WO2006074817A1 - Fliessfähige polyolefine - Google Patents
Fliessfähige polyolefine Download PDFInfo
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- WO2006074817A1 WO2006074817A1 PCT/EP2005/014164 EP2005014164W WO2006074817A1 WO 2006074817 A1 WO2006074817 A1 WO 2006074817A1 EP 2005014164 W EP2005014164 W EP 2005014164W WO 2006074817 A1 WO2006074817 A1 WO 2006074817A1
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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
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
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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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/02—Direct processing of dispersions, e.g. latex, to articles
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/10—Reinforcing macromolecular compounds with loose or coherent fibrous material characterised by the additives used in the polymer mixture
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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
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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
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
Definitions
- thermoplastic molding compositions comprising
- the invention relates to the use of the molding compositions according to the invention for the production of fibers, films and moldings as well as the moldings obtainable in this case of all kinds.
- EP-A 410 301 and EP-A 736 571 for example, halogen-containing flame-retardant polyamides and polyesters are known, in which antimony oxides are mostly used as synergist.
- 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, one observes a surprisingly low viscosity and a high reactivity due to the high number of functional groups on the spherical surface.
- the production is complicated by the fact that at each linking step protective groups must be introduced and removed again and cleaning operations. Ones are required, which is why one usually produces dendrimers only 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.
- thermoplastic compositions which contain dendrimeric polyesters as AB 2 molecule.
- a polyhydric alcohol as the core molecule reacts with dimethylolpropionic acid as the AB 2 molecule to form a dendrimeric polyester.
- a disadvantage of these mixtures is the high glass transition temperature of the dendrimeric polyesters, the comparatively complex preparation and above all the poor solubility of the dendrimers in the polyester matrix.
- the present invention therefore an object of the invention to provide thermoplastic polyolefin molding compositions which have good flowability and at the same time good mechanical properties.
- the additive should not bloom or tend to form coating.
- the molding compositions according to the invention contain from 10 to 99.99, preferably from 30 to 98, and in particular from 30 to 95,% by weight of at least one polyolefin homopolymer or copolymer.
- the component A) is preferably composed of a polyolefin homo- or copolymer, which should also be understood as meaning so-called functional polyolefin homo- or copolymer.
- Suitable polyolefin homopolymers are e.g. Polyethylene, polypropylene and polybutene.
- Suitable polyethylenes are very low (LLD-PE), low (LD-PE), medium (MD-PE) and high density (HD-PE) polyethylenes. These are short-chain or long-chain branched or linear polyethylenes which are used in a high-pressure process in the presence of radical initiators (LD / PE) or in a low-pressure process in the presence of so-called complex initiators, e.g. Phillips or Ziegler-Natta catalysts (LLD-PE, MD-PE, HD-PE) are produced.
- LLD-PE and MD-PE are introduced by copolymerization with ⁇ -olefins (e.g., butene, hexene or octene).
- LLD / PE generally has a density of 0.9 to 0.93 g / cm 3 and a melting temperature (determined by differential thermal analysis) of 120 to 13O 0 C, LD-PE a density of 0.915 to 0.935 g / cm 3 and a melting temperature of 105 to 115 0 C, MD-PE a density of 0.93 to 0.94 g / cm 3 and a melting temperature of 120 to 130 0 C and HD-PE a density of 0.94 to 0.97 g / cm 3 and a melting temperature of 128 to 136 0 C.
- Preferred LDPE and LLDPE have a density ⁇ 0.92 g / cm 3 .
- component A it is also possible to use homopolymers or copolymers of ethylene with C 3 to C 10 alk-1-enes, preferably copolymers containing from 2 to 8% by weight of at least one alk-1-ene with 4, 6 or 8 C Atoms can be used, which are obtainable by polymerization of the corresponding monomers with metallocene catalysts.
- the flowability measured as melt index MVI is generally 0.05 to 35 g / 10 '.
- the melt flow index corresponds to the amount of polymer which is pressed out within 10 minutes from the DIN 53 735 standardized test apparatus at a temperature of 190 0 C and 2.16 kg load.
- melt volume index MVI according to DIN 53 735 is generally 0.3 to 80 g / 10 min, preferably 0.5 to 35 g / 10 min at 230 0 C and 2.16 kg load.
- polypropylenes are usually carried out by low-pressure polymerization with metal-containing catalysts, for example with the aid of titanium and aluminum-containing Ziegler catalysts, or in the case of polyethylene by Phillips catalysts based on chromium-containing compounds.
- the polymerization reaction can be carried out with the usual in the art reactors, both in the gas phase, in solution or in a slurry.
- copolymers of ethylene with ⁇ -olefins such as propylene, butene, hexene, pentene, heptene and octene or with non-conjugated dienes such as norbornadiene and dicyclopentadiene.
