EP1088026A1

EP1088026A1 - Flame-proofed polyester moulding materials

Info

Publication number: EP1088026A1
Application number: EP99920747A
Authority: EP
Inventors: Martin Klatt; Michael Nam; Herbert Fisch
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 1998-05-07
Filing date: 1999-04-23
Publication date: 2001-04-04
Also published as: US6716899B1; JP2002513833A; DE19820399A1; WO1999057192A1

Abstract

The invention relates to thermoplastic moulding materials containing the following: A) 5 to 96 wt.% of a polyester; B) 1 to 30 wt.% of a phosphinic acid salt of formula (I) and/or a diphosphinic acid salt of formula (II) and/or polymers thereof, the substituents having the following meanings: R<1>, R<2> being a linear or branched C1- to C6-alkyl radical, a phenyl radical, hydrogen; R<3> being a linear or branched C1- to C10-alkylene radical, an arylene, alkylarylene or arylalkalene radical; M being an alkaline earth metal or an alkaline metal, Zn, Al, Fe, Bor; m being a whole number from 1 to 3; n being a whole number from 1 to 3; x being 1 or 2; C) 1 to 30 wt.% of at least one organic phosphorus-bearing flame-proofing agent; D) 0 to 5 wt.% of at least one ester or amide of saturated or unsaturated aliphatic carboxylic acids with 10 to 40 C-atoms with aliphatic saturated alcohols or amines with 2 to 40 C-atoms; and E) 0 to 60 wt.% other auxiliary substances, the sum of the weight percentages of the components A) to E) being 100 %.

Description

Flame retardant polyester molding compounds

description

The invention relates to thermoplastic molding compositions containing

A) 5 to 96% by weight of a polyester

B) 1 to 30% by weight of a phosphinic acid salt of the formula I and / or a diphosphinic acid salt of the formula II and / or their polymers

O

R ^l

M (I)

R2- m

p _R3 po M (II)

R ^l R2

where the substituents have the following meaning:

R ¹ , R ^{2 is} a linear or branched C 1 -C 6 -alkyl radical, phenyl radical, hydrogen,

R3 is a linear or branched C 1 -C 10 -alkylene radical, arylene, alkylarylene or arylalkylene radical,

n alkaline earth, alkali metal, Zn, AI, Fe, boron,

m is an integer from 1 to 3,

n is an integer from 1 and 3,

1 or 2 ;

C) 1 to 30% by weight of at least one organic phosphorus-containing flame retardant, D) 0 to 5% by weight of at least one ester or amide of saturated or unsaturated aliphatic carboxylic acids with 10 to 40 C atoms with aliphatic saturated alcohols or amines with 2 to 40 C atoms

E) 0 to 60% by weight of further additives,

the sum of the percentages by weight of components A) to E) being 100%.

Furthermore, the invention relates to the use of the molding compositions according to the invention for the production of fibers, films and moldings and to the moldings of any kind obtainable here.

There is increasing market interest for halogen-free flame-retardant polyesters. Essential requirements for the flame retardant are: light color, sufficient temperature stability for incorporation into thermoplastics, as well as its effectiveness in reinforced and unreinforced polymer (so-called wick effect with glass fibers).

The fire test for unreinforced polyester according to UL 94 with V-0 should be passed. For reinforced polyester, at least the classification V2 and / or the glow wire test should be passed.

In addition to the halogen-containing systems, four halogen-free FR systems are used in principle in thermoplastics:

Inorganic flame retardants, which have to be used in large quantities in order to be effective.

Nitrogen-containing FR systems, such as melamine cyanurate, which have a limited effectiveness in thermoplastics e.g. Polyamide shows. In reinforced polyamide, it is only effective in combination with shortened glass fibers. Melamine cyanurate alone is not effective in polyesters.

- Phosphorus ige FR systems that are generally not particularly effective in polyesters.

FR / phosphorus-containing FR systems, such as ammonium polyphosphates or melamine phosphates, which do not have sufficient thermal stability for thermoplastics that are processed at temperatures above 200 ° C. 3

JP-A 03/281 652 discloses polyalkylene terephthalates which contain melamine cyanurate and glass fibers, and also a phosphorus-containing flame retardant. These molding compositions contain derivatives of phosphoric acid such as phosphoric acid esters (valence level 5 +5), which tend to "bloom" when subjected to thermal stress.

These disadvantages are also evident for the combination of melamine cyanurate (MC) with resorcinol bis (diphenyl phosphate), which is known from JP-A 05/070 671. Furthermore, these molding compositions show high phenol values and insufficient mechanical properties during processing.

JP-A 09/157 503 discloses polyester molding compositions with MC, phosphorus compounds and lubricants which contain less than 15-10% reinforcing agents. Flame retardant and mechanical properties of such molding compositions are in need of improvement as well as migration and phenol formation during processing.

From EP-A 699 708 and BE-A 875 530, phosphinic acid salts are known as 20 flame retardants for polyesters.

WO 97/05705 discloses combinations of MC with phosphorus-containing compounds and lubricants for polyesters.

The present invention was therefore based on the object of providing flame-resistant polyester molding compositions which, according to Ul 94, achieve a sufficient classification and pass the glow wire test. The mold coating should be minimized and the flowability during processing should be improved.

30

We have found that this object is achieved by the thermoplastic molding compositions defined at the outset. Preferred embodiments can be found in the subclaims.

35 As component (A), the molding compositions according to the invention contain 5 to 96, preferably 10 to 70 and in particular 10 to 60% by weight of a thermoplastic polyester.

Generally, polyesters based on aromatic dicarboxylic acids and an aliphatic or aromatic dihydroxy compound are used.

A first group of preferred polyesters are polyalkylene terephthalates with 2 to 10 carbon atoms in the alcohol part. 4

Such polyalkylene terephthalates are known per se and are described in the literature. They contain an aromatic ring in the main chain, which comes from the aromatic dicarboxylic acid. The aromatic ring can also be substituted, e.g. by halogen such as chlorine and bromine or by -CC alkyl groups such as

Methyl, ethyl, i- or n-propyl and n-, i- or t-butyl groups.

