JP2000219747A - Method for molding polymeric compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To effect molding by a simple operation by melting a polymeric compound having an immeasurable glass transition temperature under heating in a low-boiling high-permittivity solvent. SOLUTION: A polymeric compound which has an immeasurable glass transition temperature and a molecular weight of 300-1,000,000 is melted under heating to 50-300 deg.C in the presence of 0.1-100 pts.wt., per pt.wt. polymeric compound, solvent having a boiling point as low as 50-150 deg.C and a specific permittivity of at least 20 (20 deg.C), and the formed fluid is molded into a specified shape. It is desirable to add 0.1-100 mass %, based on the polymeric compound, chain extender such as aspartic acid, 0.05-100 mass % acid catalyst such as phosphoric acid, and 1-90 mass % molding aid such as talc. The polymeric compounds having an immeasurable glass transition temperature are exemplified by polysuccinimide polymers and copolymers, casein, collagen, and cellulose. The low-boiling high-specific-permittivity solvents are exemplified by water, formic acid, nitromethane, and acetonitrile.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for molding a polymer compound. More specifically, the present invention
The present invention relates to a method for molding a polymer compound whose glass transition temperature (Tg) cannot be measured.

[0002] The present invention also relates to a method for producing a high molecular weight polysuccinimide-based polymer and / or copolymer. More specifically, the present invention relates to a method for easily producing a polysuccinimide-based polymer and / or copolymer having a higher molecular weight than a polysuccinimide-based polymer and / or copolymer as a raw material.

[0003]

2. Description of the Related Art In general, a polymer compound can be formed into a glass state (molten state) by heating using a glass transition. However, high-molecular compounds such as proteins and polysuccinimide-based polymers and copolymers (also collectively referred to simply as “polysuccinimide-based (co) polymer” in this specification) have decomposition temperatures and glass transitions. It is considered that the temperature is very close, and when heated for forming, it is decomposed before melting, so that there is a problem that thermoforming / working through the glass transition temperature is impossible.

Among these high molecular compounds, polysuccinimide (co) polymers are precursors of biodegradable materials because the aspartic acid main chain formed by opening of the imide ring has biodegradability. It is also expected.
For example, polyaspartic acid obtained by hydrolyzing polysuccinimide is useful as a chelating agent, a scale inhibitor, a detergent builder, a dispersant, and the like.

However, as described above, polysuccinimide (co) polymer has no glass transition temperature below its decomposition temperature and has no melting point below its thermal decomposition temperature. Cannot be applied, and the molding method is very limited.
As a method for molding a polysuccinimide-based (co) polymer, for example, a method of introducing a specific copolymer component such as an aliphatic aminocarboxylic acid in order to mold a polysuccinimide-based (co) polymer (Japanese Unexamined Patent Publication No. 165,446), a method of reacting and adding a monoamine compound to a polysuccinimide-based (co) polymer, melting it by heating, and modifying the polymer to facilitate molding (JP-A-10-139,880).
And a method of compatibilizing a polysuccinimide (co) polymer with other polymer components to obtain a moldable composition (JP-A-10-168,326), and the like.
In addition to the above-mentioned molding method, a method generally used as a method for directly molding a polysuccinimide-based (co) polymer is to convert a polysuccinimide-based (co) polymer into N, N-dimethylformamide (DMF). ), And a method of dissolving in an organic solvent and molding (JP-A-9-3214).

However, of the above methods,
-165,446, JP-A-10-139,880
The method of molding a polysuccinimide (co) polymer disclosed in Japanese Patent Application Laid-Open No. 10-168326 and Japanese Patent Application Laid-Open No. H10-168326 discloses a process for modifying a polysuccinimide (co) polymer, Since a step of introducing a specific copolymer component into the main chain, a step of adding a monoamine, and a step of compatibilizing with other polymer components are required, the operation becomes complicated, and considering mass production, it is not industrially preferable. . In addition, the method of dissolving in an organic solvent such as DMF is also safe because the organic solvent which can be used for dissolving the polysuccinimide (co) polymer has a high boiling point and a high affinity with the polysuccinimide (co) polymer. Although there is a strong desire to remove the organic solvent in consideration of the properties, there is a problem that it is difficult to remove the organic solvent from the target molded product after molding.

Therefore, there is a strong demand for a method of easily obtaining a polysuccinimide-based (co) polymer containing no organic solvent.

On the other hand, generally available polysuccinimide (co) polymers have a molecular weight of 3000 to 700.
Since it is relatively low at about 0, usable applications are limited, and even if it can be used, not so high performance is obtained.

For this reason, various methods for producing a polysuccinimide (co) polymer having a higher molecular weight have been attempted. For example, a method in which aspartic acid is polycondensed in the presence of a specific amount of an acid catalyst such as phosphoric acid or sulfuric acid (Japanese Patent Application Laid-Open No. 8-239,468), asparagine is added to a polyfunctional polymer such as polyaspartic acid (salt). A method of obtaining a polysuccinimide (co) polymer by graft-polymerizing an amino acid such as acid or glutamic acid in an aliphatic sulfur-containing organic solvent such as sulfolane or dimethyl sulfone in the presence of a catalyst such as phosphoric acid 235,372), a method of obtaining a high-molecular-weight polysuccinimide (co) polymer by polycondensation of a reaction product of aspartic acid, maleamic acid, maleic acid and ammonia in the presence of a phosphite compound (Japanese Patent Application Laid-open No. Japanese Unexamined Patent Publication No. 9-278,883), adding a predetermined amount of a catalyst and a polymerization accelerator to a polymerization system, and polymerizing under stirring in a substantially solid state to produce a high molecular weight polysuccinimide. (Japanese Patent Application Laid-Open No. 9-302,088) and a method for obtaining a chain-lengthening agent in a polycondensation system of a reaction product of aspartic acid, maleamic acid, maleic acid and ammonia. A method of adding a compound having two or more oxazoline structures and performing polycondensation to obtain a polysuccinimide-based (co) polymer (Japanese Patent Application Laid-Open No. H10-147,644) is known.
In addition to the above method, JP-A-8-302,009 discloses that polysuccinimide is heat-treated in an aqueous medium having a pH of 6 or less, preferably water, at a temperature of 50 ° C or more and less than 150 ° C. A method for treating polysuccinimide is disclosed.

