CH634860A5 - Rapidly crystallising polyester composition - Google Patents

Description

The present invention relates to a highly crystalline

Rapidly crystallizing thermoplastic mass from a high molecular weight dicarboxylic acid diol polyester, the dicarboxylic acid of which is 90-100% terephthalic acid, and a sulfonic acid ester.

Polyalkylene terephthalates have gained considerable importance as raw materials for the production of fibers, films and moldings. Due to their semi-crystalline structure, they have excellent properties, e.g. high wear resistance, good creep rupture behavior and high dimensional accuracy, and are therefore particularly well suited for the production of mechanically and thermally stressed molded parts. An additional improvement in the mechanical properties can be achieved by incorporating reinforcing materials, e.g. Glass fibers. (GB-PS 1 111 012, US-PS 3 368 995, DE-AS 2 042 447).

Due to its special physical properties, polyethylene terephthalate (PÄT) is particularly suitable for the production of fiber products and foils, but hardly for spraying, since this requires high mold temperatures (around 140 ° C) and relatively long pressing times. This serious disadvantage almost completely prevents the injection molding of polyethylene terephthalate despite its high rigidity and heat resistance.

Because of their higher crystallization speed, polypropylene terephthalate (PPT) and polybutylene terephthalate (PBT) require shorter pressing times and lower mold temperatures (about 100 ° C.), but have poorer physical properties, in particular lower heat resistance, than polyethylene terephthalate.

Efforts have now been made to create polycondensates which combine the good properties of both polyethylene terephthalate and polypropylene or polybutylene terephthalate. So z. B. is known that the tendency to crystallize polyethylene terephthalate can be improved by nucleation with finely divided, solid inorganic substances (NL-PS 6 511 744).

High crystallinity ensures hardness, dimensional stability and dimensional stability even at higher temperatures. This high crystallinity should be achieved as quickly as possible so that an optimal level of properties is obtained. In addition, the molding cycle, the length of which determines the economy of the process, depends on the mold life. These cycles are too long even at high mold temperatures and therefore make it difficult for polyethylene terephthalate to penetrate into the manufacture of molded articles by injection molding.

In addition, it has long been an intimate concern of polyester manufacturers to also provide other polyalkylene terephthalates with an increased crystallization rate and higher crystallinity.

It has now surprisingly been found that polyalkylene terephthalates have higher crystallinity and higher crystallization rates if they contain 0.5-30% by weight of sulfonic acid esters.

The present invention makes it possible to achieve the degree of crystallinity required for the high dimensional stability more quickly and thus to process the polyester compositions with greatly shortened injection cycles. Another advantage of the invention is the lowering of the mold temperature without impairing the good crystallization behavior. The injection molding compound cools down faster, which also shortens the mold life.

The invention relates to the highly crystalline, rapidly crystallizing thermoplastic composition defined in claims 1 and 2.

Another object of the present invention is the process for the preparation of the composition as defined in claim 3, wherein preferably 85-99.5% by weight of component a) and preferably 0.5-15% by weight of component b) are mixed and in the melt homogenized. The process can e.g. B. in the mixing screw; the solidified melt can then be granulated.

The dicarboxylic acid component of the dicarboxylic acid diol polyester which differs from terephthalic acid consists, for example, of phthalic acid, isophthalic acid, naphthalene-2,6-dicarboxylic acid, diphenyl-4,4'-dicarboxylic acid, adipic acid, sebacic acid, cyclohexanediacetic acid.

The diol component of the polyester mentioned, which consists of ethylene glycol, 1,3-porpanediol, 1-butanediol, 4-pentanediol, 5, 1,6-hexanediol or 1,4-cyclohexanedimethanol, can be up to 10 mol% other aliphatic diols with 3-8 C atoms, cycloaliphatic diols with 6-15 C atoms or aromatic diols with 6-21C atoms contain e.g. 3-methylpentanediol-2,4,2-methylpentanediol-1,4,2,2,4-trimethypentanedioI-l, 3,2,2-di-ethylpropanediol-1,3, hexanediol-1,3, l, 4- Di (ß-hydroxy-ethoxy) benzene, 2,2-bis (4-hydroxycyclohexyl) propane, 2,4-dihydroxy-1,1,3,3, -tetramethylcyclobutane, 2,2-bis (3-ß- hydroxyethoxyphenyl) propane, 2,2-bis (4-hydroxypropoxyphenyl) propane.

