CA1236239A - Easily demoldable and non-blocking thermoplastic polyurethane elastomers, process for their preparation and use - Google Patents
Easily demoldable and non-blocking thermoplastic polyurethane elastomers, process for their preparation and useInfo
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- CA1236239A CA1236239A CA000440937A CA440937A CA1236239A CA 1236239 A CA1236239 A CA 1236239A CA 000440937 A CA000440937 A CA 000440937A CA 440937 A CA440937 A CA 440937A CA 1236239 A CA1236239 A CA 1236239A
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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
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
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Abstract
EASILY DEMOLDABLE AND NON-BLOCKING
THERMOPLASTIC POLYURETHANE ELASTOMERS, PROCESS FOR THEIR PREPARATION AND USE
Abstract of the Disclosure Easily demoldable and non-blocking thermoplastic polyurethane elastomer composition, obtained by melting:
(A) from 50 parts to 99.5 parts by weight of a thermoplastic polyurethane elastomer with a urethane group content of from 10 50 percent by weight and a melt index of from 0.1 to 100 at 190°C, with (B) from 0.5 part to 50 parts by weight of a thermoplastic polyurethane elastomer with a urethane group content of from 20 to 60 percent by weight and a melt index of 10 to 1000 at 190°C, wherein the urethane group content of polyurethane elastomer (B) is always at least 10 percent by weight greater than that of (A) and the melt index of the polyurethane elastomer (B) is greater than or equal to that of (A) at the melt temperature. The elastomers are obtained by melting together the (A) and (B) polyurethane elastomers at tempera-tures from 140°C to 250°C, preferably in an extruder, with subsequent granulation.
THERMOPLASTIC POLYURETHANE ELASTOMERS, PROCESS FOR THEIR PREPARATION AND USE
Abstract of the Disclosure Easily demoldable and non-blocking thermoplastic polyurethane elastomer composition, obtained by melting:
(A) from 50 parts to 99.5 parts by weight of a thermoplastic polyurethane elastomer with a urethane group content of from 10 50 percent by weight and a melt index of from 0.1 to 100 at 190°C, with (B) from 0.5 part to 50 parts by weight of a thermoplastic polyurethane elastomer with a urethane group content of from 20 to 60 percent by weight and a melt index of 10 to 1000 at 190°C, wherein the urethane group content of polyurethane elastomer (B) is always at least 10 percent by weight greater than that of (A) and the melt index of the polyurethane elastomer (B) is greater than or equal to that of (A) at the melt temperature. The elastomers are obtained by melting together the (A) and (B) polyurethane elastomers at tempera-tures from 140°C to 250°C, preferably in an extruder, with subsequent granulation.
Description
~362;3~ case 1405 EASILY REMOLDABLE AND NON-BLOCKING
THERMOPLASTIC POLYURETHANE ELASTOMERS, PROCESS FOR THEIR PREPARATION AND USE
Back round of the Invention g .
1. Field of the Invention The present invention relates to thermoplastic polyurethane elastomers. More particularly, the invention relates to mixtures of flexible and rigid thermoplastic polyurethane elastomers and to their use in the preparation of films or sheets and injection molded parts.
THERMOPLASTIC POLYURETHANE ELASTOMERS, PROCESS FOR THEIR PREPARATION AND USE
Back round of the Invention g .
1. Field of the Invention The present invention relates to thermoplastic polyurethane elastomers. More particularly, the invention relates to mixtures of flexible and rigid thermoplastic polyurethane elastomers and to their use in the preparation of films or sheets and injection molded parts.
2. Description of the Prior Art Thermoplastic polyurethane elastomers have been known for some time. Their utility is based on a combine-lion of highly desirable mechanical properties coupled with the advantages of economical thermoplastic processing. By using a variety of starting materials, a wide range of mechanical properties own be obtained. ~unststoffe 68 (1978), pp. 819-825, jives an overview of thermoplastic polyurethane elastomers, their properties and applications.
Thermoplastic polyurethane elastomers can be prepared continuously or by batch processes. The most common processes used commercially are the so-called continuous-sheet process and the extrude process.
GO 1,057,018 teaches the preparation of a pro polymer from a primarily linear polyhydroxyl compound and an excess of organic diisocyanate. This prepolymer is fed into Jo ~3~3~
a mixing head by means of a metering pump and is mixed in the head with a specified amount of a low molecular weight Doyle The resulting reaction mixture is delivered onto a conveyor belt and passed through an oven heated from 70C to 130C until it solidifies. The reaction product is then granulated, tempered from 6 to 40 hours at temperatures up to 120C, and can then be processed, for example, into molded parts using injection molding machines. Tempering and granulation are processes which make the continuous-sheet process less economical.
In the extruding process, which is described index OX 20 59 570 (V. S. 3,642,964), for example, the starting components are fed directly into the extrude and the reaction takes place in the extrude under specified process conditions. The resulting polyurethane elastomers is converted into a thermoplastic directly, extruded as a strand, cooled in an inert gas atmosphere until it becomes rigid, and is then granulated. The disadvantage of this process is that the resulting thermoplastic polyurethane elastomers have Shore A harnesses of up to 95 and are not suitable for manufacturing sheets, fine sections, or hoses. Often such sheets tend to block and stick to such an extent that further processing is impossible. Although the polyurethane sheets have very good mechanical properties, they have not yet been widely used.
issue The preparation of injection-molded parts from thermoplastic polyurethane elastomers in the Shore A
hardness range from 80 to 85 and less is also very difficult due to the thermoplastic polyurethane elastomers' poor demoldability. The use of occlude release agents offers only a slight improvement.
Summary of the Invention The object of this invention was to develop thermoplastic polyurethane elastomers which do not possess the disadvantages known to the prior art and which can be processed into non-blocking and non-sticking polyurethane sheets or cagily remoldable injection molded parts.
This object was achieved employing a mixture of thermoplastic polyurethane elastomers comprising (A) from 50 parts to OWE parts by weight of a thermoplastic polyurethane elastomers with a urethane group content of from 10 to 50 percent by weight and a melt index of from 0.1 to 100 at 190C, and (B) from 0.5 part to 50 parts by weight of a thermoplastic polyurethane elastomers with a urethane group content of from 20 Jo 60 percent by weight and a melt index of from 10 to 1000 at l90~C, ~L23~3~
wherein the urethane group content of thermoplastic polyp urethane elastomers (B) must always be at least 10 percent by weight larger than that of PA), and the melt index of thermoplastic polyurethane elastomers (B) must be greater than or equal to that of (A) at the same melt temperature.
