CN117844431A - Thermoplastic polyurethane adhesive, preparation method and application thereof - Google Patents
Thermoplastic polyurethane adhesive, preparation method and application thereof Download PDFInfo
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- CN117844431A CN117844431A CN202311726362.4A CN202311726362A CN117844431A CN 117844431 A CN117844431 A CN 117844431A CN 202311726362 A CN202311726362 A CN 202311726362A CN 117844431 A CN117844431 A CN 117844431A
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- diisocyanate
- thermoplastic polyurethane
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- polyurethane adhesive
- aliphatic
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- 239000000853 adhesive Substances 0.000 title claims abstract description 36
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 36
- 239000004433 Thermoplastic polyurethane Substances 0.000 title claims abstract description 32
- 229920002803 thermoplastic polyurethane Polymers 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims description 4
- -1 aromatic diols Chemical class 0.000 claims abstract description 19
- 229920005862 polyol Polymers 0.000 claims abstract description 19
- 150000003077 polyols Chemical class 0.000 claims abstract description 19
- 239000004970 Chain extender Substances 0.000 claims abstract description 14
- 230000004913 activation Effects 0.000 claims abstract description 9
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 7
- 239000000463 material Substances 0.000 claims abstract description 7
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims description 54
- 235000019445 benzyl alcohol Nutrition 0.000 claims description 18
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 10
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 10
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 8
- 125000001931 aliphatic group Chemical group 0.000 claims description 8
- 238000001125 extrusion Methods 0.000 claims description 8
- 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 8
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 8
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 8
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims description 7
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 claims description 7
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 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 5
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 5
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 5
- 229920001610 polycaprolactone Polymers 0.000 claims description 5
- 239000004632 polycaprolactone Substances 0.000 claims description 5
- 229920005906 polyester polyol Polymers 0.000 claims description 5
- 229920000570 polyether Polymers 0.000 claims description 5
- 229920000642 polymer Polymers 0.000 claims description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- RHINSRUDDXGHLV-UHFFFAOYSA-N decane-1,2,10-triol Chemical compound OCCCCCCCCC(O)CO RHINSRUDDXGHLV-UHFFFAOYSA-N 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 229920001451 polypropylene glycol Polymers 0.000 claims description 4
- CUJPFPXNDSIBPG-UHFFFAOYSA-N 1,3-propanediyl Chemical group [CH2]C[CH2] CUJPFPXNDSIBPG-UHFFFAOYSA-N 0.000 claims description 3
- UDZBHPRIFDOBJA-UHFFFAOYSA-N 4-(3-hydroxypropyl)heptane-1,7-diol Chemical compound OCCCC(CCCO)CCCO UDZBHPRIFDOBJA-UHFFFAOYSA-N 0.000 claims description 3
- XDODWINGEHBYRT-UHFFFAOYSA-N [2-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCCCC1CO XDODWINGEHBYRT-UHFFFAOYSA-N 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical group C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 claims description 2
- 125000006527 (C1-C5) alkyl group Chemical group 0.000 claims description 2
- RTTZISZSHSCFRH-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC(CN=C=O)=C1 RTTZISZSHSCFRH-UHFFFAOYSA-N 0.000 claims description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims description 2
- 229940035437 1,3-propanediol Drugs 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
- VICIXNZSEUYGFV-UHFFFAOYSA-N 5-(2-hydroxyethyl)nonane-1,9-diol Chemical compound OCCCCC(CCO)CCCCO VICIXNZSEUYGFV-UHFFFAOYSA-N 0.000 claims description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 2
- 229920000166 polytrimethylene carbonate Polymers 0.000 claims description 2
- 229960004063 propylene glycol Drugs 0.000 claims description 2
- 235000013772 propylene glycol Nutrition 0.000 claims description 2
- 239000007858 starting material Substances 0.000 claims description 2
- 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 2
- 239000002994 raw material Substances 0.000 description 10
- 238000005453 pelletization Methods 0.000 description 6
- 229920002635 polyurethane Polymers 0.000 description 5
- 239000004814 polyurethane Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- MFBRWKCKAGAJAJ-UHFFFAOYSA-N 2-[4-[[4-(2-hydroxyethoxy)phenyl]methyl]phenoxy]ethanol Chemical compound C1=CC(OCCO)=CC=C1CC1=CC=C(OCCO)C=C1 MFBRWKCKAGAJAJ-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000012854 evaluation process Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- CUUVVDHSUIKLPH-UHFFFAOYSA-N nonane-1,2,9-triol Chemical compound OCCCCCCCC(O)CO CUUVVDHSUIKLPH-UHFFFAOYSA-N 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920003225 polyurethane elastomer Polymers 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention provides a thermoplastic polyurethane adhesive with low activation temperature and high heat resistance and application thereof. Is prepared by reacting a high molecular polyol component with a special chain extender and diisocyanate, wherein the chain extender is selected from the group consisting of aromatic diols and aliphatic alcohols. The adhesive has excellent performances of low activation temperature, high heat resistance and the like, is used for bonding in the fields of shoes, clothing and the like, and is preferably used for bonding materials used under high temperature conditions.
