CA2154619A1 - Polyurethane molding compositions - Google Patents
Polyurethane molding compositionsInfo
- Publication number
- CA2154619A1 CA2154619A1 CA002154619A CA2154619A CA2154619A1 CA 2154619 A1 CA2154619 A1 CA 2154619A1 CA 002154619 A CA002154619 A CA 002154619A CA 2154619 A CA2154619 A CA 2154619A CA 2154619 A1 CA2154619 A1 CA 2154619A1
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-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/12—Esters; Ether-esters of cyclic polycarboxylic acids
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6603—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6607—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/41—Compounds containing sulfur bound to oxygen
- C08K5/42—Sulfonic acids; Derivatives thereof
-
- 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
- C08G2125/00—Compositions for processes using internal mould release agents
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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)
- Compositions Of Macromolecular Compounds (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
A thermoplastic molding composition of A) 15 to 90 parts by weight of a thermoplastic polyure-thane produced from 1) organic diisocyanate, 2) mixtures of polypropylene oxide or polypropy-lene/ethylene oxide with polyesters of alipha-tic dicarboxylic acids with C2-6 diols with a molecular weight of 500 to 5,000, 3) a chain-extending diol with a molecular weight of 60 to 400, B) 5 to 50 parts by weight of inorganic fillers and C) 5 to 35 parts by weight of alkyl sulfonic acid esters of phenol (DIN 7723: ASE) and/or benzyl butyl phthalate (DIN 7723: BBP).
Description
Le A 30 29L forei gn countri es POLYUR~THAN13 MOT nTr7~ COMPOSITIONS
This invention relates to soft thermoplastic poly-urethane elastomer compositions with distinctly improved demolding behavior based on thermoplastic polyurethanes (TPU's), inorganic fillers and at least one special plasticizer.
In EP 0 134 455, it is shown that TPU's with a hardness of 60 to 80 Shore A can be obtained by using phthalic acid dimethoxy ethyl ester, tricresyl phosphate and/or diphenyl cresyl phosphate.
The present invention relates to very soft rubber-like elastic and thermoplastically processable molding compositions with distinctly improved demolding behavior which contain A) 15 to 90 parts by weight of a thermoplastic polyure-thane produced from 1) organic diisocyanate, 2) mixtures of polypropylene oxide or polypropy-lene/ethylene oxide with polyesters of alipha-tic dicarboxylic acids with C2_6 diols with a molecular weight of 500 to 5,000, 3) a chain-extending diol with a molecular weight of 60 to 400, B) 5 to 50 parts by weight of inorganic fillers and C) 5 to 35 parts by weight of alkyl sulfonic acid esters of phenol (DIN 7723: ASE) and/or benzyl butyl phthalate (DIN 7723: BBP).
Component A) of the molding composition according to the invention is a special thermoplastic polyurethane elastomer known in principle. Thermoplastic polyurethane 21S~619 Le A 30 297 elastomers, generally referred to in short as TPU's, are synthesized from polyols, i.e. polyethers or polyesters of relatively high molecular weight, organic diisocyanate and short-chain diols as chain-extending agent. Various S production processes are known and are operated on an industrial scale.
The TPU's used in accordance with the invention are based on aliphatic, cycloaliphatic, araliphatic, hetero-cyclic or aromatic diisocyanates of the type described, for example, in Justus Liebigs Annalen der Chemie, 562, pages 75-136. Examples of such diisocyanates are alipha-tic diisocyanates, such as hexamethylene diisocyanate;
cycloaliphatic diisocyanates, such as isophorone diiso-cyanate, l,4-cyclohexane diisocyanate, 1-methyl-2,4- and lS -2,6-cyclohexane diisocyanate and the corresponding isomer mixtures, 4,4'-, 2,4'- and 2,2'-dicyclohexyl methane diisocyanate and the corresponding isomer mix-tures; and aromatic diisocyanates, such as 2,4-tolylene diisocyanate, mixtures of 2,4- and 2,6-tolylene diisocya-nate, 4,4'-, 2,2'- and 2,2'-diphenyl methane diisocya-nate, mixtures of 2,4'- and 4,4'-diphenyl methane diiso-cyanate, urethane-modified liquid 4,4'- and/or 2,4'-diphenyl methane diisocyanates, 4,4'-diisocyanatodiphenyl ethane-(1,2)- and 1,5-naphthylene diisocyanate. 1,6-Hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexyl methane diisocyanate, diphenyl methane diisocyanate isomer mixtures containing more than 96% by weight of 4,4'-diphenyl methane diisocyanate are prefer-ably used, 4,4'-diphenyl methane diisocyanate and 1,5-naphthylene diisocyanate being particularly preferred.
