CN106675000A - Polyurethane elastomer composition of solid nanoparticle-thickened paraffin aggregate and preparation method of polyurethane elastomer composition - Google Patents
Polyurethane elastomer composition of solid nanoparticle-thickened paraffin aggregate and preparation method of polyurethane elastomer composition Download PDFInfo
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- CN106675000A CN106675000A CN201710020766.XA CN201710020766A CN106675000A CN 106675000 A CN106675000 A CN 106675000A CN 201710020766 A CN201710020766 A CN 201710020766A CN 106675000 A CN106675000 A CN 106675000A
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- paraffin
- swarms
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- nano granule
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- 239000012188 paraffin wax Substances 0.000 title claims abstract description 154
- 239000007787 solid Substances 0.000 title claims abstract description 70
- 239000000203 mixture Substances 0.000 title claims abstract description 46
- 229920003225 polyurethane elastomer Polymers 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims abstract description 21
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 20
- 239000008187 granular material Substances 0.000 claims description 65
- 230000008719 thickening Effects 0.000 claims description 63
- 229920002635 polyurethane Polymers 0.000 claims description 37
- 239000004814 polyurethane Substances 0.000 claims description 37
- 238000003756 stirring Methods 0.000 claims description 31
- 238000006243 chemical reaction Methods 0.000 claims description 25
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 24
- 239000012948 isocyanate Substances 0.000 claims description 23
- -1 Polyoxypropylene Polymers 0.000 claims description 16
- 239000000654 additive Substances 0.000 claims description 16
- 230000000996 additive effect Effects 0.000 claims description 16
- 239000002199 base oil Substances 0.000 claims description 16
- 150000002513 isocyanates Chemical class 0.000 claims description 16
- 239000005543 nano-size silicon particle Substances 0.000 claims description 15
- 238000007711 solidification Methods 0.000 claims description 15
- 230000008023 solidification Effects 0.000 claims description 15
- 239000003381 stabilizer Substances 0.000 claims description 14
- 239000001993 wax Substances 0.000 claims description 14
- 239000004014 plasticizer Substances 0.000 claims description 12
- 238000010792 warming Methods 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 11
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 10
- LNDKRVOOYMEYTC-UHFFFAOYSA-N buta-1,3-dien-1-ol Chemical compound OC=CC=C LNDKRVOOYMEYTC-UHFFFAOYSA-N 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 239000003921 oil Substances 0.000 claims description 10
- 235000019198 oils Nutrition 0.000 claims description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 8
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 8
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 8
- 229920000570 polyether Polymers 0.000 claims description 8
- 229920005862 polyol Polymers 0.000 claims description 8
- 150000003077 polyols Chemical class 0.000 claims description 8
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 8
- GTACSIONMHMRPD-UHFFFAOYSA-N 2-[4-[2-(benzenesulfonamido)ethylsulfanyl]-2,6-difluorophenoxy]acetamide Chemical compound C1=C(F)C(OCC(=O)N)=C(F)C=C1SCCNS(=O)(=O)C1=CC=CC=C1 GTACSIONMHMRPD-UHFFFAOYSA-N 0.000 claims description 7
- 101710130081 Aspergillopepsin-1 Proteins 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 102100031007 Cytosolic non-specific dipeptidase Human genes 0.000 claims description 7
- 239000010439 graphite Substances 0.000 claims description 7
- 229910002804 graphite Inorganic materials 0.000 claims description 7
- 229920001451 polypropylene glycol Polymers 0.000 claims description 7
- 239000004970 Chain extender Substances 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 6
- 150000002009 diols Chemical class 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 230000002776 aggregation Effects 0.000 claims description 5
- 238000004220 aggregation Methods 0.000 claims description 5
- 150000001298 alcohols Chemical class 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- 235000012239 silicon dioxide Nutrition 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 4
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 claims description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 3
- 239000005977 Ethylene Substances 0.000 claims description 3
- SVYKKECYCPFKGB-UHFFFAOYSA-N N,N-dimethylcyclohexylamine Chemical compound CN(C)C1CCCCC1 SVYKKECYCPFKGB-UHFFFAOYSA-N 0.000 claims description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 3
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 3
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 claims description 3
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 claims description 3
- 230000006837 decompression Effects 0.000 claims description 3
- 239000012184 mineral wax Substances 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 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
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 2
- 230000006978 adaptation Effects 0.000 claims description 2
- ZFMQKOWCDKKBIF-UHFFFAOYSA-N bis(3,5-difluorophenyl)phosphane Chemical compound FC1=CC(F)=CC(PC=2C=C(F)C=C(F)C=2)=C1 ZFMQKOWCDKKBIF-UHFFFAOYSA-N 0.000 claims description 2
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 claims description 2
- 150000004985 diamines Chemical class 0.000 claims description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 2
- 229920001748 polybutylene Polymers 0.000 claims description 2
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 2
