WO2005075565A1 - Fliessfähige polyesterformmassen - Google Patents
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- WO2005075565A1 WO2005075565A1 PCT/EP2005/001014 EP2005001014W WO2005075565A1 WO 2005075565 A1 WO2005075565 A1 WO 2005075565A1 EP 2005001014 W EP2005001014 W EP 2005001014W WO 2005075565 A1 WO2005075565 A1 WO 2005075565A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
- C08L101/005—Dendritic macromolecules
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/02—Aliphatic polycarbonates
- C08G64/0208—Aliphatic polycarbonates saturated
- C08G64/0216—Aliphatic polycarbonates saturated containing a chain-terminating or -crosslinking agent
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/04—Aromatic polycarbonates
- C08G64/06—Aromatic polycarbonates not containing aliphatic unsaturation
- C08G64/14—Aromatic polycarbonates not containing aliphatic unsaturation containing a chain-terminating or -crosslinking agent
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/16—Aliphatic-aromatic or araliphatic polycarbonates
- C08G64/1608—Aliphatic-aromatic or araliphatic polycarbonates saturated
- C08G64/1616—Aliphatic-aromatic or araliphatic polycarbonates saturated containing a chain-terminating or -crosslinking agent
Definitions
- thermoplastic molding compositions comprising
- thermoplastic polyester A) 10 to 99.99% by weight of at least one thermoplastic polyester,
- the invention relates to the use of the molding compositions according to the invention for the production of fibers, films and moldings of any kind, as well as the moldings obtainable in this case.
- Polycarbonates are usually obtained from the reaction of alcohols with phosgene or from the transesterification of alcohols or phenols with dialkyl or diaryl carbonates.
- aromatic polycarbonates which are produced for example from bisphenols, aliphatic polycarbonates play so far seen from the market volume heretofore a minor role. See also Becker / Braun, Kunststoff-Handbuch Bd. 3/1, polycarbonates, polyacetals, polyesters, cellulose esters, Carl-Hanser-Verlag, Kunststoff 1992, pages 118-119.
- the aliphatic polycarbonates described are generally linear or else built up with a low degree of branching.
- US Pat. No. 3,305,605 describes the use of solid linear polycarbonates having a molar mass above 15,000 Da as plasticizer for polyvinyl polymers.
- Dendritic polymers with perfectly symmetric structure can be prepared starting from a central molecule by controlled stepwise coupling of two or more difunctional or polyfunctional monomers with each already bound monomer.
- the number of monomer end groups (and thus of the linkages) increases exponentially, and polymers with tree-like structures, ideally spherical, whose branches each contain exactly the same number of monomer units, are obtained. Due to this perfect structure, the polymer properties are advantageous, for example Wise way to observe a surprisingly low viscosity and high reactivity due to the high number of functional groups on the spherical surface.
- production is complicated by the need to introduce and remove protecting groups at each linking step and to require purification operations, which is why dendrimers are usually only produced on a laboratory scale.
- Hyperbranched polymers can be prepared by two synthetic routes known as AB 2 and A x + By.
- a x and B y are different monomers, and the indices x and y are the number of functional groups contained in A and B, respectively, ie, the functionality of A and B.
- the AB 2 path becomes a trifunctional Monomer having a reactive group A and two reactive groups B converted to a highly or hyperbranched polymer.
- a difunctional monomer A 2 is reacted with a trifunctional monomer B 3 .
- Hyperbranched polycarbonates can also be prepared according to WO 98/50453. According to the process described there, triols are in turn reacted with carbonylbisimidazole. Initially, imidazolides are formed, which then react further intermolecularly with the polycarbonates. According to the method mentioned, the polycarbonates are obtained as colorless or pale yellow rubbery products.
- the above-mentioned syntheses of highly branched or hyperbranched polycarbonates have the following disadvantages:
- the hyperbranched products are either high-melting or rubber-like, which significantly limits later processability.
- liberated during the reaction imidazole must be laboriously removed from the reaction mixture.
- the reaction products always contain terminal imidazolide groups. These groups are labile and must be followed by a sequential step, e.g. be converted into hydroxyl groups.
- Carbonyldiimidazole is a comparatively expensive chemical that greatly increases the cost of materials.
- thermoplastic polyester molding compositions which have good flowability and at the same time good mechanical properties.
- the highly or hyperbranched polycarbonates obtainable by means of a simple and inexpensive process are suitable as significant flow improvers in thermoplastics. Furthermore, their structures can be easily adapted to the requirements of the application in thermoplastics and combine the advantageous properties due to their defined structure, such as high functionality, high reactivity, low viscosity and good solubility.
- the molding compositions according to the invention contain from 10 to 99.99, preferably from 30 to 99.5, and in particular from 30 to 99.3,% by weight of at least one thermoplastic polyester.
- polyesters A) based on aromatic dicarboxylic acids and an aliphatic or aromatic dihydroxy compound are used.
- a first group of preferred polyesters are polyalkylene terephthalates, in particular those having 2 to 10 carbon atoms in the alcohol part.
- Such polyalkylene terephthalates are known per se and described in the literature. They contain an aromatic ring in the main chain derived from the aromatic dicarboxylic acid. The aromatic ring may also be substituted, for example by halogen such as chlorine and bromine or by -CC alkyl groups such as methyl, ethyl, i- or n-propyl and n-, i- or t-butyl groups , These polyalkylene terephthalates can be prepared by reacting aromatic dicarboxylic acids, 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 or mixtures thereof. Up to 30 mol%, preferably not more than 10 mol% of the aromatic dicarboxylic acids can be replaced by aliphatic or cycloaliphatic dicarboxylic acids such as adipic acid, azelaic acid, sebacic acid, dodecanedioic acids and cyclohexanedicarboxylic acids.
- aliphatic dihydroxy compounds are diols having 2 to 6 carbon atoms, in particular 1, 2-ethanediol, 1, 3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1, 4-hexanediol, 1, 4-cyclohexanediol, 1 , 4-cyclohexanedimethanol and neopentyl glycol or mixtures thereof.
- polyesters (A) are polyalkylene terephthalates which are derived from alkanediols having 2 to 6 C atoms. Of these, particularly preferred are polyethylene terephthalate, polypropylene terephthalate and polybutylene terephthalate or mixtures thereof. Preference is furthermore given to PET and / or PBT which contain up to 1% by weight, preferably up to 0.75% by weight, of 1,6-hexanediol and / or 2-methyl-1,5-pentanediol as further monomer units.
- the viscosity number of the polyesters (A) is generally in the range from 50 to 220, preferably from 80 to 160 (measured in a 0.5% strength by weight solution in a phenol / o-dichlorobenzene mixture (wt. 1 at 25 ° C) according to ISO 1628.
- polyesters whose carboxyl end group content is up to 100 meq / kg, preferably up to 50 meq / kg and in particular up to 40 meq / kg of polyester.
- Such polyesters can, for example, according to the method of
- the carboxyl end group content is usually determined by titration methods (e.g., potentiometry).
- Particularly preferred molding compositions contain as component A) a mixture of polyesters which are different from PBT, such as, for example, polyethylene terephthalate (PET).
- PBT polyethylene terephthalate
- the proportion e.g. of the polyethylene terephthalate is preferably in the mixture up to 50, in particular 10 to 35 wt .-%, based on 100 wt .-% A).
- PET recyclates also termed scrap PET
- PBT polyalkylene terephthalates
- Post Industrial Recyclate these are production waste in polycondensation or in processing, e.g. Sprues in the injection molding processing, starting goods in the injection molding or extrusion or edge portions of extruded sheets or foils.
- Both types of recycled material can be present either as regrind or in the form of granules. In the latter case, after the separation and purification, the tube cyclates are melted in an extruder and granulated. This usually facilitates the handling, the flowability and the metering for further processing steps.
- the maximum edge length should be 10 mm, preferably less than 8 mm.
- the residual moisture content after drying is preferably ⁇ 0.2%, in particular ⁇ 0.05%.
- Suitable aromatic dicarboxylic acids are the compounds already described for the polyalkylene terephthalates. Preference is given to using mixtures of from 5 to 100 mol% of isophthalic acid and from 0 to 95 mol% of terephthalic acid, in particular mixtures of about 80% of terephthalic acid with 20% of isophthalic acid to approximately equivalent mixtures of these two acids.
- the aromatic dihydroxy compounds preferably have the general formula Z is an alkylene or cycloalkylene group having up to 8 C atoms, an aryl group having up to 12 C atoms, a carbonyl group, a sulfonyl group, an oxygen or sulfur atom or a chemical bond, and in the m has the value 0 to 2.
- the compounds may also carry C 1 -C 6 -alkyl or alkoxy groups and fluorine, chlorine or bromine as substituents on the phenylene groups.
- 2,2-di- (4'-hydroxyphenyl) propane 2,2-di- (3, 5-dichlordihydroxyphenyl) propane, 1, 1-di- (4'-hydroxyphenyl) cyclohexane, 3,4-dihydroxybenzophenone, 4 , 4-dihydroxydiphenylsulfone and 2,2-di (3 ', 5'-dimethyl-4'-hydroxyphenyl) propane
- polyalkylene terephthalates and wholly aromatic polyesters. These generally contain from 20 to 98% by weight of the polyalkylene terephthalate and from 2 to 80% by weight of the wholly aromatic polyester.
- polyester block copolymers such as copolyetheresters may also be used.
- Such products are known per se and described in the literature, for example in US Pat. No. 3,651,014. Also in the trade corresponding products are available, eg Hytrel® (DuPont).
- Suitable halogen-free polycarbonates are, for example, those based on diphenols of the general formula
- Q is a single bond, a C 1 to C 8 alkylene, a C 2 to C 3 alkylidene, a C 3 to C 6 cycloalkylidene group, a C 6 to C 1 z arylene group, and -O-, S or -SO 2 - and m is an integer from 0 to 2.
