WO1999050333A1 - Polyalkylenarylate mit hohem carboxylendgruppengehalt - Google Patents
Polyalkylenarylate mit hohem carboxylendgruppengehalt Download PDFInfo
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- WO1999050333A1 WO1999050333A1 PCT/EP1999/002029 EP9902029W WO9950333A1 WO 1999050333 A1 WO1999050333 A1 WO 1999050333A1 EP 9902029 W EP9902029 W EP 9902029W WO 9950333 A1 WO9950333 A1 WO 9950333A1
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- weight
- polyalkylene
- temperature
- zone
- arylates
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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
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
-
- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
-
- 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
-
- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
- C08G63/183—Terephthalic acids
Definitions
- the invention relates to an improved process for the preparation of polyalkylene arylates which have a high carboxyl end group content.
- the invention further relates to the polyalkylene arylates obtainable by the process according to the invention and their mixtures with polycarbonates and / or polyamides and the use of such molding compositions for the production of moldings and the moldings obtainable here.
- polyesters Processes for the production of polyesters are known, inter alia, from DE-A 25 14 116, EP-A 815 158 and GB-A 2 184 129.
- the starting materials such as diols and acids or their esters are esterified in the presence of catalysts or vice tert and thereafter polycondensed or pressure changes in a single- or multi-stage polycondensation Va ⁇ uum.
- Most known processes result in polyesters which have a low carboxyl end group content.
- Polybutylene terephthalate e.g. is characterized by its low water absorption and its high dimensional stability, as well as its good solvent resistance. On the other hand, its limited toughness, e.g. compared to polycarbonates or polyamides.
- Blends of these polymers with PBT have for some applicatio ⁇ gen the desired natural sheep skombination where you put particular good mechanical properties such as high toughness value.
- High-molecular polyester blends are produced according to the prior art by a complex compounding process, the polyester being kept at a temperature above the melting point for long residence times and having to be mixed with the blend component in this phase.
- polyester blends are produced by mixing polymers using a kneading machine (single or double shaft, in the same or opposite directions, meshing or non-meshing design) which, due to the additional process step, cause thermal damage to the polymer during the melting and mixing process .
- a kneading machine single or double shaft, in the same or opposite directions, meshing or non-meshing design
- the object of the present invention was therefore to provide an economical process by means of which polyalkylene arylates with a carboxyl end group content as high as possible can be obtained.
- a process for the preparation of polyalkylene arylates has been found in which an aromatic dicarboxylic acid or its ester or ester-forming derivative is esterified or transesterified with a molar excess of an aliphatic dihydroxy compound and the transesterification or esterification product obtained is polycondensed, which is characterized in that that the prepolymer is polycondensed with a viscosity number (VZ) of ⁇ 30 ml / g in the presence of an oxygen-containing gas.
- VZ viscosity number
- polyalkylene arylates obtainable by the process according to the invention in combination with polycarbonates and / or polyamides, show an improved phase connection, which lead to better mechanical properties.
- the molecular weight of the blend component is largely unaffected during manufacture.
- Polyalkylene arylates are known per se and are described in the literature. They contain an aromatic ring in the main chain, which comes from the aromatic dicarboxylic acid. The aromatic ring can also be substituted, for example by halogen such as 3
- Chlorine and bromine or by -CC 4 alkyl groups such as methyl, ethyl, i- or n-propyl and n-, i- or t-butyl groups.
- Preferred dicarboxylic acids are 2,6-naphthalenedicarboxylic acid and terephthalic acid or mixtures thereof. Up to 30 mol%, preferably no 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.
- the 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, 5-methyl -1,5 -Pentanediol, 1, 4 -cyclohexanediol, 1, 4 -cyclohexane-dimethanol and neopentylglycol or mixtures thereof are preferred.
- polyesters (A) are polyalkylene terephthalates which are derived from alkanediols having 2 to 10, preferably 2 to 6, carbon atoms. Of these, polyethylene terephthalate and polybutylene terephthalate or mixtures thereof are preferred in particular.
- polyethylene terephthalates and polybutylene terephthalates which contain up to 1% by weight, preferably up to 0.75% by weight, of 1,6-hexanediol and / or 5-methyl-1,5-pentanediol as further monomer units.
- the preferred production is based on the
- an aromatic dicarboxylic acid or its ester or ester-forming derivative is esterified or transesterified with a molar excess of a dihydroxy compound
- stage a) and stage b) of the process being carried out in at least two temperature zones.
