CN1989205B - Mixtures of hyperbranched polyesters and polycarbonates as additives for polyester molding compositions - Google Patents

Abstract

The invention relates to a thermoplastic molding composition comprising: A) 10 to 99.99% by weight of at least one thermoplastic polyester, B) 0.01 to 50% by weight of a mixture of: B1) at least one highly branched or hyperbranched polycarbonate having an OH value of 1 to 600 mg KOH/g polycarbonate (according to DIN 53240, Part 2), and B2) a highly branched or hyperbranched polyester of _{the type AxBy ,} where x is at least 1.1 and y is at least 2.1, and C) 0 to 60% by weight of further additives, the sum of the weight percentages of components A) to C) being 100%.

Description

Mixtures of hyperbranched polyesters and polycarbonates as additives for polyester molding compositions

The present invention relates to thermoplastic molding compositions comprising:

A) 10 to 99.99% by weight of at least one thermoplastic polyester,

B) 0.01 to 50% by weight of a mixture consisting of:

B1) at least one highly branched or hyperbranched polycarbonate with an OH number of 1-600 mg KOH/g polycarbonate (according to DIN 53240, part 2), and

B2) at least one highly branched or hyperbranched polyester of type A _x B _y , wherein x is at least 1.1 and y is at least 2.1, and

C) 0 to 60% by weight of other additives,

Wherein the sum of the weight percentages of components A) to C) is 100%.

The present invention also relates to the use of the molding compositions according to the invention for the production of fibers, films or moldings of any type, and to the moldings thus obtained.

Polycarbonates are generally obtained from the reaction of alcohols with phosgene, or from the transesterification of alcohols or phenols with dialkyl or diaryl carbonates. Aromatic polycarbonates, which are produced, for example, from bisphenols, are of industrial importance, whereas the role played by aliphatic polycarbonates has hitherto been secondary in terms of market volume. On this point see also Becker/Braun, Kunststoff-Handbuch [Plastics Handbook], Vol. 3/1, Polycarbonates, polyacetals, polyesters, cellulose esters [Polycarbonates, polyacetals, polyesters, Cellulose Esters], Carl-Hanser-Verlag, Munich 1992, pp. 118-119.

The structure of the aliphatic polycarbonates is generally linear or has a low degree of branching, for example US 3,305,605 describes the use of solid linear polycarbonates with molecular weights above 15 000 Daltons as plasticizers for polyethylene polymers agent.

To improve flow, low molecular weight additives are often added to thermoplastics. However, the effect of these additives is severely limited because, for example, when the amount of additive added increases, the reduction in mechanical properties becomes unacceptable.

Dendritic polymers called dendrimers with perfectly symmetrical structures can start from a central molecule and, in each case, be controlled by stepwise linking two or more di- or multifunctional monomers to previously bonded Prepared on combined monomers. Here, each attachment step increases the number of monomer end groups (and thus the number of linkages) exponentially, and this endows the polymer with a dendritic structure whose branches contain exactly the same number of monomers in the case of an ideal sphere. body unit. This perfect structure provides favorable polymer properties, for example its viscosity was found to be surprisingly low and also its high reactivity due to the large number of functional groups on the surface of the spheres. However, dendrimers are usually only prepared on a laboratory scale due to the complexity of this preparation due to the necessity of introducing and removing protecting groups during each ligation step, as well as the required purification operations.

However, highly branched or hyperbranched polymers can be prepared using industrial methods. They also had linear polymer chains and irregular polymer branches along the perfect dendritic structure, but this did not substantially impair the properties of the polymers compared to perfect dendrimers. Hyperbranched polymers can be prepared by two synthetic routes called _AB2 and _Ax + _By . Here A _x and B _y are different monomers, and the subscripts x and y are the number of functional groups present in A and B, respectively, ie the respective functionality of A and B. In the AB ₂ route, a trifunctional monomer with one reactive group A and two reactive groups B is reacted to give highly branched or hyperbranched polymers. In the synthesis of A _x +B _y , taking the synthesis of A ₂ +B ₃ as an example, the difunctional monomer A ₂ is reacted with the trifunctional monomer B ₃ . This firstly gives a 1:1 adduct of A and B, which has on average one functional group A and two functional groups B, which can then be reacted analogously to give highly branched or hyperbranched polymers.

Until recently, highly functional polycarbonates with defined structures have not been disclosed.

S.P.Rannard and N.J.Davis, J.Am.Chem.Soc.2000, 122, 11729 describe the preparation of perfectly branched Dendritic polycarbonate. Syntheses that provide perfect dendrimers are multi-stage and therefore costly and not very suitable for industrial scale conversion.

D.H.Bolton and K.L.Wooley, Macromolecules 1997, 30, 1890 describe the preparation of high molecular weight, very rigid hyperbranched aromatic polymers via the reaction of 1,1,1-tris(4'-hydroxyphenyl)ethane with carbonyl bis-imidazole Carbonate.

Hyperbranched polycarbonates can also be prepared according to WO 98/50453. In the method described in its specification, the triol is reacted again with carbonylbiimidazole. Initially imidazolides are produced, and these imidazolides are subsequently subjected to further intermolecular reactions to yield polycarbonates. In the mentioned process, polycarbonate is produced as a colorless or slightly yellowish rubbery product.

The mentioned synthetic methods for obtaining highly branched or hyperbranched polycarbonates have the following disadvantages:

a) Hyperbranched products have high melting points or are rubbery, which significantly limits subsequent processability.

b) The imidazole released during the reaction has to be removed from the reaction mixture by complex processes.

c) The reaction product always contains a terminal imidazolium group. These groups are unstable and must be transformed into hydroxyl groups by subsequent steps, for example.

d) Carbonyldiimidazole is a relatively expensive chemical, which greatly increases the raw material cost.

DE 102004 005652.8 and DE 102004 005657.9 have proposed new flow improvers for polyesters.

It was an object of the present invention to provide thermoplastic polyester molding compositions which have good flow properties together with good mechanical properties.

Accordingly, the molding compositions defined at the outset have been found. Preferred embodiments are given in the dependent claims.

The molding compositions of the invention comprise as component (A) 10 to 99.99% by weight, preferably 30 to 99.5% by weight, in particular 30 to 99.3% by weight of at least one thermoplastic polyester different from B).

Polyesters A) based on aromatic dicarboxylic acids and on aliphatic or aromatic dihydroxy compounds are generally used.

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

Such polyalkylene terephthalates are known per se and described in the literature. Its main chain contains aromatic rings derived from aromatic dicarboxylic acids. The aromatic rings may also be substituted, for example by halogen such as chlorine or bromine, or by C ₁ -C ₄ alkyl such as methyl, ethyl, iso- or n-propyl or n-, iso- or tert-butyl.

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

Preferred dicarboxylic acids are 2,6-naphthalene dicarboxylic acid, terephthalic acid and isophthalic acid and 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, for example by adipic acid, azelaic acid, sebacic acid, dodecanedioic acid and cyclohexane Alkanedicarboxylic acid substitution.

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 , 1,4-hexanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol and neopentyl glycol and mixtures thereof.

Particularly preferred polyesters (A) are polyalkylene terephthalates derived from alkanediols having 2 to 6 carbon atoms. Among them, polyethylene terephthalate, polytrimethylene terephthalate, and polybutylene terephthalate and mixtures thereof are particularly preferred. Preference is also given to PET and/or PBT comprising up to 1% by weight, preferably up to 0.75% by weight, of 1,6-hexanediol and/or 2-methyl-1,5-pentanediol as further monomer units.

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

Particular preference is given to polyesters in which the carboxyl end group content is at most 100 mval/kg polyester, preferably at most 50 mval/kg polyester, especially at most 40 mval/kg polyester. Such polyesters can be prepared, for example, by the method of DE-A 44 01 055. Carboxyl end group content is usually determined by titration methods such as potentiometric analysis.

Particularly preferred molding compositions comprise as component A) polyester mixtures other than PBT, for example polyethylene terephthalate (PET). For example, the proportion of polyethylene terephthalate in the mixture is preferably at most 50% by weight, especially 10 to 35% by weight, based on 100% by weight of A).

It is also advantageous to use recycled PET material (also called waste PET), if appropriate mixed with polyalkylene terephthalates such as PBT.

Recycled materials are usually:

1) Those so-called post-production recycled materials: These are production wastes during polycondensation or processing, for example slag from injection molding, raw material from injection molding or extrusion or offcuts from extruded sheets or films.

2) Post-consumer recycled materials: These are plastic products that are collected and disposed of after use by the end consumer. Blow-molded PET bottles for mineral water, soft drinks and juices are undoubtedly the main target in terms of volume.

Both types of recycled materials can be used in the form of ground material or pellets. In the latter case, the crude recycled material is separated and purified, then melted and pelletized using an extruder. This generally facilitates handling and free flow as well as metering in further processing steps.

The recycled material used may be pelletized or it may be in reground form. The side length should be no greater than 10 mm, preferably less than 8 mm.

Since polyester undergoes hydrolytic cleavage during processing (due to the presence of traces of moisture), it is advisable to pre-dry the recycled material. The residual moisture content after drying is preferably <0.2%, especially <0.05%.

Another group that should be mentioned are wholly aromatic polyesters derived from aromatic dicarboxylic acids and aromatic dihydroxy compounds.

Suitable aromatic dicarboxylic acids are the compounds previously mentioned for polyalkylene terephthalates. Preferably used mixtures consist of 5-100 mol % isophthalic acid and 0-95 mol % terephthalic acid, especially from about 50 to about 80 % terephthalic acid and 20 to about 50 % isophthalic acid Composition of formic acid.

The aromatic dihydroxy compound preferably has the formula:

Wherein 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, oxygen or sulfur, or a chemical bond, and m is 0-2. The phenylene of the compound may also be substituted by C ₁ -C ₆ alkyl or alkoxy and fluorine, chlorine or bromine.

Examples of parent compounds of these compounds are:

Dihydroxybiphenyl,

Di(hydroxyphenyl)alkanes,

Di(hydroxyphenyl)cycloalkane,

Bis(hydroxyphenyl)sulfide,

Bis(hydroxyphenyl) ether,

Di(hydroxyphenyl)ketone,

Bis(hydroxyphenyl)sulfoxide,

α,α'-bis(hydroxyphenyl)dialkylbenzene,

Bis(hydroxyphenyl)sulfone, bis(hydroxybenzoyl)benzene,

Resorcinol, and

Hydroquinone, and ring-alkylated and ring-halogenated derivatives of these compounds.