- the diphenols may also have substituents on the phenylene radicals, such as C 1 to Ce-alkyl or C 1 to C 6 -alkoxy.
- Preferred diphenols of the formula are, for example, hydroquinone, resorcinol, 4,4'-dihydroxydiphenyl, 2,2-bis (4-hydroxyphenyl) propane, 2,4-bis (4-hydroxyphenyl) -2-methylbutane, 1,1 bis (4-hydroxyphenyl) -cyclohexane.
- Particular preference is given to 2,2-bis (4-hydroxyphenyl) propane and 1,1-bis (4-hydroxyphenyl) cyclohexane, and also 1,1-bis (4-hydroxyphenyl) -3,3, 5-trimethylcyclohexane.
- both homopolycarbonates and copolycarbonates are suitable as component A, and in addition to the bisphenol A homopolymer, the copolycarbonates of bisphenol A are preferred.
- the suitable polycarbonates may be branched in a known manner, preferably by the incorporation of from 0.05 to 2.0 mol%, based on the sum of the diphenols used, of at least trifunctional compounds, for example those having three or more than three phenolic compounds OH groups.
- the relative viscosities ⁇ r ⁇ ⁇ of 1.10 to 1.50, in particular from 1.25 to 1.40 have. This corresponds to average molecular weights M w (weight average) of 10,000 to 200,000, preferably from 20,000 to 80,000 g / mol.
- the diphenols of the general formula are known per se or can be prepared by known processes.
- the polycarbonates can be prepared, for example, by reacting the diphenols with phosgene by the phase boundary process or with phosgene by the homogeneous phase process (the so-called pyridine process), the molecular weight to be set in each case being achieved in a known manner by a corresponding amount of known chain terminators , (With regard to polydiorganosiloxane-containing polycarbonates, see for example DE-OS 33 34 782).
- Suitable chain terminators include phenol, pt-butylphenol but also long-chain alkylphenols such as 4- (1, 3-tetramethyl-butyl) phenol, according to DE-OS 2842 005 or monoalkylphenols or dialkylphenols having a total of 8 to 20 carbon atoms in the alkyl substituents according to DE-A 35 06472, such as p-nonylphenyl, 3,5-dl-t-butylphenol, pt-octylphenol, p-dodecylphenol, 2- (3,5-dimethyl-heptyl) -phenol and 4- (3,5- dimethylheptyl) phenol.
- alkylphenols such as 4- (1, 3-tetramethyl-butyl) phenol, according to DE-OS 2842 005 or monoalkylphenols or dialkylphenols having a total of 8 to 20 carbon atoms in the alkyl substituents according to DE-A 35 06472,
- Halogen-free polycarbonates in the context of the present invention means that the polycarbonates are composed of halogen-free diphenols, halogen-free chain terminators and optionally halogen-free branching agents, the content of minor ppm amounts of saponifiable chlorine, resulting, for example, from the preparation of the polycarbonates with phosgene by the interfacial process, is not to be regarded as halogen-containing in the context of the invention.
- Such polycarbonates with ppm contents of saponifiable chlorine are halogen-free polycarbonates in the context of the present invention.
- suitable components A) may be mentioned amorphous polyester carbonates, wherein phosgene was replaced by aromatic dicarboxylic acid units such as isophthalic acid and / or terephthalic acid units in the preparation.
- aromatic dicarboxylic acid units such as isophthalic acid and / or terephthalic acid units in the preparation.
- bisphenol A can be replaced by bisphenol TMC.
- polycarbonates are available under the trademark APEC HT® from Bayer.
- the molding compositions according to the invention contain 0.01 to 50, preferably 0.5 to 20 and in particular 0.7 to 10 wt .-% of a highly or hyperbranched polycarbonate having an OH number of 1 to 600, preferably 10 to 550 and in particular from 50 to 550 mg KOH / g polycarbonate (according to DIN 53240, Part 2).
- Hyperbranched polycarbonates B1) in the context of this invention are understood as meaning uncrosslinked macromolecules having hydroxyl groups and carbonate groups which are structurally as well as molecularly nonuniform. You can turn off on one side starting from a central molecule analogous to dendrimers, but be constructed with uneven chain length of the branches. On the other hand, they can also be constructed linearly with functional side groups or, as a combination of the two extremes, they can have linear and branched molecular parts.
- dendrimeric and hyperbranched polymers see also PJ Flory, J. Am. Chem. Soc. 1952, 74, 2718 and H. Frey et al., Chem. Eur. J. 2000, 6, no. 14, 2499.
- hyperbranched means that the degree of branching (DB), ie the mean number of dendritic linkages plus the average number of end groups per molecule, is 10 to 99.9%, preferably 20 to 99 %, more preferably 20-95%.
- DB degree of branching
- dendrimer is understood to mean that the degree of branching is 99.9-100%
- degree of branching is 99.9-100%
- T is the average number of terminal monomer units
- Z is the average number of branched monomer units
- L is the average number of linear monomer units in the macromolecules of the respective substances.
- component B1) has a number average molecular weight M n of from 100 to 15,000, preferably from 200 to 12,000 and in particular from 500 to 10,000 g / mol (GPC, standard PMMA).
- the glass transition temperature Tg is in particular from -80 ° C to +140, preferably from -60 to 120 ° C (according to DSC, DIN 53765).
- the viscosity (mPas) at 23 ° C. is from 50 to 200,000, in particular from 100 to 150,000, and very particularly preferably from 200 to 100,000.
- Component B1) is preferably obtainable by a process comprising at least the following steps:
- the quantitative ratio of the OH groups to the carbonates in the reaction mixture is selected so that the condensation products (K) have on average either a carbonate group and more than one OH group or one OH group and more than one carbonate group.
- the starting material used may be phosgene, diphosgene or triphosgene, organic carbonates being preferred.
- radicals R used as starting material organic carbonates (A) of the general formula RO (CO) n OR are each independently a straight-chain or branched aliphatic, aromatic / aliphatic or aromatic hydrocarbon radical having 1 to 20 carbon atoms.
- the two radicals R can also be linked together to form a ring. It is preferably an aliphatic hydrocarbon radical and particularly preferably a straight-chain or branched alkyl radical having 1 to 5 C atoms, or a substituted or unsubstituted phenyl radical.
- n is preferably 1 to 3, in particular 1.
- Dialkyl or diaryl carbonates can be prepared, for example, from the reaction of aliphatic, araliphatic or aromatic alcohols, preferably monoalcohols with phosgene. Furthermore, they can also be prepared via oxidative carbonylation of the alcohols or phenols by means of CO in the presence of noble metals, oxygen or NO x .
- aliphatic, araliphatic or aromatic alcohols preferably monoalcohols with phosgene.
- they can also be prepared via oxidative carbonylation of the alcohols or phenols by means of CO in the presence of noble metals, oxygen or NO x .
- For preparation methods of diaryl or dialkyl carbonates see also "Ullmann's Encyclopedia of Industrial Chemistry", 6th Edition, 2000 Electronic Release, Verlag Wiley-VCH.
- suitable carbonates include aliphatic, aromatic / aliphatic or aromatic carbonates, such as ethylene carbonate, 1, 2 or 1, 3-propylene carbonate, diphenyl carbonate, ditolyl carbonate, dixylyl carbonate, dinaphthyl carbonate, ethyl phenyl carbonate, dibenzyl carbonate, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, dibutyl carbonate, diisobutyl carbonate, dipentyl carbonate, dihexyl carbonate, dicyclohexyl carbonate, diheptyl carbonate, dioctyl carbonate, didecylacarbonate or didodecyl carbonate.
- aliphatic, aromatic / aliphatic or aromatic carbonates such as ethylene carbonate, 1, 2 or 1, 3-propylene carbonate, diphenyl carbonate, ditolyl carbonate, dixylyl carbonate, dinaphthyl carbonate, ethy
- Examples of carbonates in which n is greater than 1 include dialkyl dicarbonates such as di (-t-butyl) dicarbonate or dialkyl tricarbonates such as di (-t-butyl tricarbonate).
- Aliphatic carbonates are preferably used, in particular those in which the radicals comprise 1 to 5 C atoms, for example dimethyl carbonate, diethyl carbonate, dipropyl carbonate, dibutyl carbonate or diisobutyl carbonate.
- the organic carbonates are reacted with at least one aliphatic alcohol (B) which has at least 3 OH groups or mixtures of two or more different alcohols.
- Examples of compounds having at least three OH groups include glycerol, trimethylolmethane, trimethylolethane, trimethylolpropane, 1, 2,4-butanetriol, tris (hydroxymethyl) amine, tris (hydroxyethyl) amine, tris (hydroxypropyl) amine, pentaerythritol, Diglycerine, triglycerol, polyglycerols, bis (tri-methylolpropane), tris (hydroxymethyl) isocyanurate, tris (hydroxyethyl) isocyanurate, phloroglucinol, trihydroxytoluene, trihydroxydimethylbenzene, phloroglucides, hexahydroxybenzene, 1,3,5-benzenetrimethanol, 1, 1,1-tris (4'-hydroxyphenyl) methane, 1,1,1-tris (4'-hydroxyphenyl) ethane, bis (tri-methylolpropane) or sugars,
- polyfunctional alcohols can also be used in mixture with difunctional alcohols (B '), with the proviso that the mean OH functionality of all the alcohols used together is greater than 2.