- 235000015112 vegetable and seed oil Nutrition 0.000 claims description 2
- 239000008158 vegetable oil Substances 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims 2
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 claims 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical group OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims 2
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims 1
- 229920000305 Nylon 6,10 Polymers 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 claims 1
- 238000013019 agitation Methods 0.000 claims 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims 1
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 claims 1
- 229960001826 dimethylphthalate Drugs 0.000 claims 1
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 claims 1
- 238000009413 insulation Methods 0.000 claims 1
- 239000012782 phase change material Substances 0.000 abstract description 6
- 230000008018 melting Effects 0.000 abstract description 5
- 238000002844 melting Methods 0.000 abstract description 5
- 239000012530 fluid Substances 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract 1
- 230000005012 migration Effects 0.000 description 13
- 238000013508 migration Methods 0.000 description 13
- MIMDHDXOBDPUQW-UHFFFAOYSA-N dioctyl decanedioate Chemical group CCCCCCCCOC(=O)CCCCCCCCC(=O)OCCCCCCCC MIMDHDXOBDPUQW-UHFFFAOYSA-N 0.000 description 11
- 229920001971 elastomer Polymers 0.000 description 11
- 239000000806 elastomer Substances 0.000 description 11
- 239000002245 particle Substances 0.000 description 6
- 238000007670 refining Methods 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 6
- 229920002121 Hydroxyl-terminated polybutadiene Polymers 0.000 description 5
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 5
- OLLFKUHHDPMQFR-UHFFFAOYSA-N dihydroxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](O)(O)C1=CC=CC=C1 OLLFKUHHDPMQFR-UHFFFAOYSA-N 0.000 description 5
- 239000002562 thickening agent Substances 0.000 description 5
- 230000008859 change Effects 0.000 description 4
- 238000004146 energy storage Methods 0.000 description 4
- 150000004767 nitrides Chemical class 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 229920001903 high density polyethylene Polymers 0.000 description 3
- 239000004700 high-density polyethylene Substances 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- NEHDRDVHPTWWFG-UHFFFAOYSA-N Dioctyl hexanedioate Chemical class CCCCCCCCOC(=O)CCCCC(=O)OCCCCCCCC NEHDRDVHPTWWFG-UHFFFAOYSA-N 0.000 description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 description 2
- 229920002367 Polyisobutene Polymers 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 2
- 238000005461 lubrication Methods 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 239000002480 mineral oil Substances 0.000 description 2
- 235000010446 mineral oil Nutrition 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920000193 polymethacrylate Polymers 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- AXKZIDYFAMKWSA-UHFFFAOYSA-N 1,6-dioxacyclododecane-7,12-dione Chemical compound O=C1CCCCC(=O)OCCCCO1 AXKZIDYFAMKWSA-UHFFFAOYSA-N 0.000 description 1
- PHZREHARUPHHCU-UHFFFAOYSA-N 4-methylbenzene-1,2,3-triol Chemical compound CC1=CC=C(O)C(O)=C1O PHZREHARUPHHCU-UHFFFAOYSA-N 0.000 description 1
- 229910017083 AlN Inorganic materials 0.000 description 1
- PIGFYZPCRLYGLF-UHFFFAOYSA-N Aluminum nitride Chemical compound [Al]#N PIGFYZPCRLYGLF-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical class OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical group OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229920000428 triblock copolymer Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
- C08L75/14—Polyurethanes having carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
- C08L75/06—Polyurethanes from polyesters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
- C08L75/08—Polyurethanes from polyethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The invention discloses a polyurethane elastomer composition of solid nanoparticle-thickened paraffin aggregate and a preparation method of the polyurethane elastomer composition. The polyurethane elastomer composition comprises 4.9%-89.99% of a polyurethane prepolymer, 0.01%-40% of a curing agent and 10%-80% of solid nanoparticle-thickened paraffin aggregate. The polyurethane prepolymer, the curing agent and the solid nanoparticle-thickened paraffin aggregate are mixed evenly and are cast, cured and molded to obtain the polyurethane elastomer composition after vacuum defoamation. The polyurethane elastomer composition has excellent properties of the polyurethane elastomer. The paraffin aggregate which is a fixed semi-fluid between a paraffin melting point and 280 DEG C is added, so that the polyurethane elastomer composition becomes a novel phase-change material which is capable of effectively preventing paraffin from flowing and significantly reducing paraffin removal and separation.
Description
Technical field
The present invention relates to contain the polyurethane elastomeric compositions of paraffin swarms body, more particularly it relates to a kind of solid
Polyurethane elastomeric compositions of paraffin swarms body of body nanometer granule thickening and preparation method thereof.
Background technology
Polyurethane elastomer is typical segmented copolymer, is made up of soft and hard segments two parts, and soft section provides elasticity, hard section
Play enhancing filling and crosslinked action, it is mechanical strength that the multiphase macromolecule has had, high rigidity and high percentage of elongation, excellent resistance to
Polishing machine, good oil resistant and resistant to many solvent nature, therefore, polyurethane elastomer is obtained in many fields of national economy
It is widely applied.
