,6-hexanediol, Mn = 164)
5) 387.2 g and 68.43 g of 4,4′-diphenylmethane diisocyanate (Mw = 250.3) were added, and the mixture was stirred at 200 ° C. After 3 hours, the reaction solution was cooled with ice water together with the container. When the temperature of the reaction solution dropped to about 100 ° C., half of the reaction solution was poured into 5 liters of water and the other half was poured into 5 liters of methanol and solidified. Each of the obtained resin solids was ground with a mixer together with pure water and filtered. This was dried under reduced pressure at 45 ° C.
8.6 g were obtained. Mw / Mn with resin powder precipitated in water
= 8.04 (Mw = 530,205, Mn = 65,91)
0), Mw / Mn with resin powder precipitated in methanol
= 4.59 (Mw = 289,893, Mn = 63,09)
3). Each GPC chart is shown in FIG. 1 (developing solution: DMF, flow rate: 1 ml / min, detection wavelength:
280 nm, the same applies hereinafter).

Example 2 The solid content in the reaction solution was 18.4%, and the reaction time was 2 hours and 30 hours.
Bisphenol in a 3-liter separable flask
A bistrimellitate dianhydride (Mw = 576.
5) 94.2 g of a polyester having carboxyl groups at both terminals (copolymer of adipic acid and 1,6-hexanediol,
Mn = 892) 350.0 g was weighed and sulfolane 2
587 g was poured into this. 100 via decompression adapter
A cooling tube connected to a milliliter eggplant flask, a nitrogen inlet cock, and a stirring blade were attached to a three-port separable cover and attached to the separable flask. The vessel was stirred at 170 ° C in an oil bath, and all the raw materials were dissolved.
When it became, 166.9 g of 4,4'-diphenylmethane diisocyanate (Mw = 250.3) was added. 4,
When 4'-diphenylmethane diisocyanate was dissolved, 0.9 g of 3-methyl-1-phenyl-3-phospholene 1-oxide was added, and stirring was continued. Two and a half hours later,
The reaction solution was cooled with ice water together with the container. When the temperature of the reaction solution dropped to about 100 ° C., half of the reaction solution was poured into 5 liters of water and solidified. The other half is methanol 5
The mixture was poured into a liter, stirred with a spoon, and allowed to stand at room temperature overnight. To this was added 2 liters of water to precipitate the resin. Each of the obtained resin solids was ground with a mixer together with pure water and filtered. This was dried under reduced pressure at 45 ° C. to obtain 565.2 g of the dried resin powder in total. Mw / Mn = 6.40 (Mw = 312,345, M
n = 48,784), and Mw / Mn = 3.60 (Mw = 177,588, M
n = 49,335). Each GPC chart is shown in FIG.

Example 3 The resin obtained in Example 2 by precipitation in water and methanol,
The solubility in cyclohexanone was measured with a benzyl alcohol-treated resin prepared separately. The resin obtained by precipitation in water remained undissolved at room temperature even after stirring all day and night. This was heated to 70 ° C. and stirred for 2 hours to completely dissolve. The resin obtained by precipitation in methanol was completely dissolved when stirred at room temperature for 24 hours. The resin treated with benzyl alcohol was completely dissolved by stirring at room temperature for about 3 hours.

