CN117209779A - Thermoplastic polyurethane elastomer material, thermoplastic polyurethane foaming material, and preparation and application thereof - Google Patents
Thermoplastic polyurethane elastomer material, thermoplastic polyurethane foaming material, and preparation and application thereof Download PDFInfo
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- CN117209779A CN117209779A CN202311045343.5A CN202311045343A CN117209779A CN 117209779 A CN117209779 A CN 117209779A CN 202311045343 A CN202311045343 A CN 202311045343A CN 117209779 A CN117209779 A CN 117209779A
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- thermoplastic polyurethane
- polyurethane elastomer
- diisocyanate
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- 239000004433 Thermoplastic polyurethane Substances 0.000 title claims abstract description 155
- 229920002803 thermoplastic polyurethane Polymers 0.000 title claims abstract description 155
- 229920001971 elastomer Polymers 0.000 title claims abstract description 87
- 239000000806 elastomer Substances 0.000 title claims abstract description 87
- 239000000463 material Substances 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 238000005187 foaming Methods 0.000 title claims abstract description 23
- 239000013067 intermediate product Substances 0.000 claims abstract description 46
- 238000006243 chemical reaction Methods 0.000 claims description 67
- 239000006261 foam material Substances 0.000 claims description 28
- 239000011324 bead Substances 0.000 claims description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 239000000725 suspension Substances 0.000 claims description 18
- 239000006260 foam Substances 0.000 claims description 17
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 16
- 238000001125 extrusion Methods 0.000 claims description 12
- -1 amine compounds Chemical class 0.000 claims description 10
- 125000005442 diisocyanate group Chemical group 0.000 claims description 9
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 claims description 8
- 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 8
- 239000001569 carbon dioxide Substances 0.000 claims description 8
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 7
- 229920005862 polyol Polymers 0.000 claims description 7
- 150000003077 polyols Chemical class 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 6
- 239000004088 foaming agent Substances 0.000 claims description 6
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 6
- WJYIASZWHGOTOU-UHFFFAOYSA-N Heptylamine Chemical compound CCCCCCCN WJYIASZWHGOTOU-UHFFFAOYSA-N 0.000 claims description 4
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- ZMSQJSMSLXVTKN-UHFFFAOYSA-N 4-[2-(2-morpholin-4-ylethoxy)ethyl]morpholine Chemical group C1COCCN1CCOCCN1CCOCC1 ZMSQJSMSLXVTKN-UHFFFAOYSA-N 0.000 claims description 3
- 239000001273 butane Substances 0.000 claims description 3
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 229920001610 polycaprolactone Polymers 0.000 claims description 3
- 239000004632 polycaprolactone Substances 0.000 claims description 3
- 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 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
- FJLUATLTXUNBOT-UHFFFAOYSA-N 1-Hexadecylamine Chemical compound CCCCCCCCCCCCCCCCN FJLUATLTXUNBOT-UHFFFAOYSA-N 0.000 claims description 2
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 claims description 2
- PWTNRNHDJZLBCD-UHFFFAOYSA-N 2-(2-pentoxyethoxy)ethanol Chemical compound CCCCCOCCOCCO PWTNRNHDJZLBCD-UHFFFAOYSA-N 0.000 claims description 2
- KOVAQMSVARJMPH-UHFFFAOYSA-N 4-methoxybutan-1-ol Chemical compound COCCCCO KOVAQMSVARJMPH-UHFFFAOYSA-N 0.000 claims description 2
- 239000004831 Hot glue Substances 0.000 claims description 2
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 2
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 claims description 2
- VXVVUHQULXCUPF-UHFFFAOYSA-N cycloheptanamine Chemical compound NC1CCCCCC1 VXVVUHQULXCUPF-UHFFFAOYSA-N 0.000 claims description 2
- 238000002844 melting Methods 0.000 claims description 2
- 230000008018 melting Effects 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- MSSNHSVIGIHOJA-UHFFFAOYSA-N pentafluoropropane Chemical compound FC(F)CC(F)(F)F MSSNHSVIGIHOJA-UHFFFAOYSA-N 0.000 claims description 2
- 239000004417 polycarbonate Substances 0.000 claims description 2
- 229920000515 polycarbonate Polymers 0.000 claims description 2
- 229920005906 polyester polyol Polymers 0.000 claims description 2
- 229920000570 polyether Polymers 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
- FJDUDHYHRVPMJZ-UHFFFAOYSA-N nonan-1-amine Chemical compound CCCCCCCCCN FJDUDHYHRVPMJZ-UHFFFAOYSA-N 0.000 claims 1
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 claims 1
- AGGKEGLBGGJEBZ-UHFFFAOYSA-N tetramethylenedisulfotetramine Chemical compound C1N(S2(=O)=O)CN3S(=O)(=O)N1CN2C3 AGGKEGLBGGJEBZ-UHFFFAOYSA-N 0.000 claims 1
- 238000010382 chemical cross-linking Methods 0.000 abstract description 8
- 239000000155 melt Substances 0.000 abstract description 8
- 210000000497 foam cell Anatomy 0.000 abstract description 3
- 238000007259 addition reaction Methods 0.000 abstract description 2
- 239000013518 molded foam Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 239000002245 particle Substances 0.000 description 9
- 210000004027 cell Anatomy 0.000 description 6
- 150000002009 diols Chemical class 0.000 description 6