Paraffin as phase-change material of good performance, because its energy storage density is big, stable chemical nature, transition temperature range
It is high, nontoxic corrosion-free and without surfusion, it has also become the focus of the research of energy storage both at home and abroad.But melting point of paraffin wax is relatively low, in fusing point
Below easily with system produce separate and high temperature melting trickling deformation problem, limit its application.To solve the high temperature of paraffin
Trickling melts out problem, and people have done substantial amounts of work.(Preparation, the Thermal Properties and such as Cemil
Thermal Reliability of Form-Stable Paraffin/Polypropylene Composite for
Thermal Energy Storage[J].J Polym Environ,2009,17:254-258) melt paraffin is added dropwise to poly-
Again by the phase change composite material of the prepared paraffin/PP of mixed liquor room temperature placement 15d in the n-heptane solution of propylene (PP), it has good
Good chemical stability.(the Form-stable paraffin/high density polyethylene such as Ahmet
composites as solid–liquid phase change material for thermal energy storage:
preparation and thermal properties[J].Energy Conversion and Management,45:
2033-2042,2004) it is cooled back to room temperature to prepare answering for dimensionally stable by the paraffin and high density polyethylene (HDPE) of mixed melting
Close phase-change material.In phase-change material, paraffin is 77% in the largest percentage that molten state is not revealed.Qinglong
(the Systematic investigation on shape stability of high-efficiency SEBS/ such as Zhang
paraffin form-stable phase change materials[J].Solar Energy Materials&Solar
Cells,2013,118:54-60) using styrene-B- (ethylene-co-butylene)-block-styrene triblock copolymer
(SEBS) it is backing material, SEBS- paraffin gels is obtained together with paraffin.The gel has no any liquid and lets out higher than paraffin melting point
Leakage, keeps certain shape under room temperature, though it is that solid-state flexural deformation phenomenon occurs as temperature is increased to 120 DEG C of complex,
Further it is increased to 150 DEG C and is changed into fluid.Existing paraffin does not trickle technology by changing the state of wax or improving paraffin
Wax aggregation prepared by fusing point, though the performance of paraffin is improved to a certain extent, in some changeable environments or extreme
Under environment, it is using being still restricted.
The content of the invention
It is an object of the invention to further solving the trickling of paraffin high temperature melts out problem, and using paraffin and elastic polyurethane
Body synthesizes new material.
The paraffin swarms body that solid nano granule is thickened is applied to into polyurethane elastomer system, by paraffin swarms body
Stronger interaction replaces interaction weak between paraffin and binding agent between binding agent, and does not destroy bonding system polymerization
Process, has the preferable compatibility with bonding system, does not affect the mechanical property of polymer and the performance of paraffin swarms body.
To solve above-mentioned technical problem, one embodiment of the present invention is employed the following technical solutions：
A kind of polyurethane elastomeric compositions of the paraffin swarms body of solid nano granule thickening, it includes that polyurethane is pre-
The paraffin swarms body of aggressiveness, firming agent and solid nano granule thickening.
The polyurethane elastomeric compositions of the paraffin swarms body of above-mentioned solid nano granule thickening are with the polyurethane bullet
Elastomeric composition gross weight is 100% meter, and the weight of the base polyurethane prepolymer for use as accounts for 4.9%~89.99%, the firming agent
Weight accounts for 0.01%~40%, and the weight of the paraffin swarms body of the solid nano granule thickening accounts for 10%~80%.
In the polyurethane elastomeric compositions of the paraffin swarms body of above-mentioned solid nano granule thickening, the polyurethane is pre-
Aggressiveness is obtained with 30%~90% isocyanates reaction with the polyether polyol of 10%~70% by weight, Huo Zhesuo
It is with the PEPA and 70%~95% isocyanates reaction system of 5%~30% by weight to state base polyurethane prepolymer for use as
, or the base polyurethane prepolymer for use as be with by weight 30%~91.5% end hydroxy butadiene and 10%~
68.5% isocyanates reaction is obtained.
In the polyurethane elastomeric compositions of the paraffin swarms body of above-mentioned solid nano granule thickening, the polyether polyols
Alcohol is in Polyoxypropylene diol, polytetrahydrofuran diol, polyoxygenated butylene dihydroxylic alcohols, polypropylene oxide trihydroxylic alcohol
Plant or various；The PEPA is polyhexamethylene adipate glycol, polyadipate ethylene glycol-butyl glycol ester diol, gathers
One or more in tetramethylene adipate glycol；The isocyanates are toluene di-isocyanate(TDI), diphenyl methane two is different
One or more in cyanate, PPDI, hexamethylene diisocyanate, isophorone diisocyanate.Wherein,
The relative molecular mass of Polyoxypropylene diol is 1000~4000, preferably 2000~3000, polyoxybutylene dihydroxylic alcohols
Relative molecular mass is 1000~4000, preferably 2000~3000；The relative molecular mass of polyoxybutylene dihydroxylic alcohols is 1000
~4000, preferably 2000~3000；The relative molecular mass of polypropylene oxide trihydroxylic alcohol be 3000~8000, preferably 3000~
5000.Wherein, the relative molecular mass of 10PE27 glycol is 1000~3000, preferably 2000~3000；Gather oneself
The relative molecular mass of diacid ethylene glycol-butyl glycol ester diol is 1000~3000, preferably 2000~3000；Polyadipate fourth two
The relative molecular mass of alcohol esterdiol is 1000~3000, preferably 2000~3000.Because of PEPA and polyether polyol
Molecular weight can affect the hardness of elastomer, and molecular weight is not within the above range, it is impossible to which the hardness for ensureing elastomer meets the requirements, especially
It is that the hardness that can cause elastomer when molecular weight is too big becomes big, from the raw material of above-mentioned relative molecular mass, just be can guarantee that
The indexs such as the hardness and elasticity of elastomer.
In the polyurethane elastomeric compositions of the paraffin swarms body of above-mentioned solid nano granule thickening, the firming agent is
One or more in plasticizer, chain extender, catalyst；The plasticizer is di-n-octyl sebacate (DOS), phthalic acid two
One or more in methyl ester, dioctyl adipate, the chain extender is BDO, 1,6- hexanediol, trihydroxy methyl benzene
One or more in alkane, 3,5- dimethythiotoluene diamines；The catalyst is triethanolamine, dimethyl cyclohexyl amine, February
One or more in dilaurylate, ferric acetyl acetonade, acetylacetone,2,4-pentanedione (HAA).