Example 4 29.4 g of sulfolane and 3-methyl-1-phenyl-3-phospholene were placed in a 200 ml separable flask treated with benzyl alcohol at a solid content ratio of 50.0% in a reaction solution for a reaction time of 30 minutes. 0.06 g of the oxide was weighed out. A cooling tube connected to a 100-ml eggplant flask via a decompression adapter, a nitrogen suction plug, and a stirring blade were attached to a three-port separable cover. The container was attached to the separable flask and the container was placed in an oil bath at 170 ° C. while passing nitrogen through the container. And stirred. When the solution temperature reaches approximately 170 ° C., hexamethylene diisocyanate (Mw = 168.
2) 2.88 g and 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride (Mw = 322.2) 2.4
3 g was added and stirred for a while. After 20 minutes, 20.0 g of a polyester having carboxyl groups at both ends (copolymer of adipic acid and 1,6-hexanediol, Mn = 1441) was added to
4'-diphenylmethane diisocyanate (Mw = 25
0.3) 3.07 g was added and stirring was continued. 30 minutes later,
11.7 g of benzyl alcohol (Mw = 108.1) was added, and the mixture was stirred for 1 hour. The obtained reaction solution was pulverized with ice water using a mixer and filtered. The obtained resin powder was reground with a pure water with a mixer and filtered. After repeating this operation three times, it was dried at 45 ° C. under reduced pressure. As a result, 27.71 g of a dried resin powder was obtained. In the reaction solution immediately before the addition of benzyl alcohol, Mw / Mn = 11.21 (Mw = 34
8,610, Mn = 31,108), Mw / Mn = 1.74 (Mw = 31,
647, Mn = 18,209). Each G
FIG. 3 shows the PC chart.

Example 5 The solid content in the reaction mixture was 30.0%, and the reaction time was 2 hours and 30 hours.
Then, 671 g of sulfolane and 0.58 g of 3-methyl-1-phenyl-3-phospholene 1-oxide were weighed and placed in a 2-liter separable flask treated with benzyl alcohol. A cooling tube connected to a 100 ml eggplant flask via a decompression adapter, a nitrogen suction plug, and a stirring blade
Attach to a separable cover, attach to a separable flask and place the container in an oil bath while passing nitrogen through the container.
Stirred at 0 ° C. When the solution temperature reaches approximately 170 ° C., hexamethylene diisocyanate (Mw = 168.2) 2
1.9 g and 36.1 g of 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride (Mw = 322.2) were added, and the mixture was stirred. After 20 minutes, 200.0 g of a polyester having a carboxyl group at both terminals (copolymer of adipic acid and 1,6-hexanediol, Mn = 1605) and 4,4 ′
-Diphenylmethane diisocyanate (Mw = 250.
3) 29.6 g was added and stirring was continued. After 2 hours and 30 minutes, benzyl alcohol (Mw = 108.1).
9 g was added and stirred for 1 hour. The obtained reaction solution was pulverized with ice water using a mixer and filtered. The obtained resin powder was reground with a pure water with a mixer and filtered. This operation 3
After repeating this process, it was dried under reduced pressure at 45 ° C. As a result, 268.6 g of a dried resin powder was obtained. In the reaction solution immediately before the addition of benzyl alcohol, Mw / Mn = 8.69 (Mw = 3
00,051, Mn = 34,538), 1 hour after benzyl alcohol treatment, Mw / Mn = 2.83 (Mw = 7)
9,928, Mn = 28,262). Each GPC chart is shown in FIG.

Example 6 The solubility in NMP of a resin obtained in Example 5 by benzyl alcohol treatment and a resin separately prepared in small amounts and prepared by precipitation in water and methanol were measured. The resin obtained by precipitation in water hardly dissolved at room temperature. When this was heated to 150 ° C. and stirred for 2 hours,
Although only a small part was dissolved, most of it remained dissolved as a translucent gel. The resin obtained by precipitation in methanol was partially dissolved at room temperature but not completely dissolved, and was completely dissolved when heated to 70 ° C. and stirred for 1 hour. The resin obtained by benzyl alcohol treatment was completely dissolved at room temperature. The solid content ratio at the time when the viscosity of the NMP solution of the resin became 70P was determined.
2.8%, 41.0% of the resin obtained by precipitation in methanol.
%Met. When the two NMP solutions were placed in a sealed container and allowed to stand at room temperature, the benzyl alcohol-treated resin maintained a uniform solution state for at least one month, but the resin obtained by precipitation in methanol became agar-like after about two weeks. Became.
FIG. 5 shows the change over time in viscosity.