Among them, preferably:

4,4'-Dihydroxybiphenyl,

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

α,α'-bis(4-hydroxyphenyl)-diisopropylbenzene,

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

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

especially

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

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

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

3,4'-Dihydroxybenzophenone,

4,4'-Dihydroxydiphenylsulfone, and

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

and mixtures thereof.

It is of course also possible to use mixtures of polyalkylene terephthalates and wholly aromatic polyesters. They generally contain 20-98% by weight of polyalkylene terephthalate and 2-80% by weight of wholly aromatic polyester.

(DuPont)。Of course, polyester block copolymers such as copolyetheresters may also be used. Such products are known per se and described in the literature, for example in US-A 3 651 014. Corresponding products are also commercially available, such as

(DuPont).

According to the invention, polyesters include halogen-free polycarbonates. Examples of suitable halogen-free polycarbonates are those based on bisphenols of the formula:

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

The phenylene groups of bisphenols may also have substituents such as C ₁ -C ₆ alkyl or C ₁ -C ₆ alkoxy.

Examples of preferred bisphenols of the above formula are hydroquinone, resorcinol, 4,4'-dihydroxybiphenyl, 2,2-bis(4-hydroxyphenyl)propane, 2,4-bis(4-hydroxy phenyl)-2-methylbutane and 1,1-bis(4-hydroxyphenyl)cyclohexane. Particularly preferred are 2,2-bis(4-hydroxyphenyl)propane and 1,1-bis(4-hydroxyphenyl)cyclohexane and 1,1-bis(4-hydroxyphenyl)-3,3 , 5-trimethylcyclohexane.

Both homopolycarbonates and copolycarbonates are suitable as component A, and preference is given to copolycarbonates of bisphenol A and homopolymers of bisphenol A.

Suitable polycarbonates can be branched in a known manner, in particular by introducing from 0.05 to 2.0 mol %, based on the total amount of bisphenols used, of at least trifunctional compounds, such as those containing three or more phenolic OH groups Those compounds are branched.

Polycarbonates which have proven to be particularly suitable have relative viscosities η _rel of 1.10-1.50, especially 1.25-1.40. This corresponds to an average molar mass M _w (weight average) of 10000-200000 g/mol, preferably 20000-80000 g/mol.

The bisphenols of the general formula are known per se or can be prepared by known methods.

For example, polycarbonates can be prepared by reacting bisphenols with phosgene in an interfacial process, or with phosgene in a homogeneous process (known as the pyridine process), and in each case the desired molecular weight can be obtained by This is obtained in a known manner using suitable amounts of known chain terminators. (For polycarbonates containing polydiorganosiloxanes see for example DE-A 33 34 782.)

Examples of suitable chain terminators are phenol, p-tert-butylphenol or long-chain alkylphenols, such as 4-(1,3-tetramethylbutyl)phenol in DE-A 28 42 005, or as in DE-A 28 42 005 - Mono- or di-alkylphenols of A-35 06 472 with a total of 8-20 carbon atoms in the alkyl substituent, such as p-nonylphenol, 3,5-di-tert-butylphenol, p- tert-octylphenol, p-dodecylphenol, 2-(3,5-dimethylheptyl)phenol and 4-(3,5-dimethylheptyl)phenol.

For the purposes of the present invention, halogen-free polycarbonates are polycarbonates consisting of halogen-free bisphenols, halogen-free chain terminators and, if used, halogen-free branching agents, wherein for the purposes of the present invention, for example, when using phosgene The low ppm levels of hydrolyzable chlorine obtained when polycarbonates are prepared in interfacial processes are not considered by the term "halogen-containing". For the purposes of the present invention, such polycarbonates having a hydrolyzable chlorine content at the ppm level are halogen-free polycarbonates.

Other suitable combinations A) that may be mentioned are amorphous polyester carbonates in which phosgene is replaced by aromatic dicarboxylic acid units, for example isophthalic acid and/or terephthalic acid units, during the preparation. On this point, further details can be found in EP-A 711 810.

EP-A 365 916 describes further suitable copolycarbonates having cycloalkyl groups as monomer units.

获得。Bisphenol A can also be replaced by bisphenol TMC. Such polycarbonates are available from Bayer under the trademark

get.

As component B), the molding compositions according to the invention comprise 0.01-50% by weight, preferably 0.5-20% by weight, especially 0.7-10% by weight, of hyperbranched or hyperbranched polycarbonates having The OH value (according to DIN 53240 part 2) is 1-600 mg KOH/g polycarbonate, preferably 10-550 mg KOH/g polycarbonate, especially 50-550 mg KOH/g polycarbonate.

For the purposes of the present invention, hyperbranched polycarbonates B1) are uncrosslinked macromolecules having hydroxyl groups and carbonate groups, which have both structural and molecular inhomogeneity. First, their structure is based on a central molecule in the same way as dendrimers, but the chain lengths of the branches are not uniform. Secondly, they can also have linear structures with functional side groups, or they can combine these two extremes, with linear and branched molecular parts. See P. J. Flory, J. Am. Chem. Soc. 1952, 74, 2718 and H. Frey et al., Chem. Eur. J. 2000, 6, no. 14, 2499 for definitions of dendritic and hyperbranched polymers.

In the context of the present invention, "hyperbranched" refers to the degree of branching (DB), i.e. the average number of dendritic connections per molecule plus the average number of end groups, of from 10 to 99.9%, preferably from 20 to 99%, especially Preferably 20 to 95%.

In the context of the present invention, "dendrimer" means a degree of branching of 99.9 to 100%. See H.Frey et al., Acta Polym.1997, 48, 30 for the definition of "degree of branching", which is defined as

$\mathrm{<span\; class="notranslate">\; DB</span>}<span\; class="notranslate">\; =</span>\frac{\mathrm{<span\; class="notranslate">\; T</span>}<span\; class="notranslate">\; +</span>\mathrm{<span\; class="notranslate">\; Z</span>}}{\mathrm{<span\; class="notranslate">\; T</span>}<span\; class="notranslate">\; +</span>\mathrm{<span\; class="notranslate">\; Z</span>}<span\; class="notranslate">\; +</span>\mathrm{<span\; class="notranslate">\; L</span>}}<span\; class="notranslate">\; \&times;</span>\mathrm{<span\; class="notranslate">\; 100</span>}<span\; class="notranslate">\; \%</span><span\; class="notranslate">\; ,</span>$

(Wherein, T is the average number of terminal monomer units in the macromolecules of each substance, Z is the average number of branched monomer units therein, and L is the average number of linear monomer units therein).

Component B1) preferably has a number-average molar mass M _n of 100-15000 g/mol, preferably 200-12000 g/mol, especially 500-10000 g/mol (GPC, PMMA standard).

The glass transition temperature Tg is in particular -80 to +140°C, preferably -60 to +120°C (according to DSC, DIN 53765).

In particular, the viscosity (mPas) at 23° C. (according to DIN 53019) is from 50 to 200,000, especially from 100 to 150,000, very particularly preferably from 200 to 100,000.

Component B1) is preferably obtainable via a process comprising at least the following steps:

a) reacting at least one organic carbonate (A) of the general formula RO[(CO)] _n OR with at least one aliphatic, aliphatic/aromatic or aromatic alcohol (B) having at least three OH, Simultaneous elimination of the alcohol ROH yields one or more condensation products (K), wherein each R independently of the other groups is a straight-chain or branched aliphatic, aromatic/aliphatic or aromatic having 1 to 20 carbon atoms A group of hydrocarbon groups, and wherein the group R can also be bonded to each other to form a ring, and n is an integer of 1-5, or

ab) reacting phosgene, diphosgene or triphosgene with the aforementioned alcohol (B) with simultaneous elimination of hydrogen chloride,

b) subjecting the condensation product (K) to an intermolecular reaction to form a high-functionality hyperbranched polycarbonate or a high-functionality hyperbranched polycarbonate,

wherein the ratio of the amount of OH groups to carbonates in the reaction mixture is chosen such that the condensation product (K) has on average one carbonate group and more than one OH group or one OH group and more than one carbonate group.

Phosgene, diphosgene or triphosgene can be used as starting material, but preference is given to using organic carbonates.

Each R group in the organic carbonate (A) used as starting material and having the general formula RO(CO) _n OR is independently a straight-chain or branched aliphatic, aromatic/ aliphatic or aromatic hydrocarbon groups. Two R groups can also be bonded to each other to form a ring. This group is preferably an aliphatic hydrocarbon group, particularly preferably a straight-chain or branched alkyl group having 1 to 5 carbon atoms, or a substituted or unsubstituted phenyl group.

In particular simple carbonates of the general formula RO(CO) _n OR are used; n is preferably 1-3, especially 1 .

For example, dialkyl carbonates or diaryl carbonates can be prepared by reacting aliphatic, araliphatic or aromatic alcohols, preferably monoalcohols, with phosgene. They can also be prepared by oxidative carbonylation of alcohols or phenols by means of CO in the presence of noble metals, oxygen or _NOx . See also "Ullmann's Encyclopedia of Industrial Chemistry", 6th edition, electronic version 2000, Verlag Wiley-VCH, for the preparation of dialkyl carbonates or diaryl carbonates.

Examples of suitable carbonates include aliphatic, aromatic/aliphatic or aromatic carbonates such as ethylene carbonate, 1,2- or 1,3-propylene carbonate, diphenyl carbonate, xylyl carbonate, Di(xylyl carbonate), dinaphthyl carbonate, ethylphenyl carbonate, dibenzyl carbonate, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, dibutyl carbonate, diisobutyl carbonate , dipentyl carbonate, dihexyl carbonate, dicyclohexyl carbonate, diheptyl carbonate, dioctyl carbonate, didecyl carbonate or bis(dodecyl carbonate).

Examples of carbonates wherein n is greater than 1 include dialkyl dicarbonates such as di-t-butyl dicarbonate, or dialkyl tricarbonates such as di-t-butyl tricarbonate.