However, Japanese Patent Application Laid-Open No. 8-239,4 discloses
No. 68, JP-A-9-235,372, JP-A-9-278,883, JP-A-9-302,088
In the poly (condensation) reaction according to the method disclosed in Japanese Patent Application Laid-Open No. 10-147,644 and Japanese Patent Application Laid-Open No. 10-147,644, an industrial production method is not always necessary because the steps are complicated and the catalyst used is expensive. Was not satisfactory. In addition to the above-mentioned drawbacks, in the method according to the above-mentioned publication, since it is necessary to perform heating in an organic solvent, this organic solvent remains in the produced polysuccinimide-based (co) polymer. Is not desirable in terms of safety, it is desirable to be completely removed. However, since the boiling point is high and the affinity with polysuccinimide (co) polymer is high, it is very difficult to remove the organic solvent. Yes,
There is also a problem that usable applications are limited.

Further, among the above methods, Japanese Patent Laid-Open No.
The method disclosed in Japanese Patent No. 2,009 uses an aqueous medium having a pH of 6 or less, such as water, instead of an organic solvent, and is preferable in terms of the safety of the product, but uses, for example, the same starting material. Comparing the weight average molecular weights (Mw) of sodium polyaspartate produced in Example 5 and Comparative Example 2 and in Example 6 and Comparative Example 4, respectively, it is found that in Example 5, the weight average molecular weight (Mw) is 10,000. 14,0 for 2
Comparative Example 4 is 5,000 compared to 2,500 in Example 6 and 5,000 in Comparative Example 4. Although the same raw material is used in these experiments, it is disclosed in JP-A-8-302,009. When produced by the disclosed method, there is a problem that the weight average molecular weight of the product is reduced, and high molecular weight may not be achieved.

[0012] For this reason, a method for producing a high-molecular-weight polysuccinimide-based (co) polymer with a simple process and at low cost has been highly desired, but has not yet existed.

[0013]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to form a polymer compound such as a polysuccinimide (co) polymer or protein which cannot be measured for its glass transition temperature (Tg) by a simple operation. To provide a way to do it.

Another object of the present invention is to provide a method for producing a polymer compound such as polysuccinimide-based (co) polymer or protein which cannot be measured for its glass transition temperature (Tg) by a simple operation without using an organic solvent. It is to provide a method that can be molded.

Another object of the present invention is to provide a simple method for obtaining a high-molecular-weight polysuccinimide (co) polymer by increasing the molecular weight of the polysuccinimide (co) polymer.

[0016]

Means for Solving the Problems The present inventors have conducted intensive studies in order to achieve the above objects, and as a result, have found that the glass transition of a polysuccinimide (co) polymer or the like which does not melt at normal temperature and normal pressure. When a polymer compound whose temperature cannot be measured is heated in the presence of a solvent having a low boiling point and a high relative dielectric constant such as water, fluidization without substantial decomposition even at a wide reaction temperature of 90 to 300 ° C. ( When the polysuccinimide-based (co) polymer in such a fluidized state is heated, the material is substantially in a molten state (in the present specification, the substance in such a state is also simply referred to as “fluid”). It has been found that the polymer can be melted without any specific decomposition and the polymer compound can be easily produced as a target molded product in such a molten state.

In addition to the above findings, the present inventors have
In order to further achieve the above objects, as a result of diligent studies, the above-mentioned fluidized polysuccinimide-based (co) polymer was mixed with a chain extender and a solvent having a low boiling point and a high dielectric constant. It has also been found that when heated below, the molecular weight of the raw material polysuccinimide-based (co) polymer can be easily increased. Based on the above findings, the present invention has been completed.

That is, the objects of the present invention are as follows:
(10).

(1) Molding of a high molecular compound which comprises heating and melting a high molecular compound whose glass transition temperature (Tg) cannot be measured in the presence of a solvent having a low boiling point and a high relative dielectric constant. Method.

(2) The method according to (1), wherein the polymer compound is a polysuccinimide-based polymer and / or copolymer.

(3) The method according to (1) or (2), wherein the solvent has a boiling point of 50 to 150 ° C. and a relative dielectric constant at 20 ° C. of 20 or more.

(4) The method according to (3), wherein the solvent is water.

(5) The method according to any one of (1) to (4), wherein the heating and melting are performed in the presence of a chain extender.

(6) The method according to any one of (1) to (5), wherein the heating and melting are performed in the presence of an acid catalyst.

(7) A high molecular weight polysuccinimide based on heating a polysuccinimide polymer and / or a polysuccinimide copolymer in the presence of a chain extender and a solvent having a low boiling point and a high relative dielectric constant. A method for producing a polymer and / or a polysuccinimide-based copolymer.

(8) The method according to (7), wherein the solvent has a boiling point of 50 to 150 ° C. and a relative dielectric constant at 20 ° C. of 20 or more.

(9) The method according to (8), wherein the solvent is water.

(10) The method according to any one of (7) to (9), wherein the heating is further performed in the presence of an acid catalyst.

[0029]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.

According to the first concept, the present invention relates to a method for producing a polymer compound whose glass transition temperature (Tg) cannot be measured (hereinafter also simply referred to as “polymer compound”) having a low boiling point and a high relative dielectric constant. An object of the present invention is to provide a method for molding a polymer compound, which comprises heating and melting and molding in the presence of a solvent.

The raw materials used in the present invention have a glass transition temperature (Tg) which cannot be measured, in other words, the glass transition temperature is very close to the decomposition temperature or the glass transition temperature itself does not exist. It is a molecular compound. Examples of such high molecular compounds include casein, collagen, gelatin, gluten, keratin, soy protein, cellulose and proteins such as quinufibroin, and polysuccinimide-based polymers and copolymers. Of these, considering the wide range of applications and excellent properties such as biodegradability,
Cellulose and polysuccinimide polymers and copolymers, particularly polysuccinimide polymers and copolymers, are preferably used in the present invention.