[0035]

According to the method for synthesizing the polymer of the present invention, it is possible to effectively stop the polymerization reaction, eliminate the association between the resins, improve the solubility of the obtained resin, and suppress the re-association. In polymer synthesis, if the component ratio is adjusted so that the desired average molecular weight is obtained at the stage of charging the raw materials,
The reaction end point can be defined only by time without paying attention to a change in viscosity or a change in molecular weight during the reaction. Thereafter, by performing the inactivation treatment according to the present invention, it is possible to obtain a resin solution having reduced aging of the polymer to an arbitrary level and having high stability over time. This resin solution can be used for coating and spinning as it is. further,
The resin solid content obtained by washing and purifying the resin solution has high solubility in a solvent, so that a high-concentration resin solution can be prepared.

[Brief description of the drawings]

FIG. 1 is a GPC chart. Solid content ratio in reaction liquid 2
3.3%, reaction time 3 hours, measured with resin powder obtained by precipitation in water and methanol. (Horizontal axis: retention time, vertical axis: detection ratio, the same applies hereinafter.)

FIG. 2 is a GPC chart. Solid content ratio in reaction liquid 1
8.4%, reaction time 2 hours 30 minutes, measured with resin powder obtained by precipitation in water and methanol.

FIG. 3 is a chart of GPC. Solid content ratio in reaction liquid 5
0.0%, reaction time 30 minutes, measured with the reaction liquid immediately before the benzyl alcohol treatment and the resin powder obtained after the treatment.

FIG. 4 is a chart of GPC. Solid content ratio in reaction liquid 3
0.0%, reaction time 2 hours 30 minutes, measured with the reaction liquid immediately before the benzyl alcohol treatment and the resin powder obtained by precipitation in water after the treatment.

FIG. 5 shows the change over time in the viscosity of a varnish prepared to have an initial viscosity of 70P for a resin powder obtained by precipitating a reaction solution in methanol and a resin powder obtained by precipitating the reaction solution in water after benzyl alcohol treatment. The graph shown.

Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat II (reference) // C08F 8/00 C08F 8/00 F term (reference) 4F071 AA60 AC05 AC12 AC19 AE19 BC00 4J002 CM041 EC037 EL027 EP016 EU026 EU047 EV306 HA03 HA06 4J031 CA06 CD09 CD10 4J043 PB22 PB23 PB24 PC015 QB15 QB26 QB31 QB32 QB33 QB58 QB68 RA05 RA06 RA24 RA35 SA06 SA11 SA42 SA43 SA44 SA71 SA78 SB01 TA02 TA12 TA13 TA22 TA38 TB03 UA041 UA121 UA121 UA121 UA121 UA121 UA121 UAUA UA760

Claims (5)

[Claims] A low molecular weight compound having a reactive functional group is added to a reaction solution in which a monomer is polymerized to increase the molecular weight of a polymer to around a target molecular weight, thereby modifying the remaining active group. Polymer synthesis method. 2. After the first monomer (A) and the second monomer (B) having reactivity with the first monomer (A) are reacted with each other by an equivalent defined by an intended average molecular weight to obtain a high molecular weight, A method for synthesizing a polymer, comprising adding a low molecular weight compound having a reactive functional group to a reaction solution to modify the remaining active group. 3. The monomer (A) has a functional group having a binding property of (—CO) ₂ O, —COOH, —OH, or —CH.
The OCH _2, monomer (B) is -NH ₂ as a functional capable of binding, -NCO or -CHOCH2 ₂ methods of synthesis polymers of which claim 2 has respectively. 4. A resin composition used in the method according to any one of claims 1 to 3, which comprises a reaction solution in which a low molecular weight compound having a reactive functional group is added to modify a remaining active group. 5. Production of a molded article in which a reaction solution obtained by adding a low-molecular weight compound having a reactive functional group according to any one of claims 1 to 3 to modify a remaining active group is used as a resin solution as it is to produce a molded article. Law.