Source: https://patents.google.com/patent/US8445576B2/en
Timestamp: 2019-03-23 17:04:20
Document Index: 753695810

Matched Legal Cases: ['art 2', 'Application No. 10200403537', '§119', 'art 2', 'art 3', 'art 3', 'art 2', 'art 2', 'in fine', 'art 2']

US8445576B2 - Continuous process for preparing polyalkylene arylates with hyperbranched polyesters and/or polycarbonates - Google Patents
Continuous process for preparing polyalkylene arylates with hyperbranched polyesters and/or polycarbonates Download PDF
US8445576B2
US8445576B2 US11/632,703 US63270305A US8445576B2 US 8445576 B2 US8445576 B2 US 8445576B2 US 63270305 A US63270305 A US 63270305A US 8445576 B2 US8445576 B2 US 8445576B2
US11/632,703
US20080033085A1 (en
2004-07-21 Priority to DE200410035357 priority Critical patent/DE102004035357A1/en
2004-07-21 Priority to DE102004035357.3 priority
2004-07-21 Priority to DE102004035357 priority
2005-07-19 Application filed by BASF SE filed Critical BASF SE
2005-07-19 Priority to PCT/EP2005/007838 priority patent/WO2006008130A1/en
2007-02-21 Assigned to BASF AKTIENGESELLSCHAFT reassignment BASF AKTIENGESELLSCHAFT ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: BRUCHMANN, BERND, EIPPER, ANDREAS, STUMBE, JEAN-FRANCOIS, WEISS, CARSTEN, GEPRAGS, MICHAEL
2008-02-07 Publication of US20080033085A1 publication Critical patent/US20080033085A1/en
2012-12-19 Assigned to BASF SE reassignment BASF SE CHANGE OF NAME (SEE DOCUMENT FOR DETAILS). Assignors: BASF AKTIENGESELLSCHAFT
2013-05-21 Publication of US8445576B2 publication Critical patent/US8445576B2/en
Continuous process for preparation of polyalkylene arylates A) comprising highly branched or hyperbranched polymers B) and, if appropriate, comprising lubricants C), by esterifying or transesterifying an aromatic dicarboxylic acid or its ester or ester-forming derivatives, with a molar excess of an aliphatic dihydroxy compound, and polycondensing the resultant transesterification or esterification product, which comprises, on achievement of at least 80% of the desired viscosity number, adding component B) and also, if appropriate, C) to the polymer melt, and, if appropriate, post-condensing the melt and then discharging, cooling, and pelletizing it, and also using, as component B), at least one highly branched or hyperbranched polycarbonate B1) with an OH number of from 1 to 600 mg KOH/g of polycarbonate (to DIN 53240, Part 2), or at least one highly branched or hyperbranched polyester B2) of AxBy type, where x is at least 1.1 and y is at least 2.1, or a mixture of these.
This application is the National Phase of International Application No.
PCT/EP2005/007838 filed on July 19, 2005; and this application claims priority to Application No. 10200403537.3 filed in Germany on Jul. 21, 2004 under 35 U.S.C. §119; the entire contents of all are hereby incorporated by reference.
The invention relates to an improved process for continuous preparation of polyalkylene arylates comprising hyperbranched polyester and/or comprising polycarbonates.
Polyalkylene arylates feature low water absorption and good dimensional stability, and also resistance to solvents.
One disadvantageous property is insufficient flowability and low crystallization rate, and these are problematic during processing of high-molecular-weight injection moldings or those with very thin walls.
Flowability can be improved simply by adding a hyperbranched polyester and/or polycarbonate—if appropriate in combination with other additives—for example as proposed in DE-A 10200400562.8 and DE-A 102004005657.9.
The prior art prepares polyesters with additives by incorporating the additives via mixing, e.g. in an extruder. The additional process step is expensive and moreover causes thermal degradation of the polymer. There is a need to improve the mechanical properties of the known molding compositions, in particular toughness and tensile strain at break. In particular, there is a need to improve flowability with very substantial retention of mechanical properties.
It was therefore an object of the present invention to provide an improved continuous process for preparation of polyalkylene arylates A) comprising hyperbranched or highly branched polymers B) and, if appropriate, comprising lubricants C), the process being more cost-effective and giving polyesters with better properties, without any substantial thermal degradation of the polymer. In particular, the intention is to improve mechanical properties, such as multiaxial impact strength, and susceptibility to yellowing, while providing better processing via rapid crystallization.
A particular intention is to improve flowability significantly, while retaining mechanical properties.
Surprisingly, it has been found that this object can be achieved by esterifying or transesterifying an aromatic dicarboxylic acid or its ester or ester-forming derivatives, with a molar excess of an aliphatic dihydroxy compound, and polycondensing the resultant transesterification or esterification product, which comprises, on achievement of at least 80% of the desired viscosity number, adding component B) and also, if appropriate, component C) to the polymer melt, and, if appropriate, post-condensing the melt and then discharging, cooling, and pelletizing it, and also using, as component B), at least one highly branched or hyperbranched polycarbonate B1) with an OH number of from 1 to 600 mg KOH/g of polycarbonate (to DIN 53240, Part 2), or at least one highly branched or hyperbranched polyester B2) of AxBy type, where x is at least 1.1 and y is at least 2.1, or a mixture of these.
The subclaims give preferred embodiments.
As component A), the molding compositions obtainable according to the invention comprise from 10 to 99.9% by weight, preferably from 50 to 99.5% by weight, and in particular from 50 to 99.3% by weight, of a thermoplastic polyalkylene arylate.
These polyalkylene arylates are obtainable by esterifying or transesterifying an aromatic dicarboxylic acid or its esters or ester-forming derivatives, with a molar excess of an aliphatic dihydroxy compound, and polycondensing the resultant transesterification or esterification product in a known manner.
Among the aliphatic dihydroxy compounds, preference is given to diols having from 2 to 6 carbon atoms, in particular 1,2-ethanediol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,4-hexanediol, 2-methyl-1,5-pentanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol and neopentylglycol, and mixtures of these.