- Copolymers A) should be understood to mean both random and block copolymers.
- Random copolymers are usually obtained by polymerizing a mixture of various monomers, block copolymers, by sequential polymerization of various monomers.
- polystyrene resin examples include polystyrene resin, polystyrene resin, polystyrene resin, polystyrene resin, polystyrene resin, polystyrene resin, polystyrene resin, polystyrene resin, polystyrene resin, polystyrene resin, polystyrene resin, polystyrene resin, polystyrene resin, polystyrene resin, polystyrene-styrene resin, polystyrene resin, polystyrene resin, polystyrene resin, polystyrene resin, polystyrene resin, polystyrene resin, polystyrene resin, polystyrene resin, polystyrene resin, polystyrene resin, polystyrene resin, polystyrene resin, polystyrene resin, polystyrene resin, polystyrene resin
- Functional monomers are to be understood as meaning monomers containing carboxylic acid, acid anhydride, acid amide, acid imide, carboxylic ester, amino, hydroxyl, epoxide, oxazoline, urethane, urea or lactam groups, which additionally have a reactive double bond.
- Examples of these are methacrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid and the alkyl esters of the above acid or its amides, maleimide, allylamine, allyl alcohol, glycidyl methacrylate, vinyl and Isopropenyloxazolin and Methacryloylcaprolactam and vinyl acetate.
- the functional monomers can be introduced either by copolymerization or by subsequent grafting in the polymer chain.
- the grafting can be carried out either in solution or in the melt, it being possible optionally to use free-radical initiators such as peroxides, hydroperoxides, peresters and percarbonates.
- the functional groups may be partially or totally reacted with metal salts such as zinc salts (often referred to as ionomers).
- Such polymers are generally available commercially (Polybond®, Exxelor®, Hostamont®, Admer®, Orevac® and Epolene®, Hostaprime®, Surlyne®).
- Suitable polyolefins are furthermore polyolefins obtainable by means of metallocene catalysts, with metallocene PE having from 2 to 8% by weight of C4, C6 or C8 comonomer units being preferred.
- 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 .-% B1) of at least one highly branched or hyperbranched polycarbonate, preferably 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) or at least one hyperbranched polyester as component B2) or mixtures thereof as explained below.
- 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. They can be constructed on the one hand, starting from a central molecule analogous to dendrimers, but 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. For the definition of 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 + Z + L (where T is the average number of terminal monomer units, Z is the average number of branched monomer units and 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 -8O 0 C to +140, preferably from -60 to 12O 0 C (according to DSC, DIN 53765).
- the viscosity (mPas) at 23 0 C is from 50 to 200,000, preferably from 100 to 150,000 and 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 .
- 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, trihydydydimethylbenzene, phloroglucides, hexahydroxybenzene, 1,3,5-benzenetrimethanol, 1, 1, 1-Tris (4
- polyhydric alcohols can also be used in mixture with difunctional alcohols (B '), with the proviso that the average 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- Hydroxycyclohexyl) propane, 1,1'-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohex
- 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%.
- the reaction of phosgene, diphosgene or triphosgene with the alcohol or alcohol mixture generally takes place with elimination of hydrogen chloride
- the reaction of the carbonates with the alcohol or alcohol mixture to give the highly functional, hyperbranched polycarbonate according to the invention takes place with elimination of the monofunctional alcohol or phenol from the carbonate.
- 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.
- alcohols such as methanol, ethanol, butanol, alcohol / water mixtures, acetone, 2-butanone, ethyl acetate, butyl acetate, methoxypropyl acetate, methoxyethyl acetate, tetrahydrofuran, dimethylformamide, di- methylacetamide, N-methylpyrrolidone, ethylene carbonate or propylene carbonate.
- a highly functional 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 not limited to the top, but products having a very large 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 no more than 500 terminal or pendant functional groups, preferably not more than 100 terminal or pendant functional groups.
- condensation product (K) either a Carbonate group or carbamoyl group and more than one OH group or one 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 n 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”.
- R has the meaning defined above and R 1 is an aliphatic or aromatic radical.
- 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 the ratio 2: 1, as shown in (IV), one obtains a molecule X 2 Y. At a ratio between 1: 1 and 2: 1, a mixture of molecules XY 2 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 the polycondensation product (P) is usually carried out at a temperature of 0 to 250 0 C, preferably at 60 to 160 0 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 phenol liberated in the reaction can be removed from the reaction equilibrium by distillation, optionally under 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 hydrogen carbonates, preferably of sodium, potassium or potassium Cesium, tertiary amines, guanidines, ammonium compounds, phosphonium compounds, aluminum, tin, zinc, titanium, zirconium or bismuth organic compounds, furthermore so-called double metal cyanide (DMC) catalysts, as described for example in DE 10138216 or in US Pat DE 10147712 described.
