JPS647104B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel resin composition, and more specifically, 2,2-bis(4-hydroxyphenyl)-propane (hereinafter referred to as bisphenol-A) or a derivative thereof and an aromatic dibasic acid or The present invention relates to a composition comprising a polyarylene ester synthesized from a derivative thereof and an oligoester having a higher aliphatic alkylamide terminal group, and having excellent mechanical properties, electrical properties, and moldability. Polyarylene ester is a thermoplastic resin that has a higher heat distortion temperature and superior mechanical and electrical properties than conventional engineering plastics, but it has a high heat distortion temperature and a very high melt viscosity. However, it has the disadvantage of being difficult to mold. Therefore, plasticizers are added as a means of improving molding performance. Hitherto, various plasticizers, such as stearic acid metal salts, fatty acid amides, and fatty alcohols, have been applied as in the case of ordinary thermoplastic resins. In addition, the addition of low molecular weight polyethylene and polyethylene glycols was
This is proposed in Publication No. -5785. however,
In these cases, although improvement in molding performance was observed, the mechanical properties and electrical properties of the polyarylene ester often deteriorated. Also,
In order to improve the moldability of polyarylene ester, the present applicant also first added polyarylene ester to polyarylene ester.
Although the addition of bis fatty acid amides, ester waxes, or metal soaps was proposed in JP-A-50-51152, the improvement in moldability was not necessarily sufficient, and in an attempt to greatly improve moldability, the addition of When the amount is increased, there remains the problem that mechanical properties and heat resistance tend to deteriorate. Therefore, the first purpose of the present invention is to improve the molding performance of polyarylene ester, the second purpose is to improve the molding performance while maintaining the excellent properties of polyarylene ester, and the third purpose is to improve the molding performance of polyarylene ester. The objective is to provide new compositions with properties not found in conventional polyarylene esters. The inventors sought to find plasticizers that are miscible with polyarylene esters in order to find plasticizers that can be used at extremely high molding temperatures and that can improve the moldability of polyarylene esters without impairing their physical properties. As a result of studying the molecular design of a compound that has a good structure and has a plasticizing effect, it was discovered that a specific oligoester can achieve the above object, and the present invention was achieved. That is, the present invention provides (A) 80 to 99.9 parts by weight of a polyarylene ester obtained from bisphenol A or its derivative and an aromatic dibasic acid or its derivative; (B) bisphenol A or its derivative and aromatic dibasic acid or its derivative; 0.1 to 20 oligoesters with a number average molecular weight of 500 to 15,000 and having a higher aliphatic alkylamide terminal group obtained from a dibasic acid or its derivative and an aliphatic primary amine or aliphatic secondary amine having 6 to 50 carbon atoms
It is a polyarylene ester composition consisting of parts by weight. The polyarylene ester used in the present invention is obtained from bisphenol A or a derivative thereof and an aromatic dibasic acid or a derivative thereof. The derivatives of bisphenol A used in the present invention include, for example, its alkali metal salts, alkaline earth metal salts, its alkyl esters or phenyl esters, or its aromatic ring substituted with an alkyl group or a halogen atom. Things can be given. If necessary, bisphenol A or its derivatives can be used in mixtures. The aromatic dibasic acid used in the present invention is represented by general formula (a). HOOC―Ar―COOH (a) In the above formula, Ar represents an arylene group such as an ortho-phenylene group, a meta-phenylene group, or a para-phenylene group, and these arylene groups are substituted with an alkyl group or a halogen atom. Good too. Mixtures of these can also be used if desired. Examples of derivatives of aromatic dibasic acids include dihalides or diesters such as alkyl esters and phenyl esters of the aromatic dibasic acids. For the synthesis of polyarylene ester, any method such as interfacial polycondensation method, solution polymerization method, melt polymerization method, etc. can be applied using both of the above-mentioned components. Suitable polyarylene esters for use in the present invention have a logarithmic viscosity in phenol/tetrachloroethane (6:4 weight ratio) of 0.4 to 1.0. The oligoester used in the present invention is a higher fatty acid obtained from bisfuecour A or a derivative thereof, an aromatic dibasic acid or a derivative thereof, and an aliphatic primary amine or aliphatic secondary amine having 6 to 50 carbon atoms. Number average molecular weight with group alkylamide end groups
500 to 15,000 oligoesters. The bisphenol A derivatives and aromatic dibasic acids or derivatives thereof used in the preparation of such oligoesters are the same as the raw materials for polyarylene ester synthesis and are as described above. Examples of aliphatic primary amines or aliphatic secondary amines having 6 to 50 carbon atoms include stearylamine, laurylamine, n-octylamine,
n-heptylamine, n-hexylamine, t-
Examples include octylamine, oleylamine, di-n-butylamine, diisopropylamine, etc.
Mixtures of these may be used if necessary. Oligoesters can be synthesized by methods such as interfacial polycondensation method, solution polycondensation method, and melt polycondensation method using the above three components, but methods using interfacial polycondensation method are accompanied by deterioration during synthesis. This is preferable in that an oligoester can be obtained without any oxidation. In the synthesis of the oligoester of the present invention, the preferred ratio of the three components used is the aromatic dibasic acid or its aromatic dibasic acid relative to the sum of the number of moles of bisphenol A or its derivative and 1/2 of the number of moles of the aliphatic amine. The ratio is such that the ratio of the number of moles of the derivative is approximately 1. The molecular weight of the oligoester can be adjusted by changing the above ratio from 1, but by changing the ratio of the number of moles of bisphenol A or its derivative to the number of moles of aliphatic amine. ,
It is possible for the aliphatic amine to also function as a molecular weight regulator during synthesis. In the present invention, the ratio of the number of moles of aliphatic amine to the number of moles of bisphenol A or its derivative is preferably 0.05 to 0.50. Hereinafter, the method for synthesizing oligoester will be explained using an interfacial polymerization method as an example. First, an aqueous solution of an acid acceptor, for example, an alkali metal hydroxide, is prepared in an amount equivalent to the sum of twice the molar amount of bisphenol A or its derivative used and the molar amount of the aliphatic amine used. death,
Add bisphenol A or a derivative thereof, then add a solution of an aliphatic amine in an organic solvent such as methylene chloride, and while stirring the mixed solution vigorously, add the acid halide of the aromatic dibasic acid or its derivative. The oligoester is obtained by adding a solution of an organic solvent, for example methylene chloride, and bringing the three components into contact. The number average molecular weight of the oligoester obtained is 500 depending on the ratio of the three components used.
It is possible to adjust the value within the range of ~15,000, but from the viewpoint of the plasticizing effect for the purpose of the present invention and the ease of manufacturing, the value is adjusted to ~1,000.
Preferably it is 5000. The blending ratio of polyarylene ester and oligoester constituting the composition of the present invention is 80:
20 to 99.9:0.1, preferably 90:10 to
The ratio is 99:1. If the content of oligoester is less than 0.1% by weight based on the total weight of polyarylene ester and oligoester, the plasticizing effect will be poor, while if it exceeds 20% by weight, the physical properties of the composition will be significantly deteriorated. Mixing of both components for producing the composition of the present invention is carried out by taking both components in a predetermined ratio and using a known mixing method such as a solution blending method, a Banbury mixer method, a roll method, or an extruder melting method. can be done. It is also possible to prepare a master chip of polyarylene ester containing a large amount of oligoester in advance, mix the polyarylene ester with the master chip, and then use it for molding. In order to improve the heat resistance, light resistance and oxidation resistance of the composition of the present invention, for example, thermal decomposition inhibitors, flame retardants,
Antioxidants, ultraviolet absorbers, etc. may also be present in the composition. In addition, pigments, dyes, other plasticizers, lubricants, etc. may also be used in the composition of the present invention, if necessary. The polyarylene ester composition of the present invention has significantly improved molding performance while retaining the excellent properties of polyarylene ester. The composition of the present invention can be made into various useful products using commonly known plastic molding methods such as press molding, injection molding, and extrusion molding using powder, chips, or other forms. Examples of such products include gears, bearings, electrical parts, containers, and a wide range of other products, which are used in a wide range of applications as products that require high performance as engineering plastics. The present invention will be explained in more detail below by showing reference examples and examples of oligoester synthesis. Reference Example 1 Synthesis of oligoester An aqueous alkaline solution consisting of 3.65 kg of bisphenol A, 1.6 kg of caustic soda and 90 kg of water was placed in a 200 mm jacketed reactor and the temperature was adjusted to 20°C. While stirring this alkaline aqueous solution with a homomixer, a solution of 2.16 kg of stearylamine dissolved in 20 methylene chloride was added. On the other hand, 2.03 kg of terephthalic acid dichloride and 2.03 kg of isophthalic acid dichloride were dissolved in 50% methylene chloride, and the temperature was adjusted to 10°C. This mixed acid chloride solution in methylene chloride is quickly added to the previously stirred solution,
Stirring was continued for 60 minutes. During this time, the reaction system was in an emulsion state, with the aqueous phase and organic phase becoming cloudy and uniformly mixed. After 60 minutes, stop stirring and then
The methylene chloride solution was separated using a liquid-liquid centrifuge rotating at 13,000 rpm, and then extracted and washed using a centrifugal countercurrent extractor. After washing, separate the methylene chloride layer,
This was concentrated by vacuum distillation to an oligomer concentration of 30%. 100 parts by weight of this concentrated methylene chloride solution was added at room temperature to 1000 parts by weight of a methanol solution being stirred with a strong stirrer to precipitate the oligoarylene ester powder. After filtering the powder using a pressure filter, wash the powder with 100 parts by weight of methanol,
The mixture was filtered under pressure in the same manner as above. The obtained oligomer powder was dried at 40°C in a vacuum dryer, and the yield was 90%. The oligomer powder obtained as described above was dissolved in deuterated chloroform, and a nuclear magnetic resonance spectrum (hereinafter referred to as NMR) was measured. The NMR signal values were as follows. δ1.05ppm ( _CH3 proton of stearyl group),
δ1.6ppm (-CH ₂ - proton of stearyl group),
δ1.75ppm (CH ₃ proton of bisphenol A skeleton), δ3.5ppm (N-CH ₂ - of stearyl amino group)
proton), δ7.05-9.05ppm (phenyl proton). The presence of an NMR peak and an amide absorption peak in the infrared absorption spectrum confirmed that the obtained oligoester was an oligoarylene ester having a stearylamide structure at the end. In addition, the number average molecular weight measured by vapor pressure equilibrium method is
It was 2500. Reference Examples 2 to 6 Oligoesters were obtained in the same manner as in Reference Example 1, except that various amines shown in Table 1 were used in place of stearylamine. The number average molecular weights of the obtained oligoesters were as shown in Table 1.