The urethane group content is that proportion, by weight, of the polyurethane elastomers which consists of urethane groups, o (NH-C-O).
The melt viscosities of thermoplastic polyurethane elastomers and their hardness increase with increasing urethane group content, while the melt index is reduced.
Previously, therefore, thermoplastic polyurethane elastomers with different urethane group contents could only be mixed together in the melt when the thermoplastic polyurethane elastomers having a higher urethane group content predomi-noted. Rigid thermoplastic polyurethane elastomers could, by this process, be modified with a lesser amount of flexible thermoplastic polyurethane elastomers.
However, it was unexpectedly found that flexible thermoplastic polyurethane elastomers can be advantageously modified with rigid thermoplastic polyurethane elastomers if the melt viscosity of the more rigid thermoplastic polyp urethane elastomers is equal to or less than that of the more eye flexible thermoplastic polyurethane elastomers base material at the same melt temperature or if the melt index of the more rigid thermoplastic polyurethane elastomers it greater than or equal to that of the more flexible thermoplastic polyurethane elastomers base material at the same melt temperature.
The thermoplastic polyurethane elastomers in accordance with the invention have Shore A harnesses from 65 to 96 and a melt index of from 0.5 to 200 at 190C and are suitable for the preparation of sheets using the blow-molding and sheet extrusion processes. The resulting sheets do not block and have a dry feel. The products can also be processed into molded parts with the aid of injection molding technology, whereby even complex molded parts can be easily remolded.
Desertion of the Preferred Embodiments Thermoplastic polyurethane elastomers PA) and thermoplastic polyurethane elastomers (B) used in accordance with the invention can be prepared by reacting at elevated temperatures, and in the presence of suitable catalysts, and in some cases auxiliaries or additives:
(a) organic diisocyanates, (b) polyhydroxyl compounds with molecular weights from S00 to 8000, and ~36~3~
(c) chain extenders with molecular weights from 60 to 400.
The following discussion applies to starting material (a) through (c) and the catalyst, auxiliaries and additives useful in the practice of this invention:
(a) Representative organic diisocyanates are aliphatic, cycloaliphatic, and, preferably, aromatic dozes-notes. Typical are: aliphatic diisocyanates such as hexamethylene diisocyanate cycloaliphatic dozes-notes such as isophorone diisocyanate, 1,4-cyclohexane diisocyanate, l-methyl-2,4- and 2,6-cyclohexane diisocyanate, as well as the corresponding isomer mixtures, 4,4'-, 2,4'- and 2,2'-dicyclohexylme~hane diisocyanate as well a the corresponding isomer mixtures, and, preferably, aromatic diisocyanates such as Tulane diisocyanate, mixtures of 2,4- and 2,6-Tulane diisocyanate, 4,4'-, 2,4'- and 2,2'-diphenyl-methane diisocyanate, mixtures of 2,4'- and 4,4'-diphenylmethane diisocyanate, urethane-modified liquid 4,4'- and/or 2,4'-diphenylmethane diisocyanates, 4,4,!_ diisocyanato-1,2-diphenylethane, mixtures of 4,4'-, 2,4'- and 2,2' diisocyanato-1,2-diphenylethane, more advantageously those with a 4,4'-diisocyanato-1,2-I
diphenylethane content of at least 95 percent by weight, and 1,5-naphthylene diisocyanate. Preferably, hexamethylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate isomer mixtures with a 4,4'-diphenylmethane diisocyanate content of greater than 96 percent by weight and, in particular, 4,4'-diphenylmethane diisocyanate and l,5-naphthalene diisocyanate are used.
(b) Polyether polyols, and preferably polyester polyols, with molecular weights from 500 to 8000, are suitable for use as the higher molecular weight polyhydroxyl compounds. However, other polymers containing hydroxyl groups can also be used, for example, polyacetals such as polyoxymethylene and, in particular, water-insolùble msthylals, e.g., polybutanediol methylol and polyp hexanediol methylol, and polycarbonates, in particular those prepared by means of the transesterification of diphenylcarbonate and hexane-1,6-diol. The pull-droxyl compounds must be predominately linear, and may be used individually or in the form of mixtures.
Suitable polyether polyols can be prepared by reacting one or several alkaline oxides having from 2 to 4 carbon atoms in the alkaline residue with an initiator molecule which contains two active hydrogen atoms.
Thermoplastic polyurethane elastomers can be prepared continuously or by batch processes. The most common processes used commercially are the so-called continuous-sheet process and the extrude process.
GO 1,057,018 teaches the preparation of a pro polymer from a primarily linear polyhydroxyl compound and an excess of organic diisocyanate. This prepolymer is fed into Jo ~3~3~
a mixing head by means of a metering pump and is mixed in the head with a specified amount of a low molecular weight Doyle The resulting reaction mixture is delivered onto a conveyor belt and passed through an oven heated from 70C to 130C until it solidifies. The reaction product is then granulated, tempered from 6 to 40 hours at temperatures up to 120C, and can then be processed, for example, into molded parts using injection molding machines. Tempering and granulation are processes which make the continuous-sheet process less economical.
In the extruding process, which is described index OX 20 59 570 (V. S. 3,642,964), for example, the starting components are fed directly into the extrude and the reaction takes place in the extrude under specified process conditions. The resulting polyurethane elastomers is converted into a thermoplastic directly, extruded as a strand, cooled in an inert gas atmosphere until it becomes rigid, and is then granulated. The disadvantage of this process is that the resulting thermoplastic polyurethane elastomers have Shore A harnesses of up to 95 and are not suitable for manufacturing sheets, fine sections, or hoses. Often such sheets tend to block and stick to such an extent that further processing is impossible. Although the polyurethane sheets have very good mechanical properties, they have not yet been widely used.
issue The preparation of injection-molded parts from thermoplastic polyurethane elastomers in the Shore A
hardness range from 80 to 85 and less is also very difficult due to the thermoplastic polyurethane elastomers' poor demoldability. The use of occlude release agents offers only a slight improvement.