The diisocyanates mentioned may be used together with a polyisocyanate in a quantity of up to 15% (based on diisocyanate) but at most in such a quantity that an uncrosslinked product is formed. Examples are triphenyl methane-4,4,4"-diisocyanate and polyphenyl polymethylene Le A 30 297 polyisocyanates.
The TPU's according to the invention are based on mixtures of polypropylene oxide or polypropylene/ethylene oxide with polyesters of aliphatic dicarboxylic acids and SC2_6 diols, more particularly butane-1,4-diol, with a molecular weight of 500 to 5,000 as relatively long-chain polyols.
The polyether polyols also have molecular weights of 500 to 5,000. Adipates are preferably used as the poly-10esters.
Preferred chain-extending agents with molecular weights of 60 to 400 are aliphatic diols cont~;n;ng 2 to 14 carbon atoms, such as for example ethanediol, hexane-1,6-diol, diethylene glycol, dipropylene glycol and, more 15particularly, butane-1,4-diol. However, diesters of terephthalic acid with glycols containing 2 to 4 carbon atoms, such as for example terephthalic acid bis-ethylene glycol or butane-1,4-diol, hydroxyalkylene ethers of hydroquinone, such as l,4-di-(~-hydroxyethyl)-hydro-20quinone for example, (cyclo)aliphatic diamines, such as for example isophorone diamine, ethylene diamine, 1,2-and 1,3-propylene diamine, N-methyl-1,3-propylene di-amine, N,N'-dimethyl ethylene diamine, and aromatic diamines, such as for example 2,4- and 2,6-tolylene 25diamine, 3,5-diethyl-2,4- and/or -2,6-tolylene diamine, and primary ortho-di-, tri- and/or tetra-alkyl substitu-ted 4,4'-diaminodiphenyl methanes. Mixtures of the chain-extending agents mentioned above may also be used.
To produce the TPU's, the synthesis components may 30be reacted, optionally in the presence of catalysts, auxiliaries and/or additives, in such quantities that the equivalence ratio of NCO groups to the sum of the NCO-reactive groups, particularly the OH groups, of the low molecular weight diols and the polyols is 0.9:1 to 1.2:1 35and preferably 0.95:1 to 1.1:1.
21S~619 Le A 30 297 The production of TPU's is known per se and is described, for example, in DE-A 2 302 564 or in GB
1,057,018.
Inorganic fillers B are, for example, calcium carbonate, barium sulfate, silicon oxide, magnesium oxide, antimony oxide or mixtures thereof. Particularly preferred fillers B are calcium carbonate and barium sulfate, optionally in conjunction with silicon dioxide, for example in the form of silicas, a mixture of 15 to 35 parts by weight of calcium carbonate with 1 to 10 parts by weight of silicon dioxide being particularly suitable.
Suitable plasticizers C are alkyl sulfonic acid esters of phenol (ASE) and benzyl butyl phthalates (BBP) and mixtures thereof.
Particularly suitable alkyl sulfonic acid esters of phenol contain alkyl groups with 10 to 20 carbon atoms, in many cases mixtures of different alkyl groups contain-ing on average 10 to 14 carbon atoms.
The molding compositions according to the invention may be produced by premixing the components in known manner (A+B+C, for example in a high-speed mixer) and compounding the resulting mixture in known units (knead-ers, extruders).
The use of silicon dioxide as a filler in the production of the compositions represents a particular embodiment of the invention. A dry and meterable compo-sition is obtained through the silicon dioxide, more particularly in the form of silica.
In order continuously to produce the molding com-positions, the individual components may be directly introduced, i.e. without premixing, into the units (extruders) mentioned above through suitable metering units, the plasticizer preferably being introduced into the already melted TPU or TPU/filler mixture.
The filler and the plasticizer may also be intro-21S~619 Le A 30 297 duced during the production of the TPU, i.e. into the not yet fully reacted reaction mixture.
