CA1257946A - Flexible elastomeric thermoplastic polyurethanes, process for their preparation and their use - Google Patents
Flexible elastomeric thermoplastic polyurethanes, process for their preparation and their useInfo
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- CA1257946A CA1257946A CA000456913A CA456913A CA1257946A CA 1257946 A CA1257946 A CA 1257946A CA 000456913 A CA000456913 A CA 000456913A CA 456913 A CA456913 A CA 456913A CA 1257946 A CA1257946 A CA 1257946A
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- polyurethane
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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
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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
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
- C08K5/523—Esters of phosphoric acids, e.g. of H3PO4 with hydroxyaryl compounds
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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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- 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
- C08L75/06—Polyurethanes from polyesters
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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
FLEXIBLE ELASTOMERIC THERMOPLASTIC POLYURETHANES, PROCESS FOR THEIR PREPARATION AND THEIR USE
Abstract of the Disclosure Soft, flexible elastic, thermoplastic poly-urethanes contain as plasticizers phthalic acid bis(methoxy-ethyl ester), tricresyl phosphate, diphenylcresyl phosphate, and polyester polyurethanes having molecular weights from 4000 to 10,000 based on 1,4'-butanediol adipate and 4,4'-diphenylmethane diisocyanate, generally in amounts from 1 to 50 weight percent. The plasticizers can be incorporated into the starting components used for preparing the poly-urethane, into the reactable polyurethane mixture during preparation, or, preferably, into the resulting thermo plastic polyurethanes.
The products are suitable for preparing sheets and molded parts, for example, pipes/tubing and profiles, and preferably for sealing profiles.
Abstract of the Disclosure Soft, flexible elastic, thermoplastic poly-urethanes contain as plasticizers phthalic acid bis(methoxy-ethyl ester), tricresyl phosphate, diphenylcresyl phosphate, and polyester polyurethanes having molecular weights from 4000 to 10,000 based on 1,4'-butanediol adipate and 4,4'-diphenylmethane diisocyanate, generally in amounts from 1 to 50 weight percent. The plasticizers can be incorporated into the starting components used for preparing the poly-urethane, into the reactable polyurethane mixture during preparation, or, preferably, into the resulting thermo plastic polyurethanes.
The products are suitable for preparing sheets and molded parts, for example, pipes/tubing and profiles, and preferably for sealing profiles.
Description
571~34~j Case 1432 FLEXIBLE EhASTOMERIC THERMOPLASTIC POLYURETHANES, PROCESS ~OR THEIR PREP~RATION AND TH~IR USE
Back~round of the Invention 1. Field of the Invention The subject invention relate~ to 80f t, flexible thermoplastic polyurethane~. More particularly, the invention relate~ to the preparal:ion of such polyurethanes by the incorporation o~ selected plasticizers which enhance rather than degrade the physical properties of the thermo-plastic polyurethanes.
Back~round of the Invention 1. Field of the Invention The subject invention relate~ to 80f t, flexible thermoplastic polyurethane~. More particularly, the invention relate~ to the preparal:ion of such polyurethanes by the incorporation o~ selected plasticizers which enhance rather than degrade the physical properties of the thermo-plastic polyurethanes.
2. Description of the Prior _rt Thermoplastic polyurethane elastomers have been known for a long time. Their commercial utility iB based on the combination of desirable physical properties coupled with the advantage~ of economic thermopla3tic processing. A
wide range of physical properties can be achieved by using different starting materials. An overview of thermoplastic polyurethane, its properties, and its applications is given, for example, in Kunststoffe 68 (1978), pp. 819-825, or in Kautschuk, Gummir Kunststoffe 35 (1982), pp. 568-584.
Thermoplastic polyurethanes can be produced by both continuous aq well as batch processes. The most well known of these processes, the sheet process and the extru-sion process, are used on a commercial scale.
, In British Patent 1,057,018, for example, a polymer i prepared from a predominately linear difunctional ~,~
i7~34~
polyol and excess organic dii~ocyanate, fed into a mixing head through a metering pump, and mixed therein with a specified amount of a low-molecular-weight diol. The resulting reaction mixture is fed onto a conveyor belt and passed through an oven heated to from 70 to 130C until it solidlfies. The reaction product is then granulated, tempered at temperatures up to 120C for Erom 6 to 40 hour~, followlng which it can be processed into molded parts on, for example, an injection molding machine.
In the extrusion process, which is described, for example, in German Patent 20 59 570 (U. S. Patent
wide range of physical properties can be achieved by using different starting materials. An overview of thermoplastic polyurethane, its properties, and its applications is given, for example, in Kunststoffe 68 (1978), pp. 819-825, or in Kautschuk, Gummir Kunststoffe 35 (1982), pp. 568-584.
Thermoplastic polyurethanes can be produced by both continuous aq well as batch processes. The most well known of these processes, the sheet process and the extru-sion process, are used on a commercial scale.
, In British Patent 1,057,018, for example, a polymer i prepared from a predominately linear difunctional ~,~
i7~34~
polyol and excess organic dii~ocyanate, fed into a mixing head through a metering pump, and mixed therein with a specified amount of a low-molecular-weight diol. The resulting reaction mixture is fed onto a conveyor belt and passed through an oven heated to from 70 to 130C until it solidlfies. The reaction product is then granulated, tempered at temperatures up to 120C for Erom 6 to 40 hour~, followlng which it can be processed into molded parts on, for example, an injection molding machine.
In the extrusion process, which is described, for example, in German Patent 20 59 570 (U. S. Patent
3,642,964), the starting components are fed directly into the extruder and the reaction i8 performed in the extruder under the specified processing conditions. The polyurethane ela~tomer which is formed i5 extruded as a strand, cooled in an inert gas atmosphere until it solidifies, and is then granulated. The disadvantage of this procedure is that the resulting thermoplastic polyurethane is not suitable for producing films, fine sections and tubing or hose. Thermo-plastic polyurethanes of identical composition are krans-parent when made by the extrusion process, but have an opaque appearance when they are made by the continuous sheet ; process. Opaque thermoplastic polyurethanes can be pro-cessed into films which are not subject to blocking, while tran~parent thermoplastic polyurethanes are not suitable for this purpose.
, ~
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In thermoplastic polyurethanes formed from linear difunctional polyols/ aromatic diLisocyanates, and diols, the hardness is regulated by the so-called rigid segments, which primarily are comprised of diisocyanate-diol segments. By properly selecting the molar proE?ortions of the starting components, thermoplastic polyurethanes having hardnesses from Shore A 80 to Shore D 74 can be produced without difficulty. Thermoplastic polyurethanes having a Shore A
hardness less than 80 can theoretically be produced in this way, however, a disadvantage i9 that such products are difficult to handle during production, since it is extremely - difficult to get them to harden to a solid form.
Thermoplastic polyurethanes in the lower hardness range exhibit flexible elastic properties~ However, in comparison with other elastic plastics, recovery is very weak and permanent set after extension is too high.
Polyurethane elastomers can also be modified by additives. In order to improve their resistance to hydrol-ysisl ortho-substituted diarylcarbodiimides may be used in amounts up to 2 weight percent. Polyurethane elastomers with low coefficients of friction may be obtained by adding suitable lubricants, for example graphite or molybdenum disulfide. In additionl large amounts of various types o fillers can be incorporated in the polyurethane elastomers in a manner similar to that encountered in rubber tech-nology.