In the present invention, the polysuccinimide (co) polymer preferably used as a raw material has at least the following formula:

[0033]

Embedded image

There is no particular limitation as long as it has a succinimide ring represented by the following formula (I) as a repeating unit, and includes all those generally called polysuccinimide (co) polymers. Specific examples include polysuccinimide, a succinimide copolymer having a repeating unit other than a succinimide ring, and a polysuccinimide derivative in which the succinimide ring of these polymers or copolymers is appropriately opened or modified. In this case, the repeating unit in the polysuccinimide-based copolymer having a repeating unit other than a succinimide ring is not particularly limited as long as it has an amino group, a functional group capable of reacting with a carboxyl group or two or more salts thereof. For example, amino acids, hydroxycarboxylic acids, hydroxycarboxylic acid amides, ammonium salts of hydroxycarboxylic acids, aminocarboxylic acids, aminocarboxylic acid amides, ammonium salts of aminocarboxylic acids, dicarboxylic acids, ammonium salts of dicarboxylic acids, and dicarboxylic acid amides Is mentioned.
Of these, amino acids, hydroxycarboxylic acids and aminocarboxylic acids are preferably used as repeating units. In the polysuccinimide-based copolymer, these repeating units may contain only one kind of component, or may contain two or more kinds of components in a block or random mixture. Furthermore, the content of the repeating unit other than the succinimide ring when using the polysuccinimide-based copolymer is not particularly limited, but is usually 50% based on the entire polysuccinimide-based copolymer.
Or less, preferably 45% or less. Of the above-mentioned polysuccinimide (co) polymers, polysuccinimide is preferably used in the present invention. In the present invention, the polysuccinimide-based (co) polymer used as a raw material may be used alone or in the form of a mixture of two or more polysuccinimide-based polymers and / or a polysuccinimide-based copolymer. Alternatively, they may be present in a form further containing other components.

In the present invention, the molecular weight of the polysuccinimide (co) polymer used as a raw material is not particularly limited, and a polysuccinimide (co) polymer having any molecular weight can be used. . Specifically, the lower limit of the molecular weight of the polysuccinimide (co) polymer is usually 300, preferably 500, more preferably 1,000, and the upper limit of the molecular weight of the polysuccinimide (co) polymer. Is usually 1,000,000
00, preferably 500,000, more preferably 10
And the molecular weight range of the polysuccinimide (co) polymer is usually from 300 to 1,000,000.
0, preferably 500 to 500,000, more preferably 1,000 to 100,000. Also, 3,000
Since a polysuccinimide (co) polymer having a molecular weight of about 0 to 7,000 can be produced or generally available, such a polysuccinimide (co) polymer may be used as it is in the present invention. . In addition, the molecular weight described in this specification is a value measured by the same method as the method described in the following Examples.

In the present invention, the method for preparing the polysuccinimide (co) polymer is not particularly limited, and for example, by heating L-aspartic acid in the presence or absence of phosphoric acid (see No.48-20,
No. 638, and P. Neri et al., J. Med. Chem., 16, 89.
3 (1973)), and can be produced by a conventionally known method using aspartic acid, ammonium (poly) ammonium aspartate, ammonium maleate or maleic amide as a starting material.

The molding method of the present invention essentially requires that a polymer compound whose glass transition temperature cannot be measured is heated and melted in the presence of a solvent having a low boiling point and a high relative dielectric constant to form the compound. At this time, as described above, by heating in the presence of a solvent having a low boiling point and a high relative dielectric constant, the raw material polymer compound such as a polysuccinimide (co) polymer is fluidized to form a fluid. . In the present specification, the terms "fluidization" and "fluid" mean that the raw material polymer compound is partially dissolved in a solvent having a low boiling point and a high relative dielectric constant and partially melts itself, It means that a uniform viscous body (a syrup state) is formed as a whole and that the state is as described above.

The solvent having a low boiling point and a high dielectric constant used in the present invention can be used without any particular limitation as long as it falls under the above definition. The lower limit of the boiling point is preferably 5
It is 0 ° C, more preferably 60 ° C, most preferably 70 ° C, and the upper limit of the boiling point of the solvent is preferably 150 ° C, more preferably 145 ° C, most preferably 120 ° C. The preferred range of the boiling point of the solvent having a low boiling point and a high relative permittivity is 50 to 150 ° C., more preferably 60 to 14 ° C.
5 ° C, most preferably 70-120 ° C.

The relative permittivity at 20 ° C. of the solvent preferably used in the present invention is preferably 20 or more, more preferably 25 or more, and most preferably 30 or more. In this case, if the boiling point of the solvent is lower than 50 ° C., the polysuccinimide (co) polymer as a raw material is not sufficiently fluidized in the solvent, which is not preferable. On the other hand, if the boiling point of the solvent exceeds 150 ° C., it is difficult to remove the solvent remaining after the reaction, which is also not preferable. In addition, 20 of the solvent
If the relative dielectric constant at ° C is less than 20, the affinity between the solvent and the polysuccinimide-based (co) polymer as a material is lowered, and the uniformity during the reaction is remarkably reduced, which is not preferable.

Specific examples of such a solvent having a low boiling point and a high dielectric constant that can be used in the present invention include water, 2,2
6-difluoropyridine, formic acid, nitromethane, acetonitrile, acrylonitrile, 2-fluoropyridine,
Examples include methanol, ethanol, isopropyl alcohol, and acetone. Of these, water and formic acid are preferably used as the solvent, and water is particularly preferably used in view of the fact that no special equipment is required for drying. In the present invention, the above-mentioned solvents may be used alone or in a mixed or dispersed state of two or more.

