KR20150023271A - Flame-retardant polyesters with polyacrylonitriles - Google Patents

Abstract

The present invention
A) 10 to 97% by weight of a thermoplastic polyester,
B) 0.1 to 60% by weight,
C) 1 to 25% by weight of a polyacrylonitrile homopolymer,
D) from 0 to 50% by weight of a fibrous or particulate filler, and
E) Additional additives 0 to 60 wt%
, Wherein the total weight percent of A) to E) is 100%.

Description

FLAME-RETARDANT POLYESTERS WITH POLYACRYLONITRILES FIELD OF THE INVENTION The present invention relates to flame-retardant polyesters having polyacrylonitrile,

The present invention

A) 10 to 97% by weight of a thermoplastic polyester,

B) 0.1 to 60% by weight,

C) 1 to 25% by weight of a polyacrylonitrile homopolymer,

D) from 0 to 50% by weight of a fibrous or particulate filler, and

E) Additional additives 0 to 60 wt%

, Wherein the total weight percent of A) to E) is 100%.

The present invention further relates to the use of molding compositions of this type for making fibers, foils and moldings, and to the resulting moldings, fibers, and foils of any type.

It is known that the addition of reactive, thermoplastic resins, especially to reinforced or filled polyesters, leads to effective flame retardancy (e.g., JP-A-2001/226570, JP-A-2000/328065). However, when the fungus is exposed to adverse conditions such as high temperature, high humidity, or the presence of alkali or oxygen, the fungus tends to form decomposition products such as phosphine and monovalent to polyvalent acids.

The stabilizing effect can be realized by adding oxides or hydroxides of zinc, magnesium, or copper. In DE-A-2625691, in addition to the stabilization through the metal oxide, the phosphor particles are complicated, and the stabilizing effect of the system is not always satisfactory.

JP-A-2005/126633 discloses polyolefins comprising polyacrylonitrile together with metal and hydroxide.

Properties that require improvement in known molding compositions are soot concentration and heat release. It is also desirable to increase the amount of post-combustion residue because the resulting carbon layer delays ignition, thereby reducing the total heat release and also the total amount of fuming.

Accordingly, it was an object of the present invention to develop a thermoplastic polyester molding composition that contains a flame retardant and exhibits reduced soot concentration and heat release, and an increased post-combustion residue amount.

The molding composition of the present invention comprises, as component (A), from 10 to 97% by weight, preferably from 20 to 95% by weight, especially from 20 to 80% by weight, of one or more thermoplastic polyesters.

The commonly used polyester A) is based on aromatic dicarboxylic acids and aliphatic or aromatic dihydroxy compounds.

A first group of preferred polyesters are those of polyalkylene terephthalate, especially having 2 to 10 carbon atoms in the alcohol moiety.

Polyalkylene terephthalates of this type are known in the art and described in the literature. The backbone thereof includes an aromatic ring derived from an aromatic dicarboxylic acid. It is also possible, for example, by a halogen, such as chlorine or bromine, or by a C ₁ -C ₄ -alkyl group, such as methyl, ethyl, iso- or n-propyl or n-, iso- or tert- There may be substitution in the ring.

Such polyalkylene terephthalates may be prepared by reacting an aliphatic dihydroxy compound with an aromatic dicarboxylic acid, or an ester or other ester-forming derivative thereof, in a manner known in the art.

Preferred dicarboxylic acids are 2,6-naphthalene dicarboxylic acid, terephthalic acid and isophthalic acid, and mixtures thereof. The aromatic dicarboxylic acid is preferably an aliphatic or alicyclic dicarboxylic acid such as adipic acid, azelaic acid, sebacic acid, dodecanedioic acid and cyclohexanedicarboxylic acid in an amount of not more than 30 mol%, preferably not more than 10 mol% .

Preferred aliphatic dihydroxy compounds are diols having 2 to 6 carbon atoms, especially 1,2-ethanediol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, Diol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol and neopentyl glycol, and mixtures thereof.

Particularly preferred polyesters (A) are polyalkylene terephthalates derived from alkane diols having 2 to 6 carbon atoms. Of these, polyethylene terephthalate, polypropylene terephthalate and polybutylene terephthalate, and mixtures thereof are particularly preferred. In addition, PET and / or PBT are preferred, wherein they contain, as further monomer units, up to 1% by weight, preferably up to 0.75% by weight, of 1,6-hexanediol and / Pentanediol.

The intrinsic viscosity of the polyester (A) is generally from 50 to 220, preferably from 50 to 220, when measured in accordance with ISO 1628 (at a concentration of 0.5% by weight in a phenol / o-dichlorobenzene mixture (at a 1: Is in the range of 80 to 160.