Particularly preferred polyesters (A) which may be mentioned are polyalkylene terephthalates, which derive from alkanediols having from 2 to 10 carbon atoms, preferably from 2 to 6 carbon atoms. Among these, particular preference is given to polyethylene terephthalate and polybutylene terephthalate, and mixtures of these.
Other preferred polyesters are polyethylene terephthalates and polybutylene terephthalates which comprise, as other monomer units, up to 1% by weight, preferably up to 0.75% by weight, based on A), of 1,6-hexanediol and/or 5-methyl-1,5-pentanediol.
These polyalkylene terephthalates are known per se and are described in the literature. Their main chain comprises an aromatic ring which derives from the aromatic dicarboxylic acid. The aromatic ring may also have substitution, e.g. by halogen, such as chlorine and bromine, or by C1-C4-alkyl groups, such as methyl, ethyl, isopropyl, n-propyl, n-butyl, isobutyl, or tert-butyl groups.
Particular preference is given to polyesters whose carboxy end group content is up to 50 meq/kg of polyester, preferably up to 30 meq/kg of polyester, and in particular up to 27 meq/kg of polyester. By way of example, these polyesters may be prepared by a method based on the process of DE-A 44 01 055. The carboxy end group content is usually determined by titration methods (e.g. potentiometry).
a) in a first stage, esterifying or transesterifying an aromatic dicarboxylic acid or its esters or ester-forming derivatives, with a molar excess of a dihydroxy compound,
b) in a second stage, precondensing the transesterification or esterification product obtained in a), and
c) in a third stage, polycondensing the product obtainable from b) to the desired viscosity number, where stages a) and b) of the process are carried out in at least two temperature zones.
Stage a) of the process is termed a transesterification or esterification reaction. This is carried out in at least two, and preferably at least three, temperature zones. The temperature here of each zone should be higher than that of the preceding zone by from 1 to 40° C., preferably from 2 to 30° C. and in particular from 5 to 10° C. The temperature range for the entire esterification reaction is generally (depending on the starting material) from 160 to 240° C., preferably from 165 to 250° C. and in particular from 180 to 240° C., and the pressure is generally from 1 to 10 bar, preferably from 1 to 4 bar and in particular from 1 to 2 bar.
Stage a) of the process preferably operates in at least two temperature zones with very substantially identical pressure conditions in the individual zones. The technical requirements, such as apparatus (e.g. in the form of reactor cascades) for creating different temperature zones are known to the person skilled in the art, and therefore need not be described here in greater detail.
The starting materials, such as diols and acids, have been described above (component A).
The reaction is usually carried out with a molar excess of diol, in order to exert the desired influence on the ester equilibrium. The molar ratios of dicarboxylic acid and/or dicarboxylic ester to diol are usually from 1:1.1 to 1:3.5, preferably from 1:1.2 to 1:2.2. It is very particularly preferable for the molar ratios of dicarboxylic acid to diol to be from 1:1.5 to 1:2, and of diester to diol to be 1:1.2 to 1:1.5.
The residence times for the entire stage a) are from 140 to 300 min, preferably from 150 to 260 min and in particular from 160 to 220 min, and the residence time for the first zone is from 100 to 190 min, preferably from 110 to 150 min, and for the second zone from 65 to 140 min, preferably from 65 to 110 min. For the preferred embodiment with three zones, the residence time in the 3rd zone is from 15 to 45 min, preferably from 15 to 30 min, with the residence times in the 2nd zone correspondingly being reduced and those in the 1st zone being retained as described above.
In the preferred embodiment of the novel process, the residence times preferably decrease from the first to the third zone in a ratio of 6:3:1.
In a particularly preferred embodiment, a catalyst and then an alkali metal compound or alkaline earth metal compound are firstly added to the dihydroxy compound, prior to stage a) of the process.
Preferred catalysts are titanium compounds and tin compounds, as disclosed inter alia in patent specifications U.S. Pat. No. 3,936,421 and U.S. Pat. No. 4,329,444. Preferred compounds which may be mentioned are tetrabutyl orthotitanate and triisopropyl titanate, and also tin dioctoate, which are usually used in stage a) in amounts of from 20 to 150 ppm, preferably from 20 to 120 ppm and in particular from 30 to 70 ppm (based on the metal).
To reduce further the carboxy end group content of the polyester it can be advantageous, before reacting the starting monomers, to add from 0.1 to 10 mmol, preferably from 0.2 to 0.65 mmol, of an alkali metal compound or alkaline earth metal compound (calculated as alkali metal or alkaline earth metal) per kg of polyester. Compounds of this type are proposed in DE-A 43 33 930. Preferred compounds which may be mentioned are sodium carbonate, sodium acetate and sodium alcoholates, in particular sodium methanolate.
The transesterification or esterification products are then transferred continuously to the precondensation stage b).
This has at least two temperature zones, preferably at least three and in particular at least four. The temperature of each zone here is higher than that of the preceding zone by from 1 to 40° C., preferably from 2 to 30° C. and in particular from 5 to 20° C. The temperature range for the entire precondensation is generally (depending on the starting materials) from 220 to 300° C., preferably from 225 to 290° C. and in particular from 240 to 290° C.
The precondensation is preferably carried out with a pressure in the first zone of from 0.5 to 1 bar, preferably from 0.6 to 0.8 bar, and in the second or last zone from 20 to 200 mbar, preferably from 25 to 150 mbar and in particular from 50 to 150 mbar. An example of a reactor which can be used industrially for this purpose is a vertical tube-bundle reactor, and other reactors for this purpose are known to the person skilled in the art.
The residence times for the entire stage b) of the process are from 10 to 80 min, preferably from 15 to 50 min and in particular from 20 to 40 min.