Alternatively, in the present invention, another solvent having a boiling point and / or a relative dielectric constant outside the preferred range according to the present invention is mixed or dispersed with the above-exemplified solvent so as to obtain a desired boiling point and a relative dielectric constant. The solvent thus obtained may be used as a solvent having a low boiling point and a high dielectric constant in the present invention. For example, in the case of a solvent having a boiling point of 50 to 150 ° C. but a relative dielectric constant of less than 20, the above-mentioned low boiling point (50 to 150 ° C.) and high relative dielectric constant ( 20 or more) or by dispersing in such a solvent. At this time, other solvents having a boiling point and / or a relative dielectric constant outside the preferred range according to the present invention include hexane, toluene and ethyl acetate.

In the present invention, the amount of the solvent having a low boiling point and a high relative dielectric constant is not particularly limited as long as the raw material polymer compound is fluidized. The lower limit of the amount of the solvent used for the dielectric constant is usually 0.1, preferably 0.1, by weight ratio with respect to the polymer compound 1.
2, more preferably 0.3, and the upper limit of the amount of the solvent having a low boiling point and a high dielectric constant is usually 100, preferably 50, Preferably it is 20, most preferably 10. In addition, the range of the amount of the solvent having a low boiling point and a high relative permittivity is usually 0.1 to 100,
Preferably 0.2 to 50, more preferably 0.3 to 20
It is. At this time, if the amount of the solvent having a low boiling point and a high relative dielectric constant is less than 0.1, the raw material polymer compound is not sufficiently fluidized, and the uniformity of the system cannot be obtained.
On the other hand, if the amount of the solvent having a low boiling point and a high relative dielectric constant exceeds 100, the starting polymer compound cannot be sufficiently increased in molecular weight, which is uneconomical and is not preferable.
Further, the lower limit of the amount of water used when the solvent having a low boiling point and high relative permittivity is water is preferably 0.1, more preferably 0.2, by weight relative to the polymer compound 1. The upper limit of the amount of water to be used is preferably 10, more preferably 2, and most preferably 1.5, by weight relative to the polymer compound 1.

The molding method of the present invention is characterized in that a polysuccinimide (co) polymer is heated in the presence of a solvent having a low boiling point and a high relative dielectric constant to make it into a fluidized state so as to be easily molded. However, the heating temperature at that time depends on the type of the starting polymer compound used and the type of solvent having a low boiling point and a high relative dielectric constant, and is not particularly limited as long as the starting polymer compound forms a fluid. The lower limit of the heating temperature is usually
50 ° C., preferably 60 ° C., more preferably 70 ° C., and most preferably 80 ° C., and the upper limit of the heating temperature is usually 300 ° C., preferably 250 ° C., more preferably 210 ° C., and most preferably. Is 200 ° C. In addition, the range of the heating temperature is usually 50 to 300 ° C.,
Preferably 60-250 ° C, more preferably 70-21.
0 ° C, and most preferably 80-200 ° C. At this time, if the heating temperature is lower than 50 ° C., the raw material polymer compound is not sufficiently fluidized, and a part thereof is dispersed as a powder, and the reaction does not easily proceed, and a uniform target product is obtained. Not so desirable. On the other hand, when the heating temperature is 300
If the temperature exceeds ℃, the raw material polymer compound is decomposed, the thermal efficiency is poor, and it is uneconomical, which is also not preferable. The reaction (heating / fluidization) time is the shortest,
Usually 1 minute, preferably 5 minutes, the longest, usually 72 hours, preferably 48 hours. When the polymer compound is a polysuccinimide (co) polymer and the solvent having a low boiling point and a high dielectric constant is water, the lower limit of the heating temperature is usually 100 ° C., preferably 110 ° C., more preferably Is 130 ° C., and the upper limit of the heating temperature is usually 2
50 ° C, preferably 210 ° C, more preferably 180 ° C
It is. Further, the range of the heating temperature when water is used as a solvent having a low boiling point and a high relative dielectric constant is usually 100 to 2 times.
50C, preferably 110-210C, and more preferably 130-180C. Furthermore, the heating time is
The shortest time is usually 1 minute, preferably 5 minutes, and the longest time is usually 72 hours, preferably 48 hours.

In the method of the present invention, other reaction conditions vary depending on the starting polymer compound used and the type of solvent having a low boiling point and a high dielectric constant, and are appropriately selected. For example, the reaction may be carried out under any of pressure, normal pressure or reduced pressure, but it is desirable to keep the temperature and pressure during the reaction constant in consideration of stabilizing the quality of the product. . It is more desirable to set the reaction temperature of the reaction system and the reflux temperature of the solvent at the pressure.

In the present invention, in order to prevent a decrease in the molecular weight of the starting polymer compound, in particular, a polysuccinimide (co) polymer, the heating and melting of the polymer compound are carried out by the presence of a chain extender and / or an acid catalyst. It is preferable to carry out below.
In this specification, the term “chain extender” has a functional group capable of reacting with an amino group and / or a carboxyl group and reacts with a polymer compound such as a polysuccinimide (co) polymer. Means an organic compound capable of producing a repeating unit.

The chain extender used in the present invention is not particularly limited as long as it has two or more functional groups capable of reacting with an amino group or a carboxyl group or a salt thereof. The same ones as known chain extenders can be used. Specifically, dicyclohexylcarbodiimide, amino acid, hydroxycarboxylic acid, hydroxycarboxylic acid amide, ammonium salt of hydroxycarboxylic acid, aminocarboxylic acid, aminocarboxylic acid amide, ammonium salt of aminocarboxylic acid, dicarboxylic acid, ammonium salt of dicarboxylic acid , Dicarboxylic amide, monoammonium aspartate, diammonium aspartate, monoammonium aspartate, diammonium aspartate, monoammonium maleate, diammonium maleate, maleic monoamide, maleic diamide, monoammonium fumarate, diammonium fumarate , Fumaric acid monoamide, fumaric acid diamide, polysuccinimide, polyaspartic acid, and the like. Of these, polysuccinimide and aspartic acid are preferably used.

The acid catalyst used in the present invention is not particularly limited, and conventionally known acid catalysts can be used. Specific examples thereof include sulfuric acid, phosphoric acid, boric acid, and paratoluenesulfonic acid. Phosphite, phosphite and the like; preferably phosphoric acid and boric acid.

