JPS63295634A - Polyester-imide - Google Patents

Abstract

PURPOSE:To obtain the title lowly water-absorptive, melt-moldable compound excellent in heat resistance, mechanical properties, dimensional stability, solvent resistance, etc. comprising specified recurring units. CONSTITUTION:An imidedicarboxylic acid (a) (esterifiable derivative) of formula I, obtained by reacting m-xylylenediamine with trimellitic anhydride and option ally esterifying the product (e.g., diphenyl N,N'-m-xylylenebistrimellitimidate) is polycondensed with 100-150mol%, based on component (a), aromatic diol (b) of formula II (wherein Ar is a bivalent aromatic group), e.g., 2,2-bis(4- hydroxyphenyl)propane, at 200-360 deg.C in the presence of, optionally, a catalyst and a stability to obtain the title compound comprising recurring units of formu la III and having an intrinsic viscosity [as measured in a solution in a phenol/ tetrachloroethane mixed solvent (weight ratio 60/40) at 35 deg.C] >=0.4.

Description

[Detailed description of the invention] Field of application in the poultry industry> The present invention relates to the popular polynisderimide,
IL< relates to a novel polynisdelimide that can be melt-molded, has heat resistance of 0, mechanical properties of 0, dimensional stability of 0, bath agent resistance of 4, and low water absorption, and is useful as engineering plastics.

<Prior art> In recent years, polymers such as polyetherimide, polynyfursulfone, and polyetherketone have been developed as resins that can be bath melt molded and have excellent mechanical properties and heat resistance.
Among these resins, it is known that amorphous (ti) resins, which have excellent molding dimensional stability, have problems in chemical resistance compared to crystalline resins. Chemical resistance tends to improve as the chemical resistance increases, and for this purpose, seeds such as polyamide and polyamide-imide are being considered. However, these polyamides and polyamide-imide certainly have poor chemical resistance. However, its use is severely limited due to its high water absorption.

On the other hand, various polymers that can be used as -ffK polyesterimide are being considered, and if you try to obtain something with high heat resistance, the polymer will be crystalline and have a high melting point, or even if it is non-grade, the melt viscosity will be low. or, those with low melt viscosity may have poor solvent resistance, resulting in poor moldability!
Things that are well-balanced with l1IQ are not necessarily ◇.

<Object of the Invention> The object of the present invention is to provide a durable polyesterimide that can be subjected to normal T6 melt molding, has excellent mechanical properties such as dimensional stability, heat resistance, and chemical resistance, and has low water absorption. It is about providing.

<Structure of the Invention> The object of the present invention as described above is to provide a repeating unit whose main polymer repeating unit is represented by the following formula (1) % formula % (1) (wherein Ar represents an aromatic group of 2i111) This can be achieved by the polyesterimide of the present invention, which is a polyesterimide consisting of the following and has an intrinsic viscosity of 0.4 or more.

The polynisdelimide of the present invention has the following formula (U)...
・Imidodicarbonate fR component represented by ([) and the following formula (1
11) % Formula %(1) (In formula (ill), Ar is the same as formula CI). ) can be obtained by polycondensation with an aromatic diol represented by:

The imidodicarboxylic acid represented by the formula (AI) can be obtained very easily from m-xylylene diamine and trimellitic anhydride by a conventionally known imidization reaction KL.

Although imidodicarboxylic acid can be used as it is for polycondensation, it is also preferable to use it as an ester-forming derivative thereof. The ester-forming derivatives include methyl,
Alkyl esters such as ethyl, phenyl.

Examples include 7-reel esters such as tolyl, among which 7-reel esters are preferred, and phenyl esters are particularly preferred. For example, when phenyl ester of imidodicarboxylic acid is used, the above imidization reaction is carried out in a phenol solvent, and the reaction is completed! ! A preferred method is to subsequently perform phenyl esterification using a phenol such as imidodicarboxylic acid #lfI&.

As an aromatic diol represented by the above formula (ill),
Specifically, 2,2-bis(4-diphenyl)
F, , <n, bis(4-hydroxydiphenyl)methane = 1tl-bis(4-hydroxyphenyl)ethane, 1.1-bis(4-hydroxydiphenyl)cyclohexane, bis(4-hydroxyphenyl)methane diphenyl)ether, bis(4-W-talkediphenyl)sulfone, bis(4
-*Droxyphenyl)ketone, bis(4-hydroxyphenyl)sulfide, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane.