These polyalkylene terephthalates can be prepared in a manner known per se by reacting aromatic dicarboxylic acids, their esters or other ester-forming derivatives with aliphatic dihydroxy compounds.

Preferred dicarboxylic acids are 2, 6-naphthalenedicarboxylic acid, terephthalic acid and isophthalic acid or mixtures thereof. Up to 30 mol%, preferably not more than 10 mol%, of the aromatic dicarboxylic acids can be replaced by aliphatic or cycloaliphatic dicarboxylic acids such as adipic acid, azelaic acid, sebacic acid, dodecanedioic acids and cyclohexanedicarboxylic acids.

Of the aliphatic dihydroxy compounds, diols having 2 to 6 carbon atoms, in particular 1,2-ethanediol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,4-hexanediol, 1,4- Cyclohexanediol, 1,4-cyclohexanedimethanol and neopentyl glycol or mixtures thereof are preferred.

Polyalkylene terephthalates which are derived from alkanediols having 2 to 6 carbon atoms can be mentioned as particularly preferred polyesters (A). Of these, polyethylene terephthalate, polypropylene terephthalate and polybutylene terephthalate or mixtures thereof are preferred in particular. Also preferred are PET and / or PBT which contain up to 1% by weight, preferably up to 0.75% by weight, of 1,6-hexanediol and / or 5-methyl-1,5-pentanediol as further monomer units contain.

The viscosity number of the polyesters (A) is generally in the range from 50 to 220, preferably from 80 to 160 (measured in a 0.5% strength by weight solution in a phenol / o-dichlorobenzene mixture (weight ratio). 1: 1 at 25 ° C) according to ISO 1628.

Particularly preferred are polyesters whose carboxyl end group content is up to 100 meq / kg, preferably up to 50 meq / kg and in particular up to 40 meq / kg polyester. Such polyesters can, for example, according to the process of DE-A 44 01 055 5 can be produced. The carboxyl end group content is usually determined by titration methods (eg potentiometry).

Particularly preferred molding compositions contain as component A) a mixture of polyethylene terephthalate (PET) and polybutylene terephthalate (PBT). The proportion of polyethylene terephthalate in the mixture is preferably up to 50, in particular 10 to 30,% by weight, based on 100% by weight of A).

Such molding compositions according to the invention show very good flame retardant properties and better mechanical properties.

It is also advantageous to use PET recyclates (also called scrap PET) in a mixture with polyalkylene terephthalates such as PBT.

Recyclates are generally understood to mean:

1) so-called post industrial recyclate: this is production waste from polycondensation or processing e.g. Sprues in injection molding processing, approach goods in injection molding processing or extrusion or edge sections of extruded sheets or foils.

2) Post consumer recyclate: these are plastic items that are collected and processed by the end consumer after use. The most dominant item in terms of quantity are blow-molded PET bottles for mineral water, soft drinks and juices.

Both types of recyclate can either be in the form of regrind or in the form of granules. In the latter case, the tube cyclates are melted and granulated in an extruder after separation and cleaning. This usually makes handling, sprinkling and metering easier for further processing steps.

Recyclates, both granulated and in the form of regrind, can be used, the maximum edge length being 6 mm, preferably less than 5 mm.

Due to the hydrolytic cleavage of polyesters during processing (due to traces of moisture), it is advisable to pre-dry the recyclate. The residual moisture content after drying is preferably 0.01 to 0.7, in particular 0.2 to 0.6%. b

Another group to be mentioned are fully aromatic polyesters which are derived from aromatic dicarboxylic acids and aromatic dihydroxy compounds.

Aromatic dicarboxylic acids which are suitable are the compounds already described for the polyalkylene terephthalates. Mixtures of 5 to 100 mol% of isophthalic acid and 0 to 95 mol% of terephthalic acid are preferred, in particular mixtures of about 80% terephthalic acid with 20% isophthalic acid to approximately equivalent mixtures of these two acids.

The aromatic dihydroxy compounds preferably have the general formula

HO OH m

in which Z represents an alkylene or cycloalkylene group with up to 8 C atoms, an arylene group with up to 12 C atoms, a carbonyl group, a sulfonyl group, an oxygen or sulfur atom or a chemical bond and in which m represents the value Has 0 to 2. The compounds I can also carry C 1 -C 6 -alkyl or alkoxy groups and fluorine, chlorine or bromine as substituents on the phenylene groups.

As the stem of these compounds, for example

Dihydroxydiphenyl,

Di (hydroxyphenyl) alkane,

Di (hydroxyphenyl) cycloalkane,

Di (hydroxyphenyl) sulfide,

Di - (hydroxyphenyl) ether, di- (hydroxyphenyl) ketone, di- (hydroxyphenyl) sulfoxide, α, α '-di (hydroxyphenyl) dialkylbenzene,

Di (hydroxyphenyl) sulfone, di (hydroxybenzoyl) benzene

Resorcinol and hydroquinone as well as ^" their nuclear alkylated or nuclear halogenated

Called derivatives.

Of these will be

4,4'-dihydroxydiphenyl,

2, 4 -Di- (4'-hydroxyphenyl) -2-methylbutane α, α '-Di- (4-hydroxyphenyl) -p-diisopropylbenzene, 7

2, 2 -di (3'-methyl -4'-hydroxyphenyl) propane and

2,2-di- (3'-chloro-4'-hydroxyphenyl) propane,

as well as in particular

2, 2 -Di - (4'-hydroxyphenyl) ropane 2, 2 -Di (3 ', 5 -dichlorodihydroxyphenyl) propane, 1,1 -Di- (4' -hydroxyphenyl) cyclohexane, 3,4 '-dihydroxybenzophenone, 4 , '-Dihydroxydiphenylsulfon and

2,2-di (3 ', 5' -dimethyl-4 '-hydroxyphenyl) propane

or mixtures thereof are preferred.

