JPS62177020A - Thermoplastic aromatic polyamide copolymer - Google Patents

Abstract

PURPOSE:To provide the titled melt-formable copolymer of both good thermal stability and fluidity, containing each specified amount of isophthalic acid, terephthalic acid and aromatic diamine residues. CONSTITUTION:The objective copolymer constituted chiefly by essential structural units of (A) formula I (R1 is 1-4C alkyl, alkoxy or halogen, a is integer 1-4), (B) formula II (n is 0 or 1) and (C) formula III, respectively. The amounts of each structural unit is such as to be 1mol of the components B plus C per 1mol of the component A and 0.70-0.02mol of the component C per 0.30-0.98mol of the component B. Furthermore, the molar ratio of the m- phenylene bond to the p-phenylene bond in the component A unit falls between 40/60 and 100/0, and also, the component A and (component B or C) are alternately linked with each other.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a novel heat-resistant thermoplastic polymer. The present invention relates to a novel thermoplastic aromatic polyamide copolymer that has both properties and is melt moldable.

<Prior Art> It has been well known that aromatic polyamides with excellent heat resistance can be obtained by generally combining isophthalic acid or terephthalic acid residues with aromatic diamine residues. For example, polyamides of the general formula are synthesized by reacting isophthalic acid dichloride and m-phenylenediamine in an equimolar ratio (e.g., Japanese Patent Publication No. 10865/1986, Japanese Patent Publication No. 17551/1982, U.S. Patent No. 3,
No. 049,511, U.S. Patent No. 3.287,3
24 specification, etc.).

Furthermore, by reacting terephthalic acid dichloride with four components: 3,4'-diaminodiphenyl ether, metaphenylenediamine, and paraphenylenediamine, an aromatic polyamide excellent in both heat resistance and rigidity can be obtained (for example, JP-A-51 Publication No.-76.386, JP-A-51-1.
34,743, JP-A-55-115,428, etc.).

Furthermore, by combining terephthalic acid dichloride and/or isophthalic acid dichloride with 2,2-bis(para-aminophenoquinphenyl)propane, an aromatic polyamide with excellent curing and fluidity can be obtained (for example, JP-A-52-23-198 No. 1, JP-A-54-77.692, JP-A-54-77.6
Publication No. 93, etc.).

<Problems to be solved by the invention> However, aromatic polyamides that have been generally proposed so far, such as A, isophthalic acid dichloride/meta-phenylene diamine polymer B, terephthalic acid dichloride/halaphenylene diamine Polycondensate C, terephthalic acid dichloride and/or isophthalic acid dichloride/4,4'-diaminodiphenyl ether polycondensate, terephthalic acid dichloride/halaphenyl diamine/metaphenyl diamine/3,4'-diaminodiphenyl ether polycondensate Although metal products have excellent properties in terms of both heat resistance and rigidity, their melt flow initiation temperature and thermal decomposition temperature are too close to each other, making it virtually impossible to melt and mold them, and they easily dissolve in solvents. The reality is that we have no choice but to adopt the so-called wet molding method.

On the other hand, as described above, a method of combining terephthalic acid dichloride and/or isophthalic acid dichloride with 2,2-bis(para-aminophenoxyphenyl)propane has been proposed as an effective method for imparting melt moldability to aromatic polyamides. This aromatic polyamide has a flow start temperature 50°C lower than the thermal decomposition temperature and has excellent thermal stability and fluidity during melt molding, so it shows good melt moldability. Since there are many ether bonds, the flexibility of the molecule becomes too high, resulting in a disadvantage that the physical properties of the molded product (particularly the bending strength and thermal properties) deteriorate.

Therefore, the present inventors have achieved good melt formability by combining good thermal stability and fluidity in the temperature range of 250 to 380°C, and improved physical properties (particularly bending strength and heat resistance) of the molded product. As a result of extensive research aimed at obtaining superior aromatic polyamides, we have developed a new thermoplastic aromatic material that has the desired properties by combining two different specific diamine components in a previously unknown composition. It was discovered that a polyamide copolymer can be obtained, and the present invention was achieved.

<Means for solving the problem> That is, the present invention has the main essential structural units of position and, and the ratio of each structural unit is substantially 1 mole of (B + C) to 1 mole of A, and 8
C is 0.70-0.0 for 0.30-0.98 mol
2 mol, and the ratio of m-phenylene bond/p-phenylene bond in A unit is 40 to 100/60.
~0 molar ratio, and a thermoplastic aromatic polyamide copolymer characterized in that A and (B or C) are alternately connected (in the formula, R1 is an alkyl group having 1 to 4 carbon atoms). , alkoxy group or )・logen group, n is O or 11
a represents O or an integer from 1 to 4).

