JPS5916567B2 - Polyamide polymer and its manufacturing method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a heat-resistant and flame-retardant polyamide polymer that is easy to mold and has excellent solubility, and a method for producing the same.

In recent years, the demand for heat-resistant and flame-retardant electrical and electronic equipment materials has increased further with the enforcement of the American UL standard.

Aromatic polyamides have traditionally been considered to be superior as heat-resistant and flame-retardant resins, but aromatic polyamides have poor processability due to their high melting point and difficulty in soluble in solvents. Currently, very few products have been commercialized. On the other hand, aliphatic polyamides, such as 6=nylon and 6.6-nylon, are in demand for fibers, plastics, sheets, etc., and are produced in large quantities in Japan, but from the point of view of flame retardancy and heat resistance. There are still some imperfections. The present invention was made in view of the above-mentioned current situation, and its purpose is to provide a heat-resistant and flame-retardant polyamide polymer having excellent solubility and moldability, and a method for producing the same.

The present invention has the following configuration to achieve the above object.

That is, the polyamide polymer of the present invention essentially has the following repeating unit (wherein R and w are the same or different and represent an alkyl group or a halogen atom, and n and n' are the same or different and are integers of 0 to 4. and X is a divalent bonding group -S
O2-, -S- or -0-, -0C-Ar-CO
- indicates a terephthalic acid residue and an isophthalic acid residue, and the ratio of terephthalic acid residue to isophthalic acid residue is 1
0:90 to 90:10), and the reduced viscosity is 0.
．． 4 to 1.5d1/y, and the method for producing it can be carried out using the general formula (where R and k are the same or different and represent an alkyl group or a halogen atom, and n and n' are the same or different) represents an integer from 0 to 4, and X represents a divalent bonding group -SO2-, -S- or -0-) and the general formula YOC-Ar-COY (in the formula -0C -Ar-CO- represents a terephthalic acid residue and an isophthalic acid residue, and the ratio of terephthalic acid residue and isophthalic acid residue is 10:90 to 90:10, and Y represents a halogen atom) By polycondensation with an aromatic dicarboxylic acid dihalide represented by the formula, essentially the following repeating unit (in the formula, R.R', N.n!, X and -0C-Ar-CO-1 are the same as the above definition) The reduced viscosity is 0.4 to 1.5.
It is characterized by producing a polyamide polymer having a ratio of d1/t.

Here, the reduced viscosity (RV) is RV=ηSp/C-17r
81-1, C: defined as the polymer concentration expressed in y/dl, 0.2 f/dl dimethylformamide solution, 30
The values are measured in degrees Celsius.

Specific examples of aromatic diamines used in the present invention include 4,4'-di(p-aminophenoxy)diphenyl sulfone, 4,1-di(p-aminophenoxy)diphenyl ether, 4,4' -di(p-aminophenoxy) diphenyl sulfide, 4,4'-di(p-aminophenoxy)-3,3'-dichloro 20 diphenyl sulfone,
4●4′-di(p-aminophenoxy)-3・31・5
・51-tetrapromodiphenyl ether, 4●l-di(p-aminophenoxy)-3,31,5,5'-tetramethyldiphenyl sulfone, 4,47-di(p-aminophenoxy)-3. Examples include 3ζ5,57-tetrapromodiphenyl sulfone and 4,41-di(p-aminophenoxy)(-3,3'-dichlorophenyl ether).