Preference is given to using aliphatic carbonates, especially those in which the radical contains 1 to 5 carbon atoms, for example dimethyl carbonate, diethyl carbonate, dipropyl carbonate, dibutyl carbonate or diisobutyl carbonate.

The organic carbonate is reacted with at least one aliphatic alcohol (B) having at least 3 OH groups or a mixture of two or more different alcohols.

Examples of compounds having at least 3 OH groups include glycerol, trimethylolmethane, trimethylolethane, trimethylolpropane, 1,2,4-butanetriol, tris(methylol)amine , tri(hydroxyethyl)amine, tri(hydroxypropyl)amine, pentaerythritol, diglycerin, triglycerol, polyglycerol, bis(trimethylolpropane), tri(hydroxymethyl)isocyanurate, isocyanurate Tris(hydroxyethyl)cyanurate, phloroglucinol, trihydroxytoluene, trihydroxydimethylbenzene, phloroglucides, hexahydroxybenzene, 1,3,5-benzenetrimethanol, 1,1,1-trismethanol (4'-Hydroxyphenyl)methane, 1,1,1-tris(4'-hydroxyphenyl)ethane, or sugars such as glucose, based on ternary or higher polyols and ethylene oxide, propylene oxide, or butylene oxide Alkene tertiary or higher polyether alcohols or polyester alcohols. Particular preference is given to glycerol, trimethylolethane, trimethylolpropane, 1,2,4-butanetriol and pentaerythritol and their polyether alcohols based on ethylene oxide or propylene oxide.

These polyols can also be used in admixture with diols (B'), provided that the average total OH functionality of all alcohols used is greater than 2. Examples of suitable compounds having two hydroxyl groups include ethylene glycol, diethylene glycol, triethylene glycol, 1,2- and 1,3-propanediol, dipropylene glycol, tripropylene glycol, neopentyl glycol, 1,2-, 1 , 3- and 1,4-butanediol, 1,2-, 1,3- and 1,5-pentanediol, hexanediol, cyclopentanediol, cyclohexanediol, cyclohexanedimethanol, Bis(4-hydroxycyclohexyl)methane, bis(4-hydroxycyclohexyl)ethane, 2,2-bis(4-hydroxycyclohexyl)propane, 1,1'-bis(4-hydroxyphenyl)-3 , 3,5-trimethylcyclohexane, resorcinol, hydroquinone, 4,4'-dihydroxyphenyl, bis(4-bishydroxyphenyl)sulfide, bis(4-hydroxyphenyl) Sulfone, bis(hydroxymethyl)benzene, bis(hydroxymethyl)toluene, bis(p-hydroxyphenyl)methane, bis(p-hydroxyphenyl)ethane, 2,2-bis(p-hydroxyphenyl)propane, 1,1-Bis(p-hydroxyphenyl)cyclohexane, dihydroxybenzophenones, dihydric polyether alcohols based on ethylene oxide, propylene oxide, butylene oxide or mixtures thereof, polytetrahydrofuran, polycaprolactone or Polyesterols based on diols and dicarboxylic acids.

Diols are used to fine-tune the properties of polycarbonates. If a diol is used, the ratio of the diol (B') to the at least triol (B) is set by a person skilled in the art according to the desired properties of the polycarbonate. Generally speaking, the amount of alcohol (B') is 0-50 mol% based on the total amount of all alcohols (B) and (B'). This amount is preferably 0-45 mol %, particularly preferably 0-35 mol %, very particularly preferably 0-30 mol %.

The reaction of phosgene, diphosgene or triphosgene with alcohols or mixtures of alcohols is usually accompanied by the elimination of hydrogen chloride, and the reaction of carbonates with alcohols or mixtures of alcohols to form the highly functional highly branched polycarbonates of the invention This is usually accompanied by elimination of monofunctional alcohols or phenols from the carbonate molecule.

After the reaction, the highly functional hyperbranched polycarbonates formed by the process according to the invention are terminated with hydroxyl and/or carbonate groups, ie without further modification. They have good solubility in various solvents such as water, alcohols such as methanol, ethanol, butanol, alcohol/water mixtures, acetone, 2-butanone, ethyl acetate, butyl acetate, acetic acid Methoxypropyl ester, methoxyethyl acetate, tetrahydrofuran, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, ethylene carbonate or 1,2-propylene carbonate.

For the purposes of the present invention, high-functionality polycarbonates are products having at least 3, preferably at least 6, more preferably at least 10 terminal or pendant functional groups in addition to the carbonate groups forming the polymer backbone. The functional groups are carbonate groups and/or OH groups. In principle there is no upper limit on the number of terminal or side functional groups, but products with a very high number of functional groups may have undesired properties, such as high viscosity or poor solubility. The high functionality polycarbonates of the present invention have generally not more than 500 terminal or pendant functional groups, preferably not more than 100 terminal or pendant functional groups.

When preparing highly functional polycarbonates B1), the ratio of OH group-containing compound to phosgene or carbonate must be adjusted such that the simplest resulting condensation product (hereinafter referred to as condensation product (K)) contains on average one carbonate group or carbamoyl group and more than one OH group or have one OH group and more than one carbonate group or carbamoyl group. Here, the simplest structure of the condensation product (K) consisting of carbonate (A) and diol or polyol (B) results in the arrangement XY _n or Y _n X, where X is a carbonate group, Y is a hydroxyl group and n Usually 1-6, preferably 1-4, particularly preferably 1-3. In this case, the only resulting reactive group is generally referred to below as the "focal group".

For example, if the reaction ratio is 1:1 in the preparation of the simplest condensation product (K) from carbonate and diol, the average result is a molecule of type XY shown in Formula 1:

During the preparation of the condensation product (K) from carbonate and triol in a reaction ratio of 1:1, the average result is a molecule of the type XY ₂ represented by the general formula 2. The focal group in this case is the carbonate group.

During the preparation of condensation products (K) from carbonates and tetrols, also in a 1:1 reaction ratio, the average result is a molecule of the type XY ₃ represented by the general formula 3 . The focal group in this case is the carbonate group.

In formulas 1-3, R is as defined at the beginning, and R ¹ is an aliphatic or aromatic group. Condensation products (K) can also be prepared, for example, as shown in formula 4, from carbonates and trihydric alcohols in a reaction molar ratio of 2:1. The average result at this point is a molecule of type _X2Y and the focal group is the OH group. In Formula 4, R and R ¹ are as defined in Formulas 1-3.

If difunctional compounds, such as dicarbonates or diols, are also added to the components, the result is, for example, chain extension as shown in formula 5. The average result again yields a molecule of type XY ₂ where the focal group is a carbonate group.

In Formula 5, ^R2 is an organic group, preferably an aliphatic group, and R and ^R1 are as defined above.

It is also possible to use two or more condensation products (K) for the synthesis. In this case, primarily two or more alcohols or two or more carbonates can be used. Furthermore, by choosing the ratio of alcohol and carbonate or phosgene used, it is possible to obtain mixtures of various condensation products with different structures. This can be exemplified by the reaction of carbonates with diols. If the starting products are reacted in a 1:1 ratio as shown in (II), then XY ₂ molecules are obtained. If the starting products are reacted in a ratio of 2:1 as shown in (IV), an _X2Y molecule is obtained. If the ratio is from 1:1 to 2:1, a mixture of _XY2 molecules and _X2Y molecules is obtained.

According to the invention, the simple condensation products (K), for example represented by formulas 1-5, preferably react intermolecularly to form highly functional polycondensation products, hereinafter referred to as polycondensation products (P). The reaction to obtain the condensation product (K) and the polycondensation product (P) is generally carried out at a temperature of 0-250° C., preferably 60-160° C., without solvent or in solution. In general, any solvent inert to the starting materials can be used at this point. Preference is given to using organic solvents such as decane, dodecane, benzene, toluene, chlorobenzene, xylene, dimethylformamide, dimethylacetamide or solvent naphtha.

In a preferred embodiment, the condensation reaction is carried out in the absence of solvent. The reaction can be accelerated by removing the phenol or monoalcohol ROH released during the reaction from the reaction equilibrium by distillation, if appropriate under reduced pressure.

If distillative removal is carried out, it is generally advantageous to use those carbonates which release alcohol ROH which boils below 140° C. during the reaction.

To accelerate the reaction, it is also possible to add catalysts or mixtures of catalysts. Suitable catalysts are compounds which catalyze esterification or transesterification, for example alkali metal hydroxides, alkali metal carbonates, alkali metal bicarbonates, preferably sodium, potassium or cesium salts, tertiary amines, guanidines, ammonium compounds, Phosphonium compounds, organoaluminum, organotin, organozinc, organotitanium, organozirconium or organobismuth compounds, as well as so-called double metal cyanide (DMC) catalysts, which are described, for example, in DE 10138216 or DE10147712.

Preference is given to using potassium hydroxide, potassium carbonate, potassium bicarbonate, diazabicyclooctane (DABCO), diazabicyclononene (DBN), diazabicycloundecene (DBU), imidazoles such as imidazole, 1-methylimidazole or 1,2-dimethylimidazole, titanium tetrabutoxide, titanium tetraisopropoxide, dibutyltin oxide, dibutyltin dilaurate, tin dioctoate, zirconium acetylacetonate or mixtures thereof.

The catalyst is generally added in an amount of 50-10000 ppm by weight, preferably 100-5000 ppm by weight, based on the amount of alcohol or alcohol mixture used.

It is also possible to control the intermolecular polycondensation reaction by adding a suitable catalyst or by choosing a suitable temperature. Furthermore, the average molecular weight of the polymer (P) can be adjusted by means of the composition of the starting components and the residence time.

Condensation products (K) and polycondensation products (P) prepared at elevated temperatures are generally stable for extended periods at room temperature.

The properties of the condensation products (K) allow polycondensation products (P) of different structures to be obtained from the condensation reaction, which are branched but not crosslinked. Furthermore, it is desirable that the polycondensation product (P) has one carbonate group as focal group and more than two OH groups or one OH group as focal group and more than two carbonate groups. The number of reactive groups is determined by the nature of the condensation products (K) used and the degree of polycondensation.