Particularly preferred are polyesters having a carboxy terminated content of not more than 100 meq / kg, preferably not more than 50 meq / kg of polyester, particularly not more than 40 meq / kg of polyester. Polyesters of this type can be prepared, for example, by the process of DE A 44 01 055. The carboxy end group content is usually confirmed by a titrimetric method (e.g., potentiometric method).

In particular, a preferred molding composition comprises as component A) a mixture of polyesters other than PBT, such as polyethylene terephthalate (PET). For example, the proportion of polyethylene terephthalate in the mixture is preferably 50% by weight or less, in particular 10 to 35% by weight, based on 100% by weight of component A).

It is also advantageous to use a PET recycle (also referred to as scrap PET), optionally mixed with a polyalkylene terephthalate, such as PBT.

The regeneration is generally

1) Known as post-industrial regeneration (production waste during polycondensation or during processing, for example sprue from injection molding, starting material from injection molding or extrusion, or edge from extruded sheet or foil Trim), or

2) Recycled after consumption (plastic items collected and processed after use by the end consumer. Blow-molded PET bottles for mineral water, soft drinks and juices are easily main products in terms of quantity).

Both types of regeneration can be used as the pulverized material or in the form of pellets. In the latter case, the crude product is separated and purified, melted and pelletized using an extruder. It is easy to handle and free flow and metering for additional steps in normal processing.

The recycled material used can be pelletized or in the form of a regrind. The edge length should be less than 10 mm, preferably less than 8 mm.

It is recommended to pre-dry the reclaimed product since the polyester undergoes hydrolytic cleavage during processing (due to trace amounts of moisture). The residual moisture content after drying is preferably < 0.2%, especially < 0.05%.

Another group to which reference is made is a fully aromatic polyester derived from an aromatic dicarboxylic acid and an aromatic dihydroxy compound.

Suitable aromatic dicarboxylic acids are the compounds previously mentioned in polyalkylene terephthalates. The mixture preferably used comprises 5 to 100 mol% isophthalic acid and 0 to 95 mol% terephthalic acid, especially about 50 to about 80% terephthalic acid and 20 to about 50% isophthalic acid.

The aromatic dihydroxy compound preferably has the formula:

Z is an alkylene or cycloalkylene group having up to 8 carbon atoms, an arylene group having up to 12 carbon atoms, a carbonyl group, a sulfonyl group, an oxygen or sulfur atom, or a chemical bond , and m is 0 to 2. The phenylene group of the compound may also be substituted by a C ₁ -C ₆ -alkyl or -alkoxy group and by fluorine, chlorine or bromine.

Examples of parent compounds of such compounds include,

Dihydroxybiphenyl,

Di (hydroxyphenyl) alkane,

Di (hydroxyphenyl) cycloalkane,

Di (hydroxyphenyl) sulfide,

Di (hydroxyphenyl) ether,

Di (hydroxyphenyl) ketone,

Di (hydroxyphenyl) sulfoxide,

?,? '- di (hydroxyphenyl) dialkylbenzene,

Di (hydroxyphenyl) sulfone, di (hydroxybenzoyl) benzene,

Resorcinol, and hydroquinone, as well as ring-alkylated and ring-halogenated derivatives thereof.

double,

4,4'-dihydroxybiphenyl,

2,4-di (4'-hydroxyphenyl) -2-methylbutane,

?,? '- di (4-hydroxyphenyl) -p-diisopropylbenzene,

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

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

Especially

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

2,2-di (3 ', 5-dichlorodihydroxyphenyl) propane,

1,1-di (4'-hydroxyphenyl) cyclohexane,

3,4'-dihydroxybenzophenone,

4,4'-dihydroxydiphenyl sulfone and

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

And mixtures thereof.

Of course, it is also possible to use a mixture of polyalkylene terephthalate and a fully aromatic polyester. Which generally comprises 20 to 98% by weight of polyalkylene terephthalate and 2 to 80% by weight of fully aromatic polyester.

Of course, it is also possible to use polyester block copolymers such as copolyether esters. Products of this type are known in the art and are described, for example, in US-A 3 651 014. A corresponding product may also for example be available from a Hytrel ^® (DuPont).

According to the present invention, the term polyester also includes halogen-free polycarbonates. Examples of suitable halogen-free polycarbonates are based on diphenols of the formula:

Wherein Q is a single bond, C ₁ -C ₈ -alkylene, C ₂ -C ₃ -alkylidene, C ₃ -C ₆ -cycloalkylidene, C ₆ -C ₁₂ -arylene group, or -O- , -S- or -SO ₂ -, and m is an integer of 0 to ₂ .