Next, to explain an example of a method for synthesizing these aromatic diamines, first, a dihydric phenol represented by the following general formula (A) is treated with an alkali such as sodium hydroxide, and then a divalent phenol represented by the general formula (B) is synthesized. Forms alkali metal salts of divalent phenols. Next, this is treated with p-nitrochlorobenzene of formula (C) to synthesize a nitro compound represented by general formula (D). In this reaction, by using an inert organic solvent with a high boiling point and high polarity as a solvent,
The reaction can proceed easily. Specific examples of such inert organic solvents include dimethyl sulfoxide,
Sulfolane, N-N-dimethylformamide, N-N-
Examples include dimethylacetamide, tetramethylurea, hexamethylphosphoramide, N-methyl-2-pyrrolidone, and the like. Next, the dinitro compound represented by the general formula (D) is reduced by a known method such as a catalytic reduction method using iron monohydrochloric acid, palladium, Raney nickel, etc. as a catalyst.
An aromatic diamine having an ether bond represented by the general formula (E) can be produced. R in each of the above formulas. R'
,N. n' and X are the same as those in general formula (1) above. In addition to the above synthesis examples, when X is -SO2-, the synthesis can also be carried out by the method shown in the following formula.
R in the above formula. k. n. n″ indicates the same as the above definition.

The above synthesis examples are merely illustrative and are not limited thereto.

In the present invention, one or more aromatic diamines represented by the general formula (1) can be used and reacted with the aromatic dicarboxylic acid dirad. Examples of the aromatic dicarboxylic acid cyhalide used in the present invention include cyclolade terephthalate, dibromide terephthalate, cyclolade isophthalate, and the like.

The purpose of the present invention can be sufficiently achieved by setting the harm between the aromatic diamine and the aromatic dicarboxylic acid dihalide in the range of 0.98 to 1.05 equivalents of the latter per 1 equivalent of the former, and the reduced viscosity is 0.40. A polyamide polymer of about 1.5 d1/t can be obtained.

In the present invention, two types of aromatic dicarboxylic acid dihalides, such as cyclolade terephthalate and cyclolade isophthalate, are used, and the mixing ratio thereof is 10:90 to 10:90.
A range of 90:10 is suitable. If the ratio of aromatic diamine and aromatic dicarboxylic acid dihalide is out of the above equivalent range, a product with a high molecular weight will not be obtained, and only an oligomer that does not exhibit a resinous shape will be obtained. In the case of equal equivalents, the maximum molecular weight of the target aromatic polyamide polymer can be obtained. Furthermore, if the mixing ratio of the aromatic dicarboxylic acid cyclolade is out of the above range, the softening point of the resulting polyamide polymer will be high, making it impossible to obtain the desired easily processable thermoplastic polymer. On the other hand, the polymer of the present invention synthesized at a mixing ratio within the above range has a low softening point of about 330°C or less, so it can be molded by extrusion molding, compression molding, injection molding, etc. with a normal molding machine. It can be molded into a variety of shapes using a method, and can be said to be revolutionary as an aromatic polyamide polymer. In the present invention, the reaction can be carried out using any known method used for the reaction between an amine and an acid, and the conditions are not particularly limited.

