CN114573784A - Lignin-based thermoplastic polyurethane elastomer material and preparation method thereof - Google Patents
Lignin-based thermoplastic polyurethane elastomer material and preparation method thereof Download PDFInfo
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- CN114573784A CN114573784A CN202210248228.7A CN202210248228A CN114573784A CN 114573784 A CN114573784 A CN 114573784A CN 202210248228 A CN202210248228 A CN 202210248228A CN 114573784 A CN114573784 A CN 114573784A
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- lignin
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- diisocyanate
- polyurethane elastomer
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- 229920005610 lignin Polymers 0.000 title claims abstract description 292
- 239000000463 material Substances 0.000 title claims abstract description 104
- 239000004433 Thermoplastic polyurethane Substances 0.000 title claims abstract description 43
- 229920001971 elastomer Polymers 0.000 title claims abstract description 43
- 239000000806 elastomer Substances 0.000 title claims abstract description 43
- 229920002803 thermoplastic polyurethane Polymers 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000002904 solvent Substances 0.000 claims abstract description 123
- 239000011259 mixed solution Substances 0.000 claims abstract description 73
- 239000003054 catalyst Substances 0.000 claims abstract description 69
- 239000006185 dispersion Substances 0.000 claims abstract description 58
- 239000007788 liquid Substances 0.000 claims abstract description 58
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000004970 Chain extender Substances 0.000 claims abstract description 30
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 25
- 238000003756 stirring Methods 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 13
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 72
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 46
- 229920000515 polycarbonate Polymers 0.000 claims description 41
- 239000004417 polycarbonate Substances 0.000 claims description 41
- 150000002009 diols Chemical class 0.000 claims description 38
- 238000005303 weighing Methods 0.000 claims description 38
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 36
- 239000000243 solution Substances 0.000 claims description 35
- 125000001931 aliphatic group Chemical group 0.000 claims description 32
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 27
- 229910052757 nitrogen Inorganic materials 0.000 claims description 23
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 21
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 11
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 9
- 229910052797 bismuth Inorganic materials 0.000 claims description 9
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 9
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 9
- VOXZDWNPVJITMN-ZBRFXRBCSA-N 17β-estradiol Chemical compound OC1=CC=C2[C@H]3CC[C@](C)([C@H](CC4)O)[C@@H]4[C@@H]3CCC2=C1 VOXZDWNPVJITMN-ZBRFXRBCSA-N 0.000 claims description 8
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 8
- 239000012974 tin catalyst Substances 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 claims description 6
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 6
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 5
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 5
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 5
- DRQFBCMQBWNTNV-UHFFFAOYSA-N 2-[bis(2-hydroxyethyl)amino]ethanol;trifluoroborane Chemical compound FB(F)F.OCCN(CCO)CCO DRQFBCMQBWNTNV-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 229920002635 polyurethane Polymers 0.000 abstract description 37
- 239000004814 polyurethane Substances 0.000 abstract description 37
- 239000011159 matrix material Substances 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 4
- 239000001257 hydrogen Substances 0.000 abstract description 4
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 4
- 238000000926 separation method Methods 0.000 abstract description 3
- 229920003225 polyurethane elastomer Polymers 0.000 description 36
- 238000006243 chemical reaction Methods 0.000 description 26
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical group CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 15
- 239000012975 dibutyltin dilaurate Substances 0.000 description 15
- 238000001816 cooling Methods 0.000 description 14
- 230000018044 dehydration Effects 0.000 description 14
- 238000006297 dehydration reaction Methods 0.000 description 14
- XLJMAIOERFSOGZ-UHFFFAOYSA-N anhydrous cyanic acid Natural products OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 description 10
- 239000012948 isocyanate Substances 0.000 description 10
- 150000002513 isocyanates Chemical class 0.000 description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N hydrochloric acid Substances Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 8
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 6
- 239000000945 filler Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 241000196324 Embryophyta Species 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 229920005862 polyol Polymers 0.000 description 3
- 150000003077 polyols Chemical class 0.000 description 3
- 239000002028 Biomass Substances 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- UQOQXWZPXFPRBR-UHFFFAOYSA-K bismuth dodecanoate Chemical group [Bi+3].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O UQOQXWZPXFPRBR-UHFFFAOYSA-K 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- XGZNHFPFJRZBBT-UHFFFAOYSA-N ethanol;titanium Chemical compound [Ti].CCO.CCO.CCO.CCO XGZNHFPFJRZBBT-UHFFFAOYSA-N 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium(IV) ethoxide Substances [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000002551 biofuel Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- SKKTUOZKZKCGTB-UHFFFAOYSA-N butyl carbamate Chemical compound CCCCOC(N)=O SKKTUOZKZKCGTB-UHFFFAOYSA-N 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 210000002421 cell wall Anatomy 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000005713 exacerbation Effects 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000010773 plant oil Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
- C08G18/6492—Lignin containing materials; Wood resins; Wood tars; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4081—Mixtures of compounds of group C08G18/64 with other macromolecular compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/44—Polycarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6648—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6651—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6648—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6655—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3271
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
- C08H6/00—Macromolecular compounds derived from lignin, e.g. tannins, humic acids
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- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
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- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Biochemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a lignin-based thermoplastic polyurethane elastomer material and a preparation method thereof, diisocyanate is dissolved in a solvent, then added into dehydrated macromolecular dihydric alcohol, and reacted for 1-2h at 60-100 ℃ to obtain a mixed solution A; adding a catalyst into the mixed solution A, reacting for 1-2h at 60-85 ℃, then adding a chain extender, and reacting for 4-8 h to obtain a mixed solution B; and adding the lignin dispersion liquid into the mixed solution B, and uniformly stirring to obtain the lignin-based thermoplastic polyurethane elastomer material. According to the invention, lignin is introduced into polyurethane, the lignin forms a microphase separation structure in a polyurethane matrix, and an interface dynamic hydrogen bond effect is formed between the lignin and a polyurethane chain segment, so that the polyurethane chain segment is easy to be oriented and crystallized in a stretching process, and the strength of the material is greatly improved.
