JPS61126137A - Thermoplastic aromatic polyamide-imide copolymer - Google Patents

Abstract

PURPOSE:To provide a heat-resistant thermoplastic polymer which has good thermal stability, flow characteristics and melt-moldability and gives moldings having well-balanced physical properties, consisting of three specified structural units. CONSTITUTION:A copolymer consists of a structural unit (A) of formula I, a structural unit (B) of formula II and a structural unit (C) of formula III in such a ratio that B+C is 1mol per mol of A and C is 8-1mol per 2-9mol of B. In the formulas, Z is a trifunctional arom. group wherein two functional groups of three functional groups are attached to neighbor carbon atom; X is O, S; Y is a group of formula IV, V or Vi; R1 is a 1-4C alkyl, alkoxy; R2 is a 1-4C alkyl, fluorine-substd. alkyl, a 6-9C arom. group; Q is direct bond, -CO-, -CH2-, -O-, -SO2-; a is 0, 1, 2; h is 0, 1-4; c is 0, 1, 2.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a novel heat-resistant thermoplastic polymer. More specifically, the purpose is to provide a new thermoplastic aromatic polyamide-imide copolymer that has good thermal stability and fluidity, especially in the temperature range of SOa to 400°C, and is capable of injection molding. (hereinafter,
It is abbreviated as polyamideimide'@FAI.

<Prior art> By polycondensing aromatic triorboxylic acid anhydride or its derivative with aromatic diamine or its derivative,
It is already well known that aromatic pAx with excellent heat resistance can be obtained.

However, until now it has been generally proposed that the aromatic F
When the purpose of using Class X as a melt molding material is that it is not necessarily satisfactory in terms of the total performance of thermal stability during melt molding, fluidity during melt molding, and physical properties of the melt molded product. It was not something that could be done.

For example, trimellit anhydride has the general formula PAD synthesized from chloride and 4,4'-diaminodiphenylphenyl ether (for example, described in Japanese Patent Publication No. 15,657/1982), which has excellent heat resistance, but the flow start temperature Since the thermal decomposition temperature is too close, melt molding is practically impossible. Also, PAU having the same general formula (for example, Canadian Patent No. 1.02 (1,2
No. 99 and PAR (described in Japanese Patent Publication No. 46-15515, for example) having the general formula also cannot be practically melt-molded because the flow start temperature and the thermal decomposition temperature are too close to each other.

As one of the attempts to improve the above-mentioned shortcomings of PAK known so far, phx is configured “□4.4′
-diaminodiphenylmethane (HzN-diaminodiphenylmethane
A method of copolymerizing nu-hon has been proposed (for example, US Pat. No. 5,748,504, JP-A-47-aOfJ
However, among these, FAI copolymerized with units with poor thermal stability is not necessarily suitable as a melt molding material because its thermal stability decreases according to its content. It is unsatisfactory.

The inherently low synthesis activity poses a major obstacle in terms of polymer productivity. 2. In any case, the copolymers proposed above are not necessarily satisfactory in practical terms.

<Problems to be Solved by the Invention> Therefore, the present inventors have developed a material that has good melt moldability by having both good thermal stability and fluidity in the temperature range of 500 to 400°C. As a result of intensive studies aimed at obtaining an aromatic FAI with excellent physical properties and puffiness of molded products, we found that different specific aromatic diamines 2
A novel thermoplastic aromatic F that has the desired properties by combining components in a hitherto unknown composition.
The present invention was achieved by discovering that an AI copolymer can be obtained.

means and actions for solving the problems, i.e.
The present invention consists of a structural unit of co\A2 formula (monNH-co-zN) and a structural unit, and the ratio of each structural unit is B to 1 mole of A2.
+O is 17μ and C is 8~9μ for B2~9μ
A thermoplastic aromatic polyamideimide copolymer characterized by having a molecular weight of 1 μm (however, 2 in the above formula is a pentafunctional aromatic compound in which two of the three functional groups are bonded to adjacent carbons). group,
&, Rt), an alkyl group having 1 to 4 carbon atoms, a fluorine-substituted alkyl group, or an aromatic group having 6 to 9 carbon atoms! group, Q is a direct bond, 11 -C-1-0H, -1-0- or -5ol-1a is 0.1 or 2, b is 0 or 1 to 4, Q is an integer of Oll or 2. vinegar. It is a simple offer. .

