CN1989205B

CN1989205B - a mixture of hyper-branched polycarbonate and hyper-branched polyester as additive of polyester molding composition

Info

Publication number: CN1989205B
Application number: CN2005800244471A
Authority: CN
Inventors: A·艾佩尔; B·布鲁赫曼; C·魏斯; J-F·斯顿伯
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2004-07-19
Filing date: 2005-07-14
Publication date: 2011-04-20
Anticipated expiration: 2025-07-14
Also published as: DE102004034835A1; CN1989205A

Abstract

Disclosed are thermoplastic molding materials containing A) 10 to 99.99 wt. % of at least one thermoplastic polyester, B) 0.01 to 50 wt. % of a mixture of B1) at least one highly branched or hyperbranched polycarbonate having a hydroxyl number of 1 to 600 mg KOH/g of polycarbonate (according to DIN 53240, part 2), and B2) a highly branched or hyperbranched polyester of type AxBy, wherein x is at least 1.1 and y is at least 2.1, and C) 0 to 60 wt. % of other additives, the sum of the percentages by weight of components A) to C) amounting to 100 percent.

Description

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

The present invention relates to thermoplastic molding compositions comprising:

A)10 to 99.99 wt.% 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 of from 1 to 600mg KOH/g of polycarbonate (according to DIN53240, second part), and

B2) at least one A_xB_yType highly branched or hyperbranched polyester 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 percentages by weight of components A) to C) is 100%.

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

Polycarbonates are generally obtained by reaction of alcohols with phosgene or by transesterification of alcohols or phenols with dialkyl or diaryl carbonates. Aromatic polycarbonates are of industrial importance, they are prepared, for example, from bisphenols, while the effect hitherto exerted by aliphatic polycarbonates has been of secondary importance in terms of market capacity. See also Becker/Braun, Kunststoff-Handbuch, Vol. 3/1, polycarbonate, polyacetal, polyester, cellulose ester, 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 having a molecular weight above 15000 dalton as plasticisers for polyethylene polymers.

To improve the flowability, low molecular weight additives are usually added to thermoplastics. However, the action of these additives is severely limited, since, for example, when the additive amount is increased, the decrease in mechanical properties becomes unacceptable.

Dendrimers called dendrimers with a perfectly symmetrical structure can be prepared starting from one central molecule, in each case by controlled stepwise attachment of two or more bi-or polyfunctional monomers to each monomer previously bonded. Here, each linking step increases the number of monomer end groups (and hence the number of linkages) exponentially, and this gives the polymer a dendritic structure, the branches of which, in the ideal case of spheres, comprise exactly the same number of monomer units. This perfect structure provides advantageous polymer properties, for example, it was found that its viscosity is surprisingly low, and also highly reactive due to the large number of functional groups on the sphere surface. However, dendrimers can generally only be prepared on a laboratory scale due to the necessity of introducing and removing protecting groups during each attachment step, and the need for purification operations, which complicate the preparation process.

However, highly branched or hyperbranched polymers can be prepared using industrial processes. They also have linear polymer chains and irregular polymer branches along a perfect dendritic structure, but this does not substantially impair the properties of the polymer compared to perfect dendrimers. Hyperbranched polymers may be referred to by the two as AB₂And A_x+B_yThe synthetic route of (1). Where A is_xAnd B_yFor different monomers, subscripts x and y are the number of functional groups present in A and B, respectively, i.e., the functionality of each of A and B. At AB₂In the route, trifunctional monomers having one reactive group A and two reactive groups B are reacted to give highly branched or hyperbranched polymers. In A_x+B_yIn the synthesis, the compound is represented by A₂+B₃Synthesis example bifunctional monomer A₂With trifunctional monomers B₃And (4) reacting. This firstly gives a 1: 1 adduct consisting of A and B, which on average has one functional group A and two functional groups B, which can then be reacted analogously to give highly branched or hyperbranched polymers.

Until recently, high functionality polycarbonates of defined structure have not been disclosed.

S.p. rannard and n.j.davis, j.am. chem.soc.2000, 122, 11729 describe the preparation of dendritic polycarbonates with perfect branching by reaction with bis-hydroxyethylamino-2-propanol using carbonyl bis-imidazole as the phosgene analogue. The synthesis method which provides perfect dendrons is a multistage synthesis method, so that the cost is high, and the method is not very suitable for conversion to an industrial scale.

D.h. bolton and k.l. wooley, Macromolecules 1997, 30, 1890 describe the preparation of high molecular weight, very rigid hyperbranched aromatic polycarbonates via the reaction of 1, 1, 1-tris (4' -hydroxyphenyl) ethane with carbonyldiimidazole.

Hyperbranched polycarbonates can also be prepared according to WO 98/50453. In the process described in the specification, the triol is reacted again with carbonyldiimidazole. Imidazolium (imidazolide) is initially produced, which is subsequently subjected to further intermolecular reactions to give polycarbonates. In the process mentioned, the polycarbonate is formed as a colorless or pale yellow rubbery product.

The mentioned synthesis processes to obtain highly branched or hyperbranched polycarbonates have the following disadvantages:

a) hyperbranched products have a high melting point or are rubbery, which significantly limits the subsequent processability.

b) The imidazole released during the reaction has to be removed from the reaction mixture by a complicated process.

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

d) Carbonyldiimidazole is a relatively expensive chemical, which adds significantly to the cost of the raw materials.

DE 102004005652.8 and DE 102004005657.9 have proposed novel flow improvers for polyesters.

It is an object of the present invention to provide thermoplastic polyester molding compositions having good flowability together with good mechanical properties.

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

The molding compositions of the invention comprise, as component (A), from 10 to 99.99% by weight, preferably from 30 to 99.5% by weight, in particular from 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 having from 2 to 10 carbon atoms in the alcohol moiety.

Polyalkylene terephthalates of this type are known per se and have been described in the literature. The main chain of which comprises aromatic rings derived from aromatic dicarboxylic acids. The aromatic rings may also be substituted, for example, by halogen, e.g. chlorine or bromine, or by C₁-C₄Alkyl is substituted by methyl, ethyl, iso-or n-propyl or n-, iso-or tert-butyl.

These polyalkylene terephthalates may 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-naphthalenedicarboxylic acid, terephthalic acid and isophthalic acid, and mixtures thereof. Up to 30 mol%, preferably not more than 10 mol%, of the aromatic dicarboxylic acids may be replaced by aliphatic or cycloaliphatic dicarboxylic acids, for example by adipic acid, azelaic acid, sebacic acid, dodecanedioic acids and cyclohexanedicarboxylic acids.

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

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

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

Particular preference is given to polyesters in which the carboxyl end group content is up to 100mval/kg of polyester, preferably up to 50mval/kg of polyester and in particular up to 40mval/kg of polyester. Polyesters of this type can be prepared, for example, by the process of DE-A4401055. The carboxyl end group content is generally determined by titration methods, such as potentiometry.

Particularly preferred molding compositions comprise, as component A), polyester mixtures which are different from PBT, for example polyethylene terephthalate (PET). For example, the proportion of polyethylene terephthalate in the mixture is preferably up to 50% by weight, in particular from 10 to 35% by weight, based on 100% by weight of A).

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

The recycled material is typically:

1) those known as post-production recycled materials: they are production waste during polycondensation or processing, for example slag from injection molding, raw materials from injection molding or extrusion, or scrap from extruded sheets or films.

