CN115947921A - Polyurethane and preparation method thereof - Google Patents
Polyurethane and preparation method thereof Download PDFInfo
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- CN115947921A CN115947921A CN202211736520.XA CN202211736520A CN115947921A CN 115947921 A CN115947921 A CN 115947921A CN 202211736520 A CN202211736520 A CN 202211736520A CN 115947921 A CN115947921 A CN 115947921A
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- 229920002635 polyurethane Polymers 0.000 title claims abstract description 109
- 239000004814 polyurethane Substances 0.000 title claims abstract description 109
- 238000002360 preparation method Methods 0.000 title claims abstract description 65
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical class O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 143
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims abstract description 29
- 239000000843 powder Substances 0.000 claims abstract description 27
- 239000003054 catalyst Substances 0.000 claims abstract description 23
- 239000004970 Chain extender Substances 0.000 claims abstract description 21
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229920005862 polyol Polymers 0.000 claims abstract description 19
- 150000003077 polyols Chemical class 0.000 claims abstract description 19
- 229920005906 polyester polyol Polymers 0.000 claims abstract description 16
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 84
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 39
- 239000000377 silicon dioxide Substances 0.000 claims description 39
- 239000002121 nanofiber Substances 0.000 claims description 29
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 29
- 229910021389 graphene Inorganic materials 0.000 claims description 27
- 229960000892 attapulgite Drugs 0.000 claims description 26
- 229910052625 palygorskite Inorganic materials 0.000 claims description 26
- 229920005610 lignin Polymers 0.000 claims description 23
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 15
- 229920000858 Cyclodextrin Polymers 0.000 claims description 14
- 239000001116 FEMA 4028 Substances 0.000 claims description 14
- WHGYBXFWUBPSRW-FOUAGVGXSA-N beta-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO WHGYBXFWUBPSRW-FOUAGVGXSA-N 0.000 claims description 14
- 235000011175 beta-cyclodextrine Nutrition 0.000 claims description 14
- 229960004853 betadex Drugs 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 150000002009 diols Chemical class 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- 229920000728 polyester Polymers 0.000 claims description 12
- 239000006185 dispersion Substances 0.000 claims description 11
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical group CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 7
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 6
- 239000002270 dispersing agent Substances 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 6
- 230000007935 neutral effect Effects 0.000 claims description 6
- 239000001361 adipic acid Substances 0.000 claims description 5
- 235000011037 adipic acid Nutrition 0.000 claims description 5
- 235000006408 oxalic acid Nutrition 0.000 claims description 5
- 229920005646 polycarboxylate Polymers 0.000 claims description 5
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 4
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 3
- 125000002723 alicyclic group Chemical group 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 238000007873 sieving Methods 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 3
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 3
- MRUXVMBOICABIU-UHFFFAOYSA-N [3,5-bis(methylsulfanyl)phenyl]methanediamine Chemical compound CSC1=CC(SC)=CC(C(N)N)=C1 MRUXVMBOICABIU-UHFFFAOYSA-N 0.000 claims description 2
- 229910052797 bismuth Inorganic materials 0.000 claims description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 2
- -1 dimethylaminoethyl Chemical group 0.000 claims description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 2
- 230000032683 aging Effects 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 13
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 230000009286 beneficial effect Effects 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000013013 elastic material Substances 0.000 description 4
- 230000002195 synergetic effect Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 230000006750 UV protection Effects 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000009471 action Effects 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002238 attenuated effect Effects 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 238000005728 strengthening Methods 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 239000002649 leather substitute Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
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- 229920002994 synthetic fiber Polymers 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The application belongs to the technical field of polyurethane, and particularly discloses polyurethane and a preparation method thereof. The polyurethane comprises 90-110 parts by weight of component A and 5-20 parts by weight of component B, wherein the component A is a polyurethane prepolymer; the component B comprises the following components in parts by weight: 30-50 parts of polyol, 1-6 parts of chain extender, 0.05-0.1 part of catalyst, 1-3 parts of nano titanium oxide powder and 1-2 parts of color paste; the component A is prepared by reacting 60-70 parts of polyester polyol, 10-20 parts of modified silica and 20-40 parts of diisocyanate at 65-75 ℃ for 2-3h to obtain a polyurethane prepolymer. The polyurethane prepared in the application has good mechanical property and mechanical stability, various performance parameters of the polyurethane are improved, and the tensile strength and the tearing strength are obviously improved.
Description
Technical Field
The application relates to the technical field of polyurethane, in particular to polyurethane and a preparation method thereof.
Background
Polyurethane is an organic polymer synthetic material, has good elasticity, wear resistance, low temperature resistance, oil resistance and tensile strength, is widely applied to the fields of buildings, households, daily necessities, traffic, household appliances and the like, and is commonly used for manufacturing trundles, sealing elements, sheaths of wires and cables, synthetic leather, shock absorption blocks and the like.