~5~
Plasticizers are only used infrequently to produce polyurethane elastomers, since these plasticizers become insoluble in the hard phase and since very few plasticizers are even compatible with polyurethane elastomers. Rollable polyurethane elastomers generally take up the plasticizers slowly and then only in limited amounts. As an additional constraint, the plasticizer must not produce any chemical side effects. For example, it has not been advisable to use phosphoric acid esters, since the traces of acid contained in them often adversely effect the resistance of the final product to aging. The addition of a plasticizer is often undesirahle since one of the desirable properties of the polyurethane elastomers themselves is that they do not contain extractable components and, therefore, do not change their composition or dimensions while in continuous contact with lubricants or solvents. An additional drawback is that the plasticizers may tend to favor, more than retard, potential hardening. Nevertheless, in some special cases phthalic acid esters, dibenzyl ethers, and liquid butadiene-acrylonitrile heteropolymers have been recommended as plasticizers, but always in relatively small amounts and usually only to provide, for example, better fabricating abilities tKunststoff-Handbuch, vol. VII, Polyurethane, by R. Vieweg and A. Hochtlen, (Munich: Carl Hanser Verlag, 1966), pp. 206 ff., especially pp. 254-55).
57~
The effect of isodecylpelargonate in amounts ranging from 0 to 20 weight percent on tensile strength and elongation on apparently non-crystallizing polyurethane elastomers based on polyoxypropylene glycols, 2,4-toluene dii~ocyanate, dipropylene glycol, and trimethylolpropane has been studied. See, for example, T. L. Smith and A. B.
Magnusson, Journal of Appl. Polymer Science, 5, (1961):
218-32.
Summary of the Invention The object of the subject invention i5 to prepare flexible, elastic thermoplastic polyurethanes having Shore A
hardnesses less than 80, which do not exhibit the previously discussed disadvantages. In addition, the compression set and residual elongation is improved in such thermoplastic polyurethanes. The thermoplastic polyurethanes obtained may also be processed into sheets or molded parts using known methods without sticking or becoming difficult to handle.
This objective was surprisingly met through the addition of selected plasticizers in amounts of up to 50 weight percent to conventional thermoplastic polyurethanes. Suitable plasticizers according to the process of the subject invention are phthalic acid bistmethoxyethyl ester), tricresylphosphate, diphenylcresylphosphate, and polyester polyurethanes having molecular weights from 4000 to lO,Q00, prepared from 1,4-butanediol adipate and 4,4,'-diphenyl-methane diisocyanate, and mixtures thereof.
~ 5 ~
By adding the selected plasticizers u~ed in accordance with the invention, tlhe hardness of conventional thermoplastic polyurethanes having Shore A hardnesses of 80 to 95, can be reduced to 60 to 80, while at the same time the flexible elastic properties are improved compared to non-modified thermopla~tic polyurethanes. In addition, compression set, permanent elongation, and rate o~ recovery are improved.
Description of the Preferred Embodiment~
The flexible elastic thermoplastic polyurethanes of the subject invention, having a Shore A hardness of 80 or less, preferably from 80 to 60, are produced from thermo-pla~tic polyurethanes having a Shore A hardnes~ of from 95 to 80, preferably from 85 to 80, a rigid segment primary melt peak of ~rom 210 to 220C, pre~erably from 212 to 218C, as measured by means of differential calorlmetry (DSC), an MFI (melt flow index) at 190C of from 0.1 to 200 preferably from Q.5 to 50 with a load weiyht corresponding to 21.6 kp. The thermoplastic polyurethanes are preferably prepared using the continuous sheat method. Such thermo-plastic polyurethanes can be prepared, for example, by reacting diisocyanates, predominately linear essentially difunctional polyols, chain extendars, catalysts, and optionally, auxiliaries or additives.
~57''34~à
Aliphatic, cycloaliphatic, and, preerably, aromatic diisocyanates may be used as the organic diisocya-nates. Typical examples are: aLiphatic diisocyanates such as hexamethylene diisocyanate; cycloaliphatic diisocyanates such as i~ophorone diisocyanate, 1,4-cyclohexane diisocya-nate, l-methyl-2 t 4- and 1-methyl-2,6-cyclohexane diisocya-nates as well a~ corresponding isomer mixtures, 4,4'-, 2,4'~, and 2,2'~dicyclohexylmethane diisocyanates as well as the corresponding isomer mixtures; and preferably, aromatic diisocyanates such as 2,4-toluene diisocyanate, mixtures of 2,4- and 2,6-toluene diisocyanate, 4,4'-, 2,4'-, and 2,2'-diphenylmethane diisocyanate, mixtures of 2,4'- and 4,4'-diphenylmethane diisocyanate, urethane-modified liquid 4,4'-and 2,4'-diphenylmethane diisocyanates, 4,4'-diisocyanato-1,2-diphenylethane, and 1,5-naphthalene diisocyanate.
Preferably, hexamethylene diisocyanate, isophorone diisocya-nate, and diphenylmethane diisocyanate isomer mixtures having a 4,4'-diphenylmethane diisocyanate content greater than 96 weight percent are used. Especially preferred are
, ~
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In thermoplastic polyurethanes formed from linear difunctional polyols/ aromatic diLisocyanates, and diols, the hardness is regulated by the so-called rigid segments, which primarily are comprised of diisocyanate-diol segments. By properly selecting the molar proE?ortions of the starting components, thermoplastic polyurethanes having hardnesses from Shore A 80 to Shore D 74 can be produced without difficulty. Thermoplastic polyurethanes having a Shore A
hardness less than 80 can theoretically be produced in this way, however, a disadvantage i9 that such products are difficult to handle during production, since it is extremely - difficult to get them to harden to a solid form.
Thermoplastic polyurethanes in the lower hardness range exhibit flexible elastic properties~ However, in comparison with other elastic plastics, recovery is very weak and permanent set after extension is too high.
Polyurethane elastomers can also be modified by additives. In order to improve their resistance to hydrol-ysisl ortho-substituted diarylcarbodiimides may be used in amounts up to 2 weight percent. Polyurethane elastomers with low coefficients of friction may be obtained by adding suitable lubricants, for example graphite or molybdenum disulfide. In additionl large amounts of various types o fillers can be incorporated in the polyurethane elastomers in a manner similar to that encountered in rubber tech-nology.
~5~
Plasticizers are only used infrequently to produce polyurethane elastomers, since these plasticizers become insoluble in the hard phase and since very few plasticizers are even compatible with polyurethane elastomers. Rollable polyurethane elastomers generally take up the plasticizers slowly and then only in limited amounts. As an additional constraint, the plasticizer must not produce any chemical side effects. For example, it has not been advisable to use phosphoric acid esters, since the traces of acid contained in them often adversely effect the resistance of the final product to aging. The addition of a plasticizer is often undesirahle since one of the desirable properties of the polyurethane elastomers themselves is that they do not contain extractable components and, therefore, do not change their composition or dimensions while in continuous contact with lubricants or solvents. An additional drawback is that the plasticizers may tend to favor, more than retard, potential hardening. Nevertheless, in some special cases phthalic acid esters, dibenzyl ethers, and liquid butadiene-acrylonitrile heteropolymers have been recommended as plasticizers, but always in relatively small amounts and usually only to provide, for example, better fabricating abilities tKunststoff-Handbuch, vol. VII, Polyurethane, by R. Vieweg and A. Hochtlen, (Munich: Carl Hanser Verlag, 1966), pp. 206 ff., especially pp. 254-55).