Description
Technical Field
The invention belongs to the field of elastomer materials, and particularly relates to a lignin-based thermoplastic polyurethane elastomer material and a preparation method thereof.
Background
Polyurethane is a block copolymer composed of polyisocyanate and polyol, and is widely used in many fields such as foam, elastomer, paint, adhesive and the like because of its unlimited potential in performance. The magical properties of polyurethanes result from their diverse raw materials, highly flexible formulation ingredients, and widely adjustable molecular structures. However, most raw materials for synthesizing polyurethane come from non-renewable petroleum resources, and the search for alternative biomass resources to synthesize polyurethane has become a hot spot for pursuing green polyurethane materials. Many researchers have used castor oil, soybean oil based polyols instead of petroleum based polyols to make polyurethanes. Plant oil yields are limited and relatively costly, and research into the production of bio-based chemicals from crops may contribute to an exacerbation of the global food crisis. Therefore, it is important to find other non-food and cheap biomass resources to synthesize polyurethane.
Lignin is the most abundant natural aromatic polymer in plant cell walls and accounts for 18% -35% of wood. Global plants produce 5-36 million tons of lignin per year. Lignin is a valuable by-product of the paper and pulp industry, which produces over 5000 million tons of lignin per year, but most of the lignin is consumed by the plant as a low cost fuel today. In addition to the traditional paper and pulp industries, the biofuel industry also produces lignin as a byproduct. Therefore, from an environmental and economic point of view, exploring a versatile strategic way of utilizing lignin is a necessary choice to achieve sustainable development and competitive industrial goals. Since lignin contains a large number of hydroxyl groups (phenolic and aliphatic), one of the most widely studied strategies is to use the hydroxyl groups in lignin as reaction sites. However, the structure and function of lignin fluctuates due to its source and processing conditions, which in turn largely affects the properties of the final polyurethane. Furthermore, these structural and functional variations may lead to different end products, which are unacceptable commercial polymers today, require high purity raw materials, have significant and repeatable reactivity. The addition of lignin as a non-covalent filler to a polyurethane matrix may be a more efficient and economically viable process. Unfortunately, the large number of aromatic and aliphatic hydroxyl groups in lignin makes it highly polar and insoluble in non-polar polyurethanes. Therefore, aiming at the problem, the invention introduces a large amount of monoisocyanate aliphatic chain segments on the lignin to modify the lignin so as to reduce the polarity of the lignin, and the modified lignin has good dispersibility in the polyurethane elastomer, thereby improving the use amount of the lignin in the polyurethane.
Disclosure of Invention
Aiming at the defect that the existing lignin material is not uniformly dispersed in polyurethane, the invention aims to provide the lignin-based thermoplastic polyurethane elastomer material, so that the lignin is well dispersed in the polyurethane material; meanwhile, the invention also provides a preparation method of the compound, which is simple, easy to operate, low in cost, scientific and reasonable.
The invention also aims to provide a preparation method of the lignin-based thermoplastic polyurethane elastomer material, which aims to improve the breaking strength and the elongation of the polyurethane elastomer. The lignin is introduced into the polyurethane, the lignin forms a microphase separation structure in a polyurethane matrix, and an interface dynamic hydrogen bond effect is formed between the lignin and a polyurethane chain segment, and the factors can promote the polyurethane chain segment to be more easily subjected to oriented crystallization in the stretching process, so that the strength of the material is greatly improved;
the above object of the present invention is achieved by the following technical solutions:
a lignin-based thermoplastic polyurethane elastomer material comprises the following raw materials in parts by weight:
further, the macromolecular dihydric alcohol is polycarbonate dihydric alcohol; the number average molecular weight of the macrodiol is 500-.
Further, the diisocyanate is one or more of diphenylmethane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, toluene diisocyanate and hexamethylene diisocyanate in any proportion.
Further, the modified lignin is prepared by the following processes:
a) adding a lignin material into a solvent, and then carrying out ultrasonic dispersion to obtain a lignin dispersion liquid;
b) under the condition of introducing nitrogen, dissolving aliphatic monoisocyanate in a solvent, and then adding the solvent into the lignin dispersion liquid to obtain a solution B;
c) adding a catalyst into the solution B, and then reacting for 3-8h at 60-85 ℃; and centrifuging, washing and drying to obtain the modified lignin.
Further, the solvent in the step a) is tetrahydrofuran; the dosage ratio of the lignin material to the solvent is 0.1-1 g: 3-30 mL;
in the step b), the solvent is tetrahydrofuran, the aliphatic monoisocyanate is methyl diisocyanate or diphenylmethane diisocyanate, and the dosage ratio of the aliphatic monoisocyanate to the solvent is 0.1-1 g: 0.3-3 mL;
the using amount of the catalyst in the step c) is 0.5 percent of the total mass of the lignin and the aliphatic monoisocyanate; the catalyst is organic bismuth catalyst, organic tin catalyst or titanate catalyst.
