JPS62169848A - Polyarylate-containing composition - Google Patents

Abstract

PURPOSE:To obtain a compsn. having excellent heat resistance, flame retardance and moldability, by blending a polyarylate with a thermoplastic polymer in a specified ratio. CONSTITUTION:A compsn. consists of 8-80wt% polyarylate composed of a repeating unit of the formula and 20-92wt% thermoplastic polymer. In the formula, Ar is a benzene or naphthalene ring; Ph is a p-phenylene, m-phenylene or o-phenylene group. The arom. ring may be substituted by halogen, a 1-20C alkyl, an aryl, an alkoxy or an aryloxy group. The polyarylate may be a copolymer with 4,4'-dicarboxydiphenyl or hydroquinone. Preferred examples of the thermoplastic polymer are polycarbonate, polysulfone, and polyethylene terephthalate.

Description

Detailed Description of the Invention (Industrial Field of Application) The present invention relates to a polyarylate-containing composition, and more particularly, to a polyarylate-containing composition containing a polyarylate and a thermoplastic polymer having heat resistance, flame retardancy, and moldability. The present invention relates to a composition with excellent properties.

(Prior Art) Polyarylate has been known as a heat-resistant polymer. For example, 4-hydroxybenzoic acid homopolymer and 4-hydroxybenzoic acid copolymer (Sumitomo Chemical, trade name ECONOL)
, or a compound consisting of bisphenol A, terephthalic acid, and isophthalic acid.
Polymer) was once proposed and is now commercially available.

Such polymers inherently have relatively high melting points or have a distribution temperature lower than the melting or softening point, resulting in poor moldability. (2) Poor color tone. (3) Poor transparency. (4) Heat resistance is insufficient. (5) It had the disadvantage of poor flame retardancy.

A heat-resistant polyarylate consisting of a specific phosphinic acid compound and TPA and/or IPA previously proposed by the present inventors (Japanese Patent Application No. 59-96196).

Certain phosphinic acid compounds, bisphenol A and IPA
Heat-resistant copolyarylate consisting of
8827), and a heat-resistant copolyarylate comprising a specific phosphinic acid compound, resorcinol, and IPA (Japanese Patent Application No. 59-202820).

Although most of these drawbacks have been solved, the results are still not completely satisfactory.

On the other hand, various thermoplastic polymers, including polyetheretherketone, polyethylene terephthalate, polybutylene terephthalate, and polycarbonate (hereinafter referred to as PC), are used as engineering plastics with good moldability, but they do not meet the requirements of plastics. The performance achieved is increasing year by year as society becomes more sophisticated.

Even in the above-mentioned polymers, which are considered to be excellent resins, even higher heat deformation resistance and flame retardance are strongly desired in many fields.

(Problems to be solved by the invention) As mentioned above, in the prior art like 1- above,
The problem remains that it is difficult to satisfy all properties such as heat resistance, flame retardance, and melt moldability.

Therefore, a principal object of the present invention is to provide a composition with excellent heat resistance that is particularly suitable for plasma spray coating and molded articles used at high temperatures.

Still another object is to provide a composition that has good heat resistance, high flame retardancy, sufficient strength, and excellent moldability.

(Means for Solving the Problems) The present inventors have developed a molded product that can be molded even at a temperature of 350°C and has excellent heat resistance without deteriorating the physical properties of the molded product.
Furthermore, as a result of intensive research into flame retardant compositions, it was discovered that a blend of 2% constant phosphorus-containing polyarylate and a thermoplastic polymer has extremely excellent properties, resulting in the present invention.

That is, the present invention provides a polyarylate-containing composition comprising 8 to 80% by weight of a polyarylate consisting of a repeating unit represented by the following structural formula (I) and 20 to 92% by weight of at least one thermoplastic polymer. The main points are as follows.

(In the formula, Ar represents a benzene ring or a naphthalene ring, and ph represents a para-phenylene group, a meta-phenylene group, or a io-orthophenylene group. However, the aromatic ring has a halogen atom or 1 to 20 carbon atoms. One component constituting the composition of the present invention is represented by the above structural formula (1). Naropo 117 from one unit I! rate. Such a polyarylate is obtained by polycondensation (II) from a phosphorus-containing aromatic diol and an aromatic dicarboxylic acid,
((V), (V) and other organic phosphorus compounds are mentioned.

f(OOH) As the aromatic dicarboxylic acid, it is preferable to use terephthalic acid frequently. If terephthalic acid is not included at all, polyarylate with low reactivity and a high degree of polymerization can be obtained when producing polyarylate. There is a problem in that the strength and other properties of the obtained polyarylate may be relatively reduced.Therefore, as the aromatic dicarboxylic acid component, for example, terephthalic acid (T
PA), inphthalic acid (IPA), TPA/IPA
molar ratio of 10/90 to 10010, preferably Ha2
0/80~90/10. Optimally 50150-80/2
It is preferable to set it to 0.