In a particularly preferred embodiment of the inventive process, use is made of four temperature zones. The relationships of temperature rising from zone to zone are as described above, and the pressure is reduced from the first to the fourth zone within the limits described. In this preferred embodiment of the tube-bundle heat exchanger, the fourth zone is composed of equipment for separating liquid and vapor phase (also termed a vapor separator). The ratio of the volume of the vapor separator to the volume in the tubes is preferably from 5 to 15:1, in particular from 8 to 13:1.
The volume ratios of the first three zones in this particularly preferred embodiment are designed in such a way that the proportion by volume made up by the first zone (volume ratios) is from 30 to 60%, preferably 50%, and that made up by the second zone is from 20 to 40%, preferably 30%, and that made up by the third zone is from 10 to 30%, preferably 20%. The temperature ranges, pressure ranges and residence times for the particularly preferred embodiment of the inventive process are listed below:
1st zone: Temperature from 230 to 270° C., preferably from 240 to 250° C., and pressure from 0.6 to 0.9 bar, preferably from 0.7 to 0.9 bar.
2nd zone: Temperature from 240 to 280° C., preferably from 250 to 270° C., and pressure from 0.2 to 0.6 bar, preferably from 0.3 to 0.5 bar.
3rd zone: Temperature from 245 to 290° C., preferably from 250 to 280° C., and pressure from 0.1 to 0.3 bar, preferably from 0.1 to 0.25 bar.
4th zone: Temperature from 250 to 300° C., preferably from 252 to 285° C., and pressure from 0.015 to 0.2 bar, preferably from 0.025 to 0.15 bar.
The catalysts mentioned above for stage a) of the process, and other additives, may be metered into stage b) of the process in the amounts mentioned.
After stage b) of the novel process, the polyester prepolymer has a viscosity number from 15 to 50 ml/g, preferably from 20 to 30 ml/g, measured on a 0.5% strength by weight solution in phenol/o-dichlorobenzene (1:1) in accordance with DIN 53728, Part 3 (1985) at 25° C.
The polyester prepolymer is then transferred to stage c) of the novel process. This is preferably carried out in a single stage at temperatures from 240 to 290° C., preferably from 240 to 270° C. and in particular from 240 to 265° C. The pressure is from 0.3 to 10 mbar, preferably from 0.3 to 5 mbar and in particular from 0.3 to 2 mbar.
It may moreover be advantageous for addition of catalysts and other additives, as described above, to continue in this stage of the process.
After the continuous polycondensation process, the polyester has a viscosity number of from 60 to 180 ml/g, preferably from 90 to 160 ml/g, determined in a 0.5% strength by weight solution in a phenol/o-dichlorobenzene mixture (ratio by weight 1:1) at 25° C. to DIN 53728, Part 3 (1985).
A substantive feature of the inventive process is that on achievement of at least 80%, preferably at least 95%, and in particular 100%, of the desired final viscosity number of the polyester, at least one highly branched or hyperbranched polycarbonate B) with an OH number of from 1 to 600 mg KOH/g of polycarbonate (to DIN 53 240, Part 2) and, if appropriate, lubricant C), is added jointly to the polymer melt, the melt is post-condensed, if appropriate, and then discharged, cooled, and pelletized. The amount preferably added as the lubricant C) is from 0.01 to 3% by weight, with preference from 0.1 to 1% by weight, and in particular from 0.2 to 0.8% by weight, based on 100% by weight of components A) to C).
The particularly preferred form of the addition is that of a suspension, component B being suspended prior to addition to the melt, if appropriate at an elevated temperature, in the lubricant. Depending on the nature of the lubricant used, it may be necessary to preheat the mixture composed of lubricant and nucleating agent to temperatures of from 30 to 150° C., preferably from 60 to 130° C., in order to prepare a suspension, and then to add the material to the polymer melt.
As example which may be mentioned of these materials is low-molecular-weight polyethylene waxes, which are known to be solid at room temperature and which have to be heated in order to prepare a suspension with the nucleating agent.
Components B) and, if appropriate, C) are preferably added during the polycondensation process on achievement of at least 80% of the desired final viscosity number. Suitable polycondensation apparatuses are known to the person skilled in the art, and no further details are therefore needed in that connection. In one particularly preferred embodiment of the inventive process, the melt may be discharged from the polycondensation reactor, and the mixture composed of B) and C) may be added by way of suitable apparatuses, e.g. a metering pump with a heating system, and the polymer melt may then be transferred into, by way of example, a Sulzer tube and condensed to the desired final viscosity number, whereupon homogenization of the melt takes place, and the material can then be discharged, cooled, and pelletized.
As component B), the molding compositions obtainable according to the invention comprise from 0.01 to 50% by weight, preferably from 0.5 to 20% by weight, and in particular from 0.7 to 10% by weight, of at least one highly branched or hyperbranched polycarbonate B1), with an OH number of from 1 to 600, preferably from 10 to 550, and in particular from 50 to 550, mg KOH/g of polycarbonate (to DIN 53240, Part 2), or of at least one polyester B2), or a mixture of these, as explained below.
For the purposes of this invention, hyperbranched polycarbonates B1) are non-crosslinked macromolecules having hydroxy groups and carbonate groups and which are structurally and molecularly non-uniform. They may firstly have a structure based on a central molecule, as is the case with dendrimers, but with non-uniform chain length of the branches. Secondly, they may also have a linear structure having functional side groups, or else, combining the two extremes, have linear and branched molecular moieties. For a definition of dendrimers and of hyperbranched polymers, see also P. J. Flory, J. Am. Chem. Soc. 1952, 74, 2718 and H. Frey et al., Chem. Eur. J. 2000, 6, No.14, 2499.
For the purposes of the present invention, “hyperbranched” means that the degree of branching (DB), i.e. the average number of dendritic linkages plus the average number of end groups per molecule, amounts to from 10 to 99.9%, preferably from 20 to 99%, particularly preferably from 20 to 95%.
For the purposes of the present invention, “dendrimeric” means that the degree of branching amounts to from 99.9 to 100%. For a definition of “degree of branching”, see H. Frey et al., Acta Polym. 1997, 48, 30, this being defined as
Component B1) preferably has a number-average molar mass Mn of from 100 to 15 000, preferably from 200 to 12 000, and in particular from 500 to 10 000 g/mol (GPC, PMMA standard).