Of course, the polyesters mentioned can be branched through three or tetravalent alcohols or three or tetra-basic acids, such as, for. B. is described in DE-OS 1 900 270 (= US-PS 3,692,744). Suitable branching agents are e.g. B. trimesic acid, pyromellitic acid, trimethylolpropane and ethane, pentaerythritol. It is advisable to use no more than 1 mol% of branching agent, based on the acid component.

The dicarboxylic acid diol polyester preferably has an intrinsic viscosity of 0.6 dl / g (determined from solution in a mixture of monohydroxybenzene and 1,1,2,2-tetrachloroethane in a weight ratio of 1: 1 at 25 ° C.). The definition of "intrinsic viscosity" corresponds to that of the "viscosity number" or the "Staudinger index".

The dicarboxylic acid diol polyesters can be prepared in a manner known per se by, for example, a) terephthalic acid and / or the corresponding dialkyl terephthalates, preferably the dimethyl esters, with 1.05 to 5.0, preferably 1.4-3, 6, moles of the diols, based on 1 mole of dicarboxylic acid component, and if appropriate the esterifying or transesterifying the branching agent in the presence of esterification and / or transesterification catalysts and b) the reaction products thus obtained in the presence of polycondensation catalysts between 200 and 320 ° under reduced pressure (<1 Torr) polycondensed.

Both the first (a) and the second step (b) of the condensation are expediently carried out in the presence of catalysts, such as those e.g. at R.E. Wilfongin J. Polym. Be. 54, 385 (1961). Some of these catalysts are more effective accelerators for esterification reaction A, others for polycondensation B, while still others are fairly effective catalysts for both (C).

Among the catalysts that are used to accelerate the

1st reaction stage are suitable (A), count

1. Lithium, sodium, potassium, calcium, strontium, boron as metals, oxides, hydrides, formates, acetates, alcoholates or glycolates;

2. Calcium and strontium chlorides and bromides

3. tertiary amines;

4. Calcium and strontium malonates, adipates, benzoates, etc .;

5. Lithium salts of dithiocarbamic acids.

634 860

Suitable catalysts (B) for catalyzing the polycondensation step are e.g.

1. molybdenum, germanium, lead, tin, antimony as metals, oxides, hydrides, formates, alcoholates or glycolates;

2. Zinc and lead perborates and borates;

3. zinc, manganese (II), cobalt, magnesium, chromium, iron and cadmium succinates, butyrates, adipates or enolates of a diketone;

4. zinc chloride and bromide;

5. lanthanum dioxide and titanate;

6. neodymium chloride;

7. mixed salts of antimony, such as. B. Potassium antimony-kicked, and salts of antimonic acids such as potassium pyroantimonate;

8. Zinc or manganese salts of dithiocarbamide acids;

9. cobalt naphthenate;

10. titanium tetrafluoride or tetrachloride;

11. alkyl orthotitanates;

12. Titanium tetrachloride ether complexes;

13. quaternary ammonium salts bearing a titanium hexaalkoxy radical; Titanium tetraalkoxides, alkali or alkaline earth metal compounds of aluminum, zirconium or titanium alkoxides;

14. organic quaternary ammonium, sulfonium, phosphonium and oxonium hydroxides and salts;

15. Barium malonate, adipate, benzoate etc.

16. Lead, zinc, cadmium or manganese salts of the monoalkyl ester of a phenylenedicarboxylic acid;

17. Antimony-catechin complexes with an amino alcohol or with an amine and an alcohol;

18. Uranium trioxide, tetrahalide, nitrate, sulfate, acetate.

Suitable catalysts C to accelerate both reaction steps are e.g.

1. barium, magnesium, zinc, cadmium, aluminum, manganese, cobalt as metals, oxides, hydrides, formates, alcoholates, glycolates, preferably acetates;

2. aluminum chloride and bromide;

3. Zinc, manganese (II), cobalt, magnesium, chromium, iron and cadmium succinates, butyrates, adipates or enolates of a diketone.