[Table] Examples 1 to 3, Comparative Examples 1 to 3 Manufactured by interfacial polymerization from a methylene chloride solution of mixed acid dichloride with a molar ratio of terephthalic acid dichloride and isophthalic acid dichloride of 1:1 and an alkaline aqueous solution of bisphenol A. Polyarylene esters with a logarithmic viscosity (phenol/tetrachloroethane (6:4 weight ratio) of 0.65) were prepared in Table 2-1.
After kneading at 320℃, the temperature was 300℃ and the pressure was 40℃ using a Koka type flow tester.
The moldability was evaluated by determining the flow rate under the conditions of Kg/cm ² and nozzle size of 1.2 mmφ×10 mm. Also,
The thermal, mechanical, and electrical properties of the composition are determined by mixing the polyarylene ester and oligoester in a super mixer, melting them in an extruder to obtain pellets, and molding the pellets at 320°C. A test piece was obtained. These test pieces were measured according to the test method shown in Table 2-1. For comparison, calcium stearate (SAC) (Comparative Example 1) was used instead of the oligoester in Reference Example 1.
Polyethylene glycol (PEG) (molecular weight 3000)
(Comparative Example 2) and ethylene bisstearamide (EBS) (Comparative Example 3) were similarly tested. The results are shown in Table 2-1. As can be seen from Table 2-1, the composition of the present invention can significantly improve moldability without degrading the inherent physical properties of the polyarylene ester.