The thermoplastic aromatic polyamide copolymer of the present invention is mainly composed of the three units indicated by A1B and C above.

A: 40 to 100 mol% of phenylene bonds in the unit are m
-phenylene bond, and specific examples thereof may include a p-phenylene bond in an amount of less than 60 mol % in the A unit, such as C1(3).

As a specific example of B unit, These units may be used alone or in combination of two or more.

−8= The number is used as one type or a mixture of two or more types.

The ratio of each of the above units in the aromatic polyamide copolymer of the present invention is such that B+C is substantially 1 mol to At mol, and C is 0.7 to 80.30 to 0.98 mol.
C is 0 to 0.02 mol, preferably 0.6 to 0.1 mol per BO34 to 0.9 mol.

If the C unit exceeds 70 mol % in (B 10 C), melt molding will become difficult and therefore unsuitable. On the other hand, if the C unit of B+C is less than 2 mol %, the aromatic polyamide copolymer will have lower fluidity during melting, and will also have worse melt moldability, which is not preferable.

The aromatic polyamide copolymer of the present invention can be produced using any of the many general production methods that have been proposed to date, but among them, the following 4 are representative examples with high practicality. Laws can be mentioned.

(1) Acid chloride method: method of reacting aromatic dicarpo/acid dichloride with aromatic diamine (for example, Japanese Patent Publication No. 35-13247, Japanese Patent Publication No. 35-14399, Japanese Patent Publication No. 46-41387, Japanese Patent Publication No. 1972) -10
863, JP-A-54-77692, etc.).

(2) Isocyanate method: A method of reacting an aromatic dicarboxylic acid with an aromatic diisocyanate (for example, Japanese Patent Publication No. 47-47596, French Patent No. 1,57)
8,154, etc.).

(3) Ester amide exchange method: A method of reacting an aromatic dicarboxylic ester with an aromatic diamine (for example, JP-A-52-82996, Belgian Patent No. 731)
, No. 420, etc.).

(4) Direct polymerization method: A method in which an aromatic dicarboxylic acid or its derivative (excluding acid chloride and ester derivatives) and an aromatic diamine are directly reacted in a polar organic solvent in the presence of a dehydration catalyst (for example, JP-A-52-58795). (Japanese Patent Application Laid-Open No. 52-58796, etc.).

Among the four methods mentioned above, the acid chloride method is the most recommended manufacturing method, as it has the advantages of relatively easy procurement of fillers and the ability to easily obtain aromatic polyamides with a high degree of polymerization through low-temperature polymerization. It is. Here, a more specific example of the production of the aromatic polyamide copolymer of the present invention by the acid chloride method is as follows. That is, the aroma is an alkyl group having 1 to 4 carbon atoms, an alkoxy group, or a halogen group,
a represents O or an integer of 1 to 4. ) 1 mol and aromatic diamine (same as in (1)) 30 to 98 (preferably 4
0 to 90) mo and a are the same as above) 0.9 to 2 (preferably 60 to 10) mol% of mixed diamines
1.1 mol is dissolved in an organic polar solvent to give -20~
Polymerization is carried out at a temperature of 80° C. in the presence or absence of a hydrogen chloride scavenger for 0.1 to IO hours −11=. The organic polar solvent used for polymerization is N, N-
N,N-dialkylcarboxylic acid amides such as dimethylacetamide, N,N-diethylacetamide, heterocyclics such as N-methylpyrrolidone, tetrahydrothiophene-1,1-dioxide 1,3-dimethyl-2-imidazolidinone, etc. compounds, and N-methylpyrrolidone and N,N-dimethylacetamide are particularly preferred.

In addition, the hydrogen chloride scavenger includes aliphatic tertiary amines such as trimethylamine, triethylamine, tripropylamine, and tributylamine, cyclic organic bases such as pyridine, lutidine, collidine, and quinoline, and organic compounds such as ethylene oxide and propylene oxide. These include oxide compounds. It is also possible to add an end-blocking agent before, during or after the polymerization reaction to block the ends of the aromatic polyamide copolymer of the present invention. Terminal capping greatly improves the thermal stability of the polyamide copolymer, which is preferable. Examples of the terminal blocking agent include acid anhydrides such as acetic anhydride, propionic anhydride, butyric anhydride, caproic anhydride, isobutyric anhydride, phthalic anhydride, benzoic anhydride, naphthalene-1,8-dicarboxylic anhydride, Acid chlorides such as acetyl chloride, propionyl chloride, butyryl chloride, benzoyl chloride, α- or β-naphthoic acid chloride, caproyl chloride, propylamine, butylamine, amylamine, aniline, p-aminoacetanilide, benzylamine, cyclohexylamine, dicyclohexyl Primary and secondary monoamines such as amines, morpholine, toluidine, diphenylamine, phenol, cresol, xylenol, t-butylphenol, methoxyphenol, β-naphthol,
Examples include monohydroxy compounds such as cumylphenol and phenylphenol nato.