For example, this can be achieved by an interfacial polycondensation method, a solution polycondensation method, a melt polycondensation method, or the like. In the interfacial polycondensation reaction, a known water-soluble neutralizing agent described below is used.
In addition, in the case of solution polycondensation method, known tertiary resins such as triethylamine, pyridine, tributylamine, pyrimidine, etc.
A neutralizing agent consisting of a grade amine is used. Moreover, olefin oxides such as propylene oxide and ethylene oxide can also be used as dehydrochlorination agents. A reaction solvent is used in the interfacial polycondensation method and the solution polycondensation method, but this solvent must be capable of dissolving at least one of aromatic diamine or aromatic dicarboxylic acid dihalide, preferably both. No. Representative examples of particularly effective solvents used in the present invention include, in the case of the interfacial polycondensation method, cyclohexanone, diisobutyl ketone, methylene chloride, trichlene, perchlorene, dichloride ethane, nitrobenzene, chloroform, carbon tetrachloride, acetophenone, p-methyl Examples include acetophenone. In the case of solution polycondensation method, N-N-dimethylformamide, N-N-diethylformamide, N-N-dimethylacetamide, N-N-diethylacetamide,
N-N-methylmethoxyacetamide, N-methyl-2
-Pyrrolidone, pyridine, dimethylsulfone, hexamethylsulfolamide, tetramethylsulfone, dimethyltetramethylenesulfone and tetramethylurea. Two or more reaction solvents may be used as a mixture if necessary to facilitate the dissolution operation.
Furthermore, in order to obtain a product with as high a molecular weight as possible, it is preferable to use a highly dehydrated solvent for dissolving the aromatic dicarboxylic acid dihalide. In particular, N-N dimethylformamide, N-N-dimethylacetamide, N-methyl-
When using a nitrogen-containing polar solvent such as 2-pyrrolidone,
It can be synthesized without using the above-mentioned neutralizing agent. Furthermore, the aromatic polyamide polymer obtained by the present invention has excellent solubility compared to conventional polymers. That is, conventionally, 5 to 10% by weight of lithium chloride, calcium chloride,
However, the aromatic polyamide polymer obtained by the present invention can be dissolved in the polar solvent up to 20 to 30% by weight without using the co-solvent, and can be used to form films and coating materials from this solution. It can be applied to As described above, the aromatic polyamide polymer obtained according to the present invention does not require the use of a co-solvent, so that metals are less likely to be contained in the polymer and it is advantageous in terms of properties. Furthermore, the effective reaction method discovered by the present inventors differs from the usual interfacial polycondensation method in which diamines are dissolved in alkaline aqueous solutions, in which diamines are dispersed in alkaline aqueous solutions, and aromatic dicarbonyl This is a method in which a solution of acid dihalide dissolved in an organic solvent is added and reacted.

By polymerizing in this method, the generated hydrogen halide is neutralized with a neutralizing agent and becomes water and metal halide and dissolves in water. When the polymer is precipitated from the organic layer, hydrochloric acid is added to the polymer. Since no residual neutralizer or neutralizing agent remains, favorable results are obtained for various properties of the polymer. In this case, the amount of alkali used is at least 1.3 equivalents, preferably 1.0 to 1.1 equivalents, of the aromatic dicarboxylic acid dihalide. Examples of the neutralizing agent used here include, but are not limited to, water-soluble sodium hydride, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, and the like. The amount of water may be sufficient as long as the neutralizing agent is sufficiently dissolved at room temperature, but of course, even if more water is used, the reaction will not be affected. The reaction temperature is a state where water is a liquid, that is, 0 to 100°C, preferably 3 to 60°C.
is within the range of The above polycondensation method can be carried out, for example, by the following procedure. First, a neutralizing agent is dissolved in an appropriate amount of water, and an aromatic diamine is added to the solution. Furthermore, a solution of aromatic dicarboxylic acid dihalide dissolved in an organic solvent is added and reacted. At this time, it is preferable to carry out the reaction in a state where the aromatic diamine is dispersed in the alkaline aqueous solution by stirring. Next, only the organic phase is separated and poured into an organic solvent that does not dissolve the polymer and is easily compatible with the reaction solvent to precipitate the polymer. By collecting a lot of this, an aromatic polyamide polymer is obtained. In the present invention, terephthalic diolide and isophthalic dihalide are used as a mixture, and the following will explain why they are superior to the case where each is used alone.

As shown in the graph in the attached drawing, when the fluidity of polymers synthesized by changing the composition ratio of cyclolade terephthalate and cyclolade isophthalate was measured using a Koka type flow tester (outflow amount), cyclolade terephthalate was The fluidity of the polymer synthesized by mixing and cyclolade isophthalate is superior to that of the polymer synthesized alone. From this result, it can be said that the melt moldability of the polymer synthesized by the mixed system is good. Note that the measurement was performed at 300°C. Next, the present invention will be explained in more detail with reference to examples, but the present invention is not limited by these in any way. Example 1 Water (31) was placed in a 151-33 flask equipped with a stirrer and a thermometer, and 80 t of sodium hydroxide was added thereto to dissolve it.