- 230000009286 beneficial effect Effects 0.000 description 5
- 229920002635 polyurethane Polymers 0.000 description 5
- 239000004814 polyurethane Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000005453 pelletization Methods 0.000 description 4
- 229920000909 polytetrahydrofuran Polymers 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- RVRHBLSINNOLPI-UHFFFAOYSA-N Lythridin Natural products COc1ccc(cc1OC)C2CC(CC3CCCCN23)OC(=O)CC(O)c4ccc(O)cc4 RVRHBLSINNOLPI-UHFFFAOYSA-N 0.000 description 1
- 229920005830 Polyurethane Foam Polymers 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- TWLCPLJMACDPFF-UHFFFAOYSA-N cyclohexane;1,2-diisocyanatoethane Chemical compound C1CCCCC1.O=C=NCCN=C=O TWLCPLJMACDPFF-UHFFFAOYSA-N 0.000 description 1
- LTNZEXKYNRNOGT-UHFFFAOYSA-N dequalinium chloride Chemical compound [Cl-].[Cl-].C1=CC=C2[N+](CCCCCCCCCC[N+]3=C4C=CC=CC4=C(N)C=C3C)=C(C)C=C(N)C2=C1 LTNZEXKYNRNOGT-UHFFFAOYSA-N 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- MVAOEXBRERPGIT-UHFFFAOYSA-N octamine Chemical compound N.N.N.N.N.N.N.N MVAOEXBRERPGIT-UHFFFAOYSA-N 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000011496 polyurethane foam Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Landscapes
- Polyurethanes Or Polyureas (AREA)
Abstract
The application discloses a thermoplastic polyurethane elastomer material, a thermoplastic polyurethane foaming material, and a preparation method and application thereof. According to the application, an intermediate product containing a single NCO group end-capped prepolymer is introduced, and an addition reaction is carried out between an NCO group in the single NCO group end-capped prepolymer and an amide bond of a thermoplastic polyurethane elastomer in a double-screw extruder, so that a molecular chain segment of the single NCO group end-capped prepolymer can be grafted onto a molecular chain segment of the thermoplastic polyurethane elastomer, the thermoplastic polyurethane can form a molecular chain segment with a branched chain structure, the melt strength of the low molecular weight thermoplastic polyurethane elastomer is improved, the foamable property of the low molecular weight thermoplastic polyurethane elastomer is further improved, and the prepared thermoplastic polyurethane foaming material has lower density, more uniform foam cells, better rebound resilience and excellent mechanical property, is basically free from chemical crosslinking, and can be recycled.
Description
Technical Field
The application relates to the field of high polymer material light weight, in particular to a thermoplastic polyurethane elastomer material, a thermoplastic polyurethane foaming material, and a preparation method and application thereof.
Background
Thermoplastic polyurethane elastomers (TPU) are semi-crystalline polymeric materials prepared by combining together diisocyanate, long chain diols and short chain diols in certain proportions on a belt system or in a reaction extruder apparatus.
The TPU has excellent mechanical properties, excellent heat resistance and chemical medium resistance and excellent wear resistance. And due to the diversity of raw material formulas, products with very wide hardness can be obtained by adjusting the proportion of each raw material.
The TPU resin is used as a matrix, and a large number of bubbles are filled in the TPU by an extrusion foaming or autoclave foaming method, so that the foaming TPU material can be obtained. These foamed TPU materials generally have a number of advantages including low density, thermal and acoustic insulation, high specific strength, high elasticity, and cushioning, and thus find wide application in packaging, industry, agriculture, transportation, military, aerospace, and commodity applications.
Thermoplastic polyurethane foam materials and methods for preparing the same have been disclosed in many patent documents, such as patent documents WO2007082838A1, WO2010136398A1, CN102276785A, and the like. When TPU is foamed, the foaming agent is generally in a molten state or a semi-molten state, and the foaming agent expands to form individual small bubbles in the TPU matrix, so that the TPU is required to have higher melt strength, on one hand, the phenomenon of hole breaking and hole stringing cannot occur, and on the other hand, a lighter material can be prepared.
The molecular chain segment of the TPU is of a linear structure, and basically no chemical crosslinking structure exists, so that the TPU can be recycled, but when the TPU is recycled, the TPU needs to be subjected to melting heating and pelleting again, so that the molecular chain segment of the TPU is shortened, the melt strength is lowered, the mechanical property is lowered, the recycled TPU cannot be subjected to foaming again, and the use in other fields is limited.
The patent specification with publication number of CN112029133A discloses a polyurethane foaming material and a preparation method thereof, wherein the polyurethane foaming material takes a thermoplastic polyurethane elastomer as a framework material, reacts with isocyanate-terminated polyurethane, water, a catalyst and optionally added functional auxiliary agents for foaming, and is prepared by an extrusion method. Among them, isocyanate-terminated polyurethanes are prepared by reacting a polymer polyol with a polyisocyanate in a stoichiometric excess, i.e., polyurethanes having isocyanate groups at both ends are used in the art of this patent.