A preparation method of a lignin-based thermoplastic polyurethane elastomer material comprises the following steps:
1) weighing 58-73 parts of macromolecular dihydric alcohol, 11-17 parts of diisocyanate, 0.04-2.5 parts of lignin or modified lignin, 4-7 parts of chain extender and 0.1-0.5 part of catalyst according to parts by weight;
adding lignin or modified lignin into a solvent, and then carrying out ultrasonic dispersion to obtain a lignin dispersion liquid;
2) dissolving diisocyanate in a solvent under the condition of introducing nitrogen, then adding the diisocyanate into the dehydrated macromolecular dihydric alcohol, and reacting for 1-2h at the temperature of 60-100 ℃ to obtain a mixed solution A;
3) adding a catalyst into the mixed solution A, reacting for 1-2h at 60-85 ℃, then adding a chain extender, and reacting for 4-8 h to obtain a mixed solution B;
adding the lignin dispersion liquid obtained in the step 1) into the mixed solution B, and uniformly stirring to obtain the lignin-based thermoplastic polyurethane elastomer material.
Further, the macrodiol is polycarbonate diol; the number average molecular weight of the macrodiol is 500-;
the diisocyanate is one or more than two of diphenylmethane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, toluene diisocyanate and hexamethylene diisocyanate which are mixed in any proportion.
Further, the modified lignin is prepared by the following processes:
a) adding a lignin material into a solvent, and then performing ultrasonic dispersion to obtain a lignin dispersion liquid, namely a solution A, wherein the ratio of the unmodified lignin material to the solvent is 0.1-1 g: 3-30 mL;
b) under the condition of introducing nitrogen, dissolving aliphatic monoisocyanate in a solvent, and then adding the solution into the solution A to obtain a solution B;
c) adding a catalyst into the solution B, and then reacting for 3-8h at 60-85 ℃; and centrifuging, washing and drying to obtain the modified lignin.
Further, the solvent in the step a) is tetrahydrofuran; the dosage ratio of the unmodified lignin material to the solvent is 0.1-1 g: 3-30 mL;
in the step b), the solvent is tetrahydrofuran, the aliphatic monoisocyanate is methyl diisocyanate or diphenylmethane diisocyanate, and the dosage ratio of the aliphatic monoisocyanate to the solvent is 0.1-1 g: 0.3-3 mL;
the using amount of the catalyst in the step c) is 0.5 percent of the total mass of the lignin and the aliphatic monoisocyanate; the catalyst is organic bismuth catalyst, organic tin catalyst or titanate catalyst.
Further, the solvent in the step 1) is tetrahydrofuran; the ratio of the lignin or the modified lignin to the solvent is 0.1-1 g: 3-30 mL;
in the step 2), the solvent is tetrahydrofuran, and the dosage ratio of diisocyanate to the solvent is 0.1-1 g: 0.3-3 mL;
the catalyst in the step 3) is an organic bismuth catalyst, an organic tin catalyst or a titanate catalyst; the chain extender is one or more than two of 1, 4-butanediol, 1, 6-hexanediamine, trimethylolpropane, triethanolamine and boron trifluoride triethanolamine mixed in any proportion.
Compared with the prior art, the lignin is chemically modified to synthesize the composite material with uniform distribution. To improve the interfacial interaction between the bio-based polyurethane and the lignin filler. In order to increase the breaking strength and elongation of the polyurethane elastomer. The lignin is introduced into the polyurethane, the lignin forms a microphase separation structure in a polyurethane matrix, and an interface dynamic hydrogen bond effect is formed between the lignin and a polyurethane chain segment, and the factors can promote the polyurethane chain segment to be more easily subjected to oriented crystallization in the stretching process, so that the strength of the material is greatly improved. The present invention is a potentially more efficient and economically viable process for incorporating lignin as a non-covalent filler into the TPU matrix.
Drawings
FIG. 1 is an infrared spectrum of unmodified lignin polyurethane prepared in example;
FIG. 2 is a graph of breaking strength versus elongation at break for polyurethane elastomers of varying lignin content obtained in the examples;
FIG. 3 is an infrared spectrum of monoisocyanate modified lignin;
FIG. 4 is a diagram of the mechanical properties of a monoisocyanate modified lignin-based polyurethane elastomer;
FIG. 5 is an electron micrograph of modified and unmodified lignin: left-unmodified; right- -monoisocyanate modified lignin. The modified lignin polyurethane elastomer is characterized by comprising the following components, by weight, (a) 5% of an unmodified lignin polyurethane elastomer is added, (b) 5% of a monoisocyanate modified lignin polyurethane elastomer is added, (c) 10% of an unmodified lignin polyurethane elastomer is added, (d) 10% of a monoisocyanate modified lignin polyurethane elastomer is added, (e) 15% of an unmodified lignin polyurethane elastomer is added, (f) 15% of a monoisocyanate modified lignin polyurethane elastomer is added, (g) 20% of an unmodified lignin polyurethane elastomer is added, (h) 20% of a monoisocyanate modified lignin polyurethane elastomer is added, (i) 25% of an unmodified lignin polyurethane elastomer is added, and (j) 25% of a monoisocyanate modified lignin polyurethane elastomer is added.