A kind of embodiment of the invention, the firming agent include by weight 75%~95% plasticizer,
3.5%~15% chain extender and 1.5%~10% catalyst.
In the polyurethane elastomeric compositions of the paraffin swarms body of above-mentioned solid nano granule thickening, the solid nano
Property granule thickening paraffin swarms body be made of with paraffin, lube base oil, additive and solid nano granule as raw material
Silicon nitride thickening paraffin swarms body, silicon dioxide thickening paraffin swarms body, aluminium nitride thickening paraffin swarms body in
One or more；Counted with wax class aggregation gross weight as 100%, the wax accounts for the 5%~95% of gross weight, the lubrication oil base
Plinth oil accounts for the 0~70% of gross weight, and the additive accounts for the 0~10% of gross weight, and the solid nano granule accounts for gross weight
5%~30%.Preferably, the wax and the gross weight of lube base oil are 74%~94%, and additive is 0~8%, Gu
Body nanometer granule is 6%~20%.
Paraffin in the paraffin swarms body of above-mentioned solid nano granule thickening is in the mineral wax that fusing point is 50~70 DEG C
One or more, the lube base oil be mineral oil, artificial oil, vegetable oil in one or more, the additive
For one or more in structural stabilizing agent, viscosity index improver, graphite；The solid nano granule is nano silicon nitride
One or more in silicon, nano silicon, nano aluminum nitride.Wherein, structural stabilizing agent may be selected dibutyitin maleate,
One or more in diphenyl silanediol；Viscosity index improver may be selected polyisobutylene (PIB), polymethacrylates
(PMA), one or more in ethylene propylene copolymer (OCP)；Graphite may be selected native graphite, crystalline flake graphite, expanded graphite
In one or more.It is one kind or many in the mineral wax that fusing point is 50~70 DEG C that the preferred version of the present invention is the paraffin
Kind；The lube base oil is mineral oil；The additive is structural stabilizing agent and expanded graphite；The solid nano
Grain is nano-silicon nitride, nano silicon or nano aluminum nitride.
Present invention also offers the polyurethane elastomeric compositions of the paraffin swarms body of above-mentioned solid nano granule thickening
Preparation method, it is comprised the following steps：
(1) by any one in polyether polyol, PEPA, end hydroxy butadiene with isocyanates in proportion
After reacting 0.5~4h at 50~100 DEG C, base polyurethane prepolymer for use as is obtained；
Preferably, the base polyurethane prepolymer for use as be with the polyether polyol of 20%~70% by weight with 30%~
80% isocyanates reaction is obtained, or the base polyurethane prepolymer for use as is the polyester polyols with 10%~30% by weight
Alcohol and 70%~90% isocyanates reaction be obtained, or the base polyurethane prepolymer for use as be with by weight 40%~
91.5% end hydroxy butadiene and the reaction of 8.5%~60% isocyanates are obtained, and reaction condition is anti-at 50~100 DEG C
Answer 1~3h.
(2) the wax class aggregation of solid nano granule thickening is prepared：If additive include structural stabilizing agent, according to than
Example, first structural stabilizing agent is dissolved in lube base oil-wax mixture, be warming up to 70~100 DEG C of stirring reactions 5~
15min；Then solid nano granule is added under the conditions of high-speed stirred, temperature is adjusted to 80~120 DEG C of stirring reactions
20~40min；Then continue to be warming up to 180~220 DEG C, at this temperature high temperature refines 1~3h；Finally stop heating, if
Also there is rest additive in addition to structural stabilizing agent, then the material obtained by step (3) is cooled to into rest additive adaptation
Rest additive is added during temperature, after stirring, continues to be cooled to room temperature；
(3) weigh firming agent in proportion, base polyurethane prepolymer for use as obtained in step (1) and solid nano obtained in step (2)
Property granule thickening paraffin swarms body, first by solid nano granule be thickened paraffin swarms body be heated to 50~90 DEG C, then
Addition base polyurethane prepolymer for use as and firming agent, mix homogeneously, then under conditions of vacuum is 50~500Pa, decompression de-bubble 2~
10min, is finally warming up to 60~100 DEG C of 1~20h of solidification, obtains the paraffin swarms body of the solid nano granule thickening
Polyurethane elastomeric compositions；
Preferably, by weight, 8%~85% base polyurethane prepolymer for use as, 0.01%~30% firming agent and 10% are taken
~80% solid nano granule thickening paraffin swarms body, by first by solid nano granule be thickened paraffin swarms body add
Heat is subsequently adding base polyurethane prepolymer for use as and firming agent to 60~80 DEG C, and mix homogeneously is then 50~400Pa's in vacuum
Under the conditions of, reduce pressure 2~6min of de-bubble, is finally warming up to 60~80 DEG C of 3~10h of solidification, obtains the solid nano granule thick
The polyurethane elastomeric compositions of the paraffin swarms body of change.
In the preparation method of the polyurethane elastomeric compositions of the paraffin swarms body of above-mentioned solid nano granule thickening, when
When the isocyanates are toluene di-isocyanate(TDI) (TDI), after solidification process terminates, need for reactant to be placed on temperature for 40
3~8d is incubated in~80 DEG C of baking oven, 3~6d is incubated preferably in 60~80 DEG C of baking oven.
Technical scheme is further detailed below.