Summary of the Invention The object of this invention was to develop thermoplastic polyurethane elastomers which do not possess the disadvantages known to the prior art and which can be processed into non-blocking and non-sticking polyurethane sheets or cagily remoldable injection molded parts.
This object was achieved employing a mixture of thermoplastic polyurethane elastomers comprising (A) from 50 parts to OWE parts by weight of a thermoplastic polyurethane elastomers with a urethane group content of from 10 to 50 percent by weight and a melt index of from 0.1 to 100 at 190C, and (B) from 0.5 part to 50 parts by weight of a thermoplastic polyurethane elastomers with a urethane group content of from 20 Jo 60 percent by weight and a melt index of from 10 to 1000 at l90~C, ~L23~3~
wherein the urethane group content of thermoplastic polyp urethane elastomers (B) must always be at least 10 percent by weight larger than that of PA), and the melt index of thermoplastic polyurethane elastomers (B) must be greater than or equal to that of (A) at the same melt temperature.
The urethane group content is that proportion, by weight, of the polyurethane elastomers which consists of urethane groups, o (NH-C-O).
The melt viscosities of thermoplastic polyurethane elastomers and their hardness increase with increasing urethane group content, while the melt index is reduced.
Previously, therefore, thermoplastic polyurethane elastomers with different urethane group contents could only be mixed together in the melt when the thermoplastic polyurethane elastomers having a higher urethane group content predomi-noted. Rigid thermoplastic polyurethane elastomers could, by this process, be modified with a lesser amount of flexible thermoplastic polyurethane elastomers.
However, it was unexpectedly found that flexible thermoplastic polyurethane elastomers can be advantageously modified with rigid thermoplastic polyurethane elastomers if the melt viscosity of the more rigid thermoplastic polyp urethane elastomers is equal to or less than that of the more eye flexible thermoplastic polyurethane elastomers base material at the same melt temperature or if the melt index of the more rigid thermoplastic polyurethane elastomers it greater than or equal to that of the more flexible thermoplastic polyurethane elastomers base material at the same melt temperature.
The thermoplastic polyurethane elastomers in accordance with the invention have Shore A harnesses from 65 to 96 and a melt index of from 0.5 to 200 at 190C and are suitable for the preparation of sheets using the blow-molding and sheet extrusion processes. The resulting sheets do not block and have a dry feel. The products can also be processed into molded parts with the aid of injection molding technology, whereby even complex molded parts can be easily remolded.
Desertion of the Preferred Embodiments Thermoplastic polyurethane elastomers PA) and thermoplastic polyurethane elastomers (B) used in accordance with the invention can be prepared by reacting at elevated temperatures, and in the presence of suitable catalysts, and in some cases auxiliaries or additives:
(a) organic diisocyanates, (b) polyhydroxyl compounds with molecular weights from S00 to 8000, and ~36~3~
(c) chain extenders with molecular weights from 60 to 400.
The following discussion applies to starting material (a) through (c) and the catalyst, auxiliaries and additives useful in the practice of this invention:
(a) Representative organic diisocyanates are aliphatic, cycloaliphatic, and, preferably, aromatic dozes-notes. Typical are: aliphatic diisocyanates such as hexamethylene diisocyanate cycloaliphatic dozes-notes such as isophorone diisocyanate, 1,4-cyclohexane diisocyanate, l-methyl-2,4- and 2,6-cyclohexane diisocyanate, as well as the corresponding isomer mixtures, 4,4'-, 2,4'- and 2,2'-dicyclohexylme~hane diisocyanate as well a the corresponding isomer mixtures, and, preferably, aromatic diisocyanates such as Tulane diisocyanate, mixtures of 2,4- and 2,6-Tulane diisocyanate, 4,4'-, 2,4'- and 2,2'-diphenyl-methane diisocyanate, mixtures of 2,4'- and 4,4'-diphenylmethane diisocyanate, urethane-modified liquid 4,4'- and/or 2,4'-diphenylmethane diisocyanates, 4,4,!_ diisocyanato-1,2-diphenylethane, mixtures of 4,4'-, 2,4'- and 2,2' diisocyanato-1,2-diphenylethane, more advantageously those with a 4,4'-diisocyanato-1,2-I
diphenylethane content of at least 95 percent by weight, and 1,5-naphthylene diisocyanate. Preferably, hexamethylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate isomer mixtures with a 4,4'-diphenylmethane diisocyanate content of greater than 96 percent by weight and, in particular, 4,4'-diphenylmethane diisocyanate and l,5-naphthalene diisocyanate are used.
(b) Polyether polyols, and preferably polyester polyols, with molecular weights from 500 to 8000, are suitable for use as the higher molecular weight polyhydroxyl compounds. However, other polymers containing hydroxyl groups can also be used, for example, polyacetals such as polyoxymethylene and, in particular, water-insolùble msthylals, e.g., polybutanediol methylol and polyp hexanediol methylol, and polycarbonates, in particular those prepared by means of the transesterification of diphenylcarbonate and hexane-1,6-diol. The pull-droxyl compounds must be predominately linear, and may be used individually or in the form of mixtures.
Suitable polyether polyols can be prepared by reacting one or several alkaline oxides having from 2 to 4 carbon atoms in the alkaline residue with an initiator molecule which contains two active hydrogen atoms.
3~3 Representative alkaline oxides ace: ethylene oxide, propylene oxide, epichlorohydrin and 1,2- and 2,3-battalion oxide. The use of ethylene oxide and mixtures of 1,2-propylene oxide and ethylene oxide it pro-furred. The alkaline oxides can be used individually, alternately, or as mixture. The following initiators are commonly used: water amino alcohols such as N-alkyldiethanolamines, for example, N-methyldiethanol-amine' and dills such as ethylene glycol, 1,3-propylene glycol, 1,4-butanediol and 1,6-hexanediol. In some cases, mixture of starter molecules can also be used. Hydroxyl group-containing polymerization products of tetrahydrofuran are also suitable polyether polyols for the practice of this invention.
Preferably used are hydroxyl group-containing polyp tetrahydrofuran and/or polyether polyols of 1,2-propylene oxide and ethylene oxide in which more than 50 percent, preferably from 60 to 80 percent, of the OH groups are primary hydroxyl groups and in which at least part of the ethylene oxide is arranged as a terminal block.