57~
The effect of isodecylpelargonate in amounts ranging from 0 to 20 weight percent on tensile strength and elongation on apparently non-crystallizing polyurethane elastomers based on polyoxypropylene glycols, 2,4-toluene dii~ocyanate, dipropylene glycol, and trimethylolpropane has been studied. See, for example, T. L. Smith and A. B.
Magnusson, Journal of Appl. Polymer Science, 5, (1961):
218-32.
Summary of the Invention The object of the subject invention i5 to prepare flexible, elastic thermoplastic polyurethanes having Shore A
hardnesses less than 80, which do not exhibit the previously discussed disadvantages. In addition, the compression set and residual elongation is improved in such thermoplastic polyurethanes. The thermoplastic polyurethanes obtained may also be processed into sheets or molded parts using known methods without sticking or becoming difficult to handle.
This objective was surprisingly met through the addition of selected plasticizers in amounts of up to 50 weight percent to conventional thermoplastic polyurethanes. Suitable plasticizers according to the process of the subject invention are phthalic acid bistmethoxyethyl ester), tricresylphosphate, diphenylcresylphosphate, and polyester polyurethanes having molecular weights from 4000 to lO,Q00, prepared from 1,4-butanediol adipate and 4,4,'-diphenyl-methane diisocyanate, and mixtures thereof.
~ 5 ~
By adding the selected plasticizers u~ed in accordance with the invention, tlhe hardness of conventional thermoplastic polyurethanes having Shore A hardnesses of 80 to 95, can be reduced to 60 to 80, while at the same time the flexible elastic properties are improved compared to non-modified thermopla~tic polyurethanes. In addition, compression set, permanent elongation, and rate o~ recovery are improved.
Description of the Preferred Embodiment~
The flexible elastic thermoplastic polyurethanes of the subject invention, having a Shore A hardness of 80 or less, preferably from 80 to 60, are produced from thermo-pla~tic polyurethanes having a Shore A hardnes~ of from 95 to 80, preferably from 85 to 80, a rigid segment primary melt peak of ~rom 210 to 220C, pre~erably from 212 to 218C, as measured by means of differential calorlmetry (DSC), an MFI (melt flow index) at 190C of from 0.1 to 200 preferably from Q.5 to 50 with a load weiyht corresponding to 21.6 kp. The thermoplastic polyurethanes are preferably prepared using the continuous sheat method. Such thermo-plastic polyurethanes can be prepared, for example, by reacting diisocyanates, predominately linear essentially difunctional polyols, chain extendars, catalysts, and optionally, auxiliaries or additives.
~57''34~à
Aliphatic, cycloaliphatic, and, preerably, aromatic diisocyanates may be used as the organic diisocya-nates. Typical examples are: aLiphatic diisocyanates such as hexamethylene diisocyanate; cycloaliphatic diisocyanates such as i~ophorone diisocyanate, 1,4-cyclohexane diisocya-nate, l-methyl-2 t 4- and 1-methyl-2,6-cyclohexane diisocya-nates as well a~ corresponding isomer mixtures, 4,4'-, 2,4'~, and 2,2'~dicyclohexylmethane diisocyanates as well as the corresponding isomer mixtures; and preferably, aromatic diisocyanates such as 2,4-toluene diisocyanate, mixtures of 2,4- and 2,6-toluene diisocyanate, 4,4'-, 2,4'-, and 2,2'-diphenylmethane diisocyanate, mixtures of 2,4'- and 4,4'-diphenylmethane diisocyanate, urethane-modified liquid 4,4'-and 2,4'-diphenylmethane diisocyanates, 4,4'-diisocyanato-1,2-diphenylethane, and 1,5-naphthalene diisocyanate.
Preferably, hexamethylene diisocyanate, isophorone diisocya-nate, and diphenylmethane diisocyanate isomer mixtures having a 4,4'-diphenylmethane diisocyanate content greater than 96 weight percent are used. Especially preferred are
4,4'-diphenylmethane diisocyanate and 1,5-naphthalene diisocyanate.
Polyether polyols and, in particular, polyester polyols are preferred as the higher molecular weight, predominately linear, essentially difunctional polyols.
Suitable molecular weights range from 500 to 8000. However, ~5~3~6 other hydroxyl-group-containing polymers, for example polyacetals such as polyoxymethylenes and especially water insoluble orMal~ such as polybutanediol formal and poly-hexanediol formal; and polycarbonates, in particular those prepared through transesterifica!tion of 1,6-hexanediol with diphenyl carbonate having the above molecular weights may al~o be used. The polyols should be predominately linear, in other words, they should have an essentially difunctional structure relative to the diisocyanate reaction. The polyols cited can be utilized as individual components or in the form of mixtures.
Suitable polye~her polyols can be prepared by reacting one or more alkylene oxide~ having from 2 to 4 carbon atoms in the alkylene radical with an initiator molecule containing two active hydrogen atoms. Typical alkylene oxides are: ethylene oxide, 1,2-propylene oxide, epichlorohydrin, and 1,2- and 2,3-butylene oxide. Ethylene oxide and mixtures of l,2-propylene oxide and ethylene oxide are preferably utilized. The alkylene oxides can be utilized individually, alternating one after another, or as mixtures~ Typical initator molecules are: water; amino alcohols such as N-alkyldiethanolamines, for example, N-methyldiethanolamine; and diols such as ethylene glycol, 1,3-propylene glycol, 1,4 butanediol, and 1,6-hexane diol.
When appropriate, mixtures of initiators can also be utilized. Suitable polyether po]yols also include hydroxyl-group-containing polymerization products of tetrahydrofuran.
Preferably used are hyclroxyl group-containing polytetrahydrofuran, and co-polyether polyols of 1,2-propylene oxide and ethylene oxicle in which more than 50 percent of the hydroxyl sroups are primary hydroxyl groups~
preferably from 60 to 80 percent, and in which at least part of the ethylene oxide is a block in terminal position.
Such co-polyether polyols can be obtained~ for example, by first polymerizing 1,2-propylene oxide onto the initiator followed by polymerization of the ethylene oxide;
or first copolymerizing the 1,2-propylene oxide in A mixture with part of the ethylene oxide followed by polymerization of the remainder of the ethylene oxide; or a step-by-step sequence can be followed in which part of the ethylene oxide is polymerized onto the initiator, then all the 1,2-propylene oxide, and finally the remainder of the ethylene oxide.
The predominately linear polyether polyols have molecular weights from 500 to 8000, preferably from 600 to 6000, and most preferably from 800 to 3500. They can be used individually or together with each other as mixtures.
Suitable polyester polyols can be prepared, for example, by reacting dicarboxylic acids having from 2 to 12 carbon atoms, preferably from 4 to 6 carbon atoms, with _ 9 _ ~ 3~
diols. Typical dicarboxylic acicls are: aliphatic dicar-boxylic acids such as succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid r and sebacic acid, and aromatic dicarboxylic acids such as phthalic acid, iso-phthalic acid, and terephthalic acid. The carboxylic acids can be utilized individually or in the form of mixtures, for example, a mixture of succinic, glutaric, and adipic acid.