2) Post-consumer recycled material: they are plastic articles 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 subject in terms of quantity.

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

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

Since polyesters undergo hydrolytic cleavage during processing (due to the presence of trace amounts of moisture), it is advisable to predry the recovered material. The residual moisture content after drying is preferably < 0.2%, in particular < 0.05%.

Another group which should be mentioned is the wholly aromatic polyesters derived from aromatic dicarboxylic acids and aromatic dihydroxy compounds.

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

The aromatic dihydroxy compound preferably has the formula:

wherein Z is alkylene or cycloalkylene having up to 8 carbon atoms, arylene having up to 12 carbon atoms, carbonyl, sulfonyl, oxygen or sulfur, or a bond, and m is 0-2. The phenylene radicals of the compounds may also be substituted by C₁-C₆Alkyl or alkoxy and fluoro, chloro or bromo.

Examples of parent compounds of these compounds are:

dihydroxybiphenyl,

Bis (hydroxyphenyl) alkanes,

Bis (hydroxyphenyl) cycloalkanes,

Bis (hydroxyphenyl) sulfide,

Bis (hydroxyphenyl) ether,

Bis (hydroxyphenyl) ketones,

Bis (hydroxyphenyl) sulfoxides,

Alpha, alpha' -bis (hydroxyphenyl) dialkylbenzene,

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

Resorcinol, and

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

Among them, preferred are:

4, 4' -dihydroxybiphenyl is substituted by a substituent,

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

alpha, alpha' -bis (4-hydroxyphenyl) p-diisopropylbenzene,

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

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

in particular

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

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

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

3, 4 '-dihydroxy-benzophenone is synthesized by the reaction of 3, 4' -dihydroxy-benzophenone,

4, 4' -dihydroxydiphenyl sulfone, 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 comprise from 20 to 98% by weight of polyalkylene terephthalate and from 2 to 80% by weight of wholly aromatic polyester.

Of course, polyester block copolymers, such as copolyetheresters, can also be used. Such products are known per se and are described in the literature, for example in US-A3651014. Corresponding products are also commercially available, for example

(DuPont)。

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

wherein Q is a single bond, C₁-C₈Alkylene radical, C₂-C₃Alkylene (alkylene), C₃-C₆Cycloalkylene (cycloalkylidene), C₆-C₁₂Arylene radicals or-O-, -S-or-SO₂-, and m is an integer of 0 to 2.

The phenylene radicals of the bisphenols may also have, for example, C₁-C₆Alkyl or C₁-C₆A substituent of an alkoxy group.

Examples of preferred bisphenols of the above formula are hydroquinone, resorcinol, 4' -dihydroxybiphenyl, 2-bis (4-hydroxyphenyl) propane, 2, 4-bis (4-hydroxyphenyl) -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 as well as 1, 1-bis (4-hydroxyphenyl) -3, 3, 5-trimethylcyclohexane.

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

Suitable polycarbonates may be branched in a known manner, in particular by incorporating from 0.05 to 2.0 mol%, based on the total amount of diphenols used, of at least trifunctional compounds, for example those containing three or more phenolic OH groups.

Polycarbonates which have proven particularly suitable have a relative viscosity η_relFrom 1.10 to 1.50, in particular from 1.25 to 1.40. This corresponds to the average molarMolar mass M_w(weight average) is 10000-.

The diphenols of the general formula are known per se or can be prepared by known processes.

For example, polycarbonates can be prepared by reacting bisphenols with phosgene in the interfacial process or with phosgene in the homogeneous-phase process (known as the pyridine process), and the desired molecular weight can in each case be achieved in a known manner by using suitable amounts of known chain terminators. (for polydiorganosiloxanone-containing polycarbonates see, for example, DE-A3334782.)

Examples of suitable chain terminators are phenol, p-tert-butylphenol or long-chain alkylphenols, such as 4- (1, 3-tetramethylbutyl) phenol in DE-A2842005, or monoalkylphenols or dialkylphenols having a total number of carbon atoms in the alkyl substituents of from 8 to 20, 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, as in DE-A-3506472.

Halogen-free polycarbonates are, for the purposes of the present invention, polycarbonates composed of halogen-free bisphenols, halogen-free chain terminators and, if used, halogen-free branching agents, where small amounts of ppm amounts of hydrolyzable chlorine, for example obtained in the preparation of polycarbonates in an interfacial process using phosgene, are not regarded as a term "halogen-containing" for the purposes of the present invention. For the purposes of the present invention, polycarbonates of this type which have a hydrolyzable chlorine content at the ppm level are halogen-free polycarbonates.

Other suitable combinations A) which may be mentioned are amorphous polyester carbonates, phosgene being replaced by aromatic dicarboxylic acid units, for example isophthalic acid and/or terephthalic acid units, during the preparation. For further details in this connection, reference is made to EP-A711810.

EP-A365916 describes other suitable copolycarbonates having cycloalkyl groups as monomer units.

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

And (4) obtaining.

As component B), the inventive molding compositions comprise from 0.01 to 50% by weight, preferably from 0.5 to 20% by weight, in particular from 0.7 to 10% by weight, of a highly branched or hyperbranched polycarbonate having an OH number (according to DIN53240 part 2) of from 1 to 600mg KOH/g of polycarbonate, preferably from 10 to 550mg KOH/g of polycarbonate, in particular from 50 to 550mg KOH/g of 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 inhomogeneities. First, their structure is based on a central molecule in the same way as dendrimers, but the chain length of the branches is not uniform. Secondly, they may also have a linear structure with functional side groups, or they may combine both extremes, having linear and branched molecular moieties. 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" means that the Degree of Branching (DB), i.e. the average number of dendritic linkages plus the average number of terminal groups per molecule, is from 10 to 99.9%, preferably from 20 to 99%, particularly preferably from 20 to 95%.

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

(wherein T is the average number of terminal monomeric units in the macromolecule of each species, Z is the average number of branching monomeric units therein, and L is the average number of linear monomeric units therein).

Component B1) preferably has a number-average molar mass M_n100-15000g/mol, preferably 200-12000g/mol, in particular 500-10000g/mol (GPC, PMMA standard).

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

In particular, the viscosity (mPas) at 23 ℃ in accordance with DIN 53019 is 50 to 200000, in particular 100-.

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

a) reacting at least one compound of the formula RO [ (CO)]_nThe organic carbonates (A) of OR are reacted with at least one aliphatic, aliphatic/aromatic OR aromatic alcohol (B) having at least three OH groups with simultaneous elimination of the alcohol ROH to give one OR more condensation products (K), where each R, independently of the other radicals, is a linear OR branched aliphatic, aromatic/aliphatic OR aromatic hydrocarbon radical having from 1 to 20 carbon atoms, and where the radicals R may also be bonded to one another to form a ring, and n is an integer from 1 to 5, OR

ab) reacting phosgene, diphosgene or triphosgene with the abovementioned alcohols (B) with elimination of hydrogen chloride,

b) subjecting the condensation product (K) to an intermolecular reaction to form a highly functional highly branched polycarbonate or a highly functional hyperbranched polycarbonate,

wherein the ratio of OH groups to the amount of carbonate in the reaction mixture is selected 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 organic carbonates are preferably used.

