JPS61126136A - Thermoplastic aromatic polyamide-imide copolymer - Google Patents

Abstract

PURPOSE:A heat-resistant, thermoplastic polymer having good heat stability, flow and melt moldability and being excellent in the balance among the properties of a molding, consisting of there specified structural units. CONSTITUTION:A copolymer consisting of a structural unit (A) of formula I, at least one structural unit (B) selected from units of formulae II and III and a structural unit (C) of formula IV, wherein one mold of B+C is present per mol of A, and 9-1mol of C is present per 1-9mol of B. In the formulae, Z is a trifunctional aromatic group in which two of the three functional groups are bonded to an adjacent carbon, R1 is a 1-4C alkyl or alkoxy, R2 is a 1-4C alkyl, alkoxy or a halogen, Y is formula V or the like, X is Y or -SO2-, R3 is a 1-4C alkyl, fluorine-substituted alkyl or the like, a is 0, 1 or 2, b is 0 or 1-4, and c is 0 or 1.

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 particularly in the temperature range of 300 to 400°C and is injection moldable. , polyamideimide is abbreviated as FAI).

<Prior art> By polycondensing an aromatic tricarboxylic acid anhydride or its derivative with an aromatic diamine or its derivative,
It is already well known that aromatic FAI with excellent heat resistance can be obtained. However, when the aromatic PAIs that have been generally proposed so far are intended to be used as melt molding materials, they have a high thermal stability during melt molding, fluidity during melt molding, The total balance of physical properties was not always satisfactory.

For example, the general formula FAI synthesized from trimellitic anhydride and 3,3'-dimethyl-4,4'-diaminobiphenyl has excellent heat resistance, but the flow initiation temperature and thermal decomposition temperature are too close to each other. Therefore, melt molding is practically impossible.

Also, PAL expressed by the general formula synthesized from trimellitic anhydride chloride and 4,4'-[sulf,honylbis(p-phenyleneoxy)]didiazine (for example, JP-A-49-129.
799) and FAI expressed by the general formula synthesized from trimellitic anhydride and L4'-(p-phenyle/diisoglopylidene)bisaniline, the difference between the flow start temperature and the thermal decomposition temperature is 50 ℃ or higher and has excellent thermal stability and fluidity during melt molding, so it shows good melt moldability. ) does not necessarily reach a satisfactory level.

<Problems to be Solved by the Invention> Therefore, the present inventors have developed a molded article that has good melt formability by having both good thermal stability and fluidity in the temperature range of 300 to 400°C, and As a result of extensive research aimed at obtaining an aromatic FAI with an excellent balance of physical properties, we found that by combining two different specific aromatic diamine components in a previously unknown composition, we were able to achieve the desired properties. New thermoplastic aromatic FA
The present invention was achieved by discovering that an I copolymer can be obtained.

means and actions for solving the problems, i.e.
The present invention is characterized in that the ratio of the selected at least one structural unit and the structural unit is such that B+C is 1 mol to 1 mol of A, and C is 9 to 1 mol to 81 to 9 mol. A thermoplastic aromatic polyamide-imide copolymer (in the formula, Z is a trifunctional aromatic group in which two of the three functional groups are bonded to adjacent carbons, and Kl is an alkyl group having 1 to 4 carbon atoms) group or alkokene group, R is an alkyl group having 1 to 4 carbon atoms, an alkoxy group or a no-open R1 group,
an alkyl group having 1 to 4 atoms, a 7-substituted alkyl group, or an aromatic group having 6 to 9 carbon atoms, Q is a direct bonding group, -C-1-C
H, -1-〇-1-S-1-Nf-1-CO- or -5O2-1a is o, i or 2. b is O or 1-4
C is an integer of 0 or l. ).

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

Z 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.

As a specific example of B unit, for example, and side chain substituted derivatives thereof.

As a specific example of C unit, for example, etc.

The proportion of each of the above units in the PAI copolymer of the present invention is:
B+C is 1 mol per 1 mol of A, and C is 9-1 mol per 81-9 mol, preferably 8-2 mol per 82-8 mol. C unit 5! it B
If the FAI content exceeds 90 mol% of +C, the resulting FAI will become crystalline and its melting point will exceed the thermal decomposition temperature, making it difficult to melt and mold, making it almost impractical as a thermoplastic material. It's inappropriate.

On the other hand, FAI obtained when the C unit of B+C decreases
The thermal properties (especially the heat distortion temperature) of
It is necessary to apply at least 10 mol % of +C.

It should be noted that the imide bond in the above A unit may be in the state of an amic acid bond as its ring-closing precursor, but may be present in a part of the A unit, for example, 50 mol% or less, preferably 30 mol% or less of the A unit. Within the scope of the present invention.

The PAI copolymer of the present invention can be produced using any of the many general production methods that have been proposed so far, but the following is a representative example of the most practical. 3
Laws can be mentioned.

