JPS6157342B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to highly crystalline and rapidly crystallizing thermoplastic compositions comprising high molecular weight polyalkylene terephthalates and sulfonic acid esters. Polyalkylene terephthalates have come to occupy a very important position as starting materials for the production of fibers, films and moldings. Owing to their partially crystalline structure, polyalkylene terephthalates exhibit very good properties, such as high wear resistance, favorable creep rupture strength and high dimensional stability, and are therefore subject to strong mechanical and thermal stresses. Particularly suitable for the production of molded articles. reinforcement,
For example, the mechanical properties can be further improved by incorporating glass fiber (United Kingdom Patent Specification No. 1111012, US Patent Specification No. 3368995,
West German Patent Application Publication No. 2042447). Due to its special physical properties, polyethylene terephthalate (PET) is particularly suitable for the production of fiber products and films, but it is hardly suitable for injection molding, since high molding temperatures ( (approximately 140°C) and a relatively long molding time. Because of this serious shortcoming,
Despite exhibiting high stiffness and resistance under heat loads, the use of polyethylene terephthalate in injection molding is almost completely precluded. Because polypropylene terephthalate (PPT) and polybutylene terephthalate (PBT) have faster crystallization rates than polyethylene terephthalate, they require less molding time and a lower molding temperature (approximately 100°C); Poor physical properties; exhibits lower resistance, especially under thermal loads. Considerable effort has been made to produce polycondensates that combine the favorable properties of both polyethylene terephthalate and polypropylene or polybutylene terephthalate. For example, the tendency of polyethylene terephthalate to crystallize can be improved by nucleation using finely divided solid inorganic materials (Dutch Patent Specification No.
No. 6511744). High crystallinity ensures hardness, dimensional stability and shape stability even at high temperatures. This high degree of crystallinity should be achieved as quickly as possible to ensure optimal properties are obtained. Furthermore, the residence time in the mold determines the injection period, and the length of the period is one of the factors determining the economics of the process. Even at high mold temperatures, this period is excessively long and for this reason is a hindrance when polyethylene terephthalate is used to produce moldings by injection molding. Additionally, it has long been a strong desire of polyester manufacturers to provide other polyalkylene terephthalates with faster crystallization rates and greater crystallinity. It has surprisingly been found in the present invention that polyalkylene terephthalates have greater crystallinity and faster crystallization rates when they contain from 0.5% to 30% by weight of sulfonic acid esters. According to the invention, it is possible to obtain the crystallinity required for high dimensional stability more quickly and it is therefore possible to process polyester compositions with significantly shortened injection cycles. A further advantage of the polyester composition according to the invention is that the molding temperature can be lowered without any negative effect on the favorable crystallization behavior. In this way, the injection molding composition cools more quickly and the residence time in the mold is therefore further reduced. The present invention therefore provides: (a) for a 0.5% by weight solution in a 1:1 weight ratio mixture of phenol and tetrachloroethane at 25°C;
at least 0.6 dl/ measured at a temperature of
g, preferably a high molecular weight polyalkylene terephthalate having an intrinsic viscosity of at least 0.8 dl/g.
