DE2639428A1 - FAST CRYSTALLIZING POLYESTER COMPOUNDS - Google Patents

Description

5090 Leverkusen, Bayerwerk Pv / AB

Fast crystallizing polyester masses

The present invention relates to highly crystalline, rapidly crystallizing thermoplastic compositions made from a high molecular weight Polyalkylene terephthalate and a sulfonic acid ester.

Polyalkylene terephthalates have considerable raw materials for the production of fibers, films and moldings Gained importance. Due to their semi-crystalline structure, they have excellent properties, such as high Wear resistance, favorable creep behavior and high dimensional accuracy, and are therefore mechanical for production and molded parts subject to high thermal loads are particularly well suited. An additional improvement to the mechanical Properties can be achieved by incorporating reinforcing materials, e.g. glass fibers (GB-PS 1 111 012, U.S. Patent 3,368,995, DT-AS 2,042,447).

Le A17 403

809810/0173

Polyethylene terephthalate (PÄT) is suitable because of its special physical properties especially for the production of fiber products and foils, but hardly for Injection molding, as this requires high mold temperatures (approx. 140 C) and relatively long pressing times. This serious one Disadvantage prevents the use of injection molding of polyethylene terephthalate despite its high rigidity and heat resistance almost perfect.

Polypropylene terephthalate (PPT) and polybutylene terephthalate (PBT) require due to their higher crystallization rate although shorter pressing times and lower mold temperatures (about 100), they have, however, compared to polyethylene terephthalate poorer physical properties, especially lower heat resistance.

There has been no shortage of efforts to create polycondensates which have the good properties of both the polyethyleneterephthalate as well as the polypropylene or polybutylene terephthalate. E.g. known that the tendency of polyethyleneterephthalate to crystallize 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. These high crystallinity should be achieved as quickly as possible so that an optimal level of properties is obtained. aside from that The injection cycle depends on the mold life, the length of which also determines the cost-effectiveness of the process. These cycles are too long even at high mold temperatures and therefore make it difficult for polyethylene terephthalate to penetrate

in the production of moldings by injection molding.

Le A 17 403 - 2 -

809810/0173

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

It has now surprisingly been found that polyalkylene terephthalates then have higher crystallinity and greater crystallization rate if they are 0.5% by weight Contain sulfonic acid esters.

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

The invention relates to highly crystalline, rapidly crystallizing thermoplastic compositions consisting of

a) 70-99.5, preferably 85-99.5% by weight of a high molecular weight polyalkylene terephthalate with an intrinsic viscosity of at least 0.6 dl / g, preferably at least 0.8 dl / g (measured as a 0.5% by weight solution in one Phenol / tetrachloroethane mixture in weight ratio

1: 1 at 25 ° C) and

b) 0.5-30, preferably 0.5-15% by weight of sulfonic acid ester, by reacting 1) an alkyl sulfochloride of the formula

Le A 17 403 - 3 -

809810/0173

R ¹ - CH_ - (CHR ² ) - CH ₀ R ³ 2 η 2

whereby

1 7 ~ R, R and R

for H, Cl, SO ₂ Cl and

stand for integers from 3-33, preferably 10-16, and the molar ratio C / SO ₂ C1 is 35 to 1.25,

2) with equivalent amounts of a compound of the formula

HO-R ⁴ (-C-0) -R ⁵

(D

wherein R ⁴

mean,

or

a divalent aromatic radical, preferably a phenylene radical, with 6-14 carbon atoms an alkyl, cycloalkyl or aryl radical

with 1-20 carbon atoms and 0 or 1

-X-Z ^ -OH

(H)

whereby R ⁶ , R ⁷ , R ⁸ and R ⁹

are identical or different, and a hydrogen atom, an alkyl radical with 1-4 C atoms, mean a chlorine or bromine atom and

a single bond, an alkylene or alkylidene radical with 1-8 carbon atoms, a

Le A 17

809810/0173

2839428

Cycloalkylene or cycloalkylidene radical with 5-15 C atoms, S, S, SO ₉ , 0 or

is available.