The sealing washer is sealed with an thing, makes it be difficult to open, plays the product of shock attenuation, give sound insulation, waterproof, thermal-insulated, fixed, effect such as dustproof, and the sealing washer of selling on the existing market is the rubber material mostly, and its mechanical properties, wearability and high pressure resistance can be relatively poor.
The polyurethane elastic material is popular because of good mechanical property, wear resistance and high pressure resistance, and has excellent ozone resistance and oil resistance, but after being placed for a long time, the polyurethane elastic material is aged, and then the mechanical property is attenuated.
Disclosure of Invention
In order to solve the problem that the polyurethane elastic material is aged after being placed for a long time, and then the mechanical property of the polyurethane elastic material is attenuated, the application provides polyurethane and a preparation method thereof.
The application provides polyurethane, which adopts the following technical scheme:
a polyurethane comprises 90-110 parts of component A and 5-20 parts of component B by weight, wherein the component A is a polyurethane prepolymer; the component B comprises the following components in parts by weight: 30-50 parts of polyol, 1-6 parts of chain extender, 0.05-0.1 part of catalyst, 1-3 parts of nano titanium oxide powder and 1-2 parts of color paste;
the component A is prepared by reacting 60-70 parts of polyester polyol, 10-20 parts of modified silica and 20-40 parts of diisocyanate at 65-75 ℃ for 2-3h to obtain a polyurethane prepolymer.
By adopting the technical scheme, the polyurethane prepolymer, the polyol, the chain extender, the catalyst and the nano titanium oxide powder are adopted to prepare the polyurethane, the obtained polyurethane has better mechanical property, heat resistance and wear resistance, various performance parameters of the polyurethane are improved, and the tensile strength and the tearing strength are obviously improved; meanwhile, the nano titanium oxide powder has higher light stability and chemical resistance, and can improve the ultraviolet resistance, mechanical property and mechanical stability of polyurethane.
The component A is prepared from polyester polyol, modified silica and diisocyanate, the modified silica has better dispersibility and can improve the dispersibility of polyurethane, and meanwhile, the modified silica can promote the polyurethane prepolymer and a chain extender to generate crosslinking to form a compact network structure and improve the mechanical property of the polyurethane; in addition, the modified silica has certain viscosity, improves the cohesiveness among all the components of the polyurethane, and further improves the wear resistance and the mechanical property of the polyurethane by matching with the nano titanium oxide powder.
Preferably, the polyester polyol is adipic acid polyester diol and/or phthalic anhydride polyester diol, and the number average molecular weight of the polyester polyol is 1000-2000.
By adopting the technical scheme, the polyester polyol molecules contain more polar ester groups, can form stronger intramolecular hydrogen bonds, and are mixed with diisocyanate and modified silica to obtain the polyurethane prepolymer with better structural strength and wear resistance, so that the prepared polyurethane has higher strength, wear resistance and mechanical properties in the subsequent polyurethane preparation process.
Preferably, the diisocyanate is toluene diisocyanate TDI-100 and/or toluene diisocyanate TDI-80.
By adopting the technical scheme, the diisocyanate is a raw material for manufacturing the polyurethane material, the special molecular structure of the isocyanate can endow the polyurethane with excellent water resistance and adhesion, and the subsequent preparation of the polyurethane has excellent application performance.
Preferably, the polyol in the component B is one or more of adipic acid polyester diol, phthalic anhydride polyester diol and alicyclic polyester diol, and the number average molecular weight is 1000-3000.
By adopting the technical scheme, the polyol is an important raw material in polyurethane preparation, the polyol has different structures, and has large influence on the performance of the polyurethane, and the polyurethane prepared from the polyol used in the application has good mechanical property, heat resistance and wear resistance.
Preferably, the chain extender is selected from one or more of 1, 4-butanediol, 1, 6-hexanediol, 3 '-dichloro-4, 4' -diaminodiphenylmethane and 3, 5-dimethylthiotoluenediamine; the catalyst is an organic bismuth catalyst or an amine catalyst.
By adopting the technical scheme, the chain extender is used for improving the mechanical property and the technological property of the polyurethane, and the chain extender reacts with the functional group on the polyurethane prepolymer chain to expand the molecular chain and increase the molecular weight, so that the length of the molecular chain is improved, the mechanical property of the polyurethane is improved, and the physical properties such as hardness, tearing strength, tensile strength and the like are improved; the catalyst promotes the efficiency of the reaction of the mixture, and the reactants react rapidly under the action of the catalyst, so that molecular chains grow rapidly and high molecular weight polymer materials are formed.