- 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 dibuty
- 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. Furthermore, 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 a carbonate group as a focal group and more than two OH groups or an OH group as a 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 product (P) to terminate the reaction is a product with groups which are reactive towards the focal group of (P) be added.
- groups which are reactive towards the focal group of (P) For example, in the case of a carbonate group as the focal group, a mono-, di- or poly-amine may be added.
- 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 in batch mode, semicontinuously or continuously.
- 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 in batch mode, semicontinuously or continuously.
- 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 introduction of a gas, preferably nitrogen, carbon dioxide or air, optionally at reduced pressure, are removed.
- the polycarbonates according to the invention can, in addition to the functional groups already obtained by the reaction, be given further functional groups.
- the functionalization can during the molecular weight build-up or even subsequently, i. take place after completion of the actual polycondensation.
- Such effects can be achieved, for example, by adding compounds during the polycondensation which, in addition to hydroxyl groups, carbonate groups or carbamoyl groups, contain further functional groups or functional elements, such as mercapto groups, primary, secondary or tertiary amino groups, ether groups, derivatives of carboxylic acids, derivatives of sulfonic acids , Derivatives of phosphonic acids, silane groups, siloxane groups, aryl radicals or long-chain alkyl radicals.
- compounds during the polycondensation which, in addition to hydroxyl groups, carbonate groups or carbamoyl groups, contain further functional groups or functional elements, such as mercapto groups, primary, secondary or tertiary amino groups, ether groups, derivatives of carboxylic acids, derivatives of sulfonic acids , Derivatives of phosphonic acids, silane groups, siloxane groups, aryl radicals or long-chain alkyl radicals.
- ethanolamine, propanolamine, isopropanolamine, 2- (butylamino) ethanol, 2- (cyclohexylamino) ethanol, 2-amino-1-butanol, 2- (2 ' aminoethoxy) ethanol or higher can be 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 synthesized, for example, by condensation of di- or higher-functional 14164
- 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.
- a big advantage of the method lies in its economy. Both the conversion to a condensation product (K) or polycondensation product (P) and the reaction of (K) or (P) to polycarbonates with other functional groups or elements can be carried out in a reaction apparatus, which is technically and economically advantageous.
- the molding compositions of the invention may comprise at least one hyperbranched polyester of the type A x B y , where
- x at least 1, preferably at least 1, 3, in particular at least 2 y at least 2.1, preferably at least 2.5, in particular at least 3
- a polyester of the type A x B y is understood to mean a condensate which is composed of an x-functional molecule A and a y-functional molecule B.
- Hyperbranched polyesters B2) in the context of this invention are understood as meaning undyed macromolecules having hydroxyl and carboxyl groups which are structurally as well as molecularly nonuniform. They can be constructed on the one hand, starting from a central molecule analogous to dendrimers, but 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. For the definition of 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.
- DB degree of branching
- Dendrimer in the context of the present invention is understood to mean that the degree of branching is 99.9-100%. For the definition of the degree of branching see H. Frey et al., Acta Polym. 1997, 48, 30 and the above formula for B1).
- the component B2) preferably has an M n of 300 to 30,000, in particular from 400 to 25,000 and very particularly from 500 to 20,000 g / mol, determined by means of GPC, standard PMMA, mobile phase dimethylacetamide.
- B2) has an OH number of 0 to 600, preferably 1 to 500, in particular from 20 to 500 mg KOH / g polyester according to DIN 53240 and preferably a COOH number of 0 to 600, preferably from 1 to 500 and in particular from 2 to 500 mg KOH / g polyester.
- the T 9 is preferably from -50 0 C to 14O 0 C and in particular from -50 to 100 0 C (by DSC, according to DIN 53765).
- such components B2) are preferred in which at least one OH or COOH number is greater than 0, preferably greater than 0.1 and in particular greater than 0.5.
- the inventive component B2) is obtainable by reacting (A) one or more dicarboxylic acids or one or more derivatives thereof with one or more at least trifunctional alcohols
- reaction in the solvent is the preferred method of preparation.
- Highly functional hyperbranched polyesters B2) in the context of the present invention are molecularly and structurally nonuniform. They differ in their molecular heterogeneity of dendrimers and are therefore produced with considerably less effort.
- the dicarboxylic acids which can be reacted according to variant (a) include, for example, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, cork acid, azelaic acid, sebacic acid, undecane- ⁇ , ⁇ -dicarboxylic acid, dodecane- ⁇ , ⁇ -dicarboxylic acid, glacial acetic acid 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 ice and trans-cyclopentane-1,3-dicarboxylic acid,
- dicarboxylic acids may be substituted with one or more radicals selected from
- Cio-alkyl for example methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso- butyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl, sec-pentyl, neo-pentyl, 1, 2
- C 3 -C 2 cycloalkyl for example cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl and Cyclodode- cyl; preferred are cyclopentyl, cyclohexyl and cycloheptyl;
- Alkylene groups such as methylene or ethylidene or
- C 6 -C 14 aryl groups such as, for example, 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.