As an example, the condensation product (K) of general formula 2 can react by three-fold intermolecular condensation to form two different polycondensation products (P) represented by general formula 6 and general 7.

In Formulas 6 and 7, R and R ¹ are as defined above.

In order to terminate the intermolecular polycondensation reaction, various methods can be adopted. For example, the temperature can be lowered to a range in which the reaction ceases and the product (K) or polycondensation product (P) is storage stable.

It is also possible to deactivate the catalyst, for example by adding Lewis or protic acids in the case of basic catalysts.

In another embodiment, once the intermolecular reaction of the condensation product (K) has produced a polycondensation product (P) with the desired degree of polycondensation, it is possible to add to the product (P) a The product of the reactive group terminates the reaction. For example, in the case of carbonates as focal group, monoamines, diamines or polyamines may be added. In the case of hydroxyl groups as focal group, it is possible, for example, to add to the product (P) mono-, di- or polyisocyanates, compounds containing epoxy groups or acid derivatives which are reactive toward OH groups.

The preparation of the high-functionality polycarbonates according to the invention is generally carried out in reactors or reactor cascades operated batchwise, semibatchwise or continuously at a pressure in the range from 0.1 mbar to 20 bar, preferably from 1 mbar to 5 bar.

By adjusting the reaction conditions as described above and, if appropriate, by selecting suitable solvents, the products according to the invention can be processed further after their preparation without further purification.

In another preferred embodiment, the product is stripped, ie removed of low molecular weight volatile compounds. For this purpose, once the desired degree of conversion has been achieved, the catalyst can optionally be deactivated and low molecular weight volatile components such as monohydric alcohols, phenols, carbonates, hydrogen chloride or volatile oligomeric or cyclic compounds can be removed by distillation, if appropriate at A gas, preferably nitrogen, carbon dioxide or air, is introduced in the distillation and the distillation is carried out, if appropriate, under reduced pressure.

In a further preferred embodiment, the polycarbonates according to the invention may contain further functional groups in addition to the functional groups which are present at this stage through the reaction. The functionalization can be carried out during the molecular weight increase or subsequently, ie after the actual polycondensation is complete.

If components having functional units or functional groups other than hydroxyl or carbonate groups are added before or during the increase in molecular weight, polycarbonate polymers with functional groups other than carbonate groups or hydroxyl groups distributed randomly are obtained .

This effect can be achieved, for example, by adding in the polycondensation process other functional groups or functional units such as mercapto groups, primary amino groups, secondary amino groups, tertiary amino groups, ether groups, carboxylic acid derivatives, in addition to hydroxyl groups, carbonate groups or carbamoyl groups. , sulfonic acid derivatives, phosphonic acid derivatives, silane groups, siloxane groups, aryl or long-chain alkyl compounds. Examples of compounds which can be used for modification by means of carbamate groups are ethanolamine, propanolamine, isopropanolamine, 2-(butylamino)ethanol, 2-(cyclohexylamino)ethanol, 2-amino- 1-Butanol, higher alkoxylation products of 2-(2'-aminoethoxy)ethanol or ammonia, 4-hydroxypiperidine, 1-hydroxyethylpiperazine, diethanolamine, dipropanolamine, Diisopropanolamine, tris(hydroxymethyl)aminomethane, tris(hydroxyethyl)aminomethane, ethylenediamine, propylenediamine, hexamethylenediamine or isophoronediamine.

An example of a compound that can be modified with mercapto groups is mercaptoethanol. For example, tertiary amino groups can be produced by introducing N-methyldiethanolamine, N-methyldipropanolamine or N,N-dimethylethanolamine. For example, ether groups can be produced by cocondensation of dihydric or higher polyhydric polyetherols. Long-chain alkyl groups can be introduced by reaction with long-chain alkane diols, and the reaction with alkyl or aryl diisocyanates leads to polycarbonates with alkyl, aryl and urethane or urea groups.

Ester groups can be produced by addition of dicarboxylic acids, tricarboxylic acids or esters such as dimethyl terephthalate or tricarboxylates.

The subsequent functionalization can be carried out by using an additional process step (step c)) in which the resulting high-functionality hyperbranched or high-functionality hyperbranched polycarbonate is combined with OH and/or carbonate groups capable of bonding with the polycarbonate or a suitable functionalizing reagent for the carbamoyl reaction.

For example, hydroxyl-containing high-functionality hyperbranched or high-functionality hyperbranched polycarbonates can be modified by adding molecules containing acid groups or isocyanate groups. For example, polycarbonates containing acid groups can be obtained by reaction with compounds containing anhydride groups.

Furthermore, hydroxyl-containing highly functional polycarbonates can also be converted into highly functional polycarbonate polyether polyols by reaction with alkylene oxides such as ethylene oxide, propylene oxide or butylene oxide.

A great advantage of the method of the invention is its cost effectiveness. Not only the reaction to form condensation product (K) or polycondensation product (P) can be carried out in one reactor, but also (K) or (P) can be reacted to form polycarbonate with other functional groups or units, which has technical and Cost efficiency advantage.

The molding composition according to the invention comprises at least one hyperbranched polyester of _{type AxBy} as component B2) of the mixture B) according to the invention, wherein

x is at least 1.1, preferably at least 1.3, especially at least 2,

y is at least 2.1, preferably at least 2.5, especially at least 3.

Of course, it is also possible to use mixtures as units A and/or B.

Polyesters of type A _x B _y are condensation products consisting of x-functional molecules A and y-functional molecules B. For example, there may be mentioned polyester compounds composed of adipic acid as molecule A (x=2) and glycerol as molecule B (y=3).

For the purposes of the present invention, hyperbranched polyesters B2) are uncrosslinked macromolecules with hydroxyl and carbonate groups, which have both structural and molecular inhomogeneity. First, their structure can be based on a central molecule in the same way as dendrimers, but with non-uniform branch chain lengths. Secondly, they can also have linear structures with functional side groups, or they can combine these two extremes, with linear and branched molecular parts. See P. J. Flory, J. Am. Chem. Soc. 1952, 74, 2718 and H. Frey et al., Chem. Eur. J. 2000, 6, no. 14, 2499 for definitions of dendritic and hyperbranched polymers.

In the context of the present invention, "hyperbranched" refers to the degree of branching (DB), i.e. the average number of dendritic connections per molecule plus the average number of end groups of 10-99.9%, preferably 20-99%, in particular Preferably 20-95%.

In the context of the present invention, "dendrimer" means a degree of branching of 99.9 to 100%. See the definition of "degree of branching" by H. Frey et al., Acta Polym. 1997, 48, 30.

Component B2) preferably has an _Mn determined by GPC, PMMA standard, dimethylacetamide eluent, of 300-30000 g/mol, especially 400-25000 g/mol, very particularly preferably 500-20000 g/mol.

According to DIN 53240, B2) preferably has an OH value of 0-600 mg KOH/g polyester, preferably 1-500 mg KOH/g polyester, in particular 20-500 mg KOH/g polyester, and preferably has a COOH value of 0 - 600mg KOH/g polyester, preferably 1-500mg KOH/g polyester, especially 2-500mg KOH/g polyester.

The Tg is preferably -50°C to 140°C, especially -50°C to 100°C (by means of DSC according to DIN 53765).

Particular preference is given to those components B2) in which at least one OH or COOH has a value greater than 0, preferably greater than 0.1, especially greater than 0.5.

Inventive component B2) is obtainable in particular by the following process, especially by the presence of solvents and optionally in the presence of inorganic catalysts, organometallic catalysts or low molecular weight organic catalysts or enzymes

(a) reacting one or more dicarboxylic acids or one or more derivatives thereof with one or more at least trihydric alcohols,

or,

(b) reacting one or more tricarboxylic acids or higher polycarboxylic acids or one or more derivatives thereof with one or more diols. Reaction in a solvent is the preferred method of preparation.

For the purposes of the present invention, the highly functional hyperbranched polyesters B2) have molecular and structural inhomogeneity. Its molecular heterogeneity distinguishes it from dendrimers, so it can be prepared at relatively low cost.

Among the dicarboxylic acids, dicarboxylic acids which can be reacted according to scheme (a) are, for example, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, acid, undecane-α, ω-dicarboxylic acid, dodecane-α, ω-dicarboxylic acid, cis- and trans-cyclohexane-1,2-dicarboxylic acid, cis- and trans-cyclohexane-1 , 3-dicarboxylic acid, cis- and trans-cyclohexane-1,4-dicarboxylic acid, cis- and trans-cyclopentane-1,2-dicarboxylic acid and cis- and trans-cyclopentane-1,3-dicarboxylic acid ,

And the above-mentioned dicarboxylic acid can be replaced by one or more groups selected from the following groups:

C ₁ -C ₁₀ Alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl , neopentyl, 1,2-dimethylpropyl, isopentyl, n-hexyl, isohexyl, sec-hexyl, n-heptyl, isoheptyl, n-octyl, 2-ethylhexyl, n-nonyl and n- Decyl,

C ₃ -C ₁₂ cycloalkyl, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl and cyclododecyl Alkyl; preferably cyclopentyl, cyclohexyl and cycloheptyl;

Alkylene groups such as methylene or ethylene, or

C ₆ -C ₁₄ aryl, such as phenyl, 1-naphthyl, 2-naphthyl, 1-anthracenyl, 2-anthracenyl, 9-anthracenyl, 1-phenanthrenyl, 2-phenanthrenyl, 3-phenanthrenyl phenanthrenyl, 4-phenanthrenyl and 9-phenanthrenyl, preferably phenyl, 1-naphthyl and 2-naphthyl, particularly preferably phenyl.

Examples of representative substituted dicarboxylic acids that may be mentioned are: 2-methylmalonic acid, 2-ethylmalonic acid, 2-phenylmalonic acid, 2-methylsuccinic acid, 2-ethyl Succinic acid, 2-phenylsuccinic acid, itaconic acid, 3,3-dimethylglutaric acid.

Among the dicarboxylic acids, it is also possible to react according to variant (a) ethylenically unsaturated acids, such as maleic acid and fumaric acid, and also aromatic dicarboxylic acids, such as phthalic acid, isophthalic acid or terephthalic acid. Phthalic acid.

Mixtures of two or more of the above representative compounds may also be used.