- Stage a) of the process is referred to as a so-called transesterification or esterification reaction.
- This is carried out in at least two, preferably at least three, temperature zones.
- the temperature of the following zone should be 1-40, preferably 2-30 and in particular 5-10 ° C higher than the temperature 4 of the previous zone.
- the temperature range for the entire esterification reaction is generally (depending on the starting material) 165 to 260, preferably 170 to 250 and in particular 180 to 240 ° C.
- the pressure is generally 1 to 10, preferably 1 to 4 and in particular from 1 to 2 bar.
- Stage a) of the process is preferably carried out in such a way that work is carried out in at least two temperature zones under largely the same pressure conditions in the individual zones.
- the technical requirements such as apparatus (e.g. in the form of boiler cascades) for creating different temperature zones are known to the person skilled in the art, which is why further details are unnecessary.
- a molar excess of diol is usually used for the reaction in order to influence the ester balance in the desired form, the molar ratios of dicarboxylic acid or
- Dicarboxylic acid esters Diol are usually 1: 1.1 to 1: 3.5, preferably 1: 1.2 to 1: 2.2. Molar ratios of dicarboxylic acid: diol from 1: 1.5 to 1: 2 and diesters: diol from 1: 1.25 to 1.5 are very particularly preferred.
- the total diol is divided into three zones as a percentage: 60 to 85 (1), 10 to 25 (2) and 5-15 (3), preferably: 70 to 80 (1), 10 to 20 (2), 5 to 10 (3).
- the residence times for the entire stage a) are 140 to 300, preferably from 150 to 260 and in particular from 160 to 220 min.
- the residence time for the first zone is from 100 to 190, preferably 110 to 150; for the second zone from 65 to 140, preferably from 65 to 110 minutes.
- the dwell time in the third zone is 15 to 45, preferably 15 to 30 minutes, the dwell times in the second Reduce the zone accordingly and keep it in the 1st zone as explained above. 5
- the residence times from the first zone to the third zone preferably decrease in a ratio of 6: 3: 1.
- a catalyst and then an (earth) alkali metal compound are first added to the dihydroxy compound before stage a) of the process.
- Preferred catalysts are titanium compounds and tin compounds such as, among others. from US 39 36 421, US 43 29 444 patents are known. Preferred compounds are tetrabutyl orthotitanate and triisopropyl titanate and tin di-octoate, which are usually used in step a) in amounts of 20 to 150, preferably 20 to 120 and in particular 30 to 70 ppm (based on the metal) .
- an alkali metal compound or alkaline earth metal compound (calculated as alkali metal or Alkaline earth metal).
- alkali metal compound or alkaline earth metal compound such compounds are proposed in DE-A 43 33 930.
- Sodium carbonate, sodium acetate and sodium alcoholates, in particular sodium methoxide, may be mentioned as preferred compounds.
- the transesterification or esterification products are then continuously transferred to the precondensation stage b).
- the temperature of the following zone is 1 to 40, preferably 2-30 and in particular 5-20 ° C higher than the temperature of the previous zone.
- the temperature range for the entire precondensation is generally (depending on the starting materials) 220 to 300, preferably 225 to 290 and in particular 240 to 290 ° C.
- the precondensation is preferably carried out in such a way that the pressure in the first zone is 0.5 to 1 bar, preferably 0.6 to 0.8 bar and in the second or last zone 20 to 200, preferably 25 to 150 mbar and is in particular 50 to 150 mbar.
- a vertical tube bundle reactor can be used for this purpose, other reactors for carrying it out are known to the person skilled in the art. 6
- the residence times for the entire stage b) of the process are from 10 to 80, preferably from 15 to 50 and in particular from 20 to 40 minutes.
- the fourth zone in this embodiment of the tube bundle heat exchanger consists of a device for separating the vapor and liquid phases (also known as vapor separation vessels), the ratio of the volume of the separation vessel to the volume in the tubes preferably being 5 to 15: 1, in particular 8 to Is 13: 1.
- the volume ratios of the first three zones are designed such that the first zone from 30 to 60, preferably 50%, the second zone from 20 to 40, preferably 30% and the third zone from 10 to 30, preferably account for 20% of the volume (volume ratio).
- the temperature ranges, pressure ranges and residence times for the particularly preferred embodiment of the process according to the invention are listed below:
- Zone temperature from 230 to 270, preferably from 240 to 250 ° C., pressure from 0.6 to 0.9, preferably from 0.7 to 0.9 bar.