- suitable compounds having two OH 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- HydroxycyclohexyI) propane, 1,1'-bis (4-hydroxyphenyl) -3,3-5-trimethylcyclohe
- the diols serve to finely adjust the properties of the polycarbonate. If difunctional alcohols are used, the ratio of difunctional alcohols B ') to the at least trifunctional alcohols (B) is determined by the person skilled in the art, depending on the desired properties of the polycarbonate. As a rule, the amount of the alcohol or alcohols (B ') is 0 to 50 mol% with respect to the total amount of all alcohols (B) and (B') together. The amount is preferably 0 to 45 mol%, particularly preferably 0 to 35 mol% and very particularly preferably 0 to 30 mol%.
- reaction of phosgene, diphosgene or triphosgene with the alcohol or alcohol mixture is generally carried out with the elimination of hydrogen chloride, the reaction of the carbonates with the alcohol or alcohol mixture to the highly functional hyperbranched polycarbonate according to the invention takes place with elimination of the monofunctional alcohol or phenol from the carbonate molecule.
- the highly functional highly branched polycarbonates formed by the process according to the invention are terminated after the reaction, ie without further modification, with hydroxyl groups and / or with carbonate groups. They dissolve well in various solvents, for example in 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 propylene carbonate.
- alcohols such as methanol, ethanol, butanol, alcohol / water mixtures, acetone, 2-butanone, ethyl acetate, butyl acetate, methoxypropyl acetate, methoxyethyl acetate, tetrahydrofuran, dimethylformamide,
- a high-functionality polycarbonate is to be understood as meaning a product which, in addition to the carbonate groups which form the polymer backbone, also has at least three, preferably at least six, more preferably at least ten functional groups.
- the functional groups are carbonate groups and / or OH groups.
- the number of terminal or pendant functional groups is in principle not limited to the top, 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 generally have not more than 500 terminal or pendant functional groups, preferably not more than 100 terminal or pendant functional groups.
- condensation product (K) contains on average either a carbonate group or carbamoyl group and more than one OH group or an OH group and more than one carbonate group or carbamoyl group.
- the simplest structure of the condensation product (K) of a carbonate (A) and a di- or polyalcohol (B) gives the arrangement XY n or Y ⁇ X, where X is a carbonate group, Y is a hydroxyl group and n usually one Number between 1 and 6, preferably between 1 and 4, particularly preferably between 1 and 3 represents.
- the reactive group which results as a single group, is referred to hereinafter generally "focal group".
- condensation product (K) from a carbonate and a trihydric alcohol at a conversion ratio of 1: 1 results in the average molecule of the type XY 2 , illustrated by the general formula 2.
- Focal group here is a carbonate group.
- R has the meaning defined above and R 1 is an aliphatic or aromatic radical.
- the preparation of the condensation product (K) can be carried out, for example, also from a carbonate and a trihydric alcohol, illustrated by the general formula 4, wherein the reaction ratio is at molar 2: 1. This results in the average molecule of type X 2 Y, focal group here is an OH group.
- R and R 1 have the same meaning as in the formulas 1 to 3.
- difunctional compounds for example a dicarbonate or a diol
- this causes an extension of the chains, as illustrated, for example, in general formula (5).
- the result is again on average a molecule of the type XY 2 , focal group is a carbonate group.
- R 2 is an organic, preferably aliphatic radical, R and R 1 are defined as described above.
- condensation products (K) it is also possible to use a plurality of condensation products (K) for the synthesis.
- several alcohols or more carbonates can be used.
- mixtures of different condensation products of different structure can be obtained by selecting the ratio of the alcohols used and the carbonates or phosgene. This is exemplified by the example of the reaction of a carbonate with a trihydric alcohol. If the starting materials are used in a ratio of 1: 1, as shown in (II), a molecule of XY 2 is obtained . If the starting materials are used in a ratio of 2: 1, as shown in (IV), one obtains a molecule X 2 Y. At a ratio of 1: 1 to 2: 1, a mixture of molecules XY and X 2 Y is obtained.
- the simple condensation products (K) described by way of example in the formulas 1 to 5 preferably react according to the invention intermolecularly to form highly functional polycondensation products, referred to hereinafter as polycondensation products (P).
- the conversion to the condensation product (K) and to the polycondensation Product (P) is usually carried out at a temperature of 0 to 250 ° C, preferably at 60 to 160 ° C in bulk or in solution.
- all solvents can be used which are inert to the respective starting materials.
- organic solvents for example decane, dodecane, benzene, toluene, chlorobenzene, xylene, dimethylformamide, dimethylacetamide or solvent naphtha.
- the condensation reaction is carried out in bulk.
- the monofunctional alcohol ROH or the phenol liberated in the reaction can be removed from the reaction equilibrium by distillation, optionally at reduced pressure, to accelerate the reaction.
- Suitable catalysts are compounds which catalyze esterification or transesterification reactions, for example alkali metal hydroxides, alkali metal carbonates, alkali hydrogencarbonates, preferably of sodium, potassium or cesium, tertiary amines, guanidines, ammonium compounds, phosphonium compounds, aluminum, tin, zinc, Titanium, zirconium or bismuth organic compounds, also called double metal cyanide (DMC) catalysts, as described for example in DE 10138216 or in DE 10147712.
- DMC double metal cyanide
- potassium hydroxide potassium carbonate, potassium bicarbonate, diazabicyclooctane (DABCO), diazabicyclononene (DBN), diazabicycloundecene (DBU), imidazoles, such as imidazole, 1-methylimidazole or 1,2-dimethylimidazole, titanium tetrabutylate, titanium tetraisopropylate, dibutyltin oxide, Dibutyltin dilaurate, Zinndioctoat, Zirkonacetyla- cetonate or mixtures thereof used.
- DABCO diazabicyclooctane
- DBN diazabicyclononene
- DBU diazabicycloundecene
- imidazoles such as imidazole, 1-methylimidazole or 1,2-dimethylimidazole
- titanium tetrabutylate titanium tetraisopropylate
- dibutyltin oxide dibutylt
- the addition of the catalyst is generally carried out in an amount of 50 to 10,000, preferably from 100 to 5000 ppm by weight, based on the amount of the alcohol or alcohol mixture used.
- the intermolecular polycondensation reaction both by adding the appropriate catalyst and by selecting a suitable temperature.
- the average molecular weight of the polymer (P) can be adjusted via the composition of the starting components and over the residence time.
- the condensation products (K) or the polycondensation products (P), which were prepared at elevated temperature, are usually stable at room temperature for a longer period.
- condensation reaction may result in polycondensation products (P) having different structures which have branches but no crosslinks.
- the polycondensation products (P) ideally have either one carbonate group as the focal group and more than two OH groups or one OH group as the focal group and more than two carbonate groups.
- the number of reactive groups results from the nature of the condensation products used (K) and the degree of polycondensation.
- R and R 1 are as defined above.
- the temperature can be lowered to a range in which the reaction comes to a standstill and the product (K) or the polycondensation product (P) is storage-stable.
- the catalyst in basic eg by addition of Lewis acids or protic acids.
- the product (P) is added to the product to terminate the reaction with a product which is reactive with the focal group of (P) groups become.
- a product which is reactive with the focal group of (P) groups become.
- a product which is reactive with the focal group of (P) groups become.
- a carbonate group as the focal group a mono-, di- or poly-amine may be added.
- a hydroxyl group as the focal group the product (P) can be added, for example, to a mono-, di- or polyisocyanate, an epoxy-group-containing compound or an OH derivative reactive acid derivative.
- the preparation of the high-functionality polycarbonates according to the invention is usually carried out in a pressure range from 0.1 mbar to 20 bar, preferably at 1 mbar to 5 bar, in reactors or reactor cascades which are operated batchwise, semicontinuously or continuously.
- the products according to the invention can be further processed after preparation without further purification.
- the product is stripped, that is, freed from low molecular weight, volatile compounds.
- the catalyst can optionally be deactivated and the low molecular weight volatiles, e.g. Monoalcohols, phenols, carbonates, hydrogen chloride or volatile oligomeric or cyclic compounds by distillation, optionally with the introduction of a gas, preferably nitrogen, carbon dioxide or air, optionally at reduced pressure, are removed.
- the polycarbonates according to the invention can be given, in addition to the functional groups already obtained by the reaction, further functional groups.
- the functionalization can during the molecular weight build-up or even subsequently, i. after completion of the actual polycondensation.
- carbamate groups for example, ethanolamine, propanolamine, isopropanolamine, 2- (butylamino) ethanol, 2- (cyclohexylamino) ethanoI, 2-amino-1-butanol, 2- (2'-amino-ethoxy) ethanol or higher
- Use alkoxylation products of ammonia 4-hydroxy-piperidine, 1-hydroxyethylpiperazine, diethanolamine, dipropanolamine, diisopropanolamine, tris (hydroxymethyl) aminomethane, tris (hydroxyethyl) amino methane, ethylene diamine, propylene diamine, hexamethylene diamine or isophorone diamine.
- Mercaptoethanol can be used for the modification with mercapto groups, for example.
- Tertiary amino groups can be produced, for example, by incorporation of N-methyldiethanolamine, N-methyldipropanolamine or N, N-dimethylethanolamine.
- Ether groups can be generated, for example, by condensation of di- or higher-functional polyetherols.
- Long-chain alkyl radicals can be introduced by reaction with long-chain alkanediols, the reaction with alkyl or aryl diisocyanates generates polycarbonates containing alkyl, aryl and urethane groups or urea groups.
- tricarboxylic acids e.g. Terephthalic acid dimethyl esters or tricarboxylic acid esters can be produced ester groups.
- step c Subsequent functionalization can be obtained by reacting the resulting highly functional, highly branched or hyperbranched polycarbonate in an additional process step (step c) with a suitable functionalizing reagent which can react with the OH and / or carbonate groups or carbamoyl groups of the polycarbonate , implements.
- Hydroxyl-containing high-functionality, highly or hyperbranched polycarbonates can be modified, for example, by addition of molecules containing acid groups or isocyanate groups.