Description
Technical Field
The invention belongs to the field of high polymer material manufacturing, and particularly relates to a thermoplastic polyurethane adhesive with low activation temperature and high heat resistance, a preparation method and application thereof.
Background
Polyurethane adhesives refer to adhesives containing urethane groups or isocyanate groups in the molecular chain, which have very excellent properties. Because of its structural characteristics, polyurethane adhesives have excellent low-temperature performance, but are easily degraded at high temperature, reducing bonding strength, and limiting the application thereof under high temperature conditions. Many patents currently seek how to obtain thermoplastic polyurethane adhesives that are highly heat resistant.
Chinese patent CN110563913a discloses that the heat resistance of polyurethane elastomer is improved by introducing a polyoxazolidone segment structure into the polyurethane molecular chain through in-situ synthesis with a diepoxy compound as a chain extender;
chinese patent CN111333814a discloses that polyester polyol, polyether polyol, polycaprolactone polyol, and polycarbonate polyol are used as polyol components, diamine containing aromatic ring and bisphenol a diol are used as chain extender to react with isocyanate to obtain thermoplastic polyurethane with good heat resistance;
however, the introduction of aromatic rings can improve the heat resistance of polyurethane, but the scheme can simultaneously lead to the deterioration of the fluidity of polyurethane adhesive, the increase of the activation temperature and the deterioration of the bonding effect, so far, thermoplastic polyurethane with low activation temperature and high heat resistance is rarely reported at home and abroad.
Accordingly, a thermoplastic polyurethane adhesive having both of the above-mentioned characteristics has been developed, and a technical problem to be solved in the art has been urgently needed.
Disclosure of Invention
The invention aims at solving the problems in the prior art and provides a thermoplastic polyurethane adhesive which has the characteristics of low polarity, high heat resistance and controllable reaction rate.
The above object of the present invention is achieved by the following technical scheme:
a low activation temperature, high heat resistant thermoplastic polyurethane adhesive comprising, based on the total mass of the adhesive:
a) 70 to 95wt%, preferably 74 to 90wt% of a polymer polyol;
b) Chain extenders, from 0 to 10% by weight, preferably from 0 to 7% by weight;
c) 5 to 35wt%, preferably 11 to 30wt% of diisocyanate;
the chain extender comprises an aromatic diol, an aliphatic diol and/or an aliphatic triol.
In the invention, the aromatic diol chain extender is one or more of the following compounds
Wherein R is a linear or branched C3-C12 alkyl group or a C3-C12 alkenyl group, R 1 And R is 2 Selected from C1-C5 alkyl, preferably 4,4' - (1, 3-propanediyl) bis [ benzyl alcohol]4,4' - (1, 6-hexanediyl) bis [ benzyl alcohol]4,4' - (1, 7-heptanediyl) bis [ benzyl alcohol]4,4' - (1, 12-dodecanediyl) bis [ benzyl alcohol]One or more of them.