The molding compositions according to the invention are very soft (Shore A hardness 55 to 85) and, even with a TPU content of only 50%, show mechanical properties comparable with many soft PVC compounds and other thermo-plastic elastomer compounds. By virtue of the excellent crystallization capacity from compounding in the melt, the virtual absence of tackiness in the mold and the low shrinkage values of the moldings, articles produced from the molding compositions according to the invention show distinctly improved demolding behavior during thermoplas-tic processing. Accordingly, they are particularly suitable as alternative products to soft PVC compounds.
Accordingly, they are particularly suitable for the production of flexible injection-molded articles and also for blow-molded articles and extrudates.
Exam;~les The following substances were used in the following Examples:
TPU 1 = Polyether/ester urethane elastomer based on 50 parts by weight of polypropylene oxide ether, MW approx. 2,000 50 parts by weight of polybutanediol adipate, MW approx. 2,000 10.5 parts by weight of butane-1,4-diol 42 parts by weight of diphenyl methane diiso-cyanate TPU 2 = Polyester urethane elastomer based on 100 parts by weight of polybutanediol adipate, MW approx. 2,000 10.5 parts by weight of butane-1,4-diol 215~619 Le A 30 297 40 parts by weight of diphenyl methane diiso-cyanate TPU 3 = Polyether urethane elastomer based on 100 parts by weight of polytetramethylene oxide ether, MW approx, 1,000 10 parts by weight of butane-1,4-diol 50 parts by weight of diphenyl methane diisocyanate Omyacarb 10 BG = Calcium carbonate of Omya Aerosil 200 V = Silicon dioxide of Degussa AG
Mesamoll 2 = Alkyl sulfonic acid ester of phenol of Bayer AG (DIN 7723: ASE) Disflamoll TKP = Tricresyl phosphate of Bayer AG (DIN
7723: TCF) 5 Vestinol AH = Dioctyl phthalate of Huls (DIN 7723:
DOP) Unimoll BB = Benzyl butyl phthalate of Bayer AG (DIN
7723: BBP).
The crystallization capacity of the products is determined by differential scanning calorimeter (DSC) measurements.
The DSC measurements were carried out with a Perkin Elmer DSC-7 as follows: the product is heated in nitrogen from -70C to 260C at a rate of 20C/minute and then cooled to -70C at a rate of 40C/minute.
The crystallization temperature in the cooling phase (exothermic peak) is directly proportional to the crys-tallization capacity.
Exam~les 1 to 7 according to the invention The TPU component was mixed for 5 minutes at room temperature in a commercial high-speed mixer with filler 2l546l9 Le A 30 297 1 and filler 2 and the plasticizer in the quantities shown in Table 1 below. The dry meterable mixture obtained was then compounded in a twin-screw extruder, the strands obtained were cooled in a water bath and then granulated.
The dried granules were injection-molded to test specimens at 195C. After heating for 15 h at 80C, the properties listed in Table 2 were observed.
Le A 30 297 2154619 s ~ ~3 ~ ~ ~ ~ m a m ~, c o c c c c ~
-- E E~ E E E E O
~ ~ a ~ E3 V. Ul U. U U V - ~1 ~ g S~ In ~ ~ o o o In ~4 o o o o o o o o o o o o a~ u u, u u u u ~ o o o o o o O ~1 a) a) a) a) a) a -~1 Vl u ~ I
O S~ o E~
o v V a) V v v v v m ~ m m m m m O ~ O O O O O
o -~1 ~ ,~ U
E~
a --I ~ E~ m E1 E~ E~ E~ E~
a ~ u\
o o In oo In In O
O ~ ~ ~ ~ ~ ~ ~ ~
u u ~ o o o o o o o u a ,~ a) ~
X X z Table 2 æ
Properties of the Examples according to the invention ~
o Example Hardness Tensile Breaking Shrinkage Crystallization Remarks No. Shore A strength elongation after temperature C
DIN 53505 (MPa) (%) heating from DSC
DIN 53504 (DIN 53504) (%) 1 69 9.9 602 1.2 92 Readily demoldable 2 71 7.5 580 0.8 95 Readily demoldable 3 64 9.1 713 1.4 95 Readily demoldable 4 73 8.4 452 1.2 87 Readily demoldable 82 6.4 522 0.8 84 Readily demoldable 6 67 8.1 602 1.6 87 Readily demoldable 7 70 5.7 495 1.2 81 Readily demoldable Le A 30 297 10 21S~619 C rA~ison ExAm~les 8 to 15 Example 8 Pure TPU 1 is used in this Example. The data determined are set out in Table 4.