Disclosure of Invention
In a first aspect, the present application provides a method for preparing a thermoplastic polyurethane elastomer material, comprising the steps of:
(1) In the presence or absence of a catalyst, mixing diisocyanate and dihydric alcohol according to a feeding ratio with an R value of 1.3-3.0, completely reacting, and then adding monohydroxy alcohol and/or monoamino amine compounds for continuous reaction to obtain an intermediate product of a prepolymer terminated by a single NCO group; the molar quantity of the monohydroxy alcohol and/or the monoaminoamine compound added is 40-60% of the molar quantity of the residual NCO groups after the complete reaction, preferably 50% of the molar quantity of the residual NCO groups after the complete reaction, which is beneficial to improving the ratio of the single NCO group end-capped prepolymer in the intermediate product, reducing the chemical crosslinking of the thermoplastic polyurethane elastomer material caused by adding the intermediate product and being beneficial to generating more branched structures of the thermoplastic polyurethane elastomer material after adding the intermediate product;
(2) The thermoplastic polyurethane elastomer and the intermediate product are put into a double-screw extruder for melt reaction and extrusion, so as to obtain the thermoplastic polyurethane elastomer material;
the thermoplastic polyurethane elastomer material contains a branched structure, and the branched structure is formed by connecting the prepolymer terminated by the single NCO group and the thermoplastic polyurethane elastomer through the reaction of NCO end groups and amide bonds.
In a second aspect, the present application provides a method for preparing a thermoplastic polyurethane foam material, comprising the steps of:
(1) In the presence or absence of a catalyst, mixing diisocyanate and dihydric alcohol according to a feeding ratio with an R value of 1.3-3.0, completely reacting, and then adding monohydroxy alcohol and/or monoamino amine compounds for continuous reaction to obtain an intermediate product of a prepolymer terminated by a single NCO group; the molar quantity of the monohydroxy alcohol and/or the monoaminoamine compound added is 40-60% of the molar quantity of the residual NCO groups after the complete reaction, preferably 50% of the molar quantity of the residual NCO groups after the complete reaction, which is beneficial to improving the ratio of the single NCO group end-capped prepolymer in the intermediate product, reducing the chemical crosslinking of the thermoplastic polyurethane elastomer material caused by adding the intermediate product and being beneficial to generating more branched structures of the thermoplastic polyurethane elastomer material after adding the intermediate product;
(2) Putting the thermoplastic polyurethane elastomer and the intermediate product into a double-screw extruder for melt reaction, extrusion and granulating to obtain thermoplastic polyurethane elastomer beads;
the thermoplastic polyurethane elastomer beads contain a branched structure, and the branched structure is formed by connecting the prepolymer terminated by the single NCO group with the thermoplastic polyurethane elastomer through the reaction of NCO end groups and amide bonds;
(3) And mixing the thermoplastic polyurethane elastomer beads, a physical foaming agent and water in a high-pressure container to form a suspension, heating and pressurizing the suspension, and finally decompressing to obtain the thermoplastic polyurethane foaming material.
According to the preparation method of the first or second aspect of the present application, in the step (1), the R value refers to the ratio of the molar equivalent of NCO groups in the diisocyanate to the molar equivalent of OH groups in the diol. An excessively large R value can result in a lower molecular weight of a single NCO group terminated prepolymer in the prepared intermediate product, which affects the melt strength of the thermoplastic polyurethane elastomer material and further affects the performance of the thermoplastic polyurethane foam material; too small an R value can result in a lower NCO group content of the single NCO group terminated prepolymer in the prepared intermediate product, which is detrimental to improving the melt strength of the thermoplastic polyurethane elastomer material and thus affecting the properties of the thermoplastic polyurethane foam.
According to the preparation method of the first or second aspect of the present application, in the step (1), the catalyst may adjust a reaction rate, and may be bis (2-morpholinoethyl) ether (DMDEE), or the like.
According to the preparation method of the first or second aspect of the present application, in the step (1), the diisocyanate may be at least one of toluene diisocyanate, diphenylmethane diisocyanate, 3-isocyanatomethylene-3, 5-trimethylcyclohexyl isocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, 1, 5-naphthalene diisocyanate, p-phenylene diisocyanate, 1, 4-cyclohexane diisocyanate, cyclohexane dimethylene diisocyanate, preferably at least one of diphenylmethane-4, 4' -diisocyanate, hexamethylene diisocyanate.
According to the preparation method of the first or second aspect of the present application, in the step (1), the diol may be a macromolecular diol having a number average molecular weight of 600 to 4000g/mol, and may be one or more selected from polyester polyol, polyether polyol, polycarbonate polyol, polycaprolactone polyol.
According to the preparation method of the first or second aspect of the present application, in the step (1), the temperature of the complete reaction may be 50 to 120 ℃, and the time of the complete reaction may be adjusted according to practical situations, and may be, for example, 10 to 180 minutes.
According to the preparation method of the first or second aspect of the present application, in the step (1), the monohydric alcohol may be at least one of diethylene glycol butyl ether, diethylene glycol monomethyl ether, 1, 4-butanediol monomethyl ether, and diethylene glycol monopentyl ether.
According to the preparation method of the first or second aspect of the present application, in the step (1), the monoamine compound may be at least one of octadecylamine, decamine, heptanamine, hexadecylamine, nonanamine, octamine, cycloheptylamine.
According to the preparation method of the first or second aspect of the present application, in the step (1), the temperature of the continuous reaction may be 70-140 ℃, the time of the continuous reaction may be adjusted according to the actual situation, and the goal may be to make the reaction proceed sufficiently, which may be 10-180min, for example. The fully reacted di-NCO-terminated substance in the step (1) has certain viscosity, and the reaction process is continued to properly raise the temperature, so that the NCO is fully reacted with the monohydroxy alcohol and/or the monoamine amine compound.
