EP1438345A1 - Pure or mixed grafted thermosetting thermoplastic polyurethane, and thermoset polyurethane obtained after crosslinking - Google Patents
Pure or mixed grafted thermosetting thermoplastic polyurethane, and thermoset polyurethane obtained after crosslinkingInfo
- Publication number
- EP1438345A1 EP1438345A1 EP02796825A EP02796825A EP1438345A1 EP 1438345 A1 EP1438345 A1 EP 1438345A1 EP 02796825 A EP02796825 A EP 02796825A EP 02796825 A EP02796825 A EP 02796825A EP 1438345 A1 EP1438345 A1 EP 1438345A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- polyurethane
- grafted
- crosslinking
- pure
- mixture
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 239000004433 Thermoplastic polyurethane Substances 0.000 title claims abstract description 46
- 229920002803 thermoplastic polyurethane Polymers 0.000 title claims abstract description 46
- 238000004132 cross linking Methods 0.000 title claims abstract description 23
- 229920001187 thermosetting polymer Polymers 0.000 title claims abstract description 18
- 229920002635 polyurethane Polymers 0.000 title claims description 29
- 239000004814 polyurethane Substances 0.000 title claims description 29
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 15
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 14
- 239000013638 trimer Substances 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 6
- 239000012948 isocyanate Substances 0.000 claims abstract description 6
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 6
- 230000000977 initiatory effect Effects 0.000 claims abstract description 3
- -1 isocyanatomethyl Chemical group 0.000 claims description 25
- 239000000203 mixture Substances 0.000 claims description 17
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 10
- 239000004743 Polypropylene Substances 0.000 claims description 8
- 150000002148 esters Chemical class 0.000 claims description 8
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 6
- 239000004698 Polyethylene Substances 0.000 claims description 6
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 6
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 6
- 239000008187 granular material Substances 0.000 claims description 5
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 claims description 5
- 229920001169 thermoplastic Polymers 0.000 claims description 5
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 claims description 4
- ZPSNFVVCGMSWID-UHFFFAOYSA-N 2-isocyanatopropan-2-ylbenzene Chemical compound O=C=NC(C)(C)C1=CC=CC=C1 ZPSNFVVCGMSWID-UHFFFAOYSA-N 0.000 claims description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 4
- FACXGONDLDSNOE-UHFFFAOYSA-N buta-1,3-diene;styrene Chemical compound C=CC=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 FACXGONDLDSNOE-UHFFFAOYSA-N 0.000 claims description 4
- 229920001577 copolymer Polymers 0.000 claims description 4
- 229920001903 high density polyethylene Polymers 0.000 claims description 4
- 239000004700 high-density polyethylene Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 4
- 229920002492 poly(sulfone) Polymers 0.000 claims description 4
- 229920001707 polybutylene terephthalate Polymers 0.000 claims description 4
- 239000004417 polycarbonate Substances 0.000 claims description 4
- 229920000573 polyethylene Polymers 0.000 claims description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 4
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 4
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 4
- 229920006324 polyoxymethylene Polymers 0.000 claims description 4
- 229920001955 polyphenylene ether Polymers 0.000 claims description 4
- 229920001155 polypropylene Polymers 0.000 claims description 4
- 239000004800 polyvinyl chloride Substances 0.000 claims description 4
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 4
- 229920001935 styrene-ethylene-butadiene-styrene Polymers 0.000 claims description 4
- 229920001897 terpolymer Polymers 0.000 claims description 4
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 3
- 239000004696 Poly ether ether ketone Substances 0.000 claims description 3
- 229920002530 polyetherether ketone Polymers 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 239000005059 1,4-Cyclohexyldiisocyanate Substances 0.000 claims description 2
- CDMDQYCEEKCBGR-UHFFFAOYSA-N 1,4-diisocyanatocyclohexane Chemical compound O=C=NC1CCC(N=C=O)CC1 CDMDQYCEEKCBGR-UHFFFAOYSA-N 0.000 claims description 2