70% to 99.5% by weight, preferably 85% by weight
99.5% by weight, and (b)(1) ^R1 - _CH2- ( ^CHR2 ) _o - _CH2R3 , where n represents an integer from 4 to ³³ ,
R ¹ , R ² and R ³ represent H, Cl or SO ₂ Cl, provided that each of the n R ² can be different, and at least one of R ¹ , R ² and R ³ is
SO ₂ Cl, and the molar ratio of C to SO ₂ Cl is between 18 and 6. In the formula, R ⁴ represents a divalent aromatic group having 6 to 14 carbon atoms, preferably a phenylene group, and R ⁵ represents hydrogen, an alkyl, cycloalkyl or aryl group containing 1 to 20 carbon atoms. and m=0 or 1, or hydroquinone or resorcinol, or In the formula, R ⁶ , R ⁷ , R ⁸ and R ⁹ can be the same or different and represent a hydrogen atom, an alkyl group containing 1 to 4 carbon atoms, a chlorine or bromine atom, and X is a direct bond, an alkylene or alkylidene group containing 1 to 8 carbon atoms, a cycloalkylene or cycloalkylidene group containing 5 to 15 carbon atoms, S,

[Formula] SO ₂ , O or

0.5% to 30% by weight of a sulfonic acid ester, which can be obtained by reacting with an equivalent amount of a compound corresponding to the formula (),
A highly crystalline and rapidly crystallizing thermoplastic composition is provided, preferably containing from 0.5% to 15% by weight. The present invention also provides at least
70 to 99.5% by weight, preferably 85 to 99.5% by weight, of a high molecular weight prealkylene terephthalate having an intrinsic viscosity of 0.6 dl/g, preferably at least 0.8 dl/g and 0.5 to 30% by weight of a sulfonic acid ester obtained by the above method. % by weight, preferably 0.5 to 15% by weight
A method of making a highly crystalline and rapidly crystallizing thermoplastic composition comprises mixing and homogenizing as a melt. The operation can take place, for example, in a mixing screw. The hardened melt can then be granulated. The invention also relates to the use of the sulfonic acid esters obtained by the above method for increasing the crystallization and crystallization rate of polyalkylene terephthalates. The dicarboxylic acid component of the polyalkylene terephthalate may contain up to 10 mol% based on the acid component of other aromatic dicarboxylic acids containing 6 to 14 carbon atoms, aliphatic dicarboxylic acids containing 4 to 8 carbon atoms, or It consists of terephthalic acid, which can be replaced by a cycloaliphatic dicarboxylic acid containing 8 to 12 carbon atoms. Examples of dicarboxylic acids of this type are phthalic acid, isophthalic acid, naphthalene-2 and 6
-dicarboxylic acid, diphenyl-4,4'-dicarboxylic acid, adipic acid, sebacic acid, and cyclohexane diacetic acid. 10 of the diol components of polyalkylene terephthalate consisting of ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol or cyclohexane-1,4-dimethanol.
Up to mol % can be replaced by other aliphatic diols containing 3 to 8 carbon atoms, cycloaliphatic diols containing 6 to 15 carbon atoms or aromatic diols containing 6 to 21 carbon atoms. I can do it.
Examples of suitable diols are 3-methyl-2,4-pentanediol, 2-methyl-1,4-pentanediol, 2,2,4-trimethyl-1,2-pentanediol, 2,2-diethyl- 1,3-propanediol, 1,3-hexanediol,
1,4-di-(β-hydroxyethoxy)-benzene, 2,2-bis-(4-hydroxy-cyclohexyl)-propane, 2,4-dihydroxy-
1,1,3,3-tetramethylcyclobutane,
They are 2,2-bis(3-β-hydroxyethoxyphenyl)-propane and 2,2-bis-(4-hydroxy-propoxyphenyl)-propane. Polyalkylene terephthalates are, for example, as described in West German Patent Application No. 1900270 (U.S. Patent No. 3,692,744).
Of course, branching can be carried out using trihydric or tetrahydric alcohols or tribasic or tetrabasic acids. Suitable branching agents are, for example, trimesic acid, pyromellitic acid, trimethylolpropane and trimethylolethane, pentaerythritol. Preferably, an amount of branching agent not exceeding 1 mol %, based on the acid component, is used. The polyalkylene terephthalate can be prepared by conventional methods using (a) terephthalic acid and/or the corresponding dialkyl terephthalate, preferably dimethyl ester, in an amount of 1.05 to 5.0 mol, preferably 1.4 to 3.6 mol, based on 1 mol of dicarboxylic acid component; esterification or transesterification using a diol and optionally a branching agent in the presence of an esterification and/or transesterification catalyst, and (b) subjecting the resulting reaction product to a polycondensation catalyst. 200°C to 200°C under reduced pressure (<1 torr)
It can be obtained by polycondensation at a temperature of 320°C. Both the first step (a) and the second step (b) of the condensation process are described, for example, in RE Wilfong, J.
