JPS6236068B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to an aromatic polyester polycarbonate resin composition with improved moldability and impact resistance. Aromatic polyester polycarbonate is a resin with a linear structure having an ester bond and a carbonate bond in the same molecule, such as 2,2-bis(4-hydroxyphenyl)propane (bisphenol A), terephthaloyl chloride. It is produced by reacting phosphorus and phosgene, and is known to have excellent mechanical properties, weather resistance, chemical resistance, and transparency. (Tokukai Akira
52-128992) However, such aromatic polyester polycarbonates have a high softening temperature and high melt viscosity, so they have the disadvantage of poor moldability. For example, when producing a molded article by injection molding, high molding temperature, mold temperature and injection pressure are required. However, using such a high temperature causes thermal deterioration of the polymer, and using a high injection pressure causes the product to become distorted, which is inconvenient.Moreover, the cost is high, so the moldability of the polymer is affected. Improvement was desired. The present inventors have conducted extensive research to improve the above-mentioned drawbacks of aromatic polyester polycarbonate, and have found that when compounding rubber with aromatic polyester polycarbonate, it is possible not only to greatly improve its moldability, but also to improve the moldability of the aromatic polyester polycarbonate. The present invention was completed based on the knowledge that impact resistance can also be improved. That is, the present invention aims to provide an aromatic polyester polycarbonate resin composition having improved moldability and impact resistance and having great industrial value, and the gist thereof is as follows: The structural unit represented by and the general formula The molar ratio of dihydroxydiaryl compound residue: terephthalic acid residue: carbonate bond is from 1:0.33 to 0.75:0.67.
0.25 aromatic polyester polycarbonate
This is an aromatic polyester polycarbonate resin composition in which 1 to 50 parts by weight of rubber (B) is blended with 100 parts by weight of (A). In addition, in the general formulas [] and [], X represents a divalent group, and the aromatic nucleus may have a substituent. The present invention will be explained in detail below. The aromatic polyester polycarbonate targeted by the present invention has, for example, the general formula (In the formula, X is a divalent group, for example