According to the preparation method of the first or second aspect of the present application, in the step (1), the number average molecular weight of the intermediate product may be 1000 to 30000g/mol.
According to the production method of the first or second aspect of the present application, in the step (2), the number average molecular weight of the thermoplastic polyurethane elastomer is preferably 30000 to 120000g/mol. In the case of a number average molecular weight of the thermoplastic polyurethane elastomer of more than 120000g/mol, the intermediate product is not essentially required to be added for branching, but can be used directly for foaming; the number average molecular weight of the thermoplastic polyurethane elastomer is too low, which requires that the molecular weight of the intermediate product is high and the addition amount is large, so that the reaction mixing effect in the twin-screw extruder is deteriorated.
According to the production method of the first or second aspect of the present application, in the step (2), the mass percentage of the intermediate product may be 1% to 30%, preferably 5% to 30%, based on 100% of the total mass of the thermoplastic polyurethane elastomer and the intermediate product, and a sufficient amount of branched structures may be ensured. The added intermediate products are too few, the branched chain structures in the thermoplastic polyurethane elastomer material are fewer, the melt strength is improved poorly, the situation of hole crossing and hole breaking of the foam holes of the plastic polyurethane foam material is easy to occur, and the corresponding rebound resilience performance and mechanical property are also poor.
According to the preparation method of the first or second aspect of the present application, in the step (2), the thermoplastic polyurethane elastomer may have a shore hardness of 40A to 80D.
According to the preparation method of the first or second aspect of the present application, in the step (2), the intermediate product may be metered into the twin-screw extruder after being heated by a hot melt adhesive machine.
According to the production method of the first or second aspect of the present application, in the step (2), the thermoplastic polyurethane elastomer may be fed into the twin-screw extruder using a weight loss scale.
According to the preparation method of the first or second aspect of the present application, in the step (2), the melt reaction extrusion temperature of the twin-screw extruder may be 100-220 ℃, the host rotation speed may be 100-300rpm, and the screw length-diameter ratio may be 30-56:1.
According to the preparation method of the second aspect of the present application, in the step (3), the physical foaming agent may be one or a mixture of several of nitrogen, carbon dioxide, butane, pentane and pentafluoropropane.
According to the preparation method of the second aspect of the present application, in the step (3), the heating temperature may be 80 to 180 ℃, and the pressurizing pressure may be 30 to 150bar.
In a third aspect, the present application provides a thermoplastic polyurethane elastomer material prepared according to the preparation method of the first aspect.
In a fourth aspect, the present application provides the use of a thermoplastic polyurethane elastomer material according to the third aspect for the preparation of a thermoplastic polyurethane foam.
In a fifth aspect, the present application provides a thermoplastic polyurethane foam prepared according to the preparation method of the second aspect.
In some embodiments, the thermoplastic polyurethane foamThe density of the material is 0.06-0.4g/cm 3 . Further, the density of the thermoplastic polyurethane foaming material is 0.06-0.3g/cm 3 。
In a sixth aspect, the present application provides the use of a thermoplastic polyurethane elastomer material according to the third aspect or a thermoplastic polyurethane foam material according to the fifth aspect in the field of shoe materials, for example in soles, insoles, uppers and the like.
The thermoplastic polyurethane foaming material has the characteristics of low density, uniform cell size, good rebound and excellent mechanical property, and the low molecular weight thermoplastic polyurethane elastomer can be used for foaming, so that the application scene of the low molecular weight thermoplastic polyurethane elastomer is widened.
Compared with the prior art, the application has the beneficial effects that:
according to the application, an intermediate product containing a single NCO group end-capped prepolymer is introduced, and an addition reaction is carried out between an NCO group in the single NCO group end-capped prepolymer and an amide bond of a thermoplastic polyurethane elastomer in a double-screw extruder, so that a molecular chain segment of the single NCO group end-capped prepolymer can be grafted onto a molecular chain segment of the thermoplastic polyurethane elastomer, further, the thermoplastic polyurethane can form a molecular chain segment with a branched chain structure, the melt strength of the low molecular weight thermoplastic polyurethane elastomer is improved, and further, the foamable property of the low molecular weight thermoplastic polyurethane elastomer is improved, and the prepared thermoplastic polyurethane foam material has lower density, more uniform foam cells, better rebound property and excellent mechanical property, is basically free from chemical crosslinking, and can be recycled.
Drawings
FIG. 1 is a photograph showing 50 times of transmission through a section microscope of a thermoplastic polyurethane foam prepared in example 1 of the present application.
FIG. 2 is a photograph showing 50 times of a cross-sectional microscope of a thermoplastic polyurethane foam prepared in comparative example 1 of the present application.
Detailed Description
The application will be further elucidated with reference to the drawings and to specific embodiments. It is to be understood that these examples are illustrative of the present application and are not intended to limit the scope of the present application.
Example 1
(1) Firstly, 47.55kg of diphenylmethane-4, 4' -diisocyanate and 100kg of polytetrahydrofuran dihydric alcohol with the number average molecular weight of 1000g/mol are added into a reaction kettle, the R value is 1.9, the temperature is raised to 100 ℃, and the reaction is carried out for 60min; after complete reaction, 14.60kg of diethylene glycol butyl ether was added to the reaction vessel, the temperature was continuously raised to 120℃and the reaction was continued for 60 minutes to prepare an intermediate product containing a single NCO group blocked prepolymer, the number average molecular weight of which was tested to be 4000g/mol. The diethylene glycol butyl ether of this example was added in an amount of 50% by mole based on the number of moles of NCO groups remaining after the complete reaction.