Of course, mixtures of polyalkylene terephthalates and fully aromatic polyesters can also be used. These generally contain 20 to 98% by weight of the polyalkylene terephthalate and 2 to 80% by weight of the fully aromatic polyester.

Polyesters for the purposes of the present invention are also to be understood as meaning polycarbonates which are obtained by polymerizing aromatic dihydroxy compounds, in particular bis (4-hydroxyphenyl) 2,2-propane (bisphenol A) or its derivatives, e.g. are available with phosgene. Corresponding products are known per se and described in the literature and for the most part are also commercially available. The amount of the polycarbonates is up to 90% by weight, preferably up to 50% by weight, based on 100% by weight of component (A).

Of course, polyester block copolymers such as copolyether esters can also be used. Products of this type are known per se and are described in the literature, for example in US Pat. No. 3,651,014. Corresponding products are also commercially available, for example Hytrel ^® (DuPont).

As component B), the molding compositions according to the invention contain 0.1 to 30, preferably 1 to 25 and in particular 10 to 20% by weight of a phosphinic acid salt of the formula (I) and / or a diphosphinic acid salt of the formula (II) and / or their Polymers

0

R ⁱ

M

R2- 8th

^■ 0 f P R3 f P 0 M _x II

_R l R

where the substituents have the following meaning:

R ^l, R ² are hydrogen, C ~ to _ß alkyl, preferably Ci to C ₄ alkyl -Al-, linear or branched, for example methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl Butyl, n-pentyl; Phenyl; preferably at least one radical R ¹ or R ² , in particular R ¹ and R ^{2, is} hydrogen;

R3 -C ~ to Cio-alkylene, linear or branched, e.g. Methylene, ethylene, n-propylene, iso-propylene, n-butylene, tert-butylene, n-pentylene, n-octylene, n-dodecylene; Aryls, e.g. Phenylene, naphthylene;

Alkylarylene, e.g. Methyl-phenylene, ethyl-phenylene, tert-butyl-phenylene, methyl-naphthylene, ethyl-naphthylene, tert. -Butyl-naphthylene;

Arylalkylene, e.g. Phenylmethylene, phenylethylene, phenylpropylene, phenylbutylene;

M is an alkaline earth metal, alkali metal, Al, Zn, Fe, boron;

m is an integer from 1 to 3;

n is an integer from 1 and 3 and

x 1 or 2

Compounds of the formula II in which R ¹ and R ^{2 are} hydrogen are particularly preferred, where M is preferably Zn or Al and calcium phosphinate is very particularly preferred.

Such products are commercially available e.g. available as calcium phosphinate.

Suitable salts of the formula I or II, in which only one radical R ¹ or R ^{2 is} hydrogen, are, for example, salts of phenylphosphinic acid, their Na and / or Ca salts being preferred. 9

Suitable organic phosphorus-containing flame retardants C) are present in the molding compositions according to the invention in amounts of 1 to 30, preferably 1 to 25 and in particular 5 to 20% by weight, based on the total weight of components A) to E).

Component C) is an organic phosphorus-containing compound in which the phosphorus has a valence level of -3 to +5. The value level is to be understood as the term "oxidation level" as used in the textbook on inorganic chemistry by A.F. Hollemann and E. Wiberg, Walter des Gruyter and Co. (1964, 57th to 70th editions), pages 166 to 177. Phosphorus compounds of valence levels -3 to +5 are derived from phosphine (-3), diphosphine (-2), phosphine oxide (-1), elemental phosphorus (+0), hypophosphorous acid (+1), phosphorous acid (+3), Hypodiphosphoric acid (+4) and phosphoric acid (+5).

Only a few examples may be mentioned from the large number of compounds containing phosphorus.

Examples of phosphorus compounds of the phosphine class which have the valence level -3 are aromatic phosphines, such as triphenylphosphine, tritolylphosphine, trinonylphosphine, trinaphthylphosphine and others. Triphenylphosphine is particularly suitable.

Examples of phosphorus compounds of the diphosphine class which have the valence level -2 are tetraphenyldiphosphine, tetraphthyldiphosphine and others. Tetranaphthyldiphosphine is particularly suitable.

Phosphorus compounds of valence level -1 are derived from phosphine oxide.

Phosphine oxides of the general formula III are suitable

R ^l

_R 2 p = o HJ.

R3

where R ¹ , R ² and R ^{3 are the} same or different alkyl, aryl, alkylaryl or cycloalkyl groups having 8 to 40 carbon atoms.

Examples of phosphine oxides are triphenylphosphine oxide, tritolylphosphine oxide, trisnonylphenylphosphine oxide, tricyclohexylphosphine oxide, tris (n-butyl) phosphine oxide, tris (n-hexyl) phosphine oxide, tris (n-octyl) phosphine oxide, tris (cyanoethyl) ) -phosphine oxide, 10

Benzylbis (cyclohexyl) phosphine oxide, benzylbisphenylphosphine oxide, phenylbis (n-hexyl) phosphine oxide. Oxidized reaction products of phosphine with aldehydes, in particular of t-butylphosphine with glyoxal, are also preferred. Triphenylphosphine oxide, tricyclohexlyphosphine oxide and tris (n-octyl) phosphine oxide are particularly preferably used.

Triphenylphosphine sulfide and its derivatives of the phosphine oxides and triphenylphosphate as described above are also suitable.

Phosphorus of grade +0 is the elementary phosphorus. Red and black phosphorus are possible. Red phosphorus is preferred.

Phosphorus compounds of the "oxidation level" +1 are e.g. Hypophosphites. Examples are organic hypophosphites, such as cellulose hypophosphite esters, esters of hypophosphorous acids with diols, e.g. of 1, 10-dodecyldiol. Substituted phosphinic acids and their anhydrides, e.g. Diphenylphosphinic acid can be used. Also suitable are di-p-tolylphosphinic acid, di-cresylphosphinic anhydride, but compounds such as hydroquinone, ethylene glycol, propylene glycol bis (diphenylphosphinic acid) esters and others are also suitable. in question. Aryl (alkyl) phosphinamides, such as e.g. Diphenylphosphinic acid dimethylamide and sulfonamidoaryl (alkyl) phosphinic acid derivatives, such as e.g. p-tolylsulfonamidodiphenylphosphinic acid. Hydroquinone and ethylene glycol bis (diphenylphosphinic acid) esters and the bisdiphenylphosphinate of hydroquinone are preferably used.