It is carried out in the presence of a catalyst of the type described in Polym. Sci. 54, 385 (1961). Some of these catalysts are more effective promoters in the esterification reaction (a), some are more effective promoters in the polycondensation reaction (b), while others is a fairly active catalyst for both (c). Catalysts suitable for promoting the first step (a) of the reaction include: 1 Lithium, sodium, potassium, calcium as the metal or as its oxide, hydride, formate, acetate, alcoholate or glycolate; Strontium, boron; 2. Calcium and strontium chlorides and bromides; 3. Tertiary amines; 4. Calcium and strontium malonates, adipates, benzoates, etc.; 5. Lithium salts of dithiocarbamic acids. Suitable catalysts for catalyzing the polycondensation step (b) include, for example, 1 metals or their oxides, hydrides,
molybdenum, germanium, lead, tin as formates, alcoholates or glycolates;
antimony; 2 borates and perborates of zinc and lead; 3 enolates of succinates, butyrates, adipates or diketones of zinc, manganese, cobalt, magnesium, chromium, iron and cadmium; 4 chlorides 5. Lanthanum dioxide and lanthanum titanate; 6. Neodymium chloride; 7. Mixed salts of antimony, such as antimony potassium tartrate and potassium pyroantimonate; 8. Zinc or manganese salts of dithiocarbamic acids; 9. Naphthenes Cobalt acid; 10 Titanium tetrafluoride or titanium tetrachloride; 11 Alkyl orthotitanate; 12 Titanium tetrachloride-ether complex; 13 Quaternary ammonium salt containing titanium hexaalkoxy group; titanium tetraalkoxide, aluminum, zirconium or titanium alkoxide alkali or alkaline earth metal compounds; 14 organic quaternary ammonium, sulfonium, phosphonium and oxonium hydroxides and salts; 15 malonates, adipates, benzoates, etc. of barium; 16 lead of phenylene dicarboxylic acids; , zinc, cadmium or manganese salts or monoalkyl esters; 17 complexes of antimony-catechol with amino alcohols or amines and alcohols; 18 uranium trioxides, tetrahalides, nitrates, sulfates and acetates. Catalysts suitable for promoting both reaction steps (c) are, for example: 1 barium, magnesium, zinc, cadmium as metals, oxides, hydrides, formates, alcoholates, glycolates, preferably as acetates; aluminum, manganese, cobalt; 2 aluminum chloride and aluminum bromide; 3 enolates of succinates, butyrates, adipates or diketones of zinc, manganese (), cobalt, magnesium, chromium, iron and cadmium. The most suitable compound to use as catalyst (a) is
Ca, Zn, Mn - salts, especially in the acetate form. The most suitable catalysts (b) are compounds of zinc, manganese, cobalt, antimony, germanium, titanium and tin, such as zinc acetate, manganese acetate,
Compounds such as antimony trioxide, antimony trichloride, antimony triacetate, germanium dioxide and germanium tetrachloride. The most suitable catalysts (c) are in particular titanium compounds, for example esters of tetraalkyltitanic acids, such as tetraisopropyl titanate, tetrabutyl titanate, with alkyl groups containing 1 to 10 carbon atoms. . The catalyst is based on the dicarboxylic acid component,
It is used in an amount of 0.001 to 0.2% by weight. Later, for example, H. Ludewig, Polyesterfasern. 2nd edition, Akademie
- Inhibitors of the type described in Verlag, Berlin. 1974 are added after the first stage of the reaction in order to suppress the catalyst and increase the stability of the final product. Examples of such inhibitors are phosphoric acid, phosphorous acid and their aliphatic, aromatic or araliphatic esters, such as 6 to 18
alkyl esters having 6 to 18 carbon atoms, in which the phenyl group is optionally substituted with 1 to 3 substituents containing 6 to 18 carbon atoms, such as trinonylphenyl, dodecylphenyl, or triphenyl phosphate. It is a phenyl ester. These inhibitors are usually based on dicarboxylic acid components.