The phenylene radical of diphenol may also have a substituent, such as C ₁ -C ₆ -alkyl or C ₁ -C ₆ -alkoxy.

Examples of preferred diphenols of the formula include hydroquinone, resorcinol, 4,4'-dihydroxybiphenyl, 2,2-bis (4-hydroxyphenyl) propane, 2,4- ) -2-methyl-butane and 1,1-bis (4-hydroxyphenyl) cyclohexane. Bis (4-hydroxyphenyl) propane and 1,1-bis (4-hydroxyphenyl) cyclohexane, and also 1,1-bis Trimethylcyclohexane is particularly preferred.

The homopolycarbonate or copolycarbonate is suitable as component A), the copolycarbonate of bisphenol A, and also the bisphenol A homopolymer.

Suitable polycarbonates are incorporated in a known manner, and certainly preferably at least trifunctional compounds, such as those having 3 or more phenolic OH groups, in an amount of 0.05 to 2.0 mol% based on the total used diphenol Can be branched.

Particularly suitable polycarbonates have a relative viscosity? _Rel of 1.10 to 1.50, in particular 1.25 to 1.40. This corresponds to an average molar mass M _w (weight-average) of 10,000 to 200,000 g / mol, preferably 20,000 to 80,000 g / mol.

The diphenols of the formula are known in the art and can be prepared by known methods.

Polycarbonates can be prepared, for example, by reacting phosgene and diphenol in phosgene in an interfacial process or in a homogeneous-phase process (known as a pyridine process) and in each case the desired molecular weight is determined by the appropriate amount of known Can be realized in a known manner by using a chain terminated settlement. (Relating to polydiorganosiloxane-containing polycarbonates, see for example DE-A 33 34 782).

Examples of suitable chain terminators include phenol, p-tert-butylphenol, or long chain alkylphenols such as 4- (1,3-tetramethylbutyl) phenol, as in DE-A 28 42 005, or DE A 35 Monoalkyl-phenols having a total of 8 to 20 carbon atoms in the alkyl substituent as in, for example, EP-A-06 472, or dialkylphenols such as p-nonylphenol, 3,5- , p-dodecylphenol, 2- (3,5-dimethylheptyl) phenol and 4- (3,5-dimethylheptyl) phenol.

For purposes of the present invention, the halogen-free polycarbonate is a polycarbonate comprising a halogen-free diphenol, a halogen-free chain terminating agent and, if used, a halogen-free branching agent, For the purpose of the present invention, the content of minor amounts of ppm levels of hydrolysable chlorine produced in the preparation of phosgene and polycarbonate in the interfacial process is not considered to refer to the term " halogen-containing "for purposes of the present invention. Polycarbonates of this type having a hydrolyzable chlorine content in the ppm level are halogen-free polycarbonates for the purposes of the present invention.

Other suitable components A) which may be mentioned are amorphous polyester carbonates, wherein the phosgene during the manufacturing process may be substituted with aromatic dicarboxylic acid units, such as isophthalic acid and / or terephthalic acid units. At this point, EP-A 711 810 can be referred to for a more detailed description.

EP-A 365 916 describes other suitable copolycarbonates having cycloalkyl radicals as monomeric units.

It is also possible that bisphenol A is substituted with bisphenol TMC. Polycarbonates of this type are available from Bayer under the trade name APEC HT ^® .

The flame retardant agent B) according to the invention is an elemental redane which can be combined with the glass fiber-reinforced molding composition and can be used in its untreated form.

Particularly suitable materials are, however, those in which phosphorus is present in the form of esters of low molecular weight liquid substances such as silicone oil, paraffin oil or phthalic acid (in particular dioctyl phthalate, EP 176 836), or adipic acid, (EP-A 384 232, DE-A 196 48 503), for example phenolic resins or aminoplastics, or else polyurethanes. The amount containing such "mucilage agent" is generally from 0.05 to 5% by weight based on 100% by weight of B).

Other materials suitable as flame retardants are, for example, concentrates of polyamides or elastomers. Particularly suitable concentrate polymers are polyolefin homopolymers and copolymers. However, the proportion of the concentrate polymer should not exceed 35% by weight, based on the weight of components A) and B) in the molding composition of the present invention.

A preferred concentrate composition comprises

B ₁ ) 30 to 90% by weight, preferably 45 to 70% by weight, of a polyamide or elastomer,

B ₂ ) is 10 to 70% by weight, preferably 30 to 55% by weight.