In addition, polyarylate, as other copolymerization components,
For example, 4,4'-dicarboxydiphenyl, bis(
4-carboxyphenyl)methane, 2゜2-bis(4-
carboxyphenyl) propane.

It may also be a copolymer of bis(4-carboxyphenyl) ether, naphthalic acid, hydroquinone, resorcinol, 6-O-2-naphthoic acid, 4-hydroxybenzoic acid, or the like.

Below, 9.10-dihydro-9-ogycer 1O-(2;'5'-dihydroxyphenyl)phosphaphenanthrene-10-oxide (P
HQ') and TPA and I as aromatic dicarboxylic acids.
A method for producing polyarylate will be explained using an example using PA.

First, equimolar moles of an acid component consisting of TPA/IPA and a diol component consisting of PHQ, and more than twice the equivalent (preferably 1.05 to 1.25 times equivalent) of acetic anhydride (Ac20) of the diol component are added to a reactor. Prepared under normal pressure.

The esterification reaction is carried out at a temperature of about 150° C. for about 2 hours. After that, the temperature is raised sequentially, and if necessary, acetic acid (A
cOH) is accumulated and subjected to an acid exchange reaction.

After that, the final product is 1 t at a temperature of usually 250 to 350°C.
2 Invention I/c by carrying out a polycondensation reaction in the melt phase or solid phase for several hours to several tens of hours under high vacuum in an open groove.
The polyarylate to be used is manufactured. usually.

A catalyst is used in the polycondensation reaction, and when producing polyarylate, for example, one or more compounds selected from various metal compounds or organic sulfonic acid compounds are used. Such metal compounds include antimony, titanium, germanium, tin, zinc, aluminum,
magnesium.

Compounds such as calcium, manganese, sodium or cobalt are used, while organic sulfonic acid compounds such as sulfosalicylic acid and 0-sulfobenzoic anhydride (O8B) are used, while dimethyltin malate (C8 ) and O8B are particularly preferably used. The amount of the catalyst added is 1 structural unit of polyarylate.
The amount used is usually 0, I x 10 to 10,010 mol, preferably 0.5 x 0 to 50 x 10 mol, most preferably 1 x 10 to 10,010 mol.

Depending on the type of structural unit of the polyarylate during the polycondensation reaction, it may solidify into a solid state, or it may be able to undergo polycondensation while remaining in a molten state.

Suitable examples of thermoplastic polymers that are other components constituting the composition of the present invention include polycarbonate (PC),
Polyetheretherketone (PEEK).

Polysulfone (PS), Polyethersulfone (PE
S), polyphenylene ether (PPEE), polyphenylene sulfide (PI) S), polyethylene terephthalate CPET'), polybutylene terephthalate (
Various thermoplastic resins, such as PBT) isobaric, can be mentioned, and PC is particularly preferably used.

As the PC, a commercially available polycarbonate (for example, "Corpilon"; manufactured by Mitsubishi Gas Chemical) may be used, and a particularly suitable PC is a 4,4-dioxydiallylalkane polycarbonate, such as bis(4-hydroxyphenyl). Methane, bis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl)propane, bis(4-hydroxy-3,5-dichlorophenyl)methane, 2゜2-bis(4-hydroxy-3, It is a PC obtained from 4,4-dioxydiphenylalkanes such as 5-dimethylphenyl)propane and bis(4-hydroxyphenyl)phenylmethane and phosgene or diphenyl carbonate. Two or more types of thermoplastic polymers can also be used.

The content ratio of the polyarylate component and the thermoplastic polymer component in the composition of the present invention is such that the polyarylate component accounts for 8 to 80 parts, preferably 20 to 80 parts, relative to the total amount of both components.
by weight, optimally from 50 to 80% by weight, while thermoplastic polymers from 20 to 92% by weight, preferably from 20 to 80% by weight.
The weight is 50 to 80 t%. If the polyarylate component exceeds these ranges, the strength will decrease.

On the other hand, if the thermoplastic polymer component is increased, the glass transition point temperature becomes low and the flame retardance becomes poor, which is not preferable.

The compositions of the invention can be prepared by homogeneously mixing the components, for example, by solution blending or by a two-roll, Banbury mixer-2 extruder or other mixing machines known in the art.

(Examples) Hereinafter, the present invention will be explained in more detail by giving examples.