【formula】

[Formula] represents -O-, -S-, -SO-, -SO ₂ -, etc. R is a hydrogen atom or a monovalent hydrocarbon group,
R' represents a divalent hydrocarbon group. Further, the aromatic nucleus may have a halogen atom or a monovalent hydrocarbon group as a substituent. ) is reacted with a terephthaloyl chloride in the presence of an organic solvent such as methylene chloride and an acid binder such as pyridine, and then phosgene is introduced into the reaction mixture to cause polycondensation. Solution polymerization method (Japanese Unexamined Patent Publication No. 1983)
-128992), or an alkaline aqueous solution of a dihydroxydiaryl compound represented by the general formula [] shown above is reacted with an organic solvent solution of terephthaloyl chloride to form an oricomer with an -OH group at the end, and then this reaction mixture is added to phosgene. is introduced to form an oligomer with a chloroformate group at the end, and a solution of this oligomer in an organic solvent is reacted with an alkaline aqueous solution of a dihydroxydiaryl compound represented by the above general formula [] to cause polycondensation. Therefore, it can be manufactured. Industrially, the latter method is advantageous in that it is not necessary to use pyridine, which has a large recovery loss and a strong odor. The amounts of the dihydroxydiaryl compound, terephthaloyl chloride, and phosgene to be used are such that the molar ratio of dihydroxydiaryl compound residue: terephthalic acid residue: carbonate bond in the resulting aromatic polyester polycarbonate is 1:0.33 or more.
0.75:0.67-0.25, preferably 1:0.33-0.49:
It is appropriately selected to be 0.67 to 0.51. If the molar ratio of terephthalic acid residues is less than this, the improvement in the glass transition point is unsatisfactory, and on the other hand, if the molar ratio of carbonate bonds is too small, the inherent properties of polycarbonate will be impaired. However, this composition molar ratio was determined by infrared spectrum analysis as −COO−
This value was determined from the peak ratio of the group 1740 cm ^-1 and the -OCOO- group 1770 cm ^-1 . Specific examples of the dihydroxydiaryl compound represented by the general formula [] include: bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 2,2-bis(4- hydroxyphenyl)propane, 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)octane, bis(4-hydroxyphenyl)phenylmethane, 2,2-bis( 4-hydroxy-3-methylphenyl)propane, 1,1-bis(4-hydroxy-3-tert-butylphenyl)propane, 2,2-bis(4-hydroxy-3-bromophenyl)propane, 2,2-bis( Bis(hydroxyaryl)alkanes such as 4-hydroxy-3,5-dibromophenyl)propane, 2,2-bis(4hydroxy-3,5-dichlorophenyl)propane, 1,1-bis(4 -hydroxyphenyl)cyclopentane, bis(hydroxyaryl) such as 1,1-bis(4-hydroxyphenyl)cyclohexane
cycloalkanes, dihydroxydiarylethers such as 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dimethylphenyl ether, 4,4'-dihydroxydiphenyl sulfide , dihydroxydiaryl sulfides such as 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfide, 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxy-3,3' - Dihydroxydiarylsulfoxides such as dimethyldiphenylsulfoxide, 4,4'-dihydroxydiphenylsulfone, dihydroxydiarylsulfones such as 4,4'-dihydroxy-3,3'-dimethyldiphenylsulfone, etc. . In addition to terephthaloyl chloride, terephthaloyl chloride has a halogen atom in its nucleus,
Terephthaloyl chloride having an alkyl group, such as 2,5-dichloroterephthaloyl chloride, 2,5-dibromoterephthaloyl chloride, chlorterephthaloyl chloride, methylterephthaloyl chloride, 2,5-dimethylterephthaloyl chloride Examples include il chloride. The aromatic polyester polycarbonate of the present invention produced in this manner has the formula η _sp /C=[η]+0.427[η] ² from η _sp measured at 20°C using a 0.6 g/dl methylene chloride solution. It is desirable that the intrinsic viscosity [η] calculated by C is 0.4 to 1.5, preferably 0.43 to 1.1. [η]
If it is too large, the moldability will be poor, and if it is too small, the mechanical properties will be insufficient. Further, the glass transition point (Tg) of the aromatic polyester polycarbonate is usually 160 to 190°C, preferably 170 to 185°C. Furthermore, it is preferable that the aromatic polyester polycarbonate has a terminal carboxy group of 10 μequivalent/g resin or less. In the present invention, the rubber to be blended with the aromatic polyester polycarbonate includes natural rubber or synthetic rubber that is rubbery at room temperature. Examples of synthetic rubbers include polybutadiene (BR), polyisoprene (IR), styrene-butadiene rubber (SBR), acrylonitrile-butadiene rubber (NBR), nitrile-isoprene rubber (NIR), polychloroprene rubber (CR), and ethylene. -Propylene rubber (EPR), ethylene-propylene-diene rubber (EPDM), butyl rubber (IIR), halogenated butyl rubber, styrene-butadiene block copolymer rubber, styrene-isoprene block copolymer rubber, rubbery chlorosulfonated polyethylene (CSM) , rubbery chlorinated polyethylene (CPE), acrylic rubber, acrylic acid alkyl ester and 2-
Copolymer of chloroethyl vinyl ether (ACM), copolymer of acrylic acid alkyl ester and acrylonitrile (ANM), urethane rubber (thermoplastic type), silicone rubber, fluoro rubber,
Polyester-polyether-polyester block copolymer rubber, ethylene-vinyl acetate rubber (EVM),