Phosphorus compounds of oxidation level +3 are derived from the phosphorous acid. Cyclic phosphonates derived from pentaerythritol, neopentyl glycol or catechol are suitable, e.g.

-o- P CH ₃

(OCH ₃ ) _x

2-x

where R is a C 1 -C ₄ -alkyl radical, preferably a methyl radical, X = 0 or 1 (Amgard® P45 from Albright & Wilson). 11

Furthermore, phosphorus of valency level +3 is contained in triaryl (alkyl phosphites, such as triphenyl phosphite, tris (4-decylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite or phenyldidecyl phosphite and others However, diphosphites, such as, for example, propylene glycol-1,2-bis (diphosphite) or cyclic phosphates derived from pentaerythritol, neopentyl glycol or pyrocatechol, are also suitable.

Methyl neopentyl glycol phosphonate and phosphite and dimethylpentaerythritol diphosphonate and phosphite are particularly preferred.

Hypodiphosphates, such as e.g. Tetraphenyl hypodiphosphate or bisneopentyl hypodiphosphate into consideration.

Alkyl and aryl-substituted phosphates are particularly suitable as phosphorus compounds of oxidation level +5. Examples are phenylbisdodecyl phosphate, phenylethyl hydrogen phosphate, phenyl bis (3, 5, 5-trimethylhexyl) phosphate, ethyl diphenyl phosphate, 2-ethyl hexyl di (tolyl) phosphate, diphenyl hydrogen phosphate,

Bis (2-ethylhexyl) p-tolyl phosphate, tritolyl phosphate, bis (2-ethyl hexyl) phenyl phosphate, di (nonyl) phenyl phosphate, phenylmethyl hydrogen phosphate, di (dodecyl) p-tolyl phosphate, p-tolyl bis (2 , 5, 5-trimethylhexyl) phosphate or 2-ethylhexyldiphenylphosph- has. Phosphorus compounds in which each radical is an aryloxy radical are particularly suitable. Triphenyl phosphate and resorcinol bis (diphenyl phosphate) (RDP) and their core-substituted derivatives of the general formula IV are very particularly suitable

OR ⁵ OR ^{6 ""} !

R0- P - R8 -OR ⁷ IV

0

in which the substituents have the following meaning:

R ⁴ -R ^{7 is} an aromatic radical with 6 to 20 C atoms, preferably a phenyl radical, which can be substituted with alkyl groups with 1 to 4 C atoms, preferably methyl,

R ^{8 is} a divalent phenol radical, preferred or - °

and n is an average value between 0.1 and 100, preferably 0.5 to 50, in particular 0.8 to 10 and very particularly 1 to 5.

The commercially available RDP products under the trademarks Fyroflex®-RDP (Akzo Nobel) and CR 733-S (Daihachi) are due to the manufacturing process mixtures of approx. 85% RDP with approx. 2.5% triphenyl phosphate and approx. 12.5% oligomeric proportions in which the degree of oligomerization is usually less than 10.

Cyclic phosphates can also be used. Diphenylpentaerythritol diphosphate and phenylneopentyl phosphate are particularly suitable.

In addition to the low molecular weight phosphorus compounds listed above, oligomeric and polymeric phosphorus compounds are also suitable.

Such polymeric, halogen-free organic phosphorus compounds with phosphorus in the polymer chain arise, for example, in the production of pentacyclic, unsaturated phosphine dihalides, as described, for example, in DE-A 20 36 173. The molecular weight measured by vapor pressure osmometry in dimethylformamide, the polyphospholine oxides should be in the range from 500 to 7,000, preferably in the range from 700 to 2,000.

The phosphorus has the oxidation state -1.

Inorganic coordination polymers of aryl (alkyl) phosphinic acids such as e.g. Poly-β-sodium (I) methylphenylphosphinate can be used. Their manufacture is specified in DE-A 31 40 520. The phosphorus has an oxidation number of +1.

Furthermore, such halogen-free polymeric phosphorus compounds can be obtained by the reaction of a phosphonic acid chloride, e.g. Phenyl, methyl, propyl, styryl and vinylphosphonic dichloride with bifunctional phenols, e.g. Hydroquinone, resorcinol, 2,3, 5-trimethylhydroquinone, bisphenol-A, tetramethylbisphenol-A arise.

Further halogen-free polymeric phosphorus compounds which can be contained in the molding compositions according to the invention are obtained by reacting phosphorus oxide trichloride or phosphoric acid ester dichlorides with a mixture of mono-, bi- and trifunctional Phenols and other hydroxyl group-bearing compounds prepared (see Houben-Weyl-Müller, Thieme-Verlag Stuttgart, Organic Phosphorus Compounds Part II (1963)). Furthermore, polymeric phosphonates can be prepared by transesterification reactions of 5-star phosphonic acids with bifunctional phenols (cf. DE-A 29 25 208) or by reactions of phosphonic acid esters with diamines or diamides or hydrazides (cf. US Pat. No. 4,403,075). However, the inorganic poly (ammonium phosphate) can also be used.

10 Oligomeric pentaerythritol phosphites, phosphates and phosphonates according to EP-B 8 486, e.g. Mobil Antiblaze® 19 (registered trademark of Mobil Oil) can be used.