- Residence time from 10 to 30, preferably from 15 to 25, minutes.
- 2nd zone temperature from 240 to 280, preferably from 250 to 270 ° C, pressure from 0.2 to 0.6, preferably from 0.3 to
- Residence time from 5 to 25, preferably from 7 to 15 minutes.
- 3rd zone temperature from 245 to 290, preferably from 250 to 280 ° C, pressure from 0.1 to 0.3, preferably from 0.1 to
- Residence time from 5 to 10, preferably from 4 to 8 minutes. 7
- 4th zone temperature from 250 to 300, preferably from 252 to 285 ° C., pressure from 0.015 to 0.2, preferably from 0.025 to 0.15 bar,
- Residence time from 10 to 30, preferably from 14 to 24, minutes.
- stage a) of the process can be metered into stage b) of the process in the amounts mentioned.
- the polyester prepolymer has a viscosity number ⁇ 30, preferably from 20 to 30 ml / g, measured as a 0.5% by weight solution in phenol / o-dichlorobenzene (1: 1) according to DIN 53728 , Part 3 (1985) at 25 ° C.
- the polyester prepolymer is then transferred to stage c) of the process according to the invention. This is preferably carried out in one stage at temperatures from 240 to 290, preferably from 240 to 270 and in particular 240 to 265 ° C.
- the pressure is 0.3 to 10, preferably 0.3 to 5 and in particular 0.3 to 2 mbar.
- the residence times are usually 30 to 180, preferably 35 to 150, minutes.
- the surface of the product can preferably be renewed.
- Surface renewal means that new polymer constantly reaches the surface of the melt, so that the exit of the diol is facilitated.
- the polycondensation of the prepolymer is carried out in the presence of an oxygen-containing gas.
- these gases should contain at least 17% by volume, preferably at least 18% by volume, of oxygen. Oxygen and air are preferably used.
- the prepolymer can be comminuted, for example ground, and then, for example, over a period of 30 minutes to 15 hours, preferably from 50 minutes to 6 hours 8th
- the polyester After the continuous polycondensation, the polyester has a viscosity number of 60 to 180, preferably 90 to 160 ml / g, determined in a 0.5% by weight solution in a phenol / o-dichlorobenzene mixture (weight ratio 1: 1 at 25 ° C) according to DIN 53728, 3rd part (1985).
- the carboxyl end group content after the polycondensation is at least 30, preferably at least 40 and in particular at least 50%, based on the sum of carboxyl and OH end groups of the polymer.
- the carpoxyl end group content is usually determined by titration methods (e.g. potentiometry).
- the polyalkylene arylates obtainable by the process according to the invention are suitable for the production of moldings of any kind. They are particularly suitable for thermoplastic molding compositions containing
- Suitable polycarbonates B) are vaten by polymerization of aromatic dihydroxy compounds, in particular bis (4-hydroxyphenyl) -2, 2 propane (bisphenol A) or its Deri ⁇ , for example with phosgene. Corresponding products are known per se and described in the literature and for the most part are also commercially available.
- the amount of the polycarbonates is up to 90% by weight, preferably up to 50% by weight, based on 100% by weight of components A) to C).
- the polyamides of the molding compositions according to the invention generally have a viscosity number of 90 to 350, preferably 110 to 240 ml / g, determined in a 0.5% strength by weight solution in 96% strength by weight sulfuric acid at 25 ° C. in accordance with ISO 307.
- Semi-crystalline or amorphous resins with a molecular weight (weight average) of at least 5,000 e.g. U.S. Patents 2,071,250, 2,071,251, 2,130,523, 2,130,948, 2,241,322, 2,312,966, 2,512,606 and 3,393,210 are preferred.
- Examples include polyamides which are derived from lactams with 7 to 13 ring members, such as polycaprolactam, polycapryllactam and polylaurinlactam, and polyamides which are obtained by reacting dicarboxylic acids with diamines.
- Alkanedicarboxylic acids having 6 to 12, in particular 6 to 10 carbon atoms and aromatic dicarboxylic acids can be used as dicarboxylic acids. Only adipic acid, azelaic acid, sebacic acid, dodecanedioic acid and terephthalic and / or isophthalic acid may be mentioned here as acids.
- Particularly suitable diamines are alkane diamines with 6 to 12, in particular 6 to 8, carbon atoms and m-xylylenediamine, di- (4-aminophenyl) methane, di- (4-aminocyclohexyl) methane, 2,2-di- (4-aminophenyl) ) propane or 2,2-di- (4-aminocyclohexyl) propane.