Preferably, the preparation method of the modified silica comprises the following steps:
s1, crushing, coarsely grinding and sieving silica to obtain silica powder, mixing the silica powder with oxalic acid, filtering, washing to be neutral, drying to obtain pretreated silica, dispersing the pretreated silica into an ethanol solution, and adding a polycarboxylate dispersant to obtain silica slurry;
s2, dispersing attapulgite in ethanol, adding modified graphene, and stirring at 80-90 ℃ for 2-3h to obtain a dispersion liquid; and S3, mixing the silica slurry obtained in the step S1, the dispersion liquid obtained in the step S2 and a silane coupling agent, and stirring at the temperature of 60-80 ℃ for 3-5 hours to obtain the modified silica.
By adopting the technical scheme, the silica is crushed and coarsely ground, part of the silica sheets are peeled off, pores are formed in the silica particles, the silica particles are in a loose state, the specific surface area of the silica is increased, oxalic acid is mixed with the silica powder, impurity minerals in the silica are removed, pore channels are dredged, the specific surface area of the silica is further increased, a polycarboxylate dispersant is added, the viscosity of a dispersion system is reduced under the action of the dispersant, the silica has good fluidity, the aggregation probability among the silica particles is reduced, and the system keeps the dispersion stability and the suspension effect.
The attapulgite is a water-containing magnesium-rich aluminosilicate clay mineral with a chain layered structure, has good mechanical stability, the modified graphene has good heat conductivity, mechanical property and corrosion resistance, the modified graphene, the attapulgite and the silica are mixed, the mechanical property of the system is enhanced by the attapulgite and the modified graphene, and meanwhile, the surface adhesion of the modified graphene can be improved by abundant active groups on the surface of the attapulgite, so that the modified graphene is loaded on the surfaces of the attapulgite and the silica, and the mechanical property and the heat resistance of the system are further improved; when the modified graphene is subsequently applied to polyurethane, the mechanical property and the thermal stability of the polyurethane are improved, meanwhile, the modified graphene, the attapulgite and the silica have good stability, the stability of the modified silica is further improved, and when the modified graphene is applied to the polyurethane, the stability of the polyurethane is further improved, so that the polyurethane still keeps good mechanical property, heat resistance and aging resistance after being placed for a long time.
The modified silica is applied to the polyurethane prepolymer, and has good dispersibility, so that the modified silica has good dispersing effect in the polyurethane prepolymer, the density, the strength and the tensile property of the polyurethane composition can be improved, the lamellar structure of the modified silica has good bonding force and compatibility with the polyurethane prepolymer, when a product is acted by an external force, the modified silica is not easy to separate from the prepolymer, cracks of the product are avoided, the effects of toughening, strengthening and improving the wear resistance and the heat resistance are achieved, and after the product is placed for a period of time, the product still has good mechanical properties.
Preferably, the mass ratio of the silica to the attapulgite to the modified graphene is 1.
By adopting the technical scheme, the mass ratio of the silica, the attapulgite and the modified graphene is limited, the modified silica with better comprehensive performance is obtained, the silica, the attapulgite and the modified graphene have a synergistic effect, the attapulgite increases the cohesiveness among the modified graphene, the silica and the attapulgite, and meanwhile, the modified silica has better dispersibility, and has better compatibility when being subsequently applied to polyurethane, so that the mechanical property and the heat resistance of the polyurethane are improved.
Preferably, the preparation method of the modified graphene comprises the following steps:
s1, dissolving polyacrylonitrile nano-fiber in NaOH solution with the mass concentration of 1-3%, soaking for 18-20h, washing with water, and drying to obtain pretreated polyacrylonitrile nano-fiber;
s2, dissolving beta-cyclodextrin in a NaOH solution with the mass concentration of 15-20%, stirring for 1-2 hours at the temperature of 85-95 ℃, then adding the pretreated polyacrylonitrile nanofiber obtained in the step S1, stirring for 2-3 hours, washing with water to be neutral, drying, and grinding to obtain a mixture;
and S3, dispersing the mixture obtained in the step S2 in water, adding graphene oxide and lignin, performing ultrasonic dispersion for 1-2 hours to obtain a dispersion liquid, and then drying to obtain the modified graphene.