Used as a starting material and having the general formula RO (CO)_nEach R group in the organic carbonate (a) of OR is independently a linear OR branched aliphatic, aromatic/aliphatic OR aromatic hydrocarbon group having 1 to 20 carbon atoms. Two R groups may also be bonded to each other to form a ring. The radical is preferably an aliphatic hydrocarbon radical, particularly preferably a linear or branched alkyl radical having from 1 to 5 carbon atoms, or a substituted or unsubstituted phenyl radical.

In particular, the general formula RO (CO)_nSimple carbonates of OR; n is preferably from 1 to 3, in particular 1.

For example, dialkyl or diaryl carbonates may be prepared from the reaction of aliphatic, araliphatic or aromatic alcohols, preferably monoalcohols, with phosgene. They may also be obtained by reacting noble metals, oxygen or NO_xBy oxidative carbonylation of alcohols or phenols with the aid of CO in the presence of a catalyst. Reference may also be made to "Ullmann's Encyclopedia of Industrial chemistry", 6 th edition, 2000 electronic edition, Verlag Wiley-VCH for the preparation of dialkyl 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, ditolyl carbonate, bis (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 didodecyl carbonate.

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

Preference is given to using aliphatic carbonates, in particular those in which the radicals contain from 1 to 5 carbon atoms, such as dimethyl carbonate, diethyl carbonate, dipropyl carbonate, dibutyl carbonate or diisobutyl carbonate.

Reacting an organic carbonate 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 (hydroxymethyl) amine, tris (hydroxyethyl) amine, tris (hydroxypropyl) amine, pentaerythritol, diglycerol, triglycerol, polyglycerol, bis (trimethylolpropane), tris (hydroxymethyl) isocyanurate, tris (hydroxyethyl) isocyanurate, phloroglucides, trihydroxybenzene, trihydroxytoluene, trihydroxydimethylbenzene, phenyloglucides, hexahydroxybenzene, 1, 3, 5-benzenetriol, 1, 1, 1-tris (4 '-hydroxyphenyl) methane, 1, 1, 1-tris (4' -hydroxyphenyl) ethane, or saccharides such as glucose, ternary or higher polyols based on ternary or higher polyols and ethylene oxide, propylene oxide or butylene oxide, or polyesterols. Particular preference is given to glycerol, trimethylolethane, trimethylolpropane, 1, 2, 4-butanetriol and pentaerythritol and also their polyetherols based on ethylene oxide or propylene oxide.

These polyols may also be used in admixture with diols (B'), provided that the average total OH functionality of all the 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-dihydroxyphenyl) 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, dihydroxybenzophenone, dihydric polyether alcohols based on ethylene oxide, propylene oxide, butylene oxide or mixtures thereof, polytetrahydrofuran, polycaprolactone or polyester alcohols based on diols and dicarboxylic acids.

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

The reaction of phosgene, diphosgene or triphosgene with the alcohol or mixture of alcohols is generally carried out with elimination of hydrogen chloride, and the reaction of the carbonate with the alcohol or mixture of alcohols to form the high-functionality, highly branched polycarbonates of the invention is generally carried out with elimination of monofunctional alcohols or phenols from the carbonate molecules.

After the reaction, the highly functional highly branched polycarbonates formed by the process of the invention have hydroxyl and/or carbonate group end caps, i.e. are not further modified. They have good solubility in various solvents, for example water, alcohols such as methanol, ethanol, butanol, alcohol/water mixtures, acetone, 2-butanone, ethyl acetate, butyl acetate, methoxypropyl acetate, 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 which, in addition to the carbonate groups forming the polymer backbone, also have at least 3, preferably at least 6, more preferably at least 10, terminal or lateral functional groups. The functional groups are carbonate groups or and/or OH groups. There is in principle no upper limit to the number of terminal or pendant functional groups, but products with a very high number of functional groups may have undesirable properties, such as high viscosity or poor solubility. The high functionality polycarbonates of the present invention have generally no more than 500 terminal or pendant functional groups, preferably no more than 100 terminal or pendant functional groups.

When preparing high-functionality polycarbonates B1), the ratio of OH-group-containing compounds to phosgene or carbonic acid ester has to be adjusted such that the simplest resulting condensation product (referred to below as condensation product (K)) contains on average one carbonate group or carbamoyl group and more than one OH group or 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) leads to the arrangement XY_nOr Y_nX, where X is a carbonate group, Y is a hydroxyl group and n is generally a number from 1 to 6, preferably from 1 to 4, particularly preferably from 1 to 3. At this time, the only resulting reactive group is hereinafter generally referred to as a "focal group".

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

in the preparation of the condensation product (K) from a carbonate and a triol in a reaction ratio of 1: 1, the average result is XY of the formula 2₂A type molecule. The focal group in this case is a carbonate group.

In the preparation of the condensation products (K) from carbonates and tetrahydric alcohols likewise in a reaction ratio of 1: 1, the average result is XY of the formula 3₃A type molecule. The focal group in this case is a carbonate group.

In the formulae 1 to 3, R is as defined at the outset, and R¹Is an aliphatic or aromatic radical. The condensation products (K) can also be prepared, for example, as shown in formula 4 from carbonates and trihydric alcohols in a molar ratio of 2: 1. When the average result is X₂Y-type molecule and focal group is OH group. In formula 4, R and R¹As defined in formulas 1-3.

If difunctional compounds, such as dicarbonates or diols, are also added to the components, the result is, for example, an extension of the chain as shown in formula 5. The average result is also XY₂A type molecule wherein the focal group is a carbonate group.

In formula 5, R²Is an organic radical, preferably an aliphatic radical, and R¹As defined above.

Two or more condensation products (K) can also be used for the synthesis. In this case, two or more alcohols or two or more carbonates may be used first. Furthermore, by selecting the proportions of alcohol and carbonate or phosgene used, it is possible to obtain mixtures of various condensation products having different structures. This may be exemplified by the reaction of a carbonate with a diol. If the starting products are reacted in a ratio of 1: 1 as Indicated In (II), XY is obtained₂A molecule. If the starting products are reacted in a ratio of 2: 1 as shown In (IV), X is obtained₂And Y molecule. If the ratio is from 1: 1 to 2: 1, XY is obtained₂Molecule and X₂A mixture of Y molecules.

According to the invention, simple condensation products (K), for example of the formulae 1 to 5, preferably undergo intermolecular reactions to form high-functionality polycondensation products, referred to below as polycondensation products (P). The reaction to give the condensation product (K) and the polycondensation product (P) is generally carried out at a temperature of from 0 to 250 ℃ and preferably from 60 to 160 ℃ in the absence of solvents or in solution. In this case, any solvent inert to the respective starting materials can generally be used. 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 a solvent. The phenol or monohydric alcohol ROH liberated during the reaction can be removed from the reaction equilibrium by distillation, if appropriate under reduced pressure, to accelerate the reaction.

If distillative removal is carried out, it is generally advantageous to use those carbonates which liberate alcohols ROH having a boiling point of less than 140 ℃ during the reaction.

To accelerate the reaction, a catalyst or a mixture of catalysts may also be added. Suitable catalysts are compounds which catalyze esterification or transesterification reactions, such as alkali metal hydroxides, alkali metal carbonates, alkali metal hydrogencarbonates, preferably sodium, potassium or cesium salts, tertiary amines, guanidines, ammonium compounds, phosphonium compounds, organoaluminum, organotin, organozinc, organotitanium, organozirconium or organobismuth compounds, and also the so-called Double Metal Cyanide (DMC) catalysts, which are described, for example, in DE 10138216 or DE 10147712.