- polycarbonates containing acid groups can be obtained by reaction with compounds containing anhydride groups.
- hydroxyl-containing high-functionality polycarbonates can also be converted into highly functional polycarbonate-polyether polyols by reaction with alkylene oxides, for example ethylene oxide, propylene oxide or butylene oxide.
- alkylene oxides for example ethylene oxide, propylene oxide or butylene oxide.
- the molding compositions according to the invention may contain from 0 to 60, in particular up to 50% by weight of further additives and processing aids which are different from B).
- the molding compositions according to the invention 0 to 5, preferably 0.05 to 3 and in particular 0.1 to 2 wt .-% of at least one ester or amide of saturated or unsaturated aliphatic carboxylic acids having 10 to 40, preferably 16 to 22 C Atoms containing aliphatic saturated alcohols or amines having 2 to 40, preferably 2 to 6 carbon atoms.
- the carboxylic acids can be 1- or 2-valent. Examples which may be mentioned are pelargonic acid, palmitic acid, lauric acid, margaric acid, dodecanedioic acid, behenic acid and particularly preferably stearic acid, capric acid and montanic acid (mixture of fatty acids having 30 to 40 carbon atoms).
- the aliphatic alcohols can be 1 to 4 valent.
- examples of alcohols are n-butanol, n-octanol, stearyl alcohol, ethylene glycol, propylene glycol, neopentyl glycol, pentaerythritol, with glycerol and pentaerythritol being preferred.
- the aliphatic amines can be monohydric to trihydric. Examples of these are stearylamine, ethylenediamine, propylenediamine, hexamethylenediamine, di (6-aminohexyl) amine, with ethylenediamine and hexamethylenediamine being particularly preferred.
- preferred esters or amides are glycerol distearate, glycerol tristearate, ethylenediamine distearate, glycerol monopalmitate, glycerol trilaurate, glycerol monobehenate and pentaerythritol tetrastearate.
- customary additives C) are, for example, in amounts of up to 40, preferably up to 30,% by weight of rubber-elastic polymers (often also referred to as impact modifiers, elastomers or rubbers).
- these are copolymers which are preferably composed of at least two of the following monomers: ethylene, propylene, butadiene, iso- butene, isoprene, chloroprene, vinyl acetate, styrene, acrylonitrile and acrylic or methacrylic esters with 1 to 18 carbon atoms in the alcohol component.
- EPM ethylene-propylene
- EPDM ethylene-propylene-diene
- EPM rubbers generally have practically no double bonds, while EPDM rubbers can have from 1 to 20 double bonds / 100 carbon atoms.
- diene monomers for EPDM rubbers for example, conjugated dienes such as isoprene and butadiene, non-conjugated dienes having 5 to 25 carbon atoms such as penta-1,4-diene, hexa-1, 4-diene, hexa-1, 5 -diene, 2,5-dimethylhexa-1,5-diene and octa-1,4-diene, cyclic dienes such as cyclopentadiene, cyclohexadienes, cyclooctadienes and dicyclopentadienes and also alkenylnorbornenes such as 5-ethylidene-2-norbornene, 5- Butylidene-2-norbornene, 2-methallyl-5-norbornene, 2-isopropenyl-5-norbornene and tricyclodienes such as 3-methyltricyclo (5.2.1.0.2.6) -3,8-decadiene or mixtures thereof.
- the diene content of the EPDM rubbers is preferably 0.5 to 50, in particular 1 to 8 wt .-%, based on the total weight of the rubber.
- EPM or EPDM rubbers may preferably also be grafted with reactive carboxylic acids or their derivatives.
- reactive carboxylic acids or their derivatives e.g. Acrylic acid, methacrylic acid and its derivatives, e.g. Glycidyl (meth) acrylate, and called maleic anhydride.
- Another group of preferred rubbers are copolymers of ethylene with acrylic acid and / or methacrylic acid and / or the esters of these acids.
- the rubbers may still contain dicarboxylic acids such as maleic acid and fumaric acid or derivatives of these acids, e.g. Esters and anhydrides, and / or monomers containing epoxy groups.
- dicarboxylic acid derivatives or monomers containing epoxy groups are preferably incorporated into the rubber by adding monomers containing dicarboxylic acid or epoxy groups of the general formulas I or II or III or IV to the monomer mixture
- CHR 7 CH (CH 2 ) m o (CHR 6 ) ⁇ CH / 0 ⁇ CHR 5 (MI)
- R 1 to R 9 represent hydrogen or alkyl groups having 1 to 6 carbon atoms and 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
- the radicals R 1 to R 9 preferably denote 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 formulas I, II and IV are maleic acid, maleic anhydride and epoxy group-containing esters of acrylic acid and / or methacrylic acid, such as glycidyl acrylate, glycidyl methacrylate and the esters with tertiary alcohols, such as t-butyl acrylate. Although the latter have no free carboxyl groups, their behavior is close to the free acids and are therefore termed monomers with latent carboxyl groups.
- the copolymers consist of 50 to 98 wt .-% of ethylene, 0.1 to 20 wt .-% of monomers containing epoxy groups and / or methacrylic acid and / or monomers containing acid anhydride groups and the remaining amount of (meth) acrylic acid esters.
- 0.1 to 40 in particular 0.3 to 20 wt .-% glycidyl acrylate and / or glycidyl methacrylate, (meth) acrylic acid and / or maleic anhydride, and 1 to 45, in particular 10 to 40 wt .-% n-butyl acrylate and / or 2-ethylhexyl acrylate.
- esters of acrylic and / or methacrylic acid are the methyl, ethyl, propyl and i- or t-butyl esters.
- vinyl esters and vinyl ethers can also be used as comonomers.
- the ethylene copolymers described above can be prepared by methods known per se, preferably by random copolymerization under high pressure and elevated temperature. Corresponding methods are generally known.
- Preferred elastomers are also emulsion polymers, their preparation e.g. at Blackley in the monograph "Emulsion Polymerization".
- the emulsifiers and catalysts which can be used are known per se.
- homogeneously constructed elastomers or those with a shell structure can be used.
- the shell-like structure is determined by the order of addition of the individual monomers; the morphology of the polymers is also influenced by this order of addition.
- acrylates such as e.g. N-butyl acrylate and 2-ethylhexyl acrylate, corresponding methacrylates, butadiene and isoprene and their mixtures called.
- monomers for the preparation of the rubber portion of the elastomers acrylates such as e.g. N-butyl acrylate and 2-ethylhexyl acrylate, corresponding methacrylates, butadiene and isoprene and their mixtures called.
- monomers may be reacted with other monomers such as e.g. Styrene, acrylonitrile, vinyl ethers and other acrylates or methacrylates such as methyl methacrylate, methyl acrylate, ethyl acrylate and propyl acrylate are copolymerized.
- the soft or rubber phase (with a glass transition temperature of below 0 ° C) of the elastomers can be the core, the outer shell or a middle shell (for elastomers with more than two-shell construction); in the case of multi-shell elastomers, it is also possible for a plurality of shells to consist of a rubber phase.
- one or more hard components having glass transition temperatures of more than 20 ° C.
- these are generally prepared by polymerization of styrene, acrylonitrile, methacrylonitrile, ⁇ -methylstyrene, p-methylstyrene, acrylic esters and methacrylic acid esters such as methyl acrylate, ethyl acrylate and methyl methacrylate as the main monomers.
- acrylic esters and methacrylic acid esters such as methyl acrylate, ethyl acrylate and methyl methacrylate as the main monomers.
- smaller proportions of other comonomers can also be used here.
- emulsion polymers which have reactive groups on the surface. Such groups are, for example, epoxy, carboxyl, latent carboxyl, amino or amide groups and functional groups obtained by concomitant use of monomers of the general formula
- R 10 is hydrogen or a C 4 to C 4 -alkyl group
- R 1 is hydrogen, a C 8 to C 8 -alkyl group or an aryl group, in particular phenyl,
- R 12 is hydrogen, a C 10 to C 10 alkyl, a C 6 to C 12 aryl group or -OR 13
- R 3 is a C to C 8 -alkyl or C 6 - may be substituted by C ⁇ 2 aryl group optionally containing N-O- or with groups,
- X is a chemical bond, a C to C 10 -alkylene or C 6 -C 2 -arylene or
- Z is a d- to C-
- the graft monomers described in EP-A 208 187 are also suitable for introducing reactive groups on the surface.
- acrylamide methacrylamide and substituted esters of acrylic acid or methacrylic acid, such as (Nt-butylamino) -ethyl methacrylate, (N, N). Dimethylamino) ethylacrylate, (N, N-dimethylamino) -methylacrylate and (N, N-diethylamino) ethylacrylate.
- the particles of the rubber phase can also be crosslinked.
- monomers acting as crosslinking agents are buta-1,3-diene, divinylbenzene, diallyl phthalate and dihydrodicyclopentadienyl acrylate, and the compounds described in EP-A 50265.
- graft-linking monomers may also be used, i. Monomers having two or more polymerizable double bonds, which react at different rates in the polymerization. Preferably, those compounds are used in which at least one reactive group polymerizes at about the same rate as the other monomers, while the other reactive group (or reactive groups) e.g. significantly slower polymerizing (polymerizing).
- the different polymerization rates bring a certain proportion of unsaturated double bonds in the rubber with it. If a further phase is subsequently grafted onto such a rubber, the double bonds present in the rubber react at least partially with the graft monomers to form chemical bindings, ie. the grafted phase is at least partially linked via chemical bonds to the graft base.
- graft-crosslinking monomers examples include allyl-containing monomers, in particular allyl esters of ethylenically unsaturated carboxylic acids such as allyl acrylate, allyl methacrylate, diallyl maleate, diallyl fumarate, diallyl itaconate or the corresponding monoallyl compounds of these dicarboxylic acids.