In order to prepare the polyester polyols, it may sometimes be advantageous to utilize the corresponding carboxylic acid derivatives instead of the carboxylic acids themselves.
Examples of such derivatives are carboxylic acid esters havin~ from 1 to 4 carbon atoms in the alcohol radical, carboxylic acid anhydrides, or carboxylic acid chlorides.
Typical examples of diols are glycols having from 2 to 10 carbon atoms, preferably from 2 to 6 carbon atoms, such as ethylene glycol, diethylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, l,10-decanediol, 2,2-dimethyl-propane-1,3-diol, 1,3-propanediol, and dipropylene glycol Depending on the desired characteristics, the diols can be used individually or as mixtures.
Also suitable are esters of the carbonic acids with the diols cited, in particular those having from 4 to 6 carbon atoms, such as 1,4-butanediol and 1,6-hexanediol, condensation products of ~-hydroxycarbonic acids, for example, ~-hydroxycaproic acid, and preferably polymeriza tion products of lactone~, for e~ample substituted ~-caprolactones.
Pre~erably used polyester polyols are: ethanediol polyadipates, 1,4-butanediol polyadipate~, ethanediol 1l4-butanediol polyadipate~, 1,6-hexanediol neopentylglycol polyadipates, 1,6-hexanediol 1,4-butanediol polyadipates, and polycaprolactones.
Suitable polyester polyols have molecular weights ranging from 500 to 6000, preferably from 1000 to ~000.
Preferable chain extenders having molecular weights from 60 to 400, preferably Erom 600 to 300, are aliphatic diols having from 2 to 12 carbon atoms, preferably 2, 4, or 6 carbon atoms, such as ethanediol, 1,6-hexanediol, diethylene glycol, dipropylene glycol, and, more preferably, 1,4-butane diol. However, die~ters of the terephthalic acid with glycols having from 2 ot 4 carbon atoms are also suitable, for example, terephthalic acid bis-ethylene glycol or bis(l,4-butanediol~, hydroxyalkylene ethers of hydro-quinone such as 1,4-bis(2-hydroxyethyl)hydroquinone;
cycloaliphatic diamines, such as isophoronediamine, ethylenediamine, 1,2-, 1,3-propylenediamine, N-methyl-1,3-propylenediamine, N,N'-dimethylethylenediamine; and aromatic diamines such as 2,4- and 2,6-toluenediamine, 3,5-diethyl-2,4 and -2,6-toluenediamine, and primary ortho-, di-, tri-, and tetraalkyl-substituted 4,4'-diaminodiphenylmethanes.
~57~:346 In order to adjust the hardnes~ and melting point of the thermoplastic polyurethanes, the amounts of difunc-tional polyol and chain extender can be varied acro~s relatively wide molar ranges. Molar ratios of the di~unc tional polyol to chain extender oE 1:1 to 1:12, preferably from 1:1.8 to 1:4.4, have proven successful, the hardness and melting point of the thermoplastic polyurethanes increasing with increasing chain extender content.
In order to produce the thermoplastic polyure-thanes, starting component diisocyanates, difunctionalpolyols and chain extenders ara reacted in the presence of catalysts, and in some cases, auxiliaries or additives in such amounts that the equivalent ratio of isocyanate groups in the diisocyanate to the sum of the hydroxyl groups or the hydroxyl and amino groups in the polyol and chain extender is from 1:0.85 to 1:1.20~ preferably from 1:0.95 ~o 1:1.05 and, most preferably approximately 1.1.02.
Suitable catalysts for accelerating the reaction between the isocyanate groups in the diisocyanates and the hydroxyl and amino groups of the difunctional polyols and chain extenders are conventional tertiary amines known in the prior art, such as triethylamine, dimethylcyclohexyl-amine, N-methylmorpholine, N,NI-dimethylpiperazine, 2-(dimethylaminoethoxy)ethanol, diazabicyclo-[2.2O2]-octane;
and in particular, organometallic compounds such as esters J~.t~7~3'~i of titanic acid, iron compounds, tin compounds, for example tin diacetate, tin dioctoate, tin dilaurate, or the tin dialkyl salts of aliphatic carboxylic acids such a~ dibutyl tin diacetate, dibutyl tin dilaurater etc. The catalysts are typically u~ed in amounts from 0.001 to 0.1 parti per 100 parts polyhydroxyl compound.
In addition to the catalysts, the starting components can also include auxiliaries or additives.
Typical, are lubricants; inhibitors; stabilizers against hydrolysis, light, heat, or discoloration; flame retardants;
dyes; pigments; inorganic and organic fillers, reinforcing agents, and plastici~ers.
Further details on the above auxiliaries and additives are found in the technical literature, for example the monograph by J. H. Saunders and K. C. Frisch, High Polymers, vol. XVI, Polyurethane, pts. 1 and 2, Verlag Interscience Publishers, 1962/1964, or German Patent 29 01 774.
The preparation of the thermoplastic polyurethanes by the continuous sheet process is performed as follows:
Diisocyanates, difunctional polyols, chain extenders, cataysts, and in some cases additives or aux-iliaries are continuously mixed with the aid of a mixing head at temperatures above the melting points of the various ~ 13 -9L~i monomers. The reaction mixture i5 fed onto a carrier, preferably a conveyor belt, and directed through a tempera-ture-controlled zone. The react;ion temperature in the temperature-controlled zone is from 60 to 200C, preferably from 100 to 180C, and the residence time i8 from 0.05 to 0.5 hour, preferably from 0.1 to 0.25 hour.
After completion of the reaction, the thermo-plastic polyurethane, which can be u~ed in accordance with the invention is allowed to cool, diced or granulated, stored, or used directly with the plasticizers used in accordance with the invention.
As already described, bis(methoxyethyl ester) of phthalic acid, tricresylphosphate, diphenylcresylphosphate or polyester polyurethanes based on l,4-butanediol adipate and 4,4'-diphenylmethane diisocyanate having a molecular weight of from 4000 to 10,000, preferably from 6000 to 8000 are used as the plasticizers. The plasticiæers used in accordance with the invention can be utilized individually or in the form of mixtures.
Suitable polyester polyurethane plasticizers are prepared, for example, through the reaction of l,4-butane-diol adipate having molecular weights from 600 to 3500, preferably approximately 2000, and 4,4'-diphenylmethane diisocyanate in the corresponding molar ratios in the presence of conventional catalysts.
~ ~ ~ 7 ~4~>
Plasticizers which are suitable for the invention are preferably liquid at 23C, and are incorporated into the thermoplastic polyurethanes in such amounts that the flexible elastic thermopla~tic polyurethane product has a Shore A hardnes~ of le~s than 80 and contains from 1 to 50 parts by weight, preferably Erom 3 to 40 parts by weight, and mo~t preferably from 10 to 40 part~ by weight o~ the plasticizer or plasticizer mixture selected in accordance with the invention; and from 99 to S0 parts by weight, preferably from 57 to 60 parts by weight, and most prefer-ably from 90 to 60 parts by weight thermoplastic poly-urethane. The preferably liquid plasticizers used in accordance with the invention can be incorporated into the thermoplastic polyurethane using various methods~ For example, the plasticizers can be mixed with the starting components before reaction, preferably into the difunctional polyol ~omponent, chain extender component, or both, so that the thermoplastic polyurethanes of the invention are prepared in the presence of the plasticizers. In another variation of the process, the plasticizers can be incorpor-ated with the partially reacted reaction mixture during the preparation of the polyurethane.