Preference is given to using potassium hydroxide, potassium carbonate, potassium hydrogencarbonate, 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 amount of catalyst added is generally from 50 to 10000ppm by weight, preferably 100 to 5000ppm by weight, based on the amount of alcohol or alcohol mixture used.

The intermolecular polycondensation reaction can also be controlled by adding a suitable catalyst or by selecting a suitable temperature. The average molecular weight of the polymer (P) can furthermore be adjusted by means of the composition of the starting components and the residence time.

The condensation products (K) and polycondensation products (P) prepared at elevated temperatures are generally stable at room temperature for a relatively long period of time.

The nature of the condensation products (K) allows polycondensation products (P) having different structures to be obtained from the condensation reaction, which are branched but not crosslinked. Furthermore, it is desirable for the polycondensation product (P) to have one carbonate group as focal group and more than two OH groups or to have 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 product (K) used and the degree of polycondensation.

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

In formulae 6 and 7, R and R¹As defined above.

To terminate the intermolecular polycondensation reaction, various means can be employed. For example, the temperature can be lowered to a range in which the reaction is stopped and the product (K) or polycondensation product (P) is storage-stable.

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

In another embodiment, once the intermolecular reaction of the condensation product (K) produces a polycondensation product (P) having the desired degree of polycondensation, the reaction can be terminated by adding a product having a group reactive with the focal group of (P) to the product (P). For example, in the case of carbonates as focal groups, monoamines, diamines or polyamines may be added. In the case of hydroxyl groups as focal groups, it is possible, for example, to add to the product (P) mono-, di-or polyisocyanates reactive toward OH groups, compounds containing epoxide groups or acid derivatives.

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

By adjusting the reaction conditions described above and, if appropriate, by selecting a suitable solvent, the products of the invention can be processed further without further purification after preparation.

In another preferred embodiment, the product is stripped, i.e. low molecular weight volatile compounds are removed. For this purpose, once the desired degree of conversion has been reached, the catalyst may optionally be deactivated and low molecular weight volatile constituents such as monohydric alcohols, phenols, carbonates, hydrogen chloride or volatile oligomeric or cyclic compounds may be removed by distillation, if appropriate with introduction of a gas, preferably nitrogen, carbon dioxide or air, and if appropriate with distillation under reduced pressure.

In another preferred embodiment, the polycarbonates according to the invention may contain further functional groups in addition to the functional groups present at this stage by reaction. The functionalization can be carried out during the increase in molecular weight or subsequently, i.e.after the actual polycondensation has been completed.

If components having other functional units or functional groups in addition to hydroxyl groups or carbonate groups are added before or during the increase in molecular weight, polycarbonate polymers having an arbitrary distribution of functional groups in addition to carbonate groups or hydroxyl groups are obtained.

This effect can be achieved, for example, by adding compounds which, in addition to hydroxyl groups, carbonate groups or carbamoyl groups, also contain further functional groups or functional units, such as mercapto groups, primary amino groups, secondary amino groups, tertiary amino groups, ether groups, carboxylic acid derivatives, sulfonic acid derivatives, phosphonic acid derivatives, silane groups, siloxane groups, aryl groups or long-chain alkyl groups, during the polycondensation. Examples of compounds which can be used for modification by means of a carbamate group are ethanolamine, propanolamine, isopropanolamine, 2- (butylamino) ethanol, 2- (cyclohexylamino) ethanol, 2-amino-1-butanol, 2- (2' -aminoethoxy) ethanol or higher alkoxylation products of 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 a mercapto group is mercaptoethanol. For example, tertiary amino groups can be generated by the introduction of N-methyldiethanolamine, N-methyldipropanolamine or N, N-dimethylethanolamine. For example, ether groups can be generated by co-condensation of dihydric or higher polyhydric polyether alcohols. The long chain alkyl groups may be introduced by reaction with long chain alkanediols, and reaction with alkyl or aryl diisocyanates produces polycarbonates having alkyl, aryl and urethane groups or urea groups.

The ester groups can be generated by addition of dicarboxylic acids, tricarboxylic acids or, for example, dimethyl terephthalate or tricarboxylic esters.

The subsequent functionalization can be carried out by using an additional process step (step c)), in which the resulting highly functional highly branched or highly functional hyperbranched polycarbonate is reacted with a suitable functionalizing agent capable of reacting with the OH and/or carbonate groups or carbamoyl groups of the polycarbonate.

For example, highly functional highly branched or highly functional hyperbranched polycarbonates containing hydroxyl groups can be modified by the addition of molecules containing acid or isocyanate groups. For example, polycarbonates containing acid groups can be obtained by reaction with compounds containing anhydride groups.

In addition, hydroxyl group-containing high-functionality polycarbonates can also be converted into high-functionality polycarbonate polyether polyols by reaction with alkylene oxides, such as ethylene oxide, propylene oxide or butylene oxide.

One great advantage of the method of the invention is its cost effectiveness. It is not only possible to carry out the reaction to form the condensation product (K) or the polycondensation product (P) in one reactor, but also to react (K) or (P) to form polycarbonates having other functional groups or units, which has technical and cost-effective advantages.

The inventive molding compositions comprise at least one A_xB_yHyperbranched polyesters of the type B) as component B2) of the mixtures B) according to the invention, where

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, mixtures can also be used as units A and/or B.

A_xB_yType polyesters are condensation products consisting of x-functional molecules A and y-functional molecules B. For example, polyester compounds consisting of adipic acid as molecule a (x ═ 2) and glycerol as molecule B (y ═ 3) may be mentioned.

For the purposes of the present invention, hyperbranched polyesters B2) are uncrosslinked macromolecules having hydroxyl groups and carbonate groups, which have both structural and molecular inhomogeneities. 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 may also have a linear structure with functional side groups, or they may combine these two extremes, with linear and branched molecular moieties. 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" means that the Degree of Branching (DB), i.e.the average number of dendritic linkages plus the average number of terminal groups per molecule, is from 10 to 99.9%, preferably from 20 to 99%, particularly preferably from 20 to 95%.

In the context of the present invention, "dendrons" means a degree of branching of from 99.9 to 100%. See h.frey et al, Acta polym.1997, 48, 30 for a definition of "branching".

Component B2) preferably has M as determined by GPC, PMMA standard, dimethylacetamide eluate_n300-30000g/mol, especially 400-25000g/mol, very especially preferably 500-20000 g/mol.

B2) preferably has an OH number of from 0 to 600mg KOH/g of polyester, preferably from 1 to 500mg KOH/g of polyester, in particular from 20 to 500mg KOH/g of polyester, and preferably has a COOH number of from 0 to 600mg KOH/g of polyester, preferably from 1 to 500mg KOH/g of polyester, in particular from 2 to 500mg KOH/g of polyester, in accordance with DIN 53240.

The Tg is preferably from-50 ℃ to 140 ℃ and in particular from-50 ℃ to 100 ℃ (by DSC according to DIN 53765).

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

Component B2) according to the invention is obtainable in particular by a process, in particular by reacting in the presence of a solvent and optionally in the presence of an inorganic, organometallic or low molecular weight organic catalyst or an enzyme

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

or,

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

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

Among the dicarboxylic acids which can be reacted according to variant (a) are, for example, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecane-alpha, omega-dicarboxylic acid, dodecane-alpha, omega-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 dicarboxylic acids may be substituted with one or more groups selected from the group consisting of:

C₁-C₁₀alkyl groups 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,

C₃-C₁₂cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl and cyclododecyl; preferably cyclopentyl, cyclohexyl and cycloheptyl;

alkylene, e.g. methylene or ethylene, or

C₆-C₁₄Aryl radicals, such as phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl and 9-phenanthryl, preferably phenyl, 1-naphthyl and 2-naphthyl, particularly preferably phenyl.

