JPS6340206B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for producing polyamide in which a polycarboxylic acid and a diisocyanate are reacted in the coexistence of an alkali metal hydroxide compound. It is already known that polyamides can be produced from polyhydric carboxylic acids and diisocyanates.
A polyamide is obtained by reacting for 20 hours. However, the products obtained by this method have a low molecular weight and are mainly used for varnishes, paints, adhesives, etc. They have a logarithmic viscosity that allows them to be processed into forms such as fibers, various molded products, and films and exhibit sufficient physical properties. It has been difficult to produce polymers with a high molecular weight of about 1.3 or higher. Furthermore, for isocyanate reactions, tertiary amines such as triethylamine and triethylenediamine, which have catalytic properties, lithium linoleate,
Salts such as sodium oleate, sodium methoxide, and cobalt naphthenate have little effect on the reaction for producing polyamide from diisocyanate and polyhydric carboxylic acid, and it has been difficult to produce high molecular weight polyamide. The inventors of the present invention have conducted intensive studies on a method for obtaining a high molecular weight polyamide by reacting this diisocyanate with a polyhydric carboxylic acid, and as a result, they have discovered an epoch-making method and have arrived at the present invention. That is, the method of the present invention comprises at least one dicarboxylic acid represented by the general formula (), a tricarboxylic acid represented by the general formula (), or a tetracarboxylic acid represented by the general formula (); At least one type of diisocyanate, general formula (), general formula (), or general formula ()
This is a method for producing a polyamide, which is characterized in that the reaction is carried out in the presence of a compound represented by the general formula () in the production of a polyamide containing one or more repeating units represented by the formula (). Here, each of the general formulas () to () means the following structures, and R ¹ to R ⁴ and M
means the following respectively. R ¹ (COOH) ₂ () R ² (COOH) ₃ () R ³ (COOH) ₄ () R ⁴ (NCO) ₂ () − [CO−R ¹ −CONH−R ⁴ −NH−] () − [CO−R ² (COOH)−CONH−R ⁴ −NH−] () −[CO−R ³ (COOH) ₂ −CONH−R ⁴ −NH−]
() MOH () R ¹ : A divalent group containing at least two carbon atoms, or a group in which these groups are substituted with a group or atom that does not substantially react with both a carboxyl group and an isocyanate group. and in the above formula
The two carboxyl groups bonded to R ¹ are bonded to two different carbon atoms contained in R ¹ . R ² : A trivalent group containing at least 3 carbon atoms, or a group in which these groups are further substituted with a group or atom that does not substantially react with both a carboxyl group and an isocyanate group, and the above-mentioned During the ceremony
The three carboxyl groups bonded to R ² are each bonded to three different carbon atoms contained in R ² . R ³ : A tetravalent group containing at least 4 carbon atoms, or a group in which such a group is further substituted with a group or atom that does not substantially react with both a carboxyl group and an isocyanate group, and the above-mentioned During the ceremony
The four carboxyl groups bonded to R ³ are each bonded to four different carbon atoms contained in R ³ . R ⁴ : A divalent group containing at least two carbon atoms, or a group in which these groups are further substituted with a group or atom that does not substantially react with both carboxyl groups and isocyanate groups, and the above-mentioned During the ceremony