- Preferred polyamides are polyhexamethylene adipic acid amide, polyhexamethylene sebacic acid amide and polycaprolactam and copolyamides 6/66, in particular with a proportion of 5 to 95% by weight of caprolactam units.
- Polyamides may also be mentioned, e.g. can be obtained by condensing 1,4-diaminobutane with adipic acid at elevated temperature (polyamide-4, 6). Manufacturing processes for polyamides of this structure are e.g. in EP-A 38 094, EP-A 38 582 and EP-A 39 524.
- Polyamides obtainable by copolymerizing two or more of the aforementioned monomers or mixtures of two or more polyamides are also suitable, the mixing ratio being arbitrary.
- those partially aromatic copolyamides such as PA 6 / 6T and PA 66 / 6T have proven particularly advantageous, the triamine content of which is less than 0.5, preferably less than 0.3% by weight (see EP-A 299 444).
- the preferred partially aromatic copolyamides with a low triamine content can be prepared by the processes described in EP-A 129 195 and 129 196. 10
- the molding compositions according to the invention can contain up to 50, in particular not more than 40,% by weight of further additives as component C).
- the molding compositions according to the invention can contain 1 to 50, preferably 5 to 40 and in particular 10 to 30% by weight of a filler as component C).
- Carbon fibers, aramid fibers and potassium titanate fibers may be mentioned as preferred fibrous fillers, with glass fibers being particularly preferred as E-glass. These can be used as rovings or cut glass in the commercially available forms.
- the fibrous fillers can be surface-pretreated with a silane compound for better compatibility with the thermoplastic.
- acicular mineral fillers are understood to be mineral fillers with a pronounced acicular character.
- An example is needle-shaped wollastonite.
- the mineral preferably has an L / D (length diameter) ratio of 8: 1 to 35: 1, preferably 8: 1 to 11: 1.
- the mineral filler can optionally have been pretreated with the abovementioned silane compounds; however, pretreatment is not essential.
- Kaolin, calcined kaolin, wollastonite, talc and chalk may be mentioned as further fillers.
- fluorine-containing ethylene polymers are mentioned. These are polymers of ethylene with a fluorine content of 55 to 76% by weight, preferably 70 to 76% by weight.
- PTFE polytetrafluoroethylene
- tetrafluoroethylene copolymers or tetrafluoroethylene copolymers with smaller proportions (generally up to 50% by weight) of copolymerizable ethylenically unsaturated monomers.
- PTFE polytetrafluoroethylene
- tetrafluoroethylene 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 ⁇ m, in particular from 0.1 to 5 ⁇ m. These small particle sizes can be achieved particularly preferably by using aqueous dispersions of fluorine-containing ethylene polymers and incorporating them, for example, into a polyester melt.
- Impact modifiers also referred to as rubber-elastic polymers or elastomers
- additives may be mentioned as additives, which may be present in amounts of up to 20% by weight, preferably up to 15% by weight.
- Conventional rubbers e.g. B. ethylene copolymers with reactive groups, acrylate rubber and polymers conjugated dienes, such as polybutadiene rubber and polyisoprene rubber.
- the diene polymers can, in a manner known per se, be partially or completely hydrogenated.
- Heat and light stabilizers, lubricants and mold release agents, colorants such as dyes and pigments in customary amounts may be mentioned as additives.
- esters or amides from at least one alcohol or amine with at least three functional groups and one or more mono- or dicarboxylic acids with 5 to 34 carbon atoms may be mentioned, pentaerythritol tetrastearate being preferred, or salts of Mg, Ca, Zn with carboxylic acids bis to 34 carbon atoms, especially calcium stearate. 12
- halogen-containing and halogen-free flame retardants such as melamine cyanurate, magnesium carbonate and / or phosphorus, which can be present in amounts of up to 15% by weight, are mentioned as suitable flame retardants.
- the desired properties of the end products can be largely controlled by the type and amount of these additives.
- the molding compositions according to the invention can be produced by processes known per se. According to a preferred embodiment
- Embodiment is carried out by adding components B) and C) to the melt of component A).
- extruders e.g. Single screw or twin screw extruders or other conventional plasticizing devices such as Brabender mills or Banbury mills.
- the molding compositions according to the invention are distinguished by better mechanical properties. They are therefore suitable for the manufacture ⁇ development of moldings of any type, in which applications are preferred in the electrical industry.