Examples include epichlorohydrin rubber. The amount of rubber compounded is 1 to 50 parts by weight, preferably 2 to 40 parts by weight, per 100 parts by weight of the aromatic polyester polycarbonate. If the amount of rubber is too small, the effects of the present invention cannot be expected. On the other hand, if the amount is too large, moldability is improved, but impact resistance and other mechanical properties are deteriorated, which is disadvantageous. Various known methods can be used to blend the aromatic polyester polycarbonate and rubber, such as dry blending the granular or powdered materials of the two using a blender or mixer, or dry blending the granular or powdered materials of the two using an extruder. A method of melt-mixing using a rubber solution and a solution of an aromatic polyester polycarbonate, a method of evaporating the solvent or precipitating a mixed composition from a mixed solution of a rubber solution and a solution of an aromatic polyester polycarbonate, or any method for producing an aromatic polyester polycarbonate. A method of adding rubber powder or a rubber solution at the step can be adopted. The composition of the present invention may include other types of resins, such as polyethylene, to the extent that their properties are not impaired.
Polyolefin resins such as polypropylene, ethylene-vinyl acetate copolymer, polyacrylate resins such as polymethyl methacrylate, ethylene-methyl methacrylate copolymer, polymethacrylic acid, polystyrene, ABS, AES
(acrylonitrile-(ethylene vinyl acetate or ethylene propylene)-styrene copolymer), ACS (acrylonitrile-chlorinated polyethylene-styrene copolymer), polystyrene resins such as SAN, MBS, polyethylene terephthalate, polybutylene terephthalate, Polyester resins such as caprolactone, polypivalolactone, polyamide resins such as nylon-6, nylon-66, nylon-610, nylon-11, nylon-12,
Polycarbonate resin, polyacetal resin, etc. may be blended. Also, phosphoric acid, phosphorous acid, their esters,
or stabilizers such as metal salts thereof, reinforcing agents such as glass fiber and carbon fiber, fillers such as silica, alumina, silica-alumina, silica-magnesia, calcium compounds, other plasticizers, lubricants, and ultraviolet absorbers. Additives such as flame retardants, dyes and pigments can also be added. The composition of the present invention has improved moldability and impact resistance without impairing the excellent properties inherent to aromatic polyester polycarbonate, so it can be used in a wide range of applications as an engineering plastic, and can be used in industrial applications. Great value. EXAMPLES The present invention will be specifically explained below with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist thereof. In the Examples, "part" indicates "part by weight", and tensile strength, bending strength and Izot impact strength are values measured based on ASTM D 638-68, ASTM D 790 and ASTM D 256, respectively. Moreover, [η] and the composition molar ratio are values determined by the method described above. Production example of aromatic polyester polycarbonate A 3% methylene chloride solution of terephthaloyl chloride and a 13% aqueous solution of bisphenol A sodium salt prepared by dissolving bisphenol A in a 5% sodium hydroxide aqueous solution were each weighed at 42.0 kg. /hr
and 16.2Kg/hr flow rate, inner diameter 30mm, length 1.5
m glass bulb packed tower, and from the supply port of the tower.
A reaction was carried out by blowing 0.95 kg/hr of phosgene from a position of 0.75 m to produce an oligomer having an ester bond and a chloroformate group at the end. A methylene chloride solution of the above oligomer obtained by separating the reaction mixture at 44.0 Kg/hr and bisphenol A were added.
5.7% aqueous solution of bisphenol A sodium salt prepared by dissolving in 2.6% aqueous sodium hydroxide solution
93.0Kg/hr, 2% aqueous solution of triethylamine 0.67
Kg/hr and p-tert-butylphenol
A polycondensation reaction was carried out by feeding 29.3 g/hr into each stirring tank so that the average residence time was 2 hours. The resulting reaction mixture was separated, and the polymer-containing methylene chloride solution was washed with water, an aqueous hydrochloric acid solution, and water, and then the methylene chloride was evaporated to dryness to form a white solid aromatic polyester polycarbonate. I got it. This polymer has an [η] of 0.81 and a glass transition temperature of
When Tg is 182°C, the molar ratio of bisphenol A residue: terephthalic acid residue: carbonate bond is 1:0.38:
It was 0.62. Examples 1 to 5 and Comparative Examples 1 to 2 Rubber powder in the amount shown in Table 1 below was melt-mixed at 300°C using an extruder to 100 parts of the aromatic polyester polycarbonate powder produced in the above production example, It was extruded into pellets. These pellets are processed into an injection molding machine (Nissei Plastics Co., Ltd.).
TS-100 model) and a test piece mold specified by ASTM. The molding temperature, mold temperature, and injection pressure at that time required the values shown in Table 1 below. The mechanical properties and heat distortion temperature of the test piece thus obtained were as shown in Table 2 below. For comparison, when no rubber is added,
and the results when the amount of rubber compounded is too large.

【table】

【table】

【table】

Claims (1)

[Claims] 1. General formula The structural unit represented by and the general formula The molar ratio of dihydroxydiaryl compound residue: terephthalic acid residue: carbonate bond is from 1:0.33 to 0.75:0.67.
0.25 aromatic polyester polycarbonate
An aromatic polyester polycarbonate resin composition comprising 1 to 50 parts by weight of rubber (B) per 100 parts by weight of (A). However, in general formulas [] and [],
X represents a divalent group, and the aromatic nucleus may have a substituent. 2. The aromatic polyester polycarbonate resin composition according to claim 1, wherein the aromatic polyester polycarbonate (A) has an intrinsic viscosity of 0.4 to 1.5. 3. The aromatic polyester polycarbonate resin composition according to claim 1, wherein the aromatic polyester polycarbonate (A) has a glass transition point of 160 to 190°C. 4. The aromatic polyester polycarbonate resin composition according to claim 1, wherein the aromatic polyester polycarbonate (A) has a terminal carboxyl group of 10 μ equivalent/g resin or less.