The thermoplastic aromatic FAI copolymer of the present invention is mainly composed of three units represented by A, B and C above.

2 in the A unit is a trifunctional aromatic group in which two of the three functional groups are bonded to adjacent carbons, and examples include the following.

For example, a specific example of B unit is and side chain substituted derivatives thereof.

As a specific example of C unit, for example, 0T1s CFis
Examples include CFI@lPm and their side chain substituted derivatives.

The ratio of each of the above units in the thermoplastic aromatic FAI copolymer of the present invention is such that B+C is 1 mole to A1 mo/I/l, and C is 8 to 1 mole to B2 to 97p. μ Preferably, C is 6 to 2 monoV for B4 to 87p.

F obtained when B units exceed 907μ% of B+C
Since AI becomes crystalline and its melting point exceeds the thermal decomposition temperature, melt molding is virtually impossible, which defeats the purpose of the present invention. When a C unit is copolymerized with a B unit, the resulting FAI gradually becomes inferior and its melt flowability is improved. but,
Copolymerization of C units tends to reduce the mechanical properties of the resulting FAI. (Izotsu) 11 This is not preferable because the impact strength decreases noticeably.

In addition, when the imide bond in the above A unit remains in the form of an amic acid bond as its ring-closing precursor, A'
It is also within the scope of the present invention when the unit is present as a part of the A units, for example, 507 μ% or less, preferably 507 μ% or less of the A units.

The thermoplastic aromatic PAZ copolymer of the present invention can be produced using any of the many general production methods that have been proposed to date, but the following are representative examples of highly practical methods: There are five methods.

(1) Incyanate method: Reacting aromatic diisocyanate with iminosica μboxylic acid synthesized from aromatic tricarboxylic acid anhydride and/or aromatic tricarboxylic acid anhydride/aromatic diamine (2/1 molar ratio) Method(
For example, Japanese Patent Publication No. 44 = + 9.274, Publication No. 2.597 of 1972, Publication of Japanese Patent Publication No. 5G-35,120 of 1972.
Publications, etc.).

(2) Acid crophyte method: A method in which aromatic tricaponic acid anhydride chloride and aromatic diamine are reacted (for example, Japanese Patent Publication No. 15.657/1983).

(3) Direct polymerization method: A method in which an aromatic tricarboxylic acid or a derivative thereof (excluding acid chloride derivatives) and an aromatic diamine are directly reacted in a polar organic solvent in the presence of a dehydration catalyst (for example, Japanese Patent Publication No. 49-4.077) Public bulletin),.

Among the above five methods, the acid chloride method has the advantage that it is relatively easy to procure raw materials, and that it is easier to obtain a highly polymerized polyamide-imide with excellent linearity (fewer branched structures) than low-temperature solution polymerization. This is the most recommended manufacturing method. Here, a more specific example of the production of the uninvented PkX copolymer by the acid crophyte method is as follows. That is, aromatic membrane tricaponic acid anhydride monocrophyte 1 mop, aromatic diamine of the following formula (1) 20 to 90 mol %, aromatic diamine of the following formula ([) 80 to IO mo/I/96 mo, A mixed diamine consisting of [
19 to 1.17 μm is dissolved in an organic polar solvent.

(Here, ~9 aromatic groups, Q is a direct result, a is 0.1 or z, b is 0 or 1 to 4, and C is an integer of 0.1 or 2. Under temperature conditions of approximately 15 to 1
After mixing for a period of time, approximately 9 to 2.0 mol of hydrogen chloride nucabenger is added as required to accelerate the polymerization reaction rate, and the polymerization reaction is completed at around room temperature in a reaction time of 05 to 10 hours.

The polymer produced at this stage contains most of the A units (for example, 50 to 100%) of the polyamide-imide copolymer of the present invention.
It has a structure in which a ring-closing precursor is converted into a 7-amide amide unit, a so-called polyamide amic acid. The organic polar solvent used in this first step is
N-N-thia μ-kylcarboxylic acid amides such as dimethylacetamide, N-methoxyhydrolidone, compound cumulative formula compounds such as tethohydrothiophenylene-1-dioxide, and phenolic compounds such as cresol and xyleno-p. /I/ etc., especially N-methylpyrrolidone and N-N
-dimethylacetamide is preferred. In addition, the hydrogen chloride scavenger added as necessary to the above first step is
Trimethylamine, triethylamine, trimethylamine, triamine
, aliphatic tertiary amines such as triglythylamine, cyclic organic bases such as pyridine, μtidine, collidine, and quinoline, and organic quinodo compounds such as ethylene oxide, glopyrene oxide, and the like.