The two isocyanate groups bonded to R ⁴ are each bonded to two different carbon atoms contained in R ⁴ . M: Alkali metal belonging to Group 1A of the Periodic Table When a polyhydric carboxylic acid and a diisocyanate are reacted in a substantially anhydrous organic polar solvent in the coexistence of an alkali metal hydroxide according to the method of the present invention, the alkali metal water The reaction rate is significantly increased and the degree of polymerization is improved compared to the case where an oxide is not present, and a linear polymer with almost no network structure (gel formation) can be produced very easily. In addition, the method of the present invention produces polyamide by a polycondensation reaction that releases carbon dioxide gas with extremely low reactivity, and compared to conventional polycondensation reactions by dehydrochlorination or dehydration, by-products of the polymerization reaction are produced. Not only is there no deterioration of the polymer due to oxidation, but the catalyst used is a very common alkali metal hydroxide, which is easy to obtain and handle, so it has great economic and industrial benefits. Typical polyvalent carboxylic acids represented by the general formulas (), (), and () include, for example, () malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, and sebacin. acid, terephthalic acid, isophthalic acid, hexahydroterephthalic acid, diphenyl ether-4,
4-dicarboxylic acid, diphenylsulfone-4,
4'-dicarboxylic acid, biphenyl-4,4'-dicarboxylic acid, thiophene-2,5-dicarboxylic acid, pyridine-2,6-dicarboxylic acid, naphthalene-
2,6-dicarboxylic acid, 4,4'-diphenyl ether-bis-trimellitic acid, 4,
4'-diphenylmethane-bis-trimellitic acid, () as butane-1,2,4-tricarboxylic acid, pentane-1,2,5-tricarboxylic acid, cyclohexane-1,2,3-tricarboxylic acid, cyclo Pentanedienyl-1,2,4-
Tricarboxylic acid, benzene-1,2,4-tricarboxylic acid, benzene-1,2,3-tricarboxylic acid, naphthalene-1,2,4-tricarboxylic acid,
naphthalene-1,2,5-tricarboxylic acid, naphthalene-2,3,5-tricarboxylic acid, naphthalene-2,3,6-tricarboxylic acid, 3,4,4'-
Biphenyltricarboxylic acid, 2,3,2'-biphenyltricarboxylic acid, 3,4,3'-diphenylsulfonetricarboxylic acid, 3,4,4'-diphenyl ethertricarboxylic acid, 3,4,4'- Benzophenonetricarboxylic acid, 3,4,3'-benzophenonetricarboxylic acid, perylene-3,4,9-tricarboxylic acid, 2-(3,4-dicarboxyphenyl)-2-(3-carboxyphenyl) enyl)propane, 2-(2,3-dicarboxyphenyl)-2-
(3-carboxyphenyl)propane, 1-(2,
3-dicarboxyphenyl)-1-(3-carboxyphenyl)ethane, 1-(3,4-dicarboxyphenyl)-1-(4-carboxyphenyl)ethane, (2,3-dicarboxyphenyl)-1-(3-dicarboxyphenyl)-1-(4-carboxyphenyl)ethane, phenyl)-(2-
carboxyphenyl)methane, 2-(3,4-dicarboxyphenyl)-5-(3-carboxyphenyl)-1,3,4-oxadiazole, 2,3,
5-pyrazinetricarboxylic acid, () as butane-1,2,3,4-tetracarboxylic acid, pentane-1,2,4,5-tetracarboxylic acid, cyclobutane-1,2,3,4-tetracarboxylic acid , cyclopentane-1,2,3,4-tetracarboxylic acid, cyclohexane-1,2,3,4-tetracarboxylic acid, benzene-1,2,4,5-tetracarboxylic acid, naphthalene-1,4, 5,8-tetracarboxylic acid, naphthalene-2,3,6,7-tetracarboxylic acid, naphthalene-1,2,4,5-tetracarboxylic acid, 3,3',4,4'-biphenyltetracarboxylic acid acid, 2,3,5,6-biphenyltetracarboxylic acid, 2,2',3,3'-biphenyltetracarboxylic acid, 2,2',6,6'-biphenyltetracarboxylic acid, 3, 3',4,4'-benzophenonetetracarboxylic acid, 2,2',3,3'-benzophenonetetracarboxylic acid, 2,3,3',4'-benzophenonetetracarboxylic acid, 3 ,3′,4,4′−
Diphenyl ether tetracarboxylic acid, 3,3',
4,4'-diphenylsulfonetetracarboxylic acid,
perylene-3,4,9,10-tetracarboxylic acid,
Phenanthrene-1,8,9,10-tetracarboxylic acid, anthracene-2,3,6,7-tetracarboxylic acid, P-benzoquinone-2,3,5,6-
Tetracarboxylic acid, azobenzene-3,3',4,
4'-tetracarboxylic acid, 2,2-bis(3,4-
dicarboxyphenyl)propane, 2,2-bis(2,3-dicarboxyphenyl)propane, 1,
1-bis(2,3-dicarboxyphenyl)ethane, bis(2,3-dicarboxyphenyl)methane, bis(3,4-dicarboxyphenyl)methane, 2,2-bis(3,4 -dicarboxyphenyl)hexafluoropropane, thiophene-2,
3,4,5-tetracarboxylic acid, furan-2,
3,4,5-tetracarboxylic acid, pyridine-2,