The dicarboxylic acids can be used as such or in the form of their derivatives.

Derivatives are preferably:

- relevant anhydrides in monomeric or polymeric form,

- mono- or dialkyl esters, preferably mono- or dimethyl esters, or corresponding mono- or diethyl esters, or mono- or dialkyl esters derived from higher alcohols such as It is n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol, n-pentanol, n-hexanol.

- and mono- and divinyl esters, and

- Mixed esters, preferably methyl ethyl esters.

In a preferred preparation, it is also possible to use mixtures of dicarboxylic acids and one or more derivatives thereof. Likewise, mixtures of two or more different derivatives of one or more dicarboxylic acids may also be used.

Particular preference is given to using succinic acid, glutaric acid, adipic acid, phthalic acid, isophthalic acid, terephthalic acid or the mono- or dimethyl esters thereof. Very particular preference is given to using adipic acid.

Examples of reactive at least trihydric alcohols are: glycerol, 1,2,4-butanetriol, 1,2,5-n-pentanetriol, 1,3,5-n-pentanetriol, 1,2,6 -n-hexanetriol, 1,2,5-n-hexanetriol, 1,3,6-n-hexanetriol, trimethylolbutane, trimethylolpropane or ditrimethylolpropane, trimethylolethane alkanes, pentaerythritol or dipentaerythritol; sugar alcohols such as mesoerythriol, threitol, sorbitol, mannitol or mixtures of at least the above trihydric alcohols. Preference is given to using glycerol, trimethylolpropane, trimethylolethane and pentaerythritol.

Examples of tricarboxylic or polycarboxylic acids which can be reacted according to scheme (b) are benzene-1,2,4-tricarboxylic acid, benzene-1,3,5-tricarboxylic acid, benzene-1,2,4,5- tetracarboxylic acid and mellitic acid.

The tricarboxylic or polycarboxylic acids can be used in the reaction according to the invention as such or as derivatives.

Derivatives are preferably:

- relevant anhydrides in monomeric or polymeric form,

- mono-, di- or trialkyl esters, preferably mono-, di- or trimethyl esters, or corresponding mono-, di- or triethyl esters, or other mono-, di- and triesters, such higher alcohols as n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol, n-pentanol, n-hexanol, or other mono-, di- or trivinyl esters .

- and mixed methyl ethyl esters.

For the purposes of the invention, it is also possible to use mixtures of tri- or polycarboxylic acids and one or more derivatives thereof. For the purposes of the invention, it is likewise possible to use mixtures of two or more different derivatives of one or more tri- or polycarboxylic acids in order to obtain component B2).

Examples of diols used in variant (b) of the present invention are ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4- Butanediol, 2,3-butanediol, 1,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol, 1,5-pentanediol, 2,3-pentanediol Alcohol, 2,4-pentanediol, 1,2-hexanediol, 1,3-hexanediol, 1,4-hexanediol, 1,5-hexanediol, 1,6-hexanediol, 2,5-hexanediol, 1,2-heptanediol, 1,7-heptanediol, 1,8-octanediol, 1,2-octanediol, 1,9-nonanediol, 1, 10-decanediol, 1,2-decanediol, 1,12-dodecanediol, 1,2-dodecanediol, 1,5-hexadiene-3,4-diol, cyclo Pentylene glycol, cyclohexanediol, inositol and derivatives, (2)-methylpentane-2,4-diol, 2,4-dimethylpentane-2,4-diol, 2-ethane Hexyl-1,3-diol, 2,5-dimethylhexane-2,5-diol, 2,2,4-trimethylpentane-1,3-diol, pinacol , diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, polyethylene glycol HO(CH ₂ CH ₂ O) _n -H or polypropylene glycol HO(CH[CH ₃ ]CH ₂ O) _n -H or two or more representative compound mixtures of the aforementioned compounds, wherein n=an integer of 4-25. Here, one or both of the hydroxyl groups in the above-mentioned diols may also be replaced by SH groups. Preference is given to ethylene glycol, 1,2-propanediol and diethylene glycol, triethylene glycol, dipropylene glycol and tripropylene glycol.

In variants (a) and (b), the molar ratio of molecules A to molecules B in the polyester A _x B _y molecules is 4:1 to 1:4, in particular 2:1 to 1:2.

The at least trihydric alcohols reacted according to variant (a) of the process according to the invention may contain hydroxyl groups which are all equally reactive. Preference is also given here to at least trihydric alcohols whose OH groups initially have the same reactivity but which, when reacted with at least one acid group, can lead to a reduction in the reactivity of the remaining OH groups due to steric or electronic effects. This applies, for example, to the use of trimethylolpropane or pentaerythritol.

However, the at least triols reacted according to variant (a) may also contain hydroxyl groups having at least two different chemical reactivities.

Here, the different reactivity of the functional groups can originate from chemical factors (eg primary/secondary/tertiary OH groups) as well as from steric factors.

For example, triols may include triols having primary and secondary hydroxyl groups, a preferred example being glycerol.

When carrying out the inventive reaction according to variant (a), it is preferred to work in the absence of diols and monohydric alcohols.

When carrying out the inventive reaction according to variant (b), it is preferred to work in the absence of mono- or dicarboxylic acids.

The process of the invention is carried out in the presence of a solvent. Examples of suitable compounds are hydrocarbons, such as alkanes or aromatic compounds. Particularly suitable alkanes are n-heptane and cyclohexane. Particularly suitable aromatic compounds are toluene, ortho-xylene, meta-xylene, para-xylene, xylene in the form of isomer mixtures, ethylbenzene, chlorobenzene and ortho- and meta-dichlorobenzene. In the absence of acidic catalysts, other very particularly suitable solvents are: ethers such as dioxane or tetrahydrofuran, and ketones such as methyl ethyl ketone and methyl isobutyl ketone.

According to the invention, the solvent is added in an amount of at least 0.1% by weight, preferably at least 1% by weight, particularly preferably at least 10% by weight, based on the weight of the starting materials used and to be reacted. It is also possible to use an excess of solvent, for example in an amount of 1.01-10 times based on the weight of the starting materials used and to be reacted. An amount of solvent greater than 100 times the weight of the starting materials used and to be reacted is disadvantageous because the reaction rate drops significantly at significantly lower reactant concentrations, resulting in uneconomically long reaction times.

To carry out the preferred process of the invention, it is possible to work in the presence of a dehydrating agent as an additive, which is added at the start of the reaction. Examples of suitable dehydrating agents are molecular sieves, especially Molecular sieves, MgSO ₄ and Na ₂ SO ₄ . During the reaction, other dehydrating agents can also be added or replaced with fresh dehydrating agents. Water or alcohol formed can also be removed during the reaction by distillation and, for example, using a water separator.

The reaction can be carried out in the absence of acidic catalysts. It is preferably carried out in the presence of an acidic inorganic, organometallic or organic catalyst, or in the presence of a mixture of two or more acidic inorganic, organometallic or organic catalysts.

Examples of acidic inorganic catalysts for the purposes of the present invention are sulfuric acid, phosphoric acid, phosphonic acid, hypophosphorous acid, aluminum sulfate hydrate, alum, acidic silica gel (pH=6, especially =5) and acidic alumina. Examples of other compounds that can be used as acidic inorganic catalysts are aluminum compounds of the general formula Al(OR) ₃ and titanates of the general formula Ti(OR) ₄ , wherein each R group can be the same or different, and are independently selected from :

C ₁ -C ₁₀ Alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl , neopentyl, 1,2-dimethylpropyl, isopentyl, n-hexyl, isohexyl, sec-hexyl, n-heptyl, isoheptyl, n-octyl, 2-ethylhexyl, n-nonyl and n- Decyl.

C ₃ -C ₁₂ cycloalkyl, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl and cyclododecyl Alkyl; preferably cyclopentyl, cyclohexyl and cycloheptyl.

Each R group in Al(OR) ₃ or Ti(OR) ₄ is preferably the same group and is selected from isopropyl or 2-ethylhexyl.

Examples of preferred acidic organometallic catalysts are selected from dialkyltin oxides _R2SnO , wherein R is as defined above. Representative compounds of particularly preferred acidic organometallic catalysts are di-n-butyltin oxide, commercially available as "oxo-tin", or di-n-butyltin dilaurate.

Preferred acidic organic catalysts are, for example, organic compounds having phosphate, sulfonic, sulfate or phosphonic acid groups. Particular preference is given to sulfonic acids, such as p-toluenesulfonic acid. Acidic ion exchangers can also be used as acidic organic catalysts, such as polystyrene resins containing sulfonic acid groups and crosslinked with about 2 mol % of divinylbenzene.

Combinations of two or more of the above catalysts may also be used. It is also possible to use those organic or organometallic catalysts in immobilized form, or to use inorganic catalysts in the form of discrete molecules.

If acidic inorganic catalysts, organometallic catalysts or organic catalysts are used according to the invention, the amount of catalyst used according to the invention is 0.1-10% by weight, preferably 0.2-2% by weight.

The process according to the invention is carried out under inert gases, for example carbon dioxide, nitrogen or noble gases, among which argon may be mentioned in particular.

The method of the present invention is carried out at a temperature of 60-200°C. Preference is given to operating at a temperature of 130-180°C, especially up to 150°C, or below. Particular preference is given to a maximum temperature of up to 145°C, very particular preference to temperatures of up to 135°C.

The pressure conditions of the process according to the invention are not critical per se. It can be operated under significant reduced pressure, for example at 10-500 mbar. The process according to the invention can also be carried out at pressures higher than 500 mbar. Due to simplicity, the reaction is preferably carried out at atmospheric pressure; however, the reaction can also be carried out under slightly increased pressure, for example up to 1200 mbar. It is also possible to work under significantly increased pressure, for example up to 10 bar. Preferably the reaction is carried out at atmospheric pressure.

The reaction time of the process according to the invention is generally 10 minutes to 25 hours, preferably 30 minutes to 10 hours, particularly preferably 1 to 8 hours.

Once the reaction is complete, the highly functional hyperbranched polyesters can be easily isolated, for example by filtration to remove the catalyst and concentrate the mixture, usually under reduced pressure. Other work-up methods with good applicability are precipitation after addition of water, followed by washing and drying.