The glass transition temperature Tg is in particular from −80 to +140° C., preferably from −60 to 120° C. (by DSC, DIN 53765).
a) reacting at least one organic carbonate (A) of the general formula RO[(CO)]nOR with at least one aliphatic, aliphatic/aromatic, or aromatic alcohol (B) which has at least 3 OH groups, with elimination of alcohols ROH to give one or more condensates (K), where each R, independently of the others, is a straight-chain or branched aliphatic, aromatic/aliphatic, or aromatic hydrocarbon radical having from 1 to 20 carbon atoms, and where the radicals R may also have bonding to one another to form a ring, and n is a whole number from 1 to 5, or
ab) reacting phosgene, diphosgene, or triphosgene with abovementioned alcohol (B) with elimination of hydrogen chloride,
The starting material used may comprise phosgene, diphosgene, or triphosgene, but preference is given here to organic carbonates.
Simple carbonates of the formula RO(CO)nOR are particularly used; n is preferably from 1 to 3, in particular 1.
Examples of suitable carbonates comprise aliphatic, aromatic/aliphatic, or aromatic carbonates, such as ethylene carbonate, propylene 1,2- or 1,3-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, didecyl carbonate, or didodecyl carbonate.
Examples of compounds having at least three OH groups comprise glycerol, trimethylolmethane, trimethylolethane, trimethylolpropane, 1,2,4-butanetriol, tris(hydroxymethyl)amine, tris(hydroxyethyl)amine, tris(hydroxypropyl)amine, pentaerythritol, diglycerol, triglycerol, polyglycerines, bis(trimethylolpropane), tris(hydroxymethyl)isocyanurate, tris(hydroxyethyl)isocyanurate, phloroglucinol, trihydroxytoluene, trihydroxydimethylbenzene, phloroglucides, hexahydroxybenzene, 1,3,5-benzenetrimethanol, 1,1,1-tris(4′-hydroxyphenyl)methane, 1,1,1-tris(4′-hydroxyphenyl)ethane, bis(trimethylolpropane), or sugars, e.g. glucose, trifunctional or higher-functionality polyetherols based on trifunctional or higher-functionality alcohols and ethylene oxide, propylene oxide, or butylene oxide, or polyesterols. Particular preference is given here to glycerol, trimethylolethane, trimethylolpropane, 1,2,4-butanetriol, pentaerythritol, and also their polyetherols based on ethylene oxide or propylene oxide.
These polyhydric alcohols may also be used in a mixture with dihydric alcohols (B′), with the proviso that the average total OH functionality of all of the alcohols used is greater than 2. Examples of suitable compounds having two OH groups comprise ethylene glycol, diethylene glycol, triethylene glycol, 1,2- and 1,3-propanediol, dipropylene glycol, tripropylene glycol, neopentyl glycol, 1,2-, 1,3-, and 1,4-butanediol, 1,2-, 1,3-, and 1,5-pentanediol, hexanediol, cyclopentanediol, cyclohexanediol, cyclohexanedimethanol, bis(4-hydroxycyclohexyl)methane, bis(4-hydroxycyclohexyl)ethane, 2,2-bis(4-hydroxycyclohexyl)propane, 1,1′-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, resorcinol, hydroquinone, 4,4′-dihydroxyphenyl, bis(4-bis(hydroxyphenyl)sulfide, bis(4-hydroxyphenyl)sulfone, bis(hydroxymethyl)benzene, bis(hydroxymethyl)toluene, bis(p-hydroxyphenyl)methane, bis(p-hydroxyphenyl)ethane, 2,2-bis(p-hydroxyphenyl)propane, 1,1-bis(p-hydroxyphenyl)cyclohexane, dihydroxybenzophenone, dihydric polyether polyols based on ethylene oxide, propylene oxide, butylene oxide, or their mixtures, polytetrahydrofuran, polycaprolactone, or polyesterols based on diols and dicarboxylic acids.
The diols serve for fine adjustment of the properties of the polycarbonates. If dihydric alcohols are used, the ratio of dihydric alcohols B′) to the at least trihydric alcohols (B) is adjusted by the person skilled in the art as a function of the desired properties of the polycarbonate. The amount of the alcohol(s) (B′) is generally from 0 to 50 mol %, based on the total amount of all of the alcohols (B) and (B′) taken together. The amount is preferably from 0 to 45 mol %, particularly preferably from 0 to 35 mol %, and very particularly preferably from 0 to 30 mol %.
For the purposes of this invention, a highly functional polycarbonate is a product which, besides the carbonate groups which form the polymer skeleton, further has at least three, preferably at least six, more preferably at least ten, terminal or pendent functional groups. The functional groups are carbonate groups and/or OH groups. There is in principle no upper restriction on the number of the terminal or pendent functional groups, but products having a very high number of functional groups can have undesired properties, such as high viscosity or poor solubility. The highly functional polycarbonates of the present invention mostly have not more than 500 terminal or pendent functional groups, preferably not more than 100 terminal or pendent functional groups.
When preparing the highly functional polycarbonates B1), it is necessary to adjust the ratio of the compounds containing OH groups to phosgene or carbonate in such a way that the simplest resultant condensate (hereinafter termed condensate (K)) comprises an average of either one carbonate group or carbamoyl group and more than one OH group or one OH group and more than one carbonate group or carbamoyl group. The simplest structure of the condensate (K) made from a carbonate (A) and a di- or polyalcohol (B) here results in the arrangement XYn or YnX, where X is a carbonate group, Y is a hydroxy group, and n is generally a number from 1 to 6, preferably from 1 to 4, particularly preferably from 1 to 3. The reactive group which is the resultant single group here is generally termed “focal group” below.