Examples 9 to 11 The TPU components were mixed for around 24 hours at room temperature in a tumble mixer with the plasticizer component in the quantities and compositions shown in Table 3. The granules thus plasticized were then proces-sed as in the Examples according to the invention. The characteristic data are shown in Table 4. During injec-tion molding to test specimens, sticking of the test specimens in the injection mold was observed.
Exam~les 12 to 15 The TPU component was mixed for about 5 minutes at room temperature in a commercial high-speed mixer with filler 1 and filler 2 and the plasticizer in the quanti-ties and composition shown in Table 3. Compounding and further processing to test specimens was carried out as in Examples 1 to 7. The data determined are set out in Table 4.
Table 3 ~ ~ison Examples - composition O
~D
Example Parts TPU Parts Filler 1 Parts Filler 2 Parts PlaticizerNo.
9 75 1 25 Mesamoll 2 2 25 Disflamoll TKP
11 75 3 25 Disflamoll TKP
12 50 3 20 Omyacarb 10 BG 5 Aerosil 200 V 25 Mesamoll 2 13 50 2 20 Omyacarb 10 BG 5 Aerosil 200 V 25 Mesamoll 2 '~
14 50 1 20 Omyacarb 10 BG 5 Aerosil 200 V 25 Disflamoll TKP cn 1 20 Omyacarb 10 BG 5 Aerosil 200 V 25 Vestinol AH C~
C~
Table 4 comp~rison Examples - propQrties r~
Example Hardness Tensile Breaking Shrinkage Crystallization Remarks No. Shore A strength elongation after temperature C
DIN 53505 (MPa) (%) heating from DSC
DIN 53504 (DIN 53504) (%) 8 80 32.5 599 3.6 74 9 65 15 800 2.8 97 Sticks in mold 27.2 602 2.4 55 Sticks in mold 11 72 25.6 602 1.6 70 Sticks in mold 12 82 6.4 522 2.4 80 13 74 17.3 599 1.2 77 Plast.exudes heavily 14 72 5.2 483 0.8 72 Plast.exudes slightly 69 4.7 369 2.0 74 Plast.exudes heavily ~
Le A 30 297 13 21 S ~61 9 Comparison of the properties of Examples 1 to 7 according to the invention with those of Comparison Examples 8 to 15 known from the literature clearly shows that the property combination (soft with adequate mechanical properties and very good demolding behavior) is only achieved in the Examples according to the inven-tion.
In the Comparison Examples, either the shrinkage values are too high (Examples 8,9,10,12, 15), the crystallization temperatures are too low (Examples 8,10,11,13,14,15,) or the plasticizers exude and cause sticking (Examples 9,10,11,13,14,15).
This invention relates to soft thermoplastic poly-urethane elastomer compositions with distinctly improved demolding behavior based on thermoplastic polyurethanes (TPU's), inorganic fillers and at least one special plasticizer.
In EP 0 134 455, it is shown that TPU's with a hardness of 60 to 80 Shore A can be obtained by using phthalic acid dimethoxy ethyl ester, tricresyl phosphate and/or diphenyl cresyl phosphate.
The present invention relates to very soft rubber-like elastic and thermoplastically processable molding compositions with distinctly improved demolding behavior which contain A) 15 to 90 parts by weight of a thermoplastic polyure-thane produced from 1) organic diisocyanate, 2) mixtures of polypropylene oxide or polypropy-lene/ethylene oxide with polyesters of alipha-tic dicarboxylic acids with C2_6 diols with a molecular weight of 500 to 5,000, 3) a chain-extending diol with a molecular weight of 60 to 400, B) 5 to 50 parts by weight of inorganic fillers and C) 5 to 35 parts by weight of alkyl sulfonic acid esters of phenol (DIN 7723: ASE) and/or benzyl butyl phthalate (DIN 7723: BBP).