Another object of the present invention is a process for the production of highly crystalline, rapidly crystallizing thermoplastic masses, characterized in that that 70-99.5, preferably 85-99.5 wt .-% of a high molecular weight polyalkylene terephthalate with an intrinsic viscosity of at least 0.6 dl / g, preferably at least 0.8 dl / g »(measured as 0.5% by weight Solution in a phenol / tetrachloroethane mixture in a weight ratio of 1: 1 at 25 C) and 0.5-30, preferably 0.5-15% by weight of fine sulfonic acid ester based on the above is obtainable, mixed and homogenized in the melt. The process can take place e.g. in the mixing screw take place; the solidified melt can then be granulated.

Another object of the present invention is Use of sulfonic acid esters based on the above Ways are available to increase the crystallization and the rate of crystallization of Polyalkylene terephthalates.

The dicarboxylic acid component of the polyalkylene terephthalate consists of terephthalic acid, which is up to 10 mol% on the acid component, by other aliphatic

Le A 17 403 - 5 -

809810/0173

Dicarboxylic acids with 6-14 carbon atoms, by aliphatic dicarboxylic acids with 4-8 carbon atoms or by cycloaliphatic ones Dicarboxylic acids with 8-12 carbon atoms can be replaced. Examples of such dicarboxylic acids are Phthalic acid, isophthalic acid, naphthalene-2,6-dicarboxylic acid, Diphenyl-4,4'-dicarboxylic acid, adipic acid, sebacic acid, Called cyclohexanediacetic acid.

The diol component of the polyalkylene terephthalate, which consists of Ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol or 1,4-cyclohexanedimethanol, can be up to 10 mol% through other aliphatic diols with 3-8 carbon atoms, cycloaliphatic diols with 6-15 carbon atoms or aromatic diols with 6-21 carbon atoms can be replaced. Examples of suitable diols are 3-methylpentanediol-2,4, 2-methylpentanediol-1,4, 2,2,4-trimethylpentanediol-1,3, 2,2-diethylpropanediol-1,3, hexanediol-1,3, 1,4-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 are listed.

Of course, the polyalkylene terephthalates can be replaced by tri or tetravalent alcohols or three or tetrasic acids are branched, as described, for example, in DT-OS 1 900 270 (= US Pat. No. 3,692,744) is. Suitable branching agents are e.g. trimesic acid, pyromellitic acid, trimethylolpropane and -ethane, Pentaerythritol. It is advisable not to use more than 1 mol%, based on the acid component, of branching agent to use.

Le A 17 403 - 6 -

809810/0173

The polyalkylene terephthalates can be prepared in a manner known per se by

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 optionally the branching agent in the presence of esterification and / or transesterification catalysts esterified or transesterified and

b) the reaction products thus obtained in the presence of polycondensation catalysts polycondensed between 200 and 320 C under reduced pressure (- £ 1 Torr).

Both the first (a) and the second (b) step of the condensation is carried out in the presence of catalysts such as those described in R.E. Wilfong in J. Polym. May be. _54_, 385 (1961). Some of these catalysts are more effective accelerators for esterification reaction A, others for polycondensation B, while still others are quite effective catalysts for both (C).

The catalysts which are suitable for accelerating the 1 · reaction stage (A) include

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 .;

Le A 17 403 - 7 -

809810/0173

5. Lithium salts of dithiocarbamic acids

Catalysts (B) suitable for catalyzing the polycondensation step are e.g.

1. Molybdenum, germanium, lead, tin, antimony as metals, oxides, hydrides, pormates, 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 a diketone;

4. zinc chloride and bromide;

5. Lanthanum dioxide and titanate;

6. neodymium chloride;

7. mixed salts of antimony such as potassium antimony tartrate and salts of antimonic acids such as potassium pyroantimonate;

8. zinc or manganese salts of dithiocarbamic acids;

9. cobalt naphthenate;

10. titanium tetrafluoride or tetrachloride;

11. alkyl orthotitanates;

12. Titanium tetrachloride ether complexes;

Le A 17 403 "- 8 -

809810/0173

13. Quaternary ammonium salts containing a titanium hexaalkoxy radical wear; 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 to accelerate both reaction steps C 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.