The most suitable compounds as catalysts A are Ca, Zn, Mn salts, especially acetates.

The most suitable catalysts B are the compounds of zinc, manganese, cobalt, antimony, germanium, titanium and tin, such as. B. zinc and manganese acetate, antimony trioxide, tri-chloride, triacetate, germanium dioxide and tetrachloride.

The most suitable catalysts C are in particular titanium compounds such as Tetraalkyltitanic acid esters with alkyl groups with 1-10 C atoms such as tetraisopropyltitanate and tetrabutyltitanate.

The catalysts are expediently used in amounts of 0.001 to 0.2% by weight, based on the dicarboxylic acid component.

Thereafter, inhibitors can be added to inhibit the catalysts after the end of the 1st reaction step and to increase the stability of the end product, such as those e.g. B. by H. Ludewig, polyester fibers, 2nd ed., Akademie Verlag, Berlin 1974 are described. Examples of such inhibitors are phosphoric acid, phosphoric acid and their aliphatic, aromatic or araliphatic esters, e.g. B. alkyl esters with 6 to 18 carbon atoms in the alcohol component, phenyl esters whose phenyl radicals are optionally substituted with 1-3 substituents with 6 to 18 carbon atoms, such as trinonyl phenyl, dodecylphenyl or triphenyl phosphate. These inhibitors are usually used in amounts of 0.01 to 0.6% by weight, based on the dicarboxylic acid component.

The polyalkylene terephthalates can be subjected to solid polycondensation to achieve an even higher molecular weight. Usually the granulated product is in a stream of nitrogen or in vacuo at a pressure below

3rd

5

10th

15

20th

25th

30th

35

40

45

50

55

60

65

634 860 4

1 Torr and a temperature that is 60-6 ° C below the polymer melting point, polycondensed in the solid phase.

Alkyl sulfochlorides which are preferably suitable for the preparation of the sulfonic acid esters described contain 1-4, preferably 5 or 1-2, -SOrCl groups distributed statistically or regularly over the hydrocarbon chain. Suitable phenols of the formula I for reaction with these alkylsulfochlorides are, for. B. phenyl, diphenyl and naphthyl derivatives, or bisphenols of the formula II are 4,4'-dihydroxydiphenyl

Bis- (P-hydroxyphenyl) alkanes, with 1-8 C atoms in the alkane residue. Bis- (P-hydroxyphenyl) cycloalkanes, with 5-15 C atoms in the cycloalkane residue

Bis (P-hydroxyphenyl) sulfide bis (P-hydroxyphenyl) ether,

Bis (P-hydroxyphenyl) sulfoxide,

Bis- (P-hydroxyphenyl) sulfones, Ô, ò-bis- (P-hydroxyphenyl) -P-diisopropyl-benzenes These bisphenols can still be nucleus-substituted in accordance with the definition of the compound of formula II contained in claim 1. The reaction partner of the sulfochloride can also be hydroquinone or resorcinol.

The sulfonic acid esters can be obtained by reacting alkyl sulfochlorides with phenols or phenol derivatives or bisphenols 25 in the presence of an acid-binding agent, predominantly pyridine or sodium hydroxide solution (phenolate) (cf. DE-PS 849 107, 849 120).

They usually have a molecular weight of 220 to 2000.

Examples of suitable sulfonic acid esters are 30 (CirC] 8) -n-alkylsulfonic acid phenyl ester (C! 2-Ci8) -n-alkyl-di (sulfonic acid phenyl ester) (CirC18) -n-alkylsulfonic acid p-octylphenyl ester (Ci2 -Ci8) -n-alkyI-sulfonic acid-p-hydroxybenzoic acid isobutyl ester 35 2,2-bis- [4- (CI2-Ci8) -n-alkylsulfonyloxyphenyl] propane 2,2-bis- [4- ( CI2-C18) -n-alkylsulfonyloxy-3,5-dichlorophenyl] propane. ——

The mixture of polyester resin and sulfonic acid ester can be produced on commercially available mixing devices. Kneaders, single-screw and twin-screw extruders are suitable as such. For further processing, the mixture obtained can be granulated after the melt has solidified. Here too, solid phase post-condensation can follow. 45