Component A) of the molding composition according to the invention is a special thermoplastic polyurethane elastomer known in principle. Thermoplastic polyurethane 21S~619 Le A 30 297 elastomers, generally referred to in short as TPU's, are synthesized from polyols, i.e. polyethers or polyesters of relatively high molecular weight, organic diisocyanate and short-chain diols as chain-extending agent. Various S production processes are known and are operated on an industrial scale.
The TPU's used in accordance with the invention are based on aliphatic, cycloaliphatic, araliphatic, hetero-cyclic or aromatic diisocyanates of the type described, for example, in Justus Liebigs Annalen der Chemie, 562, pages 75-136. Examples of such diisocyanates are alipha-tic diisocyanates, such as hexamethylene diisocyanate;
cycloaliphatic diisocyanates, such as isophorone diiso-cyanate, l,4-cyclohexane diisocyanate, 1-methyl-2,4- and lS -2,6-cyclohexane diisocyanate and the corresponding isomer mixtures, 4,4'-, 2,4'- and 2,2'-dicyclohexyl methane diisocyanate and the corresponding isomer mix-tures; and aromatic diisocyanates, such as 2,4-tolylene diisocyanate, mixtures of 2,4- and 2,6-tolylene diisocya-nate, 4,4'-, 2,2'- and 2,2'-diphenyl methane diisocya-nate, mixtures of 2,4'- and 4,4'-diphenyl methane diiso-cyanate, urethane-modified liquid 4,4'- and/or 2,4'-diphenyl methane diisocyanates, 4,4'-diisocyanatodiphenyl ethane-(1,2)- and 1,5-naphthylene diisocyanate. 1,6-Hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexyl methane diisocyanate, diphenyl methane diisocyanate isomer mixtures containing more than 96% by weight of 4,4'-diphenyl methane diisocyanate are prefer-ably used, 4,4'-diphenyl methane diisocyanate and 1,5-naphthylene diisocyanate being particularly preferred.
The diisocyanates mentioned may be used together with a polyisocyanate in a quantity of up to 15% (based on diisocyanate) but at most in such a quantity that an uncrosslinked product is formed. Examples are triphenyl methane-4,4,4"-diisocyanate and polyphenyl polymethylene Le A 30 297 polyisocyanates.
The TPU's according to the invention are based on mixtures of polypropylene oxide or polypropylene/ethylene oxide with polyesters of aliphatic dicarboxylic acids and SC2_6 diols, more particularly butane-1,4-diol, with a molecular weight of 500 to 5,000 as relatively long-chain polyols.
The polyether polyols also have molecular weights of 500 to 5,000. Adipates are preferably used as the poly-10esters.
Preferred chain-extending agents with molecular weights of 60 to 400 are aliphatic diols cont~;n;ng 2 to 14 carbon atoms, such as for example ethanediol, hexane-1,6-diol, diethylene glycol, dipropylene glycol and, more 15particularly, butane-1,4-diol. However, diesters of terephthalic acid with glycols containing 2 to 4 carbon atoms, such as for example terephthalic acid bis-ethylene glycol or butane-1,4-diol, hydroxyalkylene ethers of hydroquinone, such as l,4-di-(~-hydroxyethyl)-hydro-20quinone for example, (cyclo)aliphatic diamines, such as for example isophorone diamine, ethylene diamine, 1,2-and 1,3-propylene diamine, N-methyl-1,3-propylene di-amine, N,N'-dimethyl ethylene diamine, and aromatic diamines, such as for example 2,4- and 2,6-tolylene 25diamine, 3,5-diethyl-2,4- and/or -2,6-tolylene diamine, and primary ortho-di-, tri- and/or tetra-alkyl substitu-ted 4,4'-diaminodiphenyl methanes. Mixtures of the chain-extending agents mentioned above may also be used.
To produce the TPU's, the synthesis components may 30be reacted, optionally in the presence of catalysts, auxiliaries and/or additives, in such quantities that the equivalence ratio of NCO groups to the sum of the NCO-reactive groups, particularly the OH groups, of the low molecular weight diols and the polyols is 0.9:1 to 1.2:1 35and preferably 0.95:1 to 1.1:1.
21S~619 Le A 30 297 The production of TPU's is known per se and is described, for example, in DE-A 2 302 564 or in GB
1,057,018.