(2) 90 parts by weight of a thermoplastic polyurethane elastomer with the Shore hardness of 85A and the number average molecular weight of 70000g/mol and 10 parts by weight of the intermediate product containing the prepolymer terminated by the single NCO group in the step (1) are put into a double-screw extruder to be subjected to melt reaction extrusion, and the thermoplastic polyurethane elastomer beads with the branched structure are obtained through underwater pelletization of a die head. Wherein the length-diameter ratio of the screw of the double-screw extruder is 45:1, the temperature of the extruder is 160-190 ℃, and the rotating speed of the host machine is 200rpm.
(3) 10kg of the thermoplastic polyurethane elastomer beads with the branched chain structure in (2), 8kg of carbon dioxide and 20kg of water are put into a high-pressure container and stirred to form a suspension, then the suspension is heated to 118 ℃, the pressure is kept at 85bar, finally the pressure is quickly released, the materials are taken out to obtain a thermoplastic polyurethane foam material, and the cell size of the thermoplastic polyurethane foam material is tested by a microscope, see figure 1.
(4) The thermoplastic polyurethane foam obtained in the step (3) was filled into a mold having a length of 300 mm. Times.150 mm. Times.10 mm in thickness. The particles were bonded and molded by compressing them with water vapor at a pressure of 2bar by 10% in the thickness direction of the mold to finally obtain a molded foam, and then the molded foam was oven-dried at 70℃for 2 hours, and then left at room temperature for 2 hours, and the properties thereof were evaluated as shown in the data of Table 1.
Example 2
(1) Firstly, 36.45kg of hexamethylene diisocyanate and 100kg of polytetrahydrofuran dihydric alcohol with the number average molecular weight of 600g/mol are added into a reaction kettle, the R value is 1.3, the temperature is raised to 120 ℃, and the reaction is carried out for 20min; after complete reaction, 8.11kg of diethylene glycol butyl ether was added to the reaction vessel, the temperature was continuously raised to 140℃and reacted for 20 minutes to prepare an intermediate product containing a single NCO group blocked prepolymer, the number average molecular weight of which was tested to be 10000g/mol. The diethylene glycol butyl ether of this example was added in an amount of 50% by mole based on the number of moles of NCO groups remaining after the complete reaction.
(2) 70 parts by weight of a thermoplastic polyurethane elastomer with the Shore hardness of 55D and the number average molecular weight of 30000g/mol and 30 parts by weight of the intermediate product containing the single NCO group end-capped prepolymer in the step (1) are put into a double-screw extruder to be subjected to melt reaction extrusion, and the thermoplastic polyurethane elastomer beads with the branched structure are obtained through underwater pelletization of a die head. Wherein the length-diameter ratio of the screw of the double-screw extruder is 45:1, the temperature of the extruder is 180-220 ℃, and the rotating speed of the host machine is 300rpm.
(3) 10kg of thermoplastic polyurethane elastomer beads with branched structures in (2), 8kg of carbon dioxide and 20kg of water are put into a high-pressure container and stirred to form suspension, then the suspension is heated to 125 ℃, the pressure is kept at 90bar, finally the pressure is quickly released, the materials are taken out to obtain the thermoplastic polyurethane foam material, and the size of the foam material is tested by a microscope.
(4) The thermoplastic polyurethane foam obtained in the step (3) was filled into a mold having a length of 300 mm. Times.150 mm. Times.10 mm in thickness. The particles were cohesively molded by compressing with water vapor at a pressure of 2.3bar by 10% in the thickness direction of the mold to finally obtain a molded foam article, and then the molded foam article was oven-dried at 70℃for 2 hours, and then left at room temperature for 2 hours, and the properties thereof were evaluated as shown in the data of Table 1.
Example 3
(1) Firstly, adding 11.21kg of hexamethylene diisocyanate and 100kg of polytetramethylene glycol adipic acid dihydric alcohol with the number average molecular weight of 3000g/mol into a reaction kettle, heating to 70 ℃ and reacting for 180min, wherein the R value is 2; after complete reaction, 10.79kg of octadecylamine was added to the reaction vessel, the temperature was continuously raised to 90℃and reacted for 180 minutes to prepare an intermediate product containing a single NCO group blocked prepolymer, which was tested for a number average molecular weight of 3300g/mol. The molar amount of octadecylamine added in this example was 60% of the molar amount of NCO groups remaining after the complete reaction.
(2) 80 parts by weight of a thermoplastic polyurethane elastomer with the Shore hardness of 75D and the number average molecular weight of 50000g/mol and 20 parts by weight of the intermediate product containing the prepolymer terminated by the single NCO group in the step (1) are put into a double-screw extruder for melt reaction extrusion, and are pelletized under water through a die head, so that the thermoplastic polyurethane elastomer beads with the branched chain structure are obtained. Wherein the length-diameter ratio of the screw of the double-screw extruder is 45:1, the temperature of the extruder is 170-200 ℃, and the rotating speed of the host machine is 220rpm.