In the present invention, the paraffin swarms body of solid nano granule thickening is by paraffin and solid nano granule thickening agent
Interact, improve paraffin dropping point, wax class fusing point with the range of up to 280 DEG C as the semifluid shape not trickled, Er Qieyou
Effect reduces a point oil mass, efficiently solves the problems, such as that high temperature trickling of the paraffin in application process is melted out, and expands the use of paraffin
Scope.
By the way that the paraffin swarms body that solid nano granule is thickened is added in polyurethane elastomeric compositions, and close
The paraffin swarms body for adjusting the thickening of solid nano granule and the addition of polyurethane elastomer of reason, can make said composition simultaneous
The paraffin swarms body of tool solid nano granule thickening and the advantage of polyurethane elastomer, reduce the migration analysis of paraffin in elastomer
Go out.
The paraffin swarms body of the solid nano granule thickening that said composition mainly synthesizes early stage is added to polyurethane
In elastomer, in the case where ensureing not affecting the key property of polyurethane so as to which said composition had both possessed polyurethane elastomer
Premium properties can play the phase-change material that the high temperature that the paraffin swarms body of solid nano granule thickening has does not trickle simultaneously
Performance.The content of the test for completing herein is it is concluded that as follows：
1) the paraffin swarms body of solid nano granule thickening is stable in the building-up process of polyurethane elastomer, elastomer
Performance and outward appearance are good；
2) addition of the paraffin swarms body of solid nano granule thickening is controlled in integral polyurethane elastic composition
10%~50% (mass ratio), it is ensured that composition properties are excellent；
3) this elastic composition is compared with paraffin to be added to the compositionss obtained in polyurethane elastomer building-up process,
High temperature (70~200 DEG C) permeability amount is substantially reduced, and provable paraffin swarms body has played its excellent performance, makes paraffin in fusing point
It is relatively low with the endosmosis oil cut rate of up to high temperature range, and store a period of time elastomer in paraffin migration precipitation situation significantly change
It is kind；
4) when isocyanates are toluene di-isocyanate(TDI) (TDI), reaction needs constant temperature in an oven to be kept for one section after terminating
Time carries out curing molding, and because TDI is unstable at high temperature, more than 80 DEG C are easy for volatilizing or decompose, so solidification
Temperature is no more than 80 DEG C.
Compared with prior art, the present invention at least has the advantages that：The present invention is thickened solid nano granule
Paraffin swarms body be added in polyurethane elastomer, do not affect the synthesis of polyurethane elastomer, the paraffin swarms body and poly- ammonia
Ester elastomer system has the preferable compatibility, does not affect the mechanical property of polymer and the performance of paraffin swarms body, and significantly subtracts
Lack paraffin migration precipitation in the elastomer, expand the range of application of polyurethane elastomer.
Specific embodiment
In order that the objects, technical solutions and advantages of the present invention become more apparent, with reference to embodiments, to the present invention
It is further elaborated.It should be appreciated that specific embodiment described herein is not used to only to explain the present invention
Limit the present invention.
Embodiment 1
By 76.5g 50# heating paraffins to 100 DEG C, stirring 10min makes its dissolving complete.13.5g nano-silicon nitrides are existed
During (500 revs/min) are added to paraffin systems under the conditions of high-speed stirred, continue to stir 20min at 100 DEG C, then heat to 180
DEG C, high temperature refining 1.5h stops heating, and standing is cooled to room temperature, obtains the paraffin swarms body of nano silicon nitride silicon grain thickening.
16g end hydroxy butadienes HTPB and 8g plasticizer di-n-octyl sebacates (DOS) is weighed, stirs equal at 78 DEG C
It is even, 1.5g toluene di-isocyanate(TDI)s (TDI) are added thereto to, 10min is stirred and reacts, it is added thereto to be pre-heated to 60
DEG C 5.5g nano-silicon nitrides thickening paraffin swarms body (solid nano granule be thickened agent content 15%, paraffin:Lubrication oil base
Plinth oil is 1:0) stirring reaction 20min, is continued, under conditions of vacuum is 400Pa, reduce pressure de-bubble 6min；Then heat to
60 DEG C of solidification 8h, finally, are put into 60 DEG C in vacuum drying oven, react 4d, and taking-up is cooled to room temperature and obtains product.Store under room temperature
100d observes polyurethane elastomer surface paraffin migration situation and the paraffin to migrating out is weighed, and obtains data and is shown in Table 1.
Embodiment 2
38.5g 50# paraffin and 38.5g base oil 150BSM are heated to into 80 DEG C, 4.5g structural stabilizing agents are added thereto to
Diphenyl silanediol, stirring 10min makes its dissolving complete.By 15.0g nano-silicon nitrides (500 revs/min under the conditions of high-speed stirred
Clock) paraffin systems are added to, 120 DEG C are stirred and are warming up to, 3.5g expanded graphites are added, 40min is stirred, then heat up
To 220 DEG C, high temperature refining 2.5h stops heating, and standing is cooled to room temperature, obtains the paraffin swarms of nano silicon nitride silicon grain thickening
Body.