In the present invention, the amount of the chain extender used when the chain extender is present in the step of heating and melting the starting polymer compound depends on the type and amount of the starting material, solvent and acid catalyst used. It can be appropriately determined according to the conditions. For example,
When the polymer compound is a polysuccinimide-based (co) polymer, the lower limit of the amount of the chain extender used is preferably 0.1% with respect to the polysuccinimide-based (co) polymer.
1% by mass, more preferably 0.5% by mass;
The upper limit is an amount that is preferably 100% by mass, more preferably 50% by mass, based on the polysuccinimide (co) polymer. In this case, the range of the amount of the chain extender used is preferably 0.1 to 100% by mass, more preferably 0.5 to 50% by mass, based on the polysuccinimide (co) polymer. .

Further, in the present invention, the amount of the acid catalyst used when the acid catalyst is present in the heating / melting step of the starting polymer compound is also determined by the amount of the starting material used, the type and amount of the solvent and the chain extender, etc. Can be appropriately determined according to the conditions. For example, when the polymer compound is a polysuccinimide-based (co) polymer, the lower limit of the amount of the acid catalyst to be used is preferably 0.1% with respect to the polysuccinimide-based (co) polymer.
It is preferably 0.05% by mass, more preferably 0.1% by mass, and the upper limit thereof is preferably 100% by mass, more preferably 50% by mass, based on the polysuccinimide-based (co) polymer.
It is an amount such that it becomes% by mass. Further, the range of the amount of the acid catalyst used is, based on the polysuccinimide-based (co)
Preferably it is 0.05 to 100% by mass, more preferably 0.1 to 50% by mass. The time at which the chain extender or the acid catalyst is added to the starting polymer compound is not particularly limited, and the chain extender or the acid catalyst may be added at once with the polymer compound or may be added at once to the polymer compound. You may add sequentially.

In the present invention, the polymer compound may be heated and melted together with another molding aid. Other molding aids that can be used at this time include inorganic fillers such as zeolite, talc, glass beads, magnesium carbonate, calcium carbonate, silica, alumina and clay; polyethylene succinate, polybutylene succinate, polyhydroxybutyric acid And organic fillers such as polylactic acid and polyglutamic acid; and organic acid metal salts such as magnesium stearate. In addition, the amount of the molding aid when another molding aid is present can be appropriately determined according to the type and amount of the raw materials, the solvent, the chain extender and the acid catalyst to be used. For example, when the polymer compound is a polysuccinimide-based (co) polymer, the amount of the other molding aid added is
The lower limit is preferably 1% by mass, more preferably 3% by mass, and most preferably 5% by mass, based on the polysuccinimide (co) polymer, and the upper limit is the polysuccinimide (co) polymer. Preferably 9 for the polymer
The amount is 0% by mass, more preferably 80% by mass, and most preferably 50% by mass. The range of the addition amount of the other molding aid is preferably 1 to 90% by mass, more preferably 3 to 80% by mass, and most preferably 5 to 50% by mass based on the polysuccinimide (co) polymer. %. The timing at which the other molding aid is added to the raw material polymer compound is not particularly limited, and may be added all at once with the other molding aid or at once in the polymer compound. Alternatively, they may be added sequentially.

In this manner, heating and
Since the molten polymer compound is in a fluidized state, it can be easily formed into a desired shape according to a known molding method, for example, extrusion molding, cast molding, vacuum molding, sheet forming, or the like. The molded product has high safety and the desired properties of the product are effective because the raw material polymer compound, especially polysuccinimide (co) polymer, does not decompose or lose its molecular weight during the heating and melting process. Is maintained. Further, the shape of the molded product obtained by the method of the present invention is not particularly limited, and is appropriately selected depending on the intended use.

According to a second concept, the present invention provides a method for heating a polysuccinimide-based polymer and / or a polysuccinimide-based copolymer in the presence of a chain extender and a solvent having a low boiling point and a high dielectric constant. The present invention provides a method for producing a high molecular weight polysuccinimide-based polymer and / or a polysuccinimide-based copolymer comprising:

In the above concept, the definitions of “polysuccinimide (co) polymer”, “chain extender” and “solvent having a low boiling point and a high dielectric constant” are the same as those in the first concept. is there.

In the production method of the second concept, a polysuccinimide (co) polymer is heated and fluidized in the presence of a solvent having a low boiling point and a high relative dielectric constant, and the poly (succinimide) is polymerized with a chain extender. The succinimide (co) polymer is characterized in that it has a high molecular weight, and the heating temperature at that time depends on the raw material polysuccinimide (co) polymer, chain extender, low boiling point and high relative dielectric constant. There is no particular limitation as long as the temperature is such that the raw material polysuccinimide-based (co) polymer can form a fluid. The lower limit of the heating temperature is usually 50 ° C, preferably 60 ° C, more preferably 70 ° C, and the upper limit of the heating temperature is usually 30 ° C.
0 ° C., preferably 250 ° C., more preferably 210 ° C. The range of the heating temperature is usually 50 to 300.
° C, preferably 60 to 250 ° C, more preferably 70 to 250 ° C.
210 ° C. At this time, if the heating temperature is lower than 50 ° C., the raw material polysuccinimide-based (co) polymer does not sufficiently fluidize, and a part thereof is dispersed as a powder, and the chain extender is sufficiently polysuccinimide-based ( Does not act on the (co) polymer,
Sufficient high molecular weight cannot be obtained. On the other hand, when the heating temperature exceeds 300 ° C., the raw material polysuccinimide-based (co) polymer is decomposed, and the polysuccinimide-based (co) polymer also cannot be increased in molecular weight. The heating time also varies depending on the conditions such as the raw material polysuccinimide (co) polymer, the type of the chain extender, the solvent having a low boiling point and the high dielectric constant, and the heating temperature. However, the heating time is usually 1 minute, preferably 5 minutes, and the upper limit of the heating time is usually 72 hours, preferably 48 hours.