(3) 10kg of the thermoplastic polyurethane elastomer beads with the branched chain structure in the step (2), 8kg of carbon dioxide, 4kg of nitrogen and 20kg of water are put into a high-pressure container and stirred to form suspension, then the suspension is heated to 128 ℃, the pressure is kept at 150bar, finally the pressure is quickly released, the materials are taken out to obtain the thermoplastic polyurethane foam material, and the cell size of the thermoplastic polyurethane foam material is tested by a microscope.
(4) The thermoplastic polyurethane foam obtained in the step (3) was filled into a mold having a length of 300 mm. Times.150 mm. Times.10 mm in thickness. The particles were cohesively molded by compressing with water vapor at a pressure of 2.6bar by 10% in the thickness direction of the mold to finally obtain a molded foam article, and then the molded foam article was oven-dried at 70℃for 2 hours, and then left at room temperature for 2 hours, and the properties thereof were evaluated as shown in the data of Table 1.
Example 4
(1) Firstly, 75.07kg of diphenylmethane-4, 4' -diisocyanate and 100kg of polycaprolactone diol with the number average molecular weight of 1000g/mol are added into a reaction kettle, the R value is 3, the temperature is raised to 50 ℃, and the reaction is carried out for 120min; after complete reaction, 18.43kg of heptylamine was added to the reaction vessel, and the reaction was continued at 70℃for 120 minutes to prepare an intermediate product containing a single NCO group blocked prepolymer, which was tested for a number average molecular weight of 1100g/mol. The amount of heptylamine added in this example was 40% by mole of the number of NCO groups remaining after the complete reaction.
(2) 95 parts by weight of a thermoplastic polyurethane elastomer with the Shore hardness of 60A and the number average molecular weight of 120000g/mol and 5 parts by weight of the intermediate product containing the single NCO group end-capped prepolymer in the step (1) are put into a double screw extruder to be subjected to melt reaction extrusion, and are pelletized under water through a die head, so that the thermoplastic polyurethane elastomer beads with the branched chain structure are obtained. Wherein the length-diameter ratio of the screw of the double-screw extruder is 45:1, the temperature of the extruder is 100-130 ℃, and the rotating speed of the host machine is 100rpm.
(3) 10kg of the thermoplastic polyurethane elastomer beads with the branched chain structure in the step (2), 8kg of butane and 20kg of water are put into a high-pressure container and stirred to form suspension, then the suspension is heated to 108 ℃, the pressure is kept at 30bar, finally the pressure is quickly released, the materials are taken out to obtain the thermoplastic polyurethane foam material, and the cell size of the thermoplastic polyurethane foam material is tested by a microscope.
(4) The thermoplastic polyurethane foam obtained in the step (3) was filled into a mold having a length of 300 mm. Times.150 mm. Times.10 mm in thickness. The particles were cohesively molded by compressing with water vapor at a pressure of 1.3bar by 10% in the thickness direction of the mold to finally obtain a molded foam article, and then the molded foam article was oven-dried at 70℃for 2 hours, and then left at room temperature for 2 hours, and the properties thereof were evaluated as shown in the data of Table 1.
Comparative example 1
This comparative example 1 does not add an intermediate product containing a single NCO group terminated prepolymer, and comprises the following steps:
(1) 100 parts by weight of thermoplastic polyurethane elastomer with the Shore hardness of 85A and the number average molecular weight of 70000g/mol are put into a double-screw extruder to be melted, reacted and extruded, and the thermoplastic polyurethane elastomer beads are obtained through underwater pelleting of a die head. Wherein the length-diameter ratio of the screw of the double-screw extruder is 45:1, the temperature of the extruder is 160-190 ℃, and the rotating speed of the host machine is 200rpm.
(2) 10kg of the thermoplastic polyurethane elastomer beads in (1), 8kg of carbon dioxide and 20kg of water are put into a high-pressure container and stirred to form a suspension, then the suspension is heated to 110 ℃ (the foaming temperature is optimally adjusted according to the molecular weight of the thermoplastic polyurethane elastomer beads), the pressure is kept at 85bar, finally the pressure is quickly released, the materials are taken out to obtain a thermoplastic polyurethane foam material, and the size of the foam material is tested by a microscope, see figure 2.
(3) The thermoplastic polyurethane foam obtained in the step (2) was filled into a mold having a length of 300 mm. Times.150 mm. Times.10 mm in thickness. The particles were bonded and molded by compressing 10% with water vapor having a pressure of 1.6bar (the pressure is optimally adjusted according to the molecular weight of the thermoplastic polyurethane foam) in the thickness direction of the mold, and the molded foam was finally obtained, and then oven-dried at 70℃for 2 hours, and then left at room temperature for 2 hours, and the properties thereof were evaluated as shown in the data of Table 1.
Comparative example 2
The intermediate product of this comparative example 2 is free of NCO end-capping, and comprises the following specific steps:
(1) Firstly, 47.55kg of diphenylmethane-4, 4' -diisocyanate and 100kg of polytetrahydrofuran dihydric alcohol with the number average molecular weight of 1000g/mol are added into a reaction kettle, the R value is 1.9, the temperature is raised to 100 ℃, and the reaction is carried out for 60min; after complete reaction, 29.18kg of diethylene glycol butyl ether is added into a reaction kettle, the temperature is continuously raised to 120 ℃, the reaction is carried out for 60 minutes, an intermediate product without NCO end capping is prepared, and the number average molecular weight is 4200g/mol. The molar amount of diethylene glycol butyl ether added in this example was 100% of the molar amount of NCO groups remaining after the complete reaction.