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

Among the dicarboxylic acids which can be reacted according to variant (a) are also ethylenically unsaturated acids, such as maleic acid and fumaric acid, and aromatic dicarboxylic acids, such as phthalic acid, isophthalic acid or terephthalic acid.

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

The dicarboxylic acids themselves may be used as well as their derivative forms.

The derivatives are preferably:

-related anhydrides in monomeric or polymeric form,

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

And mono-and divinyl esters, and

mixed esters, preferably methylethyl esters.

In a preferred preparation process, it is also possible to use mixtures of dicarboxylic acids and one or more of their derivatives. 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 at least trihydric alcohols which can be reacted are: glycerol, 1, 2, 4-butanetriol, 1, 2, 5-pentanetriol, 1, 3, 5-pentanetriol, 1, 2, 6-n-hexanetriol, 1, 2, 5-n-hexanetriol, 1, 3, 6-n-hexanetriol, trimethylolbutane, trimethylolpropane or ditrimethylolpropane, trimethylolethane, pentaerythritol or dipentaerythritol; sugar alcohols, for example, erythromycinol, threitol, sorbitol, mannitol or mixtures of at least the trihydric alcohols mentioned above. Preference is given to using glycerol, trimethylolpropane, trimethylolethane and pentaerythritol.

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

Tricarboxylic acids or polycarboxylic acids may be used in the reaction according to the invention as such or in the form of derivatives.

The derivatives are preferably:

-a related anhydride in monomeric or polymeric form,

mono-, di-or trialkyl esters, preferably mono-, di-or trimethyl esters, or the corresponding mono-, di-or triethyl esters, or other mono-, di-and triesters derived from higher alcohols, such 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 present invention, it is also possible to use mixtures of tri-or polycarboxylic acids and one or more of their derivatives. For the purposes of the present 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, 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, cyclopentanediol, cyclohexanediol, inositol and derivatives, (2) -methylpentaneAlkane-2, 4-diol, 2, 4-dimethylpentane-2, 4-diol, 2-ethylhexane-1, 3-diol, 2, 5-dimethylhexane-2, 5-diol, 2, 4-trimethylpentane-1, 3-diol, pinacol, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, polyethylene glycol HO (CH)₂CH₂O)_nH or polypropylene glycol HO (CH [ CH ]₃]CH₂O)_n-H or a mixture of two or more representative of the above compounds, wherein n ═ an integer from 4 to 25. Here, one or both of the hydroxyl groups of the above-mentioned diols may also be replaced by SH groups. Preference is given to ethylene glycol, 1, 2-propylene glycol and diethylene glycol, triethylene glycol, dipropylene glycol and tripropylene glycol.

In schemes (a) and (b), in polyester A_xB_yThe molar ratio of molecules A to B in the molecule is from 4: 1 to 1: 4, in particular from 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 as a result of steric or electronic effects. This applies, for example, to the case of trimethylolpropane or pentaerythritol.

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

The different reactivity of the functional groups can be due here to chemical factors (e.g.primary/secondary/tertiary OH groups) and also to steric factors.

For example, the triol may comprise a triol having primary and secondary hydroxyl groups, a preferred example being glycerol.

When carrying out the reaction according to variant (a), it is preferred to operate in the absence of diols and monoalcohols.

When carrying out the reaction according to the invention according to variant (b), preference is given to operating 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 aromatics. Particularly suitable alkanes are n-heptane and cyclohexane. Particularly suitable aromatics are toluene, o-xylene, m-xylene, p-xylene, xylene in the form of an isomer mixture, ethylbenzene, chlorobenzene and o-and m-dichlorobenzene. Other very particularly suitable solvents when no acidic catalyst is present 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 from 1.01 to 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, since the reaction rate decreases significantly at significantly reduced 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 additive, which is added at the beginning of the reaction. Examples of suitable dehydrating agents are molecular sieves, especiallyMolecular sieve, MgSO₄And Na₂SO₄. During the reaction, it is also possible to add further dehydrating agent or to replace the dehydrating agent by fresh dehydrating agent. The water or alcohol formed can also be removed during the reaction by distillation and, for example, using a water separator.

The reaction may be carried out in the absence of an acidic catalyst. Preferably in the presence of an acidic inorganic, organometallic or organic catalyst or in the presence of a mixture consisting of two or more acidic inorganic, organometallic or organic catalysts.

For the purposes of the present invention, acidic inorganic catalystsExamples of agents are sulfuric acid, phosphoric acid, phosphonic acid, hypophosphorous acid, hydrated aluminum sulfate, alum, acidic silica gel (pH 6, especially 5), and acidic alumina. Examples of other compounds which can be used as acidic inorganic catalysts are those of the general formula Al (OR)₃And an aluminum compound of the formula Ti (OR)₄Wherein each R group may be the same or different and is independently selected from:

C₁-C₁₀alkyl groups 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.

C₃-C₁₂Cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl and cyclododecyl; cyclopentyl, cyclohexyl and cycloheptyl groups are preferred.

Al(OR)₃Or Ti (OR)₄Each R group in (a) 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, which is commercially available as "oxo-tin", or di-n-butyltin dilaurate.

Preferred acidic organic catalysts are, for example, organic compounds having a phosphate group, a sulfonic acid group, a sulfate group or a phosphonic acid group. Sulfonic acids, such as p-toluenesulfonic acid, are particularly preferred. Acidic ion exchangers can also be used as acidic organic catalysts, for example polystyrene resins which contain sulfonic acid groups and are 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, organometallic or organic catalysts are used according to the invention, the catalysts are used in amounts of from 0.1 to 10% by weight, preferably from 0.2 to 2% by weight, according to the invention.

The process of the invention is carried out in an inert gas, for example in carbon dioxide, nitrogen or noble gases, among which mention may be made in particular of argon.

The process of the invention is carried out at a temperature of from 60 to 200 ℃. Preference is given to operating at temperatures of 130 ℃ and 180 ℃ and in particular up to 150 ℃ or below. Particular preference is given to temperatures up to a maximum of 145 ℃ and very particular preference to temperatures up to 135 ℃.

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

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

Once the reaction has ended, the highly functional hyperbranched polyesters can be easily isolated, for example by removing the catalyst by filtration and concentrating the mixture, the concentration process here usually being carried out under reduced pressure. Other work-up methods with good suitability are precipitation after addition of water, followed by washing and drying.

Component B2) may also be prepared in the presence of enzymes or enzymatic breakdown products (according to DE-A10163163). For the purposes of the present invention, the term acidic organic catalyst does not include the dicarboxylic acids reacted according to the invention.

Preference is given to using lipases or esterases. Lipases and esterases with good suitability are from Candida cylindracea (Candida cylindracea), Candida lipolytica (Candida lipolytica), Candida rugosa (Candida rugosa), Candida antarctica (Candida antarctica), Candida utilis (Candida utilis), Chromobacter viscosum, Geotrichum candidum (Geotrichum candidum), Mucor javanicus (Mucor javanicus), Mucor miehei (Mucor mihei), porcine pancreas, Pseudomonas sp., Pseudomonas fluorescens (Pseudomonas fluorescens), Pseudomonas cepacia (Pseudomonas cepacia), Rhizopus rhizogenes (Rhizopus arrhizus), Rhizopus delemar (Rhizopus rhizophilus), Rhizopus delemar (Rhizopus), Rhizopus niveus (Rhizopus), Aspergillus niger (Rhizopus), Bacillus subtilis and Bacillus subtilis). Candida antarctica lipase B is particularly preferred. The listed enzymes are available, for example, from Novozymes Biotech Inc. of Denmark.