To this solution, 864 tons of 4,4-di(p-aminophenoxy)diphenylsulfone was added and stirred to disperse. A solution of cyclolad terephthalate 203y and cyclolade isophthalate 203f dissolved in cyclohexanone 101 was quickly added to this, and the mixture was vigorously stirred at 20°C. After 3 hours, stirring was stopped and the mixture was separated into an organic phase and an aqueous phase, and only the organic phase was poured into methanol to precipitate the polymer, and the precipitate was collected and dried.

Reduced viscosity of the obtained aromatic polyetheramide polymer (
η8,/C) was 0.68 dj/y (0.27/dl dimethylformamide solution, 30°C; all the following examples were conducted under the same conditions).

The softening point was about 280°C. This polymer was injection molded at 350°C to prepare various test pieces, and their properties were investigated. The results are shown in the table below. Example 2 768 tons of 4,4'-di(p-aminophenoxy)diphenyl ether were placed in a 15' three-neck flask equipped with a stirrer, a thermometer, and a calcium chloride tube, and 101 tons of N-methyl-2-pyrrolidone was added. and dissolved.

The surroundings of this reaction vessel were cooled in a water bath to bring the liquid temperature to 2°C.
Add a mixture of 81.27 cyclolad terephthalate and 324.87 cyclolad isophthalate to this little by little.
Added over 0 minutes. While stirring for 3 hours after the addition was completed, the solution gradually became viscous. After the reaction was completed, the solution was poured into water to precipitate the polymer, which was collected and dried. The resulting polymer had a reduced viscosity of 0.86 d1/7. The softening point was approximately 275°C. This polymer was compression molded to make resin plates, and various properties were investigated.
The results are shown in the table. Example 3 41ml of water was placed in a 151ml three-loaf flask equipped with a stirrer and a thermometer, and 82.47ml of sodium hydroxide was added thereto and dissolved.

To this solution, 864 tons of 4,4'-di(p-aminophenoxy)diphenylsulfone was added and stirred to disperse it.
A solution prepared by dissolving 125,57 t of cyclolad terephthalate and 292.7 t of cyclolad isophthalate in 91 cyclohexanone was added thereto, and the mixture was vigorously stirred at 10°C.
After the reaction was completed, stirring was stopped and the mixture was separated into an aqueous phase and an organic phase. Only the organic phase was poured into a methanol-acetone mixed solvent to precipitate the polymer. A lot of this polymer was collected and dried.
The reduced viscosity of the obtained polymer was 0.91 d1/7. The softening point was 270°C. This polymer was injection molded to create various test pieces and their properties were investigated. The results are shown in the table. Example 4 In the same flask as Example 2, add 4.4'-
Add 1002 f of di(p-aminophenoxy)-3,3'-dichlorodiphenyl sulfone, 4.51 g of N-methyl-2-pyrrolidone and 4 g of N-N-dimethylacetamide.
．． 51 was added and dissolved.

The reaction vessel was cooled to 3°C with an ice bath. To this, a mixture consisting of 284.2f cyclolad terephthalate and 121.87 cyclolad isophthalate was slowly added little by little over time. After the addition was completed, the reaction was allowed to proceed for 3 hours.
After the reaction was completed, the solution was poured into water to precipitate, and a lot was collected and dried. The reduced viscosity of this polymer is 1.03d1/f
The softening point was 310°C. This polymer was compression molded to create a resin plate, and its properties were investigated. The results are shown in the table. Example 5 Water 31 and sodium hydroxide 807 were placed in the same flask as in Example 1 to prepare an alkaline aqueous solution.

To this was added 800f of 4.eedi(p-aminophenoxy)diphenyl sulfide, and the mixture was vigorously stirred to disperse. To this, a solution of 40.67 y of cyclolad terephthalate and 365.4 y of cyclolad isophthalate dissolved in 101 cyclohexanone was quickly added while maintaining the reaction temperature at 40°C. Immediately after the addition, the temperature rose to 50°C, but the reaction was allowed to continue for 3 hours. After the reaction is complete, only the cyclohexanone phase is poured into methanol to precipitate the polymer.
The polymer was removed and dried. The reduced viscosity of this polymer is 0.
57 d1/t, and the softening point was 265°C. Various molded products were made by injection molding this polymer, and their properties were investigated. The results are shown in the table. Example 6 Into the same flask as in Example 2, 864 tons of 4.4''-di(p-※※aminophenoxy)diphenylsulfone was added, and 4.51 tons of N-methyl-2-pyrrolidone and 4.51 tons of N-N-dimethylacetamide were added. 51 was added and dissolved.