(2) 90 parts by weight of the thermoplastic polyurethane elastomer with the Shore hardness of 85A and the molecular weight of 70000g/mol and 10 parts by weight of the NCO-free end-capped intermediate product in the step (1) are put into a double-screw extruder to be melted and extruded, and the thermoplastic polyurethane elastomer beads without branched structures are obtained through underwater pelletization of a die head. Wherein the length-diameter ratio of the screw of the double-screw extruder is 45:1, the temperature of the extruder is 160-190 ℃, and the rotating speed of the host machine is 200rpm.
(3) 10kg of thermoplastic polyurethane elastomer beads without branched structures in (2), 8kg of carbon dioxide and 20kg of water are put into a high-pressure container and stirred to form suspension, then the suspension is heated to 113 ℃ (the foaming temperature is optimally adjusted according to the actual condition of the thermoplastic polyurethane elastomer beads), the pressure is kept at 85bar, finally the pressure is relieved rapidly, the materials are taken out to obtain the thermoplastic polyurethane foam material, and the size of the foam material is tested by a microscope.
(4) The thermoplastic polyurethane foam obtained in the step (3) was filled into a mold having a length of 300 mm. Times.150 mm. Times.10 mm in thickness. The molded foam product was finally obtained by compressing the particles by 10% in the thickness direction of the mold using water vapor having a pressure of 1.8bar (the pressure is optimally adjusted according to the actual condition of the thermoplastic polyurethane foam material) and bonding the particles, and then oven-drying the molded foam product at 70℃for 2 hours, and then standing at room temperature for 2 hours, and the properties thereof were evaluated as shown in the data of Table 1.
Comparative example 3
In the comparative example 3, no monohydroxy alcohol and/or monoaminoamine compound are added, namely, the intermediate products are isocyanate double-end caps, and the specific steps are as follows:
(1) Firstly, 47.55kg of diphenylmethane-4, 4' -diisocyanate and 100kg of polytetrahydrofuran dihydric alcohol with the number average molecular weight of 1000g/mol are added into a reaction kettle, the R value is 1.9, the temperature is raised to 100 ℃, and the reaction is carried out for 60min; after complete reaction, a double NCO-terminated intermediate product was obtained, which was tested for a number average molecular weight of 3900g/mol.
(2) 90 parts by weight of the thermoplastic polyurethane elastomer with the Shore hardness of 85A and the molecular weight of 70000g/mol and 10 parts by weight of the NCO-free end-capped intermediate product in the step (1) are put into a double-screw extruder to be melted and extruded, and the thermoplastic polyurethane elastomer beads without branched structures are obtained through underwater pelletization of a die head. Wherein the length-diameter ratio of the screw of the double-screw extruder is 45:1, the temperature of the extruder is 160-190 ℃, and the rotating speed of the host machine is 200rpm.
(3) 10kg of thermoplastic polyurethane elastomer beads without branched structures in (2), 8kg of carbon dioxide and 20kg of water are put into a high-pressure container to be stirred to form suspension, then the suspension is heated to 128 ℃ (the foaming temperature is optimally regulated according to the actual condition of the thermoplastic polyurethane elastomer beads), the pressure is kept at 85bar, finally the pressure is relieved rapidly, the materials are taken out to obtain the thermoplastic polyurethane foam material, and the size of the foam material is tested by a microscope.
(4) The thermoplastic polyurethane foam obtained in the step (3) was filled into a mold having a length of 300 mm. Times.150 mm. Times.10 mm in thickness. The molded foam product was finally obtained by compressing the particles by 10% in the thickness direction of the mold using water vapor having a pressure of 2.6bar (the pressure is optimally adjusted according to the actual condition of the thermoplastic polyurethane foam material) and bonding the particles, and then oven-dried at 70℃for 2 hours, and then left at room temperature for 2 hours, and the properties thereof were evaluated as shown in the data of Table 1.
TABLE 1
As can be seen from the data in table 1 and the figures, the thermoplastic polyurethane foam of the present application and its articles have lower density, more uniform cells, better resilience and excellent mechanical properties. Comparative example 1 because of the low molecular weight and low melt viscosity of the thermoplastic polyurethane elastomer, the prepared thermoplastic polyurethane foam material has the conditions of hole crossing and hole breaking in the cells, and the corresponding rebound resilience performance and mechanical property are also poor. Comparative example 2 the same problem as in comparative example 1 was found due to the thermoplastic polyurethane elastomer which did not react to form a branched structure. The intermediate products added in the comparative example 3 are isocyanate double-ended, the thermoplastic polyurethane elastomer is subjected to chemical crosslinking, the melt strength of the thermoplastic polyurethane elastomer is improved, and the thermoplastic polyurethane foam material with lower density, more uniform foam cells and better rebound resilience performance can be prepared during foaming, but because of the existence of a chemical crosslinking structure, the bonding performance among the beads is deteriorated during the steam molding processing, so that the mechanical performance of the thermoplastic polyurethane foam material product is greatly reduced, and in addition, the prepared thermoplastic polyurethane foam material can not be recycled any more because more chemical crosslinking structures are generated.
Further, it is to be understood that various changes and modifications of the present application may be made by those skilled in the art after reading the above description of the application, and that such equivalents are intended to fall within the scope of the application as defined in the appended claims.