As component D), the molding compositions according to the invention can contain 0 to 15 5, preferably 0.05 to 3 and in particular 0.1 to 2% by weight of at least one ester or amide of saturated or unsaturated aliphatic carboxylic acids with 10 to 40, preferably 16 to 22 ° C. - Contain atoms with aliphatic saturated alcohols or amines with 2 to 40, preferably 2 to 6 carbon atoms. 20th

The carboxylic acids can be 1- or 2-valent. Examples include pelargonic acid, palmitic acid, lauric acid, margaric acid, decadedioic acid, behenic acid and particularly preferably stearic acid, capric acid and montanic acid (mixture of fatty acids with 30 to 25 40 C atoms).

The aliphatic alcohols can be 1- to 4-valent. Examples of alcohols are n-butanol, n-octanol, stearyl alcohol, ethylene glycol, propylene glycol, neopentyl glycol, pentaerythritol, 30 glycerol and pentaerythritol being preferred.

The aliphatic amines can be 1- to 3-valent. Examples include stearylamine, ethylenediamine, propylenediamine, hexamethylenediamine, di (6-aminohexyl) amine, ethylenediamine and hexamethylenediamine being particularly preferred. Preferred esters or amides are correspondingly glycerol distearate, glycerol tristearate, ethylenediamine distearate, glycerol monopalmitate, glycerol trilaurate, glycerol monobehenate and pentaerythritol tetrastearate.

Mixtures of different esters or amides or esters with amides can also be used in combination, the mixing ratio being arbitrary.

The molding compositions according to the invention can contain, as component E), from 0 to 45 60, in particular up to 50% by weight of further additives. 14

Customary additives E) are, for example, in amounts up to 40, preferably up to 30% by weight of rubber-elastic polymers (often also referred to as impact modifiers, elastomers or rubbers).

In general, these are copolymers which are preferably composed of at least two of the following monomers: ethylene, propylene, butadiene, isobutene, isoprene, chloroprene, vinyl acetate, styrene, acrylonitrile and acrylic or methacrylic acid esters with 1 to 18 C - Atoms in the alcohol component.

Such polymers are e.g. in Houben-Weyl, Methods of Organic Chemistry, Vol. 14/1 (Georg-Thieme-Verlag, Stuttgart, 1961). Pages 392 to 406 and in the monograph by C.B. Bucknall, "Toughened Plastics" (Applied Science Publishers, London, 1977).

Some preferred types of such elastomers are presented below.

Preferred types of such elastomers are the so-called ethylene-propylene (EPM) or ethylene-propylene-diene (EPDM) rubbers.

EPM rubbers generally have practically no more double bonds, while EPDM rubbers can have 1 to 20 double bonds / 100 carbon atoms.

Examples of diene monomers for EPDM rubbers are conjugated dienes such as isoprene and butadiene, non-conjugated dienes having 5 to 25 carbon atoms such as penta-1,4-diene, hexa-1,4-diene, hexa-l , 5-diene, 2, 5-dimethylhexa-l, 5-diene and octa-1, -diene, cyclic dienes such as cyclopentadiene, cyclohexadienes, cyclooctadienes and dicyclopentadiene, and alkenylnorbornenes such as 5-ethylidene-2-norobornene, 5-butylidene -2-norbornene, 2-methallyl-5-norbornene, 2-isopropenyl-5-norbornene and tricyclodienes such as 3-methyl-tricyclo (5.2.1.0.2.6) -3, 8-decadiene or mixtures thereof. Hexa-1,5-diene, 5-ethylidene norbornene and dicyclopentadiene are preferred. The diene content of the EPDM rubbers is preferably 0.5 to 50% by weight, in particular 1 to 8% by weight, based on the total weight of the rubber.

EPM or EPDM rubbers can preferably also be grafted with reactive carboxylic acids or their derivatives. Examples include acrylic acid, methacrylic acid and their derivatives, for example glycidyl (meth) acrylate, and maleic anhydride. 15

Another group of preferred rubbers are copolymers of ethylene with acrylic acid and / or methacrylic acid and / or the esters of these acids. The rubbers can still dicarboxylic acids such as maleic acid and fumaric acid or derivatives of these acids, for example esters and anhydrides, and / or epoxy groups contained ^¬ contain tend monomers. These dicarboxylic acid derivatives or monomers containing epoxy groups are preferably incorporated into the rubber by adding monomers of general formulas I or II or III or IV containing dicarboxylic acid or epoxy groups to the monomer mixture

R ¹ C (COOR ² ) = C (COOR ³ ) R ⁴ (I)

RR ⁴

(II)

CO CO

0

/ \

CHR ⁷ = CH (CH ₂ ) _m 0 (CHR ⁶ ) _g CH CHR ^{5 (} III ⁾

CH ₂ = CR ⁹ COO— (CH ₂ ) _P —CH CHR ^{8 (} IV ⁾

\ /

0

where R ¹ to R ^{9 represent} hydrogen or alkyl groups having 1 to 6 carbon atoms and m is an integer from 0 to 20, g is an integer from 0 to 10 and p is an integer from 0 to 5.

The radicals R ¹ to R ^{9 are} preferably hydrogen, where m is 0 or 1 and g is 1. The corresponding compounds are maleic acid, fumaric acid, maleic anhydride, allyl glycidyl ether and vinyl glycidyl ether.

Preferred compounds of the formulas I, II and IV are maleic acid, maleic anhydride and epoxy group-containing esters of acrylic acid and / or methacrylic acid, such as glycidyl acrylate, glycidyl methacrylate and the esters with tertiary alcohols, such as t-butyl acrylate. Although the latter have no free carboxyl groups, their behavior is close to that of the free acids and 16 are therefore referred to as monomers with latent carboxyl groups.

The copolymers advantageously consist of 50 to 98% by weight of ethylene, 0.1 to 20% by weight of monomers containing epoxy groups and / or monomers containing methacrylic acid and / or monomers containing acid anhydride and the remaining amount of (meth) acrylic acid esters.

Copolymers of are particularly preferred

50 to 98, in particular 55 to 95% by weight of ethylene,

0.1 to 40, in particular 0.3 to 20% by weight of glycidyl acrylate and / or glycidyl methacrylate, (meth) acrylic acid and / or maleic anhydride, and

1 to 45, in particular 10 to 40% by weight of n-butyl acrylate and / or 2-ethylhexyl acrylate.