These polyether polyols can be obtained, for example, by first polymerizing the 1,2-propylene oxide onto the I
initiator and then the ethylene oxide, or first copolymerizing the entire 1,2-propylene oxide in a mixture with part of the ethylene oxide onto the initiator, followed by polymerizing the remaining ethylene oxide, or gradually polymerizing a first portion of the ethylene oxide onto the initiator, followed by all the l,2-propylene oxide and finally adding the remaining portion of the ethylene oxide.
The polyether polyols previously described have molecular weights from 500 to 8000, preferably 600 to 6000, and more preferably 800 to 3500. They can be used individually or as mixtures.
Suitable polyester polyols can be prepared, for example, from dicarboxylic acids with from 2 to 12 carbon atoms and polyfunctional alcohols. Represent--live dicarboxylic acids are: aliphatic dicarboxylic acids such as succinic acid, glutaric acid, adipic acid, octanedioic acid, azelaic acid, and sebacic acid and aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, and terephthalic acid. The car-boxlike acids can be used singly or as mixtures, e.g., in the form of a succinic, glutaric, and adipic acid mixture. It is sometimes desirable in preparing the I
polyester polyol3 to use the corresponding carboxylic acid derivatives in place of the carboxylic acid.
Typical derivatives are carboxylic acid esters having from 1 to 4 carbon atoms in the alcohol residue, carboxylic acid androids, or carboxylic acid Shelley-rides. Examples of polyfunctional alcohols are:
glycols having from 2 to 10, preferably 2 to 6, carbon atoms such a ethylene glycol, diethylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,10-lo decanediol, 2,2-dimethyl-1,3-propanediol, 1,3-propane-dill, and dipropylene glycol. Depending on the desired characteristics, the polyfunctional alcohol can be used individually or as mixtures.
Esters of the carboxylic acid with the cited dills are also suitable, in particular those having from 4 to 6 carbon atoms, such as 1,4-butanediol and/or 1,6-hexanediol, condensation products of ~-hydroxycar-boxlike acids, for example, ~-hydroxycaproic acid and preferably polymerization products of lactose for example, in some cases, substituted ~-caprolactones.
Among the polyester polyols preferably used are:
poly(ethyleneadipate), poly(l,4-butyleneadipate), poly~co(ethylene-1,4-butylene)adipate), poly(co(hexa-~3623~
methylene-neopentylene)adipate), poly(co(hexamethylene-1,4-butylene)adipate~) and polycaprolactones.
The polyester polyols have molecular weights from 500 to 6000, preferably from 800 to 3500.
(c) Representative chain extender with molecular weights from 60 to 400, preferably 60 to 300, are generally aliphatic dills having 2 to 12 carbon atoms, preferably with 2, 4 or 6 carbon atoms, such as ethylene glycol, 1,6-hexanediol, diethylene glycol, dipropylene glycol and, in particular, 1,4-butanediol. However, also suitable are divesters of terephthalic acid with glycols having 2 to 4 carbon atoms such as terephthalic acid bis-ethylene glycol or l,~-butanediol and hydroxy-alkaline ethers of hydroquinone such as Boyce-hydroxyethyl)hydroquinone.
Suitable catalysts which in particular accelerate the reaction between the isocyanate groups in the dozes-notes (a) and the hydroxyl groups in starting materials (b) and I are conventional tertiary amine known in the prior art such as triethylamine, dimethylcyclohexylamine, N-methylmorpholine, N,N'-dimethyl piperazine, diazabicyclo-t2.2.2Joctane, and, in particular, organo-metallic compounds such as alkyltitanates, iron compounds, tin compounds, ego, tin diacetate, tin dictate, tin dilaurate or the tin dialkyl salts of aliphatic carboxylic acid, such as dibutyl tin diacetate, dibutyl tin dilaurate, etc. The catalysts are generally used in amount from 0.001 to 0.1 parts per weight based on 100 parts by weight polyhydroxyl compound.
In addition to catalysts, auxiliaries or additive can also be incorporated in the starting materials. Typical examples are lubricant, inhibitors, combustion retardants, stains, pigments, inorganic and/or organic fillers, reinform cuing material, and stabilizers against hydrolysis, light, heat, or discoloring.
Further information concerning the auxiliaries or additives referred to above can be found in the technical literature, for example, the monograph by J. I. Saunders and K. C. Fresh, High Polymers, vol. XVI, Polyurethane, pp. 1 and 2, Intrusions Publishers, 1962/64, or in DE OX
29 01 774.
In order to prepare the thermoplastic polyurethane elastomers, starting materials (a), (b) and (c) are reacted in the presence of catalysts and, in some cases, auxiliaries or additives, in such amount that the equivalent ratio of isocyanate groups in the diisocyanates relative to the sum of the hydroxyl groups in components (b) and (c) is from 1:0.85 to 1:1.20, preferably from 1:0.95 to 1:1.05, more preferably approximately 1:1.02.
I
To adjust the hardness and molt index, starting materials (b) and (c) can be used in relatively broad molar ratios, whereby the hardness and melt viscosity increase as the chain extender content (c) increase, while the melt index decreases In order to prepare the flexible thermoplastic polyurethane elastomers (A) which can be used in accordance with the invention and which has a urethane group content from 10 to 50 percent by weight, preferably from 15 to 40 percent by weight, a Shore A hardness of approximately 60 to 95, preferably from 70 to 90, and a melt index of from 0.1 to 100 at l90~C, preferably from 1 to 40, molar ratios of polyhydroxyl compounds (b) relative to chain extenders (c) of from 1:0.85 to 1:1.20, preferably from 1:0.95 to 1:1.05, are used The flexible thermoplastic polyurethane eras-tower A can be prepared in the sheet or extrude method by the continual mixture of starting materials, allowing the reaction mixture to completely react on a conveyor belt or in the extrude at temperatures from 60C to 250C and then granulating the resulting thermoplastic polyurethane elastomers.