By adopting the technical scheme, the polyacrylonitrile nanofibers are corroded by NaOH solution, so that holes are generated on the surfaces of the polyacrylonitrile nanofibers, the lignin has high mechanical strength, elasticity and fluidity, the lignin is loaded on the surfaces and in the holes of the polyacrylonitrile nanofibers, the mechanical property of polyurethane is improved, and meanwhile, the polyacrylonitrile nanofibers are loaded on the surfaces of graphene oxide, so that the mechanical property, the antibacterial property and the antistatic property of the graphene oxide are improved; in addition, the polyacrylonitrile nanofibers and the graphene oxide have a strong adsorption effect, the hydrophilicity of the graphene is improved, the graphene can be effectively promoted to be uniformly dispersed in water, and the agglomeration probability of the graphene oxide is reduced. The beta-cyclodextrin has certain viscosity, increases the cohesiveness among polyacrylonitrile nanofibers, lignin and graphene oxide, and is beneficial to increasing the stability of the structure of the modified graphene, meanwhile, the beta-cyclodextrin is mixed with a NaOH solution to stabilize the molecular structure of the beta-cyclodextrin, prevent the beta-cyclodextrin from being decomposed due to high-temperature heating, further facilitate subsequent mixing with the graphene oxide and the lignin, further facilitate stabilizing the mechanical property of the modified graphene, stabilize the structure of the modified graphene for a long time, and be beneficial to maintaining the mechanical property of the modified graphene.
Preferably, the mass ratio of the polyacrylonitrile nanofibers, the lignin and the graphene oxide is 1.2-0.5.
By adopting the technical scheme, the mass ratio of the polyacrylonitrile nanofiber, the beta-cyclodextrin and the graphene oxide is controlled, the modified graphene with better mechanical property is obtained, the polyacrylonitrile nanofiber, the lignin and the graphene oxide have a synergistic effect, the polyacrylonitrile nanofiber and the lignin increase the mechanical property of the graphene oxide, and meanwhile, the agglomeration probability of the graphene oxide is reduced, the subsequent structural stability of the modified graphene is facilitated, and the subsequent mechanical property and structural stability of polyurethane are further facilitated to be improved.
In a second aspect, the present application also provides a method for preparing polyurethane, comprising the steps of:
uniformly mixing polyol, a chain extender, color paste, nano titanium oxide powder and a catalyst to obtain a component B, mixing the component A and the component B, stirring for 30-60s at 60-80 ℃, pouring into a mold, curing for 4-5h at 25-35 ℃, and then post-vulcanizing for 8-10h at 80-90 ℃ to obtain the polyurethane.
In summary, the present application has the following beneficial effects:
1. according to the preparation method, polyurethane prepolymer, polyol, a chain extender, a catalyst and nano titanium oxide powder are adopted to prepare polyurethane, the obtained polyurethane has good mechanical property, heat resistance and wear resistance, various performance parameters of the polyurethane are improved, and the tensile strength and the tear strength are obviously improved; meanwhile, the nano titanium oxide powder has higher light stability and chemical resistance, and can improve the ultraviolet resistance, mechanical property and mechanical stability of polyurethane.
2. The component A is prepared from polyester polyol, modified silica and diisocyanate, the modified silica has good dispersibility and can improve the dispersibility of polyurethane, and the modified silica can promote polyurethane prepolymer and chain extender to generate crosslinking to form a compact network structure and improve the mechanical property of the polyurethane; in addition, the modified silica has certain viscosity, improves the cohesiveness among all the components of the polyurethane, and further improves the wear resistance and the mechanical property of the polyurethane by matching with the nano titanium oxide powder.
3. The modified silica is applied to the polyurethane prepolymer, because the modified silica has good dispersibility, the dispersing effect of the modified silica in the polyurethane prepolymer is better, the density of a polyurethane composition can be improved, the strength and the tensile property are improved, the lamellar structure of the modified silica has better bonding force and compatibility with the polyurethane prepolymer, when a product is acted by external force, the modified silica is not easy to separate from the prepolymer, the product is prevented from cracking, the effects of toughening, strengthening and improving the wear resistance and the heat resistance are achieved, and after the product is placed for a period of time, the product still has better mechanical properties.
Detailed Description
The present application will be described in further detail with reference to examples.
The raw materials used in the examples and comparative examples were all commercially available, wherein the chain extender was 1, 4-butanediol, the catalyst was dimethylaminoethyl, the polyester polyol was an adipic acid-based polyester diol, the polyol was an alicyclic polyester diol, and the diisocyanate was toluene diisocyanate TDI-100.
Preparation of modified silica
Preparation examples 1 to 1
The preparation method of the modified silica comprises the following steps:
s1, crushing, coarsely grinding and sieving 1kg of silica to obtain silica powder, mixing the silica powder with 10L of oxalic acid, filtering, washing to be neutral, drying to obtain pretreated silica, dispersing the pretreated silica into 15L of ethanol solution, and adding 0.5kg of polycarboxylate dispersant to obtain silica slurry;
s2, dispersing attapulgite in 10L of ethanol, adding modified graphene, and stirring at 85 ℃ for 3 hours to obtain a dispersion liquid; wherein the mass ratio of the silica, the attapulgite and the modified graphene is 1.7;
and S3, mixing the silica slurry obtained in the step S1, the dispersion liquid obtained in the step S2 and 0.2kg of silane coupling agent, and stirring at the temperature of 70 ℃ for 4 hours to obtain the modified silica.