Component B2) can also be prepared in the presence of enzymes or decomposition products of enzymes (according to DE-A 101 63163). For the purposes of the present invention, the term acidic organic catalysts does not include the dicarboxylic acids reacted according to the invention.

Preference is given to using lipases or esterases. Lipases and esterases with good applicability are those from Candida cylindracea, Candida lipolytica, Candida rugosa, Candida antarctica, Candida utilis, Chromobacterium viscosum, Geolrichum viscosum, Geotrichum candidum, Mucor javanicus, Mucor mihei, porcine pancreas, pseudomonas spp.), Pseudomonas fluorescens, Pseudomonas cepacia, Rhizopus arrhizus, Rhizopus delemar, Rhizopus niveus, rice Rhizopus oryzae, Aspergillus niger, Penicillium roquefortii, Penicillium camembertii or esterases from Bacillus spp. and Bacillus thermoglucosidasius. Candida antarctica lipase B is particularly preferred. The listed enzymes are commercially available, for example, from Novozymes Biotech Inc., Denmark.

上的形式使用。固定酶的方法本身是已知的，例如由Kurt Faber的“Biotransformations in organicchemistry”，1997年第3版，Springer Verlag，第3.2章“Immobilization”第345-356页已知。固定化酶可例如从丹麦Novozymes Biotech Inc.购得。Enzymes are preferably immobilized, for example, on silica gel and

The above form is used. Methods for immobilizing enzymes are known per se, eg from Kurt Faber, "Biotransformations in organic chemistry", 3rd edition, 1997, Springer Verlag, chapter 3.2 "Immobilization", pp. 345-356. Immobilized enzymes are commercially available, for example, from Novozymes Biotech Inc., Denmark.

The immobilized enzyme is used in an amount of 0.1-20% by weight, especially 10-15% by weight, based on the total amount of raw materials used and to be reacted.

The process of the invention is carried out at a temperature higher than 60°C. It is preferred to operate at a temperature of 100°C or below. Preference is given to a temperature of up to 80°C, very particular preference to a temperature of 62-75°C, still more preference to a temperature of 65-75°C.

The process of the invention is carried out in the presence of a solvent. Examples of suitable compounds are hydrocarbons, such as paraffins or aromatics. Particularly suitable paraffins are n-heptane and cyclohexane. Particularly suitable aromatic compounds are toluene, ortho-xylene, meta-xylene, para-xylene, xylene in the form of isomer mixtures, ethylbenzene, chlorobenzene and ortho- and meta-dichlorobenzene. Other very particularly suitable solvents are: ethers such as dioxane or tetrahydrofuran, and ketones such as methyl ethyl ketone and methyl isobutyl ketone.

The amount of solvent added is at least 5 parts by weight, preferably at least 50 parts by weight, particularly preferably at least 100 parts by weight, based on the weight of the starting materials used and to be reacted. A solvent amount greater than 10,000 parts by weight is undesirable because the reaction rate drops significantly at significantly lower concentrations, resulting in uneconomically long reaction times.

The process according to the invention is carried out at pressures above 500 mbar. Preference is given to reacting at atmospheric pressure or slightly increased pressure, for example up to 1200 mbar. It is also possible to operate under significant pressure, for example up to 10 bar. Preference is given to reacting at atmospheric pressure.

The reaction time of the process according to the invention is generally 4 hours to 6 days, preferably 5 hours to 5 days, particularly preferably 8 hours to 4 days.

Once the reaction is complete, the highly functional hyperbranched polyester can be easily isolated, for example by filtration to remove the catalyst and concentrate the mixture, usually under reduced pressure. Other work-up methods with good applicability are precipitation after addition of water, followed by washing and drying.

The highly functional hyperbranched polyesters obtainable by the process according to the invention are characterized by a particularly low content of discoloration and resinizing substances. For the definition of hyperbranched polymers see also: P. J. Flory, J. Am. Chem. Soc. 1952, 74, 2718 and A. Sunder et al., Chem. Eur. J. 2000, 6, no. 1, 1-8. However, in the context of the present invention, "high functionality hyperbranched" means that the degree of branching, i.e. the average number of dendritic linkages per molecule plus the average number of end groups is 10-99.9%, preferably 20-99% , particularly preferably 30-90% (on this point see H. Frey et al., Acta Polym. 1997, 48, 30).

The molar mass M _w of the polyester according to the invention is 500-50000 g/mol, preferably 1000-20000 g/mol, particularly preferably 1000-19000 g/mol. The polydispersity is 1.2-50, preferably 1.4-40, particularly preferably 1.5-30, very particularly preferably 1.5-10. They are generally readily soluble, i.e. clear solutions can be prepared using up to 50% by weight and in some cases even up to 80% by weight of the polyesters of the invention in tetrahydrofuran (THF), n-butyl acetate, ethanol and numerous other solvents, And there are no gel particles visible to the naked eye.

The high-functionality hyperbranched polyesters of the present invention are carboxyl-terminated, carboxyl- and hydroxyl-terminated, preferably hydroxyl-terminated polyesters.

The ratio of components B1):B2) is preferably 1:20 to 20:1, in particular 1:15 to 15:1, very particularly 1:5 to 5:1.

The hyperbranched polycarbonates B1)/polyesters B2) used are in the form of particles with a particle size of 20-500 nm. These nanoparticles are present in the polymer blend as fine dispersions and have a particle size in the composite of 20-500 nm, preferably 50-300 nm.

high speed购得。Such composite materials can

high speed purchased.

The molding compositions according to the invention can comprise 0 to 60% by weight, in particular up to 50% by weight, of additives and processing aids other than B) as component C).

The molding compositions according to the invention may contain 0-5% by weight, preferably 0.05-3% by weight, in particular 0.1-2% by weight of at least one saturated or As component C), esters or amides of unsaturated aliphatic carboxylic acids with aliphatic saturated alcohols or amines having 2 to 40 carbon atoms, preferably 2 to 6 carbon atoms, or amines.

Carboxylic acids can be monobasic or dibasic acids. Examples that may be mentioned are pelargonic acid, palmitic acid, lauric acid, margaric acid, dodecanedioic acid, behenic acid, particularly preferably stearic acid, capric acid and montanic acid (having 30-40 carbon atoms). mixture of fatty acids).

Aliphatic alcohols can be mono to tetrahydric alcohols. Examples of alcohols are n-butanol, n-octanol, stearyl alcohol, ethylene glycol, propylene glycol, neopentyl glycol, pentaerythritol, preferably glycerol and pentaerythritol.

Aliphatic amines can be mono-, di- or triamines. Examples of these amines are stearylamine, ethylenediamine, propylenediamine, hexamethylenediamine, di(6-aminohexyl)amine, particular preference being given to ethylenediamine and hexamethylenediamine. Correspondingly, preferred esters or amides are glyceryl distearate, glyceryl tristearate, ethylenediamine distearate, glyceryl monopalmitate, glyceryl trilaurate, glyceryl monobehenate and pentaerythritol tetrastearate.

It is also possible to use mixtures of various esters or amides, or mixtures of esters and amides in combination, where the mixing ratio is determined as desired.

Examples of amounts of other customary additives C) are up to 40% by weight, preferably up to 30% by weight, of elastomeric polymers (also often referred to as impact modifiers, elastomers or rubbers).

These very general copolymers are preferably composed of at least two of the following monomers: ethylene, propylene, butadiene, isobutylene, isoprene, chloroprene, vinyl acetate, styrene, acrylonitrile and Acrylates and/or methacrylates with 1 to 18 carbon atoms.

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

Some preferred types of these elastomers are described below.

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

EPM rubber usually has practically no residual double bonds, while EPDM rubber can have 1-20 double bonds per 100 carbon atoms.

Examples of diene monomers that may be mentioned for EPDM rubbers are conjugated dienes such as isoprene and butadiene, non-conjugated dienes having 5 to 25 carbon atoms such as 1,4-pentanediene ene, 1,4-hexadiene, 1,5-hexadiene, 2,5-dimethyl-1,5-hexadiene and 1,4-octadiene, cyclodienes such as cyclopentadiene , cyclohexadiene, cyclooctadiene and dicyclopentadiene, and alkenyl norbornene such as 5-ethylidene-2-norbornene, 5-butylene-2-norbornene, 2- Methallyl-5-norbornene and 2-isopropenyl-5-norbornene, and tricyclic dienes such as 3-methyltricyclo[5.2.1.0 ^2,6 ]-3,8-decane dienes, and mixtures thereof. Preference is given to 1,5-hexadiene, 5-ethylidene norbornene and dicyclopentadiene. The diene content of the EPDM rubber is preferably 0.5-50% by weight, especially 1-8% by weight, based on the total weight of the rubber.

EPM and EPDM rubbers can also preferably be grafted with reactive carboxylic acids or derivatives thereof. Examples are acrylic acid, methacrylic acid and derivatives thereof, such as glycidyl (meth)acrylate and maleic anhydride.

Copolymers of ethylene with acrylic acid and/or methacrylic acid and/or with esters of these acids are another group of preferred rubbers. Such rubbers may also contain dicarboxylic acids such as maleic acid and fumaric acid or derivatives of these acids such as esters and anhydrides, and/or monomers containing epoxy groups. These monomers comprising dicarboxylic acid derivatives or comprising epoxy groups are preferably incorporated into the rubber by addition to the mixture of monomers comprising dicarboxylic acid groups and/or epoxy groups and having the formulas I, II, III or IV.

R ¹ C(COOR ² )=C(COOR ³ )R ⁴ (I)

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

^R1 to ^R9 are preferably hydrogen, wherein m is 0 or 1 and g is 1. 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 (meth)acrylates containing epoxy groups such as glycidyl acrylate and glycidyl methacrylate, and esters with tertiary alcohols such as acrylic acid tert-butyl ester. Although the latter have no free carboxyl groups, their properties are close to those of the free acids and are therefore called monomers with latent carboxyl groups.

Advantageously, the copolymer comprises 50-98% by weight of ethylene, 0.1-20% by weight of epoxy- and/or methacrylic acid-containing monomers and/or anhydride-containing monomers, with the remainder being (form base) acrylate.

Particularly preferred copolymers consist of the following monomers:

50-98% by weight, especially 55-95% by weight of ethylene,

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

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

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

Apart from these, usable comonomers are vinyl esters and vinyl ethers.