The polyamides used in the masterbatch are preferably PA6 and / or PA66 in order to avoid side effects on the molding composition from incompatibility or melting point differences.

The average size (d ₅₀ ) of phosphorus particles dispersed in the molding composition is preferably from 0.0001 to 0.5 mm; Particularly 0.001 to 0.2 mm.

The content of component B) in the molding composition of the invention is 0.1 to 60% by weight, preferably 0.5 to 40% by weight, in particular 1 to 15% by weight, based on the total of components A) to E).

The molding composition of the invention comprises as component C) 1 to 25% by weight, preferably 1 to 15% by weight, in particular 1 to 11% by weight, of a polyacrylonitrile homopolymer. This is the term for a polymer of the structure:

Polymers of this type can be prepared by free-radical polymerization of acrylonitrile, where conventional industrial polymerization processes are generally carried out in water with an initiator.

The average molecular weight M _W of the preferred polyacrylonitrile is from 10,000 to 400,000, in particular from 50,000 to 350,000 according to DIN 55672-2: 2008-06 by GPC, Part 2, PMMA (standard) as eluent.

Particularly preferred are polyacrylonitriles which are mixed and blended in the form of powders, pellets, chips or tablets with other components A) and B), and also D) and E).

The fibrous or particulate filler D) (different from E), which may be mentioned, is selected from the group consisting of carbon fibers, glass fibers, glass beads, amorphous silica, calcium silicate, calcium metasilicate, magnesium carbonate, kaolin, chalk, powder quartz, Barium sulfate, and feldspar, and the amount thereof which can be used is 1 to 50% by weight, particularly 5 to 45% by weight, preferably 10 to 40% by weight.

Preferred fibrous fillers that may be mentioned are carbon fibers, aramid fibers and potassium titanate fibers, with glass fibers in the E-glass form being particularly preferred. It can be used as a roving or in a commercially available form of chopped glass.

The fibrous filler could be surface-pretreated with a silane compound to improve compatibility with the thermoplastic resin.

Suitable silane compounds have the formula:

(X- (CH ₂ ) _n ) _k -Si- (OC _m H _{2m + 1} ) _4-k

Here, the definition of the substituent is as follows:

X is NH ₂ -,

, HO-,

n is an integer of 2 to 10, preferably 3 to 4,

m is an integer of 1 to 5, preferably 1 to 2,

k is an integer of 1 to 3, preferably 1.

Preferred silane compounds are aminopropyltrimethoxysilane, aminobutyltrimethoxysilane, aminopropyltriethoxysilane and aminobutyltriethoxysilane, and also the corresponding silanes containing a glycidyl group as substituent X.

The amount of silane compound used for surface coating is generally 0.01 to 2% by weight, preferably 0.025 to 1.0% by weight, especially 0.05 to 0.5% by weight (D).

Needle-shaped mineral fillers are also suitable.

For the purposes of the present invention, the needle-shaped mineral filler is a mineral filler having strongly developed acicular characteristics. An example is bedding wollastonite. The mineral is preferably L / D (length to diameter) ratio of 8: 1 to 35: 1, preferably 8: 1 to 11: 1. Mineral fillers can optionally be pretreated with the silane compounds described above, but pretreatment is not necessary.

Other fillers that may be mentioned are preferably 0.1-10% amount of kaolin, calcined kaolin, wollastonite, talc and chalk, and additionally, a platelike or needle-shaped nanofiller. Preferred materials used for this purpose are boehmite, bentonite, montmorillonite, vermiculite, hectorite, and laponite. In order to obtain excellent compatibility between the sheet-like nanofiller and the organic binder, the sheet-like nanofiller is organically reinforced according to the prior art. Addition of a sheet-like or acicular nanofiller to the nanocomposite of the present invention leads to an additional increase in mechanical strength.

The molding composition of the present invention may comprise 0 to 60% by weight, in particular not more than 50% by weight, in particular not more than 30% by weight, of further additives and processing aids as component E).

The molding composition of the present invention comprises as component E) from 10 to 40 carbon atoms, preferably from 16 to 40 carbon atoms, with saturated aliphatic alcohols or amines having from 2 to 40 carbon atoms, preferably from 2 to 6 carbon atoms. From 0 to 5% by weight, preferably from 0.05 to 3% by weight, in particular from 0.1 to 2% by weight, of at least one ester or amide of a saturated or unsaturated aliphatic carboxylic acid having 22 carbon atoms.

The carboxylic acid may be mono- or di-carboxylic acid. Examples which may be mentioned are pelargonic acid, palmitic acid, lauric acid, margaric acid, dodecanedioic acid, behenic acid and particularly preferably stearic acid, capric acid and also montanic acid (30 to 40 A mixture of fatty acids having carbon atoms).