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 claims description 2
- DFJNWFIZSRMSFS-UHFFFAOYSA-N 1-isocyanato-2-(4-isocyanatophenyl)-3-methylbenzene Chemical compound CC1=CC=CC(N=C=O)=C1C1=CC=C(N=C=O)C=C1 DFJNWFIZSRMSFS-UHFFFAOYSA-N 0.000 claims description 2
- WJIOHMVWGVGWJW-UHFFFAOYSA-N 3-methyl-n-[4-[(3-methylpyrazole-1-carbonyl)amino]butyl]pyrazole-1-carboxamide Chemical compound N1=C(C)C=CN1C(=O)NCCCCNC(=O)N1N=C(C)C=C1 WJIOHMVWGVGWJW-UHFFFAOYSA-N 0.000 claims description 2
- JRQLZCFSWYQHPI-UHFFFAOYSA-N 4,5-dichloro-2-cyclohexyl-1,2-thiazol-3-one Chemical compound O=C1C(Cl)=C(Cl)SN1C1CCCCC1 JRQLZCFSWYQHPI-UHFFFAOYSA-N 0.000 claims description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 2
- BJRMDQLATQGMCQ-UHFFFAOYSA-N C=C.C=CC=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 Chemical compound C=C.C=CC=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 BJRMDQLATQGMCQ-UHFFFAOYSA-N 0.000 claims description 2
- 229920001634 Copolyester Polymers 0.000 claims description 2
- OWIKHYCFFJSOEH-UHFFFAOYSA-N Isocyanic acid Chemical compound N=C=O OWIKHYCFFJSOEH-UHFFFAOYSA-N 0.000 claims description 2
- 229920000265 Polyparaphenylene Polymers 0.000 claims description 2
- 239000004793 Polystyrene Substances 0.000 claims description 2
- 229920010524 Syndiotactic polystyrene Polymers 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- XLJMAIOERFSOGZ-UHFFFAOYSA-N anhydrous cyanic acid Natural products OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 claims description 2
- JEHIQDWSSMKVGH-UHFFFAOYSA-N dihydroxy-(4-isocyanatophenoxy)-sulfanylidene-$l^{5}-phosphane Chemical compound OP(O)(=S)OC1=CC=C(N=C=O)C=C1 JEHIQDWSSMKVGH-UHFFFAOYSA-N 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- DGTNSSLYPYDJGL-UHFFFAOYSA-N phenyl isocyanate Chemical compound O=C=NC1=CC=CC=C1 DGTNSSLYPYDJGL-UHFFFAOYSA-N 0.000 claims description 2
- 229920000515 polycarbonate Polymers 0.000 claims description 2
- 229920001470 polyketone Polymers 0.000 claims description 2
- AZYRZNIYJDKRHO-UHFFFAOYSA-N 1,3-bis(2-isocyanatopropan-2-yl)benzene Chemical compound O=C=NC(C)(C)C1=CC=CC(C(C)(C)N=C=O)=C1 AZYRZNIYJDKRHO-UHFFFAOYSA-N 0.000 claims 1
- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 0.000 claims 1
- 230000007420 reactivation Effects 0.000 abstract 1
- 239000000463 material Substances 0.000 description 11
- 238000013329 compounding Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 230000004927 fusion Effects 0.000 description 7
- 230000009466 transformation Effects 0.000 description 7
- 238000001035 drying Methods 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000004606 Fillers/Extenders Substances 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- 238000003490 calendering Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 150000001282 organosilanes Chemical class 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000004416 thermosoftening plastic Substances 0.000 description 2
- 229920002943 EPDM rubber Polymers 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- KQWGXHWJMSMDJJ-UHFFFAOYSA-N cyclohexyl isocyanate Chemical compound O=C=NC1CCCCC1 KQWGXHWJMSMDJJ-UHFFFAOYSA-N 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000012815 thermoplastic material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/83—Chemically modified polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/0895—Manufacture of polymers by continuous processes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
- C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
- C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
-
- 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
Definitions
- the invention relates to a grafted thermosetting thermoplastic polyurethane (TPU), pure or mixed, which has the advantage of self-crosslinking in the presence of water or not, only under high temperature conditions (at least above 85 ° C. , advantageously greater than 90 ° C.) and in the absence of a catalyst. It also relates to pure polyurethane or the ⁇ nodurci mixture after self-crosslinking of said thermosetting TPU.
- TPU thermosetting thermoplastic polyurethane
- thermoplastic materials are used for the development of certain products such as hot fluid transport tubes, electric cables, solid wheels, seals, silent blocks, shoe soles, etc.