In the method of the present invention, other reaction conditions vary depending on the raw material polysuccinimide-based (co) polymer and the type of solvent having a low boiling point and a high dielectric constant, and are appropriately selected. For example, the reaction may be carried out under any of the following conditions: increased pressure, normal pressure or reduced pressure.
In view of stabilizing the quality of the product, it is desirable to keep the temperature and pressure during the reaction constant. It is more desirable to set the reaction temperature of the reaction system and the reflux temperature of the solvent at the pressure.

In the present invention, it is preferable to further heat the polysuccinimide-based (co) polymer in the presence of an acid catalyst in order to promote the increase in the molecular weight of the starting polysuccinimide-based (co) polymer.

The acid catalyst that can be used at this time is not particularly limited, and a conventionally known acid catalyst can be used. Specifically, sulfuric acid, phosphoric acid, boric acid, p-toluenesulfonic acid, phosphorous acid, Phosphoric acid esters and the like; preferably phosphoric acid and boric acid. The amount of the acid catalyst to be used can be appropriately determined according to the type and amount of the solvent and the chain extender to be used, the reaction conditions, and the like. ) For polymers,
It is preferably 0.05% by mass, more preferably 0.1% by mass, and the upper limit of the amount of the acid catalyst used is preferably 50% by mass, more preferably 50% by mass, based on the polysuccinimide (co) polymer. Is 40% by mass. The range of the amount of the acid catalyst used is preferably 0.05 to 50% by mass, more preferably 0.1 to 40% by mass, based on the polysuccinimide-based (co) polymer. The timing of adding the acid catalyst to the raw material polysuccinimide (co) polymer is as follows:
There is no particular limitation, and they may be added together with the polysuccinimide-based (co) polymer, or may be added all at once or sequentially to the polysuccinimide-based (co) polymer.

According to such a method, it is possible to achieve a high molecular weight polysuccinimide (co) polymer without using an organic solvent and by a simple operation.

The high-molecular-weight polysuccinimide-based (co) polymer thus produced can be used for various purposes, for example, a water-absorbing resin (material), a detergent, a builder for a detergent, a scale, etc. Inhibitors, chelating agents, humectants,
It can be used as a dispersant and an additive for fertilizers, or as a raw material thereof. More specifically, the water-absorbing resin (material) is disclosed in JP-A-11-5840,
JP-A-1-5838, JP-A-11-1559, JP-A-11-1557, JP-A-10-292044
And polyisocyanimide (co) polymers produced by the production method of the present invention by known methods such as JP-A-10-511423.

Furthermore, the high molecular weight polysuccinimide (co) polymer of the present invention becomes a biodegradable polyaspartic acid when hydrolyzed by adding an alkali. It also has the advantage of being particularly useful as a conductive resin material.

[0061]

The present invention will now be described more specifically with reference to examples.

The molecular weight was measured using gel permeation chromatography (GPC) under the following conditions. Also,
The calibration curve is for Sun-Entific Polymer Products
(Scientific Polymer Product) using polyethylene glycol standard. Regarding the molecular weight of each sample, all samples were relatively monodisperse (Mw / M
n = 2), so the peak top molecular weight was adopted as the molecular weight.

[0063] <Molecular weight measurement method> Detector: RI Column: Shodex Ohpak KF-G Shodex Ohpak SB-805HQ Shodex Ohpak KB-803 Shodex Ohpak KB-803 Shodex Ohpak KB-802.5 Carrier: NaH ₂ PO ₄ · 2H ₂ O 15.6 g NaCl 11.7 g Water 1000.0 g pH 7.0 Flow rate: 1.0 ml / min Temperature: 40 ° C. Preparation Example 1 245 g of maleic anhydride and 500 g of water were put into an eggplant-shaped flask and dissolved. Add 25% ammonia water 170
g was slowly dropped so as not to bump. When uniform, turn the solution on a rotary evaporator to an oil bath temperature of 10
The mixture was concentrated under reduced pressure while heating at 0 ° C. until crystals were deposited. The obtained monoammonium maleate was placed on a stainless steel pad, and heated at 180 ° C. for 3 hours using a hot air drier. After cooling, polysuccinimide with a molecular weight of 6720 was obtained.

Preparation Example 2 1 kg of L-aspartic acid was placed in a stainless steel pad,
This was further filled with 1 kg of water. The mixture was heated at 205 ° C. for 18 hours with a hot air drier and then cooled to obtain polysuccinimide. The molecular weight of the polysuccinimide thus obtained was 8,960.

Preparation Example 3 122.5 g of maleic anhydride and 250 g of water were placed in an eggplant-shaped flask and dissolved. 25% ammonia water 85
g was slowly dropped so as not to bump. When the solution becomes uniform, use a rotary evaporator to cool the solution to an oil bath temperature of 100 ° C.
While heating at, the mixture was concentrated under reduced pressure until crystals precipitated. The obtained monoammonium maleate was put on a stainless steel pad, and heated at 185 ° C. for 2.5 hours using a hot air drier. After cooling, polysuccinimide with a molecular weight of 3950 was obtained.

Example 1 10 g of the polysuccinimide powder obtained in Preparation Example 1 and 6 g of water were placed in an eggplant-shaped flask and heated on a water bath at 130 ° C., and after about 6 minutes, the system was uniformly dissolved. As a result, a uniform polysuccinimide fluid was obtained. Then, after pouring this polysuccinimide fluid onto a stainless steel pad covered with a Teflon sheet,
Time, completely remove the water by hot air drying,
A sheet-like molded product having a thickness of about 3 mm was obtained.

When the sheet-like molded product of polysuccinimide thus obtained was weighed, it was 6 g, and no change in the weight of the raw material polysuccinimide was observed. Therefore, it was considered that decomposition of polysuccinimide did not occur. Is done.

Example 2 10 g of the polysuccinimide powder obtained in Preparation Example 1 and 20 g of water were placed in an eggplant-shaped flask and heated on a water bath at 130 ° C., and after about 12 minutes, the system was uniformly dissolved. As a result, a uniform polysuccinimide fluid was obtained.
Next, a small amount (about 10 g) of water was expelled from the polysuccinimide fluid by blowing air over the fluid surface, and the viscosity was adjusted to a moderate level (about 5 Pa · sec). Further, a sheet-like molded product having a thickness of about 3 mm was obtained in the same manner as in Example 1, except that the polysuccinimide fluid whose viscosity was appropriately adjusted was used instead.