Aliphatic alcohols may be monosubstituted to tetrasubstituted. Suitable alcohols are n-butanol, n-octanol, stearyl alcohol, ethylene glycol, propylene glycol, neopentyl glycol, pentaerythritol, preferably ethylene glycol, glycerol and pentaerythritol.

The aliphatic amine can be monosubstituted to tri-substituted. Examples thereof include stearylamine, ethylenediamine, propylenediamine, hexamethylenediamine, di (6-aminohexyl) amine, particularly preferably ethylenediamine and hexamethylenediamine. Preferred esters or amides are accordingly glycerol distearate, glycerol tristearate, ethylenediamine distearate, glycerol monopalmitate, glycerol tribolate, glycerol monobehenate, and pentaerythritol tetrastearate.

It is also possible to use mixtures of various esters or mixtures of various amides, or mixtures of esters and amides in any desired mixing ratio.

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

It is preferably a very common copolymer comprising two or more of the following monomers: ethylene, propylene, butadiene, isobutene, isoprene, chloroprene, vinyl acetate, styrene, acrylonitrile and the like having from 1 to 18 carbon atoms in the alcohol component Nitriles and acrylates and / or methacrylates.

Polymers of this type are described, for example, in Houben-Weyl, Methoden der organischen Chemie, Vol. 14/1 (Georg-Thieme-Verlag, Stuttgart, Germany, 1961), pages 392-406, and in the monograph by C.B. Bucknall, "Toughened Plastics" (Applied Science Publishers, London, UK, 1977).

Some preferred types of such elastomers are described below.

Preferred types of such elastomers are known as ethylene-propylene (EPM) and ethylene-propylene-diene (EPDM) rubbers.

EPM rubbers generally have virtually no residual double bonds, but EPDM rubbers can have 1 to 20 double bonds per 100 carbon atoms.

Examples which may be referred to as diene monomers of EPDM rubbers include conjugated dienes such as isoprene and butadiene, non-conjugated dienes having from 5 to 25 carbon atoms such as 1,4-pentadiene, 1,4 Hexadiene, 1,5-hexadiene, 2,5-dimethyl-1,5-hexadiene and 1,4-octadiene, cyclic dienes such as cyclopentadiene, cyclohexadiene, cyclooctadiene and dicyclo Pentadienes and also alkenylnorbornenes such as 5-ethylidene-2-norbornene, 5-butylidene-2-norbornene, 2-methallyl-5-norbornene and 2- Phenyl-5-norbornene, and tricyclodiene such as 3-methyltricyclo [5.2.1.0 ^2,6 ] -3,8-decadiene, and mixtures thereof. 1,5-hexadiene, 5-ethylidene norbornene and dicyclopentadiene are preferable. The diene content of the EPDM rubber is preferably 0.5 to 50% by weight, especially 1 to 8% by weight, based on the total weight of the rubber.

The EPM and EPDM rubbers can also preferably be grafted by reactive carboxylic acids or by their derivatives. Examples which may be mentioned here are acrylic acid, methacrylic acid and derivatives thereof such as glycidyl (meth) acrylate, and also maleic anhydride.

Copolymers of acrylic acid and / or methacrylic acid and / or esters of such acids with ethylene are another group of preferred rubbers. The rubber may also additionally comprise dicarboxylic acids such as maleic acid and fumaric acid, or derivatives of such acids, such as esters and anhydrides, and / or monomers containing epoxy groups. The monomer containing a dicarboxylic acid derivative or containing an epoxy group is preferably prepared by adding a monomer having a dicarboxylic acid group and / or an epoxy group to the monomer mixture and having the following formula (I), (II), (III) Lt; / RTI &gt;

Wherein R ¹ to R ⁹ are hydrogen or an alkyl group having ¹ to 6 carbon atoms, m is an integer of 0 to 20, g is an integer of 0 to 10, and p is an integer of 0 to 5.

R ¹ to R ⁹ are preferably hydrogen, wherein 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 formulas (I), (II) and (IV) are (meth) acrylates including maleic acid, maleic anhydride and epoxy groups such as glycidyl acrylate and glycidyl methacrylate, and esters with tertiary alcohols, butyl acrylate. The latter does not have a free carboxyl group, but its aspect is close to that of the free acid and is accordingly referred to as a monomer having a latent carboxyl group.

The copolymer advantageously comprises 50 to 98% by weight of ethylene, 0.1 to 20% by weight of monomers comprising epoxy groups and / or monomers comprising methacrylic acid and / or acid anhydride groups, the balance being (meth) acrylic Rate.