16.5g end hydroxy butadienes HTPB and 9g plasticizer di-n-octyl sebacates (DOS) is weighed, stirs equal at 85 DEG C
It is even, 2.0g toluene di-isocyanate(TDI)s (TDI) are added thereto to, add 1 drop dibutyl tin laurate (DBTL) and stir
And 10min is reacted, it is added thereto to be pre-heated to the paraffin swarms body (solid nano of 60 DEG C of 6g nano-silicon nitrides thickening
Grain thickening agent content 18.5%, paraffin:Lube base oil is 1:1), continue stirring reaction 20min, be 300Pa in vacuum
Under conditions of, reduce pressure de-bubble 5min；70 DEG C of solidification 6h are then heated to, finally, is put into 60 DEG C in vacuum drying oven, react 6d, taken
Go out to be cooled to room temperature and obtain product.100d observation polyurethane elastomer surface paraffin migration situations are stored under room temperature and to migrating out
Paraffin weighed, obtain data and be shown in Table 1.
Embodiment 3
By 87.0g 50# heating paraffins to 100 DEG C, stirring 10min makes its dissolving complete.By 13.0g nano silicons
During (600 revs/min) are added to paraffin systems under the conditions of high-speed stirred, 120 DEG C of stirring 30min are stirred and are warming up to,
200 DEG C are then heated to, high temperature refining 1.5h stops heating, and standing is cooled to room temperature, obtains nanometer silicon dioxide particle thickening
Paraffin swarms body.
17.0g end hydroxy butadienes HTPB and 8.5g plasticizer di-n-octyl sebacates (DOS) is weighed, is stirred at 80 DEG C
Uniformly, 1.8g toluene di-isocyanate(TDI)s (TDI) are added thereto to, 10min is stirred and react, are added thereto to be pre-heated to
(solid nano granule is thickened agent content 13%, paraffin to the paraffin swarms body of 80 DEG C of 6g nano silicons thickening:Lubricating oil
Base oil is 1:0) stirring reaction 20min, is continued, under conditions of vacuum is 200Pa, reduce pressure de-bubble 4min；Then heat up
To 70 DEG C of solidification 5h, finally, it is put into 55 DEG C in vacuum drying oven, reacts 7d, taking-up is cooled to room temperature and obtains product.Store under room temperature
100d observes polyurethane elastomer surface paraffin migration situation and the paraffin to migrating out is weighed, and obtains data and is shown in Table 1.
Embodiment 4
92.5g 50# paraffin and 5.0g structural stabilizing agent diphenyl silanediols are heated to into 100 DEG C, stirring 10min makes it
Dissolving is complete.By 8.0g nano silicons during (600 revs/min) are added to paraffin systems under the conditions of high-speed stirred, stirring
It is uniform and be warming up to 120 DEG C, 4.5g expanded graphites are added, 30min is stirred, 200 DEG C are then heated to, high temperature refining 1.8h stops
Only heat, standing is cooled to room temperature, obtain the paraffin swarms body of nanometer silicon dioxide particle thickening.
50g end hydroxy butadienes HTPB and 20g DOS are weighed, are stirred at 80 DEG C, be added thereto to 4g TDI,
The HAA solution of 3 drops 0.5% is added, 10min is stirred and react, is added thereto to be pre-heated to 90 DEG C of 15g nanometers two
(solid nano granule is thickened agent content 11.4%, paraffin to the paraffin swarms body of silicon oxide thickening:Lube base oil is 1:
0) stirring reaction 20min, is continued, under conditions of vacuum is 100Pa, reduce pressure de-bubble 3min；Then heat to 80 DEG C of solidifications
3h, finally, is put into 50 DEG C in vacuum drying oven, reacts 10d, and taking-up is cooled to room temperature and obtains product.100d observations are stored under room temperature
The polyurethane elastomer surface paraffin migration situation and paraffin to migrating out is weighed, obtains data and is shown in Table 1.
Embodiment 5
38.5g 50# paraffin and 38.5g base oil 150BSM are heated to into 80 DEG C, 4.5g structural stabilizing agents are added thereto to
Diphenyl silanediol, stirring 10min makes its dissolving complete.By 15.0g nano aluminum nitrides (500 revs/min under the conditions of high-speed stirred
Clock) paraffin systems are added to, 120 DEG C are stirred and are warming up to, 3.5g expanded graphites are added, 40min is stirred, then heat up
To 220 DEG C, high temperature refining 2.5h stops heating, and standing is cooled to room temperature, obtains the paraffin swarms of nano silicon nitride alumina particles thickening
Body.
16g Polyoxypropylene diols and 8g plasticizer phthalic acid dimethyl esters are weighed, is stirred at 85 DEG C, to
1.5g PPDIs are wherein added, 1g1 is added, 4- butanediols stir and react 10min, are added thereto to
It is pre-heated to paraffin swarms body (solid nano granule thickening agent content 18.5%, the stone of 50 DEG C of 6g nano aluminum nitrides thickening
Wax:Lube base oil is 1:1) stirring reaction 20min, is continued, under conditions of vacuum is 300Pa, reduce pressure de-bubble 5min；
70 DEG C of solidification 6h are then heated to, taking-up is cooled to room temperature and obtains product.100d observation elastic polyurethane body surfaces are stored under room temperature
The face paraffin migration situation and paraffin to migrating out is weighed, obtains data and is shown in Table 1.
Embodiment 6
The paraffin swarms preparation of nano silicon nitride alumina particles thickening is with embodiment 5.