- the temperature in the second reaction zone was 195 ° C. at a pressure of 1.03 bar and an average residence time of 65 min.
- the temperature in the third reaction zone was 203 ° C. at a pressure of 1.04 bar and an average residence time of 40 min.
- the temperature in the fourth reaction zone was 242 ° C. at a pressure of 700 mbar and an average residence time of 22 minutes.
- the temperature in the fifth reaction zone was 246 ° C. at a pressure of 400 mbar and an average residence time of 12 minutes.
- the temperature in the sixth reaction zone was 248 ° C. at a pressure of 150 mbar and an average residence time of 6 minutes.
- the temperature in the seventh reaction zone was 247 ° C. at a pressure of 50 mbar and an average residence time of 18 minutes.
- the precondensate had a VZ of 26 ml / g, hydroxyl / end group content (HEG) of 463 meq / kg and carboxyl / end group content (CEG) of 12 meq / kg.
- the precondensate was ground and transferred to a polycondensation reactor without further addition of catalysts.
- the temperature in the first reaction zone was 165 ° C. at a pressure of 1.03 bar and an average residence time of 184 min.
- the temperature in the second reaction zone was 175 ° C. at a pressure of 1.03 bar and an average residence time of 65 min.
- the temperature in the third reaction zone was 205 ° C. at a pressure of 1.04 bar and an average residence time of 40 min.
- the transesterification product was fed to a vertical tube which was divided into 4 heating zones.
- the temperature in the fourth reaction zone was 242 ° C. at a pressure of 700 mbar and an average residence time of 22 min. 14
- the temperature in the fifth reaction zone was 246 ° C. at a pressure of 400 mbar and an average residence time of 12 minutes.
- the temperature in the sixth reaction zone was 248 ° C. at a pressure of 150 mbar and an average residence time of 6 min.
- the temperature in the seventh reaction zone was 247 ° C. at a pressure of 50 mbar and an average residence time of 18 min.
- the precondensate had a VZ of 29 ml / g, hydroxyl / end group content ( HEG) of 545 meq / kg and carboxyl / end group content (CEG) of 10 meq / kg.
- the precondensate was ground and transferred to a polycondensation reactor without further addition of catalysts.
- the powdered prepolymer (PI or P2) was gassed with air (10 l / h) after transfer to a 1 l polycondensation reactor with anchor stirrer at 23 ° C. overnight.
- the reactor was evacuated in 6 stages (750, 500, 250, 100, 50 mbar, 1 mbar), and the contents were polycondensed with stirring (30 rpm; at the end 15 rpm) at 250 ° C . After reaching the maximum viscosity build-up (160 min), the vacuum was broken and the product removed.
- the product obtained had the following composition
- the polycondensation was carried out analogously, with no gassing being carried out during the condensation, and the final vacuum reached being 0.4 mbar.
- the comparison products obtained had the following composition:
- the polymers obtained from examples (AI, A2) and from the comparative examples (VI, V2) were mixed with polycarbonate from bisphenol-A with a VZ of 64 ml / g (Lexan R) 61 from GEP) on a twin-screw extruder (ZSK 30, 200 rpm, 10 kg / h throughput and 250 ° C.)
- the composition contained 50% polycarbonate.
- the mechanical data were determined in accordance with the ISO standards specified below.
- the VZ was measured at 25 ° C. on a 0.5% solution of the polymer in a 1: 1 mixture of phenol / o-dichlorobenzene.
- the VZ of the PC extract was measured in CH 2 C1 2 at 23 ° C. 16
- the carboxyl end groups were determined by potentiometric titration of the acetic acid released when a sample of the polymer dissolved in nitrobenzene was reacted with a defined excess of potassium acetate.