(1) Incyanate method: A method of reacting aromatic diiso7anate with iminodicarboxylic acid synthesized from aromatic tricarboxylic anhydride and/or aromatic tricarboxylic anhydride/aromatic diamine (2/1 molar ratio) (For example, Japanese Patent Publication No. 44-19,274, Japanese Patent Publication No. 45-2
, No. 397, Special Publication No. 33, 120 of 1980, etc.).

(2) Acid chloride method: A method in which an aromatic tricharta/acid anhydride chloride is reacted with an aromatic diamine (for example, Japanese Patent Publication No. 15,637/1984).

(3) Direct polymerization method: A method in which an aromatic tricarboxylic acid or its derivative (excluding acid chloride derivatives) and an aromatic diamide are directly reacted in a polar organic solvent in the presence of a dehydration catalyst (for example, Japanese Patent Publication No. 49-4077 Publication No.).

Among the above three methods, the acid chloride method is preferred because it is relatively easy to procure raw materials, and it is easy to obtain FAI with a high degree of polymerization with excellent linearity (less branched structure) due to low-temperature solution polymerization. It has many advantages and is the most recommended manufacturing method. Here, a more specific example of the production of the PAI copolymer of the present invention by the acid chloride method is as follows.

That is, a mixture consisting of 1 mol of aromatic tricarboxylic acid anhydride monochloride and 10 to 90 mol % of an aromatic diamine of the following formula (1) or (1 formula) and 90 to 10 mol % of an aromatic diamine of the following formula 0.9 to L1 mol of diamine are dissolved in an organic polar solvent.

X is Y or a -SO,- group, R is an alkyl group or alkogia group having 1 to 4 carbon atoms, and R2 is R.

or a halogen group, R3 is an alkyl group having 1 to 4 carbon atoms,
Fluorine-substituted alkyl group or carbon then -20-8
After mixing for about 0.5 to 1 hour at a temperature of 0°C, if necessary, about 0.9 to 2.0 mol of hydrogen chloride scavenger is added to accelerate the reaction rate. The polymerization reaction is completed in about 0.5 to 10 hours.

The polymer produced in this step has a structure in which most of the A units (for example, 50 to 100%) of the PAI copolymer of the present invention are converted to the amide amic acid units of the ring-closing precursor, so-called polyamide amic acid t-components. ing. The organic polar solvent used in this first step is
These include N11N-dialkylcarboxylic acid amides such as dimethylacetamide, heterocyclic compounds such as N-methylpyrrolidone and tetrahydrothio7!7-1ill-dioxide, and phenols such as cresol and xylenol, and in particular, N-methylpyrrolidone. / and N@N-
Dimethylacetamide is preferred. In addition, the hydrogen chloride scavenger added as required for the first step is:
Aliphatic tertiary amines such as trimethylamine, triethylamine, tripropylamine, tributylamine, cyclic organic bases such as pyridine, lutidine, choline, quinoline, organic oxide compounds such as ethylene oxide, propylene oxide, etc. It is.

The polyamide amic acid obtained in the first step above is then subjected to a second dehydration ring closure step, and the polyamide amic acid obtained in the first step is then subjected to a second dehydration ring closure step. Ming's PAI
Converted to copolymer.

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. There are two types of liquid phase ring closure: a liquid phase chemical ring closure method using a chemical dehydrating agent, and a simple liquid phase thermal ring closure method. Chemical ring closure methods include aliphatic anhydrides such as acetic anhydride, gropionic anhydride, POClj.

SOC1! It is carried out at a temperature of 0 to 120<0>C using a chemical dehydrating agent such as P20s. Further, the liquid phase thermal ring closure method is carried out by heating the polyamide/amic acid solution to 50 to 400°C, preferably 100 to 250°C. In this case, azeotropic solvents such as benzene, toluene, xylene, etc.
It is more effective when used in combination with chlorobenzene, etc. In the in-phase thermal ring closure, first, a polyamide-amic acid polymer is isolated from the polyamide-amic acid solution obtained in the first step,
This is done by heat treating it in a solid state.

As a precipitant for isolating polyamide 0 amic acid polymer,
A liquid that is miscible with the reaction mixture solvent, but in which the polyamide/amic acid itself is insoluble, such as water, methanol, etc., is employed. Heat treatment is usually 150 to 350
℃ and 0.5 to 50 hours to ensure the desired ring closure rate and melting fluidity.

Care must be taken because if the treatment is carried out in the 250 to 350° C. range for too long, the polymer itself tends to form a three-dimensional crosslinked structure, which significantly reduces the fluidity during melting.

Specific examples of the aromatic diamines represented by the above general formulas (1), (I') and (1) include the divalent aromatic residues shown above as specific examples of the B unit and C unit of the present invention. It is displayed with an amino group (C-NHt) attached on both sides.