The abovementioned ethylene copolymers can be prepared by methods known per se, preferably by random copolymerization at elevated pressure and temperature. Suitable methods are known.

Other preferred elastomers are emulsion polymers, the preparation of which is described, for example, in Blackley's monograph "Emulsion Polymerization". Emulsifiers and catalysts which can be used are known per se.

In principle, homogeneously structured elastomers or those with a shell structure can be used. The shell structure depends on the order of addition of the individual monomers. The morphology of the polymer is also affected by this order of addition.

Monomers which may be mentioned here only as examples for the preparation of the rubber part of the elastomer are acrylates such as n-butyl acrylate and 2-ethylhexyl acrylate, the corresponding methacrylates, butadiene and isoprene alkenes and their mixtures. These monomers can be copolymerized with other monomers, such as styrene, acrylonitrile, vinyl ether, and with other acrylates or methacrylates, such as methyl methacrylate, methyl acrylate, ethyl acrylate or propyl acrylate.

The soft or rubbery phase (glass transition temperature below 0°C) of the elastomer can be the core, outer shell or intermediate shell (in the case of elastomers with more than two shells). Elastomers having more than one shell may also have more than one shell consisting of the rubber phase.

If, in addition to the rubber phase, one or more hard components (glass transition temperature above 20°C) are included in the structure of the elastomer, they are usually prepared by polymerizing the following main monomers: styrene, acrylonitrile, Methacrylonitrile, alpha-methylstyrene, p-methylstyrene, or acrylates or methacrylates such as methyl acrylate, ethyl acrylate or methyl methacrylate. Besides these, it is also possible to use smaller proportions of other comonomers.

The use of emulsion polymers which have reactive groups on their surface has proven to be advantageous in certain cases. Examples of such groups are epoxy groups, carboxyl groups, latent carboxyl groups, amino groups and amido groups, as well as functional groups which can be introduced by simultaneously using monomers of the formula:

in:

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 can be substituted by O- or N-containing groups if desired,

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

Y is O-Z or NH-Z, and

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

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

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

The rubber phase particles may also be crosslinked. Examples of crosslinking monomers are 1,3-butadiene, divinylbenzene, diallyl phthalate and dihydrodicyclopentadienyl acrylate, and the compounds described in EP-A 50265.

Monomers known as graft-bonded monomers, ie, having two or more polymerizable double bonds that react at different rates during polymerization, may also be used. Preference is given to using compounds in which at least one reactive group polymerizes at approximately the same rate as the other monomers, while the other reactive groups polymerize eg significantly slower. Different polymerization rates produce a certain proportion of unsaturated double bonds in the rubber. If another phase is subsequently grafted onto this type of rubber, at least some of the double bonds present in the rubber react with the grafted monomers to form chemical bonds, i.e. the grafted phase is at least to some extent chemically bonded to the grafted matrix .

Examples of such graft-bonding monomers are allyl group-containing monomers, especially allyl esters of ethylenically unsaturated carboxylic acids, such as allyl acrylate, allyl methacrylate, maleic acid Diallyl esters, diallyl fumarate and diallyl itaconate, and the corresponding monoallyl compounds of these carboxylic acids. Besides these, there are numerous other suitable graft-bonding monomers. For further details see for example US-A 4 148 846.

The proportion of these crosslinking monomers in the impact-modifying polymer is generally at most 5% by weight, preferably not more than 3% by weight, based on the impact-modifying polymer.

Some preferred emulsion polymers are listed below. Mention may be made here primarily of graft polymers having a core and at least one outer shell and having the following structure:

type core forming monomer monomer that forms the shell I 1,3-Butadiene, isoprene, n-butyl acrylate, ethylhexyl acrylate or mixtures thereof Styrene, Acrylonitrile, Methyl Methacrylate II Same as I, but use crosslinker at the same time Same as I

III Same as I or II n-butyl acrylate, ethyl acrylate, methyl acrylate, 1,3-butadiene, isoprene, ethylhexyl acrylate IV Same as I or II As I or III, but using monomers with reactive groups as described herein V Styrene, acrylonitrile, methyl methacrylate or mixtures thereof The first shell consists of the monomers as described under I and II for the core, the second shell consists of the monomers as described under I or IV for the shell

，得自BASF AG)获得。These graft polymers, especially ABS polymers and/or ASA polymers, are preferably used in the impact modification of PBT in an amount of up to 40% by weight, if appropriate together with up to 40% by weight of polyethylene terephthalate Alcohol ester mixed use. Such blend products can be trademarked (previous

, obtained from BASF AG).

In addition to graft polymers whose structure has more than one shell, it is also possible to use homogeneous, i.e. single-shelled polymers consisting of or derived from 1,3-butadiene, isoprene and n-butyl acrylate. Copolymer elastomers. These products can also be prepared by the concomitant use of 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, Grafted polymers consisting of esters or a core based on butadiene with an outer shell consisting of the above-mentioned copolymers, and copolymers of ethylene with comonomers providing reactive groups.

The elastomers can also be prepared by other conventional methods, for example by suspension polymerization.

Silicone rubbers are also 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, mixtures of the types of rubber listed above may also be used.

Fibrous or granular fillers C) that may be mentioned are carbon fibers, glass fibers, glass beads, amorphous silica, asbestos, calcium silicate, calcium metasilicate, magnesium carbonate, kaolin, chalk, powdered quartz, mica, Barium sulfate and feldspar are used in amounts of up to 50% by weight, especially up to 40% by weight.

Preferred fibrous fillers that may be mentioned are carbon fibers, aramid fibers and potassium titanate fibers, glass fibers in the form of E glass being particularly preferred. They are available as rovings or as commercially available chopped glass.

Particular preference is given to mixtures of glass fibers C) and component B), the ratio of glass fibers C) to component B) being from 1:100 to 1:2, preferably from 1:10 to 1:3.

Fibrous fillers can be surface pretreated with silane compounds to improve compatibility with thermoplastics.

Suitable silane compounds have the formula:

(X-(CH2) _n ) _k -Si-(OC _m H2 _m+1 ) _4-k

in:

X is NH ₂ -, HO-,

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

m is an integer of 1-5, preferably 1-2, and

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

Preferred silane compounds are aminopropyltrimethoxysilane, aminobutyltrimethoxysilane, aminopropyltriethoxysilane and aminobutyltriethoxysilane, as well as the corresponding silane.

The amount of silane compound used for the surface coating is usually 0.05-5% by weight, preferably 0.5-1.5% by weight, especially 0.8-1% by weight (based on C).

Acicular mineral fillers are also suitable.

For the purposes of the present invention, acicular mineral fillers are mineral fillers which have a strongly developed acicular character. An example is acicular wollastonite. The mineral preferably has an L/D (length to diameter) ratio of 8:1 to 35:1, preferably 8:1 to 11:1. The mineral fillers can, if desired, be pretreated with the abovementioned silane compounds, but pretreatment is not essential.

Other fillers that may be mentioned are kaolin, calcined kaolin, wollastonite, talc and chalk.

The thermoplastic molding compositions according to the invention may contain, as component C), customary processing aids, such as stabilizers, oxidation inhibitors, agents against thermal and UV decomposition, lubricants and mold release agents, colorants such as dyes and Pigments, nucleating agents, plasticizers, etc.

Examples of oxidation inhibitors and thermal stabilizers that may be mentioned are hindered phenols and/or phosphites, hydroquinones, secondary aromatic amines such as diphenylamine, various substituted members of these groups and mixtures thereof, based on thermoplastic The concentration of these substances is up to 1% by weight of the molding composition.

UV stabilizers which may be mentioned are various substituted resorcinols, salicylates, benzotriazoles and benzophenones, which are generally used in amounts of up to 2% by weight, based on the molding composition.

Colorants that can be added are inorganic pigments such as titanium dioxide, ultramarine blue, iron oxide, and carbon black, and organic pigments such as phthalocyanine, quinacridone-based pigments, and perylene-based pigments, and dyes such as nigrosine and anthraquinone.

Nucleating agents which can be used are sodium phenylphosphinate, aluminum oxide, silica, preferably talc.

Other lubricants and release agents are generally used in amounts of up to 1% by weight. Preference is given to long-chain fatty acids (such as stearic acid or behenic acid), their salts (such as calcium stearate or zinc stearate), or montan waxes (of long-chain saturated carboxylic acids with a chain length of 28-32 carbon atoms). mixture), or calcium montanate or sodium montanate, or low molecular weight polyethylene wax or low molecular weight polypropylene wax.

Examples of plasticizers that may be mentioned are dioctyl phthalate, dibenzyl phthalate, butylbenzyl phthalate, hydrocarbon oils and N-(n-butyl)benzenesulfonamide.

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

Examples of such polymers are polytetrafluoroethylene (PTFE), tetrafluoroethylene-hexafluoropropylene copolymers and copolymers of tetrafluoroethylene with minor proportions (usually up to 50% by weight) of copolymerizable ethylenically unsaturated monomers thing. These substances are described, for example, in "Vinyl and Related Polymers" by Schildknecht, Wiley-Verlag, 1952, pp. 484-494 and "Fluoropolymers" by Wall (Wiley Interscience, 1972).

These fluorine-containing vinyl polymers are homogeneously distributed in the molding composition and preferably have a particle size d ₅₀ (number average) of 0.05-10 μm, especially 0.1-5 μm. These small particle sizes can be obtained with particular preference by using aqueous dispersions of fluoroethylene polymers and incorporating them into polyester melts.

The thermoplastic molding compositions of the invention can be prepared by methods known per se by mixing the starting components into customary mixing equipment such as screw extruders, Brabender mixers or Banbury mixers and subsequently extruding them. The extrudate can be cooled and comminuted. It is also possible to premix the individual components and then add them separately to the remaining raw materials and/or likewise in the form of a mixture. The mixing temperature is usually 230-290°C.

In a further preferred method of operation, components B), and if appropriate C), can be mixed, compounded and pelletized with polyester prepolymers. The resulting pellets are then concentrated in the solid phase continuously or batchwise under an inert gas at a temperature below the melting point of component A) until the desired viscosity is reached.