When the sheet-like molded product of polysuccinimide thus obtained was weighed, it was 10 g,
Since no change in the weight of the raw material polysuccinimide was observed, it is considered that the decomposition of the polysuccinimide did not occur.

Example 3 10 g of the polysuccinimide powder obtained in Preparation Example 1 and 10 g of water were placed in an eggplant-shaped flask and heated on a water bath at 130 ° C., and after about 10 minutes, the system was uniformly dissolved. As a result, a uniform polysuccinimide fluid was obtained.
Next, by sending argon gas to the fluid surface,
A small amount (about 5 g) of water was expelled from the polysuccinimide fluid, and the viscosity was adjusted moderately (about 10 Pa · sec). Further, the procedure of Example 1 was repeated except that the polysuccinimide fluid whose viscosity was appropriately adjusted was used instead.
In the same manner as in the above, a sheet-like molded product having a thickness of about 3 mm was obtained.

When the sheet-like molded product of polysuccinimide thus obtained was weighed, it was 10 g,
Since no change in the weight of the raw material polysuccinimide was observed, it is considered that the decomposition of the polysuccinimide did not occur.

Example 4 10 g of the polysuccinimide powder obtained in Preparation Example 1 and 5 g of water were placed in an eggplant-shaped flask and heated on a water bath at 130 ° C., and after about 4 minutes, the system was uniformly dissolved. As a result, a uniform polysuccinimide fluid was obtained. Next, a small amount (about 2 g) of water was expelled from the polysuccinimide fluid by sending nitrogen gas to the fluid surface, and the viscosity was adjusted to a moderate level (about 50 Pa · sec). Further, a sheet-like molded product having a thickness of about 3 mm was obtained in the same manner as in Example 1, except that the polysuccinimide fluid whose viscosity was appropriately adjusted was used instead.

When the sheet-like molded product of polysuccinimide thus obtained was weighed, it was 10 g,
Since no change in the weight of the raw material polysuccinimide was observed, it is considered that the decomposition of the polysuccinimide did not occur.

Example 5 50 g of the polysuccinimide powder and 50 g of water obtained in Preparation Example 1 were placed in an eggplant-shaped flask. After 5 days, the polysuccinimide was fluidized. The polysuccinimide fluid was poured into a stainless steel pad, and dried at 160 ° C. for 3 hours using a hot air drier.

The molecular weight of the thus obtained polysuccinimide having a high molecular weight was 7148 as measured by the above method.

Example 6 50 g of the polysuccinimide powder obtained in Preparation Example 1, 50 g of water and 5 g of maleic acid monoamide as a chain extender were placed in an eggplant-shaped flask. After 5 minutes, the polysuccinimide was fluidized. The polysuccinimide fluid was poured into a stainless steel pad, and dried at 160 ° C. for 3 hours using a hot air drier.

The molecular weight of the high-molecular-weight polysuccinimide thus obtained was measured to be 7332 by the above method.

Example 7 30 g of the polysuccinimide powder obtained in Preparation Example 1, 30 g of water and 3 g of phosphoric acid as an acid catalyst were placed in an eggplant-shaped flask. After 5 days, the polysuccinimide was fluidized. After pouring the polysuccinimide fluid into a stainless steel pad, the hot air drier was used at a temperature of 160 ° C. for 3 hours.
Dried.

The molecular weight of the thus obtained polysuccinimide having a high molecular weight was determined to be 7,405 by the above method.

Example 8 30 g of polysuccinimide powder obtained in Preparation Example 1, 30 g of water, maleic acid monoamide 10 as a chain extender
g and 3 g of phosphoric acid as an acid catalyst were placed in an eggplant-shaped flask, and polysuccinimide was fluidized after 5 hours. The polysuccinimide fluid was poured into a stainless steel pad, and dried at 160 ° C. for 3 hours using a hot air drier.

The molecular weight of the high molecular weight polysuccinimide thus obtained was measured by the above-mentioned method and found to be 8509.

Example 9 A slurry obtained by thoroughly mixing 30 g of the polysuccinimide powder obtained in Preparation Example 3 and 20 g of water was placed in a 30 ml Labo Plastomill (manufactured by Toyo Seiki Seisaku-Sho, Ltd.) and stirred (rotor rotation speed: 50 rpm). The reaction was performed at 260 ° C. for 4 hours. The molecular weight of the obtained product was 4290.

Example 10 A slurry obtained by thoroughly mixing 20 g of the polysuccinimide powder obtained in Preparation Example 3, 15 g of water, 5 g of L-aspartic acid as a chain extender, and 5 g of an 85% aqueous phosphoric acid solution as an acid catalyst was used in a volume of 30 ml. Into a Labo Plast Mill (manufactured by Toyo Seiki Seisaku-sho, Ltd.) and agitated (rotor rotation speed 50 rpm)
The reaction was carried out at 230 ° C. for 0.5 hour. The molecular weight of the obtained product was 4620.

Comparative Example 1 5 g of the polysuccinimide powder obtained in Preparation Example 2 was placed in a beaker and heated at 205 ° C. for 2 hours using a hot air drier. After cooling, powdery polysuccinimide having a molecular weight of 9700 was obtained.

Example 11 5 g of the polysuccinimide powder obtained in Preparation Example 2 and 2.5 g of water were placed in a beaker, and the temperature was adjusted to 2 using a hot air drier.
Heated at 05 ° C. for 2 hours. After cooling, the molecular weight is 1001
No lump polysuccinimide was obtained.

Example 12 5 g of the polysuccinimide powder obtained in Preparation Example 2 and 5 parts of water
g in a beaker, and the temperature was 205 ° C. using a hot air drier.
For 2 hours. After cooling, a massive polysuccinimide having a molecular weight of 11140 was obtained.