- Thermoplastic polyurethanes are used in these different applications, in particular for their ease of implementation and their exceptional quality at room temperature, their flexibility and their mechanical resistance.
- these materials have the disadvantage of being not very resistant to heat so that the products obtained from these materials, depending on their use, have a short lifespan when used in an atmosphere with a temperature relatively high.
- thermosetting polyurethane resins if they are actually intended to resist heat, remain very difficult to shape, so that their use is limited.
- the objective has therefore been to develop polyurethanes having the physical characteristics and the ease of transformation of thermoplastic polyurethanes and the characteristics thermomechanics of thermosetting polyurethanes, and in particular their temperature resistance.
- thermoset finished product it was necessary to make the TPU crosslinkable so that they can be further processed, that is to say shaped, then only then, crosslinked to obtain a thermoset finished product.
- the Applicant has proposed in document FR-A-2 794 759 to graft hydrolyzed organosilanes on thermoplastic polyurethanes using a diisocyanate acting as a bridging agent between the polymer chain and the organosilane.
- This bridging agent also makes it possible to attach the aminosilane and prevents it from breaking the main chains of the polyurethane.
- the Applicant has found that the crosslinking begins at ambient temperature and in the presence of moisture, thus prohibiting the storage of the TPU in a sustainable manner.
- the crosslinking phenomenon accelerates during drying (around 80 ° C) making the TPU unfit to be transformed. It is known in fact that this heating phase, before transformation, is essential because a tiny presence of water would cause crosslinking in the extruder at the time of transformation, leading to mechanical breakages of great importance.
- This process also has the disadvantage of requiring a high content and number of reagents, thereby creating an additional cost, which limits the volume of final applications.
- the Applicant has found that the TPU thus grafted could not be transformed at a temperature higher than approximately 180 ° C. insofar as, beyond this temperature, the bonds allowing the subsequent crosslinking created were quickly broken.
- the objective which the invention proposes to solve is to provide a TPU having the following characteristics: - inability to self-crosslink in the presence of water at a temperature below at least 85 ° C, that is to say at a temperature of at least 5 ° C, advantageously 10 ° C above the drying temperature (approximately 80 ° C) of TPU grafted before transfoimation, - reduced number of constituents,
- the Applicant sought to graft directly on the TPU a diisocyanate (for example MDI), in the absence of silane.
- a diisocyanate for example MDI
- the reaction rates of diisocyanates with thermoplastic polyurethanes in reactors of the internal or external mixer type were then studied. It has been found that the grafting reaction of one of the two functions (NCO) of the diisocyanate was very rapid under pressure and at temperature, in the absence of water. The function (NCO) remaining free became less reactive.
- a thermoplastic polyurethane sees its MVR (MELT VOLUME RATE) reduced by 2 after its grafting with diisocyanate. The grafted TPU then becomes very sensitive to water due to the presence of the free (NCO) function.
- This material in the form of granules cannot be stored for a long time, cannot be easily handled by the final transformer because it cannot be transported by suction and wait for its implementation in the open air, without being dried at the last moment as all commercially available thermoplastic polyurethanes.
- the final drying crosslinks the polyurethane in its granulated form and does not allow its thermoplastic transformation.
- it is especially important not to transform the grafted polyurethane diisocyanate without drying it because a tiny presence of water would cause crosslinking, which would lead to mechanical breakages of great importance during the transformation.
- the grafted TPU proposed by the invention solves all of these problems. More specifically, the invention relates to a thermosetting thermoplastic polyurethane grafted, pure or as a mixture, capable of being obtained by direct grafting onto a pure thermoplastic polyurethane or as a mixture, of a crosslinking agent chosen from the group comprising trimers of suitable diisocyanates. initiating the crosslinking reaction at a temperature above 85 ° C and blocked isocyanates, solid or liquid, whose release point is above 85 ° C
- pure or mixed TPU means a TPU alone or in mixture with at least one thermoplastic polymer chosen from the group comprising, without limitation, the
- PE polyethylene
- PP polypropylene
- thermoplastic polymer ratio will vary depending on the desired mechanical characteristics of the final mixture, in practice between 100/00 and 40/60, advantageously 70/30.
- thermosetting polyurethane is new with regard to the state of the art known to the Applicant, not only by its structure (limited number of constituents and specific crosslinking agent), but also by its behavior.