Further preferred esters of acrylic and / or methacrylic acid are the methyl, ethyl, propyl and i- or t-butyl esters.

In addition, vinyl esters and vinyl ethers can also be used as comonomers.

The ethylene copolymers described above can be prepared by processes known per se, preferably by random copolymerization under high pressure and elevated temperature. Appropriate methods are generally known.

Preferred elastomers are also emulsion polymers, the production of which e.g. in Blackley in the monograph "Emulsion Polymerization" is described. The emulsifiers and catalysts that can be used are known per se.

In principle, homogeneous elastomers or those with a shell structure can be used. The shell-like structure is determined by the order of addition of the individual monomers; the morphology of the polymers is also influenced by this sequence of pulls.

The monomers for the production of the rubber part of the elastomers are only representative of acrylates such as n-butyl acrylate and 2-ethylhexyl acrylate, corresponding methacrylates, butadiene and isoprene and mixtures thereof. These monomers can be combined with other monomers such as styrene, acrylonitrile, vinyl ethers and other acrylates or methacrylates such as methyl metha- acrylate, methyl acrylate, ethyl acrylate and propyl acrylate are copolymerized.

The soft or rubber phase (with a glass transition temperature below 0 ° C) of the elastomers can be the core, the outer shell or a middle shell (in the case of elastomers with more than two layers). in the case of multi-layer elastomers, several shells can also consist of a rubber phase.

If, in addition to the rubber phase, one or more hard components (with glass transition temperatures of more than 20 ° C.) are involved in the construction of the elastomer, these are generally polymerized by styrene, acrylonitrile, methacrylonitrile, α-methylstyrene, p-methylstyrene, acrylic acid esters and methacrylic acid esters such as methyl acrylate, ethyl acrylate and methyl methacrylate as main monomers. In addition, smaller proportions of further comonomers can also be used here.

In some cases it has proven to be advantageous to use emulsion polymers which have reactive groups on the surface. Such groups are e.g. Epoxy, carboxyl, latent carboxyl, amino or amide groups as well as functional groups by the use of monomers of the general formula

RIO _R ll

I I

CH ₂ = CXNCR ¹²

II 0

can be introduced

where the substituents can have the following meanings:

R ^{10 is} hydrogen or a C 1 -C ₄ -alkyl group,

R ^{11 is} hydrogen, a C 1 -C 6 -alkyl group or an aryl group, in particular phenyl,

R ^{12 is} hydrogen, a Cχ ~ to Cio-alkyl, a Cε to Cι ₂ aryl group or -OR ¹³

R ^{13 is} a C 1 to C ₈ alkyl or C ₆ to C ₂ aryl group, which can optionally be substituted with 0 or N-containing groups, 18th

X is a chemical bond, a Cι ~ to Cι ₀ -alkylene or Cg-

Ci ₂ ~ arylene group or

0

Y O-Z or NH-Z and

Z a Cι ~ to Cι ₀ alkylene or Cg to Cι ₂ arylene group.

The graft monomers described in EP-A 208 187 are also suitable for introducing reactive groups on the surface.

Further examples include acrylamide, methacrylamide and substituted esters of acrylic acid or methacrylic acid such as (Nt-butylamino) ethyl methacrylate, (N, N-dimethylamino) ethyl acrylate, (N, N-dimethylamino) methyl acrylate and (N, N-diethylamino) called ethyl acrylate.

The particles of the rubber phase can also be crosslinked. Monomers acting as crosslinkers are, for example, buta-1,3-diene, divinylbenzene, diallyl phthalate and dihydrodicyclopentadienyl acrylate, and the compounds described in EP-A 50 265.

So-called graft-linking monomers can also be used, i.e. Monomers with two or more polymerizable double bonds, which react at different rates during the polymerization. Compounds are preferably used in which at least one reactive group polymerizes at about the same rate as the other monomers, while the other reactive group (or reactive groups) e.g. polymerizes much slower (polymerize). The different polymerization rates result in a certain proportion of unsaturated double bonds in the rubber. If a further phase is subsequently grafted onto such a rubber, the double bonds present in the rubber react at least partially with the graft monomers to form chemical bonds, i.e. the grafted phase is at least partially linked to the graft base via chemical bonds.

Examples of such graft-crosslinking monomers are monomers containing allyl groups, in particular allyl esters of ethylenically unsaturated carboxylic acids such as allyl acrylate, allyl methacrylate,

Diallyl maleate, diallyl fumarate, diallyl itaconate or the corresponding monoallyl compounds of these dicarboxylic acids. Besides there are 19 there are a large number of other suitable graft-crosslinking monomers; for further details, reference is made here, for example, to US Pat. No. 4,148,846.

In general, the proportion of these crosslinking monomers in the impact-modifying polymer is up to 5% by weight, preferably not more than 3% by weight, based on the impact-modifying polymer.

10 Some preferred emulsion polymers are listed below. First of all, graft polymers with a core and at least one outer shell are to be mentioned, which have the following structure:

J.-J

Type Monomers for the Core Monomers for the Shell

I buta-1, 3-diene, isoprene, styrene, acrylonitrile, n-butyl acrylate, ethyl methyl methacrylate, hexyl acrylate or their

? .n mixtures

II as I but with the use of I networkers

III as I or II n-butyl acrylate, ethyl acrylate, methyl acrylate, buta-1, 3-diene, isoprene,

25 ethyl hexyl acrylate

IV as I or II as I or III but using Mi using monomers with reactive groups as described herein

30 V styrene, acrylonitrile, first shell made of monomers

Methyl methacrylate or as described under I and II for the core mixtures of the second shell as under I or IV for the shell wrote 5

These graft polymers, in particular ABS and / or ASA polymers in amounts of up to 40% by weight, are preferably used for impact modification of PBT, optionally in a mixture with up to 40% by weight of polyethylene terephthalate. Corresponding 0 blend products are available under the trademark Ultradur®S (formerly Ultrablend®S from BASF AG). ABS / ASA mixtures with polycarbonates are commercially available under the trademark Terblend® (BASF AG). 5 Instead of graft polymers with a multi-layer structure, it is also possible to use homogeneous, ie single-layer elastomers composed of buta-l, 3-diene, isoprene and n-butyl acrylate or their copolymers 20 are used. These products can also be prepared by using crosslinking monomers or monomers with reactive groups.