- substituted dicarboxylic acids include: 2-methylmalonic acid, 2-ethylmalonic acid, 2-phenylmalonic acid, 2-methylsuccinic acid, 2-ethylsuccinic acid, 2-phenylsuccinic acid, itaconic acid, 3,3-dimethylglutaric acid.
- dicarboxylic acids which can be reacted according to variant (a) include ethylenically unsaturated acids, such as, for example, maleic acid and fumaric acid, and aromatic dicarboxylic acids, for example phthalic acid, isophthalic acid or terephthalic acid.
- the dicarboxylic acids can be used either as such or in the form of derivatives.
- Mono- or dialkyl esters preferably mono- or dimethyl esters or the corresponding mono- or diethyl esters, but also those of higher alcohols such as, for example, n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol, n-pentanol , n-hexanol-derived mono- and dialkyl esters,
- mixed esters preferably methyl ethyl esters.
- Succinic acid, glutaric acid, adipic acid, phthalic acid, isophthalic acid, terephthalic acid or their mono- or dimethyl esters are particularly preferably used. Most preferably, adipic acid is used.
- trifunctional alcohols for example, can be implemented: glycerol, butane-1,2,4-triol, n-pentane-1, 2,5-triol, n-pentane-1, 3,5-triol, n-hexane-1 , 2,6-triol, n-hexane-1, 2,5-triol, n-hexane-1,3,6-triol, trimethylolbutane, trimethylolpropane or di-trimethylolpropane, trimethylolethane, pentaerythritol or dipentaerythritol; Sugar alcohols such as mesoerythritol, threitol, sorbitol, mannitol or mixtures of the above at least trifunctional alcohols. Preference is given to using glycerol, trimethylolpropane, trimethylolethane and pentaerythritol.
- convertible tricarboxylic acids or polycarboxylic acids are, for example, 1, 2,4-benzenetricarboxylic acid, 1,3,5-benzenetricarboxylic acid, 1,2,4,5-Benzoltetra- carboxylic acid and mellitic acid.
- Tricarboxylic acids or polycarboxylic acids can be used in the reaction according to the invention either as such or in the form of derivatives.
- Mono-, di- or trialkyl preferably mono-, di- or trimethyl esters or the corresponding mono-, di- or triethyl esters, but also those of higher alcohols such as n-propanol, iso-propanol, n-butanol, isobutanol , tertiary
- diols for variant (b) of the present invention include ethylene glycol, propane-1,2-diol, propane-1,3-diol, butane-1,2-diol, butane-1,3-diol, butane-1 , 4-diol, butane-2,3-diol, pentane-1, 2-diol, pentane-1, 3-diol, pentane-1, 4-diol, pentane-1, 5-diol, pentane-2,3 -diol, pentane-2,4-diol, hexane-1, 2-diol, hexane-1, 3-diol, hexane-1, 4-diol, hexane-1,5-diol, hexane-1, 6-diol , Hexane-2,5-diol, heptane-1, 2-diol 1,
- Diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, polyethylene glycols HO (CH 2 CH 2 O) n -H or polypropylene glycols HO (CH [CH 3 ] CH 2 O) n -H or mixtures of two or more representatives of the above compounds, wherein n is an integer and n 4 - 25.
- one or both hydroxyl groups in the abovementioned diols can also be substituted by SH groups.
- the molar ratio of molecules A to molecules B in the A x B y polyester in variants (a) and (b) is 4: 1 to 1: 4, in particular 2: 1 to 1: 2.
- the at least trifunctional alcohols reacted according to variant (a) of the process may each have hydroxyl groups of the same reactivity. Also preferred here are at least trifunctional alcohols whose OH groups are initially identically reactive, but in which a drop in reactivity due to steric or electronic influences can be induced in the remaining OH groups by reaction with at least one acid group. This is the case, for example, when using trimethylolpropane or pentaerythritol.
- the at least trifunctional alcohols reacted according to variant (a) can also have hydroxyl groups with at least two chemically different reactivities.
- the different reactivity of the functional groups can be based either on chemical (for example primary / secondary / tertiary OH group) or on steric causes.
- the triol may be a triol having primary and secondary hydroxyl groups, preferred example being glycerin.
- the triol or the mixture of at least trifunctional alcohols may also be mixed with difunctional alcohols, preferably up to 50 mol%, based on the polyol mixture, but preference is given to working in the absence of diols and monofunctional alcohols.