In the invention, the aliphatic triol is one or more of C4-C20 aliphatic triol, preferably trimethylolpropane, 1,2, 10-decanetriol, 1,2, 9-nonantriol, 4- (3-hydroxypropyl) -1, 7-heptanediol and 5- (2-hydroxyethyl) -1, 9-nonanediol.
In the invention, the aliphatic diol is one or more of C4-C12 straight-chain aliphatic diol, preferably 1, 4-butanediol, 1, 6-hexanediol, 1, 2-cyclohexanedimethanol and neopentyl glycol.
In the present invention, the mass ratio of the aromatic diol to the aliphatic alcohol (aliphatic diol or aliphatic triol or the sum of aliphatic diol and aliphatic triol) is 1:0.2 to 1, preferably 1:0.25 to 0.5.
In the present invention, the polymer polyol is one or more selected from the group consisting of polyester polyol, polycaprolactone polyol and polyether polyol.
In the present invention, the polyester polyol is selected from PEA, PBA and PHA, preferably PBA and PHA, and has a number average molecular weight of 2000 to 3000g/mol.
In the present invention, the polyether polyol is selected from polytetramethylene ether glycol (PTMEG), polyethylene glycol (PEG) and polypropylene glycol (PPG), preferably polytetramethylene ether glycol (PTMEG), and has a number average molecular weight of 2000 to 3000g/mol.
In the present invention, the polycaprolactone polyol starter is selected from the group consisting of 1, 3-propanediol, 1, 2-ethanediol, 1, 2-propanediol, 1, 4-butanediol, 1, 6-hexanediol, neopentyl glycol, preferably 1, 2-ethanediol, 1, 4-butanediol, neopentyl glycol, and has a number average molecular weight of 2000 to 3000g/mol.
In the present invention, the diisocyanate is one or more of diphenylmethane diisocyanate, hexamethylene diisocyanate, 4-dicyclohexylmethane diisocyanate, toluene diisocyanate, isophorone diisocyanate, m-xylylene diisocyanate, 1, 5-naphthalene diisocyanate, preferably one or more of hexamethylene diisocyanate, diphenylmethane diisocyanate and isophorone diisocyanate.
In another aspect, the present invention also provides a method for preparing a thermoplastic polyurethane adhesive, the method comprising the steps of: mixing polymer polyol with diisocyanate and chain extender, and screw reaction extrusion.
In the present invention, the extrusion temperature of the reactive extrusion is 130 to 200 ℃, preferably 140 to 180 ℃.
Finally, the invention provides the application of the thermoplastic polyurethane adhesive in bonding nonpolar materials under high temperature conditions, such as bonding at high use temperature in the fields of footwear and the like.
Compared with the prior art, the invention has the following positive effects:
the invention adopts the chain extender combination with a specific structure to bring a diphenyl structure, thereby improving the heat resistance of the adhesive, reducing the density of benzene rings and increasing the flexibility of the system by long carbon chains among the benzene rings, and regulating and controlling the crystallinity of the system by matching with the aliphatic chain extender, so that the system obtains lower activation temperature. Compared with the existing product, the product has low activation temperature (40 ℃), better heat resistance (100 ℃, heat resistance for 0min is below 20mm, and the minimum of 4 mm), and excellent comprehensive performance.
Detailed Description
The following describes the method of practicing the invention in detail, but the invention is not limited thereby.
All the raw materials can be purchased commercially.
Raw materials and sources:
hexanediol (microphone, 98%)
Butanediol (microphone Lin, 98%)
Neopentyl glycol (Michelin, 98%)
4,4' - (1, 3-propanediyl) bis [ benzyl alcohol ] (Chongqing FuTeng, 98%)
4,4' - (1, 6-hexanediyl) bis [ benzyl alcohol ] (Chongqing FuTENG, 98%)
4,4' - (1, 7-heptanediyl) bis [ benzyl alcohol ] (Chongqing FuTeng, 98%)
2,2' - ((methylenebis (4, 1-phenylene)) bis (oxy) diethanol (Chongqing FuTeng, 98%)
Hexamethylene diisocyanate (Wanhua chemistry, 99.5%)
Diphenylmethane diisocyanate (Wanhua chemistry, 99.5%)
Isophorone diisocyanate (Wanhua chemistry, 99.5%).