Preparation examples 1 to 2
The difference from preparation example 1-1 is that step S1 was not carried out.
Preparation examples 1 to 3
The difference from preparation example 1-1 is that in step S2, attapulgite was not added.
Preparation examples 1 to 4
The difference from preparation example 1-1 is that in step S2, no modified graphene is added.
Preparation examples 1 to 5
The difference from preparation example 1-1 is that in step S2, the modified graphene was replaced with an equal amount of graphene.
Preparation examples 1 to 6
The difference from preparation example 1-1 is that the mass ratio of silica, attapulgite and modified graphene is 1.
Preparation examples 1 to 7
The difference from preparation example 1-1 is that the mass ratio of silica, attapulgite and modified graphene is 1.
Preparation examples 1 to 8
The difference from preparation example 1-1 is that the mass ratio of the silica, the attapulgite and the modified graphene is 1.
Preparation example of modified graphene
Preparation example 2-1
The preparation method of the modified graphene comprises the following steps:
s1, dissolving 1.2kg of polyacrylonitrile nano-fiber in 10L of NaOH solution with the mass concentration of 2%, soaking for 20h, washing with water, and drying to obtain pretreated polyacrylonitrile nano-fiber;
s2, dissolving 0.2kg of beta-cyclodextrin in 5L of NaOH solution with the mass concentration of 20%, stirring for 2 hours at the temperature of 90 ℃, then adding the pretreated polyacrylonitrile nanofiber obtained in the step S1, stirring for 3 hours, washing with water to be neutral, drying, and grinding to obtain a mixture;
s3, dispersing the mixture obtained in the step S2 in water, adding graphene oxide and lignin, performing ultrasonic dispersion for 2 hours to obtain a dispersion liquid, and then drying to obtain modified graphene; wherein the mass ratio of the polyacrylonitrile nano-fiber to the lignin to the graphene oxide is 1.35.
Preparation examples 2 to 2
The difference from preparation example 2-1 is that step S1 was not performed.
Preparation examples 2 to 3
The difference from preparation example 2-1 is that in step S2, no beta-cyclodextrin was added.
Preparation examples 2 to 4
The difference from preparation example 2-1 is that no lignin was added in step S3.
Preparation examples 2 to 5
The difference from preparation example 2-1 is that in step S2, the NaOH solution was replaced with an equal amount of deionized water.
Preparation examples 2 to 6
The difference from preparation example 2-1 is that the mass ratio of polyacrylonitrile nanofibers, lignin and graphene oxide is 1.
Preparation examples 2 to 7
The difference from preparation example 2-1 is that the mass ratio of polyacrylonitrile nanofibers, lignin and graphene oxide is 1.
Preparation examples 2 to 8
The difference from preparation example 2-1 is that the mass ratio of polyacrylonitrile nanofibers, lignin and graphene oxide is 1.
Examples
Example 1
A polyurethane comprises 100kg of component A and 12kg of component B by weight, wherein the component A is a polyurethane prepolymer; the component B comprises the following components: 40kg of polyol, 3kg of chain extender, 0.08kg of catalyst, 2kg of nano titanium oxide powder and 2kg of color paste;
the component A is prepared by reacting 65kg of polyester polyol, 15kg of modified silica and 30kg of diisocyanate at the temperature of 70 ℃ for 3 hours to obtain a polyurethane prepolymer.
The preparation method of the polyurethane comprises the following steps:
uniformly mixing polyol, a chain extender, color paste, nano titanium oxide powder and a catalyst to obtain a component B, mixing the component A and the component B, stirring for 45s at 70 ℃, pouring into a mold, curing for 5h at 30 ℃, and then post-vulcanizing for 9h at 85 ℃ to obtain the polyurethane.
Modified silica was prepared by using preparation example 1-1; the modified graphene was prepared according to preparation example 2-1.
Example 2
A polyurethane, differing from example 1 in that modified silica was prepared by using preparation examples 1 to 2.
Example 3
A polyurethane which differs from example 1 in that modified silica was prepared by the use of preparation examples 1 to 3.
Example 4
A polyurethane which differs from example 1 in that modified silica was prepared by the use of preparation examples 1 to 4.
Example 5
A polyurethane which differs from example 1 in that modified silica was prepared by the use of preparation examples 1 to 5.
Example 6
A polyurethane which differs from example 1 in that modified silica was prepared by the use of preparation examples 1 to 6.
Example 7
A polyurethane which differs from example 1 in that modified silica was prepared by the use of preparation examples 1 to 7.
Example 8
A polyurethane which differs from example 1 in that modified silica was prepared by the use of preparation examples 1 to 8.
Example 9
A polyurethane, which is different from example 1 in that modified graphene was prepared using preparation examples 2-2.