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- Polymers & Plastics (AREA)
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- Compositions Of Macromolecular Compounds (AREA)
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Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US09/646,174 US6232435B1 (en) | 1998-04-01 | 1999-03-25 | Polyalkylene arylates containing a high proportion of carboxyl end groups |
JP2000541230A JP2002509963A (ja) | 1998-04-01 | 1999-03-25 | 末端カルボキシル基を高含有量で有するポリアルキレンアリレート |
KR1020007010925A KR20010042360A (ko) | 1998-04-01 | 1999-03-25 | 카르복실 말단기 함량비가 높은 폴리알킬렌 아릴레이트 |
EP99915704A EP1070092A1 (de) | 1998-04-01 | 1999-03-25 | Polyalkylenarylate mit hohem carboxylendgruppengehalt |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19814529.2 | 1998-04-01 | ||
DE19814529A DE19814529A1 (de) | 1998-04-01 | 1998-04-01 | Polyalkylenarylate mit hohem Carbonylendgruppengehalt |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1999050333A1 true WO1999050333A1 (de) | 1999-10-07 |
Family
ID=7863194
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP1999/002029 WO1999050333A1 (de) | 1998-04-01 | 1999-03-25 | Polyalkylenarylate mit hohem carboxylendgruppengehalt |
Country Status (7)
Country | Link |
---|---|
US (1) | US6232435B1 (de) |
EP (1) | EP1070092A1 (de) |
JP (1) | JP2002509963A (de) |
KR (1) | KR20010042360A (de) |
CN (1) | CN1154680C (de) |
DE (1) | DE19814529A1 (de) |
WO (1) | WO1999050333A1 (de) |
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DE19929791A1 (de) * | 1999-06-29 | 2001-02-01 | Basf Ag | Verfahren zur kontinuierlichen Herstellung von Polybutylenterephthalat aus Terephthalsäure und Butandiol |
US6472500B2 (en) | 2000-06-17 | 2002-10-29 | General Electric Company | Crystalline polyester resins and processes for their preparation |
DE10127938A1 (de) * | 2001-06-08 | 2002-07-25 | Basf Ag | Verfahren zur Herstellung von (Meth)acrylsäureestern |
US6653440B2 (en) * | 2001-11-13 | 2003-11-25 | Mitsubishi Gas Chemical Company | Process for producing copolyester resin |
EP1378533A1 (de) * | 2002-07-04 | 2004-01-07 | General Electric Company | Krystalline Polyesterharze und Verfahren zu ihrer Herstellung |
DE102004005652A1 (de) | 2004-02-04 | 2005-08-25 | Basf Ag | Fließfähige Polyesterformmassen |
DE102004005657A1 (de) * | 2004-02-04 | 2005-08-25 | Basf Ag | Fließfähige Polyesterformmassen |
MY139705A (en) * | 2004-07-19 | 2009-10-30 | Basf Ag | Mixtures of hyperbranched polyesters with polycarbonates as additive for polyester molding compositions |
DE102004035357A1 (de) * | 2004-07-21 | 2006-03-16 | Basf Ag | Kontinuierliches Verfahren zur Herstellung von Polyalkylenarylaten mit hyperverzweigten Polyestern und/oder Polycarbonaten |
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 |
DE102004059243A1 (de) * | 2004-08-10 | 2006-02-23 | Basf Ag | Thermoplastische Formmassen mit verbesserten Fließ- und Entformungseigenschaften |
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 |
DE102005002044A1 (de) * | 2005-01-14 | 2006-07-20 | Basf Ag | Fließfähige Polyester mit Hydrolyseschutz |
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1999
- 1999-03-25 US US09/646,174 patent/US6232435B1/en not_active Expired - Fee Related
- 1999-03-25 EP EP99915704A patent/EP1070092A1/de not_active Withdrawn
- 1999-03-25 CN CNB998046027A patent/CN1154680C/zh not_active Expired - Fee Related
- 1999-03-25 WO PCT/EP1999/002029 patent/WO1999050333A1/de not_active Application Discontinuation
- 1999-03-25 KR KR1020007010925A patent/KR20010042360A/ko not_active Application Discontinuation
- 1999-03-25 JP JP2000541230A patent/JP2002509963A/ja not_active Withdrawn
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US4740580A (en) * | 1986-04-14 | 1988-04-26 | U C B, S.A. | One-step process for the preparation of carboxyl group-terminated polyesters |
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DE4401055A1 (de) * | 1994-01-15 | 1995-07-20 | Basf Ag | Verfahren zur Herstellung von thermoplastischen Polyestern mit niedrigem Carboxylendgruppengehalt |
DE19505185A1 (de) * | 1995-02-16 | 1996-10-24 | Basf Ag | Biologisch abbaubare Polymere, Verfahren zu deren Herstellung sowie deren Verwendung zur Herstellung bioabbaubarer Formkörper |
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Also Published As
Publication number | Publication date |
---|---|
KR20010042360A (ko) | 2001-05-25 |
CN1295588A (zh) | 2001-05-16 |
JP2002509963A (ja) | 2002-04-02 |
EP1070092A1 (de) | 2001-01-24 |
US6232435B1 (en) | 2001-05-15 |
DE19814529A1 (de) | 1999-10-07 |
CN1154680C (zh) | 2004-06-23 |
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