Example 1
PBA2000 accounting for 150Kg of the total mass of the raw materials, isophorone diisocyanate 60Kg, 4' - (1, 6-hexanediyl) bis [ benzyl alcohol ] and 4Kg of 1, 6-hexanediol are added into an extruder to be uniformly mixed, and are extruded through twin-screw reaction (the extruder temperature is 150 ℃ in the first area, 160 ℃ in the second area, 160 ℃ in the third area, 170 ℃ in the seventh area, 160 ℃ in the eighth area, 160 ℃ in the ninth area and 160 ℃ in the tenth area) and then the thermoplastic polyurethane adhesive is prepared through underwater pelletization.
Example 2
PBA3000 accounting for 164Kg of the total mass of the raw materials, 43Kg of 4, 4-diphenylmethane diisocyanate, 4Kg of 4,4' - (1, 3-propylenediyl) bis [ benzyl alcohol ],1.9Kg of 1,2, 10-decanetriol are added into an extruder to be uniformly mixed, and are extruded through twin-screw reaction (the extruder temperature is 160 ℃ in a first area, 160 ℃ in a second area, 160 ℃ in a third area, 160 ℃ in a fourth area and 160 ℃ in a fifth area, 160 ℃ in a sixth area, 160 ℃ in a seventh area and 160 ℃ in an eighth area, 160 ℃ in a ninth area and 160 ℃ in a tenth area) and then the thermoplastic polyurethane adhesive is prepared through underwater pelletization.
Example 3
PHA3000 accounting for 168Kg of the total mass of the raw materials, 29Kg of hexamethylene diisocyanate, 2Kg of 1, 4-butanediol, 6Kg of 4,4' - (1, 6-hexanediyl) bis [ benzyl alcohol ] and 2.1Kg of 4- (3-hydroxypropyl) -1, 7-heptanediol are added into an extruder to be uniformly mixed, and are extruded through a double screw reaction (the extruder temperature is 160 ℃ in a first area, 160 ℃ in a second area, 180 ℃ in a third area, 180 ℃ in a fourth area and five areas, 170 ℃ in a sixth area, 170 ℃ in a seventh area and 170 ℃ in an eighth area, and 170 ℃ in a tenth area) and the die head temperature is 170 ℃ in a die head, and then the thermoplastic polyurethane adhesive is prepared through underwater pelletization.
Example 4
PCDL3000 accounting for 166Kg of total mass of raw materials, isophorone diisocyanate 38Kg, neopentyl glycol 1.8Kg, 4' - (1, 7-heptadiyl) bis [ benzyl alcohol ] are added into an extruder to be uniformly mixed, and are extruded by twin-screw reaction (the extruder temperature is 170 ℃ in the first area, 180 ℃ in the second area, 180 ℃ in the third area, 180 ℃ in the seventh area and eight areas, 190 ℃ in the ninth area and 180 ℃ in the tenth area, and 180 ℃ in the die head temperature), and then the thermoplastic polyurethane adhesive is prepared by underwater pelletization.
Example 5
PBA3000 accounting for 162Kg of the total mass of the raw materials, 6Kg of hexamethylene diisocyanate 6Kg of 4,4' - (1, 3-propylenediyl) bis [ benzyl alcohol ] and 1.6Kg of 1,2, 10-decanetriol are added into an extruder to be uniformly mixed, and are extruded through twin-screw reaction (the extruder temperature is 170 ℃ in a first area, 170 ℃ in a second area, 180 ℃ in a third area, 180 ℃ in a fourth area and 180 ℃ in a fifth area, 180 ℃ in a sixth area, 180 ℃ in a seventh area and 180 ℃ in a eighth area, 180 ℃ in a ninth area and 180 ℃ in a tenth area) and then the thermoplastic polyurethane adhesive is prepared through underwater pelletization.