To protect against thermo-oxidative degradation, the usual amounts, preferably 0.001 to 0.5% by weight, based on the unfilled and unreinforced copolyesters, of stabilizers can be added to the copolyesters. Suitable as such are, for example, phenols and phenol derivatives, preferably sterile-hindered phenols which contain alkyl substituents with 1-6 C atoms in both o-positions to the phenolic hydroxyl group, amines, preferably secondary arylamines and their derivatives, phosphates and phosphites, preferably their aryl derivatives, quinones, copper salts of organic acids, addition compounds of copper (I) halides with phosphites, such as, for example, 4,4'-bis (2,6-di-tert-butylphenol), 1, 3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxy-benzyl) benzene, 4,4'-butylidene-bis- (6-tert . -butyl-m-cresol), 3,5-di-tert. -butyl-4-hydroxy-benzyl-phosphonic acid diethyl ester, N, N'-bis (ß-naphthyl) -p- 60 phenylenediamine, N, N'-bis (l-methylheptyl) -p-phenylenediamine, phenyl ß-naphthalene-amine, 4,4'-bis- (ö, ö, -dimethylbenzyl) -diphenylamine, 1,3,5-tris- (3,5-di-tert-butyl-4-hydroxy- hydrocinna-moyl) -hexahydro-s-triazine, hydroquinone, p-benzoquinone, toluene-hydroquinone, p-tert-butylbenzate catechol, chloranil, naphthochi-65 non, copper naphthenate, copper octoate, Cu (I) Cl / triphenylphosphate, CU (I) Cl / trimethylphosphite, Cu (I) Cl / trischloroethylphosphite, Cu (I) Cl / tripropylphosphite, p-nitrosodimethylaniline.

The polyester composition according to the invention can be reinforced with reinforcing materials. Metals, silicates, carbon, glass, especially in the form of fibers, fabrics or mats, have proven themselves as reinforcing materials. Glass fibers are preferred reinforcing material.

In addition, if desired, inorganic or organic pigments, dyes, lubricants and release agents such as zinc stearate, montan waxes, UV absorbers, etc. be sold in usual quantities.

In order to obtain flame-retardant products, 2 to 20% by weight, based on the molding composition, of flame retardants known per se, e.g. B. halogen-containing compounds, elementary phosphorus or phosphorus compounds, phosphorus / nitrogen compounds, antimony trioxide or mixtures of these substances, preferably antimony trioxide, decarbromobiphenyl ether and tetrabromobisphenol-A polycarbonate, are added.

The rate of crystallization of the polyester injection molding composition according to the invention can be increased further by adding 0.01 to 1% by weight, based on unfilled and unreinforced polyester, of nucleating agents. As such, the compounds known to the person skilled in the art such as, for. B. in the plastics manual, Volume VIII, "Polyester", Carl Hanser Verlag, Munich, 1973, page 701, are described.

The polyester composition according to the invention is an excellent starting material for the production of all types of molded articles by injection molding.

Table 1 shows the mold stand and total injection cycle times of some embodiments of the polyester resin composition based on PÄT and alkylsulfonic acid phenyl ester (Example 1-15) according to the invention in comparison to the unmodified polyethylene terephthalate.

Table 1

Aikylsulfonic acid processing conditions

Type Amount Cylin Form- Form- Total (wt. Temperature- spritzig) peratur rature time pour cycle (° C) (° C) (s) lus (s)