The polyamideimide acid obtained in the first step above is subsequently subjected to a second dehydration ring closure step to convert it into the PAD copolymer of the present invention. The dehydration ring closure operation is carried out either by liquid phase ring closure in solution or solid phase thermal ring closure by heating in a solid.

For liquid phase ring closure, there is a liquid phase conversion method using a chemical dehydrating agent,
There are two simple liquid phase thermal confinement methods.

The chemical ring closure method is performed using #acid anhydride, aliphatic anhydride such as gropionic anhydride, POCl3. Using chemical dehydrating agents such as halogen compounds such as 80012, P2O,
It is carried out at a temperature of Q% + 20 °C.

In addition, in the liquid phase mature ring closure method, polyamide/amic acid solution is
This is carried out by heating at 0 to 400°C, preferably 100 to 250°C.

In this case, it is more effective to use an azeotropic solvent useful for removing water, such as benzene, toluene, xylene, chlorobenzene, etc. in combination. The solid phase thermal ring closure is carried out by first isolating a polyamide/amic acid polymer from the polyamide/amic acid solution obtained in the first step and heat-treating it in a solid state. As a precipitant for isolating the polyamide/amic acid polymer, a liquid such as water, methanol, etc., which is miscible with the reaction mixture solvent but in which the polyamide/amic acid itself is insoluble, is employed. The heat treatment is usually selected from conditions of 150 to 350°C and 115 to 5 hours to ensure the desired ring closure rate and melting fluidity. If the treatment is carried out in the 250-550°C range for too long, the polymer itself will form a three-dimensional crosslinked structure.
Care must be taken as this tends to significantly reduce fluidity during melting.

The specific examples of the aromatic diamines represented by the above general formulas (1) and (11) have amines on both sides of the 29-valent aromatic residues shown above as specific examples of the B unit and C unit of the present invention. It is displayed with a mino group (-NFE2) attached.

By the production method detailed above, the PA copolymer which is the object of the present invention can be obtained.
It is possible to copolymerize other copolymerization components other than those constituting the B and C units within a quantitative range that does not significantly reduce the melt processability and physical properties of PAD. and is included within the scope of the present invention. .

The PA engineering copolymer of the present invention has a structure in which the imide units are partially open amic acid bonds, but most have a ring-closed structure, and in N-methylpyrrolidone solvent, the polymer Logarithmic viscosity (η1nh7 value is 125 or more, preferably [L3
It is a polymer with a high polymerization degree of 0 or more, and can be used for various purposes such as those listed below.

Compression molding is carried out after tri-blending different types of polymers, additives, fillers, reinforcing agents, etc. according to the requirements of the PAI copolymer powder of the present invention.
Extrusion molding and injection molding are carried out under the conditions of "Q Okg/lx". Extrusion molding and injection molding are carried out by tri-blending the FAI copolymer of the present invention with different polymers, additives, fillers, reinforcing agents, etc. as necessary. The process is carried out by supplying the extruder or injection molding machine to an extruder or an injection molding machine at a temperature of 300 to 400°C.Special aroma of the present invention 1!1. PA engineering copolymer is 500
It has an extremely good balance of thermal stability and flow properties in the range of ~400°C, making it useful for extrusion molding and injection molding.

Furthermore, by further subjecting the molded article obtained by heating and melting molding the PAK copolymer of the present invention to heat treatment under high-temperature conditions, physical properties such as heat distortion temperature, tensile strength, bending strength, and abrasion and abrasion characteristics were greatly improved. Molded products can be obtained. Such heat treatment conditions include heating the molded product at a temperature of 200°C or higher and below the glass transition temperature of the molded product, particularly at a temperature of 220°C or higher and below (glass transition temperature -5°C) of the molded product for 5 hours or more; In particular, it is appropriate to heat for 10 hours or more.If the heat treatment temperature exceeds the glass transition temperature of the molded product, the molded product will be deformed during the heat treatment, which is undesirable because there is a strong tendency to impair its practicality.This heat treatment is There are no particular restrictions on the equipment used, but a normal electric heating oven can suffice to achieve the purpose.