Example 10
A polyurethane, differing from example 1 in that modified graphene was prepared using preparation examples 2 to 3.
Example 11
A polyurethane, differing from example 1 in that modified graphene was prepared using preparation examples 2 to 4.
Example 12
A polyurethane, differing from example 1 in that modified graphene was prepared using preparation examples 2 to 5.
Example 13
A polyurethane, differing from example 1 in that modified graphene was prepared using preparation examples 2 to 6.
Example 14
A polyurethane, differing from example 1 in that modified graphene was prepared using preparation examples 2 to 7.
Example 15
A polyurethane, differing from example 1 in that modified graphene was prepared using preparation examples 2 to 8.
Example 16
A polyurethane which differs from example 1 in that it comprises 90kg of component a and 20kg of component B, component a being a polyurethane prepolymer; the component B comprises the following components: 30kg of polyol, 1kg of chain extender, 0.05kg of catalyst, 1kg of nano titanium oxide powder and 2kg of color paste;
the component A is prepared by reacting 60kg of polyester polyol, 10kg of modified silica and 20kg of diisocyanate at the temperature of 65 ℃ for 3h to obtain a polyurethane prepolymer.
Example 17
A polyurethane which differs from that of example 1 in comprising 110kg of component A and 5kg of component B, component A being a polyurethane prepolymer; the component B comprises the following components: 50kg of polyol, 6kg of chain extender, 0.1kg of catalyst, 3kg of nano titanium oxide powder and 1kg of color paste;
the component A is prepared by reacting 70kg of polyester polyol, 20kg of modified silica and 40kg of diisocyanate at the temperature of 75 ℃ for 2h to obtain a polyurethane prepolymer.
Comparative example
Comparative example 1
A polyurethane which differs from that of example 1 in that it comprises 80kg of component A and 30kg of component B, component A being a polyurethane prepolymer; the component B comprises the following components: 20kg of polyol, 0.5kg of chain extender, 0.3kg of catalyst, 5kg of nano titanium oxide powder and 0.5kg of color paste;
the component A is prepared by reacting 50kg of polyester polyol, 8kg of modified silica and 15kg of diisocyanate at the temperature of 55 ℃ for 1 hour to obtain a polyurethane prepolymer.
Comparative example 2
A polyurethane which differs from example 1 in that it comprises 120kg of component a and 3kg of component B, component a being a polyurethane prepolymer; the component B comprises the following components: 60kg of polyol, 8kg of chain extender, 0.02kg of catalyst, 0.5kg of nano titanium oxide powder and 3kg of color paste;
the component A is prepared by reacting 80kg of polyester polyol, 25kg of modified silica and 50kg of diisocyanate at the temperature of 85 ℃ for 4 hours to obtain a polyurethane prepolymer.
Comparative example 3
A polyurethane which differs from example 1 in that the modified silica is replaced by an equal amount of silica.
Comparative example 4
A polyurethane, differing from example 1 in that no nano titanium oxide powder was added.
Comparative example 5
A polyurethane, differing from example 1 in that no modified silica was added.
Performance test
The polyurethanes prepared in the examples and comparative examples were subjected to mechanical property tests.
Specifically, a polyurethane sample is placed in an aging oven at 150 ℃ for storage, taken out during testing, immediately moved into a high-temperature chamber at 150 ℃, stabilized for 30min and subjected to a high-temperature tensile test, and the tensile property is tested according to GB/T6344-1986 'determination of tensile strength and elongation at break of soft foam'; the tearing strength is implemented according to the GB10808-89 standard; the test results are shown in Table 1.
TABLE 1 testing of examples and comparative examples
As can be seen from Table 1, the polyurethanes prepared in examples 1,6 to 7, 13 to 14 and 16 to 17 of the present application have good mechanical properties and mechanical stability, the initial tensile strength reaches 55MPa, the elongation at break reaches 500%, the tear strength reaches 125KN/m, the polyurethane has better tensile strength even under high temperature (150 ℃) conditions, and the polyurethane still has better tensile strength after being subjected to high temperature aging treatment for 60 days, and the tensile strength reaches 50MPa.
The modified silica in example 2 was not treated with oxalic acid and no polycarboxylate dispersant was added. As shown in Table 1, compared with example 1, the initial tensile strength is 51MPa, the elongation at break is 550%, the tear strength is 105KN/m, the tensile strength is 45MPa after 2h of aging treatment at high temperature (150 ℃), and the tensile strength reaches 40MPa after 60d of high-temperature aging treatment, which indicates that the pretreatment of the modified silica obviously affects the mechanical properties of the subsequent polyurethane, and simultaneously obviously affects the aging resistance of the polyurethane, and the tensile property after the high-temperature treatment is obviously reduced.