- allyl-containing monomers in particular allyl esters of ethylenically unsaturated carboxylic acids such as allyl acrylate, allyl methacrylate, diallyl maleate, diallyl fumarate, diallyl itaconate or the corresponding monoallyl compounds of these dicarboxylic acids.
- allyl-containing monomers in particular allyl esters of ethylenically unsaturated carboxylic acids such as allyl acrylate, allyl methacrylate, diallyl maleate, diallyl fumarate, diallyl itaconate or the corresponding monoally
- the proportion of these crosslinking monomers in the impact-modifying polymer is up to 5% by weight, preferably not more than 3% by weight, based on the impact-modifying polymer.
- graft polymers having a core and at least one outer shell, which have the following structure:
- graft polymers in particular ABS and / or ASA polymers in amounts of up to 40% by weight, are preferably used for the impact modification of PBT, if appropriate in a mixture with up to 40% by weight of polyethylene terephthalate.
- Corresponding blend products are available under the trademark Ultradur®S (formerly Ultrablend® of BASF AG).
- graft polymers having a multi-shell structure instead of graft polymers having a multi-shell structure, homogeneous, i. single-shell elastomers of buta-1,3-diene, isoprene and n-butyl acrylate or copolymers thereof are used. These products can also be prepared by concomitant use of crosslinking monomers or monomers having reactive groups.
- emulsion polymers examples include n-butyl acrylate / (meth) acrylic acid copolymers, n-butyl acrylate / glycidyl acrylate or n-butyl acrylate / glycidyl methacrylate copolymers, graft polymers having an inner core of n-butyl acrylate or butadiene-based and an outer shell the aforementioned copolymers and copolymers of ethylene with comonomers providing reactive groups.
- the described elastomers may also be prepared by other conventional methods, e.g. by suspension polymerization.
- Silicone rubbers as described in DE-A 3725 576, EP-A 235 690, DE-A 38 00603 and EP-A 319290, are likewise preferred. Of course, it is also possible to use mixtures of the rubber types listed above.
- Fibrous or particulate fillers D which may be mentioned are carbon fibers, glass fibers, glass beads, amorphous silicic acid, asbestos, calcium silicate, calcium metasilicate, magnesium carbonate, kaolin, chalk, powdered quartz, mica, barium sulfate and feldspar, in amounts of up to 50 Wt .-%, in particular up to 40% are used.
- Preferred fibrous fillers are carbon fibers, aramid fibers and potassium titanate fibers, glass fibers being particularly preferred as E glass. These can be used as rovings or cut glass in the commercial forms.
- the fibrous fillers can be surface-pretreated with a silane compound.
- Suitable silane compounds are those of the general formula
- n is an integer from 2 to 10, preferably 3 to 4, m is an integer from 1 to 5, preferably 1 to 2, k is an integer from 1 to 3, preferably 1
- Preferred silane compounds are aminopropyltrimethoxysilane, aminobutyltrimethoxysilane, aminopropyltriethoxysilane, aminobutyltriethoxysilane and the corresponding silanes which contain a glycidyl group as substituent X.
- the silane compounds are generally used in amounts of 0.05 to 5, preferably 0.5 to 1, 5 and in particular 0.8 to 1 wt .-% (based on C) for surface coating.
- acicular mineral fillers are also suitable.
- the term "needle-shaped mineral fillers” is understood to mean a mineral filler with a pronounced, needle-like character.
- An example is acicular wollastonite.
- the mineral has an L / D (Length diameter) ratio of 8: 1 to 35: 1, preferably from 8: 1 to 11: 1.
- the mineral filler may optionally be pretreated with the silane compounds mentioned above; however, pretreatment is not essential.
- Kaolin, calcined kaolin, wollastonite, talc and chalk are mentioned as further fillers.
- thermoplastic molding compositions of the invention may contain conventional processing aids such as stabilizers, antioxidants, agents against thermal decomposition and decomposition by ultraviolet light, lubricants and mold release agents, colorants such as dyes and pigments, nucleating agents, plasticizers, etc.
- antioxidants and heat stabilizers sterically hindered phenols and / or phosphites, hydroquinones, aromatic secondary amines such as diphenylamines, various substituted representatives of these groups and mixtures thereof in concentrations up to 1 wt .-%, based on the weight of the thermoplastic molding compositions mentioned.
- UV stabilizers which are generally used in amounts of up to 2% by weight, based on the molding composition, of various substituted resorcinols, salicylates, benzotriazoles and benzophenones may be mentioned.
- inorganic pigments such as titanium dioxide, ultramarine blue, iron oxide and carbon black, furthermore organic pigments such as phthalocyanines, quinacridones, perylenes and also dyes such as nigrosine and anthraquinones as colorants.
- the nucleating agents used may be sodium phenylphosphinate, aluminum oxide, silicon dioxide and preferably talc.
- lubricants and mold release agents are usually used in amounts of up to 1 wt .-%.
- Preferred are long-chain fatty acids (eg stearic acid or behenic acid), their salts (eg Ca or Zn stearate) or montan waxes (mixtures of straight-chain, saturated carboxylic acids with chain lengths of 28 to 32 carbon atoms) and Ca or Na.
- long-chain fatty acids eg stearic acid or behenic acid
- their salts eg Ca or Zn stearate
- montan waxes mixturetures of straight-chain, saturated carboxylic acids with chain lengths of 28 to 32 carbon atoms
- Ca or Na calcium or Na
- plasticizers are dioctyl phthalate, dibenzyl phthalate, butyl benzyl phthalate, hydrocarbon oils and N- (n-butyl) benzenesulfonamide.
- the novel molding materials may contain from 0 to 2% by weight of fluorine-containing ethylene polymers. These are polymers of ethylene with a fluorine content of 55 to 76 wt .-%, preferably 70 to 76 wt .-%.
- PTFE polytetrafluoroethylene
- tetrafluoroethylene-hexafluoropropylene copolymers or tetrafluoroethylene copolymers with smaller proportions (generally up to 50% by weight) of copolymerizable ethylenically unsaturated monomers.
- PTFE polytetrafluoroethylene
- tetrafluoroethylene-hexafluoropropylene copolymers or tetrafluoroethylene copolymers with smaller proportions (generally up to 50% by weight) of copolymerizable ethylenically unsaturated monomers.
- fluorine-containing ethylene polymers are homogeneously distributed in the molding compositions and preferably have a particle size d 50 (number average) in the range from 0.05 to 10 .mu.m, in particular from 0.1 to 5 .mu.m. These small particle sizes can be achieved particularly preferably by using aqueous dispersions of fluorine-containing ethylene polymers and incorporating them into a polyester melt.
- the novel thermoplastic molding compositions can be prepared by processes known per se, in which the starting components are mixed in customary mixing devices, such as screw extruders, Brabender mills or Banbury mills, and then extruded. After extrusion, the extrudate can be cooled. and crushed. It is also possible to premix individual components and then to add the remaining starting materials individually and / or likewise mixed.
- the mixing temperatures are usually 230 to 290 ° C.
- the components B) and optionally C) can be mixed with a polyester prepolymer, formulated and granulated.
- the resulting granules are then condensed in solid phase under inert gas continuously or discontinuously at a temperature below the melting point of component A) to the desired viscosity.
- thermoplastic molding compositions according to the invention are characterized by good flowability combined with good mechanical properties.
- the processing of the molding compositions is possible without problems and in short cycle times and is therefore particularly suitable for thin-walled components (nano-molded parts).
- Component A / 1 Polybutylenterephathalat having a viscosity number VN of 130 ml / g and a Carbonxylend phenomenongehalt of 34 meq / kg (Ultradur B 4520 ® from BASF AG) (VN measured in 0.5 wt .-% solution of phenol / o-dichlorobenzene ), 1: 1 mixture at 25 ° C, containing 0.65 wt .-% pentaerythritol tetrastearate (component C / 1 based on 100 wt .-% A).
- Component A / 3 Polytrimethylene terephthalate PTT with a VN of 106 ml / g
- Component A / 4 Polycarbonate based on bisphenol A and diphenyl carbonate with a VZ of 59 ml / g
- Polybutylene terephthalate having a viscosity number VZ of 160 ml / g and a Carboxyl phenomenonhalt of 28 mev / kg (Ultradur ⁇ B 6550 BASF AG (VZ measured in 0.5 wt .-% solution of phenol / o-dichlorobenzene), 1: 1 Mixture at 25 ° C.
- Polybutylene terephthalate having a viscosity number VZ of 107 ml / g and a Carboxyl phenomenonhalt of 31 mev / kg (Ultradur ⁇ B 2550 BASF AG (VZ measured in 0.5 wt .-% solution of phenol / o-dichlorobenzene), 1: 1 Mixture at 25 ° C.
- the distilled ethanol was collected in a cooled round bottomed flask, weighed and the conversion percentage determined in relation to the theoretically possible full conversion (see Table 1).
- reaction products were then analyzed by gel permeation chromatography, eluent was dimethylacetamide, polymethylmethacrylate (PMMA) was used as standard.
- PMMA polymethylmethacrylate
- TMP trimethylolpropane
- DEC diethyl carbonate
- EO ethylene oxide
- the components A) to C) were mixed on a twin-screw extruder at 250 to 260 ° C and extruded into a water bath. After granulation and drying, specimens were sprayed and tested on an injection molding machine.
- the MVR was determined according to ISO 1133, the modulus of elasticity according to ISO 527-2, the Charpy impact strength according to ISO 179-2 / 1 eU.
- VZ ISO 1628 in phenol / o-dichlorobenzene 1: 1, 25 ° C, the yield / elongation at break according to ISO 527-2.