Le A 17 403 - 9 -

809810/0173

The compounds most suitable as catalysts A are Ca, Zn, Mn salts, in particular as 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, trichloride, triacetate, germanium dioxide and tetrachloride.

The most suitable catalysts C are, in particular, titanium compounds such as B. Tetraalkyltitanic acid esters with alkyl groups with 1-10 carbon atoms such as tetraisopropyl titanate and tetrabutyl titanate.

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

Thereafter, to inhibit the catalysts after completion of the 1st reaction step and to increase the stability Inhibitors added to the end product, such as those found in H. Ludewig, polyester fibers, 2nd edition, Akademie-Verlag, Berlin 1974 are described. Examples of such inhibitors are phosphoric acid, phosphorous acid and their aliphatic, aromatic or araliphatic esters, e.g. alkyl esters with 6 to 18 carbon atoms in the alcohol component, phenyl esters, whose phenyl radicals are optionally substituted by 1-3 substituents with 6 to 18 carbon atoms, such as trinonylphenyl, 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 used.

To achieve an even higher molecular weight, the polyalkylene terephthalates can be a solid polycondensation subject. Usually the granulated product is used

Le A 17 403 - 10 -

809810/0173

in a stream of nitrogen or in vacuo at a pressure below 1 Torr and a temperature which is 60 - 6 ° C below the Polymer melting point is, polycondensed in the solid phase.

Alkyl sulfochlorides which are preferably suitable for the preparation of the sulfonic acid esters to be used according to the invention contain 1-4, preferably 1-2, —SO ₂ —Cl groups distributed statistically or regularly over the hydrocarbon chain. Phenols I suitable for reaction with these alkyl sulfochlorides are, for. B. phenyl, diphenyl and naphthyl derivatives, or bisphenols II are z. B.

Hydroquinone,

Resorcinol,

Dihydroxydiphenyl

Bis (hydroxyphenyl) alkanes.

Bis (hydroxyphenyl) cycloalkanes, bis (hydroxyphenyl) sulfides Bis (hydroxyphenyl) ethers, bis (hydroxyphenyl) sulfoxides, bis (hydroxyphenyl) sulfones, oC, cL -Bis- (hydroxyphenyl) -diisopropyl-benzenes

and their ring-alkylated and ring-halogenated compounds.

The sulfonic acid esters are made by reacting alkyl sulfo " Chlorides with phenols or phenol derivatives or bisphenols in the presence of an acid-binding agent, predominantly Pyridine or sodium hydroxide solution (phenolate), obtained (cf. DTPS 849 107, 849 120).

They usually have a molecular weight of 220 to 2000.;

Le A 17 403 , - 11 -

809810/0173

Examples of suitable sulfonic acid esters are (C ₁ 2 ~ Ci 8) "alkylsulfonic acid p-phenyl ester (C." - Cjg) -Alklyl-di (sulfonic acid p-phenyl ester) (C ₁ 2 "^ S) ~ alkyl-sulfonic acid- p-phenyl-octyl ester

(C- -J-G) Q) -Alkyl-sulfonic acid-p-hydroxybenzoic acid-isobutyl ester

2,2-bis - ((C ₂ -C ^] 8) ~ ^al kylsulfonsäure-4-phenyl) propane

2,2-BiS-C (C. 2 ~ ^C 18 ^ -alkylsulphonic acid-3,5-dichloro-4-phenyl ester) propane.

The ¹ preparation of the mixture of polyester resin and sulfonic acid ester can be carried out on commercially available mixing devices. Kneaders, single-screw and twin-screw extruders are suitable as such

obtained mixture can be granulated after solidification of the melt. Solid-phase post-condensation can also occur here connect.