Examples include 3,5,6-tetracarboxylic acid. Among those listed above, () is particularly adipic acid, terephthalic acid, isophthalic acid, diphenyl ether-4,4'-dicarboxylic acid, pyridine-
2,6-dicarboxylic acid, sebacic acid, 4,4'-diphenylmethane-bis-trimellitic acid, 4,4'-diphenyl ether-bis-trimellitic acid, () as pentane-1,
2,5-tricarboxylic acid, cyclohexane-1,
2,3-tricarboxylic acid, benzene-1,2,4
-tricarboxylic acid, naphthalene-1,4,5-tricarboxylic acid, naphthalene-2,3,6-tricarboxylic acid, 3,4,4'-biphenyltricarboxylic acid, 3,4,4'-diphenyl ethertricarboxylic acid , 3,4,3'-benzophenonetricarboxylic acid, () as butane-1,2,3,4-tetracarboxylic acid, benzene-1,2,4,5-tetracarboxylic acid, naphthalene-1,4 , 5,8-tetracarboxylic acid, naphthalene-2,3,6,7-
Tetracarboxylic acid, 3,3',4,4'-biphenyltetracarboxylic acid, 3,3'4,4'-diphenyl ethertetracarboxylic acid, 3,3',4,4'-diphenylsulfone tetra Carboxylic acids or mixtures thereof are preferred in view of the chemical, thermal, electrical properties and processability of the polymer. Examples of the diisocyanate represented by the above general formula () include 1,2-diisocyanateethane, 1,2-diisocyanatepropane, tetramethylene-1,4-diisocyanate, pentamethylene-1,5-diisocyanate, and hexamethylene-1,6-diisocyanate. -Diisocyanate, nonamethylene-1,9-diisocyanate, decamethylene-
1,10-diisocyanate, ω,ω′-dipropyl ether diisocyanate, cyclohexane-
1,4-diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, hexahydrobiphenyl-4,4'-diisocyanate, hexahydrodiphenyl ether-4,4'-diisocyanate, phenylene-1,3-diisocyanate, phenylene -1,4-diisocyanate, toluylene-2,6-diisocyanate, toluylene-2,4-diisocyanate, 1-methoxybenzene-2,4-diisocyanate, 1-chlorophenylene diisocyanate, tetrachlorophenylene diisocyanate, metaxylylene diisocyanate Isocyanate, paraxylylene diisocyanate,
diphenylmethane-4,4'-diisocyanate,
Diphenyl sulfide-4,4'-diisocyanate, diphenyl sulfone-4,4'-diisocyanate, diphenyl ether-4,4'-diisocyanate, diphenyl ether-3,4'-diisocyanate, diphenyl ketone-4, 4'-diisocyanate, naphthalene-2,6-diisocyanate, naphthalene-1,4-diisocyanate, naphthalene-1,5-diisocyanate, 2,4'-
Biphenyl diisocyanate, 4,4'-biphenyl diisocyanate, 3,3'-dimethoxy-4,
Examples include 4'-biphenyl diisocyanate, anthraquinone-2,6-diisocyanate, triphenylmethane-4,4'-diisocyanate, and azobenzene-4,4'-diisocyanate. Among those listed above, hexamethylene-1,6-
Diisocyanate, dicyclohexylmethane
4,4'-diisocyanate, phenylene-1,3
-diisocyanate, phenylene-1,4-diisocyanate, toluylene-2,4-diisocyanate, toluylene-2,6-diisocyanate, diphenylmethane-4,4'-diisocyanate, diphenyl ether-4,4'-diisocyanate, or this A mixture of
It is preferable in terms of chemical, thermal, electrical properties and processability of the polymer. Further, examples of the alkali metal hydroxide represented by the above general formula () include lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, and francium hydroxide. Lithium, sodium hydroxide, potassium hydroxide, or a mixture thereof is preferred in terms of catalytic effect. In the reaction of polyhydric carboxylic acid and diisocyanate according to the present invention, a polymer with a high degree of polymerization, which was not possible with conventional polymerization technology of polyhydric carboxylic acid and diisocyanate, can be produced using alkali hydroxide, which is an inexpensive and easy-to-handle compound. It can be manufactured extremely easily by coexisting metals. The method of the present invention involves combining the above-mentioned polyhydric carboxylic acid and diisocyanate in the coexistence of the above-mentioned alkali metal hydroxide, generally in an anhydrous organic polar solvent under a stream of anhydrous inert gas such as nitrogen or under reduced pressure. The polymerization reaction is carried out while removing by-product carbon dioxide gas. The polymerization reaction temperature ranges from room temperature to 250℃, especially 50℃.