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

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

Butyl acrylate and / or 2-ethylhexyl acrylate

Is particularly preferred.

Other preferred (meth) acrylates are methyl, ethyl, propyl, isobutyl and tert-butyl esters.

Other materials that may be used at the same time include vinyl esters and vinyl ethers as comonomers.

The ethylene copolymers described above can be produced by a process known in the art, preferably by random copolymerization at high pressure and elevated temperature. Suitable processes are well known.

Another preferred elastomer is an emulsion polymer prepared by Blackley, for example, in the "emulsion polymerization ". Emulsifiers and catalysts that can be used are known in the art.

In principle, it is possible to use a homogeneously structured elastomer or any other shell structure. The shell type structure is determined by the order of addition of the individual monomers; The form of the polymer is also influenced by the order of addition.

For the preparation of the rubber part of the elastomer, for merely representative capabilities, the monomers which may be mentioned here are acrylates such as n-butyl acrylate and 2-ethylhexyl acrylate, the corresponding methacrylates, butadiene and isoprene, And also mixtures thereof. The monomers may be copolymerized with other monomers such as styrene, acrylonitrile, vinyl ethers and other acrylates or methacrylates such as methyl methacrylate, methyl acrylate, ethyl acrylate or propyl acrylate.

The soft or rubber phase of the elastomer (having a glass transition temperature below 0 ° C) may be a core, an outer envelope or an intermediate shell (in the case of an elastomer having a structure of two or more shells). The elastomer having more than one shell may also have more than one shell comprising a rubber phase.

When at least one light component (having a glass transition temperature of greater than 20 占 폚) is included in the elastomeric structure in addition to the rubber phase, it is generally used as the main monomer, such as styrene, acrylonitrile, methacrylonitrile, Styrene, p-methylstyrene, or an acrylate or methacrylate such as methyl acrylate, ethyl acrylate or methyl methacrylate. In addition, a relatively small proportion of other comonomers may also be used here.

In some cases it has proved advantageous to use an emulsion polymer having reactive groups on its surface. Examples of groups of this type are functional groups which can be introduced by the use of epoxy, carboxy, latent carboxy, amino and amide groups, and also the use of monomers of the formula:

In the above formula, the definition of a substituent may be as follows:

R ¹⁰ is hydrogen or C ₁ -C ₄ - alkyl,

R ¹¹ is hydrogen or C ₁ -C ₈ -alkyl or aryl, especially phenyl,

R ¹² is hydrogen, C ₁ -C ₁₀ -alkyl, C ₆ -C ₁₂ -aryl or -OR ¹³ ,

R ¹³ is C ₁ -C ₈ -alkyl or C ₆ -C ₁₂ -aryl which may optionally be substituted by O- or N-containing groups,

X is a chemical bond, C ₁ -C ₁₀ -alkylene or C ₆ -C ₁₂ -arylene, or

ego,

Y is O-Z or NH-Z,

Z is C ₁ -C ₁₀ -alkylene or C ₆ -C ₁₂ -arylene.

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

Other examples that may be mentioned are acrylamide, methacrylamide and substituted acrylates or methacrylates such as (N-tert-butylamino) ethyl methacrylate, (N, N-dimethyl- (N, N-dimethylamino) methyl acrylate and (N, N-diethylamino) ethyl acrylate.

The rubber phase particles can also be crosslinked. Examples of crosslinking monomers are 1,3-butadiene, divinylbenzene, diallyl phthalate and dihydrodicyclopentadienyl acrylate, and also the compounds described in EP-A 50 265.

It is also possible to use monomers known as graft-linking monomers, i.e. monomers having two or more polymerizable double bonds reacting at different rates during the polymerization. Although one or more reactive groups are polymerized at about the same rate as the other monomers, it is preferred that other reactive groups (or reactive groups) are of the type that are polymerized, e.g., more significantly, slowly. Different polymerization rates produce a certain proportion of double bond unsaturation in the rubber. When another phase is grafted onto the rubber of this type, at least some of the double bonds present in the rubber react with the graft monomer to form a chemical bond, i.e., the grafted phase has at least some chemical bonding to the graft base .

Examples of graft-linking monomers of this type are monomers containing allyl groups, especially allyl esters of ethylenically unsaturated carboxylic acids such as allyl acrylate, allyl methacrylate, diallyl maleate, diallyl fumarate and diallyl Itaconate, and the corresponding monoallyl compound of the dicarboxylic acid. There are a wide variety of other suitable graft-linking monomers as well. For further details, see, for example, US-A 4 148 846.