Example 6
Adding BDO-PCL3000 accounting for 180Kg of the total mass of the raw materials, 40Kg of isophorone diisocyanate, 1.9Kg of 1, 2-cyclohexanedimethanol and 6Kg of 4,4' - (1, 7-heptanediyl) bis [ benzyl alcohol ] into an extruder, uniformly mixing, performing twin-screw reaction extrusion (the extruder temperature is 160 ℃ in a first area, 160 ℃ in a second area, 170 ℃ in a third area, 170 ℃ in a fourth area and 170 ℃ in a fifth area, 180 ℃ in a sixth area, 170 ℃ in a seventh area and 170 ℃ in an eighth area, 170 ℃ in a ninth area and 170 ℃ in a tenth area), and granulating under water to obtain the thermoplastic polyurethane adhesive.
Comparative example 1
Adding 169Kg of PBA3000, 41Kg of hexamethylene diisocyanate and 2Kg of 1, 4-butanediol into an extruder, uniformly mixing, extruding by twin-screw reaction (the extruder temperature is 160 ℃ in the first area, 160 ℃ in the second area, 170 ℃ in the third area, 170 ℃ in the fourth area and five areas, 180 ℃ in the sixth area, 180 ℃ in the seventh area and eight areas, 170 ℃ in the ninth area and 170 ℃ in the tenth area) and granulating under water to obtain the thermoplastic polyurethane adhesive.
Comparative example 2
Adding PBA3000 accounting for 168Kg of the total mass of the raw materials, 24Kg of hexamethylene diisocyanate and 6Kg of 4,4' - (1, 7-heptadiyl) bis [ benzyl alcohol ] into an extruder, uniformly mixing, extruding by twin-screw reaction (the extruder temperature is 160 ℃ in the first region, 160 ℃ in the second region, 170 ℃ in the third region, 180 ℃ in the fourth region and the fifth region, 170 ℃ in the sixth region, 170 ℃ in the seventh region and eight region, 170 ℃ in the ninth region and 170 ℃ in the tenth region), and granulating under water to obtain the thermoplastic polyurethane adhesive.
Comparative example 3
Adding PBA3000 accounting for 168Kg of the total mass of the raw materials and 24Kg of hexamethylene diisocyanate, 6Kg of 2,2' - ((methylene bis (4, 1-phenylene)) bis (oxy) diethanol into an extruder, uniformly mixing, carrying out twin-screw reaction extrusion (the extruder temperature is 160 ℃ in the first area, 160 ℃ in the second area, 170 ℃ in the third area, 180 ℃ in the fourth area and 170 ℃ in the fifth area, 180 ℃ in the sixth area, 170 ℃ in the seventh area and 170 ℃ in the eighth area, 170 ℃ in the ninth area and 170 ℃ in the tenth area), and carrying out underwater pelletization to obtain the thermoplastic polyurethane adhesive.
The thermoplastic polyurethane elastomer properties were tested as follows:
hardness was measured according to astm d 2240; tensile strength was tested according to GB/T528-2009 standard; the peeling strength is that a specific temperature is used for activating a bonding spline (the base material is PVC) after the glue is coated, and the peeling strength is tested after 5 minutes; the heat-resistant test base material is polyester canvas, a sample strip is attached, a 500 g weight is hung, the test base material is placed in a 100 ℃ oven, the test base material is tested within 30 minutes, and the pull-off length of a test piece (if the test piece falls in the middle, the falling time is recorded).
The instruments used in the experimental and evaluation process are as follows:
the performance data of the TPU provided by the above examples and comparative examples are shown below:
Claims (9)
1. a low activation temperature, high heat resistant thermoplastic polyurethane adhesive comprising, based on the total mass of the adhesive:
a) 70 to 95wt%, preferably 74 to 90wt% of a polymer polyol;
b) Chain extenders, from 0 to 10% by weight, preferably from 0 to 7% by weight;
c) 5 to 35wt%, preferably 11 to 30wt% of diisocyanate;
the chain extender comprises an aromatic diol and an aliphatic alcohol, wherein the aliphatic alcohol is selected from aliphatic diols and/or aliphatic triols.