The rigid By thermoplastic polyurethane elicit-mews utilizable in accordance with the invention and having a urethane group content of from 20 to 60 percent by weigh, preferably from 25 to 50 percent by weight, a Shore A
harridan of approximately 70 to 98, preferably from 80 to 95, and a melt index of from 10 to 1000 at 190C, preferably from 30 to 300, are prepared from the polyhydroxyl compounds (b) and the chain extenders I in molar ratios of from 1:0.85 to 1:1.20, preferably from 1:0.95 to 1:1.05 using the continuous sheet method. To do this, the starting materials, containing, in some cases, auxiliaries or additives, are continually mixed together at temperatures above the melting point of starting materials pa) through (c) with the help of a mixing head. The reaction mixture is applied onto a carrier, preferably a conveyor belt, and is then directed through a temperature-controlled zone of from 1 to 20 m length, preferably from 3 to 10 m, at a speed of from 1 to 20 m/min., preferably from 4 to 10 m/min. The reaction temperature in the temperature-controlled zone is from 60 to 200C, preferably 100 to 180C. Depending on the isn't percentage in the reaction mixture, the reaction is controlled either by cooling or heating so that up to 90 mole percent, preferably up to 80 mole percent, diisocyanate is reacted and the reaction mixture solidifies at the desired reaction temperature. Based on the free pulses-ante content of the rigidified product, which can be from 10 to 50 mole percent, preferably from 15 to 30 mole percent, rigid B thermoplastic polyurethane elastomers with very low melt viscosities, correspondingly high melt indices, are obtained To prepare the easily remoldable, non blocking thermoplastic polyurethane elastomers, from 50 lo 99.5 parts by weight, preferably from 70 to 35 parts by weight, of the (A) thermoplastic polyurethane, and from 0.5 part to 50 part by weight, preferably from 5 to 30 parts by weight, of the By thermoplastic polyurethane elastomers, are melted together in the practice of the invention, at temperatures of from 140 to SKYE, preferably from 190 to 220C, in conventional equipment used for the thermoplastic processing of plastics, e.g., kneaders and, preferably, extrudes, and are then granulated, whereby auxiliaries and/or additives can also be incorporated in the melt during this process step. The following examples illustrate the applicants' invention without limiting its practice in any way.
I
Exam l Eighty part by weight of a thermoplastic polyp urethane elastomers (A) prepared from 1,4-butanediol polyp adipate having a molecular weight of 2000, 1,4-butanediol as the chain extender and 4,4'-diisocyanatodiphenylmethane, with a urethane group-content of 30 percent by weight and a melt index of 2 in accordance with DIN ~3,735 at 190C with a loading weight of 21 kg, was mixed together by means of a single-shaft extrude at 190C with 20 parts by weight of a thermoplastic polyurethane elastomers (B) consisting of the same components as in (A) but with a urethane group content of 40.3 percent by weight and a melt index of 24 at 190C, said mixing taking place in the melt at a temperature of 205C, and was then processed into a granulate.
A blown sheet was then prepared from the granulate using the conventional method. The sheet did not block and exhibited a dry feel.
Comparison Examples A and B
When a similar procedure was used as in Example 1, but with thermoplastic polyurethane elastomers having a melt index of 0.1 in place of the type (B) thermoplastic polyp urethane elastomers with a melt index of 24, the comparison thermoplastic polyurethane elastomers could not be melted into the PA) thermoplastic polyurethane elastomers I
A sheet prepared using the blow process solely from the (A) thermoplastic polyurethane elastomers in accordance with Example 1 stuck together so badly that it could no longer be pulled off the supply roll.
Example 2 Ninety parts by weight of a thermoplastic polyp urethane ela~tomer (A) with a urethane group content of 35 percent by weight, a Shore A hardness of 83, and a melt index of 1.5 at 190 with a loading weight of 21.6 kg were melted together with 10 parts by weight of a thermoplastic polyurethane elastomers (B) having a urethane group content of 45 percent by weight, a Shore A hardness of 95, and a melt index under the above conditions of 120. Said melting together took place in an extrude at 200C. The mixture was injection molded in the conventional way on an injection molding machine to form molded parts, whereby said molded parts could readily be remolded after 20 Seconds.
By addition of an increased amount of the (B) thermoplastic polyurethane elastomers the hardness of the resulting end product was slightly increased to Shore A 85. The mechanical properties remain unchanged within the accuracy limits of the measuring methods.
Comparison Exam~e_C and D
Molded parts prepared from a thermoplastic polyurethane elas~omer (A) in accordance with Example 2 required two minutes before they could be remolded.
When a thermoplastic polyurethane elastomers with a Shore A hardness of 85 was prepared and processed into molded parts without the addition of a type (B) thermoplastic polyurethane elastomers the same poor de-molding characteristic resulted.
Example 3 Seventy parts by weight of a type (A) thermos plastic polyurethane elastomers with a urethane group content of 22 percent by weight, a Shore A hardness of 65, and a melt index of 31 at 190C with a loading weight of 21.6 kg were melted together with 30 parts by weight of a type (B) thermoplastic polyurethane elastomers with a urethane group content of 35 percent by weight, a Shore A hardness of 85, and a melt index under the above conditions of 36, in an extrude at 200C. A blown sheet was prepared from the resulting thermoplastic polyurethane elastomers which, at a sheet thickness of 100 em, had an elongation of 550 percent and a tensile strength of 70 N/mm~.
It was not possible to prepare a blown sheet from the pure (A) thermoplastic polyurethane elastomers
Preferably used are hydroxyl group-containing polyp tetrahydrofuran and/or polyether polyols of 1,2-propylene oxide and ethylene oxide in which more than 50 percent, preferably from 60 to 80 percent, of the OH groups are primary hydroxyl groups and in which at least part of the ethylene oxide is arranged as a terminal block.
These polyether polyols can be obtained, for example, by first polymerizing the 1,2-propylene oxide onto the I
initiator and then the ethylene oxide, or first copolymerizing the entire 1,2-propylene oxide in a mixture with part of the ethylene oxide onto the initiator, followed by polymerizing the remaining ethylene oxide, or gradually polymerizing a first portion of the ethylene oxide onto the initiator, followed by all the l,2-propylene oxide and finally adding the remaining portion of the ethylene oxide.
The polyether polyols previously described have molecular weights from 500 to 8000, preferably 600 to 6000, and more preferably 800 to 3500. They can be used individually or as mixtures.
Suitable polyester polyols can be prepared, for example, from dicarboxylic acids with from 2 to 12 carbon atoms and polyfunctional alcohols. Represent--live dicarboxylic acids are: aliphatic dicarboxylic acids such as succinic acid, glutaric acid, adipic acid, octanedioic acid, azelaic acid, and sebacic acid and aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, and terephthalic acid. The car-boxlike acids can be used singly or as mixtures, e.g., in the form of a succinic, glutaric, and adipic acid mixture. It is sometimes desirable in preparing the I
polyester polyol3 to use the corresponding carboxylic acid derivatives in place of the carboxylic acid.