2.2-bis(3,5-dichloro-4-cycloquinphenyl)propane, 2.2-bis(3,5-dibrom-4
-Hydroxyphenyl)furopane.

Examples include 2.2-bis(4-hydroxyphenyl)hexafluoropropane, resorcinol, and phenolphthalein. Among these aromatic diols, 2.
2-bis(4-human-0,000-diphenyl)propane is particularly preferred. These aromatic diols can be used in one or two or more types. Further, the aromatic diol may be used as it is, or may be used as an ester-forming a-conductor. Examples of the ester-forming derivative include acetate and the like.

The polyesterimide of the present invention may be copolymerized with a small amount of other carboxylic acids in addition to the imidodicarboxylic acid represented by formula m1 (■) above. Examples of other types of dicarboxylic acids that can be copolymerized include prephthalic acid, isophthalic acid, diphenyldicarboxylic acid, and naphthalene-2,6-dicarboxylic acid.

4.4'-i or 3,4'-diphenyl ether dicarbonate fermentation Diphenoxyethane dicarbonate fermentation.

4.41- or 394'-diphenylsulfonedicarboxylic acid, p-oxybenzoic acid, cohelic acid, 7-divinyl,
Examples include heptavananic acid.

The amount of ore used for these other types of carboxylic acids is preferably 50 mol % or less, more preferably 40 mol % or less based on the total carboxylic acids used.
The content is preferably 30 mol% or less, preferably 30 mol% or less.

Further, in the polyesterimide of the present invention, the aromatic diol represented by the formula (Ill) above may be replaced with a small amount of other 1m component. The components include aliphatic or monocyclic diols such as 6-diol, ethylene glycol, neobenzene gelylcol, cyclohexane-1,4-dimethane, 4*4'-diaminodiphenylmethane, 4*4'- Diaminodiphenylsulfone.

3.3'-Diaminodiphenyl sulfone-4w4'-Diaminodiphenyl ether, 314'-:)7zNodiphenyl ether 1m-xylylenediamine.

Inphorone diamine, hexamethylene diamine.

Examples include amine M such as dodecamethylene diamine, P-7ζ-benzoic acid*m-7i-benzoic acid, and aminocarboxylic acids. Here, when using amines and 7minocarbons a, 7! Some of the de-bonds will be converted into co-x-bonds.

The proportion of the above components used is preferably 50 mol % or less, more preferably 40 mol % or less, particularly preferably 30 mol % or less, based on the total 1 tK of the aromatic diol and other components.

The polyester imide of the present invention can be obtained by a conventionally known IS method using the imidodicarbonate final component or a component mainly composed thereof and the aromatic diol or a component mainly composed thereof. Examples of the shaping condensation method include a method of di-clutch esterification of a dicarboxylic acid and a diol, a method of reaction of a dicarboxylic acid ester and a diol, and a method of reaction of a dicarboxylic acid and a diol ester. Among these, it is preferable to use the reaction between the dicarboxylic acid ester and the diol ◎ In this Mld1 reaction, the dicarboxylic acid component and the diol component are charged at a rate of 1 diol to tC of the dicarboxylic acid.
00-150 mol%, preferably 100-125 mol%
1 shift. Ti shrinkage@1 temperature is usually 200~36 +
) C, preferably at 240 to 340° C., and by-products (I/lI, water, phenol, etc.) produced by reaction 1C are distilled out of the trr system. The reaction atmosphere at that time is usually pressurized to normal pressure to a slightly higher pressure, and in the final stage of 1:1, the reaction atmosphere is less than 1 dragon IIg. In the case of pressurized to normal pressure reactions, it is preferable to carry out the reaction under an atmosphere of an inert gas such as iris or argon.

It is preferable to use a catalyst and/or a stabilizer during the polycondensation reaction. /! As an i+ medium, 7 nzā nan,
Metal compounds such as titanium, tin, germanium, sodium, potassium, lithium, calcium, magnesium, aluminum, lead, and manganese can be mentioned, and stabilizers include triphenylphosphite and triphenylphos77-),). Preferred examples include phosphide derivatives such as riaenylphosphine and trimethylphosphite.

The polynisdelimide of the present invention was prepared at 35°C using a mixed solvent of phenol/tetracoolethane (weight ratio 60/40).
It is necessary that the intrinsic viscosity measured at Φ is 0.4 or more. If the intrinsic viscosity is 0.4 or less, the resulting molded product will have low mechanical strength, which is not preferred. The intrinsic viscosity is preferably 0.45 or more, particularly preferably 0.5 or more.