It has been found to be particularly effective, and therefore a preferred embodiment, to use processes in which the plasticizers usable in accordance with the ~ ~i7'(34~à
invention are incorporated into the fully reacted and, in some cases, granulated thermoplastic polyurethane. In thi~
way, the plasticizers can be incorporated by means of tumbling, for example in a horizontal mixer with simulta-neous heating of the granulated thermoplastic polyurethane, for example to approximately 50 to 60C. Preferably, the plasticizers are incorporated into the thermoplastic polyurethane via the melt at temperatures from 180 to 200C
with the aid of extruders, which may be equipped with special devices such as metering pumps.
The soft, flexible elastic thermoplastic polyure-thanes of the invention have hardnesses from Shore A 60 to 80 depending on the type and amount o plasticizer incor-porated, and have tensile strengths in accordance with DIN 53 504 of approximately 25 to 50 N/mm2~ Compression set and permanent elongation are noticably improved over the unmodified thermoplastic polyurethane. For example, while a thermoplastic polyurethane having a Shore A hardness of 85 has a permanent elongation without plasticizer of from 4 to 6 percent after being subjected to an elongation of 100 percent, after incorporating 20 weight percent tricresyl phosphate, the same thermoplastic polyurethane had a Shore A
hardness of 70 and a permanent elongation of from 1 to 2 percent. Based on a significantly higher recovery rate, molded parts produced from the thermoplastic polyurethane of ~.~5~94~;
the invention very quickly return to their original shape after a load on them is released.
The products are utilized for preparing sheets and molded parts, and preferably fine sections, tubing and hose. They are particularly suited for preparing ceiling profiles, for example those used for windows and door seals, and for lip seals.
Exampl~e_l Seventy-five parts by weight of a thermoplastic polyurethane prepared from a 1,4-butanediol adipate having a molecular weight of 2000 and 4,4L'-diphenylmethane diisoc~a-nate, having a hardness of Shore A 85, a MFI at 190C of 1.2 with a load weight of 21.6 kp, and a primary melt peak for the rigid segments of 214C, measured by means of differen-tial ~canning calorimetry, was mixed together for one hour with 25 parts by weight of phthalic acid bis(methoxyethyl ester) in a heated horizontal mixer at 60C and was then processed in a screw-type extruder.
The resulting thermoplastic polyurethane had a Shore A hardness of 72 and a MFI of 90 at 190C with a load weight of 21.6 kp. The tensile strength in accordance with DIN 53 504 was 34 N/mm2 and the permanent elongation after 100 percent elongation loading for 30 minutes was 1.8 percent, while the unmodified original thermoplastic polyurethane produced a permanent elongation of 4.5 percent under identical conditions.
Example 2 Eighty parts by weight of a thermoplastic poly-urethane based on 1,4-butanediol adipate and 4,4'-diphenyl-methane diisocyanate with the properties described in Example 1 was mixed with 20 parts by weight diphenylcresyl phosphate in a heated horizontal mixer at 50C for one J ~3 L/~ ~j hour. The completely tack-free granulate was processed into molded parts at 205C using an illjection molding machine.
The resulting molded parts had a Shore A hardness of 74 and a MFI of 43 at 190C with a load weight of 21.6 kp. The tensile ~trength in accordance with DIN 53 504 was 38 N/mm2. The compression Sl~t in accordance with DIN 53 517 at 70C was 35 percent, while a compression set of 45 percent was obtained for the thermoplastic polyure thane without the diphenylcresylphosphate.
Example 3 Eighty parts by weight of a thermoplastic polyure-thane having a Shore A hardness of 81 and a MFI of 6.0 at 190C with a load weight of 21L 6 kp, prepared from a polytetramethylene ether glycol having a molecular weight of 2000 and 4,~'-diphenylmethane diisocyanate, was mixed with 20 parts by weight tricresylphosphate at 50C for one hour in a horizontal mixer.
It wa~ possible to process the dry granu]ate directly using an injection molding machine or a screw extruder into sealing profiles. The molded part obtained thereby had a Shore A hardness of 70, a MFI of 82 at 190C
with a load weight of 21.6 kp, a tensile strength in accordance with DIN 53 504 of 30 N/mm2, and a permanent elongation after 100 percent elongation for 30 minutes of 1.3 percent, whlle the permanent elongation for the thermo-~s~
plastic polyurethane to which no tricresylphosphate had been added was 4.8 percent.
Example 4 Sixty parts by weight of a thermoplastic polyure-thane elastomer having the characteristic data descr~bed in Example 3 and based on polytetramethylene ether glycol and 4,4'-diphenylmethanediisocyanate was mixed together with 40 part~ by weight phthalic acid di(methoxyethyl ester) at 185C in a screw extruder and was processed into a granulate using the conventional method.
A molded part produced from the granulate had a Shore A hardness of 60, a tensile strength in accordance with DIN 53 504 of 28 N/mm2, and a compression set in accordance with DIN 53 517 of 40 percent at 70C, while the initial material had a compression set of 48 percent.
Comparison Examples When 80 parts by weight of the thermoplastic polyurethanes described in Examples 1-4 were treated in granulate form with 20 parts by weight phthalic acid dibutyl ester a typical phthalate ester plasticizer, at 60C for 24 hours in a horizontal mixer, the plasticizer was distributed across the surface of the granulate but was not incorporated in the thermoplastic polyurethane. The granulate remained we~. When the phthalic acid dibutyl ester was incorporated directly into the thermoplastic polyurethane melt in a - 2~ ~
7~4~;
screw-type extruder, dry granulate~ were first obtained, however the plasticizer begin to migrate out of these granulates after approximately 24 hours. The wet granulate~
could not be processed into molded parts~
Polyether polyols and, in particular, polyester polyols are preferred as the higher molecular weight, predominately linear, essentially difunctional polyols.
Suitable molecular weights range from 500 to 8000. However, ~5~3~6 other hydroxyl-group-containing polymers, for example polyacetals such as polyoxymethylenes and especially water insoluble orMal~ such as polybutanediol formal and poly-hexanediol formal; and polycarbonates, in particular those prepared through transesterifica!tion of 1,6-hexanediol with diphenyl carbonate having the above molecular weights may al~o be used. The polyols should be predominately linear, in other words, they should have an essentially difunctional structure relative to the diisocyanate reaction. The polyols cited can be utilized as individual components or in the form of mixtures.
Suitable polye~her polyols can be prepared by reacting one or more alkylene oxide~ having from 2 to 4 carbon atoms in the alkylene radical with an initiator molecule containing two active hydrogen atoms. Typical alkylene oxides are: ethylene oxide, 1,2-propylene oxide, epichlorohydrin, and 1,2- and 2,3-butylene oxide. Ethylene oxide and mixtures of l,2-propylene oxide and ethylene oxide are preferably utilized. The alkylene oxides can be utilized individually, alternating one after another, or as mixtures~ Typical initator molecules are: water; amino alcohols such as N-alkyldiethanolamines, for example, N-methyldiethanolamine; and diols such as ethylene glycol, 1,3-propylene glycol, 1,4 butanediol, and 1,6-hexane diol.