For film and fiber manufacturing applications, the polymerization termination solution can be applied to a dry or wet-dry casting process.
Furthermore, the isolated polymer can be melt-molded by adding suitable additives as necessary. The laminate is impregnated with a cloth or mat monocopolymer solution composed of glass fiber, carbon fiber, asbestos fiber, etc., and then precured by drying/heating to obtain a prepreg.
It is produced by pressing under the conditions of 400° C. and 50 to 100°C.

For paint applications, after adding and mixing different types of solvents to the polymerization-completed solution as needed, the concentration can be adjusted and the solution can be put to practical use as it is.

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

Note that the values of %, parts, and ratios used in this example indicate the values of weight %, parts by weight, and weight ratio, respectively, unless otherwise specified. Further, the value of the logarithmic viscosity, which is a guideline for the molecular weight of the polymer, was measured in N-methyl-2-pyrrolidone solvent at a polymer concentration α of 5% and a temperature of 50°C. The melt viscosity of the polymer was determined by using a "Koka-type Flow Tester" manufactured by Shimadzu Corporation. After placing a sample that had been dried to an absolutely dry state in advance in a cylinder heated to 560°C and retaining it for 8 minutes, The measurement was performed under the conditions of a shear rate of about 1 and OOO5ea-'.The glass transition temperature was also measured using a PerkinElmer Model IB DSC device.

The various physical properties were measured according to the following method.

Bending stress: ASTM D790 bending modulus
... ASTM D7?0 heat distortion temperature ...
・・ASTMD648-56CIIL&6kg/cm
Example 1 ``Inner volume 5 equipped with a stirrer, thermometer and nitrogen gas inlet tube
g's glass seperate rug! Fufusco 4.4'-ji7mi/
Sif enitV :t, -f Iv I 61L 5
g (a84moA/), 2.2-his (4-7t/7Z
21V) fcI/<:/B 1.5g (rLA6Mo7L
/) and anhydrous N-N-dimethypacetamytom 000
g was charged and stirred 4 times to obtain a homogeneous solution. The reaction mixture was cooled to -10°C in a dry ice/acetone bath and 4-
(Chlorophomi tv > flA hydrophthalic acid 255 g (
1,207 N) was added in small portions at such a rate that the temperature was maintained at -10 to -5°C. After continuing stirring at 20° C. for an additional hour, 152 g (1.5 μm) of anhydrous triethyl amine was added in portions at a rate sufficient to maintain the temperature below about 30° C.

Next, the polymerization finished liquid was gradually poured into water under high-speed stirring to precipitate the polymer into particles, and then the precipitated polymer was crushed into a fine powder using an impact crusher. After washing with water/dehydration and then drying in a hot air dryer at 150°C for 5 hours and then at 200°C for 5 hours, the logarithmic viscosity was 172.
Approximately 400 g of polymer powder was obtained.

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

iQ Fim H3 A/B/c-1,2/cL84/a,56 (Moy ratio)
-++ + 00/70/S O (7p ratio) elemental analysis results Next, the obtained copolymer powder was treated with tetrafluoroethylene resin (Asahi Glass Co., Ltd. 1' Avron Polymist) as an anti-burning agent. After adding 315% of 1p-5" and 15% of titanium oxide, the mixture was fed to a Prabender Plastoglar 7 Ext/I'-der (processing temperature 340 to 560°C) and extruded twice while being melted and kneaded. A uniformly mixed pellet was obtained.The melt viscosity of this pellet was 8. Temperature 330-56
(1'c, pressure 50 - IGO 11g/α2) A test piece was prepared by applying the same pressure and the physical properties were measured, and the results shown in Table 1 below were obtained.

Table 1 Next, compression molded test pieces obtained under the same conditions as above were placed in a hot air dryer and dried overnight at 150°C, then heat treated at 245°C for 24 hours and then at 255°C for 48 hours. The physical properties after heat treatment were 7°C for the following nail AJ table OL, which was significantly improved compared to the results in Table 1.

%2 table (after heat treatment) Example 2 4.4'-diaminodiphenis pμ as diamine component
Phyto15 [1g ((L60mo/L/) and 4.4'
-(P-phenylene-di-iso-10-pylidene)bis72! J
All except using 20 & 4g ([L60mon)!
! The same operation as in the first half of Example 1 was carried out to obtain about 500 g of copolymer powder having a logarithmic viscosity of α52. The theoretical structural unit formula and corresponding molecular formula of this copolymer are as follows, and the results of single element analysis also showed good agreement with this theoretical value.