Typical derivatives are carboxylic acid esters having from 1 to 4 carbon atoms in the alcohol residue, carboxylic acid androids, or carboxylic acid Shelley-rides. Examples of polyfunctional alcohols are:
glycols having from 2 to 10, preferably 2 to 6, carbon atoms such a ethylene glycol, diethylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,10-lo decanediol, 2,2-dimethyl-1,3-propanediol, 1,3-propane-dill, and dipropylene glycol. Depending on the desired characteristics, the polyfunctional alcohol can be used individually or as mixtures.
Esters of the carboxylic acid with the cited dills are also suitable, in particular those having from 4 to 6 carbon atoms, such as 1,4-butanediol and/or 1,6-hexanediol, condensation products of ~-hydroxycar-boxlike acids, for example, ~-hydroxycaproic acid and preferably polymerization products of lactose for example, in some cases, substituted ~-caprolactones.
Among the polyester polyols preferably used are:
poly(ethyleneadipate), poly(l,4-butyleneadipate), poly~co(ethylene-1,4-butylene)adipate), poly(co(hexa-~3623~
methylene-neopentylene)adipate), poly(co(hexamethylene-1,4-butylene)adipate~) and polycaprolactones.
The polyester polyols have molecular weights from 500 to 6000, preferably from 800 to 3500.
(c) Representative chain extender with molecular weights from 60 to 400, preferably 60 to 300, are generally aliphatic dills having 2 to 12 carbon atoms, preferably with 2, 4 or 6 carbon atoms, such as ethylene glycol, 1,6-hexanediol, diethylene glycol, dipropylene glycol and, in particular, 1,4-butanediol. However, also suitable are divesters of terephthalic acid with glycols having 2 to 4 carbon atoms such as terephthalic acid bis-ethylene glycol or l,~-butanediol and hydroxy-alkaline ethers of hydroquinone such as Boyce-hydroxyethyl)hydroquinone.
Suitable catalysts which in particular accelerate the reaction between the isocyanate groups in the dozes-notes (a) and the hydroxyl groups in starting materials (b) and I are conventional tertiary amine known in the prior art such as triethylamine, dimethylcyclohexylamine, N-methylmorpholine, N,N'-dimethyl piperazine, diazabicyclo-t2.2.2Joctane, and, in particular, organo-metallic compounds such as alkyltitanates, iron compounds, tin compounds, ego, tin diacetate, tin dictate, tin dilaurate or the tin dialkyl salts of aliphatic carboxylic acid, such as dibutyl tin diacetate, dibutyl tin dilaurate, etc. The catalysts are generally used in amount from 0.001 to 0.1 parts per weight based on 100 parts by weight polyhydroxyl compound.
In addition to catalysts, auxiliaries or additive can also be incorporated in the starting materials. Typical examples are lubricant, inhibitors, combustion retardants, stains, pigments, inorganic and/or organic fillers, reinform cuing material, and stabilizers against hydrolysis, light, heat, or discoloring.
Further information concerning the auxiliaries or additives referred to above can be found in the technical literature, for example, the monograph by J. I. Saunders and K. C. Fresh, High Polymers, vol. XVI, Polyurethane, pp. 1 and 2, Intrusions Publishers, 1962/64, or in DE OX
29 01 774.
In order to prepare the thermoplastic polyurethane elastomers, starting materials (a), (b) and (c) are reacted in the presence of catalysts and, in some cases, auxiliaries or additives, in such amount that the equivalent ratio of isocyanate groups in the diisocyanates relative to the sum of the hydroxyl groups in components (b) and (c) is from 1:0.85 to 1:1.20, preferably from 1:0.95 to 1:1.05, more preferably approximately 1:1.02.
I
To adjust the hardness and molt index, starting materials (b) and (c) can be used in relatively broad molar ratios, whereby the hardness and melt viscosity increase as the chain extender content (c) increase, while the melt index decreases In order to prepare the flexible thermoplastic polyurethane elastomers (A) which can be used in accordance with the invention and which has a urethane group content from 10 to 50 percent by weight, preferably from 15 to 40 percent by weight, a Shore A hardness of approximately 60 to 95, preferably from 70 to 90, and a melt index of from 0.1 to 100 at l90~C, preferably from 1 to 40, molar ratios of polyhydroxyl compounds (b) relative to chain extenders (c) of from 1:0.85 to 1:1.20, preferably from 1:0.95 to 1:1.05, are used The flexible thermoplastic polyurethane eras-tower A can be prepared in the sheet or extrude method by the continual mixture of starting materials, allowing the reaction mixture to completely react on a conveyor belt or in the extrude at temperatures from 60C to 250C and then granulating the resulting thermoplastic polyurethane elastomers.
The rigid By thermoplastic polyurethane elicit-mews utilizable in accordance with the invention and having a urethane group content of from 20 to 60 percent by weigh, preferably from 25 to 50 percent by weight, a Shore A
harridan of approximately 70 to 98, preferably from 80 to 95, and a melt index of from 10 to 1000 at 190C, preferably from 30 to 300, are prepared from the polyhydroxyl compounds (b) and the chain extenders I in molar ratios of from 1:0.85 to 1:1.20, preferably from 1:0.95 to 1:1.05 using the continuous sheet method. To do this, the starting materials, containing, in some cases, auxiliaries or additives, are continually mixed together at temperatures above the melting point of starting materials pa) through (c) with the help of a mixing head. The reaction mixture is applied onto a carrier, preferably a conveyor belt, and is then directed through a temperature-controlled zone of from 1 to 20 m length, preferably from 3 to 10 m, at a speed of from 1 to 20 m/min., preferably from 4 to 10 m/min. The reaction temperature in the temperature-controlled zone is from 60 to 200C, preferably 100 to 180C. Depending on the isn't percentage in the reaction mixture, the reaction is controlled either by cooling or heating so that up to 90 mole percent, preferably up to 80 mole percent, diisocyanate is reacted and the reaction mixture solidifies at the desired reaction temperature. Based on the free pulses-ante content of the rigidified product, which can be from 10 to 50 mole percent, preferably from 15 to 30 mole percent, rigid B thermoplastic polyurethane elastomers with very low melt viscosities, correspondingly high melt indices, are obtained To prepare the easily remoldable, non blocking thermoplastic polyurethane elastomers, from 50 lo 99.5 parts by weight, preferably from 70 to 35 parts by weight, of the (A) thermoplastic polyurethane, and from 0.5 part to 50 part by weight, preferably from 5 to 30 parts by weight, of the By thermoplastic polyurethane elastomers, are melted together in the practice of the invention, at temperatures of from 140 to SKYE, preferably from 190 to 220C, in conventional equipment used for the thermoplastic processing of plastics, e.g., kneaders and, preferably, extrudes, and are then granulated, whereby auxiliaries and/or additives can also be incorporated in the melt during this process step. The following examples illustrate the applicants' invention without limiting its practice in any way.