Example 3 without adding attapulgite in the modified silica, it is seen from table 1 that, compared with example 1, the initial tensile strength is 42MPa, the tear strength is 85KN/m, the tensile strength is 37MPa after 2h of aging treatment at high temperature (150 ℃), and the tensile strength reaches 25MPa after 60d of high temperature aging treatment; example 4 without adding modified graphene to the modified silica, it is seen from table 1 that, compared to example 1, the initial tensile strength is 40MPa, the tear strength is 82KN/m, the tensile strength is 35MPa after 2h of aging treatment at high temperature (150 ℃), and the tensile strength reaches 22MPa after 60d of high temperature aging treatment; the mechanical properties and mechanical stability of the modified silica are influenced by the addition of the modified graphene and the attapulgite; in example 8, the mass ratio of the silica, the attapulgite and the modified graphene is changed, and compared with examples 1 and 3-4, the initial tensile strength, the tear strength and the tensile strength after the high-temperature aging treatment for 60d are obviously reduced compared with those of example 1, but are superior to those of example 3-4, which shows that the silica, the attapulgite and the modified graphene have a synergistic effect, the attapulgite increases the cohesiveness among the modified graphene, the silica and the attapulgite, and meanwhile, the modified silica has good dispersibility, and has good compatibility when being subsequently applied to polyurethane, so that the mechanical property of the polyurethane is improved.
Example 5 uses the same amount of graphene instead of modified graphene, and as seen from table 1, compared with example 1, the initial tensile strength, tear strength and tensile strength after high-temperature aging treatment for 60d are significantly reduced, which indicates that the modified graphene prepared by the present application has good mechanical properties, so that the modified graphene has good mechanical stability when applied to polyurethane.
In the embodiment 9, polyacrylonitrile nano-fibers in the modified graphene are not treated by a NaOH solution, and in the embodiment 12, β -cyclodextrin is also not treated by a NaOH solution, and as shown in table 1, compared with the embodiment 1, the initial tensile strength, the tear strength and the tensile strength after the high-temperature aging treatment for 60d are obviously reduced, which indicates that holes are formed on the surface of the polyacrylonitrile nano-fibers treated by the NaOH solution, which is beneficial to the subsequent loading of lignin, and further improves the mechanical properties of the modified graphene; the beta-cyclodextrin treated by the NaOH solution has a stable molecular structure, prevents the beta-cyclodextrin from being decomposed due to high-temperature heating, is favorable for being subsequently mixed with graphene oxide and lignin, and is favorable for stabilizing the mechanical property of the modified graphene.
In example 10, beta-cyclodextrin is not added to the modified graphene, and as shown in table 1, compared with example 1, the initial tensile strength is 48MPa, the tear strength is 101KN/m, the tensile strength is 47MPa after 2h of aging treatment at high temperature (150 ℃), and the tensile strength reaches 36MPa after 60d of high-temperature aging treatment; in example 11, no lignin is added to the modified graphene, and as shown in table 1, compared with example 1, the initial tensile strength is 46MPa, the tear strength is 98KN/m, the tensile strength is 45MPa after 2h of aging treatment at high temperature (150 ℃), and the tensile strength reaches 32MPa after 60d of high-temperature aging treatment; the method shows that the mechanical property of the modified graphene is obviously influenced without adding beta-cyclodextrin or lignin, so that the mechanical stability of subsequent polyurethane is influenced; in example 15, the mass ratio of the polyacrylonitrile nanofibers, the lignin and the graphene oxide is changed, compared with examples 1 and 10-11, the initial tensile strength, the tear strength and the tensile strength after the high-temperature aging treatment for 60d are obviously reduced compared with those of example 1, but are better than those of examples 10-11, which shows that the polyacrylonitrile nanofibers, the lignin and the graphene oxide have a synergistic effect, and the polyacrylonitrile nanofibers and the lignin increase the mechanical properties of the graphene oxide, thereby being beneficial to subsequently improving the mechanical properties and the structural stability of polyurethane.
Comparative examples 1-2 change the content of each raw material component in the polyurethane, and compared with examples 1 and 16-17, it is seen from table 1 that the initial tensile strength, the tear strength and the tensile strength after the high-temperature aging treatment for 60d are obviously reduced, which indicates that each raw material component of the polyurethane has better mechanical properties and mechanical stability in a certain range.
Comparative example 3 replaces modified silica with the same amount of silica, and as compared with example 1, as shown in table 1, the initial tensile strength, the tear strength and the tensile strength after the high-temperature aging treatment for 60 days are obviously reduced, which indicates that the modified silica prepared by the method has better mechanical properties and better mechanical stability when being applied to polyurethane.