When appropriate, mixtures of initiators can also be utilized. Suitable polyether po]yols also include hydroxyl-group-containing polymerization products of tetrahydrofuran.
Preferably used are hyclroxyl group-containing polytetrahydrofuran, and co-polyether polyols of 1,2-propylene oxide and ethylene oxicle in which more than 50 percent of the hydroxyl sroups are primary hydroxyl groups~
preferably from 60 to 80 percent, and in which at least part of the ethylene oxide is a block in terminal position.
Such co-polyether polyols can be obtained~ for example, by first polymerizing 1,2-propylene oxide onto the initiator followed by polymerization of the ethylene oxide;
or first copolymerizing the 1,2-propylene oxide in A mixture with part of the ethylene oxide followed by polymerization of the remainder of the ethylene oxide; or a step-by-step sequence can be followed in which part of the ethylene oxide is polymerized onto the initiator, then all the 1,2-propylene oxide, and finally the remainder of the ethylene oxide.
The predominately linear polyether polyols have molecular weights from 500 to 8000, preferably from 600 to 6000, and most preferably from 800 to 3500. They can be used individually or together with each other as mixtures.
Suitable polyester polyols can be prepared, for example, by reacting dicarboxylic acids having from 2 to 12 carbon atoms, preferably from 4 to 6 carbon atoms, with _ 9 _ ~ 3~
diols. Typical dicarboxylic acicls are: aliphatic dicar-boxylic acids such as succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid r and sebacic acid, and aromatic dicarboxylic acids such as phthalic acid, iso-phthalic acid, and terephthalic acid. The carboxylic acids can be utilized individually or in the form of mixtures, for example, a mixture of succinic, glutaric, and adipic acid.
In order to prepare the polyester polyols, it may sometimes be advantageous to utilize the corresponding carboxylic acid derivatives instead of the carboxylic acids themselves.
Examples of such derivatives are carboxylic acid esters havin~ from 1 to 4 carbon atoms in the alcohol radical, carboxylic acid anhydrides, or carboxylic acid chlorides.
Typical examples of diols are glycols having from 2 to 10 carbon atoms, preferably from 2 to 6 carbon atoms, such as ethylene glycol, diethylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, l,10-decanediol, 2,2-dimethyl-propane-1,3-diol, 1,3-propanediol, and dipropylene glycol Depending on the desired characteristics, the diols can be used individually or as mixtures.
Also suitable are esters of the carbonic acids with the diols cited, in particular those having from 4 to 6 carbon atoms, such as 1,4-butanediol and 1,6-hexanediol, condensation products of ~-hydroxycarbonic acids, for example, ~-hydroxycaproic acid, and preferably polymeriza tion products of lactone~, for e~ample substituted ~-caprolactones.
Pre~erably used polyester polyols are: ethanediol polyadipates, 1,4-butanediol polyadipate~, ethanediol 1l4-butanediol polyadipate~, 1,6-hexanediol neopentylglycol polyadipates, 1,6-hexanediol 1,4-butanediol polyadipates, and polycaprolactones.
Suitable polyester polyols have molecular weights ranging from 500 to 6000, preferably from 1000 to ~000.
Preferable chain extenders having molecular weights from 60 to 400, preferably Erom 600 to 300, are aliphatic diols having from 2 to 12 carbon atoms, preferably 2, 4, or 6 carbon atoms, such as ethanediol, 1,6-hexanediol, diethylene glycol, dipropylene glycol, and, more preferably, 1,4-butane diol. However, die~ters of the terephthalic acid with glycols having from 2 ot 4 carbon atoms are also suitable, for example, terephthalic acid bis-ethylene glycol or bis(l,4-butanediol~, hydroxyalkylene ethers of hydro-quinone such as 1,4-bis(2-hydroxyethyl)hydroquinone;
cycloaliphatic diamines, such as isophoronediamine, ethylenediamine, 1,2-, 1,3-propylenediamine, N-methyl-1,3-propylenediamine, N,N'-dimethylethylenediamine; and aromatic diamines such as 2,4- and 2,6-toluenediamine, 3,5-diethyl-2,4 and -2,6-toluenediamine, and primary ortho-, di-, tri-, and tetraalkyl-substituted 4,4'-diaminodiphenylmethanes.
~57~:346 In order to adjust the hardnes~ and melting point of the thermoplastic polyurethanes, the amounts of difunc-tional polyol and chain extender can be varied acro~s relatively wide molar ranges. Molar ratios of the di~unc tional polyol to chain extender oE 1:1 to 1:12, preferably from 1:1.8 to 1:4.4, have proven successful, the hardness and melting point of the thermoplastic polyurethanes increasing with increasing chain extender content.
In order to produce the thermoplastic polyure-thanes, starting component diisocyanates, difunctionalpolyols and chain extenders ara reacted in the presence of catalysts, and in some cases, auxiliaries or additives in such amounts that the equivalent ratio of isocyanate groups in the diisocyanate to the sum of the hydroxyl groups or the hydroxyl and amino groups in the polyol and chain extender is from 1:0.85 to 1:1.20~ preferably from 1:0.95 ~o 1:1.05 and, most preferably approximately 1.1.02.
Suitable catalysts for accelerating the reaction between the isocyanate groups in the diisocyanates and the hydroxyl and amino groups of the difunctional polyols and chain extenders are conventional tertiary amines known in the prior art, such as triethylamine, dimethylcyclohexyl-amine, N-methylmorpholine, N,NI-dimethylpiperazine, 2-(dimethylaminoethoxy)ethanol, diazabicyclo-[2.2O2]-octane;
and in particular, organometallic compounds such as esters J~.t~7~3'~i of titanic acid, iron compounds, tin compounds, for example tin diacetate, tin dioctoate, tin dilaurate, or the tin dialkyl salts of aliphatic carboxylic acids such a~ dibutyl tin diacetate, dibutyl tin dilaurater etc. The catalysts are typically u~ed in amounts from 0.001 to 0.1 parti per 100 parts polyhydroxyl compound.
In addition to the catalysts, the starting components can also include auxiliaries or additives.
Typical, are lubricants; inhibitors; stabilizers against hydrolysis, light, heat, or discoloration; flame retardants;
dyes; pigments; inorganic and organic fillers, reinforcing agents, and plastici~ers.
Further details on the above auxiliaries and additives are found in the technical literature, for example the monograph by J. H. Saunders and K. C. Frisch, High Polymers, vol. XVI, Polyurethane, pts. 1 and 2, Verlag Interscience Publishers, 1962/1964, or German Patent 29 01 774.
The preparation of the thermoplastic polyurethanes by the continuous sheet process is performed as follows:
Diisocyanates, difunctional polyols, chain extenders, cataysts, and in some cases additives or aux-iliaries are continuously mixed with the aid of a mixing head at temperatures above the melting points of the various ~ 13 -9L~i monomers. The reaction mixture i5 fed onto a carrier, preferably a conveyor belt, and directed through a tempera-ture-controlled zone. The react;ion temperature in the temperature-controlled zone is from 60 to 200C, preferably from 100 to 180C, and the residence time i8 from 0.05 to 0.5 hour, preferably from 0.1 to 0.25 hour.
After completion of the reaction, the thermo-plastic polyurethane, which can be u~ed in accordance with the invention is allowed to cool, diced or granulated, stored, or used directly with the plasticizers used in accordance with the invention.