The condensate (K) may, by way of example, also be prepared from a carbonate and a trihydric alcohol, as illustrated by the general formula 4, the molar reaction ratio being 2:1. Here, the average result is a molecule of X2Y type, an OH group being focal group here. In formula 4, R and R1 are as defined in formulae 1 to 3.
It is also possible to use two or more condensates (K) for the synthesis. On the one hand, two or more alcohols or two or more carbonates can be used here. Furthermore, mixtures of various condensates of different structure can be obtained via the selection of the ratio of the alcohols used and of the carbonates or the phosgenes. This will be illustrated taking the example of the reaction of a carbonate with a trihydric alcohol. If the starting materials are reacted in a ratio of 1:1, as illustrated in (II), the product is an XY2 molecule. If the starting materials are reacted in a ratio of 2:1, as illustrated in (IV), the product is an X2Y molecule. If the ratio is from 1:1 to 2:1, the product is a mixture of XY2 and X2Y molecules.
The nature of the condensates (K) permits polycondensates (P) with different structures to result from the condensation reaction, these having branching but no crosslinking. Ideally, furthermore, the polycondensates (P) have either one carbonate group as focal group and more than two OH groups or else one OH group as focal group and more than two carbonate groups. The number of the reactive groups here is the result of the nature of the condensates (K) used and the degree of polycondensation.
The catalyst may also be deactivated, by way of example in the case of basic catalysts via addition of Lewis acids or proton acids.
In another preferred embodiment, the product is stripped, i.e. freed from low-molecular-weight, volatile compounds. For this, once the desired degree of conversion has been reached, the catalyst is optionally deactivated, and the low-molecular-weight volatile constituents, e.g. monoalcohols, phenols, carbonates, hydrogen chloride, or volatile oligomeric or cyclic compounds, can be removed by distillation, if appropriate with introduction of a gas, preferably nitrogen, carbon dioxide, or air, if appropriate at reduced pressure.
Effects of this type may, by way of example, be achieved via addition, during the polycondensation, of compounds which bear other 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, besides hydroxy groups, carbonate groups or carbamoyl groups. Examples of compounds which may be used for modification by means of carbamate groups are ethanolamine, propanolamine, isopropanolamine, 2-(butylamino)ethanol, 2-(cyclohexylamino)ethanol, 2-amino-1-butanol, 2-(2′-aminoethoxy)ethanol or higher alkoxylation products of ammonia, 4-hydroxypiperidine, 1-hydroxyethylpiperazine, diethanolamine, dipropanolamine, diisopropanolamine, tris(hydroxymethyl)aminomethane, tris(hydroxyethyl)aminomethane, ethylenediamine, propylenediamine, hexamethylenediamine or isophoronediamine.
An example of a compound which may be used for modification with mercapto groups is mercaptoethanol. By way of example, tertiary amino groups can be produced via incorporation of N-methyldiethanolamine, N-methyidipropanolamine or N,N-dimethylethanolamine. By way of example, ether groups may be generated via co-condensation of di- or higher-functionality polyetherols. Long-chain alkyl radicals can be introduced via reaction with long-chain alkanediols, and reaction with alkyl or aryl diisocyanates generates polycarbonates having alkyl, aryl, and urethane groups or urea groups.
Ester groups can be produced via addition of dicarboxylic acids or tricarboxylic acids, or, by way of example, dimethyl terephthalate, or tricarboxylic esters.
By way of example, highly functional highly branched, or highly functional hyperbranched polycarbonates comprising hydroxy groups can be modified via addition of molecules comprising acid groups or isocyanate groups. By way of example, polycarbonates comprising acid groups can be obtained via reaction with compounds comprising anhydride groups.
Highly functional polycarbonates comprising hydroxy groups may moreover also be converted into highly functional polycarbonate polyether polyols via reaction with alkylene oxides, such as ethylene oxide, propylene oxide or butylene oxide.
A great advantage of the process is its cost-effectiveness. The reaction to give a condensate (K) or polycondensate (P) and the reaction of (K) or (P) to give polycarbonates having other functional groups or elements can take place in one reaction apparatus, and this is technically and economically advantageous.
As component B2), the molding compositions obtainable according to the invention may comprise from at least 0.01 to 50% by weight, preferably from 0.5 to 20% by weight, and in particular from 0.7 to 10% by weight, of at least one hyperbranched polyester of AxBy type, where
x is at least 1.1, preferably at least 1.3, in particular at least 2, and
The units A and, respectively, B used may also, of course, comprise mixtures. An AxBy-type polyester is a condensate composed of an x-functional molecule A and a y-functional molecule B. By way of example, mention may be made of a polyester composed of adipic acid as molecule A (x=2) and glycerol as molecule B (y=3).
For the purposes of this invention, hyperbranched polycarbonates B2) are non-crosslinked macromolecules having hydroxy groups and carboxy groups, these having both structural and molecular non-uniformity. Their structure may firstly be based on a central molecule in the same way as dendrimers, but with non-uniform chain length of the branches. Secondly, they may also have a linear structure with functional pendent groups, or else they combine the two extremes, having linear and branched molecular portions. See also P. J. Flory, J. Am. Chem. Soc. 1952, 74, 2718, and H. Frey et al., Chem. Eur. J. 2000, 6, No. 14, 2499 for the definition of dendrimeric and hyperbranched polymers.
For the purposes of the present invention, it is also possible to use a mixture composed of a tri- or polycarboxylic acid and one or more of its derivatives. For the purposes of the present invention it is likewise possible to use a mixture of two or more different derivatives of one or more tri- or polycarboxylic acids, in order to obtain component B.