I
Exam l Eighty part by weight of a thermoplastic polyp urethane elastomers (A) prepared from 1,4-butanediol polyp adipate having a molecular weight of 2000, 1,4-butanediol as the chain extender and 4,4'-diisocyanatodiphenylmethane, with a urethane group-content of 30 percent by weight and a melt index of 2 in accordance with DIN ~3,735 at 190C with a loading weight of 21 kg, was mixed together by means of a single-shaft extrude at 190C with 20 parts by weight of a thermoplastic polyurethane elastomers (B) consisting of the same components as in (A) but with a urethane group content of 40.3 percent by weight and a melt index of 24 at 190C, said mixing taking place in the melt at a temperature of 205C, and was then processed into a granulate.
A blown sheet was then prepared from the granulate using the conventional method. The sheet did not block and exhibited a dry feel.
Comparison Examples A and B
When a similar procedure was used as in Example 1, but with thermoplastic polyurethane elastomers having a melt index of 0.1 in place of the type (B) thermoplastic polyp urethane elastomers with a melt index of 24, the comparison thermoplastic polyurethane elastomers could not be melted into the PA) thermoplastic polyurethane elastomers I
A sheet prepared using the blow process solely from the (A) thermoplastic polyurethane elastomers in accordance with Example 1 stuck together so badly that it could no longer be pulled off the supply roll.
Example 2 Ninety parts by weight of a thermoplastic polyp urethane ela~tomer (A) with a urethane group content of 35 percent by weight, a Shore A hardness of 83, and a melt index of 1.5 at 190 with a loading weight of 21.6 kg were melted together with 10 parts by weight of a thermoplastic polyurethane elastomers (B) having a urethane group content of 45 percent by weight, a Shore A hardness of 95, and a melt index under the above conditions of 120. Said melting together took place in an extrude at 200C. The mixture was injection molded in the conventional way on an injection molding machine to form molded parts, whereby said molded parts could readily be remolded after 20 Seconds.
By addition of an increased amount of the (B) thermoplastic polyurethane elastomers the hardness of the resulting end product was slightly increased to Shore A 85. The mechanical properties remain unchanged within the accuracy limits of the measuring methods.
Comparison Exam~e_C and D
Molded parts prepared from a thermoplastic polyurethane elas~omer (A) in accordance with Example 2 required two minutes before they could be remolded.
When a thermoplastic polyurethane elastomers with a Shore A hardness of 85 was prepared and processed into molded parts without the addition of a type (B) thermoplastic polyurethane elastomers the same poor de-molding characteristic resulted.
Example 3 Seventy parts by weight of a type (A) thermos plastic polyurethane elastomers with a urethane group content of 22 percent by weight, a Shore A hardness of 65, and a melt index of 31 at 190C with a loading weight of 21.6 kg were melted together with 30 parts by weight of a type (B) thermoplastic polyurethane elastomers with a urethane group content of 35 percent by weight, a Shore A hardness of 85, and a melt index under the above conditions of 36, in an extrude at 200C. A blown sheet was prepared from the resulting thermoplastic polyurethane elastomers which, at a sheet thickness of 100 em, had an elongation of 550 percent and a tensile strength of 70 N/mm~.
It was not possible to prepare a blown sheet from the pure (A) thermoplastic polyurethane elastomers
Claims (18)
1. An easily demolded and non-blocking thermo-plastic polyurethane elastomer composition obtained by melting:
(A) 50 parts to 99.5 parts by weight of a thermoplastic polyurethane elastomer containing 10 to 50 percent by weight of urethane groups and having a melt index of from 0.1 to 100 at 190°C, with (B) 0.5 part to 50 parts by weight of a thermoplastic polyurethane elastomer containing 20 to 60 percent by weight urethane groups and having a melt index of from 10 to 1000 at 190°C, wherein the urethane group content of polyurethane elas-tomer (B) is always at least 10 percent by weight greater than that of (A) and the melting index of the polyurethane elastomer (B) at the melt temperature is greater than or equal to that of (A).
(A) 50 parts to 99.5 parts by weight of a thermoplastic polyurethane elastomer containing 10 to 50 percent by weight of urethane groups and having a melt index of from 0.1 to 100 at 190°C, with (B) 0.5 part to 50 parts by weight of a thermoplastic polyurethane elastomer containing 20 to 60 percent by weight urethane groups and having a melt index of from 10 to 1000 at 190°C, wherein the urethane group content of polyurethane elas-tomer (B) is always at least 10 percent by weight greater than that of (A) and the melting index of the polyurethane elastomer (B) at the melt temperature is greater than or equal to that of (A).
2. The composition as recited in claim 1, wherein (A) and (B) are produced by reacting, in the presence of a suitable catalyst, (a) an aromatic diisocyanate, (b) a predominately linear polyhydroxyl compound, and (c) 1,4-butanediol.
3. The composition as recited in claim 2 wherein the aromatic diisocyanate is 4,4'-diphenylmethane diisocya-nate.
4. The composition as recited in claim 2 wherein the predominately linear polyhydroxyl compound is selected from the group consisting of:
(1) 500 molecular weight to 6000 molecular weight polyalkylene glycol polyadipates with 2 to 6 carbon atoms in the alkylene residue, and (2) 500 molecular weight to 8000 molecular weight polytetrahydrofuran.
(1) 500 molecular weight to 6000 molecular weight polyalkylene glycol polyadipates with 2 to 6 carbon atoms in the alkylene residue, and (2) 500 molecular weight to 8000 molecular weight polytetrahydrofuran.