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 sterically hindered phenols which contain alkyl substituents with 1-6 carbon 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 to phosphites, such as 4.4 ^l -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), 3,5 -Di-tert-butyl-4-hydroxy-benzyl-phosphonic acid diethyl-

Le A 17 403 - 12 -

809810/0173

ester, Ν, Ν'-bis- (ß-naphthyl) -p-phenylenediamine, N, N'-bis- (1-methylheptyl) -p-phenylenediamine, phenyl-ß-naphthalamine, 4,4'-bis- ( . ^., > Ju, -dimethylbenzy 1) -diphenylamine, 1,3,5-tris- (3,5-di-tert-butyl-4-hydroxy-hydrocinnamoyl) -hexahydro-s-triazine, hydroquinone, p -Benzoquinone, toluhydroquinone, p-tert-butylbenzcatechol, chloranil, naphthoquinone, copper naphthenate, copper octoate, Cu (I) Cl / triphenyl phosphate, CU (I) Cl / trimethyl phosphite, Cu (I) Cl / trischloroethyl phosphite, CU (I) Tripropyl phosphite, p-nitrosodimethylaniline.

The polyester compositions according to the invention can be reinforced with reinforcing materials be reinforced. Metals, silicates, carbon and glass are mainly used as reinforcing materials in the form of fibers, fabrics or mats. Glass fibers are the 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. are added in the usual amounts.

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

The rate of crystallization of the polyester injection molding compositions according to the invention can be adjusted by adding from 0.01 to 1

Le A 17 403 - 13 -

80981 0/0173

% By weight, based on the unfilled and unreinforced Polyester, nucleating agents can be increased. The compounds known to the person skilled in the art are suitable as such as described, for example, in the Kunststoff-Handbuch, Volume VIII, "Polyester", Carl Hanser Verlag, Munich, 1973, page 701 are.

The polyester breeds according to the invention are excellent Starting materials for the production of moldings of all kinds by injection molding.

Table 1 gives the mold stand and total injection cycle times some inventive polyester resin compositions based on PÄT and phenyl alkylsulfonate (Examples 1-15) in comparison to the unmodified polyethylene terephthalate.

Le A 17 403-14 ■

809810/0173

Table 1

ο co

OO CD CD

^ J CO

■ Example 1 • 2 Alkylsulfenic acid esters Amount (wt .-%) cylinder Processing conditions time ( s ) i 125 4.0 10 Total injection molding cycle 9.5 Ni 15.5 • Art ■ I temperature Mold temperature! Form stand 110 2.5 (s) 19.5 tJ 3 (° c) (° C) 7th CO 4th 80 0 16.5 K> (C ₁₂ -C ₁₈ ) ^6th OO Alkyl sulfone acid-p- 3 260 13.5 phenyl ester 5 260 130 12.0 ^ VJI If O 10 260 120 6th Il (C ₁₂ -C ₁₈ ) - 110 Alkyl-di- sulfonic acid 3 260 p-phenyl ester 5 260 Il 10 260 Il

Le A17 403

- 15 -

Table 1 OO
O 9 / Continue. Amount (wt. %) cylinder Processing conditions Shape status Total injection molding cycle CT) example CO ^ω 10 temperature Mold temperature time (s) (s) CO ^ β j
Alkyl sulfonic acid esters ^ (° C) (° c) 18.5> O Art N) 16.5,000 7th 14.5 (C ₁₂ -C ₁₈ ) - 11 Alkyl sulfone 3 260 5 14.5 12th acid-p- 125 phenyloctyl 5 260 0 9.5 <^> ester 110 10 260 0 9.5 η 80 H (C ₁₂ -C ₁₈ ) - Alkyl sulfone 3 260 9 acid p-hydroxy 130 benzoic acid iso- 5 260 7th butyl ester 10 260 120 5 110 n ti

Le A17 403

- 1ό -

Table 1 / continued.