Examples of diols used for variant (b) of the present invention are 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-2,4diol, 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, 1,7-heptanediol, 1,8-octanediol, 1,2-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,2-decanediol, 1,12-dodecanediol, 1,2-dodecanediol, 1,5-hexadiene-3,4-diol, cyclopentanediols, cyclohexanediols, inositol and derivatives, (2)-methylpentane-2,4-diol, 2,4-dimethylpentane-2,4-diol, 2-ethylhexane-1,3-diol, 2,5-dimethylhexane-2,5-diol, 2,2,4-trimethylpentane-1,3-diol, pinacol, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, polyethylene glycols HO(CH2CH2O)n—H or polypropylene glycols HO(CH[CH3]CH2O)n—H or mixtures of two or more representative compounds of the above compounds, where n is a whole number and n=4 to 25. One, or else both, hydroxy groups here in the abovementioned diols may also be substituted by SH groups. Preference is given to ethylene glycol, propane-1,2-diol, and diethylene glycol, triethylene glycol, dipropylene glycol, and tripropylene glycol.
The inventive process is carried out in the presence of a solvent. Examples of suitable solvents are hydrocarbons, such as paraffins or aromatics. Particularly suitable paraffins are n-heptane and cyclohexane. Particularly suitable aromatics are toluene, ortho-xylene, meta-xylene, para-xylene, xylene in the form of an isomer mixture, ethylbenzene, chlorobenzene and ortho- and meta-dichlorobenzene. Other very particularly suitable solvents in the absence of acidic catalysts are: ethers, such as dioxane or tetrahydrofuran, and ketones, such as methyl ethyl ketone and methyl isobutyl ketone.
To carry out the process preferred according to the invention, operations may be carried out in the presence of a dehydrating agent as additive, added at the start of the reaction. Suitable examples are molecular sieves, in particular 4A molecular sieve, MgSO4, and Na2SO4. During the reaction it is also possible to add further dehydrating agent or to replace dehydrating agent by fresh dehydrating agent. During the reaction it is also possible to remove the water or alcohol formed by distillation and, for example, to use a water separator.
The process is preferably carried out under inert gas, e.g. under carbon dioxide, nitrogen, or a noble gas, among which mention may particularly be made of argon.
The process is preferably carried out at temperatures of from 60 to 200° C. It is preferable to operate at temperatures of from 130 to 180° C., in particular up to 150° C., or below that temperature. Maximum temperatures up to 145° C. are particularly preferred, and temperatures up to 135° C. are very particularly preferred.
Once the reaction has ended, the highly functional hyperbranched polyesters B2) can easily be isolated, e.g. by removing the catalyst by filtration and concentrating the mixture, the concentration process here usually being carried out at reduced pressure. Other work-up methods with good suitability are precipitation after addition of water, followed by washing and drying.
The process is carried out at temperatures above 60° C. It is preferable to operate at temperatures of 100° C. or below that temperature. Preference is given to temperatures up to 80° C., very particular preference is given to temperatures of from 62 to 75° C., and still more preference is given to temperatures of from 65 to 75° C.
The process is carried out in the presence of a solvent. Examples of suitable solvents are hydrocarbons, such as paraffins or aromatics. Particularly suitable paraffins are n-heptane and cyclohexane. Particularly suitable aromatics are toluene, ortho-xylene, meta-xylene, para-xylene, xylene in the form of an isomer mixture, ethylbenzene, chlorobenzene and ortho- and meta-dichlorobenzene. Other very particularly suitable solvents are: ethers, such as dioxane or tetrahydrofuran, and ketones, such as methyl ethyl ketone and methyl isobutyl ketone.
The reaction time for the process is usually from 4 hours to 6 days, preferably from 5 hours to 5 days, and particularly preferably from 8 hours to 4 days.
Once the reaction has ended, the highly functional hyperbranched polyesters B2) can easily be isolated, e.g. by removing the enzyme by filtration and concentrating the mixture, the concentration process here usually being carried out at reduced pressure. Other work-up methods with good suitability are precipitation after addition of water, followed by washing and drying.
The highly functional hyperbranched polyesters B2) feature particularly low contents of discolored and resinified material. For the definition of hyperbranched polymers, see also: P. J. Flory, J. Am. Chem. Soc. 1952, 74, 2718, and A. Sunder et al., Chem. Eur. J. 2000, 6, No.1, 1-8. However, in the context of the present invention, “highly functional hyperbranched” means that the degree of branching, i.e. the average number of dendritic linkages plus the average number of end groups per molecule is from 10 to 99.9%, preferably from 20 to 99%, particularly preferably from 30 to 90% (see in this connection H. Frey et al. Acta Polym. 1997, 48, 30).
The polyesters B2) according to the invention have a molar mass M, of from 500 to 50 000 g/mol, preferably from 1000 to 20 000 g/mol, particularly preferably from 1000 to 19 000 g/mol. The polydispersity is from 1.2 to 50, preferably from 1.4 to 40, particularly preferably from 1.5 to 30, and very particularly preferably from 1.5 to 10. They are usually very soluble, i.e. clear solutions can be prepared using up to 50% by weight, in some cases even up to 80% by weight, of the polyesters according to the invention in tetrahydrofuran (THF), n-butyl acetate, ethanol, and numerous other solvents, with no gel particles detectable by the naked eye.
The highly functional hyperbranched polyesters B2) according to the invention are carboxy-terminated, carboxy- and hydroxy-terminated, and preferably hydroxy-terminated.
The ratios of the components B1): B2) are preferably from 1:20 to 20:1, in particular from 1:15 to 15:1, and very particularly preferably from 1:5 to 5:1, if B1 is used in a mixture with B2.
The hyperbranched polycarbonates B1/polyesters B2 used are particles whose size is from 20 to 500 nm. These nanoparticles are present in fine dispersion in the polymer blend, and the size of the particles in the compounded material is from 20 to 500 nm, preferably from 50 to 300 nm.
Suitable lubricants C) are low-molecular-weight polyethylene waxes which may preferably comprise functional groups, such as glycidyl group and/or carboxy group, with a number-average molar mass Mn of from 500 to 20 000 g/mol, preferably from 1000 to 10 000 g/mol, in particular from 1000 to 5000 g/mol, and very particularly preferably from 1000 to 3000 g/mol.