- the Applicant has in fact found that, quite surprisingly, the selection of the crosslinking agent, in the absence of silane, avoids the triggering of a crosslinking phenomenon at room temperature despite the presence of water and it was necessary, to initiate crosslinking, to increase the temperature to around at least 85 ° C, or up to a temperature above the drying temperature (80 ° C), in the absence of a catalyst.
- the crosslinking is carried out at a temperature above 100 ° C, between 110 and 130 ° C or more, depending on the release temperature of the diisocyanate, for 2 hours, after an initial moisture recovery of the polymer for 24 hours.
- room temperature it is possible to crosslink the thermosetting TPU of the invention, but only in the presence of a catalyst of the tin or bismuth type and in several days.
- the grafted thermoplastic polyurethane of the invention does not react or very little with water at temperatures below 85 ° C, advantageously 100 ° C, which allows it to be stored in the open air in standard poly bags.
- thermoplastic polyurethane after grafting, was only reduced by a factor of 1.5 instead of 2 when the polyurethane is grafted with a diisocyanate, which makes it possible to widen the working range.
- the MVR of the material is further reduced by a factor of 2, which improves the rheology of the polymer in the extrude ⁇ se and calibrators, and reduces the formation of rotassures during injection into molds.
- the grafted polyurethane has a behavior closer to that of polyethylenes than standard thermoplastic polyurethanes.
- the Applicant has observed that the crosslinking bonds have a much higher temperature resistance than the bonds obtained with the diisocyanates used alone or in the presence of silanes. This characteristic makes it possible, in the event of a mixture of TPU with other polymers, not to break the crosslinking bonds, and therefore not to lose the mechanical, thermal and chemical characteristics of the mixture during final processing, at elevated temperatures above 180 ° C.
- the crosslinking agent is a diisocyanate trimer or a blocked isocyanate, the basic molecules of which are each chosen from the group comprising FIPDI (5-isocyanato-1 (isocyanatomethyl) -1,3, 3-trimethyicycioexane), HDI (1,6-diisocyanatoexane), TDI (1-3 diisocyanatomethylbenzene), 2,4'-MDI (1 isocyanato-2 (4-isocyanatophenyl) methyl-benzene), 4.4 'MDI (1,1-methylene bis (4-isocyanatobenzene)), 2,4-TDI (2,4 diisocyanato-1-methylbenzene) and PPDI (1,4-diisocyanatobenzene), Hj 2 MDI (1, 1 -m ethylene bis (4-isocyanatocyclohexane)), CHDI (trans-1,4-diiso
- the blocking molecule is any molecule usually used (caprolactam, oxime, etc.) and perfectly known to those skilled in the art, in particular molecules. described in the publications: .Wicks Prog. Org. Coat. 9, p3, 1981 and L.TLPhai et al Makromol. Chem. 186, 1189, 1984.
- the crosslinking agent represents between 0.5 and 20% by mass of the grafted polyurethane, alone or as a mixture.
- the crosslinking agent is a trimer of IPDI and represents between 1 and 6% by mass of the polyurethane grafted alone or as a mixture.
- the grafted TPU of the invention is in the form of granules which can be stored in the state and subsequently transformed directly by the transformer by extrusion, calendering, injection, etc., and as already said, at temperatures high above 180 ° C due to the choice of crosslinking agent.
- the TPU is grafted then transformed directly continuously so as to obtain profiles of determined shape.
- the invention also relates to the process for manufacturing the grafted polyurethane previously described, which consists in reacting, at a temperature of at least 85 ° C., a thermoplastic polyurethane, pure or in mixture, with one of the crosslinking agents previously described, advantageously a trimer of IPDI, then recovering the grafted thermosetting thermoplastic polyurethane obtained.
- crosslinking agents because of their structure, makes it possible to slow down the grafting reaction and indeed to avoid the complete crosslinking of the TPU during the manufacture of the grafted polymer at a temperature above 85 ° C.
- the invention also relates to the thermoset polyurethane capable of being obtained after self-crosslinking of the thermosetting thermoplastic polyurethane graft previously described.
- Material 58447 witness: viscosity measured on melt indexer at 210 ° C under 8.16 kg 40.