The proportion of the crosslinking monomer in the impact reinforcing polymer is generally not more than 5% by weight, preferably not more than 3% by weight, based on the impact reinforcing polymer.

Some preferred emulsion polymers are listed below. A graft polymer having a core and at least one outer shell and having the following structure may be mentioned:

It is preferred that the graft polymer, in particular the ABS polymer and / or the ASA polymer, is used in an amount of up to 40% by weight, based on the impact reinforcement of the PBT, optionally in a mixture with up to 40% by weight of polyethylene terephthalate. A blend product of this type is obtainable by name Ultradur ^® S (formerly Ultrablend ^® S of BASF AG).

It is also possible to use a homogeneous, i.e. single-shell, elastomer comprising 1,3-butadiene, isoprene and n-butyl acrylate or copolymers thereof, instead of a graft polymer having a structure of more than one shell. The product can also be produced by the use of a crosslinking monomer or a monomer having a reactive group.

Examples of preferred emulsion polymers are n-butyl acrylate / (meth) acrylic acid copolymers, n-butyl acrylate / glycidyl acrylate copolymers or n-butyl acrylate / glycidyl methacrylate copolymers, n- A graft polymer having an internal core made of butyl acrylate or based on butadiene and an outer envelope made of a copolymer of ethylene and a comonomer providing a reactive group as described above.

The described elastomers may also be produced by other conventional processes, for example by suspension polymerization.

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

Of course, it is also possible to use mixtures of the rubber types listed above.

The thermoplastic molding composition of the present invention comprises as component E) a conventional processing aid such as a stabilizer, an oxidative retarder, a formulation which inhibits decomposition by heat and ultraviolet rays, a lubricant and a releasing agent, a colorant such as a dye and a pigment, Forming agents, plasticizers, and the like.

Examples which may be mentioned as oxidation retardants and thermostabilizers are those which contain, based on the weight of the thermoplastic molding composition, a sterically hindered phenol and / or phosphite, hydroquinone, aromatic secondary amine, such as diphenylamine , Various substituted members of the above group, and mixtures thereof.

UV stabilizers which can be mentioned and used in amounts of generally up to 2% by weight, based on the molding composition, are the various substituted resorcinol, salicylate, benzotriazole, and benzophenone.

Coloring agents that may be added are inorganic pigments such as titanium dioxide, ultramarine blue, iron oxide, and carbon black, and also organic pigments such as phthalocyanine, quinacridone and perylene, and also dyes such as nigrosine and anthraquinone.

Nucleating agents which can be used are sodium phenylphosphinate, alumina, silica, preferably talc powder.

Other lubricants and release agents are usually used in amounts of up to 1% by weight. Long chain fatty acids such as stearic acid or behenic acid, salts thereof (e.g. calcium stearate or zinc stearate) or montan wax (mixture of linear saturated carboxylic acids having 28 to 32 carbon atoms in chain length), or Calcium montanate or sodium montanate, or low molecular weight polyethylene wax or low molecular weight polypropylene wax.

Examples of plasticizers which may be mentioned are dioctyl phthalate, dibenzyl phthalate, butyl benzyl phthalate, hydrocarbon oil and N- (n-butyl) benzenesulfonamide.

The molding compositions of the present invention may also comprise from 0 to 2% by weight of a fluorine-containing ethylene polymer. It is a polymer of ethylene with a fluorine content of 55-76% by weight, preferably 70-76% by weight.

Examples thereof are polytetrafluoroethylene (PTFE), tetrafluoroethylene-hexafluoropropylene copolymer and tetrafluoroethylene (PTFE) having a relatively low proportion (generally not more than 50% by weight) of copolymerizable ethylenically unsaturated monomers Lt; / RTI &gt; This is described, for example, by Schildknecht in ["Vinyl and Related Polymers", Wiley-Verlag, 1952, pages 484-494] and Wall of ["Fluoropolymers" (Wiley Interscience, 1972)].

These fluorine-containing ethylenic polymer having a homogeneous distribution in the molding composition preferably 0.05~10 ㎛, in particular a particle size range of 0.1~5 ㎛ has a d ₅₀ (numerical average). The small particle size is particularly preferably achieved by the use of an aqueous dispersion of a fluorine-containing ethylene polymer and its incorporation into a polyester melt.

The thermoplastic molding composition of the present invention can be prepared by mixing the starting components in a conventional mixing apparatus such as a screw extruder, a Brabender mixer or a Benbury mixer, and then extruding the starting components by a method known in the art. The extrudate can be cooled and milled. It is also possible to pre-mix the individual components and then add the remaining starting materials individually and / or as a mixture. The mixing temperature is generally 230 to 290 ° C.