The aromatic polyamide copolymer solution thus obtained is stirred and mixed with a liquid that is miscible with the solvent but does not dissolve the aromatic polyamide copolymer, such as water or methanol, and then sifted. The aromatic polyamide copolymer can be isolated by this method.

In addition, as an alternative method to the acid chloride polymerization method, a solution in which 0.9 to 1.1 moles of the above diamine (1) and a mixed diamine consisting of diamine (1) are dissolved in an organic solvent that is sparingly soluble in water, and A solution of 1 mole of the dicarboxylic acid chloride dissolved in an organic solvent is dispersed or suspended in an aqueous solution containing a water-soluble hydrogen chloride scavenger under high-speed stirring, and reacted at 0 to 80°C for 0.1 to 10 hours. method is also possible. Examples of the poorly water-soluble organic solvent used in this method include chlorobenzene, dichloroethane, trichloroethane, tetrachloroethane, chloroform, dichloromethane, methyl ethyl ketone, cyclohexanone, acetophenone, and methyl acetophenone. Water-soluble hydrogen chloride scavengers include, for example, inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, and potassium hydrogen carbonate, and aliphatic tertiary amines shown in the above hydrogen chloride scavengers. and water-soluble cyclic organic bases.

Specific examples of the above-mentioned aromatic dicarboxylic acid dichloride are shown in the form in which -CI is attached to the carbonyl groups on both sides of the divalent aromatic group shown above as a specific example of the A unit of the present invention, and aromatic diamine Specific examples of (1) and aromatic diamine (It) are included in B of the present invention.

By the production method detailed above, the aromatic polyamide copolymer which is the object of the present invention can be obtained. It is possible to copolymerize and use the system units together in a quantitative range (for example, 30 mol% or less) that does not significantly reduce the melt processability and physical properties of the resulting aromatic polyamide copolymer. and is included within the scope of the present invention. In addition, the aromatic polyamide copolymer of the present invention may contain structural units other than amide (for example, imide group units, etc.) in an amount that does not significantly reduce the melt processability and physical properties of the resulting copolymer. target range (
For example, it is also possible to use them together in an amount of 30 mol % or less) and introduce copolymerization, which is included in the scope of the present invention.

The aromatic polyamide copolymer of the present invention has an logarithmic viscosity (ηinh) value of 0.25 or more, preferably 0.30 or more, measured at 30°C at a polymer concentration of 0.5% by weight in an N-methylpyrrolidone solvent. It is a highly polymerized polymer and can be used for various purposes such as those listed below.

Compression molding is carried out after tri-blending the aromatic polyamide copolymer powder of the present invention with different polymers, additives, fillers, reinforcing agents, etc. as necessary, and then processing the mixture at 250 to 380°C, preferably at 280 to 350°C. It is carried out under pressure conditions of 50 to 500 and 9/d. For extrusion molding and injection molding, the aromatic polyamide copolymer of the present invention is tri-blended with different polymers, additives, fillers, reinforcing agents, etc. as necessary, or this is pelletized by extruding it. Feed the pellets to an extrusion molding machine or an injection molding machine,
It is carried out under a temperature condition of -380°C, preferably 280-350°C. In particular, the aromatic polyamide copolymer of the present invention has an excellent balance of thermal stability and flow characteristics in the 250 to 380°C range, and is useful for extrusion molding and injection molding.

For film and fiber manufacturing applications, the polymerization termination liquid can be applied in a dry or wet-dry casting process, or the isolated polymer can be melt-molded with appropriate additives added as needed. .

The laminate is made by impregnating a cloth or mat made of glass fiber, carbon fiber, asbestos fiber, etc. with a copolymer solution, and then precuring it by drying/heating to obtain a prepreg. °C, 50-3001
- Manufactured by pressing under conditions of cr/d.

For paint applications, different types of solvents may be added and mixed to the polymerization-completed solution as needed, and then the concentration may be adjusted and used for practical use as is.

The composition of the present invention may contain the following fillers in an amount of 70 Mfit% or less, if necessary.