Detailed Description
The present invention is further illustrated by the following examples, but the scope of the present invention is not limited thereto, and modifications of the technical solutions of the present invention by those skilled in the art should be within the scope of the present invention.
The present invention is a potentially more efficient and economically viable process for incorporating lignin as a non-covalent filler into the TPU matrix. Unfortunately, lignin contains a large number of aromatic and aliphatic hydroxyl groups, making it highly polar and therefore insoluble in TPU. Therefore, the invention provides a thermoplastic polyurethane elastomer composite material taking modified lignin as a filler, which comprises the following raw materials in parts by mass:
the macromolecular dihydric alcohol is polycarbonate dihydric alcohol; the number average molecular weight of the macrodiol is 500-. Other dihydric alcohols have poor water resistance and poor mechanics, so the polycarbonate dihydric alcohol is adopted in the invention.
The diisocyanate is one or more than two of diphenylmethane diisocyanate (MDI), isophorone diisocyanate (IPDI), dicyclohexylmethane diisocyanate (HMDI), Toluene Diisocyanate (TDI) and Hexamethylene Diisocyanate (HDI) which are mixed in any proportion.
The modified lignin is obtained by reacting lignin with monoisocyanate with different chain lengths. The modified lignin in the embodiment of the invention is prepared by the following steps:
1) weighing a solvent and an unmodified lignin material, adding the unmodified lignin material into the solvent, and then performing ultrasonic dispersion to obtain an unmodified lignin dispersion liquid, wherein the ratio of the unmodified lignin material to the solvent is 0.1-1 g: 3-30 mL, namely determining a solution A; the solvent is tetrahydrofuran.
2) Introducing nitrogen, weighing a certain amount of aliphatic monoisocyanate, dissolving in a solvent, and adding into the solution A to obtain a solution B; wherein the aliphatic monoisocyanate is methyl diisocyanate or diphenylmethane diisocyanate. The dosage ratio of the aliphatic monoisocyanate to the solvent is 0.1-1 g: 0.3-3 mL; the solvent is tetrahydrofuran.
3) Weighing a certain amount of catalyst, adding the catalyst into the solution B, and then reacting for 3-8h at 60-85 ℃; wherein, the dosage of the catalyst is 0.5 percent of the total mass of the lignin and the aliphatic monoisocyanate; the catalyst is organic bismuth catalyst, organic tin catalyst or titanate catalyst. The preferred organotin catalyst is dibutyltin dilaurate. The organic bismuth catalyst is bismuth laurate and titanate catalyst tetraethyl titanate.
4) Centrifuging and washing the modified lignin obtained by the reaction in the step 3), removing redundant monoisocyanate, and treating for 24 hours in an oven at 50 ℃ to obtain the modified lignin.
A method for preparing the lignin-based thermoplastic polyurethane elastomer material comprises the following steps:
1) weighing a solvent and an unmodified lignin (or modified lignin) material, adding the unmodified lignin (or modified lignin) into the solvent, and then performing ultrasonic dispersion to obtain an unmodified lignin (or modified lignin) dispersion liquid, wherein the ratio of the unmodified lignin material (or modified lignin) to the solvent is 0.1-1 g: 3-30 mL; (preferably, the ratio of the unmodified lignin material (or modified lignin) to the solvent is 1g: 30mL), and ultrasonic dispersion is performed after stirring to obtain a lignin dispersion liquid.
2) Weighing a certain amount of dihydric alcohol, adding the dihydric alcohol into a three-neck flask, dehydrating at 115 ℃ in a vacuum state, and cooling to 60-85 ℃ after dehydration;
3) introducing nitrogen, dissolving a certain amount of isocyanate in a solvent, adding the solvent into dihydric alcohol, and performing reaction at the temperature of 60-100 ℃ for 5-8h to obtain a mixed solution A; wherein the dosage ratio of the isocyanate to the solvent is 0.1-1 g: 0.3-3 mL, preferably, the dosage ratio of the isocyanate to the solvent is 1g: 5 mL.
4) Adding the unmodified lignin (or modified lignin) dispersion liquid obtained in the step 1) into the mixed solution A in the step 3), and stirring to uniformly disperse the unmodified lignin dispersion liquid into the mixed solution A to obtain a mixed solution B;
5) and (3) after reacting for 1h at the temperature of 60-85 ℃, adding a certain amount of catalyst dibutyltin dilaurate into the system, reacting for 1h, adding a chain extender, and reacting for 4h to obtain the lignin-based thermoplastic polyurethane elastomer material.
The chain extender is one or more than two of 1, 4-butanediol, 1, 6-hexanediamine, trimethylolpropane, triethanolamine and boron trifluoride triethanolamine mixed in any proportion.
The following are specific examples.
Comparative example 1
The preparation method of the polyurethane elastomer comprises the following steps:
1) weighing 18g of polycarbonate diol, adding the polycarbonate diol into a three-neck flask, dehydrating the polycarbonate diol in a vacuum state at 115 ℃ for 1.5h, and cooling to 60 ℃ after the dehydration is finished to obtain a solution A;
2) introducing nitrogen, dissolving 3g of diisocyanate (diphenylmethane diisocyanate) in tetrahydrofuran, adding the solution A into the solution A for reaction, adding 0.1095g of dibutyltin dilaurate catalyst after 1h of reaction, measuring the content of isocyanic acid radical by using n-phenylenediamine-hydrochloric acid after 1h of reaction, and adding chain extenders with the mass of isocyanic acid radical and the like into the solution A for reaction for 4h to obtain the polyurethane elastomer.