- compositions according to the invention and the results of the measurements can be taken from the tables.
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Abstract
Description
Claims
Priority Applications (11)
Application Number | Priority Date | Filing Date | Title |
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EP05707138A EP1713861B1 (de) | 2004-02-04 | 2005-02-02 | Fliessfähige polyesterformmassen |
PL05707138T PL1713861T3 (pl) | 2004-02-04 | 2005-02-02 | Plastyczne tłoczywa poliestrowe |
JP2006551786A JP4651043B2 (ja) | 2004-02-04 | 2005-02-02 | 流動能を有するポリエステル成形材料 |
KR1020067017828A KR101152506B1 (ko) | 2004-02-04 | 2005-02-02 | 유동성 폴리에스테르 성형 조성물 |
CA2554037A CA2554037C (en) | 2004-02-04 | 2005-02-02 | Fluid polyester moulding masses |
BRPI0507266A BRPI0507266B1 (pt) | 2004-02-04 | 2005-02-02 | massas de moldagem termoplásticas, e, uso das mesmas |
AU2005211503A AU2005211503B2 (en) | 2004-02-04 | 2005-02-02 | Fluid polyester moulding masses |
DE502005000708T DE502005000708D1 (de) | 2004-02-04 | 2005-02-02 | Fliessfähige polyesterformmassen |
US10/587,997 US20090030140A1 (en) | 2004-02-04 | 2005-02-02 | Fluid polyester molding masses |
IL176785A IL176785A (en) | 2004-02-04 | 2006-07-11 | Thermoplastic molding compositions and uses thereof |
US13/482,496 US8410227B2 (en) | 2004-02-04 | 2012-05-29 | Fluid polyester moulding masses |
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DE102004005652.8 | 2004-02-04 | ||
DE102004005652A DE102004005652A1 (de) | 2004-02-04 | 2004-02-04 | Fließfähige Polyesterformmassen |
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US11/587,997 A-371-Of-International US20070246059A1 (en) | 2004-04-30 | 2005-04-29 | Accessory |
US13/482,496 Continuation US8410227B2 (en) | 2004-02-04 | 2012-05-29 | Fluid polyester moulding masses |
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US (2) | US20090030140A1 (de) |
EP (1) | EP1713861B1 (de) |
JP (1) | JP4651043B2 (de) |
KR (1) | KR101152506B1 (de) |
CN (1) | CN100506910C (de) |
AT (1) | ATE361950T1 (de) |
AU (1) | AU2005211503B2 (de) |
BR (1) | BRPI0507266B1 (de) |
CA (1) | CA2554037C (de) |
DE (2) | DE102004005652A1 (de) |
ES (1) | ES2285679T3 (de) |
IL (1) | IL176785A (de) |
MY (1) | MY139459A (de) |
PL (1) | PL1713861T3 (de) |
WO (1) | WO2005075565A1 (de) |
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---|---|---|---|---|
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US7842653B2 (en) * | 2005-06-16 | 2010-11-30 | Council Of Scientific & Industrial Research | Process for the preparation of lubricants |
DE102005034980A1 (de) * | 2005-07-22 | 2007-01-25 | Basf Ag | Fasern und Flüssigkeitsbehälter aus PET |
CN101134839B (zh) * | 2007-09-30 | 2011-01-12 | 深圳市科聚新材料有限公司 | 一种阻燃玻纤增强聚碳酸酯材料及其制备方法 |
JP2009191194A (ja) * | 2008-02-15 | 2009-08-27 | Jsr Corp | ポリカーボネートの製造方法 |
EP2452230B1 (de) * | 2009-07-10 | 2013-11-20 | Basf Se | Tonerharze für elektronische kopierzwecke |
US11390675B2 (en) | 2016-09-21 | 2022-07-19 | Nextcure, Inc. | Antibodies for Siglec-15 and methods of use thereof |
CN106674966A (zh) * | 2016-12-27 | 2017-05-17 | 上海普利特化工新材料有限公司 | 一种低收缩率高流动性纤维增强pc和abs合金材料及其制备方法 |
US10053533B1 (en) | 2017-04-13 | 2018-08-21 | Presidium Usa, Inc. | Oligomeric polyol compositions |
KR102240713B1 (ko) | 2018-07-31 | 2021-04-14 | 롯데첨단소재(주) | 폴리에스테르 수지 조성물 및 이를 이용한 성형품 |
CN115109403B (zh) * | 2022-08-08 | 2023-09-26 | 温州科尔新材料有限公司 | 一种高强度耐磨pc材料及其制备工艺 |
Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6037444A (en) * | 1995-12-22 | 2000-03-14 | Courtaulds Coatings (Holdings) Limited | Selective chemical reactions and polymers of controlled architecture produced thereby |
WO2000058385A1 (de) * | 1999-03-25 | 2000-10-05 | Bayer Aktiengesellschaft | Hochverzweigte polykondensate |
EP1099727A2 (de) * | 1999-11-09 | 2001-05-16 | Basf Aktiengesellschaft | Fliessfähige Polyamide |
US20020120076A1 (en) * | 2000-12-21 | 2002-08-29 | Degussa Ag | Free flowing polyester molding composition |
US6497959B1 (en) * | 2000-03-30 | 2002-12-24 | General Electric Company | Use of dendrimers as a processing aid and surface modifier for thermoplastic resins |
WO2003004546A1 (de) * | 2001-07-03 | 2003-01-16 | Bühler AG | Modifizierte nachkondensierte polyester |
EP1424360A1 (de) * | 2002-11-26 | 2004-06-02 | Bayer Aktiengesellschaft | Hochfliessfähige Polymerzusammensetzungen mit verzweigten Fliesshilfsmitteln |
WO2004087785A1 (de) * | 2003-04-04 | 2004-10-14 | Bayer Materialscience Ag | Hochverzweigte polycarbonate und copolycarbonate mit verbesserter fliessfähigkeit, ihre herstellung und verwendung |
WO2004111126A1 (en) * | 2003-06-11 | 2004-12-23 | Bp Corporation North America Inc. | Crystallizable thermoplastic resins and dendrimers with improved fabrication characteristics |
Family Cites Families (98)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE55319C (de) | Firma E. HERR-MANN & COHEN in Paris, 5 Rue de Chateaudun | Steinkohlen-Feuerungsanlage | ||
DE55320C (de) | E. CHRISTOPH in Wolfenbüttel, Mühlenstrafse 1 | Elektrische Signalvorrichtung mit einem an einem Leitungsdraht befestigten Schwimmer | ||
CA733567A (en) | 1966-05-03 | G. Williams Albert | Spinning of fibers from oxymethylene polymers | |
DE222868C (de) | 1907-11-05 | 1910-06-07 | ||
US3479314A (en) | 1960-07-22 | 1969-11-18 | Celanese Corp | Oxymethylene polymer composition and fiber produced therefrom |
US3305605A (en) | 1964-02-04 | 1967-02-21 | Union Carbide Corp | Compositions containing polycarbonate plasticizers |
NL6710503A (de) | 1966-08-06 | 1968-02-07 | ||
US3491048A (en) | 1967-09-11 | 1970-01-20 | Donald E Sargent | Silicone oil modified oxymethylene polymer |
SU519449A1 (ru) | 1973-02-20 | 1976-06-30 | Киевский технологический институт легкой промышленности | Термопластична формовочна композици |
GB1458561A (en) | 1974-03-07 | 1976-12-15 | Mitsubishi Rayon Co | Polyester fibres having excellent dyeability |
US4002581A (en) | 1975-12-08 | 1977-01-11 | General Electric Company | Foamed thermoplastic compositions of a linear polyester and an ionically crosslinked copolymer |
DE2703051A1 (de) | 1977-01-26 | 1978-07-27 | Bayer Ag | Hydrophile polyesterfaeden |
JPS53130351A (en) | 1977-04-18 | 1978-11-14 | Toyobo Petcord | High tenacity polyester textile goods for reinforcing rubber wares |
US4261216A (en) * | 1978-12-26 | 1981-04-14 | Eaton Corporation | Synchronized transmission |
US4239677A (en) | 1979-01-08 | 1980-12-16 | General Electric Company | Modified polyester compositions |
US4351916A (en) | 1980-09-09 | 1982-09-28 | E. I. Du Pont De Nemours And Company | Polyoxymethylene molding blends |
DE3039114A1 (de) | 1980-10-16 | 1982-05-13 | Bayer Ag, 5090 Leverkusen | Thermoplastische polyester-formmassen mit verbesserter zaehigkeit |
EP0088486A3 (de) * | 1982-02-05 | 1985-05-22 | Automotive Products Public Limited Company | Übertragung einer Drehbewegung |
FR2548319B1 (fr) * | 1983-06-28 | 1985-12-20 | Renault Vehicules Ind | Transmission a continuite de couple avec boite de vitesses mecanique et convertisseur |
DE3524234A1 (de) | 1985-07-06 | 1987-01-08 | Bayer Ag | Neue pfropfpolymerisate und deren abmischungen mit polyamiden |
US5250595A (en) | 1985-12-25 | 1993-10-05 | Kanegafuchi Kagaku Kogyo Kabushiki Kaisha | Flame-retardant resin composition |
DE3606982A1 (de) | 1986-03-04 | 1987-09-10 | Bayer Ag | Pfropfpolymerisate auf kautschukpolymeren mit blockartiger struktur |