HO ~ (H3CFh A / B / c = t 2 / α6 / α6 (7μ ratio, 100150150 (mole ratio)) Next, using the obtained copolymer, tetrafluoroethylene resin was prepared in the same manner as in Example 1. After blending α5% and titanium oxide 0.5%, a melt mixing operation was performed to obtain pellets.This pellet was then compression molded under the same conditions as in Example 1 to prepare a test piece, and the physical properties were measured. The results shown in Table 5 below were obtained.Table 5 also shows the physical properties of this test piece after heat treatment under the same conditions as in Example 1.Heat treatment 〇Table 3 Example 5 As the diamine component, 4.4'-(ppheniVndioquinfupisaniline + 22-68 ((L42moA/) and 2,2-bis (4-7 Minofueni/l/) Propa7
Approximately 450 g of a copolymer powder with a logarithmic viscosity of a and 55 was obtained by carrying out all the same operations as in the first half of Example 1 except using 17 & 5 g ((L78 MoJv). This copolymer had the following theoretical 111 ta unit and molecular formula. The elemental analysis results also agreed well with this theoretical value.

H.O. Oh.

A/B/C+=i, 2/α42/Q, 7
8 (mole ratio + 00155/65 (mole ratio)) Next, using the obtained polymer, after blending tetrafluoroethylene resin (L5%) and titanium oxide [L5%], - After repeated kneading, the bath melt viscosity is 6XIO'
Obtained boiz pellets.

Next, this PVC was compression molded under the same conditions as in Example 1 to prepare a test piece, and the physical properties were measured, and the following results were obtained.

Comparative example 1 a,4'-J amino diphene as a diamine component.

NILET A/ 240g (1,27 l/
All examples except that 260 g (1,2 mo/L/) of 4,4'-diaminodizeni μ sulfide or 350 g (1,27 N) of 4,4'-p aminophenoxybenceph were used alone. Approximately 400 g of polymer powders having logarithmic viscosities [L84.0.54 and 168] were obtained by carrying out the same operation as in 1. Next, the obtained polymer was blended with 15% tetra7tethylene resin and 5% titanium oxide [L] in the same manner as in Example 1. ~56
When we performed the melt mixing operation by supplying the product to a temperature of 0°C, a smooth melt line did not appear, and the rotational torque applied to the extruder shaft exceeded the allowable limit of the equipment, resulting in virtually no melting. Therefore, by using only the first component of each of the diamines used in Examples 1, 2 and 3, only polyamideimide, which is difficult to melt and mold, could be produced.

Examples 4 to 7 Copolymers were obtained by carrying out the same operations as in Example 1 except for using the two diamines shown in Table 4.

These copolymers each had the theoretical structural unit formula shown in Table 4, and the elemental analysis results also agreed well with the theoretical values. Next, the obtained copolymer was compression molded (processing temperature: 350-400℃)
A test piece was prepared under a pressure of 50 to 100 kg/cs''31, and the physical properties were measured, and the results shown in Table 4 were obtained.

Claims (1)

[Claims] A, a structural unit of the formula ▲ there are mathematical formulas, chemical formulas, tables, etc. ▼ B, a structural unit of the formula ▲ there are mathematical formulas, chemical formulas, tables, etc. ▼ and C, a structural unit of the formula ▲ there are mathematical formulas, chemical formulas, tables, etc. It consists of ▼ structural units, and the ratio of each structural unit is B to 1 mole of A.
+C is 1 mole, and C is 8 to 2 to 9 moles of B
A thermoplastic aromatic polyamide-imide copolymer having a molecular weight of 1 mol. (However, Z in the above formula is a trifunctional aromatic group in which two of the three functional groups are bonded to adjacent carbons, X is oxygen or sulfur, and Y is ▲ mathematical formula, chemical formula, table, etc.) ▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ or ▲There are mathematical formulas, chemical formulas, tables, etc.▼ Group, R_1 is an alkyl group or alkoxy group with 1 to 4 carbon atoms, R_2 is an alkyl group with 1 to 4 carbon atoms, Fluorine-substituted alkyl group or aromatic group with 6 to 9 carbon atoms, Q is a direct bond, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, -CH_2-
, -O- or -SO_2-, a is 0, 1 or 2, b
represents 0 or an integer of 1 to 4, and c represents an integer of 0, 1 or 2. )