As already described, bis(methoxyethyl ester) of phthalic acid, tricresylphosphate, diphenylcresylphosphate or polyester polyurethanes based on l,4-butanediol adipate and 4,4'-diphenylmethane diisocyanate having a molecular weight of from 4000 to 10,000, preferably from 6000 to 8000 are used as the plasticizers. The plasticiæers used in accordance with the invention can be utilized individually or in the form of mixtures.
Suitable polyester polyurethane plasticizers are prepared, for example, through the reaction of l,4-butane-diol adipate having molecular weights from 600 to 3500, preferably approximately 2000, and 4,4'-diphenylmethane diisocyanate in the corresponding molar ratios in the presence of conventional catalysts.
~ ~ ~ 7 ~4~>
Plasticizers which are suitable for the invention are preferably liquid at 23C, and are incorporated into the thermoplastic polyurethanes in such amounts that the flexible elastic thermopla~tic polyurethane product has a Shore A hardnes~ of le~s than 80 and contains from 1 to 50 parts by weight, preferably Erom 3 to 40 parts by weight, and mo~t preferably from 10 to 40 part~ by weight o~ the plasticizer or plasticizer mixture selected in accordance with the invention; and from 99 to S0 parts by weight, preferably from 57 to 60 parts by weight, and most prefer-ably from 90 to 60 parts by weight thermoplastic poly-urethane. The preferably liquid plasticizers used in accordance with the invention can be incorporated into the thermoplastic polyurethane using various methods~ For example, the plasticizers can be mixed with the starting components before reaction, preferably into the difunctional polyol ~omponent, chain extender component, or both, so that the thermoplastic polyurethanes of the invention are prepared in the presence of the plasticizers. In another variation of the process, the plasticizers can be incorpor-ated with the partially reacted reaction mixture during the preparation of the polyurethane.
It has been found to be particularly effective, and therefore a preferred embodiment, to use processes in which the plasticizers usable in accordance with the ~ ~i7'(34~à
invention are incorporated into the fully reacted and, in some cases, granulated thermoplastic polyurethane. In thi~
way, the plasticizers can be incorporated by means of tumbling, for example in a horizontal mixer with simulta-neous heating of the granulated thermoplastic polyurethane, for example to approximately 50 to 60C. Preferably, the plasticizers are incorporated into the thermoplastic polyurethane via the melt at temperatures from 180 to 200C
with the aid of extruders, which may be equipped with special devices such as metering pumps.
The soft, flexible elastic thermoplastic polyure-thanes of the invention have hardnesses from Shore A 60 to 80 depending on the type and amount o plasticizer incor-porated, and have tensile strengths in accordance with DIN 53 504 of approximately 25 to 50 N/mm2~ Compression set and permanent elongation are noticably improved over the unmodified thermoplastic polyurethane. For example, while a thermoplastic polyurethane having a Shore A hardness of 85 has a permanent elongation without plasticizer of from 4 to 6 percent after being subjected to an elongation of 100 percent, after incorporating 20 weight percent tricresyl phosphate, the same thermoplastic polyurethane had a Shore A
hardness of 70 and a permanent elongation of from 1 to 2 percent. Based on a significantly higher recovery rate, molded parts produced from the thermoplastic polyurethane of ~.~5~94~;
the invention very quickly return to their original shape after a load on them is released.
The products are utilized for preparing sheets and molded parts, and preferably fine sections, tubing and hose. They are particularly suited for preparing ceiling profiles, for example those used for windows and door seals, and for lip seals.
Exampl~e_l Seventy-five parts by weight of a thermoplastic polyurethane prepared from a 1,4-butanediol adipate having a molecular weight of 2000 and 4,4L'-diphenylmethane diisoc~a-nate, having a hardness of Shore A 85, a MFI at 190C of 1.2 with a load weight of 21.6 kp, and a primary melt peak for the rigid segments of 214C, measured by means of differen-tial ~canning calorimetry, was mixed together for one hour with 25 parts by weight of phthalic acid bis(methoxyethyl ester) in a heated horizontal mixer at 60C and was then processed in a screw-type extruder.
The resulting thermoplastic polyurethane had a Shore A hardness of 72 and a MFI of 90 at 190C with a load weight of 21.6 kp. The tensile strength in accordance with DIN 53 504 was 34 N/mm2 and the permanent elongation after 100 percent elongation loading for 30 minutes was 1.8 percent, while the unmodified original thermoplastic polyurethane produced a permanent elongation of 4.5 percent under identical conditions.
Example 2 Eighty parts by weight of a thermoplastic poly-urethane based on 1,4-butanediol adipate and 4,4'-diphenyl-methane diisocyanate with the properties described in Example 1 was mixed with 20 parts by weight diphenylcresyl phosphate in a heated horizontal mixer at 50C for one J ~3 L/~ ~j hour. The completely tack-free granulate was processed into molded parts at 205C using an illjection molding machine.
The resulting molded parts had a Shore A hardness of 74 and a MFI of 43 at 190C with a load weight of 21.6 kp. The tensile ~trength in accordance with DIN 53 504 was 38 N/mm2. The compression Sl~t in accordance with DIN 53 517 at 70C was 35 percent, while a compression set of 45 percent was obtained for the thermoplastic polyure thane without the diphenylcresylphosphate.
Example 3 Eighty parts by weight of a thermoplastic polyure-thane having a Shore A hardness of 81 and a MFI of 6.0 at 190C with a load weight of 21L 6 kp, prepared from a polytetramethylene ether glycol having a molecular weight of 2000 and 4,~'-diphenylmethane diisocyanate, was mixed with 20 parts by weight tricresylphosphate at 50C for one hour in a horizontal mixer.
It wa~ possible to process the dry granu]ate directly using an injection molding machine or a screw extruder into sealing profiles. The molded part obtained thereby had a Shore A hardness of 70, a MFI of 82 at 190C
with a load weight of 21.6 kp, a tensile strength in accordance with DIN 53 504 of 30 N/mm2, and a permanent elongation after 100 percent elongation for 30 minutes of 1.3 percent, whlle the permanent elongation for the thermo-~s~
plastic polyurethane to which no tricresylphosphate had been added was 4.8 percent.
Example 4 Sixty parts by weight of a thermoplastic polyure-thane elastomer having the characteristic data descr~bed in Example 3 and based on polytetramethylene ether glycol and 4,4'-diphenylmethanediisocyanate was mixed together with 40 part~ by weight phthalic acid di(methoxyethyl ester) at 185C in a screw extruder and was processed into a granulate using the conventional method.
A molded part produced from the granulate had a Shore A hardness of 60, a tensile strength in accordance with DIN 53 504 of 28 N/mm2, and a compression set in accordance with DIN 53 517 of 40 percent at 70C, while the initial material had a compression set of 48 percent.