Inorganic fillers B are, for example, calcium carbonate, barium sulfate, silicon oxide, magnesium oxide, antimony oxide or mixtures thereof. Particularly preferred fillers B are calcium carbonate and barium sulfate, optionally in conjunction with silicon dioxide, for example in the form of silicas, a mixture of 15 to 35 parts by weight of calcium carbonate with 1 to 10 parts by weight of silicon dioxide being particularly suitable.
Suitable plasticizers C are alkyl sulfonic acid esters of phenol (ASE) and benzyl butyl phthalates (BBP) and mixtures thereof.
Particularly suitable alkyl sulfonic acid esters of phenol contain alkyl groups with 10 to 20 carbon atoms, in many cases mixtures of different alkyl groups contain-ing on average 10 to 14 carbon atoms.
The molding compositions according to the invention may be produced by premixing the components in known manner (A+B+C, for example in a high-speed mixer) and compounding the resulting mixture in known units (knead-ers, extruders).
The use of silicon dioxide as a filler in the production of the compositions represents a particular embodiment of the invention. A dry and meterable compo-sition is obtained through the silicon dioxide, more particularly in the form of silica.
In order continuously to produce the molding com-positions, the individual components may be directly introduced, i.e. without premixing, into the units (extruders) mentioned above through suitable metering units, the plasticizer preferably being introduced into the already melted TPU or TPU/filler mixture.
The filler and the plasticizer may also be intro-21S~619 Le A 30 297 duced during the production of the TPU, i.e. into the not yet fully reacted reaction mixture.
The molding compositions according to the invention are very soft (Shore A hardness 55 to 85) and, even with a TPU content of only 50%, show mechanical properties comparable with many soft PVC compounds and other thermo-plastic elastomer compounds. By virtue of the excellent crystallization capacity from compounding in the melt, the virtual absence of tackiness in the mold and the low shrinkage values of the moldings, articles produced from the molding compositions according to the invention show distinctly improved demolding behavior during thermoplas-tic processing. Accordingly, they are particularly suitable as alternative products to soft PVC compounds.
Accordingly, they are particularly suitable for the production of flexible injection-molded articles and also for blow-molded articles and extrudates.
Exam;~les The following substances were used in the following Examples:
TPU 1 = Polyether/ester urethane elastomer based on 50 parts by weight of polypropylene oxide ether, MW approx. 2,000 50 parts by weight of polybutanediol adipate, MW approx. 2,000 10.5 parts by weight of butane-1,4-diol 42 parts by weight of diphenyl methane diiso-cyanate TPU 2 = Polyester urethane elastomer based on 100 parts by weight of polybutanediol adipate, MW approx. 2,000 10.5 parts by weight of butane-1,4-diol 215~619 Le A 30 297 40 parts by weight of diphenyl methane diiso-cyanate TPU 3 = Polyether urethane elastomer based on 100 parts by weight of polytetramethylene oxide ether, MW approx, 1,000 10 parts by weight of butane-1,4-diol 50 parts by weight of diphenyl methane diisocyanate Omyacarb 10 BG = Calcium carbonate of Omya Aerosil 200 V = Silicon dioxide of Degussa AG
Mesamoll 2 = Alkyl sulfonic acid ester of phenol of Bayer AG (DIN 7723: ASE) Disflamoll TKP = Tricresyl phosphate of Bayer AG (DIN
7723: TCF) 5 Vestinol AH = Dioctyl phthalate of Huls (DIN 7723:
DOP) Unimoll BB = Benzyl butyl phthalate of Bayer AG (DIN
7723: BBP).
The crystallization capacity of the products is determined by differential scanning calorimeter (DSC) measurements.
The DSC measurements were carried out with a Perkin Elmer DSC-7 as follows: the product is heated in nitrogen from -70C to 260C at a rate of 20C/minute and then cooled to -70C at a rate of 40C/minute.
The crystallization temperature in the cooling phase (exothermic peak) is directly proportional to the crys-tallization capacity.
Exam~les 1 to 7 according to the invention The TPU component was mixed for 5 minutes at room temperature in a commercial high-speed mixer with filler 2l546l9 Le A 30 297 1 and filler 2 and the plasticizer in the quantities shown in Table 1 below. The dry meterable mixture obtained was then compounded in a twin-screw extruder, the strands obtained were cooled in a water bath and then granulated.
The dried granules were injection-molded to test specimens at 195C. After heating for 15 h at 80C, the properties listed in Table 2 were observed.