(a) Wear resistance improvers: graphite, carborundum, silica powder, molybdenum disulfide, fluororesin, etc., (b
) Reinforcement agent: glass fiber, carbon fiber, boron fiber, silicon carbide fiber, carbon whisker, asbestos fiber,
Asbestos, metal fibers, (C) Flame retardant improvers: antimony trioxide, magnesium carbonate, calcium carbonate, etc., (electrical property improving agents): clay, mica, etc., (e) Tracking resistance improvers: asbestos, silica, graphite, etc.
(a) Acid resistance improvers: barium sulfate, silica, calcium metasilicate, etc. (b) Thermal conductivity improvers: iron, zinc,
Metal powders such as aluminum and copper, (/l) other glass beads, glass spheres, calcium carbonate, alumina, talc, diatomaceous earth, hydrated alumina, mica, shirasu balloons, asbestos, various gold j, fluoride, inorganic materials Pigments etc. 2
Includes synthetic and natural compounds that are stable above 50°C.

<Example> Hereinafter, the present invention will be explained in further detail with reference to Examples.

It should be noted that the values of %, parts and ratios used in this example indicate the values of % by weight, parts by weight and weight ratio, respectively, unless otherwise specified. Further, the value of the logarithmic viscosity (η1nh), which is a measure of the molecular weight of the polymer, was measured in N-methyl-2-pyrrolidone solvent at a polymer concentration of 0.5% and a temperature of 30°C.

Note that measurements of various physical properties were performed according to the following methods.

Bending stress...ASTM D790 bending modulus...
...ASTM D790 heat distortion temperature...AST
M D648-56 (18,56 kq/cI) Example 1 Content size 5 l equipped with stirrer, thermometer and nitrogen inlet tube
168.2 y (0.84 mol) of 3,4'-diaminodiphenyl ether was placed in a separable glass flask.
, m-phenyl diamine 38.9 y (0.36 mol) and anhydrous N,N-dimethylacetamide (hereinafter referred to as D
2,000 y of IViA (abbreviation: IViA) was charged and stirred to obtain a homogeneous solution. Next, triethylamine 141.
After adding 7f (1.4 mol), the reaction system was cooled to -Io°C in a dry ice/methanol bath, and isophthalic acid dichloride 243.69 (1.2 mol) was added to bring the temperature of the polymerization system to below 10°C. It was divided into small portions at such a speed that it was maintained. After the addition was completed, stirring was continued for 1 hour at 20°C, and then 8.439 (0.06 mol) of benzoyl chloride was added as a terminal treatment agent, and stirring was further continued for 1 hour at 20°C.

Next, the polymerization finished liquid is gradually poured into water under high-speed stirring to precipitate the polymer into flakes.Then, the precipitated polymer is crushed into a fine powder using an impact crusher, and then thoroughly washed with water.
After dehydration and then drying in a hot air dryer at 150°C for 5 hours and then at 200'C for 3 hours, the logarithmic viscosity was 0.7.
Approximately 3381 polymer powders of No. 8 were obtained.

The theoretical structural unit formula % formula % and the corresponding molecular formula of the copolymer obtained here are as follows, and it has a structure in which A units and B or C units are alternately connected, and the copolymer has a structure in which A units and B or C units are alternately connected. The elemental analysis results of the polymer were in good agreement with the theoretical values, as shown below.

-100/70/30 (mole ratio) Elemental analysis results Next, the obtained copolymer powder was fed to a Brabender Plastograph extruder (processing temperature 310-330°C) and extruded while melt-kneading. A uniform pellet was obtained. Next, the obtained pellets are put into a small injection molding machine (
Processing temperature 310-330℃, pressure 1,700-2,10℃
0 kq/d) to prepare test pieces and measure their physical properties, and the results shown in Table 1 below were obtained.

Table 1 Comparative Example 1 m-phenylenediamine as diamine component 129.8
All Example 1 except that 9 (1,2 mol) was used alone.
The same operation as in the first half was carried out to obtain 266 g of polymer powder having a logarithmic viscosity of 0.51.

Next, the obtained polymer was used in the same manner as in Example 1 using a Brabender Plastograph extruder = (processing temperature 320
-360℃), but a smooth melted state did not develop, and the rotational torque applied to the extruder shaft exceeded the allowable limit of the device, making it impossible to make melt-mixed pellets. could not.

As described above, if only the second component of the diamine used in Example 1 is used as the diamine component, only an aromatic polyamide that is difficult to melt mold can be produced.

Comparative Example 2 A polymer with a logarithmic viscosity of 0.81 was prepared by carrying out the same operations as in Example 1, except that 240.3 y (1.2 mol) of 3,4'-diaminodiphenyl ether was used alone as the diamine component. 376 g of combined powder was obtained.