Comparison Examples When 80 parts by weight of the thermoplastic polyurethanes described in Examples 1-4 were treated in granulate form with 20 parts by weight phthalic acid dibutyl ester a typical phthalate ester plasticizer, at 60C for 24 hours in a horizontal mixer, the plasticizer was distributed across the surface of the granulate but was not incorporated in the thermoplastic polyurethane. The granulate remained we~. When the phthalic acid dibutyl ester was incorporated directly into the thermoplastic polyurethane melt in a - 2~ ~
7~4~;
screw-type extruder, dry granulate~ were first obtained, however the plasticizer begin to migrate out of these granulates after approximately 24 hours. The wet granulate~
could not be processed into molded parts~
Claims (10)
1. A flexible, elastomeric polyurethane having a shore A hardness lower than 80 and comprising:
A) a thermoplastic polyurethane prepared by reacting a diisocyanate, a predominately linear difunctional polyol, a chain extender in the presence of a urethane catalyst, and optionally additives or auxiliaries, and B) a plasticizer selected from the group consisting of (i) bis-(methoxyethyl)-phthalate, (ii) tricresylphosphate, (iii) diphenylcresylphosphate, (iv) poly-ester urethanes having molecular weights from 4000 to 10,000 prepared from 1,4-butanediol adipate/4,4'-diphenylmethane diisocyanate and (v) mixtures thereof.
A) a thermoplastic polyurethane prepared by reacting a diisocyanate, a predominately linear difunctional polyol, a chain extender in the presence of a urethane catalyst, and optionally additives or auxiliaries, and B) a plasticizer selected from the group consisting of (i) bis-(methoxyethyl)-phthalate, (ii) tricresylphosphate, (iii) diphenylcresylphosphate, (iv) poly-ester urethanes having molecular weights from 4000 to 10,000 prepared from 1,4-butanediol adipate/4,4'-diphenylmethane diisocyanate and (v) mixtures thereof.
2. The elastomeric polyurethane of claim 1 wherein said thermoplastic polyurethane is prepared using a continuous sheet process.
3. The elastomeric polyurethane of claim 1 wherein the amount of said plasticizer is from about 1 part to 50 parts by weight per 100 parts of elastomeric polyure-thane.
4. The elastomeric polyurethane of claim 1 wherein said difunctional polyol have a molecular weight of 500 to 8000, and wherein said chain extender has a molecular weight of from 60 to 400.
5. The elastomeric polyurethane of claim 1 wherein said thermoplastic polyurethane is characterized by: (a) a hardness of from Shore A 95 to Shore A 60, (b) a primary melt peak of the rigid segments as determined by DSC
of from 210° to 220°C, and (c) a melt viscosity corres-ponding to a melt flow index of from 0.1 to 200 at 190°C
with a load weight of 21.6 kp.
of from 210° to 220°C, and (c) a melt viscosity corres-ponding to a melt flow index of from 0.1 to 200 at 190°C
with a load weight of 21.6 kp.
6. The elastomeric polyurethane of claim 1 wherein said elastomeric polyurethane has a hardness of from Shore A 60 to Shore A 80.
7. The elastomeric polyurethane of claim 1 wherein said diisocyanate is selected from the group consisting of 4,4'-diphenylmethane diisocyanate and 1,5-naphthalene diisocyanate.
8. The elastomeric polyurethane of claim 1 wherein said difunctional polyol is selected from the group consisting of polycaprolactones, polytetramethylene ether glycols, and polyester polyols of adipic acid and 2 to 6 carbon diols.
9. The elastomeric polyurethane of claim 1 wherein said plasticizer is added to the unreacted diisocya-nate, difunctional polyol, chain extender and urethane catalyst mixture.
10. The elastomeric polyurethane of claim 1 wherein said plasticizer is incorporated into the previously reacted thermoplastic polyurethane.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP3323520.1 | 1983-06-30 | ||
| DE3323520A DE3323520A1 (en) | 1983-06-30 | 1983-06-30 | SOFT, RUBBER-ELASTIC, THERMOPLASTIC POLYURETHANES, METHOD FOR THE PRODUCTION AND USE THEREOF |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1257946A true CA1257946A (en) | 1989-07-25 |
Family
ID=6202743
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000456913A Expired CA1257946A (en) | 1983-06-30 | 1984-06-19 | Flexible elastomeric thermoplastic polyurethanes, process for their preparation and their use |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0134455B2 (en) |
| JP (1) | JPH075830B2 (en) |
| AT (1) | ATE33142T1 (en) |
| CA (1) | CA1257946A (en) |
| DE (2) | DE3323520A1 (en) |
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| MX2020013986A (en) * | 2018-06-28 | 2021-03-25 | Emerald Kalama Chemical Llc | Improved reactive polyurethane systems. |
| CN115703896A (en) * | 2021-08-11 | 2023-02-17 | 山东雷德新材料有限公司 | Thermoplastic polyurethane elastomer foam material and preparation method and application thereof |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3541274A (en) * | 1968-07-03 | 1970-11-17 | Du Pont | Polyester cine film splicing composition containing a polyesterurethane,a hydrogen - bonding solvent and an organic solvent |
| GB1584780A (en) * | 1977-12-07 | 1981-02-18 | Ici Ltd | Polyurethane compositions |
| JPS5483939A (en) * | 1977-12-19 | 1979-07-04 | Matsushita Electric Ind Co Ltd | Flame-retardant adhesive |
| GB2021603A (en) * | 1978-05-24 | 1979-12-05 | Ici Ltd | Thermoplastic polyurethane compositions |
| DD143370A3 (en) * | 1978-06-27 | 1980-08-20 | Ulrich Donnerstag | THERMOPLASTIC POLYURETHANE |
-
1983
- 1983-06-30 DE DE3323520A patent/DE3323520A1/en not_active Withdrawn
-
1984
- 1984-06-19 CA CA000456913A patent/CA1257946A/en not_active Expired
- 1984-06-28 EP EP84107461A patent/EP0134455B2/en not_active Expired - Lifetime
- 1984-06-28 AT AT84107461T patent/ATE33142T1/en not_active IP Right Cessation
- 1984-06-28 DE DE8484107461T patent/DE3470052D1/en not_active Expired
- 1984-06-29 JP JP59133424A patent/JPH075830B2/en not_active Expired - Lifetime
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5747588A (en) * | 1993-06-25 | 1998-05-05 | Refac International, Ltd. | Thermoplastic urethane elastometric alloys |
| 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 |
| US6790916B2 (en) | 2002-02-23 | 2004-09-14 | Bayer Aktiengesellschaft | Process for the preparation of soft, low-shrinkage, thermoplastic polyurethane elastomers which can be easily released from the mold |
| EP1757655A2 (en) | 2005-08-25 | 2007-02-28 | Lanxess Deutschland GmbH | Thermoplastic polyuréthanes |
| EP1932863A2 (en) | 2006-12-11 | 2008-06-18 | Bayer MaterialScience AG | Soft thermoplastic polyurethane elastomers and processes for their preparation and use |
| WO2020099540A1 (en) | 2018-11-15 | 2020-05-22 | Ingevity Uk Ltd. | Polyurethane or polyurethane-urea compositions with reduced cold hardening |
| WO2024030264A1 (en) | 2022-08-05 | 2024-02-08 | Ingevity Uk Ltd. | Bio-based polyols for high performance polyurethane applications |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0134455A1 (en) | 1985-03-20 |
| JPS6026056A (en) | 1985-02-08 |
| DE3470052D1 (en) | 1988-04-28 |
| ATE33142T1 (en) | 1988-04-15 |
| EP0134455B2 (en) | 1991-06-26 |
| DE3323520A1 (en) | 1985-01-10 |
| EP0134455B1 (en) | 1988-03-23 |
| JPH075830B2 (en) | 1995-01-25 |
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