℃ to 200℃ from the viewpoint of reaction rate and side reactions, and the polymerization reaction time is 1 hour to 20 hours, preferably 2 hours to 10 hours at the selected temperature, so that substantially no carbon dioxide gas is produced. The time period is chosen such that no occurrence of this phenomenon is observed. As the organic polar solvent, N,N-dimethylacetamide, N,N-diethylacetamide, N,N
- amide compounds such as dimethylformamide, N-methyl-2-pyrrolidone, hexamethylphosphoric triamide, or γ-butyrolactone;
Lactone compounds and sulfone compounds such as tetramethylene sulfone and diphenyl sulfone can be used. Furthermore, in addition to these organic polar solvents, other solvents such as benzene, toluene, xylene, cyclohexane, pentane, heptane, methylene chloride, tetrahydrofuran, cyclohexanone, dioxane, etc., which do not substantially react with carboxyl groups and isocyanate groups are required. It may be added as appropriate. In the method of the present invention, the method, order, and timing of addition of the polyhydric carboxylic acid, diisocyanate, and alkali metal hydroxide can be arbitrarily selected. The raw material monomer concentration at the start of polymerization is selected from a range of 50 g/·solvent to 400 g/·solvent, and this concentration is selected depending on the reactivity of the raw monomer and the solubility of the polymer in the polymerization solvent. Depending on the raw material monomer concentration at the start of the polymerization reaction, it is preferable to add the solvent continuously or discontinuously to the extent that stirring is not hindered due to thickening of the system during polymerization or addition of raw materials. . The molar ratio of diisocyanate/polycarboxylic acid in this polymerization reaction is preferably in the range of 0.7 to 1.30, preferably in the range of 0.90 to 1.15, from the viewpoint of reducing the possibility of forming a network structure in the resulting polymer. The amount of the metal is preferably in the range of 0.5 to 20 mol%, preferably in the range of 1 to 10 mol%, based on the polyhydric carboxylic acid. The method of the present invention will be explained below with reference to examples, but the present invention is of course not limited to these examples. The symmetrical viscosity value (ηinh) shown in the examples is a value measured according to the following formula. ηinh=ln(t/to)/c to: Flow time of the solvent using an Ubbelohde viscometer t: Flow time of a diluted polymer solution using an Ubbelohde viscometer c: g of polymer dissolved in 100 ml of solvent In the examples, values are shown that were measured at a temperature of 30°C after dissolving 0.1g of polymer in 100ml of concentrated sulfuric acid. Furthermore, the meanings of the abbreviations used in the examples are shown below. TDI65/35: Toluylene-2,4-diisocyanate/toluylene-2,6-diisocyanate (molar ratio = 65:35) TDI80/20: Toluylene-2,4-diisocyanate/toluylene-2,6-diisocyanate (molar ratio = 80:20) TDI100: Toluylene-2,4-diisocyanate MDI: Diphenylmethane-4,4'-diisocyanate HMDI: Hexamethylene-1,6-diisocyanate DPDI: Diphenyl ether-4,4'-diisocyanate IPA: Isophthalic acid TPA : Terephthalic acid TMA: Trimellitic acid BTA: Butanetetracarboxylic acid PMA: Pyromellitic acid TEDA: Triethylenediamine SO: Sodium oleate SM: Sodium methoxide CN: Cobalt naphthenate Pre-stirring: Acid, solvent, and alkali metal hydroxide at 80°C
Simultaneous stirring for 1 hour: Simultaneously charging acid, isocyanate, solvent, and alkali metal hydroxide Example 1 IPA21.43 was placed in a 500 ml separable flask equipped with a stirrer, reflux condenser, thermometer, and nitrogen inlet.