Next, the obtained polymer was fed to a Brabender extruder (processing temperature 310 to 330°C) in the same manner as in Example 1, and extrusion was performed while melt-kneading, and the melt viscosity was extremely high. Although uniform pellets were obtained, they were significantly colored. Next, a piece was made using a small injection molding machine (processing temperature: 310~) using the obtained pellet, and physical properties were measured, and the results shown in Table 2 below were obtained.

Table 2 As shown in Table 2, although melt molding is possible if only the first diamine component used in Example 1 is used as the diamine component, the melt viscosity during melt mixing is extremely high and the thermal stability is poor. The strength and heat resistance of the obtained molded product were also inferior to those of the molded product of Example 1.

Example 2 3,4'-diaminodiphenyl ether 192.2 f/(0.96 mo#) was placed in the same reactor as in Example 1.
m-phenylenediamine26. OII (0.24 mol) MAC 2,000f was charged and stirred to obtain a homogeneous solution. The reaction system was then cooled in a water bath and the isophthalic acid dichloride I 70.5 f (0,84 mol) and terephthalic acid dichloride 73.19 (0,36 mol)
was added in small portions at such a rate as to keep the temperature of the polymerization system below 20°C. After the addition was completed, stirring was continued for 1.5 hours at 30°C, and the resulting polymerized liquid was subjected to the same post-treatment operation as in Example 1, resulting in copolymer powder 3 with a logarithmic viscosity of 0.74.
53f was obtained.

The theoretical structural unit formula and corresponding molecular formula of this copolymer are as follows, and the elemental analysis results also showed good agreement with the theoretical values.

A11. +CO÷C0-), child C8H i0□m C,
(N1(ONH-), +C6Ha N2 +A I
/AI/B/C=0.8410.3610.9610.
24 (mole ratio) -70/3'O/80/20
(Mole ratio) Next, using the obtained copolymer, melt mixing operation was performed in the same manner as in Example 1 to obtain pellets.

Next, this pellet is compression molded (processing temperature 310-340
℃ and a pressure of 50 to 100°C and a pressure of 50 to 9/d) to prepare test pieces and measure their physical properties, and the results shown in Table 3 below were obtained.

Table 3 Comparative Example 3 Terephthalic acid dichloride 243.6F (1
.
56g was obtained.

Next, the obtained polymer was used in the same manner as in Example 2 to produce Prabender Plast Graphextruder (processing temperature: 320°C).
-360℃), but a smooth melted state did not develop, and the rotational torque applied to the extruder shaft exceeded the allowable limit of the device, making it impossible to melt and knead the pellets. could not.

As described above, if the acid component in Example 2 is changed to terephthalic acid chloride alone, which is outside the scope of the present invention, only an aromatic polyamide copolymer that is difficult to melt mold is obtained.

Examples 3 to 6 Copolymers were obtained by carrying out the same operations as in Example 2 except for using the acid component and diamine component shown in Table 5.

These copolymers each had the theoretical structural unit formula shown in Table 5, and the elemental analysis results also agreed well with the theoretical values. Next, the obtained polymer was melt-extruded into pellets in the same manner as in the second half of Example 1. This pellet is compression molded (processing temperature 300-350℃, pressure 50-100'kQ/
A test piece was prepared using d) and the physical properties were measured, and the results shown in Table 5 were obtained.

<Effects of the invention> The aromatic polyamide copolymer of the present invention has a temperature of 250 to 380°C.
It has good melt moldability due to the combination of good thermal stability and fluidity in the temperature range of High performance materials and molded articles can be created. Utilizing their excellent heat resistance and mechanical properties, these materials and molded articles are widely used in fields such as electric + 1 electronic parts, aerospace equipment parts, automobile parts, and office equipment parts.

Patent application Daitoshi Co., Ltd. 30 (complete)

Claims (1)

[Scope of Claims] A, Structural unit of formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ B, Structural units of formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ and C, Formula ▲ Numerical formulas, chemical formulas, tables, etc. The structural unit of
．． C is 0.70-0.02 for 30-0.98 mol
m-phenylene bond/p in A unit
- A thermoplastic aromatic polyamide copolymer characterized in that the ratio of phenylene bonds is 40 to 100/60 to 0 molar ratio, and A and (B or C) are alternately connected. (However, R_1 in the formula is an alkyl group having 1 to 4 carbon atoms,
an alkoxy group or a halogen group, n is 0 or 1, and a is 0 or an integer of 1-4. )