Le A 30 297 2154619 s ~ ~3 ~ ~ ~ ~ m a m ~, c o c c c c ~
-- E E~ E E E E O
~ ~ a ~ E3 V. Ul U. U U V - ~1 ~ g S~ In ~ ~ o o o In ~4 o o o o o o o o o o o o a~ u u, u u u u ~ o o o o o o O ~1 a) a) a) a) a) a -~1 Vl u ~ I
O S~ o E~
o v V a) V v v v v m ~ m m m m m O ~ O O O O O
o -~1 ~ ,~ U
E~
a --I ~ E~ m E1 E~ E~ E~ E~
a ~ u\
o o In oo In In O
O ~ ~ ~ ~ ~ ~ ~ ~
u u ~ o o o o o o o u a ,~ a) ~
X X z Table 2 æ
Properties of the Examples according to the invention ~
o Example Hardness Tensile Breaking Shrinkage Crystallization Remarks No. Shore A strength elongation after temperature C
DIN 53505 (MPa) (%) heating from DSC
DIN 53504 (DIN 53504) (%) 1 69 9.9 602 1.2 92 Readily demoldable 2 71 7.5 580 0.8 95 Readily demoldable 3 64 9.1 713 1.4 95 Readily demoldable 4 73 8.4 452 1.2 87 Readily demoldable 82 6.4 522 0.8 84 Readily demoldable 6 67 8.1 602 1.6 87 Readily demoldable 7 70 5.7 495 1.2 81 Readily demoldable Le A 30 297 10 21S~619 C rA~ison ExAm~les 8 to 15 Example 8 Pure TPU 1 is used in this Example. The data determined are set out in Table 4.
Examples 9 to 11 The TPU components were mixed for around 24 hours at room temperature in a tumble mixer with the plasticizer component in the quantities and compositions shown in Table 3. The granules thus plasticized were then proces-sed as in the Examples according to the invention. The characteristic data are shown in Table 4. During injec-tion molding to test specimens, sticking of the test specimens in the injection mold was observed.
Exam~les 12 to 15 The TPU component was mixed for about 5 minutes at room temperature in a commercial high-speed mixer with filler 1 and filler 2 and the plasticizer in the quanti-ties and composition shown in Table 3. Compounding and further processing to test specimens was carried out as in Examples 1 to 7. The data determined are set out in Table 4.
Table 3 ~ ~ison Examples - composition O
~D
Example Parts TPU Parts Filler 1 Parts Filler 2 Parts PlaticizerNo.
9 75 1 25 Mesamoll 2 2 25 Disflamoll TKP
11 75 3 25 Disflamoll TKP
12 50 3 20 Omyacarb 10 BG 5 Aerosil 200 V 25 Mesamoll 2 13 50 2 20 Omyacarb 10 BG 5 Aerosil 200 V 25 Mesamoll 2 '~
14 50 1 20 Omyacarb 10 BG 5 Aerosil 200 V 25 Disflamoll TKP cn 1 20 Omyacarb 10 BG 5 Aerosil 200 V 25 Vestinol AH C~
C~
Table 4 comp~rison Examples - propQrties r~
Example Hardness Tensile Breaking Shrinkage Crystallization Remarks No. Shore A strength elongation after temperature C
DIN 53505 (MPa) (%) heating from DSC
DIN 53504 (DIN 53504) (%) 8 80 32.5 599 3.6 74 9 65 15 800 2.8 97 Sticks in mold 27.2 602 2.4 55 Sticks in mold 11 72 25.6 602 1.6 70 Sticks in mold 12 82 6.4 522 2.4 80 13 74 17.3 599 1.2 77 Plast.exudes heavily 14 72 5.2 483 0.8 72 Plast.exudes slightly 69 4.7 369 2.0 74 Plast.exudes heavily ~
Le A 30 297 13 21 S ~61 9 Comparison of the properties of Examples 1 to 7 according to the invention with those of Comparison Examples 8 to 15 known from the literature clearly shows that the property combination (soft with adequate mechanical properties and very good demolding behavior) is only achieved in the Examples according to the inven-tion.
In the Comparison Examples, either the shrinkage values are too high (Examples 8,9,10,12, 15), the crystallization temperatures are too low (Examples 8,10,11,13,14,15,) or the plasticizers exude and cause sticking (Examples 9,10,11,13,14,15).