- the tricarboxylic acid or the carboxylic acid mixture of at least trifunctional carboxylic acids may also be mixed with difunctional carboxylic acids, preferably up to 50 mol%, based on the acid mixture, but preference is given to working in the absence of mono- or dicarboxylic acids.
- Suitable are, for example, hydrocarbons such as paraffins or aromatics. loading especially suitable paraffins are n-heptane and cyclohexane. Particularly suitable aromatics are toluene, ortho-xylene, meta-xylene, para-xylene, xylene as a mixture of isomers, ethylbenzene, chlorobenzene and ortho- and meta-dichlorobenzene. Furthermore, as solvents in the absence of acidic catalysts are particularly suitable: ethers such as dioxane or tetrahydrofuran and ketones such as methyl ethyl ketone and methyl isobutyl ketone.
- the amount of added solvent is at least according to the invention
- 0.1 wt .-% based on the mass of the starting materials to be reacted, preferably at least 1 wt .-% and more preferably at least
- a dehydrating agent to work as an additive, which is added at the beginning of the reaction.
- Suitable examples are molecular sieves, in particular molecular sieve 4A, MgSO 4 and Na 2 SO 4 . It is also possible during the reaction to add further de-watering agent or to replace de-watering agent with fresh de-watering agent. It is also possible to distill off water or alcohol formed during the reaction and to use, for example, a water separator.
- the process can be carried out in the absence of acidic catalysts.
- alumium compounds of the general formula Al (OR) 3 and titanates of the general formula Ti (OR) 4 can be used as acidic inorganic catalysts, wherein the radicals R may be the same or different and are independently selected from each other
- C 1 -C 4 -alkyl radicals for example methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neo -Pentyl, 1, 2-di- methylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec-hexyl, n-heptyl, iso-heptyl, n-octyl, 2-ethylhexyl, n-nonyl or n-decyl,
- C 3 -C 12 -cycloalkyl radicals for example cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl and cyclododecyl; preferred are cyclopentyl, cyclohexyl and cycloheptyl.
- radicals R in Al (OR) 3 or Ti (OR) 4 are preferably identical and selected from isopropyl or 2-ethylhexyl.
- Preferred acidic organometallic catalysts are, for example, selected from dialkyltin oxides R 2 SnO, where R is as defined above.
- a particularly preferred representative of acidic organometallic catalysts is di-n-butyltin oxide, which is commercially available as so-called oxo-tin, or di-n-butyltin dilaurate.
- Preferred acidic organic catalysts are acidic organic compounds with, for example, phosphate groups, sulfonic acid groups, sulfate groups or phosphonic acid groups. Particularly preferred are sulfonic acids such as para-toluene sulfonic acid. It is also possible to use acidic ion exchangers as acidic organic catalysts, for example polystyrene resins containing sulfonic acid groups, which are crosslinked with about 2 mol% of divinylbenzene.
- acidic inorganic, organometallic or organic catalysts according to the invention 0.1 to 10% by weight, preferably 0.2 to 2% by weight, of catalyst is used.
- the process according to the invention is carried out under an inert gas atmosphere, that is to say, for example, under carbon dioxide, nitrogen or noble gas, of which in particular argon can be mentioned.
- the inventive method is carried out at temperatures of 60 to 200 0 C.
- the pressure conditions of the method according to the invention are not critical per se. You can work at significantly reduced pressure, for example at 10 bis 64
- the process according to the invention can also be carried out at pressures above 500 mbar.
- the reaction is preferably at atmospheric pressure; but it is also possible to carry out at slightly elevated pressure, for example up to 1200 mbar. You can also work under significantly increased pressure, for example at Drucket! up to 10 bar.
- the reaction is preferably at atmospheric pressure.
- the reaction time of the process according to the invention is usually 10 minutes to 25 hours, preferably 30 minutes to 10 hours and more preferably one to 8 hours.
- the highly functional hyperbranched polyester can be easily isolated, for example by filtering off the catalyst and concentration, wherein the concentration is usually carried out at reduced pressure. Further suitable work-up methods are precipitation after addition of water and subsequent washing and drying.
- component B2) can be prepared in the presence of enzymes or decomposition products of enzymes (according to DE-A 101 63163).
- the dicarboxylic acids reacted according to the invention do not belong to the acidic organic catalysts in the sense of the present invention.
- lipases or esterases are Candida cylindracea, Candida lipolytica, Candida rugosa, Candida antarctica, Candida utilis, Chromobacterium viscosum, Geolrichum viscosum, Geotrichum candidum, Mucorjavanicus, Mucor mihei, pig pancreas, Pseudomonas spp., Pseudomonas fluorescens, Pseudomonas cepacia, Rhizopus arrhizus, Rhizopus delemar, Rhizopus niveus, Rhizopus oryzae, Aspergillus niger, Penicillium roquefortii, Penicillium camembertii or Esterase from Bacillus spp. and Bacillus thermoglucosidase.