1

(C] 2-CI8) -n-alkyl sulfonic acid

phenyl ester

3rd

260

125

4.0

13.5

2nd

(C | 2-Cjg) -n-alkyl sulfonic acid

phenyl ester

5

260

110

2.5

12.0

3rd

(Ci2-Cig) -n- alkyl sulfonic acid

phenyl ester

10th

260

80

0

9.5

4th

(Ci2-Cis) -n-

Alkyl di

sulfonic acid

phenyl ester

3rd

260

130

10th

19.5

5

(C12-C18) -n-

Alkyl di

sulfonic acid

phenyl ester

5

260

120

7

16.5

6

(Ci2-C | 8) -n-

Alkyl di

sulfonic acid

phenyl ester

10th

260

110

6

15.5

7

(Ci2-C, 8) -n-alkylsulfonic acid-p-octylphenyl-

ester

3rd

260

125

5

14.5

5

634 860

8 (C12-C18) -n-alkyl-sulfonic acid-p-octylphenyl-

ester 5 260 110 0 9.5

9 (C12-C18) -n-alkylsulfonic acid-p-octylphenyl-

ester 10 260 80 0 9.5

10 (C12-CI8) -n-alkylsulfonic acid-p-hydroxybenzoic acid iso-

butyl ester 3 260 130 9 18.5

11 (C12-C18) -n-alkylsulfonic acid-p-hydroxybenzoic acid-isobu-

tylester 5 260 120 7 16.5

12

(Ci2-C | 8) -n-alkylsulfonic acid-p-hydroxybenzoic acid iso-

butyl ester

10th

260

110 5

14.5

13

(2,2-bis- [4- (C12-Ci8) -n-alkylsul-fonyloxy-phe-

nyl] propane

3rd

260

130 10

19.5

14

2,2-bis- [4- (Cn-Ci8) -n-alkylsul-fonyloxy-phe-

nylj propane

5

260

125 8

17.5

15

2,2-bis- [4- (Clr C] 8) -n-alkylsul-fonyloxy-phe-

nyl] propane

10th

260

120 5

14.5

16 - - 270 140 30 39.5

M

Claims (5)

634 860 PATENT CLAIMS 1. Rapidly crystallizing mass based on a dicarboxylic acid-diol polyester which may be branched by trihydric or tetravalent alcohol or trihydric or tetra-basic acid, the dicarboxylic acid component of which is 90 to 100 mol% terephthalic acid, the optionally present terephthalic acid phthalic acid is a different part of the dicarboxylic acid component aromatic dicarboxylic acid with no more than 14 C atoms, aliphatic dicarboxylic acid with 4 to 8 C atoms, sebacic acid or cycloaliphatic dicarboxylic acid with 8 to 12 C atoms, and its diol component to 90 to 100 mol% of ethylene glycol , 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol or 1,4-cyclohexanedimethanol, the part of the diol component which is optionally present here being aliphatic diol having 3 to 8 carbon atoms , Cycloaliphatic diol with 6 to 15 carbon atoms or aromatic diol with 6 to 21 carbon atoms, characterized in that it is used to increase the crystallization and the crystall rate of allization contains a sulfonic acid ester, which by reacting 20 (1) a sulfochloride of the formula 3. A process for the preparation of the composition according to claim 2, characterized in that components a) and b) are mixed and homogenized in the melt. 10th 15 R1-CH2- (CHR2) n-CH2R3 wherein R1, R2 and R3 are H, Cl or S02C1 and n are an integer from 3-33, the molar ratio C / SÒ2C135 to 1.25, with the equivalent amount of (2) a monohydroxy compound of the formula O 25th 30th H0-R4 (-C-0) m-R5 (I) wherein R4 is a divalent aromatic radical with 6-14 C atoms, R5 crc20 alkyl or a cycloalkyl or aryl radical with up to 20 C atoms and m is zero or 1, or a dihydroxyl compound of the formula 35 40 (II) 45 wherein R6, R7, R8 and R9 are the same or different and hydrogen, alkyl with 1-4 C atoms or chlorine or bromine and X is a single compound, an alkylene or alkylidene radical with 1-8 C atoms, a cycloalkylene or cycloalkylidene radical with 5-15 carbon atoms, S, S, S02, O or 50 O ch3 c I. ch. ÏH3 -C 55 ch. mean, or is available with hydroquinone or resorcinol. 2. Composition according to claim 1, characterized in that it, based on the total weight of components a) and b), a) 70-99.5% by weight of a high molecular weight dicarboxylic acid diol polyester as defined in claim 1, which has an intrinsic viscosity of at least 0.6 dl / g, measured at 25 ° C on a solution in a mixture of Monohydroxybenzene and 1,1,2,2-tetrachloroethane in a weight ratio of 1: 1, and b) contains 0.5-30% by weight of a sulfonic acid ester obtainable from (1) and (2) as defined in claim 1. 60 65