DE3703790A1 (de) | 1987-02-07 | 1988-08-18 | Hoechst Ag | Kontinuierliches verfahren zur entfernung instabiler anteile aus rohem oxymethylencopolymerisat |
DE3725576A1 (de) | 1987-08-01 | 1989-02-09 | Bayer Ag | Formmassen aus aromatischem polyester und gepfropftem silikonkautschuk |
JPH01146958A (ja) | 1987-12-04 | 1989-06-08 | Polyplastics Co | 熱可塑性樹脂組成物 |
DE3800603A1 (de) | 1988-01-12 | 1989-07-20 | Bayer Ag | Formmassen aus aromatischen polyestern, vinyl-copolymerisaten und gepfropftem siliconkautschuk |
AU631582B2 (en) * | 1989-02-23 | 1992-12-03 | General Electric Company | Blends of polyesters and high flow polycarbonate |
DE3924869A1 (de) | 1989-07-27 | 1991-01-31 | Basf Ag | Flammgeschuetzte thermoplastische formmassen |
US5157076A (en) | 1989-12-07 | 1992-10-20 | The B.F. Goodrich Company | Thermoplastic elastomers with improved abrasion resistance |
US5136014A (en) | 1990-06-22 | 1992-08-04 | E. I. Du Pont De Nemours And Company | Hyperbranched polyesters |
DE59108450D1 (de) | 1990-11-09 | 1997-02-13 | Basf Ag | Thermoplastische Formmassen |
EP0558556B1 (de) | 1990-11-19 | 1997-04-23 | Cornell Research Foundation, Inc. | Hyperverzweigte polyester |
US5314949A (en) | 1991-01-24 | 1994-05-24 | Idemitsu Petrochemical Co., Ltd. | Polycarbonate resin composition |
DE4139962A1 (de) | 1991-12-04 | 1993-06-09 | Basf Ag, 6700 Ludwigshafen, De | Blockcopolymere aus acrylat- und methacrylateinheiten |
AU661794B2 (en) | 1992-10-21 | 1995-08-03 | Bayer Aktiengesellschaft | A sheathing material for optical fibres, based on polyalkylene terephthalate/polycarbonate |
DE4307392C2 (de) | 1993-03-10 | 2001-03-29 | Klaus Bloch | Monofil mit erhöhter Hydrolysebeständigkeit auf Basis Polyester für die Verwendung in technischen Geweben und Verfahren zu dessen Herstellung |
JP3017376B2 (ja) | 1993-06-18 | 2000-03-06 | ポリプラスチックス株式会社 | 高重合度ポリオキシメチレン3元共重合体の製造方法 |
JP3989028B2 (ja) * | 1993-08-10 | 2007-10-10 | 日本ペイント株式会社 | 水性塗料組成物およびそれを用いる塗装方法 |
DE4327245A1 (de) | 1993-08-13 | 1995-02-16 | Hoechst Ag | Verfahren zur Herstellung von Polyacetalen |
DE4328004A1 (de) | 1993-08-20 | 1995-02-23 | Basf Ag | Verfahren zur Herstellung von schlagzähen und transparenten thermoplastischen Werkstoffen und Mittel hierfür |
US5480944A (en) | 1993-08-23 | 1996-01-02 | Alliedsignal Inc. | Interpenetrating blends of linear polymers and compatible fractal polymers |
DE4401055A1 (de) | 1994-01-15 | 1995-07-20 | Basf Ag | Verfahren zur Herstellung von thermoplastischen Polyestern mit niedrigem Carboxylendgruppengehalt |
US5348699A (en) | 1994-03-02 | 1994-09-20 | Eastman Chemical Company | Fibers from copolyester blends |
EP0682057A1 (de) | 1994-05-09 | 1995-11-15 | Dsm N.V. | Verfahren zur Verbesserung der Verarbeitungscharacteristika von Polymerzusammensetzungen und dadurch erhaltene Polymerzusammensetzungen |
JPH0848861A (ja) * | 1994-08-05 | 1996-02-20 | Mitsubishi Chem Corp | 熱可塑性樹脂組成物 |
DE19512407A1 (de) | 1995-04-03 | 1996-10-10 | Basf Ag | Flammgeschützte thermoplastische Formmassen |
CN1105748C (zh) | 1995-08-31 | 2003-04-16 | Basf公司 | 具有低雾度的热塑性模塑材料 |
JP3115515B2 (ja) | 1995-10-03 | 2000-12-11 | ポリプラスチックス株式会社 | ポリアセタール共重合体の製造方法 |
NL1001753C2 (nl) | 1995-11-28 | 1997-05-30 | Dsm Nv | Samenstelling omvattende een kunststof en een additief. |
SE509240C2 (sv) | 1996-05-28 | 1998-12-21 | Perstorp Ab | Termoplastisk kompound bestående av en termoplastisk polymer bunden till en dendritisk eller hyperförgrenad makromolekyl samt komposition och produkt därav |
DE19648503A1 (de) * | 1996-11-22 | 1998-05-28 | Basf Ag | Flammgeschützte thermoplastische Formmassen |
GB2324797A (en) | 1997-05-02 | 1998-11-04 | Courtaulds Coatings | Hyperbranched polymers |
DE19745921A1 (de) | 1997-10-17 | 1999-04-22 | Basf Ag | Verwendung von hochmolekularen Polyesterformmassen |
DE19802820C1 (de) * | 1998-01-26 | 1999-12-16 | Getrag Getriebe Zahnrad | Kraftfahrzeug-Stufengetriebe |
DE19814529A1 (de) | 1998-04-01 | 1999-10-07 | Basf Ag | Polyalkylenarylate mit hohem Carbonylendgruppengehalt |
US6252025B1 (en) | 1998-08-11 | 2001-06-26 | Eastman Kodak Company | Vinyl hyperbranched polymer with photographically useful end groups |
DE19956539A1 (de) | 1999-11-24 | 2001-05-31 | Basf Ag | Thermisch stabile Polyesterformmassen |
DE10006037A1 (de) | 2000-02-10 | 2001-08-16 | Basf Ag | Verfahren zur Herstellung von Polyoxymethylenen |
US7015261B1 (en) | 2000-11-17 | 2006-03-21 | Arkema Inc. | Impact modifier combination for polymers |
JP4636705B2 (ja) * | 2001-02-20 | 2011-02-23 | 出光興産株式会社 | ポリカーボネートの製造方法 |
US6534600B2 (en) | 2001-03-26 | 2003-03-18 | Michigan Molecular Institute | Hyperbranched polyureas, polyurethanes, polyamidoamines, polyamides and polyesters |
JP2002294060A (ja) * | 2001-03-28 | 2002-10-09 | Teijin Ltd | 熱可塑性樹脂組成物 |
DE10136911A1 (de) | 2001-07-30 | 2003-02-20 | Buehler Ag | Modifizierte nachkondensierte Polyester |
US6541599B1 (en) | 2001-07-31 | 2003-04-01 | Eastman Kodak Company | Process for manufacture of soluble highly branched polyamides, and at least partially aliphatic highly branched polyamides obtained therefrom |
DE10147712A1 (de) | 2001-09-27 | 2003-04-17 | Basf Ag | Verfahren zur Herstellung aliphatischer Polycarbonate |
FR2833604B1 (fr) | 2001-12-17 | 2004-03-12 | Rhodianyl | Composition polymere thermoplastique comprenant un copolyamide hyperbranche, et articles realises a partir de cette composition |
FR2833603A1 (fr) | 2001-12-17 | 2003-06-20 | Rhodianyl | Composition polymere thermoplastique comprenant un copolyamide hyperbranche, et articles realises a partir de cette composition |
DE10163163A1 (de) | 2001-12-20 | 2003-07-03 | Basf Ag | Verfahren zur Herstellung hochfunktioneller, Hyperverzweigter Polyester durch enzymatische Veresterung |
US6794450B2 (en) | 2002-03-06 | 2004-09-21 | General Electric Company | High flow compositions of compatibilized poly(arylene ether) polyamide blends |
US7166657B2 (en) | 2002-03-15 | 2007-01-23 | Eastman Kodak Company | Article utilizing highly branched polymers to splay layered materials |
DE10219508A1 (de) | 2002-04-30 | 2003-11-13 | Basf Ag | Verfahren zur Herstellung hochfunktioneller, hyperverzweigter Polyester |
DE10240817A1 (de) | 2002-08-30 | 2004-03-11 | Basf Ag | Verfahren zur Herstellung hyperverzweigter, wasserlöslicher Polyester |
DE10251294B4 (de) | 2002-11-04 | 2007-05-16 | Ems Chemie Ag | Polyamidformmasse und deren Verwendung |
US7475241B2 (en) | 2002-11-22 | 2009-01-06 | Cisco Technology, Inc. | Methods and apparatus for dynamic session key generation and rekeying in mobile IP |
EP1424362A1 (de) | 2002-11-27 | 2004-06-02 | DSM IP Assets B.V. | Verfahren zur Herstellung einer Zusammensetzung |
US7342059B2 (en) | 2003-01-13 | 2008-03-11 | Eastman Chemical Company | Polyester-polycarbonate blends useful for extrusion blow-molding |
DE10304341A1 (de) | 2003-02-03 | 2004-08-12 | Basf Ag | Hydrolysebeständige Polyester |
FR2856693B1 (fr) | 2003-06-26 | 2005-08-26 | Rhodia Eng Plastics Srl | Composition a base de matrice polyamide et/ou polyester et articles realises a partir de cette composition |
DE10335959A1 (de) | 2003-08-04 | 2005-02-24 | Basf Ag | Alkohole als Cokatalysatoren bei der POM-Herstellung |
US7169880B2 (en) | 2003-12-04 | 2007-01-30 | Eastman Chemical Company | Shaped articles from cycloaliphatic polyester compositions |
DE102004005652A1 (de) | 2004-02-04 | 2005-08-25 | Basf Ag | Fließfähige Polyesterformmassen |
DE102004005657A1 (de) | 2004-02-04 | 2005-08-25 | Basf Ag | Fließfähige Polyesterformmassen |