Example 1
The preparation method of the unmodified lignin polyurethane elastomer comprises the following steps:
1) weighing 0.9g of tetrahydrofuran and unmodified lignin material, adding the unmodified lignin material into the tetrahydrofuran, and then performing ultrasonic dispersion to obtain unmodified lignin dispersion liquid, wherein the ratio of the unmodified lignin material to the tetrahydrofuran is 0.1 g:3 mL;
2) weighing 18g of polycarbonate diol, adding the polycarbonate diol into a three-neck flask, dehydrating the polycarbonate diol in a vacuum state at 115 ℃ for 1.5h, and cooling to 60 ℃ after the dehydration is finished to obtain a solution A;
3) introducing nitrogen, dissolving 3g of diisocyanate (diphenylmethane diisocyanate) in a solvent (solute: 1g:3mL), adding the solution into the solution A, and reacting to obtain a mixed solution B;
4) after the mixed solution A is reacted for 1 hour at the temperature of 60 ℃, 0.1095g of dibutyltin dilaurate catalyst is added into the system, after the reaction for 1 hour, the content of isocyanic acid radical is measured by using n-phenylenediamine-hydrochloric acid, and chain extender (1, 6-hexamethylene diamine) with equal mass is added for reaction for 4 hours to obtain mixed solution B.
5) Adding the unmodified lignin dispersion liquid obtained in the step 1) into the mixed solution B obtained in the step 4), and stirring to uniformly disperse the unmodified lignin dispersion liquid into the mixed solution B to obtain a lignin-based thermoplastic polyurethane elastomer material, wherein the mass of the unmodified lignin is 5% of that of the polycarbonate diol;
example 2
The preparation method of the unmodified lignin polyurethane elastomer comprises the following steps:
1) weighing 1.8g of solvent and unmodified lignin material, adding the unmodified lignin material into tetrahydrofuran, and then performing ultrasonic dispersion to obtain unmodified lignin dispersion liquid, wherein the ratio of the unmodified lignin material to the tetrahydrofuran is 1g: 30 mL;
2) weighing 18g of polycarbonate diol, adding the polycarbonate diol into a three-neck flask, dehydrating the polycarbonate diol for 1.5h at the temperature of 115 ℃ in a vacuum state, and cooling the polycarbonate diol to 60 ℃ after the dehydration is finished;
3) introducing nitrogen, dissolving 3g of diisocyanate (diphenylmethane diisocyanate) in a solvent (solute: solvent 1g:3mL), adding the solvent into dihydric alcohol, and reacting to obtain a mixed solution A;
4) after the mixed solution A is reacted for 1 hour at 85 ℃, 0.114g of dibutyltin dilaurate catalyst is added into the system, after the reaction for 1 hour, the content of isocyanic acid radical is measured by using n-phenylenediamine-hydrochloric acid, and chain extender (triethanolamine) with equal mass is added for reaction for 4 hours, so as to obtain mixed solution B.
5) Adding the unmodified lignin dispersion liquid obtained in the step 1) into the mixed solution B obtained in the step 4), and stirring to uniformly disperse the unmodified lignin dispersion liquid into the mixed solution B to obtain the lignin-based thermoplastic polyurethane elastomer material, wherein the mass of the unmodified lignin is 10% of that of the dihydric alcohol.
Example 3
The preparation method of the unmodified lignin polyurethane elastomer comprises the following steps:
1) weighing 2.7g of solvent and unmodified lignin material, adding the unmodified lignin material into tetrahydrofuran, and then performing ultrasonic dispersion to obtain unmodified lignin dispersion liquid, wherein the ratio of the unmodified lignin material to the tetrahydrofuran is 0.1 g: 30 mL;
2) weighing 18g of polycarbonate diol, adding the polycarbonate diol into a three-neck flask, dehydrating the polycarbonate diol for 1.5h at the temperature of 115 ℃ in a vacuum state, and cooling the polycarbonate diol to 60 ℃ after the dehydration is finished;
3) introducing nitrogen, dissolving 3g of diisocyanate (diphenylmethane diisocyanate) in a solvent (solute: solvent 1g:3mL), adding the solvent into dihydric alcohol, and reacting to obtain a mixed solution A;
4) after the mixed solution A is reacted for 1 hour at 70 ℃, 0.1185g of dibutyltin dilaurate catalyst is added into the system, after 1 hour, the content of isocyanic acid radical is measured by using n-phenylenediamine-hydrochloric acid, and chain extender (boron trifluoride triethanolamine) with equal mass is added for reaction for 4 hours to obtain mixed solution B.
5) Adding the unmodified lignin dispersion liquid obtained in the step 1) into the mixed solution B obtained in the step 4), and then singulating, stirring to uniformly disperse the unmodified lignin dispersion liquid into the mixed solution B to obtain the lignin-based thermoplastic polyurethane elastomer material, wherein the mass of the unmodified lignin is 15% of that of the dihydric alcohol.