The enzyme is preferably immobilized, for example, on silica gel and

the above form is used. Methods for immobilizing enzymes are known per se, for example from Kurt Faber "transformations in organic chemistry", 3 rd edition 1997, Springer Verlag, chapter 3.2 "Immobilization", page 345-356. Immobilized enzymes are available, for example, from Novozymes Biotech inc.

The amount of immobilized enzyme is from 0.1 to 20% by weight, in particular from 10 to 15% by weight, based on the total amount of starting materials used and to be reacted.

The process of the invention is carried out at a temperature above 60 ℃. Preferably at a temperature of 100 ℃ or below 100 ℃. Preferably at a temperature of at most 80 ℃ and very particularly preferably at a temperature of from 62 to 75 ℃ and even more preferably at a temperature of from 65 to 75 ℃.

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 alkanes are n-heptane and cyclohexane. Particularly suitable aromatics are toluene, o-xylene, m-xylene, p-xylene, xylene in the form of an isomer mixture, ethylbenzene, chlorobenzene and o-and m-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 solvent is added in an amount of 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. The solvent amount of more than 10000 parts by weight is not desirable because the reaction rate is significantly decreased at a significantly decreased concentration, resulting in an uneconomically long reaction time.

The process of the invention is carried out at a pressure of 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 at pressures up to 10 bar. The reaction is preferably carried out at atmospheric pressure.

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

Once the reaction has ended, the highly functional hyperbranched polyesters can be easily isolated, for example by removing the catalyst by filtration and concentrating the mixture, the concentration process usually being carried out under reduced pressure. Other work-up methods with good suitability are precipitation after addition of water, followed by washing and drying.

The highly functional hyperbranched polyesters obtainable by the process of the invention are characterized by a particularly low content of discoloring and resinifying substances. Hyperbranched polymers are also defined in: flory, j.am.chem.soc.1952, 74, 2718 and a.sunder et al, chem.eur.j.2000, 6, No.1, 1-8. However, "highly functional hyperbranched" in the context of the present invention means that the degree of branching, i.e.the average number of dendritic linkages plus the average number of end groups per molecule, is from 10 to 99.9%, preferably from 20 to 99%, particularly preferably from 30 to 90% (see in this connection H.Frey et al, Acta Polym.1997, 48, 30).

Molar mass M of the polyesters of the invention_w500-50000g/mol, preferably 1000-20000g/mol, particularly preferably 1000-19000 g/mol. The polydispersity is from 1.2 to 50, preferably from 1.4 to 40, particularly preferably from 1.5 to 30, very particularly preferably from 1.5 to 10. They are generally readily soluble, i.e.clear solutions can be prepared using up to 50% by weight, 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 without visible gel particles.

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

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

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

Such composite materials may be

high speed was purchased.

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

The novel molding compositions may comprise, as component C), 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 from 10 to 40 carbon atoms, preferably from 16 to 22 carbon atoms, with an aliphatic saturated alcohol or amine having from 2 to 40 carbon atoms, preferably from 2 to 6 carbon atoms.

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

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

The aliphatic amines may 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. Accordingly, preferred esters or amides are glyceryl distearate, glyceryl tristearate, ethylenediamine distearate, glyceryl monopalmitate, glyceryl trilaurate, glyceryl monobehenate and pentaerythritol tetrastearate.

Mixtures of various esters or amides, or combinations of esters and amides, may also be used, where the mixing ratio is determined as desired.

Examples of amounts of other conventional 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 common 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 having 1 to 18 carbon atoms in the alcohol moiety.

Such polymers are described, for example, in Houben-Weyl, Methoden der organischen Chemie, Vol. 14/1 (Georg-Thieme-Verlag, Stuttgart, Germany, 1961), p.392-.

Some preferred types of these elastomers will be described below.

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

EPM rubbers are generally virtually free of residual double bonds, whereas EPDM rubbers may have from 1 to 20 double bonds per 100 carbon atoms.

Examples of diene monomers which may be mentioned for the EPDM rubber are conjugated dienes such as isoprene and butadiene, nonconjugated 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, cyclohexadienes, cyclooctadienes and dicyclopentadiene, and also alkenylnorbornenes such as 5-ethylidene-2-norbornene, 5-butylidene-2-norbornene, 2-methallyl-5-norbornene and 2-isopropenyl-5-norbornene, and tricyclodienes such as 3-methyltricyclo [5.2.1.0^2,6]-3, 8-decadiene, and mixtures thereof. 1, 5-hexadiene, 5-ethylidenenorbornene and dicyclopentadiene are preferred. The diene content of the EPDM rubbers is preferably from 0.5 to 50% by weight, in particular from 1 to 8% by weight, based on the total weight of the rubber.

EPM and EPDM rubbers may 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 comprise 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 a monomer mixture which comprises dicarboxylic acid groups and/or epoxy groups and has the formula I, II, III or IV.

R¹C(COOR²)＝C(COOR³)R⁴ (I)

Wherein R is¹To R⁹Is 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.

R¹To R⁹Preference is given to hydrogen, where m is 0 or 1 and g is 1. The corresponding compounds are maleic acid, fumaric acid, maleic anhydride, allyl glycidyl ether and vinyl glycidyl ether.

Preferred compounds of the formulae I, II and IV are maleic acid, maleic anhydride and epoxy-containing (meth) acrylates such as glycidyl acrylate and glycidyl methacrylate, and also esters with tertiary alcohols such as tert-butyl acrylate. Although the latter have no free carboxyl groups, their properties approach those of the free acids and are therefore referred to as monomers having latent carboxyl groups.

Advantageously, the copolymer comprises from 50 to 98% by weight of ethylene, from 0.1 to 20% by weight of monomers containing epoxy groups and/or methacrylic acid and/or monomers containing acid anhydrides, the remainder being (meth) acrylates.

Particularly preferred copolymers are composed of the following monomers:

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

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

1 to 45% by weight, in particular 10 to 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.

In addition to these, comonomers which can be used are vinyl esters and vinyl ethers.

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

Other preferred elastomers are Emulsion polymers, prepared, for example, as described 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 monomers. The morphology of the polymer is also affected by this order of addition.

Monomers which may be mentioned here by way of example only for the preparation of the rubber portion of the elastomer are acrylates such as n-butyl acrylate and 2-ethylhexyl acrylate, the corresponding methacrylates, butadiene and isoprene and mixtures thereof. These monomers may be copolymerized with other monomers, for example with styrene, acrylonitrile, vinyl ethers, and with other acrylates or methacrylates, for example methyl methacrylate, methyl acrylate, ethyl acrylate or propyl acrylate.

The soft or rubbery phase (glass transition temperature below 0 ℃) of the elastomer may be the core, the shell or an 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 composed of a rubber phase.

If one or more hard components (glass transition temperature higher than 20 ℃) are included in the structure of the elastomer in addition to the rubber phase, they are generally 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. In addition to these, it is also possible to use other comonomers in smaller proportions.