Examples of preferred emulsion polymers are n-butyl acrylate / (meth) acrylic acid copolymers, n-butyl acrylate / glycidyl acrylate or n-butyl acrylate / glycidyl methacrylate copolymers, graft polymers with an inner core of n-butyl acrylate or based on a butadiene and an outer shell from the above mentioned copolymers and copolymers of ethylene with comonomers which provide reactive groups.

The elastomers described can also be made by other conventional methods, e.g. by suspension polymerization.

Silicone rubbers as described in DE-A 37 25 576, EP-A 235 690, DE-A 38 00 603 and EP-A 319 290 are also preferred.

Of course, mixtures of the rubber types listed above can also be used.

Fibrous or particulate fillers are carbon fibers, glass fibers, glass spheres, amorphous silica, asbestos, calcium silicate, calcium metasilicate, magnesium carbonate, kaolin, chalk, powdered quartz, mica, barium sulfate and feldspar, which are present in quantities of up to 50% by weight. , in particular 1 to 40%, in particular 20 to 35% by weight, are used.

Carbon fibers, aramid fibers and potassium titanate fibers may be mentioned as preferred fibrous fillers, with glass fibers being particularly preferred as E-glass. These can be used as rovings or cut glass in the commercially available forms.

The fibrous fillers can be surface-pretreated with a silane compound for better compatibility with the thermoplastic.

Suitable silane compounds are those of the general formula

⁽ X- (CH ₂ ) _n ) -Si- (0-C _m H _{2m +} ι) ₄ -k

in which the substituents have the following meaning: 21

X NH ₂ -, CH ₂ -CH-, HO-, 0

n is an integer from 2 to 10, preferably 3 to 4 m is an integer from 1 to 5, preferably 1 to 2 k is an integer from 1 to 3, preferably 1

Preferred silane compounds are aminopropyltrimethoxysilane, _A minobutyltrimethoxysilan, aminopropyltriethoxysilane, triethoxysilane aminobutyl and the corresponding silanes which contain, as substituent X a glycidyl group.

The silane compounds are generally used in amounts of 0.05 to 5, preferably 0.5 to 1.5 and in particular 0.8 to 1% by weight (based on D) for surface coating.

Acicular mineral fillers are also suitable.

For the purposes of the invention, acicular mineral fillers are understood to be mineral fillers with a pronounced acicular character. An example is needle-shaped wollastonite. The mineral preferably has an L / D (length diameter) ratio of 8: 1 to 35: 1, preferably 8: 1 to 11: 1. The mineral filler can optionally have been pretreated with the abovementioned silane compounds; however, pretreatment is not essential.

Kaolin, calcined kaolin, wollastonite, talc and chalk may be mentioned as further fillers.

As component E), the thermoplastic molding compositions according to the invention can contain customary processing aids such as stabilizers, oxidation retardants, agents against heat decomposition and decomposition by ultraviolet light, lubricants and mold release agents, colorants such as dyes and pigments, nucleating agents, plasticizers, etc.

Examples of oxidation retarders and heat stabilizers are sterically hindered phenols and / or phosphites, hydroquinones, aromatic secondary amines such as diphenylamines, various substituted representatives of these groups and their mixtures in concentrations of up to 1% by weight, based on the weight of the thermoplastic molding compositions called. Various substituted resorcinols, salicylates, benzotriazoles and benzophenones may be mentioned as UV stabilizers, which are generally used in amounts of up to 2% by weight, based on the molding composition.

Inorganic pigments such as titanium dioxide, ultramarine blue, iron oxide and carbon black, organic pigments such as phthalocyanines, quinacridones, perylenes and dyes such as nigrosine and anthraquinones can also be added as colorants.

Sodium phenylphosphinate, aluminum oxide, silicon dioxide and preferably talc can be used as nucleating agents.

Lubricants and mold release agents which are different from D) and are usually used in amounts of up to 1% by weight are preferably long-chain fatty acids (eg stearic acid or behenic acid), their salts (eg Ca or Zn stearate) or Montan waxes (mixtures of straight-chain, saturated carboxylic acids with chain lengths of 28 to 32 carbon atoms) as well as low molecular weight polyethylene or polypropylene waxes.

Examples of plasticizers are phthalic acid dioctyl ester, phthalic acid dibenzyl ester, phthalic acid butyl benzyl ester, hydrocarbon oils, N- (n-butyl) benzenesulfonamide.

The molding compositions according to the invention can also contain 0 to 2% by weight of fluorine-containing ethylene polymers. These are polymers of ethylene with a fluorine content of 55 to 76% by weight, preferably 70 to 76% by weight.

Examples of these are polytetrafluoroethylene (PTFE), tetrafluoroethylene-hexafluoropropylene copolymers or tetrafluoroethylene copolymers with smaller proportions (generally up to 50% by weight) of copolymerizable ethylenically unsaturated monomers. These are e.g. by Schildknecht in "Vinyl and Related Polymers",

Wiley-Verlag, 1952, pages 484 to 494 and by Wall in "Fluoropolymers" (Wiley Interscience, 1972).

These fluorine-containing ethylene polymers are homogeneously distributed in the molding compositions and preferably have a particle size d ₅ o (number average) in the range of 0.05 to 10 .mu.m, in particular from 0.1 to 5 microns. These small particle sizes can be achieved particularly preferably by using aqueous dispersions of fluorine-containing ethylene polymers and incorporating them into a polyester melt. The thermoplastic molding compositions according to the invention can be prepared by processes known per se, in which the starting components are mixed in conventional mixing devices such as screw extruders, Brabender mills or Banbury mills and then extruded. After the extrusion, the extrudate can be cooled and crushed. Individual components can also be premixed and then the remaining starting materials added individually and / or likewise mixed. The mixing temperatures are usually 230 to 290 ° C.