- Candida antarctica lipase B The enzymes listed are commercially available, for example from Novozymes
- the enzyme is preferably used in immobilized form, for example on silica gel or Lewatit®.
- Processes for the immobilization of enzymes are known per se, for example from Kurt Faber, "Biotransformations in Organic Chemistry", 3rd edition 1997, Springer Verlag, Chapter 3.2 "Immobilization” page 345-356. Immobilized enzymes are commercially available, for example from Novozymes Biotech Inc., Denmark.
- the amount of immobilized enzyme used is 0.1 to 20 wt .-%, in particular 10 to 15 wt .-%, based on the mass of the total starting materials to be reacted.
- the inventive process is carried out at temperatures above 6O 0 C. Preferably, one works at temperatures of 100 0 C or below. Temperatures are preferred to 80 ° C, very particularly preferably from 62 to 75 0 C and even more preferably from 65 to 75 0 C.
- Suitable are, for example, hydrocarbons such as paraffins or aromatics.
- paraffins are n-heptane and cyclohexane.
- aromatics are toluene, ortho-xylene, meta-xylene, para-xylene, xylene as a mixture of isomers, ethylbenzene, chlorobenzene and ortho- and meta-dichlorobenzene.
- ethers such as dioxane or tetrahydrofuran and ketones such as methyl ethyl ketone and methyl isobutyl ketone.
- the amount of solvent added is at least 5 parts by weight, based on the mass of the starting materials to be reacted, preferably at least 50 parts by weight and more preferably at least 100 parts by weight. Amounts of more than 10,000 parts by weight of solvent are not desirable, because at significantly lower concentrations, the reaction rate decreases significantly, which leads to uneconomically lank long implementation periods.
- the process according to the invention is carried out at pressures above 500 mbar.
- the reaction is at atmospheric pressure or slightly elevated pressure, for example up to 1200 mbar. You can also work under significantly elevated pressure, for example, at pressures up to 10 bar.
- the reaction is preferably at atmospheric pressure.
- the reaction time of the method according to the invention is usually 4 hours to 6 days, preferably 5 hours to 5 days and more preferably 8 hours to 4 days.
- the highly functional hyperbranched polyester can be isolated, for example by filtering off the enzyme and concentration, wherein the concentration is usually carried out at reduced pressure. Further suitable work-up methods are precipitation after addition of water and subsequent washing and drying.
- high-functionality, hyperbranched polyesters obtainable by the process according to the invention are distinguished by particularly low levels of discoloration and resinification.
- hyperbranched polymers see also 'PJ. Flory, J. Am. Chem. Soc. 1952, 74, 2718 and A. Sunder et al., Chem. Eur. J. 2000, 6, No.1, 1-8.
- "highly functional hyperbranched” means that the degree of branching, that is to say the average number of dendritic linkages plus the average number of end groups per molecule, is 10 - 99.9%, preferably 20 - 99%, more preferably 30-90% (see H. Frey et al., Acta Polym., 1997, 48, 30).
- the polyesters of the invention have a molecular weight M w of from 500 to 50,000 g / mol, preferably from 1,000 to 20,000, particularly preferably from 1,000 to 19,000.
- the polydispersity is from 1, 2 to 50, preferably 1, 4 to 40, particularly preferably 1, 5 to 30 and most preferably 1, 5 to 10. They are usually readily soluble, that is, clear solutions of up to 50 wt .-%, in some cases even up to 80 wt .-%, of the polyester according to the invention in tetrahydrofuran (THF) 1 n-butyl acetate, ethanol and numerous other solvents without the naked eye gel particles are detectable.
- THF tetrahydrofuran
- the high-functionality hyperbranched polyesters according to the invention are carboxy-terminated, carboxy- and hydroxyl-terminated and are preferably terminated by hydroxyl groups.
- the ratios of components B1) to B2) are preferably from 1:20 to 20: 1, in particular from 1:15 to 15: 1 and very particularly from 1: 5 to 5: 1, when used in a mixture.
- 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.
- molding compositions of 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 with 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.
- additives C) are, for example, in amounts of up to 40, preferably up to 30 wt .-% 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, isobutene, isoprene, chloroprene, vinyl acetate, styrene, acrylonitrile and acrylic or methacrylic esters with 1 to 18 C Atoms in the alcohol component.