Comparative example 4 without adding nano titanium oxide powder, compared to example 1, as shown in table 1, the initial tensile strength was 35MPa, the tear strength was 75KN/m, the tensile strength was 30MPa after aging treatment at high temperature (150 ℃) for 2 hours, and the tensile strength reached 18MPa after aging treatment at high temperature for 60 days; the nano titanium oxide powder has higher light stability and chemical resistance, and can improve the ultraviolet resistance, mechanical property and mechanical stability of polyurethane.
Comparative example 5 in which no modified silica was added, as compared with example 1, it is seen from Table 1 that the initial tensile strength was 3,0MPa, the tear strength was 70KN/m, the tensile strength was 25MPa after aging treatment at high temperature (150 ℃) for 2 hours, and the tensile strength reached 11MPa after aging treatment at high temperature for 60 days; the modified silica is shown to be capable of promoting the polyurethane prepolymer and the chain extender to generate crosslinking, so that a compact network structure is formed, the mechanical property of the polyurethane is improved, and the prepared polyurethane has a uniform and stable structure and better mechanical stability.
The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.
Claims (10)
1. The polyurethane is characterized by comprising 90-110 parts by weight of a component A and 5-20 parts by weight of a component B, wherein the component A is a polyurethane prepolymer; the component B comprises the following components in parts by weight: 30-50 parts of polyol, 1-6 parts of chain extender, 0.05-0.1 part of catalyst, 1-3 parts of nano titanium oxide powder and 1-2 parts of color paste;
the component A is prepared by reacting 60-70 parts of polyester polyol, 10-20 parts of modified silica and 20-40 parts of diisocyanate at 65-75 ℃ for 2-3h to obtain a polyurethane prepolymer.
2. The polyurethane of claim 1, wherein the polyester polyol is adipic acid polyester diol and/or phthalic anhydride polyester diol, and the number average molecular weight of the polyester polyol is 1000 to 2000.
3. A polyurethane according to claim 1 wherein the diisocyanate is toluene diisocyanate TDI-100 and/or toluene diisocyanate TDI-80.
4. The polyurethane of claim 1, wherein the polyol in the component B is one or more of adipic acid polyester diol, phthalic anhydride polyester diol and alicyclic polyester diol, and the number average molecular weight is 1000-3000.
5. The polyurethane of claim 1, wherein the chain extender is selected from one or more of 1, 4-butanediol, 1, 6-hexanediol, 3 '-dichloro-4, 4' -diaminodiphenylmethane and 3, 5-dimethylthiotoluenediamine; the catalyst is an organic bismuth catalyst or an amine catalyst (the amine catalyst is dimethylaminoethyl).
6. The polyurethane of claim 1, wherein the preparation method of the modified silica comprises the following steps:
s1, crushing, coarsely grinding and sieving silica to obtain silica powder, mixing the silica powder with oxalic acid, filtering, washing to be neutral, drying to obtain pretreated silica, dispersing the pretreated silica into an ethanol solution, and adding a polycarboxylate dispersant to obtain silica slurry;
s2, dispersing attapulgite in ethanol, adding modified graphene, and stirring at 80-90 ℃ for 2-3h to obtain a dispersion liquid;
and S3, mixing the silica slurry obtained in the step S1, the dispersion liquid obtained in the step S2 and a silane coupling agent, and stirring at the temperature of 60-80 ℃ for 3-5 hours to obtain the modified silica.
7. The polyurethane of claim 6, wherein the mass ratio of the silica to the attapulgite to the modified graphene is 1.
8. The polyurethane of claim 6, wherein the preparation method of the modified graphene comprises the following steps:
s1, dissolving polyacrylonitrile nano-fibers in a NaOH solution with the mass concentration of 1-3%, soaking for 18-20h, washing with water, and drying to obtain pretreated polyacrylonitrile nano-fibers;
s2, dissolving beta-cyclodextrin in a NaOH solution with the mass concentration of 15-20%, stirring for 1-2 hours at the temperature of 85-95 ℃, then adding the pretreated polyacrylonitrile nanofiber obtained in the step S1, stirring for 2-3 hours, washing with water to be neutral, drying, and grinding to obtain a mixture;
and S3, dispersing the mixture obtained in the step S2 in water, adding graphene oxide and lignin, performing ultrasonic dispersion for 1-2 hours to obtain a dispersion liquid, and then drying to obtain the modified graphene.
9. The polyurethane of claim 8, wherein the mass ratio of the polyacrylonitrile nanofibers, the lignin and the graphene oxide is 1.
10. A process for the preparation of a polyurethane according to any one of claims 1 to 9, comprising the steps of: uniformly mixing polyol, a chain extender, color paste, nano titanium oxide powder and a catalyst to obtain a component B, mixing the component A and the component B, stirring for 30-60s at 60-80 ℃, pouring into a mold, curing for 4-5h at 25-35 ℃, and then post-vulcanizing for 8-10h at 80-90 ℃ to obtain polyurethane.
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