It is used in an amount of 0.01 to 0.6% by weight. To obtain even higher molecular weights, the polyalkylene terephthalates can be subjected to solid-phase polycondensation reactions. For this purpose, the granular product is conventionally polycondensed in the solid phase at temperatures of 60 DEG C. to 6 DEG C. below the melting point of the polymer in a stream of nitrogen or in a vacuum at a pressure below 1 Torr. The alkyl sulfochlorides used according to the invention and preferably used to produce the sulfonic esters contain 1 to 4, preferably 1 or 2, molecules statistically or uniformly distributed in the hydrocarbon chain. Contains SO ₂ −Cl group. Suitable phenols of the formula () for reaction with these alkyl sulfochlorides are, for example, phenyl, diphenyl and naphthyl derivatives; compatible bisphenols of the formula () are, for example, dihydroxydiphenyl,
Bis-(hydroxyphenyl)-alkane, bis-
(hydroxyphenyl)-cycloalkane, bis-
(hydroxyphenyl)-sulfide, bis-
(hydroxyphenyl)-ether, bis-(hydroxyphenyl)-sulfoxide, bis-(hydroxyphenyl)-sulfone, α・α-bis-(hydroxyphenyl)-diisopropylbenzene, and their nuclei are alkylated. Or it is a halogenated compound. Hydroquinone and resorcinol are also used for reaction with alkyl sulfochlorides. Sulfonic acid esters are obtained by reacting alkyl sulfochlorides with phenols or phenol derivatives or bisphenols, generally in the presence of an acid binder such as pyridine or sodium hydroxide (phenol salts) (West German Patent Specification No. 849 107). No. 849120). The sulfonic acid ester has a molecular weight ranging from 220 to 2000. Examples of suitable sulfonic acid esters are (C ₁₂ -C ₁₈ )
-alkylsulfonic acid-p-phenyl ester,
( _C12 - _C18 )-alkyl-di-(sulfonic acid-p-
phenyl ester), ( _C12 - _C18 )-alkyl-sulfonic acid-p-isooctylphenyl ester,
an ester of ( _C12 - _C18 )-alkyl-sulfonic acid and p-isobutyloxycarbonylphenol;
2,2-bis[p-(( _C12 - _C18 )-alkylsulfonyloxy)-phenyl]-propane, 2,2-
It is bis-[p-(( _C12 - _C18 )-alkylsulfonyloxy)-3,5-dichloro-phenyl]-propane. Mixtures of polyester resins and sulfonic esters can be prepared in conventional mixing equipment such as kneaders, single-screw and twin-screw extruders. For subsequent manipulation, the resulting mixture can be granulated after the melt has solidified. In this case too, a post-condensation reaction in the solid phase can be carried out subsequently. To protect against thermal oxidative degradation, stabilizers can be added to the copolyester in customary amounts, preferably from 0.001 to 0.5% by weight, based on the unfilled and unreinforced copolyester. Suitable stabilizers are, for example, phenols and phenol derivatives, preferably sterically hindered phenols containing C _{1-6 -alkyl} substituents in both o-positions of ^the phenolic hydroxyl group, and amines, preferably di- arylamines and their derivatives, phosphates, phosphites, preferably their aryl derivatives, and quinones, copper salts of organic acids, addition compounds of copper () halides and phosphites, and, for example, 4,4-bis-(2,6-di-
tert-butylphenol), 1,3,5-trimethyl-2,4,6-tris-(3,5-di-tert
-butyl-4-hydroxybenzyl)-benzene, 4,4'-butylidene-bis-(6-tert-butyl-m-cresol), diethyl 3,5-di-tert-butyl-4-hydroxy-benzylphosphonate Ester, N・N'-bis-(β-naphthyl)
-p-phenylenediamine, N・N'-bis-(1
-methylheptyl)-p-phenylenediamine,
Phenyl-β-naphthalamine, 4,4'-bis-
(α・α-dimethylbenzyl)-diphenylamine, 1,3,5-tris-(3,5-di-tert-
Butyl-4-hydroxyhydrocinamoyl)-hexahydro-S-triazine, hydroquinone,
p-benzoquinone, toluhydroquinone, p-
tert-butylpyrocatechol, chloranil, naphthoquinone, copper naphthenate, copper octoate, Cu
()Cl/triphenyl phosphate, Cu()Cl/trimethyl phosphite, Cu()Cl/tris-chloroethyl phosphite, Cu()Cl/tripropyl phosphite, p-nitrosodimethylaniline. Polyester compositions according to the invention can be reinforced with reinforcing agents. Suitable reinforcing materials are mainly metals, silicates, carbon, in the form of textiles or mats.