Example 13 5 g of the polysuccinimide powder obtained in Preparation Example 2 and 1 part of water
0 g was placed in a beaker, and heated to a temperature of 205 using a hot air dryer.
Heated at ° C for 2 hours. After cooling, a massive polysuccinimide having a molecular weight of 11,800 was obtained.

Example 14 5 g of the polysuccinimide powder obtained in Preparation Example 2, 5 g of the polysuccinimide obtained in Example 13 as a chain extender and 10 g of water were placed in a beaker, and the temperature was 205 ° C. using a hot air drier. For 2 hours. After cooling, molecular weight 2
5994 mass of polysuccinimide was obtained.

Example 15 10 g of the polysuccinimide powder obtained in Preparation Example 2
10 g of a mixed solvent obtained by mixing 5 g of water and 5 g of ethanol was placed in an eggplant-shaped flask and heated on an oil bath at 130 ° C. 6
After minutes, the system was in a homogeneous state and a uniform polysuccinimide fluid was obtained. Next, a small amount of a solvent (about 5 g) is expelled from the fluid from the polysuccinimide by sending air to the surface of the fluid, and the viscosity is adjusted to an appropriate level (about 10 Pa · s).
Adjusted to c). Further, a sheet-like molded product having a thickness of about 3 mm was obtained in the same manner as in Example 1, except that the polysuccinimide fluid whose viscosity was appropriately adjusted was used instead. The molecular weight of the molded polysuccinimide thus obtained was 9,120.

Example 16 10 g of a mixed solvent obtained by mixing 10 g of the polysuccinimide powder obtained in Preparation Example 2, 5 g of water and 5 g of ethyl acetate was placed in an eggplant-shaped flask and heated on an oil bath at 130 ° C. After 6 minutes, the system was homogeneous and a uniform polysuccinimide fluid was obtained. Next, a small amount of solvent (approximately 5
g) and moderate viscosity (about 10 Pa · sec)
Was adjusted. Further, a sheet-like molded product having a thickness of about 3 mm was obtained in the same manner as in Example 1, except that the polysuccinimide fluid whose viscosity was appropriately adjusted was used instead. The molecular weight of the molded polysuccinimide thus obtained was 9410.

Example 17 10 g of a mixed solvent obtained by mixing 10 g of the polysuccinimide powder obtained in Preparation Example 2, 5 g of water and 5 g of toluene was placed in an eggplant-shaped flask and heated on an oil bath at 130 ° C. After 6 minutes, the system was homogeneous and a uniform polysuccinimide fluid was obtained. Next, a small amount of solvent (approximately 5
g) and moderate viscosity (about 10 Pa · sec)
Was adjusted. Further, a sheet-like molded product having a thickness of about 3 mm was obtained in the same manner as in Example 1 except that the polysuccinimide fluid whose viscosity was appropriately adjusted was used instead. The molecular weight of the molded polysuccinimide thus obtained was 8,980.

Example 18 15 g of the polysuccinimide powder obtained in Preparation Example 2, 5 g of water, and 5 g of polyethylene succinate as a molding aid
Was placed in a 30 ml Labo Plastomill (manufactured by Toyo Seiki Seisaku-sho, Ltd.), and reacted at 230 ° C. for 0.5 hour while stirring (rotor rotation speed: 50 rpm). The molecular weight could not be measured because the obtained lumpy product was insoluble in the solvent, but the weight was 20 g, and no change was observed in the total weight of the raw material polysuccinimide and the molding aid. It is considered that no decomposition occurred.

The results of Examples 5 to 18 and Comparative Example 1 are summarized in Table 1 below.

[0094]

[Table 1]

From the results shown in Table 1, when polysuccinimide is heated in the presence of both the chain extender and the acid catalyst, the raw material polystyrene is significantly more than when only one of them is used or when both are not used. It is shown that high molecular weight succinimide can be achieved.

[0096]

According to the present invention, a polymer compound whose glass transition temperature cannot be measured, such as a polysuccinimide (co) polymer or protein, is heated in the presence of a solvent having a low boiling point and a high dielectric constant. By melting, the polymer compound can be formed into a desired shape by a simple operation without using an organic solvent. In addition to the above advantages, the polymer compound is decomposed by heating and melting in the presence of a solvent having a low boiling point and a high dielectric constant and a chain extender and / or an acid catalyst to decompose the polymer compound (ie, , The molecular weight can be reduced to a desired shape by a simple operation without using an organic solvent.

Further, according to the present invention, by heating a polysuccinimide-based (co) polymer in the presence of a chain extender and a solvent having a low boiling point and a high dielectric constant, an organic solvent is not used and The molecular weight of the raw material polysuccinimide-based (co) polymer can be easily increased. Further, in addition to the above advantages, by heating the polysuccinimide-based (co) polymer in the presence of a chain extender, a solvent having a low boiling point and a high dielectric constant, and an acid catalyst, a further raw material polysuccinimide-based (co) polymer can be obtained. ) A high molecular weight polymer can be achieved.

Claims (7)

[Claims] 1. A method for molding a polymer compound comprising heating and melting a polymer compound whose glass transition temperature (Tg) cannot be measured in the presence of a solvent having a low boiling point and a high relative dielectric constant. . 2. The method according to claim 1, wherein the polymer compound is a polysuccinimide-based polymer and / or copolymer. 3. The method according to claim 1, wherein the solvent has a boiling point of 50 to 150 ° C. and a relative dielectric constant at 20 ° C. of 20 or more. 4. The method according to claim 1, wherein the heating and melting are performed in the presence of a chain extender. 5. The method according to claim 1, wherein the heating and melting are performed in the presence of an acid catalyst. 6. A high molecular weight polysuccinimide-based polymer comprising heating a polysuccinimide-based polymer and / or a polysuccinimide-based copolymer in the presence of a chain extender and a solvent having a low boiling point and a high dielectric constant. A method for producing a coalesced and / or polysuccinimide copolymer. 7. The method according to claim 6, wherein said heating is further performed in the presence of an acid catalyst.