By the production method detailed above, the PAI copolymer targeted by the present invention can be obtained, but the PAI copolymer that also produces other copolymer components other than the components constituting the A unit, B unit, and C unit in the reaction system Copolymerization in combination in a quantitative range that significantly reduces the melt processability and physical properties of
It is possible and within the scope of this invention.

The PAI copolymer of the present invention has a structure in which the imide units are partially ring-opened amic acid bonds, but the majority has a ring-closed structure, and the polymer concentration in N-methylpyrrolidone solvent is 0.5% by weight, a highly polymerized polymer with a logarithmic viscosity (η1nh) value measured at 30°C of 0.25 or more, preferably 0.30 or more, and is used for various purposes such as the following. be able to.

Compression molding is performed by tri-blending the PAI copolymer powder of the present invention with different polymers, additives, fillers, reinforcing agents, etc. as necessary, and then processing the mixture at a temperature of usually 300 to 400°C and a pressure of 50 to 500°C.
#/d conditions. In addition, extrusion molding and injection molding are performed by tri-blending the PAI copolymer of the present invention with different polymers, additives, fillers, reinforcing agents, etc. as necessary, or by pelletizing this by extruding it into pellets. Feed to extrusion molding machine or injection molding machine, 30
It is carried out under temperature conditions of 0 to 400°C. In particular, the aromatic PAI copolymer of the present invention has an excellent balance of thermal stability and fluidity in the 300 to 400°C region, and is useful for extrusion molding and injection molding.

In addition, by further subjecting the molded product obtained by heating and melting molding the PAI copolymer of the present invention to heat treatment under high temperature conditions, a molded product with further improved physical properties such as heat distortion temperature, tensile strength, bending strength, and friction and wear properties can be obtained. Obtainable. 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 220°C or higher and below (glass transition temperature -5°C) of the molded product for 5 hours or more, especially 10 hours. It is appropriate to heat the mixture more than that. If the heat treatment temperature exceeds the glass transition temperature of the molded article, the molded article is undesirably deformed during the heat treatment and has a strong tendency to impair its practicality. Although there are no particular restrictions on the equipment that performs this heat treatment, a normal electric heating 9-type open can sufficiently achieve the purpose.

For film and fiber manufacturing applications, polymerization termination solutions can be applied in dry or wet-dry casting processes;
Furthermore, the isolated polymer can be melt-molded by adding suitable additives as necessary. 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.
Manufactured by pressing under conditions of 0°C and 50 to 300 #/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.

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 of 0.5% and a temperature of 30°C.

The melt viscosity of the polymer was measured using a "Koka-type Flow Tester" manufactured by Shimadzu Corporation. A sample that had been dried to an absolutely dry state was placed in a cylinder heated to 360°C, where it remained for 8 minutes, and then sheared. The measurement was carried out under a kinetic condition of 1,0005 ec-. Also, the glass transition temperature is made by PerkinElmer! Measurement was performed using a B-type DSC device.

In addition, measurements of each plant material were performed according to the following method.

Bending stress...ASTM D790 bending modulus...
... 〃 Heat distortion temperature ... ASTM D648-56 (18
, 56 kq/d) <Example> Example 1 Internal volume 5 equipped with a stirrer, thermometer and nitrogen gas inlet pipe
3,3'-dimethyl-4,4'-diaminobiphenyl 127.4 F (0
, 60 mol), 4-4'-sulfonylbis(p-phenyleneoxy)cyanily/259.5 y (0,60
mol) and anhydrous N-N-dimethylacetamide 2,0
00f was charged and stirred to obtain a homogeneous solution. The reaction mixture was cooled to -10°C in a dry ice/acetone bath and
-(Chloroformyl)phthalic anhydride 253f (120 mol) was added portionwise in small portions at such a rate that the temperature was maintained between -1θ and -5°C. After continuing stirring at 20°C for an additional hour, 152F (1.5 moles) of anhydrous triethylamine was added in portions at a rate sufficient to maintain the temperature below about 30°C.

Next, the polymerized liquid is gradually poured into water under high-speed stirring to precipitate the polymer into particles.Then, the precipitated polymer is crushed into a fine powder using an impact crusher, and then thoroughly washed with water and dehydrated. and then in a hot air dryer at 150°C for 5 hours, followed by 2
After drying at 00°C for 3 hours, about 48 of polymer powders with a logarithmic viscosity of 0.52 were obtained.

The theoretical structural unit formula and the corresponding molecular formula of the copolymer obtained here are as follows, and B has a structure in which A units and B or C111 positions are alternately connected, and the copolymer The elemental analysis results shown below showed good agreement with the theoretical values.