Example 4
The preparation method of the unmodified lignin polyurethane elastomer comprises the following steps:
1) weighing 3.6g of solvent and unmodified lignin material, adding the unmodified lignin material into tetrahydrofuran, and then performing ultrasonic dispersion to obtain unmodified lignin dispersion liquid, wherein the ratio of the unmodified lignin material to the tetrahydrofuran is 1g:3 mL;
2) weighing 18g of polycarbonate diol, adding the polycarbonate diol into a three-neck flask, dehydrating the polycarbonate diol for 1.5h at the temperature of 115 ℃ in a vacuum state, and cooling the polycarbonate diol to 60 ℃ after the dehydration is finished;
3) introducing nitrogen, dissolving 3g of diisocyanate (diphenylmethane diisocyanate) in a solvent (solute: solvent 1g:3mL), adding the solvent into dihydric alcohol, and reacting to obtain a mixed solution A;
4) after the mixed solution A is reacted for 1 hour at the temperature of 80 ℃, 0.123g of dibutyltin dilaurate catalyst is added into the system for reaction for 1 hour, the content of isocyanic acid radical is measured through n-phenylenediamine-hydrochloric acid, and chain extender (1, 6-hexamethylene diamine) with equal mass is added for reaction for 4 hours to obtain mixed solution B.
5) Adding the unmodified lignin dispersion liquid obtained in the step 1) into the mixed solution B obtained in the step 4), and stirring to uniformly disperse the unmodified lignin dispersion liquid into the mixed solution B to obtain the lignin-based thermoplastic polyurethane elastomer material, wherein the mass of the unmodified lignin is 20% of that of the dihydric alcohol.
Example 5
The preparation method of the modified lignin polyurethane elastomer comprises the following steps:
1) weighing 0.9g of solvent and modified lignin material, adding the modified lignin material into tetrahydrofuran, and then performing ultrasonic dispersion to obtain modified lignin dispersion liquid, wherein the ratio of the modified lignin material to the tetrahydrofuran is 0.5 g: 15 mL;
2) weighing 18g of polycarbonate diol, adding the polycarbonate diol into a three-neck flask, dehydrating the polycarbonate diol under vacuum at 115 ℃ for 1.5h, and cooling the polycarbonate diol to 60 ℃ after the dehydration is finished;
3) introducing nitrogen, dissolving 3g of diisocyanate (diphenylmethane diisocyanate) in a solvent, adding the solvent into the glycol obtained in the step 2) after the water is removed, and reacting to obtain a mixed solution A;
4) adding 0.1095g of dibutyltin dilaurate catalyst into the system after the mixed solution A reacts for 1h, measuring the content of isocyanic acid radical through n-phenylenediamine-hydrochloric acid after the mixed solution A reacts for 1h, and adding chain extender (1, 6-hexamethylene diamine) with equal mass to react for 4h to obtain mixed solution B;
5) adding the unmodified lignin dispersion liquid obtained in the step 1) into the mixed solution B obtained in the step 4), and stirring to uniformly disperse the unmodified lignin dispersion liquid into the mixed solution B to obtain the lignin-based thermoplastic polyurethane elastomer material, wherein the mass of the unmodified lignin is 5% of that of the dihydric alcohol.
Example 6
The preparation method of the modified lignin polyurethane elastomer comprises the following steps:
1) weighing 1.8g of solvent and modified lignin material, adding the modified lignin material into tetrahydrofuran, and then performing ultrasonic dispersion to obtain modified lignin dispersion liquid, wherein the ratio of the modified lignin material to the tetrahydrofuran is 3 g: 10 mL;
2) weighing 18g of polycarbonate diol, adding the polycarbonate diol into a three-neck flask, dehydrating the polycarbonate diol for 1.5h at the temperature of 115 ℃ in a vacuum state, and cooling the polycarbonate diol to 60 ℃ after the dehydration is finished;
3) introducing nitrogen, dissolving 3g of diisocyanate (diphenylmethane diisocyanate) in a solvent (solute: solvent: 1:3), adding the solvent into the glycol obtained in the step 2) after the water is removed, and reacting to obtain a mixed solution A;
4) after the mixed solution A reacts for 1 hour, 0.114g of dibutyltin dilaurate catalyst is added into the system, after the reaction for 1 hour, the content of isocyanic acid radical is measured by n-phenylenediamine-hydrochloric acid, and chain extender with equal mass is added for reaction for 4 hours to obtain mixed solution B;
5) adding the unmodified lignin dispersion liquid obtained in the step 1) into the mixed solution B obtained in the step 4), and stirring to uniformly disperse the unmodified lignin dispersion liquid into the mixed solution B to obtain the lignin-based thermoplastic polyurethane elastomer material, wherein the mass of the unmodified lignin is 10% of that of the dihydric alcohol.
Example 7
The preparation method of the modified lignin polyurethane elastomer comprises the following steps:
1) weighing 2.7g of solvent and modified lignin material, adding the modified lignin material into tetrahydrofuran, and then performing ultrasonic dispersion to obtain modified lignin dispersion liquid, wherein the ratio of the modified lignin material to the tetrahydrofuran is 0.6 g: 20 mL;
2) weighing 18g of polycarbonate diol, adding the polycarbonate diol into a three-neck flask, dehydrating the polycarbonate diol for 1.5h at the temperature of 115 ℃ in a vacuum state, and cooling the polycarbonate diol to 60 ℃ after the dehydration is finished;
3) introducing nitrogen, dissolving 3g of diisocyanate (diphenylmethane diisocyanate) in a solvent (solute: solvent: 1:3), adding the solvent into the glycol obtained in the step 2) after the water is removed, and reacting to obtain a mixed solution A;
4) after the mixed solution A is reacted for 1 hour, 0.1185g of dibutyltin dilaurate catalyst is added into the system, after the reaction is performed for 1 hour, the content of isocyanic acid radical is measured through n-phenylenediamine-hydrochloric acid, and chain extender with equal mass is added for reaction for 4 hours to obtain mixed solution B;
5) adding the modified lignin dispersion liquid obtained in the step 1) into the mixed solution B obtained in the step 4), and stirring to uniformly disperse the modified lignin dispersion liquid into the mixed solution B to obtain the lignin-based thermoplastic polyurethane elastomer material, wherein the mass of the modified lignin is 15% of that of the dihydric alcohol.