The polyesterimide of the present invention, for example, one using 2,2-bis(4-hydroxyphenyl)propane as the aromatic diol, is an amorphous polymer with a glass transition temperature of 193° C. and has excellent heat resistance. In addition, it has excellent mechanical properties and solvent resistance, and low water absorption, so its industrial value as a new resin is extremely large.

The polynisdelimide of the present invention is required to be used as an absorbent, an oxidizing agent, a coloring agent, and a lubricant.

#l11ait You may allocate the amount of filler for each planting item.

<Effects of the Invention> The conventional bath melt molding of the present invention as described above, such as extrusion molding, extrusion molding, and injection molding, is effective, and the molded product obtained by mochi melting is , mechanical properties 0
It not only has excellent dimensional stability, heat resistance, and chemical resistance, but also has low water absorption, making it extremely suitable as an engineering plastic.

<Examples> The present invention will be described in detail below with reference to Examples. In the examples, "1 part" means "heavy filtration part"; the intrinsic viscosity is phenol/tetrachloroethane mixed bath medium (weight ratio t
jO/40) was measured once a month at 35°C. In addition, the glass transition temperature (Tg) of the polymer was determined using DSC at the heating rate [
ll111 was determined at 10°C/min.

Examples 1 to 5 636 parts of N+N'-m-xylylene-bistrimeritimid diphenyl ester, tetrabutyl titanate)
0.17 parts and a predetermined amount of the aromatic diol shown in 1 were charged into a glass reactor equipped with a stirring device and a Shinpei distillation system, and heated at 250°C for 30 minutes and at 290°C for 30 minutes in a phonetic air flow.
Heat reaction at 0℃ for 30 minutes, then about 10w1 in 15 minutes
190 vacuum, IJ to the east, 5 m agricultural IIg high No. 4
I had him serve me downstairs. All of the obtained polymers were brown, transparent, and amorphous, and their Tg values shown in Table 1K were excellent in heat resistance.

Example 6 The polymer obtained in Example 1 was dried with hot air at 150° C. for 4 hours, and then injection molded under the conditions of a polymer temperature of 111:325° C., a metal content of 130° C., and a molding cycle of about 3 minutes.

The obtained molded product is transparent and has a tensile strength of 580 hours/d, a tensile modulus of elasticity of 16,200 kg/m, and a bending strength of 1,200 to/d9.
The bending elastic modulus was 18,000 kg/Makoto.

Example 7. Comparative example 1 77 tons of the molded product obtained in Example 6, xylene.

The bath agent resistance was evaluated by immersing it in triclene for 24 hours at room temperature. The results are shown in Precept 2. Comparative example 1 is shown in Table 2.
(Poly7 rylate resin (Unitika U-polymer (8)
)), it can be seen that although the polynisderimide of the present invention is an amorphous polymer, it has extremely excellent bath agent resistance.

Table 2 Example 8 636 g of N+N'-m-xylylene bistrimeritimid diphenyl ester, 116 parts of hydroquinone, 0.14 parts of 7-thimony oxide, and 0.2 triphenyl phosphate
The reactor was placed in the same reactor as in Example 1 and purged with nitrogen, then the temperature was raised to 330°C over 50 minutes at 250°C under normal pressure for 20 minutes. The reaction was carried out for 40 minutes under high vacuum of KO,4n+l19.

The obtained polymer was transparent, brown, and amorphous, and had a Tg of 1.
At 84°C, the intrinsic viscosity was 0.60.

In this example, hydroquinone is used as the aromatic diol represented by the above formula (lit), but in producing the polyesterimide of the present invention, in addition to hydroquinone, methyl/S hydroquinone, enalhydroquinone, n-propylhydroquinone, inpropylhydroquinone, t-bunalhydroquinone, t-7
Milhydroquinone, cool hydroquinone. Phenylhydroquinone, penzylnohydroquinone.

α-phenyl ether hydrochlorinone can also be used.

Claims (1)

[Claims] The main polymer repeating unit is the following formula (I)▲Numerical formula,
There are chemical formulas, tables, etc. ▼ ...(I) (However, in formula (I), Ar represents a divalent aromatic group.) Consists of repeating units represented by phenol/
A polyesterimide characterized by having an intrinsic viscosity of 0.4 or more as measured at 35°C using a tetrachloroethane mixed solvent (weight ratio 60/40).