50g polybutylene glyool adipates and 8g plasticizer dioctyl adipates are weighed, is stirred at 85 DEG C, to
2.1g methyl diphenylene diisocyanates are wherein added, 1 drop ferric acetyl acetonade is added, 10min, Xiang Qi is stirred and react
Middle addition is pre-heated to paraffin swarms body (the solid nano granule thickening agent content of 60 DEG C of 7g nano silicons thickening
18.5%, paraffin:Lube base oil is 1:1) stirring reaction 20min, is continued, under conditions of vacuum is 300Pa, decompression
De-bubble 5min；70 DEG C of solidification 6h are then heated to, taking-up is cooled to room temperature and obtains product.100d observation polyurethane is stored under room temperature
The surface of elastomer paraffin migration situation and paraffin to migrating out is weighed, obtains data and is shown in Table 1.
Embodiment 7
50g 50# paraffin and 2.5g structural stabilizing agent diphenyl silanediols are heated to into 100 DEG C, stirring 10min makes its molten
Solution is complete.By 8.0g nano silicons during (600 revs/min) are added to paraffin systems under the conditions of high-speed stirred, stirring is equal
It is even and be warming up to 120 DEG C, 1.5g expanded graphites are added, 30min is stirred, 195 DEG C are then heated to, high temperature refining 1.8h stops
Heating, standing is cooled to room temperature, obtains the paraffin swarms body of nanometer silicon dioxide particle thickening.
50g polyoxygenated butylene dihydroxylic alcohols and 10g DOS are weighed, is stirred at 80 DEG C, be added thereto to 4g six sub-
Methyl diisocyanate, adds the dimethyl cyclohexyl amine of 2 drops, stirs and react 10min, is added thereto to be pre-heated to
(solid nano granule is thickened agent content 12.9%, paraffin to the paraffin swarms body of 80 DEG C of 15g nano silicons thickening:Profit
Lubricant base oil is 1:0) stirring reaction 20min, is continued, under conditions of vacuum is 100Pa, reduce pressure de-bubble 5min；Then
80 DEG C of solidification 3h are warming up to, finally, are put into 50 DEG C in vacuum drying oven, react 10d, taking-up is cooled to room temperature and obtains product.Room temperature
Lower storage 100d observes polyurethane elastomer surface paraffin migration situation and the paraffin to migrating out is weighed, and obtains data and sees
Table 1.
Embodiment 8
The paraffin swarms preparation of nano silicon nitride alumina particles thickening is with embodiment 7.
45g polyhexamethylene adipate glycols and 7g plasticizer dioctyl adipates are weighed, is stirred at 85 DEG C, to
4g isophorone diisocyanate is wherein added, 1 drop triethanolamine is added, 10min is stirred and react, is added thereto to
It is pre-heated to paraffin swarms body (solid nano granule thickening agent content 12.9%, the stone of 50 DEG C of 7g nano aluminum nitrides thickening
Wax:Lube base oil is 1:0) stirring reaction 20min, is continued, under conditions of vacuum is 300Pa, reduce pressure de-bubble 5min；
70 DEG C of solidification 6h are then heated to, taking-up is cooled to room temperature and obtains product.100d observation elastic polyurethane body surfaces are stored under room temperature
The face paraffin migration situation and paraffin to migrating out is weighed, obtains data and is shown in Table 1.
Comparative example
16g end hydroxy butadienes HTPB and 8g DOS are weighed, is stirred at 82 DEG C, be added thereto to 1.5g
TDI, stirs and reacts 10min, is added thereto to 6g 50# paraffin, continues stirring reaction 20min, vacuum be 50~
Under conditions of 400Pa, reduce pressure 2~6min of de-bubble；60~80 DEG C of 3~10h of solidification are then heated to, finally, vacuum drying oven is put into
In 55 DEG C, react 7d, taking-up is cooled to room temperature and obtains product.Store 100d observation polyurethane elastomers surface paraffin under room temperature to move
Condition of the shifting one's love and paraffin to migration precipitation is weighed, obtains data and is shown in Table 1.
The each embodiment product analyses result of table 1
From table 1 it follows that the paraffin swarms that the solid nano granule that preparation method of the present invention is prepared is thickened
Its elasticity of the polyurethane elastomeric compositions of body is good, and the paraffin swarms body has the preferable compatibility with polyurethane elastomer system,
And observe the polyurethane elastomer polyurethane bullet is significantly reduced compared with paraffin refined wax polyurethane elastomer after storing a period of time
The migration precipitation of paraffin in gonosome.
Although reference be made herein to invention has been described for explanatory embodiment of the invention, however, it is to be understood that ability
Field technique personnel can be designed that a lot of other modification and embodiment, and these modifications and embodiment will fall public in the application
Within the spirit opened and spirit.
Claims (10)
1. polyurethane elastomeric compositions of the paraffin swarms body of a kind of solid nano granule thickening, it is characterised in that it includes
The paraffin swarms body of base polyurethane prepolymer for use as, firming agent and solid nano granule thickening.
2. polyurethane elastomeric compositions of the paraffin swarms body of solid nano granule according to claim 1 thickening,
It is characterized in that being counted as 100% with the polyurethane elastomeric compositions gross weight, the weight of the base polyurethane prepolymer for use as is accounted for
4.9%~89.99%, the weight of the firming agent accounts for 0.01%~40%, and the paraffin of the solid nano granule thickening gathers
The weight of collective accounts for 10%~80%.
3. polyurethane elastomeric compositions of the paraffin swarms body of solid nano granule according to claim 2 thickening,
It is characterized in that the base polyurethane prepolymer for use as is the polyether polyol and 30%~90% with 10%~70% by weight
Isocyanates reaction be obtained, or the base polyurethane prepolymer for use as be with by weight 5%~30% PEPA with
70%~95% isocyanates reaction is obtained, or the base polyurethane prepolymer for use as is with 30%~91.5% by weight
End hydroxy butadiene and the reaction of 8.5%~70% isocyanates are obtained.