It has proven advantageous in some cases to use emulsion polymers which have reactive groups on their surface. Examples of such groups are epoxy, carboxyl, latent carboxyl, amino and amide groups, and functional groups which can be introduced by the simultaneous use of monomers of the formula:

wherein:

R¹⁰is hydrogen or C₁-C₄An alkyl group, a carboxyl group,

R¹¹is hydrogen or C₁-C₈Alkyl or aryl, especially phenyl,

R¹²is hydrogen, C₁-C₁₀Alkyl radical, C₆-C₁₂Aryl OR-OR¹³，

R¹³Is C₁-C₈Alkyl or C₆-C₁₂Aryl, which may be substituted if desired by O-or N-containing groups,

x is a bond or C₁-C₁₀Alkylene or C₆-C₁₂Arylene, or

Y is O-Z or NH-Z, and

z is C₁-C₁₀Alkylene or C₆-C₁₂An arylene group.

The graft monomers described in EP-A208187 are also suitable for introducing reactive groups at the surface.

Further examples which may be mentioned are acrylamide, methacrylamide and substituted acrylates or methacrylates, such as (N-tert-butylamino) ethyl methacrylate, (N, N-dimethylamino) ethyl acrylate, (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 also the compounds described in EP-A50265.

Monomers known as graft-linking monomers, i.e. monomers having two or more polymerizable double bonds that react at different rates during the polymerization, can also be used. It is preferred to use compounds in which at least one reactive group polymerizes at about the same rate as the other monomers, while the other reactive groups polymerize, for example, significantly more slowly. The different polymerization rates produce a certain proportion of unsaturated double bonds in the rubber. If a further phase is subsequently grafted onto such rubbers, the double bonds present in at least some of the rubbers react with the graft monomers to form chemical bonds, i.e.the grafted phase has at least some degree of chemical bonding to the graft base.

Examples of such graft-linking monomers 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 compounds of these carboxylic acids. In addition to these, there are numerous other suitable graft-linking monomers. For further details, reference is made, for example, to US-A4148846.

The proportion of these crosslinking monomers in the impact-modifying polymer is generally up to 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 first of the graft polymers having a core and at least one shell and having the following structure:

type (B)	Core-forming monomers	Housing-forming unit
			I	1, 3-butadiene, isoprene, n-butyl acrylate, ethylhexyl acrylate or mixtures thereof	Styrene, acrylonitrile, methyl methacrylate
II	As in I, but with the use of a cross-linking agent	Same as I

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

These graft polymers, in particular ABS polymers and/or ASA polymers, are preferably used in an amount of up to 40% by weight for the impact modification of PBT, if appropriate in combination with up to 40% by weight of polyethylene terephthalate. Such blended products may be trademarked(previous one)

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-shell, elastomers composed of 1, 3-butadiene, isoprene and n-butyl acrylate or copolymers derived from these. These products can also be prepared by using crosslinking monomers or monomers having reactive groups simultaneously.

Examples of preferred emulsion polymers are n-butyl acrylate- (meth) acrylic acid copolymers, n-butyl acrylate-glycidyl acrylate or n-butyl acrylate-glycidyl methacrylate copolymers, graft polymers having a core consisting of n-butyl acrylate or based on butadiene and having a shell consisting of the abovementioned copolymers, and copolymers of ethylene with comonomers which provide reactive groups.

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

Silicone rubbers are also preferred, as described in DE-A3725576, EP-A235690, DE-A3800603 and EP-A319290.

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

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

Preferred fibrous fillers which may be mentioned are carbon fibers, aramid fibers and potassium titanate fibers, glass fibers in the form of E glass being particularly preferred. They may be used 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) and component B) being from 1: 100 to 1: 2, preferably from 1: 10 to 1: 3.

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

Suitable silane compounds have the formula:

(X-(CH2)_n)_k-Si-(O-C_mH2_m+1)_4-k

wherein:

x is NH₂-，HO-，

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

m is an integer from 1 to 5, preferably from 1 to 2, and

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

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

The amount of silane compound usually used for surface coating is from 0.05 to 5% by weight, preferably from 0.5 to 1.5% by weight, in particular from 0.8 to 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 with strongly developed acicular character. An example is acicular wollastonite. The mineral preferably has an L/D (length to diameter) ratio of from 8: 1 to 35: 1, preferably from 8: 1 to 11: 1. The mineral filler may be pretreated with the above silane compound, if desired, but the pretreatment is not essential.

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

The thermoplastic molding compositions of the invention may comprise, as component C), customary processing aids, for example stabilizers, oxidation inhibitors, agents against thermal and UV decomposition, lubricants and mold release agents, colorants such as dyes and pigments, nucleating agents, plasticizers, and the like.

Examples of oxidation inhibitors and heat stabilizers which may be mentioned are sterically hindered phenols and/or phosphites, hydroquinones, aromatic secondary amines such as diphenylamines, variously substituted members of these groups and mixtures thereof, in concentrations of up to 1% by weight, based on the weight of the thermoplastic 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 which may be added are inorganic pigments, such as titanium dioxide, ultramarine blue, iron oxide and carbon black, and also organic pigments, such as phthalocyanines, quinacridone pigments and perylene pigments, and also dyes, such as nigrosine and anthraquinone.

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

Other lubricants and mold release agents are generally used in amounts of up to 1% by weight. Preference is given to long-chain fatty acids (e.g.stearic acid or behenic acid), salts thereof (e.g.calcium stearate or zinc stearate), or montan waxes (mixtures of long-chain saturated carboxylic acids having chain lengths of from 28 to 32 carbon atoms), or calcium montanate or sodium montanate, or low-molecular-weight polyethylene waxes or low-molecular-weight polypropylene waxes.

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

The molding compositions of the present invention may comprise from 0 to 2% by weight of a fluorine-containing ethylene polymer. These are ethylene polymers having a fluorine content of from 55 to 76% by weight, preferably from 70 to 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. These substances are described, for example, in Schildknecht, "Vinyl and Related Polymers", Wiley-Verlag, 1952, pp.484-494 and Wall, "Fluoropolymers" (Wiley Interscience, 1972).

These fluorine-containing ethylene polymers are distributed homogeneously in the molding composition and preferably have a particle size d₅₀(number average) of 0.05 to 10 μm, in particular 0.1 to 5 μm. These small particle sizes can be obtained particularly preferably by using an aqueous dispersion of a fluorine-containing ethylene polymer and incorporating it into a polyester melt.

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

In a further preferred process, component B), and if appropriate C), can be mixed with the polyester prepolymer, compounded and pelletized. The resulting pellets are then solid phase concentrated, continuously or batchwise, in 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 flowability and good mechanical properties.

In particular, the processing of the components (without caking or caking) is not difficult and can be carried out in a short cycle time, in particular allowing application as thin-walled components.

The morphology of the selected composite was studied using transmission electron microscopy. Good dispersion of the particles in the blend was observed. The particle size was found to be 20-500 nm.

These materials are suitable for producing fibers, films and moldings of any type, in particular for applications as stoppers, switches, box parts, box covers, headlight covers, spray heads, fittings, irons, rotary switches, oven controls, fryer lids, door handles, (rear) mirror housings (mirrorhousing), tailgate glass wipers and optical conductor sheaths.