2. The thermoplastic polyurethane adhesive of claim 1 wherein the aromatic diol chain extender is one or more of the following compounds having the structure
Wherein R is a linear or branched C3-C12 alkyl group or a C3-C12 alkenyl group, R 1 And R is 2 Selected from C1-C5 alkyl groups, e.g. 4,4' - (1, 3-propanediyl) bis [ benzyl alcohol]4,4' - (1, 6-hexanediyl) bis [ benzyl alcohol]4,4' - (1, 7-heptanediyl) bis [ benzyl alcohol]4,4' - (1, 12-dodecanediyl) bis [ benzyl alcohol]One or more of them.
3. Thermoplastic polyurethane adhesive according to claim 1 or 2, characterized in that the aliphatic triol is a C4-C20 aliphatic triol, preferably trimethylolpropane, 1,2, 10-decanetriol,
one or more of 1,2, 9-nonatriol, 4- (3-hydroxypropyl) -1, 7-heptanediol, 5- (2-hydroxyethyl) -1, 9-nonanediol; and/or the aliphatic diol is a C4-C12 straight chain aliphatic diol,
preferably one or more of 1, 4-butanediol, 1, 6-hexanediol, 1, 2-cyclohexanedimethanol, neopentyl glycol.
4. A thermoplastic polyurethane adhesive according to any one of claims 1 to 3, wherein the mass ratio of aromatic diol to aliphatic alcohol is 1:0.2 to 1, preferably 1:0.25 to 0.5.
5. The thermoplastic polyurethane adhesive of any one of claims 1-4, wherein the polymeric polyol is selected from one or more of a polyester polyol, a polycaprolactone polyol, and a polyether polyol; preferably, the polyester polyol is selected from PEA, PBA and PHA, more preferably PBA and PHA, having a number average molecular weight of 2000 to 3000g/mol; the polyether polyol is selected from polytetramethylene ether glycol (PTMEG), polyethylene glycol (PEG) and polypropylene glycol (PPG), more preferably polytetramethylene ether glycol (PTMEG) with the number average molecular weight of 2000-3000 g/mol; the polycaprolactone polyol starter is selected from 1, 3-propanediol, 1, 2-ethanediol, 1, 2-propanediol, 1, 4-butanediol, 1, 6-hexanediol, neopentyl glycol, more preferably 1, 2-ethanediol, 1, 4-butanediol, neopentyl glycol, and has a number average molecular weight of 2000-3000 g/mol.
6. The thermoplastic polyurethane adhesive of any of claims 1-5 wherein the diisocyanate is one or more of diphenylmethane diisocyanate, hexamethylene diisocyanate, 4-dicyclohexylmethane diisocyanate, toluene diisocyanate, isophorone diisocyanate, m-xylylene diisocyanate, 1, 5-naphthalene diisocyanate, preferably one or more of hexamethylene diisocyanate, diphenylmethane diisocyanate and isophorone diisocyanate.
7. A process for preparing a thermoplastic polyurethane adhesive as claimed in any one of claims 1 to 6, comprising the steps of: mixing polymer polyol with diisocyanate and chain extender, and screw reaction extrusion.
8. The process according to claim 7, wherein the reactive extrusion has an extrusion temperature of 130 to 200 ℃, preferably 140 to 180 ℃.
9. Thermoplastic polyurethane adhesives according to any one of claims 1 to 6 or thermoplastic polyurethane adhesives prepared by the preparation method according to claim 7 or 8 are used for bonding in the fields of footwear and the like, preferably for bonding materials used under high temperature conditions.
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| CN202311726362.4A CN117844431A (en) | 2023-12-15 | 2023-12-15 | Thermoplastic polyurethane adhesive, preparation method and application thereof |
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| CN202311726362.4A CN117844431A (en) | 2023-12-15 | 2023-12-15 | Thermoplastic polyurethane adhesive, preparation method and application thereof |
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