- the viscosity of the material constituting the test piece is no longer measurable by the indexing melt
- the Kofler melting point goes from 185 ° C for the controls to 240 ° C for the material of the test piece
- estane 58315 ether type Estane 58315 ether type, Hardness 85 Shore A, Kofler Fusion around 150 ° C
- a mixture of 58315 with 4 pcr of Vestanat was carried out in a single screw extruder of the same type as that of Example 1, to obtain granules of 58315 grafted. After storage for one month, the grafted granule was dried in a ventilated oven at 80 ° C for two hours, then transformed on a calender at 190 ° C to obtain a sheet 1 millimeter thick. The same calendering operation was carried out with the control 58315.
- test pieces were cut to carry out a "hot set test" specific to the cable manufacturer. In an oven at 200 ° C, the material is subjected to a stress of 0.2 MPA. The test piece broke before two minutes. The crosslinked test piece has passed the 15-minute limit.
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- General Chemical & Material Sciences (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polyurethanes Or Polyureas (AREA)
- Organic Insulating Materials (AREA)
Abstract
Description
Claims
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR0113849 | 2001-10-26 | ||
FR0113849A FR2831542B1 (en) | 2001-10-26 | 2001-10-26 | THERMOPLASTIC THERMOPLASTIC POLYURETHANNE GRAFT, PURE OR IN MIXTURE, AND POLYURETHANE THERMODURCI OBTAINED AFTER RETICULATION |
PCT/FR2002/003646 WO2003035711A1 (en) | 2001-10-26 | 2002-10-24 | Pure or mixed grafted thermosetting thermoplastic polyurethane, and thermoset polyurethane obtained after crosslinking |
Publications (1)
Publication Number | Publication Date |
---|---|
EP1438345A1 true EP1438345A1 (en) | 2004-07-21 |
Family
ID=8868749
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP02796825A Withdrawn EP1438345A1 (en) | 2001-10-26 | 2002-10-24 | Pure or mixed grafted thermosetting thermoplastic polyurethane, and thermoset polyurethane obtained after crosslinking |
Country Status (10)
Country | Link |
---|---|
US (1) | US20040236035A1 (en) |
EP (1) | EP1438345A1 (en) |
JP (1) | JP2005506416A (en) |
KR (1) | KR20040047970A (en) |
CN (1) | CN1575307A (en) |
BR (1) | BR0213147A (en) |
CA (1) | CA2464684A1 (en) |
FR (1) | FR2831542B1 (en) |
NO (1) | NO20041963L (en) |
WO (1) | WO2003035711A1 (en) |
Families Citing this family (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE10356610A1 (en) | 2003-12-01 | 2005-06-30 | Basf Ag | Process for the reaction of (i) thermoplastic polyurethanes with (ii) isocyanate-containing compounds |
DE10356611A1 (en) * | 2003-12-01 | 2005-06-30 | Basf Ag | Process for the reaction of (i) thermoplastic polyurethanes with (ii) isocyanate-containing compounds |
DE102005028056A1 (en) * | 2005-06-16 | 2006-12-21 | Basf Ag | Thermoplastic polyurethane containing isocyanate |
FR2890226B1 (en) * | 2005-08-26 | 2007-09-28 | Nexans Sa | ENERGY AND / OR TELECOMMUNICATION CABLE WITH RETICULATED THERMOPLASTIC POLYURETHANE SHEATH |
CA2653658C (en) * | 2006-06-14 | 2014-05-06 | Huntsman International Llc | Cross-linkable thermoplastic polyurethanes |
WO2008045853A1 (en) * | 2006-10-13 | 2008-04-17 | Lubrizol Advanced Materials, Inc. | Thermoplastic polyurethanes containing a salt of zirconium phosphate |
CA2675765C (en) | 2007-01-18 | 2015-03-17 | Lubrizol Advanced Materials, Inc. | Cured in place pipe liner |
FR2919873B1 (en) * | 2007-08-07 | 2009-11-20 | Setup Performance | POSTERTICULAR THERMOPLASTIC MATERIAL AFTER PROCESSING AND STABLE MOLDED ARTICLES WITH VERY HIGH TEMPERATURE OBTAINED AFTER PROCESSING |