B, =Q-iQ-3o-○-0 唖chi, Shima 4H1g 0
4 minutes A/B/C= 1210.610.6 (molar ratio)
= loo/s O150 (mole ratio) Elemental analysis results Next, the obtained copolymer powder was treated with tetrafluoroethylene resin (Asahi Glass Co., Ltd. Paflon Bolimist F-s''>o, After adding s% and 0.5% titanium oxide, the Brabender Plastograph extruder (
The pellets were fed to a treatment temperature of 340 to 360° C. and extruded while being melted and kneaded twice to obtain uniformly blended pellets. Next, the obtained pellets are compression molded (processing temperature 330-36
A test piece was prepared at 0° C. and a pressure of 50 to 100 #/i), and the physical properties were measured, and the results shown in Table 1 below were obtained.

Table 1 Next, under the same conditions as above, a compression molded test piece was placed in a hot air dryer and dried at 150°C for a day and night, and then dried at 245°C for 24 hours.
When heat treatment was subsequently performed at 260° C. for 48 hours, the physical properties after heat treatment were as shown in Table 2 below, which were significantly improved compared to the results in Table 1.

Table 2 (after heat treatment) Example 2 As a diamine component, 4-4'-propylbis (p-7
All operations were the same as in the first half of Example 1, except that Enile/Oquin) dianiline 147.8f (0.36 mol) and 3,3-dimethoxy-4,4-diaminobia z=#205.2F (0.84 mol) were used. The logarithmic viscosity is 0.46.
About 500f of copolymer powder was obtained.

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

A/B/C = 1210.3610.84 (mole ratio) = 100/30/70 (mole ratio) Next, using the obtained copolymer, tetrafluoroethylene resin 0.596 was prepared in the same manner as in Example 1. After blending 0.5% of titanium oxide and 0.5% of titanium oxide, a melt mixing operation was performed to obtain pellets. Next, this pellet 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.

Example 3 2,2-bis(4-aminophenyl)propane 8L51C0,36 and 3,3-dimethyl-4 as diamine components
The same procedure as in the first half of Example I was carried out except that -4-diaminobiphenyl 178.3F (0.84 mol) was used to obtain about 40 Of copolymer powder with a logarithmic viscosity of 0.42. This copolymer consisted of the following theoretical structural units and molecular formula, and the elemental analysis results also agreed well with the theoretical values.

Next, the obtained polymer was used in the same manner as in Example 1 to obtain 0.0% tetrafluoroethylene resin. After blending 5% and 0.5% of titanium oxide, a melt mixing operation was performed to obtain pellets. Next, this pellet was compression molded under the same conditions as in Example 1 to create a test piece, and the physical properties before and after heat treatment were measured in the same manner as in Example 1, and the results shown in Table 3 below were obtained. .

Table 3 Comparative Example 1 3,3'-dimethoxy-4,4'- as diamine component
Diaminobiphenyl 293.2F (12 mol), 303
'-Dimethyl-4-4'-diaminobiphenyl254.
The same procedure as in the first half of Example 1 was carried out except that 8f (12 mol) or benzidine 221f (12 mol) was used alone, and the logarithmic viscosity was 0.47 and 0.4, respectively.
Approximately 450-500 f of polymer powder of 1 and 0.55 was obtained. Next, the obtained polymer was used in the same manner as in Example I.
0.5% fat and 70.5% titanium oxide
After blending, when we fed it to a Verabender gelastograph extruder (processing temperature 340-360℃) and performed a melt cross-fertilization operation, a smooth melted state did not appear, and the rotational torque value applied to the extruder shaft exceeded the permissible limit of the equipment, and virtually no melt crosstalk was possible.

As described above, if only the second component of the diamine used in Examples 1 and 2 was used, only polyamideimide, which was difficult to melt mold, could be produced.

All other operations were the same as in Example 1 to obtain a copolymer.

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 pressure of 50 to 100#/L4) was applied to prepare a test piece, and the physical properties were measured, and the results shown in Table 4 were obtained.

Claims (1)

[Scope of Patent Claims] A, Structural unit of the formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ B, Formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ and Formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ Selected from The ratio of each structural unit is 1 mole of B+C to 1 mole of A, and B1 to B9. A thermoplastic aromatic polyamide-imide copolymer characterized in that C is 9 to 1 mole per mole. (However, Z in the formula is a trifunctional aromatic group in which two of the three functional groups are bonded to adjacent carbons, R_1 is an alkyl group or alkoxy group having 1 to 4 carbon atoms, R_2
is an alkyl group having 1 to 4 carbon atoms, an alkoxy group or a halogen group, Y is ▲Mathematical formula, chemical formula, table, etc.▼, ▲Mathematical formula, chemical formula,
There are tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ group, Group group, Q is a direct bond, -C-, -CH_2-, -O-, -S-, -NH-CO- or -SO_2-, a is 0, 1 or 2, b is 0 or 1
An integer of ~4, c represents 0 or 1. )