The molecular weight is usually determined via gel permeation chromatography (GPC), using an LDPE standard. The melt viscosity is preferably from 10 to 10 000 mm2/g (to DIN 51562), preferably from 100 to 5000 mm2/g, in particular from 100 to 3000 mm2/g, and very particularly from 100 to 2000 mm2/g, at a temperature of 120° C.
The polyethylenes containing acid groups or containing epoxy groups may be copolymers of ethylene with α,β-unsaturated acid compounds or with epoxy compounds, or else polyethylenes onto which acid compounds or epoxy compounds are grafted.
The polyethylenes may be prepared by the high-, medium-, or low-pressure process. Use may be made of high-density polyethylenes (HDPEs) (range from 0.94 to 0.97 g/cm3), preferably prepared by the Phillips process (medium-pressure process), or else of low-density polyethylenes (LDPEs) (range from 0.91 to 0.94 g/cm3), in particular of low-density linear polyethylenes, preferably prepared by the gas-phase process.
The person skilled in the art is aware of processes for preparation of these copolymers (e.g. Ullmanns Enzyklopädie der Technischen Chemie [Ullmann's Encyclopedia of Industrial Chemistry], 4th edition, vol. 19, pp. 169-175).
Suitable products are commercially available with the trademark Luwax® (BASF AG), Hoechst-Wachs® PED 191, or H12 (Hoechst AG), or else Poligen® EAS-1 (BASF AG).
Other lubricants are esters or amides of saturated or unsaturated aliphatic carboxylic acids having from 10 to 40, preferably from 16 to 22, carbon atoms, with saturated aliphatic alcohols or amines having from 2 to 40, preferably 2 to 6, carbon atoms.
The carboxylic acids may be mono- or dibasic. 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 also montanic acid (a mixture of fatty acids having from 30 to 40 carbon atoms).
The aliphatic alcohols may be mono- to tetrahydric, and it is not necessary for all of the OH groups here to have been esterified. Examples of alcohols are n-butanol, n-octanol, stearyl alcohol, ethylene glycol, propylene glycol, neopentyl glycol, pentaerythritol, preference being given to glycerol and pentaerythritol.
The aliphatic amines may be mono- to trifunctional. Examples of these are stearylamine, ethylenediamine, propylenediamine, hexamethylenediamine, di(6-aminohexyl)amine, particular preference being given to ethylenediamine and hexamethylenediamine. Preferred esters or amides are correspondingly glycerol distearate, ethylenediamine distearate, glycerol monopalmitate, glycerol trilaurate, glycerol monobehenate, and pentaerythritol tetrastearate.
It is also possible to use mixtures of various esters or amides, or esters with amides combined, in any desired mixing ratio.
The morphology of selected compounded materials was studied via transmission electron microscopy. Good dispersion of the particles in the blend is seen. Particle sizes of from 20 to 500 nm were found.
The polyesters obtainable by the process described above have improved mechanical properties, in particular multiaxial impact strength, less susceptibility to yellowing, and better processability, because susceptibility to crystallization has been substantially improved. Flowability, in particular, has been markedly improved, with very substantial retention of mechanical properties.
For other applications, the inventive polyesters may be blended with further additives, preferably for electrical and electronic applications, optical waveguides, etc.
distillate, based on weight number
full conversion Mw Visc. 23° [mg
TMP × K2CO3 90 5907 1810 300
1.2 PO 2164
Mn Mw (mg (mg
Monomer (g/mol) (g/mol) KOH/g) KOH/g)
B 2 Terephthalic acid and 900 2390 416 0
1589 g (8.19 mol) of dimethyl terephthalate and 628 g (6.83 mol) of glycerol formed an initial charge in a 5 l glass flask equipped with stirrer, internal thermometer, gas inlet tube, reflux condenser, and vacuum connection with cold trap. 4.4 g of di-n-butyltin oxide commercially available as Fascat® 4201 were added and the mixture was heated with the aid of an oil bath to an internal temperature of 140° C. A reduced pressure of 50 mbar was applied in order to remove water formed during the reaction. The reaction mixture was held at the stated temperature and stated pressure for 34 hours. The mixture was then cooled to room temperature, giving 1750 g of hyperbranched polyester in the form of a clear, highly viscous liquid. The analytical data are given in table 2 above.
881.8 g of DMT and 563.7 g of 1,4-butanediol were continuously fed into a reaction zone. 781.8 mg of tetrabutyl orthotitanate and 99 microliters of a 30% strength by weight solution of NaOCH3 in methanol were continuously incorporated into the butanediol here by mixing, prior to contact with the DMT.
The temperature in the first reaction zone was 185° C. at a pressure of 1 bar with an average residence time of 182 min.
The temperature in the second reaction zone was 205° C. at a pressure of 1 bar with an average residence time of 63 min.
These polyester molding compositions can then also be blended with further additives, fillers, etc. to give other product compositions.
The temperature in the third reaction zone was 210° C. at a pressure of 1 bar with an average residence time of 40 min.
The distillate produced here, which comprised BDO, DMT, THF, and water, were separated in a column system, DMT and BDO being returned to the reaction. At 93% conversion, the transesterification product was passed to a vertical tube, divided into four heating zones.
The temperature in the fourth reaction zone was 247° C. at a pressure of 700 mbar, with an average residence time of 22 min.
The temperature in the fifth reaction zone was 252° C. at a pressure of 400 mbar, with an average residence time of 11 min.
The temperature in the sixth reaction zone was 255° C. at a pressure of 150 mbar, with an average residence time of 5 min.
The temperature in the seventh reaction zone was 256° C. at a pressure of 30 mbar, with an average residence time of 18 min.
The excess BDO and the reaction products, such as THF and water, were removed at the upper end of the reaction tube. The precondensate was transferred into a polycondensation reactor (zone 8) without further addition of catalysts.
The temperature in the eighth reaction zone was 257° C. at a pressure of 0.4 mbar, with an average residence time of 115 min and a surface renewal rate of 4 m2/h*kg PBT.