- EPM ethylene-propylene
- EPDM ethylene-propylene-diene
- EPM rubbers generally have virtually no double bonds, while EPDM rubbers can have 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 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
- R 1 to R 9 are 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 the formulas I, II and IV are maleic acid, maleic anhydride and epoxy groups-containing esters of acrylic acid and / or methacrylic acid, such as glycidyl acrylate, glycidyl methacrylate and the esters with tertiary alcohols, such as 64
- 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
- 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.
- monomers for the preparation of the rubber part of the elastomers are acrylates such as, for example, n-butyl acrylate and 2-ethylhexyl acrylate, corresponding methacrylates, butadiene and isoprene, and mixtures thereof. These monomers can be reacted with other monomers such as, for example, styrene, acrylonitrile, vinyl ethers and other monomers.
- 29 ren 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 below 0 ° C.) of the elastomers can be the core, the outer shell or a middle shell (in the case of elastomers with a more than two-shell structure); 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 on the structure of the elastomer involved, these are generally prepared by polymerization of styrene, acrylonitrile, methacrylonitrile, ⁇ -methylstyrene, p-methylstyrene , Acrylic acid esters and methacrylic acid esters such as methyl acrylate, ethyl acrylate and methyl methacrylate produced as main monomers. In addition, smaller proportions of other comonomers can also be used here.
- emulsion polymers which have reactive groups on the surface.
- groups are e.g. 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 1 - to C 4 -alkyl group
- R 11 is hydrogen, a C 1 - to C 8 -alkenyl group or an aryl group, in particular phenyl,
- R 12 is hydrogen, a C 1 - to C 10 -alkyl, a C 6 - to C 12 ⁇ -aryl group or -OR 13
- R 13 is a C 1 - to C 8 -alkyl or C 6 - to C 12 -aryl group which may optionally be substituted by O- or N-containing groups, P2005 / 014164
- X is a chemical bond, a Cr to Cio-alkylene or or
- Z is a Ci to C 10 alkylene or C 6 - to C 2 arylene group.
- 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 1 N-dimethylamino) ethyl acrylate, (N, N-dimethylamino) methyl acrylate and (N 1 N-diethylamino) called ethyl acrylate.
- 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 also the compounds described in EP-A 50 265.
- graft-linking monomers can 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. polymerized much slower (polymerize).
- 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 grafting monomers to form chemical bonds, 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.
- graftlinking monomer for further details, reference is made here, for example, to US Pat. No. 4,148,846.
- 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 with a core and at least one outer shell are listed.
- graft polymers with a core and at least one outer shell are to be named here, which have the following structure:
- 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-die ⁇ , 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 of the above copolymers and copolymers of ethylene with comonomers which provide reactive groups.
- the elastomers described can also be prepared by other customary processes, for example by suspension polymerization.
- Silicone rubbers as described in DE-A 37 25 576, EP-A 235 690, DE-A 38 00 603 and EP-A 319 290, are likewise preferred.
- fibrous or particulate fillers C are carbon fibers, glass fibers, glass beads, amorphous silica, asbestos, calcium silicate, calcium metasilicate, magnesium carbonate, kaolin, chalk, powdered quartz, mica, barium sulfate and feldspar called in amounts 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 for better compatibility with the thermoplastic 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 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.
- oxidation inhibitors and heat stabilizers are sterically hindered phenols and / or phosphites, hydroquinones, aromatic secondary amines such as diphenylamines, various substituted representatives of these groups and mixtures thereof in concentrations of up to 1% by weight, based on the weight of the thermoplastic molding compositions called.
- 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.
- sodium phenylphosphinate, alumina, silica and preferably talc may be used as nucleating agents.
- 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 C atoms
- Ca or Na montanate and also low molecular weight polyethylene or polypropylene waxes.
- plasticizers are dioctyl phthalate, dibenzyl phthalate, butyl benzyl phthalate, hydrocarbon oils, 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 amounts (as a rule up to 50% by weight) of copolymerizable ethylenically unsaturated monomers.
- PTFE polytetrafluoroethylene
- tetrafluoroethylene-hexafluoropropylene copolymers or tetrafluoroethylene copolymers with smaller amounts (as a rule 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 of 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 comminuted. 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 29O 0 C.
- thermoplastic molding compositions according to the invention are characterized by good flowability combined with good mechanical properties.
- the processing of the individual components is possible without problems and in short cycle times, so that in particular dere thin-walled components come as an application in question, the mold covering is very low.
- Component A is a compound having Component A:
- 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).
- TMP trimethylolpropane
- the components A) and B) was mixed on a twin-screw extruder at 230 0 C and extruded in a water bath. After granulation and drying, specimens were sprayed and tested on an injection molding machine.
- the granules were injection molded into shoulder bars according to ISO 527-2 and a tensile test was performed. In addition, impact strength was determined according to ISO 179-2, MVR (ISO 1133) and the flow method were tested.
- compositions according to the invention and the results of the measurements are shown in the table.