[Table] In addition, Table 2-2 lists the measured values of pellets molded after being held in a molten state for 5 minutes at 320°C. The compositions of the present invention retain the excellent mechanical properties of polyarylene esters and exhibit very good retention stability.

【table】

[Table] Examples 4 to 7 Take 98 parts by weight of the polyarylene ester of Example 1 and 2 parts by weight of the oligoesters of Reference Examples 2 to 6,
Molding processability and physical properties were measured in the same manner as in Example 1. The results were as shown in Table 3. As can be seen from Table 3, the composition of the present invention does not reduce the inherent physical properties of the polyarylene ester.
Improves moldability. In addition, the color tone of the external appearance of each molded product was the same as that of the molded product without the addition of oligoester.

【table】

Claims (1)

[Claims] 1 (A)2,2-bis(4-hydroxyphenyl)
- 80 to 99.9 parts by weight of a polyarylene ester obtained from propane or a derivative thereof, an aromatic dibasic acid or a derivative thereof, and (B) 2,2-bis(4-hydroxyphenyl)-propane or a derivative thereof. , an aromatic dibasic acid or a derivative thereof, and a carbon number of 6
Oligoesters with a number average molecular weight of 500 to 15,000 having higher aliphatic alkylamide end groups obtained from ~50 aliphatic primary amines or aliphatic secondary amines
A polyarylene ester composition comprising 0.1 to 20 parts by weight.