Examples

And (2) component A:

polybutylene terephthalate with a viscosity number VN of 130mL/g at 25 ℃ and a carboxyl end group content of 34meq/kg (B4520 from BASF AG) (VN measured in a 0.5% strength by weight solution of phenol/o-dichlorobenzene (1: 1 mixture), baseAt 100% by weight of A), it contains 0.65% by weight of pentaerythritol tetrastearate (component C1).

Description of the preparation of polycarbonate B1:

general description of the operation:

as shown in table 1, equimolar amounts of polyol and diethyl carbonate were mixed in a three-necked flask equipped with a stirrer, a reflux condenser and an internal thermometer, and 250ppm of catalyst (based on the amount of alcohol) was added. The mixture is subsequently heated to 100 ℃ with stirring, to 140 ℃ in the test marked by the reference symbol, and stirred at this temperature for 2 hours. Evaporative cooling caused by the liberated monohydric alcohol lowers the temperature of the reaction mixture as the reaction proceeds. Now, the reflux condenser was replaced by a tilting condenser, ethanol was removed by distillation and the temperature of the reaction mixture was slowly raised to 160 ℃.

The ethanol removed by distillation was collected in a cooled round-bottom flask and weighed, from which the conversion was determined, based on the percentage of complete conversion theoretically possible (see table 1).

The reaction product was then analyzed by gel permeation chromatography, eluting with dimethylacetamide and a standard of Polymethylmethacrylate (PMMA).

Table 1:

based on the complete conversion of the molecular weight

Ethanol distillate M of_wViscosity 23 ℃ OH number

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

TMP×1.2PO K₂CO₃ 90 1836 7150 455

1292

Component B2):

table 2:

monomer

Mn(g/mol)

Mw(g/mol )

OH number (mg KOH/g)

Acid value (mg KOH/g)

Viscosity, 23 ℃ [ mPas ]]

B2/1

Terephthalic acid and glycerol

900

2390

416

0

2500

B2/2

Adipic acid and glycerol

1730

2580

295

167

4020

Preparation of B2/1:

1589g (8.19mol) of dimethyl terephthalate and 628g (6.38mol) of glycerol form the starting charge in a 5L glass flask equipped with stirrer, internal thermometer, gas inlet tube, reflux condenser and vacuum connected to a cold trap. 4.4g of water are added

4201 commercially available di-n-butyltin oxide, the mixture is heated to an internal temperature of 140 ℃ 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 held at the temperature and the pressure for 34 hours. Then mixing the mixtureCooling to room temperature gave 1750g of the hyperbranched polyester in the form of a transparent, high-viscosity liquid. The analytical data are given in table 2 above.

Preparation of B2/2:

2016g (13.8mol) of adipic acid and 1059g (11.51mol) of glycerol form the starting charge in a 5L glass flask equipped with a stirrer, an internal thermometer, a gas inlet tube, a reflux condenser and a vacuum connected to a cold trap. 3.04g of water are added4201 commercially available di-n-butyltin oxide, the mixture was heated to an internal temperature of 125 ℃ by means of an oil bath. To remove the water formed during the reaction, a reduced pressure of 100 mbar is applied. The reaction mixture was kept at said temperature and said pressure for 11 hours. The mixture was then cooled to room temperature, yielding 2645g of the hyperbranched polyester in the form of a clear, high-viscosity liquid. The analytical data are given in table 2 above.

Preparation of the moulding compositions:

components A) to C) were blended in a twin-screw extruder at 250-260 ℃ and extruded into a water bath. After the material was granulated and dried, the test specimens were injection molded and tested.

According to ISO527-2, pellets were injection molded to give dumbbell-shaped specimens and subjected to tensile testing. The impact toughness was also determined according to ISO179-2, and the 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 shows the compositions of the invention and their test results.

Table 3:

component (wt.%)]	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 Properties

Maximum tensile stress (N/mm) ISO527-2	58.26	59.7	59.6	60.3	59.6	59.7	59.8
								Tensile stress at break (N/mm) ISO527-2	25.7	47.8	47.6	55.6	50.7	48.4	48.7

Tensile strain at yield (%) ISO527-2	3.7	3.8	3.8	3.9	3.9	3.8	3.8
								Modulus of elasticity (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

Cyclone 260/80-2 mm (mm)

33

48

46

56

55

48

52

Claims

1. A thermoplastic molding composition comprising:

A)10 to 99.99 wt.% 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 of from 1 to 600mg KOH/g polycarbonate according to DIN53240 in the second part, and

B2) at least one A_xB_yHighly branched or hyperbranched polyesters of the type wherein x is at least 1.1 and y is at least 2.1And an

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

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

2. The thermoplastic molding composition as claimed in claim 1, in which component B1) has a number-average molar mass M_nIs 100-15000 g/mol.

3. The thermoplastic molding composition as claimed in claim 1 or 2, in which component B1) has a glass transition temperature Tg of from-80 ℃ to 140 ℃.

4. The thermoplastic molding composition as claimed in claim 1 or 2, in which component B1) has a viscosity of from 50 to 200000mPas at 23 ℃ in accordance with DIN 53019.

5. The thermoplastic molding composition as claimed in claim 1 or 2, in which component B1) is obtained by a process comprising at least the following steps:

a) reacting at least one compound of the formula RO [ (CO)]_nThe organic carbonates (A) of OR are reacted with at least one aliphatic, aliphatic/aromatic OR aromatic alcohol (B) having at least three OH groups with elimination of the alcohol ROH to give one OR more condensation products (K), where each R, independently of the other radicals, is a linear OR branched aliphatic, aromatic/aliphatic OR aromatic hydrocarbon radical having from 1 to 20 carbon atoms, and where the radicals R may also be bonded to one another to form a ring, and n is an integer from 1 to 5, OR

6. The thermoplastic molding composition as claimed in claim 1 or 2, in which component B2) has a number-average molar mass M_n300-30000 g/mol.

7. The thermoplastic molding composition as claimed in claim 1 or 2, in which component B2) has a glass transition temperature Tg of from-50 to 140 ℃.

8. The thermoplastic molding composition as claimed in claim 1 or 2, in which component B2) has an OH number according to DIN53240 of from 0 to 600mg KOH/g of polyester.

9. The thermoplastic molding composition as claimed in claim 1 or 2, in which component B2) has a COOH number according to DIN53240 of from 0 to 600mg KOH/g of polyester.

10. The thermoplastic molding composition as claimed in claim 1 or 2, in which component B2) has at least one OH or COOH number greater than 0.

11. The thermoplastic molding composition as claimed in claim 1 or 2, wherein component B2) is composed of:

(a) one or more dicarboxylic acids, or one or more derivatives thereof, with one or more at least trihydric alcohols, where the derivatives are the relevant anhydrides, mono-or dialkyl esters, mono-and divinyl esters and mixed esters, in monomeric or polymeric form,

or

(b) One or more tricarboxylic or higher polycarboxylic acids, or one or more derivatives thereof, with one or more diols, wherein the derivatives are the relevant anhydrides, mono-, di-or trialkyl esters, mono-, di-or trivinyl esters and mixed methylethyl esters, in monomeric or polymeric form.

12. The thermoplastic molding composition as claimed in claim 1 or 2, wherein the ratio of components B1) to B2) is from 1: 20 to 20: 1.

13. Use of the thermoplastic molding composition as claimed in any of claims 1 to 12 for the production of fibers, foils or moldings of any type.

14. Any type of fibers, foils or moldings obtainable from the thermoplastic molding compositions as claimed in any of claims 1 to 12.