EP2445968B1 (en) * | 2009-06-23 | 2013-08-21 | Basf Se | Polyurethane on the basis of soft thermoplastic polyurethane |
US20120164445A1 (en) * | 2010-08-25 | 2012-06-28 | Bostik, Inc. | Fire Extinguishing Core |
DE102016013868A1 (en) * | 2016-11-28 | 2018-05-30 | Carl Freudenberg Kg | Polymer mixture for seals |
CN109517573A (en) * | 2018-10-20 | 2019-03-26 | 佛山市顺德区蓝德堡实业有限公司 | Hot melt polyurethane adhesive and preparation method thereof for the fitting of SBR fabric |
JP2022551928A (en) * | 2019-10-09 | 2022-12-14 | デュポン ポリマーズ インコーポレイテッド | Improved thermoplastic polyurethane |
Family Cites Families (11)
Publication number | Priority date | Publication date | Assignee | Title |
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JPS582063B2 (en) * | 1980-05-29 | 1983-01-13 | 大日精化工業株式会社 | Manufacturing method for thermosetting polyurethane molded products |
DE3590249T1 (en) * | 1984-05-30 | 1986-06-26 | Sunstar Giken K.K., Takatsuki, Osaka | Polyurethane adhesive |
EP0539802A1 (en) * | 1991-10-28 | 1993-05-05 | Bayer Ag | Free-flowing, optionally expandable, thermoplastic processable and therewith post-crosslinkable polyurethane powder |
DE4209709A1 (en) * | 1992-03-25 | 1993-09-30 | Bayer Ag | Free-flowing, thermoplastic, crosslinkable polyurethane powder |
JP3205784B2 (en) * | 1992-08-03 | 2001-09-04 | 関西ペイント株式会社 | Self-crosslinking resin |
EP0611077A3 (en) * | 1993-02-08 | 1994-12-28 | Rohm & Haas | Polyurethane elastomer blends. |
DE19628444A1 (en) * | 1996-07-15 | 1998-01-22 | Bayer Ag | New high-solids 2 K PUR binder combinations |
US6258310B1 (en) * | 1999-03-18 | 2001-07-10 | Basf Corporation | Cross-linking thermoplastic polyurethane |
US6142189A (en) * | 1999-07-15 | 2000-11-07 | Dayco Products, Inc. | Method for manufacturing a high performance crosslinked thermoplastic hose and a high performance crosslinked thermoplastic hose produced thereby |
DE19953445A1 (en) * | 1999-11-06 | 2001-05-17 | Basf Coatings Ag | Self-crosslinking polyurethanes and graft copolymers based on polyurethane and their use in the production of coating materials, adhesives and sealants |
DE10004726A1 (en) * | 2000-02-03 | 2001-08-16 | Basf Coatings Ag | Aqueous coating material curable thermally and / or with actinic radiation and its use |
-
2001
- 2001-10-26 FR FR0113849A patent/FR2831542B1/en not_active Expired - Fee Related
-
2002
- 2002-10-24 CA CA002464684A patent/CA2464684A1/en not_active Abandoned
- 2002-10-24 JP JP2003538223A patent/JP2005506416A/en not_active Withdrawn
- 2002-10-24 BR BR0213147-1A patent/BR0213147A/en not_active IP Right Cessation
- 2002-10-24 CN CNA028212983A patent/CN1575307A/en active Pending
- 2002-10-24 WO PCT/FR2002/003646 patent/WO2003035711A1/en active Application Filing
- 2002-10-24 KR KR10-2004-7006161A patent/KR20040047970A/en not_active Application Discontinuation
- 2002-10-24 EP EP02796825A patent/EP1438345A1/en not_active Withdrawn
-
2004
- 2004-04-20 US US10/828,114 patent/US20040236035A1/en not_active Abandoned
- 2004-04-27 NO NO20041963A patent/NO20041963L/en unknown
Non-Patent Citations (1)
Title |
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See references of WO03035711A1 * |
Also Published As
Publication number | Publication date |
---|---|
FR2831542A1 (en) | 2003-05-02 |
CN1575307A (en) | 2005-02-02 |
BR0213147A (en) | 2004-10-19 |
NO20041963L (en) | 2004-04-27 |
CA2464684A1 (en) | 2003-05-01 |
FR2831542B1 (en) | 2005-02-25 |
KR20040047970A (en) | 2004-06-05 |
WO2003035711A1 (en) | 2003-05-01 |
US20040236035A1 (en) | 2004-11-25 |
JP2005506416A (en) | 2005-03-03 |
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