In another preferred mode of operation, components B) and C), and optionally D) and E), are mixed, blended and pelletized with the prepolymer. The resulting pellets are then solid-phase condensed continuously or batchwise under an inert gas at a temperature below the melting point of component A) until the desired viscosity is reached.

The polyester molding compositions of the present invention are characterized by excellent flame retardancy and relatively low soot concentration and heat release. The amount of residue after combustion is increased.

Molded or semi-finished products intended for production from the thermoplastic molding compositions of the present invention may be used, for example, in automotive, electrical, electronics, telecommunications, information and telecommunications, consumer electronics, Can be used in other transport means, in ships, in spaceships, in domestic sectors, in office equipment, in sports, in machinery, and also in articles and building components that generally require increased flame retardancy.

Some examples include: Plug connectors, plugs, plug parts, cable harness parts, circuit mounts, circuit mount parts, three-dimensional injection molded circuit mounts, electrical connecting members, and mechanical and electrical components.

The following ingredients were used:

Component A: Polybutylene terephthalate (BASF SE) having an intrinsic viscosity IV of 107 ml / g, identified in a 0.5 wt.% Solution of phenol / o-dichlorobenzene (1: 1) at 25 DEG C in accordance with DIN 53728 / Ultradur ^® B2550 was used).

Ingredient B): 50% master batch of PBT.

Component C1): Polyacrylonitrile homopolymer

M _w : GPC, part 2, according to PMMA standard 313,400 g / mol in accordance with DIN 55672-2: 2008-06

Component C2): Polyacrylonitrile homopolymer

M _w : GPC, part 2, according to PMMA standard 156,000 g / mol in accordance with DIN 55672-2: 2008-06

Component C3): Polyacrylonitrile copolymer (for comparison)

Poly (vinylidene chloride-co-acrylonitrile), 80/20, CAS: 9010-76-8

Component C4): Styrene-acrylonitrile copolymer (comparative)

A random copolymer of 24% acrylonitrile and 76% styrene

Component D1: Standard chopped glass fiber for polyester having an average thickness of 10 [mu] m

Component E): pentaerythritol tetrastearate

Preparation of molding compositions and moldings

Harmonization was used to produce a suitable plastic molding composition. To this end, the individual components are mixed with a ZSK 26 double screw extruder at a throughput of 20 kg / h with a flat temperature profile at about 270 DEG C and discharged in the form of a strand, cooled to pelletize and pelletized. The test specimens listed in the table were injection molded in an Arburg 420 ° C injection molding machine at a melt temperature of about 260 ° C and a mold temperature of about 80 ° C.

The mechanical properties were confirmed in accordance with ISO 527-2 / 1A / 5 and the (no) notch Charpy impact resistance was confirmed according to ISO 179-2 / 1eU.

The fire protection properties were measured in accordance with UL 94 on 0.8 mm specimens.

Soot concentration, heat release, and post-combustion residue were identified in accordance with ISO 5660-1: 2002.

The composition and measurement results of the molding composition are shown in the table.

[Table 1]

[Table 2-4]

Claims (7)

A) 10 to 97% by weight of a thermoplastic polyester,
B) 0.1 to 60% by weight,
C) 1 to 25% by weight of a polyacrylonitrile homopolymer,
D) from 0 to 50% by weight of a fibrous or particulate filler, and
E) Additional additives 0 to 60 wt%
Wherein the total weight percent of A) to E) is 100%. The method according to claim 1,
A) 10 to 97% by weight,
B) 0.5 to 40% by weight,
C) 1 to 15% by weight,
D) 1 to 50% by weight,
E) 0 to 50 wt%
&Lt; / RTI &gt; 3. The method according to claim 1 or 2,
A) 20 to 95% by weight,
B) 0.5 to 40% by weight,
C) 1 to 15% by weight,
D) 5 to 45% by weight,
E) 0 to 30 wt%
&Lt; / RTI &gt; 4. The thermoplastic molding composition according to any one of claims 1 to 3, wherein the average molecular weight M _w of component C) is from 10,000 to 400,000 according to DIN 55672-2: 2008-06, part 2 (GPC standard PMMA) . The composition according to any one of claims 1 to 4, wherein component C) is mixed with the other components A) and B) and optionally also D) and E) in the form of a pellet, powder, &Lt; / RTI &gt; by weight of the thermoplastic molding composition. Use of the thermoplastic molding composition according to any one of claims 1 to 5 for producing fibers, foils, and moldings. A fiber, foil or molding obtainable from the thermoplastic molding composition according to any one of claims 1 to 5.