Claims (10)
1. A method for preparing a thermoplastic polyurethane elastomer material, comprising the steps of:
(1) In the presence or absence of a catalyst, mixing diisocyanate and dihydric alcohol according to a feeding ratio with an R value of 1.3-3.0, completely reacting, and then adding monohydroxy alcohol and/or monoamino amine compounds for continuous reaction to obtain an intermediate product of a prepolymer terminated by a single NCO group; the molar amount of the monohydroxy alcohol and/or the monoamine compound added is 40-60% of the molar amount of the residual NCO groups after the complete reaction, preferably 50% of the molar amount of the residual NCO groups after the complete reaction;
(2) The thermoplastic polyurethane elastomer and the intermediate product are put into a double-screw extruder for melt reaction and extrusion, so as to obtain the thermoplastic polyurethane elastomer material;
the thermoplastic polyurethane elastomer material contains a branched structure, and the branched structure is formed by connecting the prepolymer terminated by the single NCO group and the thermoplastic polyurethane elastomer through the reaction of NCO end groups and amide bonds.
2. The preparation method of the thermoplastic polyurethane foaming material is characterized by comprising the following steps:
(1) In the presence or absence of a catalyst, mixing diisocyanate and dihydric alcohol according to a feeding ratio with an R value of 1.3-3.0, completely reacting, and then adding monohydroxy alcohol and/or monoamino amine compounds for continuous reaction to obtain an intermediate product of a prepolymer terminated by a single NCO group; the molar amount of the monohydroxy alcohol and/or the monoamine compound added is 40-60% of the molar amount of the residual NCO groups after the complete reaction, preferably 50% of the molar amount of the residual NCO groups after the complete reaction;
(2) Putting the thermoplastic polyurethane elastomer and the intermediate product into a double-screw extruder for melt reaction, extrusion and granulating to obtain thermoplastic polyurethane elastomer beads;
the thermoplastic polyurethane elastomer beads contain a branched structure, and the branched structure is formed by connecting the prepolymer terminated by the single NCO group with the thermoplastic polyurethane elastomer through the reaction of NCO end groups and amide bonds;
(3) And mixing the thermoplastic polyurethane elastomer beads, a physical foaming agent and water in a high-pressure container to form a suspension, heating and pressurizing the suspension, and finally decompressing to obtain the thermoplastic polyurethane foaming material.
3. The method according to claim 1 or 2, wherein in step (1):
the catalyst is bis (2-morpholinoethyl) ether;
the diisocyanate is at least one of toluene diisocyanate, diphenylmethane diisocyanate, 3-isocyanatomethylene-3, 5-trimethylcyclohexyl isocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, 1, 5-naphthalene diisocyanate, p-phenylene diisocyanate, 1, 4-cyclohexane diisocyanate and cyclohexanedimethylene diisocyanate, preferably at least one of diphenylmethane-4, 4' -diisocyanate and hexamethylene diisocyanate;
the dihydric alcohol is macromolecular dihydric alcohol with the number average molecular weight of 600-4000g/mol, and is selected from one or more of polyester polyol, polyether polyol, polycarbonate polyol and polycaprolactone polyol;
the temperature of the complete reaction is 50-120 ℃;
the monohydroxy alcohol is at least one of diethylene glycol butyl ether, diethylene glycol monomethyl ether, 1, 4-butanediol monomethyl ether and diethylene glycol monopentyl ether;
the monoamine compound is at least one of octadecylamine, tetramine, heptylamine, hexadecylamine, nonylamine, octylamine and cycloheptylamine;
the temperature of the continuous reaction is 70-140 ℃;
the number average molecular weight of the intermediate product is 1000-30000g/mol.
4. The method according to claim 1 or 2, wherein in step (2):
the number average molecular weight of the thermoplastic polyurethane elastomer is 30000-120000g/mol;
the mass percentage of the intermediate product is 1-30%, preferably 5-30%, based on 100% of the total mass of the thermoplastic polyurethane elastomer and the intermediate product;
the Shore hardness of the thermoplastic polyurethane elastomer is 40A-80D;
heating the intermediate product by adopting a hot melt adhesive machine, and metering and putting the heated intermediate product into the double-screw extruder;
the thermoplastic polyurethane elastomer can be metered into the twin-screw extruder by adopting a weightlessness scale;
the melting reaction extrusion temperature of the double-screw extruder is 100-220 ℃, the rotation speed of a host machine is 100-300rpm, and the length-diameter ratio of a screw is 30-56:1.
5. The method according to claim 2, wherein in step (3):
the physical foaming agent is one or a mixture of more of nitrogen, carbon dioxide, butane, pentane and pentafluoropropane;
the heating temperature is 80-180 ℃, and the pressurizing pressure is 30-150bar.
6. The thermoplastic polyurethane elastomer material prepared by the preparation method according to claim 1.
7. Use of the thermoplastic polyurethane elastomer material according to claim 6 for the preparation of thermoplastic polyurethane foam materials.
8. The thermoplastic polyurethane foam material prepared by the preparation method of claim 2.
9. The thermoplastic polyurethane foam according to claim 8, wherein the density of the thermoplastic polyurethane foam is 0.06-0.4g/cm 3 Preferably 0.06-0.3g/cm 3 。
10. Use of the thermoplastic polyurethane elastomer material according to claim 6 or the thermoplastic polyurethane foam material according to claim 8 or 9 in the field of shoe materials.
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