example Alkyl sulfonic acid esters Amount (wt .-%) cylinder Processing conditions (s) ■ i 10 j
j Total injection molding Art temperature Mold temperature Mold life ί 8
ί cycle (s) (° O (° C) VJi ¹ I.
j 30
i 13th 2,2-bis - ((C ₁₂ - C ₁₈ ) -alkylsul- OO
CD fonsäure-4- CO phenyl ester) 3 260 19.5 OO propane 130 CD 5 260 17.5 "* O 14th Il 10 260 125 14.5 Ca) 15th Il - 270 120 39.5 16 - 140

Le A17 403

- 17 -

CD NJ

Claims (3)

1. Highly crystalline, rapidly crystallizing thermoplastic masses consisting of a) 70-99.5 % by weight of a high molecular weight polyalkylene terephthalate with an intrinsic viscosity of at least 0.6 dl / g (measured as a 0.5% by weight solution in a phenol / tetrachloroethane mixture in a weight ratio of 1: 1 at 25 ° C) and b) 0.5-30% by weight of sulfonic acid ester obtained by reaction 1) an alkyl sulfochloride of the formula R ¹ - CH ₀ - (CHR ² ) - CH. R ³ whereby R ¹ , R ² and R ³ for H, Cl, SO ₂ Cl and η for integers, from 3-33 stand and the molar ratio C / SO ₂ C1 is 35 to 1.25, 2) with equivalent amounts of a compound of the formula HO-R ⁴ (-C-0) -R ⁵ (D. wherein 4th R is a bivalent aromatic radical with 6-14 carbon atoms, R an alkyl, cycloalkyl or aryl radical with 1-20 carbon atoms and m ο or 1 mean, Le A 17 403 - 18 - 809810/0173 ORIGINAL INSPECTED or 2639A28 -XC ^X ) -OH (ID whereby R ⁶ , R ⁷ , R ⁸ and R ^{9 are} identical or different and a hydrogen atom, an alkyl radical with 1-4 C atoms, a chlorine or bromine atom mean and χ a single bond, an alkylene or Alkylidene radical with 1-8 carbon atoms, a cycloalkylene or cycloalkylidene radical with 5-15 carbon atoms, S, S, SO-, 0 or is available. 2. A method for producing the masses according to claim 1, characterized marked that one 70-99.5 wt. # Of a high molecular weight polyalkylene terephthalate with an intrinsic viscosity of at least 0.6 dl / g (measured as a 0.5 wt .- # solution in a phenol / tetrachloroethane mixture in a weight ratio of 1: 1 at 25 ° C) and 0.5-30% by weight of a sulfonic acid ester based on the above specified manner is available, mixed and homogenized in the melt. Le A 17 403 - 19 - 809810/0173 3. Use of sulfonic acid esters, which are produced by reaction (1) of an alkyl sulfochloride of the formula R ¹ - CH ₀ - (CHR ² ) - CH_ R ³ Z η 2 whereby 12 R , R and R for H, Cl, SO ₂ Cl and stand for whole numbers, from 3-33 and the molar Ratio C / SO-Cl is 35 to 1.25, (2) with equivalent amounts of a compound of the formula , 4 HO-R (-C-0) -I . m (D wherein R ⁴ R ⁵ mean, or a bivalent aromatic radical with 6-14 carbon atoms, an alkyl, cycloalkyl or aryl radical with 1-20 carbon atoms and 0 or (II) where 6 7 8 R, R, R and R are the same or different and Le A 17 -20 - 809810/0173 a hydrogen atom, an alkyl radical with 1-4 C atoms, a chlorine or bromine atom mean and a single bond, an alkylene or alkylidene radical with 1-8 carbon atoms, a cycloalkylene or cycloalkylidene radical with 5-15 carbon atoms, S, S, SO ₉ , 0 or Il * J oil, is available to increase crystallization and the Rate of crystallization of polyalkylene terephthalates. Le A 17 403 '- 21 - 809810/0173