5. The composition as recited in claim 1 wherein the thermoplastic polyurethane elastomer (A) has a Shore A
hardness of 60 to 95 and thermoplastic polyurethane elas-tomer (B) has a Shore A hardness of 70 to 98, with the hardness of (B) being greater than that of (A).
hardness of 60 to 95 and thermoplastic polyurethane elas-tomer (B) has a Shore A hardness of 70 to 98, with the hardness of (B) being greater than that of (A).
6. The composition as recited in claim 2 wherein the thermoplastic polyurethane elastomer (A) has a Shore A
hardness of 60 to 95 and thermoplastic polyurethane elas-tomer (B) has a Shore A hardness of 70 to 98, with the hardness of (B) being greater than that of (A).
hardness of 60 to 95 and thermoplastic polyurethane elas-tomer (B) has a Shore A hardness of 70 to 98, with the hardness of (B) being greater than that of (A).
7. The composition as recited in claim 1, wherein the thermoplastic polyurethane elastomer (B) contains 10 to 50 mole-percent free polyisocyanate based on the organic polyisocyanate.
8. The composition as recited in claim 2, wherein the thermoplastic polyurethane elastomer (B) contains 10 to 50 mole-percent free polyisocyanate based on the organic polyisocyanate.
9. The composition as recited in claim 1, wherein the thermoplastic polyurethane elastomer (B) is produced in accordance with a continuous sheet process.
10. The composition as recited in claim 2, wherein the thermoplastic polyurethane elastomer (B) is produced in accordance with a continuous sheet process.
11. The composition as recited in claim 1, wherein an additive or auxiliary is added before melting (A) with (B).
12. A thermoplastic polyurethane elastomer molding obtained by selecting as the thermoplastic polyurethane elastomer, the composition as recited in claim 1.
13. A thermoplastic polyurethane elastomer molding obtained by selecting as the thermoplastic polyurethane elastomer, the composition as recited in claim 2.
14. A thermoplastic polyurethane elastomer molding obtained by selecting as the thermoplastic polyurethane elastomer, the composition as recited in claim 3.
15. The thermoplastic polyurethane elastomer molding as recited in claim 12 wherein the molding is in the form of a sheet of film.
16. The thermoplastic polyurethane elastomer molding as recited in claim 12 wherein the molding is an injection molded thermoplastic polyurethane elastomer part.
17. A thermoplastic polyurethane composition as recited in claim 1, further comprising selecting a melting temperature from about 140°C to about 250°C.
18. A thermoplastic polyurethane composition as recited in claim 17 wherein the composition is granulated.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19823241666 DE3241666A1 (en) | 1982-11-11 | 1982-11-11 | Easily demoldable and non-blocking, thermoplastic polyurethane elastomers, process for their production and use |
| DEP3241666.0 | 1982-11-11 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1236239A true CA1236239A (en) | 1988-05-03 |
Family
ID=6177827
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000440937A Expired CA1236239A (en) | 1982-11-11 | 1983-11-10 | Easily demoldable and non-blocking thermoplastic polyurethane elastomers, process for their preparation and use |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0111682B1 (en) |
| AT (1) | ATE32344T1 (en) |
| CA (1) | CA1236239A (en) |
| DE (2) | DE3241666A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6218479B1 (en) | 1999-02-25 | 2001-04-17 | Bayer Aktiengesellschaft | Nonrigid, thermoplastic moulding compositions |
| US6527995B1 (en) | 1999-07-15 | 2003-03-04 | Bayer Aktiengesellschaft | Process for preparing soft, elastic polyurethane |
| CN107163552A (en) * | 2017-06-30 | 2017-09-15 | 宁波格林美孚新材料科技有限公司 | A kind of method that secondary granulation strengthens TPUE |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3903537A1 (en) * | 1989-02-07 | 1990-08-09 | Basf Ag | REFRIGERANT IMPACT TOE, FLOWABLE, THERMOPLASTIC POLYURETHANE ELASTOMER COMPOSITIONS, METHOD FOR THEIR PRODUCTION AND THEIR USE |
| DE4442380A1 (en) * | 1994-11-29 | 1996-05-30 | Wolff Walsrode Ag | Waterproof and breathable fabrics made from resin mixtures of thermoplastic polyurethanes |
| DE102013018101A1 (en) * | 2013-10-23 | 2015-04-23 | Kraiburg Tpe Gmbh & Co. Kg | Thermoplastic elastomer compositions with silicone oil resistance |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1480472A (en) * | 1975-03-14 | 1977-07-20 | Kuraray Co | Sheet material |
| GB2021603A (en) * | 1978-05-24 | 1979-12-05 | Ici Ltd | Thermoplastic polyurethane compositions |
| JPS58164637A (en) * | 1982-03-26 | 1983-09-29 | Dainippon Ink & Chem Inc | Thermoplastic polyurethane elastomer composition |
-
1982
- 1982-11-11 DE DE19823241666 patent/DE3241666A1/en not_active Withdrawn
-
1983
- 1983-10-24 AT AT83110595T patent/ATE32344T1/en not_active IP Right Cessation
- 1983-10-24 EP EP83110595A patent/EP0111682B1/en not_active Expired
- 1983-10-24 DE DE8383110595T patent/DE3375578D1/en not_active Expired
- 1983-11-10 CA CA000440937A patent/CA1236239A/en not_active Expired
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6218479B1 (en) | 1999-02-25 | 2001-04-17 | Bayer Aktiengesellschaft | Nonrigid, thermoplastic moulding compositions |
| US6527995B1 (en) | 1999-07-15 | 2003-03-04 | Bayer Aktiengesellschaft | Process for preparing soft, elastic polyurethane |
| CN107163552A (en) * | 2017-06-30 | 2017-09-15 | 宁波格林美孚新材料科技有限公司 | A kind of method that secondary granulation strengthens TPUE |
Also Published As
| Publication number | Publication date |
|---|---|
| DE3241666A1 (en) | 1984-05-17 |
| DE3375578D1 (en) | 1988-03-10 |
| EP0111682B1 (en) | 1988-02-03 |
| EP0111682A3 (en) | 1985-05-08 |
| EP0111682A2 (en) | 1984-06-27 |
| ATE32344T1 (en) | 1988-02-15 |
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