According to a preferred procedure, components B) to D) and, if appropriate, customary additives E) can be mixed, made up and granulated with a polyester prepolymer. The granules obtained are then in the solid phase under inert gas continuously or batchwise at a

Temperature below the melting point of component A) condensed to the desired viscosity.

The thermoplastic molding compositions according to the invention are notable for good mechanical properties and good flame retardant properties while passing the glow wire test. The processing takes place largely without changing the polymer matrix and improved flowability and the mold covering is greatly reduced. They are suitable for the production of fibers, foils and moldings, in particular for applications in the electrical and electronics sector. These applications include, in particular, lamp parts such as lamp sockets and holders, plugs and connector strips, coil formers, housings for capacitors or contactors, as well as fuse switches, relay housings and reflectors.

Examples

Component A): polybutylene terephthalate with a viscosity number of 130 ml / g and a carboxyl end group content of 34 meq / kg (Ultradur® B 4500 from BASF AG) (VZ measured in 0.5% by weight solution of phenol / o-dichlorobenzene) , l: l mixture at 25 ° C according to ISO 1628.

Component B / l: calcium phosphinate

Component B / 2: AI (CH ₃ C ₂ H ₅ P0 ₂ ) ₃

Component C:

Resorcinol bis (diphenyl phosphate) (CR 733-S from Daihachi) 24

Component D: pentaerythritol tetrastearate (Loxiol® VPG 861 der

Henkel KGaA)

Component E: chopped glass fiber with a thickness of 10 μm (epoxy-silanized size).

Components A) to E) were mixed in a twin-screw extruder at 250 to 260 ° C and extruded in a water bath. After granulation and drying, test specimens were injected and tested on an injection molding machine.

The fire test was carried out in accordance with UL 94 on 1/16 inch test specimens with normal conditioning.

The test of the stability at elevated operating temperatures was carried out as follows: molded parts (small plates 60x60x2 mm, approx. 11 g) were injected. One molded part was weighed on the analytical balance and heated to the specified temperature in an aluminum pan in a convection oven.

After the respective storage time (3 days at 150 ° C.), the samples cooled under vacuum were weighed out on the analytical balance and the weight loss was determined.

The flowability was measured with a flow spiral (1.5 mm) at a spray pressure of 37 bar at 260 ° C.

The glow wire test was carried out on platelets 60 x 60 mm with 1 mm thickness at 960 ° C. The glow wire was held on the test specimen for 30 seconds and the afterburning time of the molded part in seconds and the flame height in mm were determined.

The composition of the molding compounds and the results of the measurements can be found in the table.

25

table

Example IV 2V 3 4 5

Component A 49.7 49.7 49.7 49.7 50 [% by weight]

Component Bl 20-10-10 [% by weight]

Component B2 - 20 - 10 - [% by weight]

Component C - - [wt%] 10 10 10

Component D 0.3 0.3 [% by weight] 0.3 0.3 -

Component E 30 30 [% by weight] 30 30 30

UL94 V0 V0 VO VO VO

Afterburn time 20 22 [sec] 15 18 16

Flame height [mm] 46 45 25 35 25

Flowability 190 180 270 270 260 [mm]

Weight loss 0.23 0.27 0.25 0.25 0.53 [%]

V = for comparison

Claims

26 patent claims

Thermoplastic molding compositions containing

A) 5 to 96 wt .-% of a polyester

Rl

M (I)

R ^{2 '} m

0

PR ³ M „(II)

R ^l R ²

where the substituents have the following meaning:

R ^{3 is} a linear or branched C 1 -C 6 -alkylene radical, arylene, alkylarylene or arylalkylene radical,

M alkaline earth metal, alkali metal, Zn, AI, Fe, boron,

m is an integer from 1 to 3,

n is an integer from 1 and 3,

x 1 or 2;

C) 1 to 30% by weight of at least one organic phosphorus-containing flame retardant,

D) 0 to 5% by weight of at least one ester or amide of saturated or unsaturated aliphatic carboxylic acids with 10 to 40 carbon atoms. 27 men with aliphatic saturated alcohols or amines with 2 to 40 C atoms

E) 0 to 60% by weight of further additives,

the sum of the percentages by weight of components A) to E) being 100%.

2. Thermoplastic molding compositions according to claim 1, containing as flame retardant C) at least one phosphine oxide of the general formula III

R ^l

_R 2 - p = 0 in

R ³

where R ¹ , R ² and R ³ denote the same or different alkyl, aryl, alkylaryl or cycloalkyl groups with 8 to 40 C atoms.

3. Thermoplastic molding compositions according to claims 1 or 2, in which component C) is composed of triphenylphosphine oxide, triphenylphosphine sulfide, triphenylphosphate, resorcinol bis (diphenylphosphate) or triphenylphosphine or mixtures thereof.

4. Thermoplastic molding compositions according to claims 1 to 3, containing 1 to 40% by weight of a fibrous filler as component E).

5. Thermoplastic molding compositions according to claims 1 to 4, in which component D) is pentaerythritol tetrastearate.

6. Thermoplastic molding compositions according to claims 1 to 5, in which component A) consists of a mixture of polyethylene terephthalate and polybutylene terephthalate.

7. Thermoplastic molding compositions according to claim 6, in which the proportion of polyethylene terephthalate in the mixture 10 to

Is 30% by weight.

8. Thermoplastic molding compositions according to claims 6 or 7, in which the polyethylene terephthalate consists of a recyclate with a residual moisture content of 0.01 to 0.7%. 28

9. Use of the thermoplastic molding compositions according to claims 1 to 8, for the production of fibers, films and moldings.

10. Moldings obtainable from the thermoplastic molding compositions according to claims 1 to 8.