The thermoplastic molding compositions according to the invention are characterized by good flow properties together with good mechanical properties.

In particular, the processing of the individual components (without agglomeration or agglomeration) is trouble-free and can be carried out in short cycle times, allowing in particular applications as thin-walled components.

Investigate the morphology of the selected composites using transmission electron microscopy. It was observed that the particles dispersed well in the blend. The particle size was found to be 20-500 nm.

These materials are suitable for the production of fibers, films and moldings of any kind, especially as stoppers, switches, box parts, box lids, headlight bezels, spray heads, fittings, irons, rotary switches, oven controls, fryers Applications for pot lids, door handles, (back) mirror housings, tailgate glass wipers and optical conductor housings.

Example

Component A:

Polybutylene terephthalate (polybutylene terephthalate) with a viscosity value VN of 130 mL/g and a carboxyl end group content of 34 meq/kg at 25°C B 4520 from BASF AG) (VN is measured in a solution of phenol/o-dichlorobenzene (1:1 mixture) at a concentration of 0.5% by weight), based on 100% by weight of A), which contains 0.65% by weight of pentaerythritol tetra Stearate (component C1).

Instructions for the preparation of polycarbonate B1:

General Operating Instructions:

As shown in Table 1, equimolar amounts of polyol and diethyl carbonate were mixed in a three-necked flask equipped with a stirrer, reflux condenser, and built-in thermometer, and 250 ppm catalyst (based on the amount of alcohol) was added. The mixture was subsequently heated with stirring to 100° C., in the experiments marked with * to 140° C., and stirred at this temperature for 2 hours. As the reaction proceeds, evaporative cooling caused by the liberated monoalcohol lowers the temperature of the reaction mixture. Now, replacing the reflux condenser with a tilting condenser, the ethanol was removed by distillation and the temperature of the reaction mixture was slowly raised to 160°C.

The ethanol that was distilled off was collected in a cooled round bottom flask and weighed, from which the conversion was determined, based on the theoretically possible percentage of complete conversion (see Table 1).

The reaction products were then analyzed by gel permeation chromatography with dimethylacetamide as the eluent and polymethylmethacrylate (PMMA) as the standard.

Table 1:

Based on complete conversion Molecular weight

Ethanol Distillate _Mw Viscosity 23° OH Value

Amount of alcohol catalyst [mol%] M _n [mPas] [mg KOH/g]

TMP×1.2PO K ₂ CO ₃ 90 1836 7150 455

                                                             

Component B2):

Table 2:

monomer Mn(g/mol) Mw(g/mol) OH value (mg KOH/g) Acid value (mg KOH/g) Viscosity, 23℃[mPas] B2/1 Terephthalic acid and glycerin 900 2390 416 0 2500

B2/2 Adipic acid and glycerin 1730 2580 295 167 4020

Preparation of B2/1:

4201购得的二正丁基氧化锡，借助油浴将该混合物加热至内部温度为140℃。为了除去反应期间形成的水，使用50毫巴的减压。使反应混合物在所述温度和所述压力下保持34小时。然后将混合物冷却至室温，得到1750g透明的、高粘度液体形式的超支化聚酯。分析数据在上述表2中给出。1589 g (8.19 mol) of dimethyl terephthalate and 628 g (6.38 mol) of glycerol were formed in a 5 L glass flask equipped with a stirrer, built-in thermometer, gas inlet tube, reflux condenser, and vacuum equipment connected to a cold trap. material. Add 4.4g to

4201 commercially available di-n-butyltin oxide, and the mixture was heated to an internal temperature of 140°C by means of an oil bath. To remove the water formed during the reaction, a reduced pressure of 50 mbar was used. The reaction mixture was maintained at said temperature and said pressure for 34 hours. The mixture was then cooled to room temperature, yielding 1750 g of the hyperbranched polyester in the form of a clear, highly viscous liquid. The analytical data are given in Table 2 above.

Preparation of B2/2:

2016 g (13.8 mol) of adipic acid and 1059 g (11.51 mol) of glycerol were used to form an initial charge in a 5 L glass flask equipped with a stirrer, built-in thermometer, gas inlet tube, reflux condenser and vacuum connected to a cold trap. Add 3.04g to 4201 commercially available di-n-butyltin oxide, the mixture was heated to an internal temperature of 125°C by means of an oil bath. To remove the water formed during the reaction, a reduced pressure of 100 mbar was applied. The reaction mixture was maintained at the temperature and pressure for 11 hours. The mixture was then cooled to room temperature, yielding 2645 g of the hyperbranched polyester in the form of a clear, highly viscous liquid. The analytical data are given in Table 2 above.

Preparation of the molding composition:

Components A) to C) were blended in a twin-screw extruder at 250-260°C and extruded into a water bath. After the material was pelletized and dried, test samples were injection molded and tested.

According to ISO 527-2, pellets were injection molded to obtain dumbbell-shaped samples and subjected to tensile testing. Impact toughness was also determined according to ISO 179-2, viscosity (PBT solvent according to DIN 53728: phenol/1,2-dichlorobenzene (1:1) ISO 1628), MVR (ISO 1133) and flow properties were also determined.

Table 3 presents the compositions of the present invention and their test results.

table 3:

Components [weight%] Example 1C Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 A+C 100.00 99.00 99.00 98.50 98.50 98.50 98.50 B1 0.50 0.50 1.00 1.00 0.50 0.50 B2/1 0.50 0.50 1.00 B2/2 0.50 0.50 1.00

VN, ISO 1628 118 117 112.6 113.7 103.7 109.6 107.1 MVR(275℃; 2.16kg)ISO 1133 67.1 119 122 177 173 136 147

Mechanical behavior

Maximum tensile stress (N/mm) ISO 527-2 58.26 59.7 59.6 60.3 59.6 59.7 59.8 Tensile stress at break (N/mm)ISO 527-2 25.7 47.8 47.6 55.6 50.7 48.4 48.7

Tensile strain at yield (%)ISO 527-2 3.7 3.8 3.8 3.9 3.9 3.8 3.8 Elastic modulus (N/mm) ISO527-2 2570 2585 2597 2611 2583 2589 2605 Impact resistance, -30℃, ISO179-2 140 123 167 116 88.3 115 149 Notched impact resistance, ISO179-2 3.8 3.3 3.3 3.1 3.2 3.3 3.2

Swirl flow 260/80℃-2mm(mm) 33 48 46 56 55 48 52

Claims (14)

1. A thermoplastic molding composition comprising: A) 10 to 99.99% by weight of at least one thermoplastic polyester, B) 0.01 to 50% by weight of a mixture consisting of: B1) at least one highly branched or hyperbranched polycarbonate having an OH number according to DIN 53240 part 2 of 1-600 mg KOH/g polycarbonate, and B2) at least one highly branched or hyperbranched polyester of type A _x B _y , wherein x is at least 1.1 and y is at least 2.1, and C) 0 to 60% by weight of other additives, Wherein the sum of the weight percentages of components A) to C) is 100%. 2. The thermoplastic molding composition as claimed in claim 1, wherein component B1) has a number-average molar mass _Mn of 100 to 15000 g/mol. 3. The thermoplastic molding composition as claimed in claim 1 or 2, wherein component B1) has a glass transition temperature Tg of -80°C to 140°C. 4. The thermoplastic molding composition as claimed in claim 1 or 2, wherein component B1) has a viscosity according to DIN 53019 of 50-200000 mPas at 23°C. 5. The thermoplastic molding composition as claimed in claim 1 or 2, wherein component B1) is obtained by a process comprising at least the following steps: a) reacting at least one organic carbonate (A) of the general formula RO[(CO)] _n OR with at least one aliphatic, aliphatic/aromatic or aromatic alcohol (B) having at least three OH, Simultaneous elimination of the alcohol ROH yields one or more condensation products (K), wherein each R independently of the other groups is a straight-chain or branched aliphatic, aromatic/aliphatic or Aromatic hydrocarbon group, and wherein the group R can also bond with each other to form a ring, and n is an integer of 1-5, or ab) reacting phosgene, diphosgene or triphosgene with the aforementioned alcohol (B) with simultaneous elimination of hydrogen chloride, b) subjecting the condensation product (K) to an intermolecular reaction to form a high-functionality hyperbranched polycarbonate or a high-functionality hyperbranched polycarbonate, wherein the ratio of the amount of OH groups to carbonates in the reaction mixture is chosen such that the condensation product (K) has on average one carbonate group and more than one OH group or one OH group and more than one carbonate group. 6. The thermoplastic molding composition as claimed in claim 1 or 2, wherein the number-average molar mass M _n of component B2) is 300 to 30 000 g/mol. 7. The thermoplastic molding composition as claimed in claim 1 or 2, wherein component B2) has a glass transition temperature Tg of -50 to 140°C. 8. The thermoplastic molding composition as claimed in claim 1 or 2, wherein component B2) has an OH number according to DIN 53240 of 0 to 600 mg KOH/g polyester. 9. The thermoplastic molding composition as claimed in claim 1 or 2, wherein component B2) has a COOH value according to DIN 53240 of 0 to 600 mg KOH/g polyester. 10. The thermoplastic molding composition as claimed in claim 1 or 2, wherein component B2) has at least one OH or COOH value greater than zero. 11. The thermoplastic molding composition as claimed in claim 1 or 2, wherein component B2) consists of: (a) one or more dicarboxylic acids, or one or more derivatives thereof, and one or more at least trihydric alcohols, wherein the derivatives are related anhydrides, mono- or dialkyl esters, mono- and divinyl esters and mixed esters, or (b) one or more tricarboxylic acids or higher polycarboxylic acids, or one or more derivatives thereof and one or more diols, wherein the derivatives are the relevant anhydrides in monomeric or polymeric form, Mono-, di- or trialkyl esters, mono-, di- or trivinyl esters and mixed methyl ethyl esters, obtained. 12. The thermoplastic molding composition as claimed in claim 1 or 2, wherein the ratio of components B1):B2) is from 1:20 to 20:1. 13. Use of a thermoplastic molding composition as claimed in any one of claims 1 to 12 in the production of fibers, foils or moldings of any type. 14. Fibers, foils or moldings of any type obtained from a thermoplastic molding composition as claimed in any one of claims 1-12.