The reaction vessel was cooled to 3°C with an ice bath. To this, a mixture consisting of 365.4 t of cyclolad terephthalate and 40.6 y of cyclolad isophthalate was slowly added little by little over time. After the addition was completed, this solution was poured into water to precipitate it, and a lot was collected and dried. This polymer had a reduced viscosity of 0.72 d1/t and a softening point of 330°C. This polymer was compression molded to create a resin plate, and its properties were investigated. The results are shown in the table. Comparative Example 1 3 f water in the same flask as Example 1! and 80f of sodium hydroxide to prepare an alkaline aqueous solution.

To this, 864 tons of 4,45-di(p-aminophenoxy)diphenylsulfone was added and dispersed by vigorous stirring. To this dispersion, a solution of 406 t of cycloladate terephthalate dissolved in 101 cyclohexanone was quickly added to react at 20°C. After reacting for 3 hours, only the cyclohexanone phase was poured into methanol to precipitate the polymer.

Unlike the polymers of Examples 1 to 6, this polymer showed no solubility at all without a co-solvent, and its reduced viscosity could not be measured. Furthermore, the softening point was 360° C. or higher, making it impossible to use it as a normal thermoplastic resin. This shows that it has excellent heat resistance and has excellent properties as an engineering plastic.

It also has excellent flame retardancy, with self-extinguishing properties and non-combustibility. Furthermore, as can be seen by comparing Examples 1 and 3 with Comparative Example 1, by using a mixture of cyclolade terephthalate and cyclolade isophthalate, the resulting aromatic polyamide polymer was used as an engineering plastic. The present invention is significant in that it has been found to be applicable to plastic resins.

Furthermore, the polymer obtained according to the present invention can be used not only as an engineering plastic but also as a varnish or fiber due to its excellent solubility.

[Brief explanation of the drawing]

The drawing is a graph showing the fluidity of the polymer of the present invention synthesized by changing the composition ratio of cyclolade terephthalate and cyclolade isophthalate.

Claims (1)

[Claims] 1 Essentially the following repeating unit ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R and R' are the same or different and represent an alkyl group or a halogen atom, and n and n' are the same Or differently 0~
-SO_2-, which represents an integer of 4, and X is a divalent bonding group
, -S- or -O-, -OC-Ar-CO- represents a terephthalic acid residue and an isophthalic acid residue, and the ratio of terephthalic acid residue and isophthalic acid residue is 10:9.
0 to 90:10), and the reduced viscosity is 0.4 to 90:10.
Polyamide polymer with 1.5 dl/g. 2 General formula ▲ Numerical formula, chemical formula, table, etc. ▼
-SO_2-, which represents an integer of 4, and X is a divalent bonding group
, -S- or -O-) and the general formula YOC-Ar-COY (in the formula -OC-Ar-
CO- represents a terephthalic acid residue and an isophthalic acid residue, and the ratio of terephthalic acid residue and isophthalic acid residue is 10:90 to 90:10, and Y represents a halogen atom). A repeating unit consisting essentially of the following, characterized by polycondensation with an aromatic dicarboxylic acid dihalide ▲
There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R, R', n, n', X and -OC-Ar-CO
- is the same as the above definition), and the reduced viscosity is 0.4 to 1.
．． A method for producing a polyamide polymer having a yield of 5 dl/g. 3. The method according to claim 2, wherein the aromatic diamine is dispersed in an alkaline aqueous solution, and a solution of an aromatic dicarboxylic acid dihalide dissolved in an organic solvent is added thereto for polycondensation.