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Dispersion Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2007550715A JP2008527121A (ja) | 2005-01-14 | 2005-12-31 | 流動性ポリオレフィン |
US11/813,638 US20080097033A1 (en) | 2005-01-14 | 2005-12-31 | Flowable Polyolefins |
EP05821929A EP1846497A1 (de) | 2005-01-14 | 2005-12-31 | Fliessfähige polyolefine |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE102005002119A DE102005002119A1 (de) | 2005-01-14 | 2005-01-14 | Fließfähige Polyolefine |
DE102005002119.0 | 2005-01-14 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2006074817A1 true WO2006074817A1 (de) | 2006-07-20 |
Family
ID=35945086
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2005/014164 WO2006074817A1 (de) | 2005-01-14 | 2005-12-31 | Fliessfähige polyolefine |
Country Status (7)
Country | Link |
---|---|
US (1) | US20080097033A1 (de) |
EP (1) | EP1846497A1 (de) |
JP (1) | JP2008527121A (de) |
KR (1) | KR20070104584A (de) |
CN (1) | CN101098923A (de) |
DE (1) | DE102005002119A1 (de) |
WO (1) | WO2006074817A1 (de) |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
ES2746204T3 (es) * | 2010-10-11 | 2020-03-05 | Novomer Inc | Mezclas de polímeros |
EP3030612A1 (de) * | 2013-08-09 | 2016-06-15 | Dow Global Technologies LLC | Ethylenbasierte polymerzusammensetzungen für blasformanwendungen |
KR102644544B1 (ko) | 2016-09-21 | 2024-03-11 | 넥스트큐어 인코포레이티드 | Siglec-15를 위한 항체 및 이의 사용 방법 |
US10053533B1 (en) | 2017-04-13 | 2018-08-21 | Presidium Usa, Inc. | Oligomeric polyol compositions |
CN115785572B (zh) * | 2022-12-13 | 2023-11-14 | 金发科技股份有限公司 | 一种超耐热氧老化聚丙烯组合物及其制备方法和应用 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB2324797A (en) * | 1997-05-02 | 1998-11-04 | Courtaulds Coatings | Hyperbranched polymers |
US5998565A (en) * | 1995-11-28 | 1999-12-07 | Dsm N.V. | Composition comprising a plastic and an additive |
EP1424362A1 (de) * | 2002-11-27 | 2004-06-02 | DSM IP Assets B.V. | Verfahren zur Herstellung einer Zusammensetzung |
WO2005075563A1 (de) * | 2004-02-04 | 2005-08-18 | Basf Aktiengesellschaft | FLIEßFÄHIGE POLYESTERFORMMASSEN |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE10163163A1 (de) * | 2001-12-20 | 2003-07-03 | Basf Ag | Verfahren zur Herstellung hochfunktioneller, Hyperverzweigter Polyester durch enzymatische Veresterung |
US6818695B2 (en) * | 2002-05-20 | 2004-11-16 | 3M Innovative Properties Company | Extrudable thermoplastic compositions |
-
2005
- 2005-01-14 DE DE102005002119A patent/DE102005002119A1/de not_active Withdrawn
- 2005-12-31 WO PCT/EP2005/014164 patent/WO2006074817A1/de active Application Filing
- 2005-12-31 CN CNA2005800463958A patent/CN101098923A/zh active Pending
- 2005-12-31 EP EP05821929A patent/EP1846497A1/de not_active Withdrawn
- 2005-12-31 JP JP2007550715A patent/JP2008527121A/ja not_active Withdrawn
- 2005-12-31 KR KR1020077018107A patent/KR20070104584A/ko not_active Application Discontinuation
- 2005-12-31 US US11/813,638 patent/US20080097033A1/en not_active Abandoned
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5998565A (en) * | 1995-11-28 | 1999-12-07 | Dsm N.V. | Composition comprising a plastic and an additive |
GB2324797A (en) * | 1997-05-02 | 1998-11-04 | Courtaulds Coatings | Hyperbranched polymers |
EP1424362A1 (de) * | 2002-11-27 | 2004-06-02 | DSM IP Assets B.V. | Verfahren zur Herstellung einer Zusammensetzung |
WO2005075563A1 (de) * | 2004-02-04 | 2005-08-18 | Basf Aktiengesellschaft | FLIEßFÄHIGE POLYESTERFORMMASSEN |
Also Published As
Publication number | Publication date |
---|---|
JP2008527121A (ja) | 2008-07-24 |
US20080097033A1 (en) | 2008-04-24 |
EP1846497A1 (de) | 2007-10-24 |
KR20070104584A (ko) | 2007-10-26 |
CN101098923A (zh) | 2008-01-02 |
DE102005002119A1 (de) | 2006-07-27 |
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