Claims (3)
1. A thermoplastic molding composition of A) 15 to 90 parts by weight of a thermoplastic polyure-thane produced from 1) organic diisocyanate,
2) mixtures of polypropylene oxide or polypropy-lene/ethylene oxide with polyesters of alipha-tic dicarboxylic acids with C2-6 diols with a molecular weight of 500 to 5,000,
3) a chain-extending diol with a molecular weight of 60 to 400, B) 5 to 50 parts by weight of inorganic fillers and C) 5 to 35 parts by weight of alkyl sulfonic acid esters of phenol and/or benzyl butyl phthalate.
2. Molding compositions as claimed in claim 1, in which A) is a thermoplastic polyurethane of 1) organic diisocyanate 2) mixtures of polypropylene oxide with a poly-ester of adipic acid with a C2-6 diol having a molecular weight of 500 to 5,000, 3) a chain-extending diol with a molecular weight of 60 to 400 and B) is a mixture of 15 to 35 parts by weight of calcium carbonate and/or barium sulfate and, optionally, 1.0 to 10 parts by weight of silicon dioxide.
2. Molding compositions as claimed in claim 1, in which A) is a thermoplastic polyurethane of 1) organic diisocyanate 2) mixtures of polypropylene oxide with a poly-ester of adipic acid with a C2-6 diol having a molecular weight of 500 to 5,000, 3) a chain-extending diol with a molecular weight of 60 to 400 and B) is a mixture of 15 to 35 parts by weight of calcium carbonate and/or barium sulfate and, optionally, 1.0 to 10 parts by weight of silicon dioxide.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4426943A DE4426943A1 (en) | 1994-07-29 | 1994-07-29 | Polyurethane molding compounds |
| DEP4426943.9 | 1994-07-29 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2154619A1 true CA2154619A1 (en) | 1996-01-30 |
Family
ID=6524470
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002154619A Abandoned CA2154619A1 (en) | 1994-07-29 | 1995-07-25 | Polyurethane molding compositions |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP0695786B1 (en) |
| CA (1) | CA2154619A1 (en) |
| DE (2) | DE4426943A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6218479B1 (en) | 1999-02-25 | 2001-04-17 | Bayer Aktiengesellschaft | Nonrigid, thermoplastic moulding compositions |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003085042A1 (en) * | 2002-04-11 | 2003-10-16 | Huntsman International Llc | Modified thermoplastic polyurethanes |
| DE102005040131A1 (en) | 2005-08-25 | 2007-03-01 | Lanxess Deutschland Gmbh | Thermoplastic polyurethanes |
| CN102127293B (en) * | 2010-01-12 | 2012-10-03 | 深圳市富洋密封件有限公司 | Formula and production process of thermoplastic polyurethane hydraulic sealing ring material |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE673744A (en) | 1964-12-14 | |||
| DE2302564C3 (en) | 1973-01-19 | 1985-02-07 | Bayer Ag, 5090 Leverkusen | Process for the production of polyurethane elastomers |
| US4349640A (en) * | 1978-09-14 | 1982-09-14 | Monsanto Company | Inhibition of polyurethane hardening |
| DE3323520A1 (en) | 1983-06-30 | 1985-01-10 | Basf Ag, 6700 Ludwigshafen | SOFT, RUBBER-ELASTIC, THERMOPLASTIC POLYURETHANES, METHOD FOR THE PRODUCTION AND USE THEREOF |
-
1994
- 1994-07-29 DE DE4426943A patent/DE4426943A1/en not_active Withdrawn
-
1995
- 1995-07-18 EP EP95111218A patent/EP0695786B1/en not_active Expired - Lifetime
- 1995-07-18 DE DE59507942T patent/DE59507942D1/en not_active Expired - Fee Related
- 1995-07-25 CA CA002154619A patent/CA2154619A1/en not_active Abandoned
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6218479B1 (en) | 1999-02-25 | 2001-04-17 | Bayer Aktiengesellschaft | Nonrigid, thermoplastic moulding compositions |
Also Published As
| Publication number | Publication date |
|---|---|
| DE59507942D1 (en) | 2000-04-13 |
| EP0695786A1 (en) | 1996-02-07 |
| DE4426943A1 (en) | 1996-02-01 |
| EP0695786B1 (en) | 2000-03-08 |
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