Example 8
The preparation method of the modified lignin polyurethane elastomer comprises the following steps:
1) weighing 3.6g of solvent and modified lignin material, adding the modified lignin material into tetrahydrofuran, and then performing ultrasonic dispersion to obtain modified lignin dispersion liquid, wherein the ratio of the modified lignin material to the tetrahydrofuran is 0.9 g: 27 mL;
2) weighing 18g of polycarbonate diol, adding the polycarbonate diol into a three-neck flask, dehydrating the polycarbonate diol for 1.5h at the temperature of 115 ℃ in a vacuum state, and cooling the polycarbonate diol to 60 ℃ after the dehydration is finished;
3) introducing nitrogen, dissolving 3g of diisocyanate (diphenylmethane diisocyanate) in a solvent (solute: solvent: 1:3), adding the solvent into the glycol obtained in the step 2) after the water is removed, and reacting to obtain a mixed solution A;
4) after the mixed solution A reacts for 1 hour, 0.123g of dibutyltin dilaurate catalyst is added into the system, after the reaction for 1 hour, the content of isocyanic acid radical is measured by n-phenylenediamine-hydrochloric acid, and chain extender with equal mass is added for reaction for 4 hours to obtain mixed solution B;
5) adding the modified lignin dispersion liquid obtained in the step 1) into the mixed solution B obtained in the step 4), and stirring to uniformly disperse the modified lignin dispersion liquid into the mixed solution B to obtain the lignin-based thermoplastic polyurethane elastomer material, wherein the mass of the modified lignin is 20% of that of the dihydric alcohol.
The polyurethane elastomers prepared using comparative example 1 and examples 1 to 8 were cut into dumbbell test pieces using a cutter. The polyurethane elastomer is subjected to tensile test through a universal mechanical testing machine, and the experimental tensile speed is 100 mm/min. The tensile strength of the GBT528-2009 elastomer was measured for the breaking strength and elongation at break of the polyurethane elastomer, and the properties are shown in Table 1 below:
TABLE 1 breaking Strength and elongation at Break
Note: "virgin" refers to unmodified lignin; "modified" refers to modified lignin.
The experimental detection proves that the tensile strength and the elongation at break of the prepared lignin-containing environment-friendly polyurethane elastomer material can be improved by increasing the introduction amount of the lignin. Meanwhile, the modified lignin can be used in polyurethane elastomers in an improved way. The tensile strength and the elongation at break of the polyurethane elastomer are both superior to those of the polyester polyurethane elastomer prepared by the prior art (5.0MPa, 300.07%, data source: CN 110183615A).
The surfaces of the polyurethane elastomers prepared in comparative example 1 and examples 1 to 8 were observed by SEM, and the surfaces of the polyurethane elastomers were observed by varying the amount of the modified lignin added.
Example 9
The modified lignin is prepared by the following steps:
1) weighing a solvent and an unmodified lignin material, adding the unmodified lignin material into the solvent, and then performing ultrasonic dispersion to obtain an unmodified lignin dispersion liquid, wherein the ratio of the unmodified lignin material to the solvent is 0.1 g:3mL, designated as solution A; the solvent is tetrahydrofuran.
2) Introducing nitrogen, weighing a certain amount of aliphatic monoisocyanate, dissolving in a solvent, and adding into the solution A to obtain a solution B; wherein the aliphatic monoisocyanate is methyl diisocyanate. The dosage ratio of the aliphatic monoisocyanate to the solvent is 1g:3 mL; the solvent is tetrahydrofuran.
3) Weighing a certain amount of catalyst, adding the catalyst into the solution B, and then reacting for 3 hours at 85 ℃; wherein the using amount of the catalyst is 0.5 percent of the total mass of the lignin and the aliphatic monoisocyanate; the catalyst is a titanate catalyst (tetraethyl titanate).
4) Centrifuging and washing the modified lignin obtained by the reaction in the step 3), removing redundant monoisocyanate, and treating for 24 hours in an oven at 50 ℃ to obtain the modified lignin.
A preparation method of a lignin-based thermoplastic polyurethane elastomer material comprises the following steps:
1) weighing a solvent and a modified lignin material, adding the modified lignin into the solvent, and then performing ultrasonic dispersion to obtain a modified lignin dispersion liquid, wherein the ratio of the modified lignin to the solvent is 1g: 30 mL; stirring and then carrying out ultrasonic dispersion to obtain lignin dispersion liquid.
2) Weighing a certain amount of dihydric alcohol, adding the dihydric alcohol into a three-neck flask, dehydrating at 115 ℃ in a vacuum state, and cooling to 60 ℃ after dehydration;
3) introducing nitrogen, dissolving a certain amount of isocyanate (isophorone diisocyanate) in a solvent, adding the solvent into dihydric alcohol, and performing reaction at 70 ℃ for 7 hours to obtain a mixed solution A; wherein the dosage ratio of the isocyanate to the solvent is 1g: 5 mL.