It's glass. Preferably, glass fibers are used as reinforcement. Additionally, if desired, conventional amounts of inorganic or organic pigments, dyes, lubricants and mold release agents such as zinc stearate, montan waxes, UV absorbers, etc. can be added. In order to obtain flame-retardant products, flame retardants known per se, e.g. halogen-containing compounds,
elemental phosphorus or phosphorus compounds, phosphorus-nitrogen compounds, antimony trioxide or equivalent mixtures of these substances, preferably antimony trioxide,
Deca-bromophenyl ether and tetrabromobisphenol-A-polycarbonate can be included in the composition in amounts of 2 to 20% by weight, based on the molding composition. The crystallization rate of the polyester injection molding composition according to the invention can be further increased by the addition of a nucleating agent in an amount of 0.01 to 1% by weight, based on the unfilled and unreinforced polyester. Suitable nucleating agents are known to the expert and include, for example
Kunststoff-Handbuch. Volume 8, “Polyester”,
Compounds such as those described in Carl Hanser Verlag, Munich, 1973, page 701. The polyester compositions according to the invention are excellent starting materials for the production of all types of moldings by injection molding. Table 1 shows some polyester resin compositions (Examples 1 to 15) based on PET and alkyl sulfonic acid phenyl esters according to the present invention.
The mold residence time and total injection cycle time of the polyethylene terephthalate are shown by comparison with unmodified polyethylene terephthalate.

【table】

Claims (1)

[Claims] 1 (a) 1 of phenol and tetrachloroethane:
For a 0.5 wt% solution in a 1 wt ratio mixture
At least 0.6 as measured at a temperature of 25°C
70 to 99.5% by weight of a high molecular weight polyalkylene terephthalate having ^an intrinsic viscosity of dl/g, and (b)(1) R1 ^- _CH2- ( ^CHR2 ) _o - _CH2R3 , where n is 4 to 33 represents an integer up to
R ¹ , R ² and R ³ represent H, Cl or SO ₂ Cl, provided that each of the n R ² can be different, and at least one of R ¹ , R ² and R ³ is
SO ₂ Cl, and the molar ratio of C to SO ₂ Cl is between 18 and 6. In the formula, R ⁴ represents a difunctional aromatic group containing 6 to 14 carbon atoms, R ⁵ represents hydrogen, an alkyl, cycloalkyl or aryl group containing 1 to 20 carbon atoms, and m=0 or 1, or hydroquinone or resorcinol, or In the formula, R ⁶ , R ⁷ , R ⁸ and R ⁹ are the same or different and represent a hydrogen atom, an alkyl group containing 1 to 4 carbon atoms, a chlorine or bromine atom, and X is a single bond. , an alkylene or alkylidene group containing 1 to 8 carbon atoms, a cycloalkylene or cycloalkylidene group containing 5 to 15 carbon atoms, S, [formula] SO ₂ , O or [formula] Sulfonic acid esters that can be obtained by reacting with equivalent amounts of the corresponding compounds
A highly crystalline and rapidly crystallizing thermoplastic composition comprising 0.5 to 30% by weight.