After discharge from the eighth reaction zone, the melt, at 257° C. (100% of final viscosity number) was treated by adding 1% by weight, based on A) and B), of component B2) in liquid form (T of feed line=80° C.).
The method was based on example 1, but the amount of B2) added was 2% by weight, based on 100% by weight of A) and B).
Components A) and B2) or B1) were compounded in the usual way, the component A) used comprising polybutylene terephthalate with a viscosity number VN of 130 ml/g and a carboxy end group content of 34 meq/kg (Ultradur® B4500 from BASF AG), VN measured in 0.5% strength by weight solution composed of phenol/o-dichlorobenzene, 1:1 mixture at 25° C.
The method was based on inventive example 1, but 0.75% by weight of B1), based on 100% by weight of A) and B), was used at room temperature (RT).
The method was based on inventive example 1, but 1% by weight of B1), based on 100% by weight of A) and B), was used at RT.
Processing to Give Moldings
The products obtained from the inventive examples and also from comparative examples A and B were injection molded to give the moldings needed for toughness tests. The melt temperature was 260° C. and the mold temperature was 80° C.
Viscosity number was measured at 25° C. on a 0.5% solution of the polymer in a 1:1 mixture composed of phenol/o-dichlorobenzene (DIN 53728).
The tensile test was carried out to ISO 527-2 (with max. tensile stress and tensile strain at break) and the Charpy impact toughness to ISO 179-1eU.
The results of the tests are found in table 3.
Inv. Inv. Comp. Inv. Inv. Comp.
ex. 1 ex. 2 A ex. 3 ex. 4 B
VN [g/l] 127 118 115 118 112 109
MVR (275° C.; 2.16 kg) 67 98 85 94 115 99
Modulus of elasticity [mPa] 2594 2543 2469 2604 2536 2581
Tensile stress at max. [N/mm] 72 64 58 61 57 58
Notched Charpy [kJ/m2] 4.9 3.4 1.6 5.3 4.7 4.1
Tensile strain at break [%] 48.6 36.5 19.7 33.7 42.3 19.7
Flow spiral, 260° C./80° C. 2 mm 46 51 49 49 55 48
1. A continuous process for preparation of polyalkylene arylates A) comprising hyperbranched polymers B) and, optionally, comprising lubricants C), by
esterifying or transesterifying an aromatic dicarboxylic acid or its ester or ester-forming derivatives, with a molar excess of an aliphatic dihydroxy compound, and
polycondensing the resultant transesterification or esterification product, which comprises, on achievement of at least 80% of a selected viscosity number, adding component B) and also, optionally, C) to the polymer melt of polyalkylene arylates A), wherein the amount of component B) added is from 0.01 to 10% by weight, based on 100% by weight of components A) to C), and, optionally,
post-condensing the melt and then discharging, cooling, and pelletizing it, and also using, as component B), at least one hyperbranched polycarbonate B1) with an OH number of from 1 to 600 mg KOH/g of polycarbonate (to DIN 53240, Part 2), or at least one hyperbranched polyester B2) of AxBy type, where x is at least 1.1 and y is at least 2.1, or a mixture of these;
wherein the degree of branching for B1) and B2) is between 10 and 99.9%.
2. The process according to claim 1, wherein the amount of component B) added is from 0.1 to 10% by weight, based on 100% by weight of components A) to C).
3. The process according to claim 1, which uses a polyalkylene terephthalate.
4. The process according to claim 1, wherein, as lubricant, use is made of esters or amides of carboxylic acids having from 10 to 40 carbon atoms, or a mixture of these.
5. The process according to claim 1, which uses pentaerythritol tetrastearate as lubricant.
6. The process according to claim 1, wherein B) is suspended prior to addition to the melt, optionally at an elevated temperature, in the lubricant C).
7. The process according to claim 6, wherein the temperature at which the suspension is prepared for addition to the polymer melt is from 30 to 150° C.
8. The process according to claim 1, which uses, as component B1), a polycarbonate with a number-average molar mass Mn of from 100 to 15 000 g/mol.
9. The process according to claim 1, which uses, as component B1), a polycarbonate with a glass transition temperature Tg of from −80 to 140° C.
10. The process according to claim 1, which uses, as component B1), a polycarbonate with a viscosity (mPas) at 23° C. of from 50 to 200 000 to DIN 53019.
11. The process according to claim 1, which uses, as component B2), a polyester with a number-average molar mass Mn of from 300 to 30 000 g/mol.
12. The process according to claim 1, which uses, as component B2), a polyester with an OH number (to DIN 53 240) of from 0 to 600 mg KOH/g of polyester.
13. The process according to claim 1, which uses, as component B2), a polyester with a COOH number (to DIN 53 240) of from 0 to 600 mg KOH/g of polyester.
14. The process according to claim 1, which uses, as component B2), a polyester, where at least one OH number or one COOH number is greater than 0.
15. The process according to claim 2, which uses a polyalkylene terephthalate.
16. The process according to claim 2, wherein, as lubricant, use is made of esters or amides of carboxylic acids having from 10 to 40 carbon atoms, or a mixture of these.
17. The process according to claim 3, wherein, as lubricant, use is made of esters or amides of carboxylic acids having from 10 to 40 carbon atoms, or a mixture of these.
18. The process according to claim 2, which uses pentaerythritol tetrastearate as lubricant.
19. The process according to claim 3, which uses pentaerythritol tetrastearate as lubricant.
US11/632,703 2004-07-21 2005-07-19 Continuous process for preparing polyalkylene arylates with hyperbranched polyesters and/or polycarbonates Expired - Fee Related US8445576B2 (en)
DE200410035357 DE102004035357A1 (en) 2004-07-21 2004-07-21 A continuous process for preparing polyalkylene arylates with hyperbranched polyesters and / or polycarbonates
DE102004035357.3 2004-07-21
DE102004035357 2004-07-21
PCT/EP2005/007838 WO2006008130A1 (en) 2004-07-21 2005-07-19 Continuous method for producing polyalkylene arylates containing hyperbranched polyesters and/or polycarbonates
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