ATE383401T1 (de) | 2004-08-10 | 2008-01-15 | Basf Ag | Polymerblends aus styrolcopolymeren und hyperverzweigten polycarbonaten oder polyestern |
DE102004038979A1 (de) | 2004-08-10 | 2006-02-23 | Basf Ag | Schlagzähmodifizierte Polyester mit hyperverzweigten Polyestern |
DE102004038976A1 (de) | 2004-08-10 | 2006-02-23 | Basf Ag | Fließfähige Polyesterformmassen mit ASA/ABS und SAN |
KR100616620B1 (ko) | 2004-09-22 | 2006-08-28 | 삼성전기주식회사 | 이온풍을 이용한 무소음 고효율 방열장치 |
DE102004049342A1 (de) | 2004-10-08 | 2006-04-13 | Basf Ag | Fließfähige Thermoplaste mit halogenfreiem Flammschutz |
DE102004050025A1 (de) | 2004-10-13 | 2006-04-20 | Basf Ag | Fließfähige Thermoplaste mit Halogenflammschutz |
DE102004051241A1 (de) | 2004-10-20 | 2006-05-04 | Basf Ag | Fließfähige Polyamide mit hyperverzweigten Polyestern/Polycarbonaten |
DE102004051214A1 (de) | 2004-10-20 | 2006-05-04 | Basf Ag | Fließfähige Polyoxymethylene |
FR2877659B1 (fr) | 2004-11-08 | 2007-01-12 | Reel Soc Par Actions Simplifie | Dispositif elevateur, notamment pour permettre l'acces du personnel de maintenance aux differentes parties d'un avion |
DE102004057867A1 (de) | 2004-11-30 | 2006-06-01 | Basf Ag | Verfahren zur Herstellung von Polyoxymethylenen |
DE102005004856A1 (de) | 2005-02-01 | 2006-08-03 | Basf Ag | Fliessfähige Polyester mit Carbodilmid-Stabilisatoren |
DE102005012482A1 (de) | 2005-03-16 | 2006-09-21 | Basf Ag | Verfahren zur Herstellung von Polyoxymethylenen |
DE102005027549A1 (de) | 2005-06-14 | 2006-12-21 | Basf Ag | Mehrkomponentenformkörper mit Polyesterschichten |
DE102005034980A1 (de) | 2005-07-22 | 2007-01-25 | Basf Ag | Fasern und Flüssigkeitsbehälter aus PET |
DE102005034999A1 (de) | 2005-07-22 | 2007-01-25 | Basf Ag | Fließfähige Polyester mit Polyesterelastomeren |
JP4175366B2 (ja) | 2005-12-26 | 2008-11-05 | 富士ゼロックス株式会社 | 符号化装置および方法 |
-
2004
- 2004-02-04 DE DE102004005652A patent/DE102004005652A1/de not_active Withdrawn
-
2005
- 2005-02-02 KR KR1020067017828A patent/KR101152506B1/ko active IP Right Grant
- 2005-02-02 US US10/587,997 patent/US20090030140A1/en not_active Abandoned
- 2005-02-02 CN CNB2005800041477A patent/CN100506910C/zh not_active Withdrawn - After Issue
- 2005-02-02 ES ES05707138T patent/ES2285679T3/es active Active
- 2005-02-02 JP JP2006551786A patent/JP4651043B2/ja active Active
- 2005-02-02 PL PL05707138T patent/PL1713861T3/pl unknown
- 2005-02-02 WO PCT/EP2005/001014 patent/WO2005075565A1/de active IP Right Grant
- 2005-02-02 EP EP05707138A patent/EP1713861B1/de active Active
- 2005-02-02 AU AU2005211503A patent/AU2005211503B2/en not_active Ceased
- 2005-02-02 AT AT05707138T patent/ATE361950T1/de active
- 2005-02-02 BR BRPI0507266A patent/BRPI0507266B1/pt active IP Right Grant
- 2005-02-02 CA CA2554037A patent/CA2554037C/en not_active Expired - Fee Related
- 2005-02-02 DE DE502005000708T patent/DE502005000708D1/de active Active
- 2005-02-03 MY MYPI20050420A patent/MY139459A/en unknown
-
2006
- 2006-07-11 IL IL176785A patent/IL176785A/en not_active IP Right Cessation
-
2012
- 2012-05-29 US US13/482,496 patent/US8410227B2/en active Active
Patent Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6037444A (en) * | 1995-12-22 | 2000-03-14 | Courtaulds Coatings (Holdings) Limited | Selective chemical reactions and polymers of controlled architecture produced thereby |
WO2000058385A1 (de) * | 1999-03-25 | 2000-10-05 | Bayer Aktiengesellschaft | Hochverzweigte polykondensate |
EP1099727A2 (de) * | 1999-11-09 | 2001-05-16 | Basf Aktiengesellschaft | Fliessfähige Polyamide |
US6497959B1 (en) * | 2000-03-30 | 2002-12-24 | General Electric Company | Use of dendrimers as a processing aid and surface modifier for thermoplastic resins |
US20020120076A1 (en) * | 2000-12-21 | 2002-08-29 | Degussa Ag | Free flowing polyester molding composition |
WO2003004546A1 (de) * | 2001-07-03 | 2003-01-16 | Bühler AG | Modifizierte nachkondensierte polyester |
EP1424360A1 (de) * | 2002-11-26 | 2004-06-02 | Bayer Aktiengesellschaft | Hochfliessfähige Polymerzusammensetzungen mit verzweigten Fliesshilfsmitteln |
WO2004087785A1 (de) * | 2003-04-04 | 2004-10-14 | Bayer Materialscience Ag | Hochverzweigte polycarbonate und copolycarbonate mit verbesserter fliessfähigkeit, ihre herstellung und verwendung |
WO2004111126A1 (en) * | 2003-06-11 | 2004-12-23 | Bp Corporation North America Inc. | Crystallizable thermoplastic resins and dendrimers with improved fabrication characteristics |
Non-Patent Citations (2)
Title |
---|
CARR P L ET AL: "Dielectric and mechanical characterization of aryl ester dendrimer/PET blends", POLYMER, ELSEVIER SCIENCE PUBLISHERS B.V, GB, vol. 37, no. 12, 1996, pages 2395 - 2401, XP004069150, ISSN: 0032-3861 * |
JANG J ET AL: "CRYSTALLIZATION BEHAVIOR OF POLY(ETHYLENE TEREPHTHALATE) BLENDED WITH HYPERBRANCHED POLYMERS: THE EFFECT OF TERMINAL GROUPS AND COMPOSITION OF HYPERBRANCHED POLYMERS", MACROMOLECULES, AMERICAN CHEMICAL SOCIETY, EASTON, PA, US, vol. 33, no. 33, 2000, pages 1864 - 1870, XP001079109, ISSN: 0024-9297 * |
Cited By (27)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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US8410227B2 (en) | 2004-02-04 | 2013-04-02 | Basf Se | Fluid polyester moulding masses |
WO2006008130A1 (de) * | 2004-07-21 | 2006-01-26 | Basf Aktiengesellschaft | Kontinuierliches verfahren zur herstellung von polyalkylenarylaten mit hyperverzweigten polyestern und/oder polycarbonaten |
US8362146B2 (en) | 2004-08-10 | 2013-01-29 | Basf Se | Impact-modified polyesters with hyperbranched polyesters/polycarbonates |
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US8425829B2 (en) | 2007-11-20 | 2013-04-23 | Basf Se | Use of thermoplastic molding materials for GID/WIT |
WO2009065833A1 (de) * | 2007-11-20 | 2009-05-28 | Basf Se | Verwendung von thermoplastischen formmassen für gid/wit |
CN101868503B (zh) * | 2007-11-20 | 2014-03-26 | 巴斯夫欧洲公司 | 热塑性模塑材料用于gid/wit的用途 |
US9426986B2 (en) | 2009-05-11 | 2016-08-30 | Basf Se | Hyperbranched polycarbonates for solubilizing poorly soluble active substances |
WO2012016927A1 (de) | 2010-08-02 | 2012-02-09 | Basf Se | Langfaserverstärkte polyester |
WO2013020820A1 (en) | 2011-08-05 | 2013-02-14 | Basf Se | Associative thickeners based on hyperbranched polymers |
WO2015200272A3 (en) * | 2014-06-23 | 2016-03-03 | Sabic Global Technologies B.V. | Filler reinforced thermoplastic compositions with improved bonding strength |
Also Published As
Publication number | Publication date |
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CA2554037A1 (en) | 2005-08-18 |
DE502005000708D1 (de) | 2007-06-21 |
CA2554037C (en) | 2012-05-01 |
EP1713861A1 (de) | 2006-10-25 |
US8410227B2 (en) | 2013-04-02 |
US20090030140A1 (en) | 2009-01-29 |
AU2005211503A1 (en) | 2005-08-18 |
US20120232212A1 (en) | 2012-09-13 |
BRPI0507266B1 (pt) | 2015-11-03 |
IL176785A (en) | 2010-12-30 |
DE102004005652A1 (de) | 2005-08-25 |
MY139459A (en) | 2009-10-30 |
ES2285679T3 (es) | 2007-11-16 |
PL1713861T3 (pl) | 2007-10-31 |
EP1713861B1 (de) | 2007-05-09 |
CN1918234A (zh) | 2007-02-21 |
JP4651043B2 (ja) | 2011-03-16 |
JP2007520608A (ja) | 2007-07-26 |
AU2005211503B2 (en) | 2010-07-15 |
KR20070001992A (ko) | 2007-01-04 |
ATE361950T1 (de) | 2007-06-15 |
IL176785A0 (en) | 2006-10-31 |
CN100506910C (zh) | 2009-07-01 |
KR101152506B1 (ko) | 2012-07-05 |
BRPI0507266A (pt) | 2007-06-26 |
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