g (0.1290mol), lithium hydroxide 0.073g (3.0×
10 ⁻³ mol) and anhydrous N-methyl-2-pyrrolidone
255 ml was charged and sealed with dry nitrogen. This flask was heated in an oil bath, and the contents were heated and stirred at 80°C for 1 hour to form a homogeneous solution free of insoluble matter, and then cooled to 50°C. Add 24.27g of TDI80/20 to the resulting homogeneous solution.
(0.1394 mol) was added and heated again in an oil bath, and the contents were heated and stirred at 140°C for 4 hours to obtain a viscous brown reaction liquid. This reaction solution was poured into 1000 ml of methanol that was being stirred vigorously to precipitate the polymer, which was then thoroughly washed with methanol and dried at 150°C under reduced pressure for 3 hours to obtain 30.53 g of pale yellow powder. . The logarithmic viscosity of this polymer was 1.58. Comparative Example 1 24.40 g of IPA was placed in the same reactor as Example 1.
(0.1469mol) Anhydrous N-methyl-2-pyrrolidone
260 ml and 27.62 g (0.1586 mol) of TDI80/20 were charged and sealed with dry nitrogen. This flask was heated in an oil bath and the contents were heated and stirred at 140°C for 4 hours to obtain a brown reaction liquid with low viscosity. This reaction solution was treated in the same manner as in Example 1 to form a pale yellow powder.
26.68g was obtained. The logarithmic viscosity of this polymer is 0.50
It was hot. Examples 2 to 17 and Comparative Examples 2 to 13 Tables 1, 2, 3, and 3 show the results of experiments conducted with various monomer and additive combinations using equipment similar to that shown in Example 1 and Comparative Example 1. 4.

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Claims (1)

[Scope of Claims] 1 At least one type of dicarboxylic acid represented by the general formula (), tricarboxylic acid represented by the general formula (), or tetracarboxylic acid represented by the general formula (), and at least one type of tetracarboxylic acid represented by the general formula () In the production of a polyamide containing one or more repeating units represented by general formula (), general formula (), or general formula () from at least one diisocyanate, in the coexistence of a compound represented by general formula (). A method for producing polyamide, which is characterized by reacting with. R ¹ (COOH) ₂ () R ² (COOH) ₃ () R ³ (COOH) ₄ () R ⁴ (NCO) ₂ () − [CO−R ¹ −CONH−R ⁴ −NH−] () − [CO−R ² (COOH)−CONH−R ⁴ −NH−] () −[CO−R ³ (COOH) ₂ −CONH−R ⁴ −NH−]
() MOH () However, in the above formula, R ^{1 to 4} and M mean the following. R ¹ : A divalent group containing at least two carbon atoms, or a group in which these groups are further substituted with a group or atom that does not substantially react with both a carboxyl group and an isocyanate group, and the above-mentioned During the ceremony
The two carboxyl groups bonded to R ¹ are bonded to two different carbon atoms contained in R ¹ . R ² : A trivalent group containing at least 3 carbon atoms, or a group in which these groups are further substituted with a group or atom that does not substantially react with both a carboxyl group and an isocyanate group, and the above-mentioned During the ceremony
The three carboxyl groups bonded to R ² are each bonded to three different carbon atoms contained in R ² R ³ : A tetravalent group containing at least 4 carbon atoms or A group in which these groups are substituted with a group or atom that does not substantially react with both a carboxyl group and an isocyanate group, and in the above formula:
The four carboxyl groups bonded to R ³ are each bonded to four different carbon atoms contained in R ³ . R ⁴ : A divalent group containing at least two carbon atoms, or a group in which these groups are further substituted with a group or atom that does not substantially react with both carboxyl groups and isocyanate groups, and the above-mentioned During the ceremony
The two isocyanate groups bonded to R ⁴ are each bonded to two different carbon atoms contained in R ⁴ . M: Alkali metal belonging to Group 1A of the periodic table