4. polyurethane elastomeric compositions of the paraffin swarms body of solid nano granule according to claim 3 thickening,
It is characterized in that the polyether polyol be Polyoxypropylene diol, polytetrahydrofuran diol, polyoxygenated butylene dihydroxylic alcohols,
One or more in polypropylene oxide trihydroxylic alcohol；The PEPA is polyhexamethylene adipate glycol, polyadipate
One or more in ethylene glycol-butyl glycol ester diol, polybutylene glyool adipate；The isocyanates are that toluene two is different
Cyanate, methyl diphenylene diisocyanate, PPDI, hexamethylene diisocyanate, the isocyanide of isophorone two
One or more in acid esters.
5. polyurethane elastomeric compositions of the paraffin swarms body of solid nano granule according to claim 2 thickening,
It is characterized in that the firming agent is one or more in plasticizer, chain extender, catalyst；The plasticizer is decanedioic acid two
One or more in monooctyl ester, dimethyl phthalate, dioctyl adipate, the chain extender be BDO, 1,6-
One or more in hexanediol, trihydroxy methyl benzene alkane, 3,5- dimethythiotoluene diamines；The catalyst be triethanolamine,
One or more in dimethyl cyclohexyl amine, dibutyl tin laurate, ferric acetyl acetonade, acetylacetone,2,4-pentanedione.
6. polyurethane elastomeric compositions of the paraffin swarms body of solid nano granule according to claim 5 thickening,
It is characterized in that the firming agent include 75%~95% plasticizer by weight, 3.5%~15% chain extender and
1.5%~10% catalyst.
7. polyurethane elastomeric compositions of the paraffin swarms body of solid nano granule according to claim 2 thickening,
It is characterized in that the paraffin swarms body of the solid nano granule thickening is with paraffin, lube base oil, additive and consolidates
Body nanometer granule is the paraffin swarms body of silicon nitride thickening, the paraffin swarms body of silicon dioxide thickening, nitridation made by raw material
One or more in the paraffin swarms body of aluminum thickening；Counted with wax class aggregation gross weight as 100%, the wax accounts for gross weight
5%~95%, the lube base oil accounts for the 0~70% of gross weight, and the additive accounts for the 0~10% of gross weight, described
Solid nano granule accounts for the 5%~30% of gross weight.
8. polyurethane elastomeric compositions of the paraffin swarms body of solid nano granule according to claim 7 thickening,
It is characterized in that it is one or more in 50~70 DEG C of mineral wax that the paraffin is fusing point, the lube base oil is ore deposit
One or more in thing oil, artificial oil, vegetable oil, the additive is in structural stabilizing agent, viscosity index improver, graphite
One or more；The solid nano granule be the one kind in nano-silicon nitride, nano silicon, nano aluminum nitride or
It is various.
9. described in claim 1~8 any one solid nano granule thickening paraffin swarms body polyurethane elastomer
The preparation method of compositionss, it is characterised in that comprise the following steps：
(1) by any one in polyether polyol, PEPA, end hydroxy butadiene with isocyanates in proportion 50
React after 0.5~4h at~100 DEG C, obtain base polyurethane prepolymer for use as；
(2) the wax class aggregation of solid nano granule thickening is prepared：If additive includes structural stabilizing agent, proportionally, first
Structural stabilizing agent is dissolved in lube base oil-wax mixture, 70~100 DEG C of 5~15min of stirring reaction are warming up to；So
Solid nano granule is added under agitation afterwards, temperature is adjusted to 80~120 DEG C of 20~40min of stirring reaction；Connect
And be continuously heating to 180~220 DEG C, at this temperature high temperature refines 1~3h；Finally stop heating, if removing structural stabilizing agent
Outside also have rest additive, then by the material obtained by step (3) be cooled to rest additive adaptation temperature when add
Rest additive, after stirring, continues to be cooled to room temperature；
(3) weigh firming agent in proportion, base polyurethane prepolymer for use as obtained in step (1) and solid nano obtained in step (2)
The paraffin swarms body of grain thickening, is first heated to 50~90 DEG C by the paraffin swarms body that solid nano granule is thickened, and is subsequently adding
Base polyurethane prepolymer for use as and firming agent, mix homogeneously, then under conditions of vacuum is 50~500Pa, decompression de-bubble 2~
10min, is finally warming up to 60~100 DEG C of 1~20h of solidification, obtains the paraffin swarms body of the solid nano granule thickening
Polyurethane elastomeric compositions.
10. polyurethane elastomeric compositions of the paraffin swarms body of solid nano granule according to claim 9 thickening
Preparation method, it is characterised in that when the isocyanates are toluene di-isocyanate(TDI), after solidification process terminates, needing will be anti-
Thing is answered to be placed on 3~8d of insulation in the baking oven that temperature is 40~80 DEG C.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109776922A (en) * | 2019-01-29 | 2019-05-21 | 天津百恩威新材料科技有限公司 | A kind of wax/elastic resin composite grain, its preparation method and the application in production polishing wheel |
| CN109776922B (en) * | 2019-01-29 | 2021-05-14 | 天津百恩威新材料科技有限公司 | Wax/elastic resin compound particle, preparation method thereof and application thereof in manufacturing polishing wheel |
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| CN106675000B (en) | 2019-03-22 |
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