The glass transition temperature and melting point of the polymers in the nine examples were measured using a differential scanning calorimeter (Model DSC-2, manufactured by PerkinElmer) at a heating rate of 20° C./min.

Izot impact strength was measured at 1/8 inch thickness according to the ASTM D 256 standard.

Flame retardancy is according to UL-94 standard and JIS
It was determined by the limit oxygen index according to the K 7201 standard.

The moldability was evaluated using the J-100-3 molding machine manufactured by Nippon Steel Corporation to determine the conditions for molding a 100φ x 1/8 inch disk test piece and based on the following criteria.

A score of 0 or more was considered a pass.

◎: Injection time is 10 seconds or less and molding temperature is 330℃
Below ◎: Injection time is 10 seconds or less and molding temperature is 330℃
Less than O: Injection time is 10 to 15 seconds and molding temperature is 330
Less than ℃ △: Injection time is 15 to 30 seconds and molding temperature is 330
Less than ℃ ×: Injection time is 30 seconds or more or molding temperature is 330℃
Examples 1 to 3 PHQ and acetic anhydride were charged into an esterification reactor at a molar ratio of 1:2.5, and diacetate (PHQ-A) was produced by esterifying the mixture in acetic anhydride under reflux.

PHQ-A and TPA were charged in a 1:1 molar ratio to a condensation reactor, and 1 x 10 mol of dimethyl tin maleate (C3) was added as a catalyst per 1 mol of the structural unit of polyarylate. The reaction was allowed to proceed with mixing for 8 hours at °C. The esterification reaction rate calculated from the weight of distilled acetic acid was about 95%.

This reaction product was further heated at 320°C under a reduced pressure of 0.1 torr.
The temperature was finally raised to 340°C and condensation was carried out for a total of 10 hours. During this time, the product went from a molten state to a solid state.

Note that no sublimation of the raw materials PHQ-A and TPA was observed during the reduced pressure reaction.

This polymer and PC (Mitsubishi Gas Chemical's "Nipilon S"
2000J) in the ratio shown in Table 1 in a mixer, and then a screw extruder equipped with a die with a diameter of 4 mφ at the tip (screw diameter 30 + nmφ, Lβ = 20
) and extruded the strands at a screw rotation speed of 30 rpm and a processing temperature according to the mixing ratio shown in Table 1.
Granular samples were obtained by cutting to length.

Using this sample, a sample piece with dimensions of 1/8" x 1/8" x 5" was molded and subjected to physical property tests. The results are shown in Table 1.

Examples 1 to 24 Mixing and extrusion were carried out in the same manner as in Example 1, except that the Ikenonetsumachi plastic injection resin shown in Table 1 was used instead of PC.

The material was cut and molded, and its physical properties were evaluated.

The results are shown in Table 1.

In the table, PEEK is ICI's product name rPEIDKJ.

PS is the product name "Cordel Polysulfone" manufactured by UCC.

pgs is a product name of rVICTREX (R) J manufactured by ICI.
, PPE stands for Noryl J manufactured by GE, PPS stands for polyphenylene sulfide resin manufactured by Philinobus Petroleum.

Comparative Example 1 The polyarylate obtained in Example was used alone at 42
It was molded at 0°C and its physical properties were evaluated. The results are shown in Table 2.

Comparative Examples 2 to 9 The thermoplastic resin used in Examples 1 to 8 was individually molded, and its physical properties were evaluated. The results are shown in Table 2.

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□> , >;>>i Table 2 (Effects of the Invention) The composition of the present invention optimizes the high heat resistance and flame retardancy of polyarylate and the excellent moldability of thermoplastic polymer. It has a balance of

As described above, the composition of the present invention is heat resistant and flame retardant.

Since it has all three properties of formability in a well-balanced manner, it is particularly useful as an engineering plastic.

Claims (2)

[Claims] (1) A polyarylate-containing composition comprising 8 to 80% by weight of a polyarylate consisting of repeating units represented by the following structural formula (I) and 20 to 92% by weight of at least one thermoplastic polymer. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) (In the formula, Ar represents a benzene ring or naphthalene ring, and Ph represents a para-phenylene group, meta-phenylene group, or ortho-phenylene group. However, aromatic rings are halogen atoms. or may be substituted with an alkyl group, aryl group, alkoxy group or allyloxy group having 1 to 20 carbon atoms.) (2) The composition according to claim 1, wherein the thermoplastic polymer is polycarbonate, polyetheretherketone, polysulfone, polyethersulfone, polyphenylene ether, polyphenylene sulfide, polyethylene terephthalate or polybutylene terephthalate.