4) Adding the modified lignin dispersion liquid obtained in the step 1) into the mixed solution A in the step 3), and stirring to uniformly disperse the unmodified lignin dispersion liquid into the mixed solution A to obtain a mixed solution B;
5) and (3) after reacting for 2h at the temperature of 60 ℃, adding a certain amount of catalyst dibutyltin dilaurate into the system, reacting for 2h, adding a chain extender, and reacting for 4h to obtain the lignin-based thermoplastic polyurethane elastomer material. Wherein the mass part ratio of the catalyst, the modified lignin material and the chain extender is 0.5: 2.5: 4.
the chain extender is a mixture of trimethylolpropane and triethanolamine.
Example 10
The modified lignin is prepared by the following steps:
1) weighing a solvent and an unmodified lignin material, adding the unmodified lignin material into the solvent, and then performing ultrasonic dispersion to obtain an unmodified lignin dispersion liquid, wherein the ratio of the unmodified lignin material to the solvent is 1g: 20mL is determined as solution A; the solvent is tetrahydrofuran.
2) Introducing nitrogen, weighing a certain amount of aliphatic monoisocyanate, dissolving in a solvent, and adding into the solution A to obtain a solution B; wherein the aliphatic monoisocyanate is diphenylmethane diisocyanate. The dosage ratio of the aliphatic monoisocyanate to the solvent is 0.1 g: 1 mL; the solvent is tetrahydrofuran.
3) Weighing a certain amount of catalyst, adding the catalyst into the solution B, and then reacting for 8 hours at 60 ℃; wherein, the dosage of the catalyst is 0.5 percent of the total mass of the lignin and the aliphatic monoisocyanate; the catalyst is an organic bismuth catalyst (bismuth laurate).
4) Centrifuging and washing the modified lignin obtained by the reaction in the step 3), removing redundant monoisocyanate, and treating for 24 hours in an oven at 50 ℃ to obtain the modified lignin.
A preparation method of a lignin-based thermoplastic polyurethane elastomer material comprises the following steps:
1) weighing a solvent and a modified lignin material, adding the modified lignin into the solvent, and then performing ultrasonic dispersion to obtain a modified lignin dispersion liquid, wherein the ratio of the modified lignin to the solvent is 0.6 g: 10 mL; stirring and then carrying out ultrasonic dispersion to obtain lignin dispersion liquid.
2) Weighing a certain amount of dihydric alcohol, adding the dihydric alcohol into a three-neck flask, dehydrating at 115 ℃ in a vacuum state, and cooling to 85 ℃ after dehydration;
3) introducing nitrogen, dissolving a certain amount of isocyanate (a mixture of dicyclohexylmethane diisocyanate and toluene diisocyanate in any proportion) in a solvent, adding the solvent into dihydric alcohol, and performing reaction at 80 ℃ for 5 hours to obtain a mixed solution A; wherein the dosage ratio of the isocyanate to the solvent is 0.4 g: 0.9 mL.
4) Adding the modified lignin dispersion liquid obtained in the step 1) into the mixed solution A in the step 3), and stirring to uniformly disperse the unmodified lignin dispersion liquid into the mixed solution A to obtain a mixed solution B;
5) after reacting for 1h at 75 ℃, adding a certain amount of catalyst dibutyltin dilaurate into the system, reacting for 1h, adding a chain extender, and reacting for 4h to obtain the lignin-based thermoplastic polyurethane elastomer material. Wherein the mass part ratio of the catalyst to the modified lignin material is 0.1: 0.04. wherein the mass part ratio of the catalyst, the modified lignin material and the chain extender is 0.5: 2.5: 4.
the chain extender is 1, 4-butanediol.
Example 11
A preparation method of a lignin-based thermoplastic polyurethane elastomer material comprises the following steps:
1) weighing a solvent and an unmodified lignin material, adding the unmodified lignin into the solvent, and then performing ultrasonic dispersion to obtain an unmodified lignin dispersion liquid, wherein the ratio of the unmodified lignin material to the solvent is 0.5 g: 5 mL; stirring and then carrying out ultrasonic dispersion to obtain lignin dispersion liquid.
2) Weighing a certain amount of dihydric alcohol, adding the dihydric alcohol into a three-neck flask, dehydrating at 115 ℃ in a vacuum state, and cooling to 70 ℃ after dehydration;
3) introducing nitrogen, dissolving a certain amount of diisocyanate (hexamethylene diisocyanate) in a solvent, adding the solvent into dihydric alcohol, and performing reaction at the temperature of 60-100 ℃ for 5-8h to obtain a mixed solution A; wherein the dosage ratio of the isocyanate to the solvent is 0.1-1 g: 0.3-3 mL, preferably, the dosage ratio of the isocyanate to the solvent is 1g: 5 mL.
4) Adding the unmodified lignin dispersion liquid obtained in the step 1) into the mixed solution A obtained in the step 3), and stirring to uniformly disperse the unmodified lignin dispersion liquid into the mixed solution A to obtain a mixed solution B;
5) after reacting for 1h at the temperature of 80 ℃, adding a certain amount of catalyst dibutyltin dilaurate into the system, reacting for 1h, adding a chain extender, and reacting for 4h to obtain the lignin-based thermoplastic polyurethane elastomer material. Wherein the mass part ratio of the catalyst, the modified lignin material and the chain extender is 0.1: 0.04: 7.
the chain extender is trimethylolpropane.
Example 12
A preparation method of a lignin-based thermoplastic polyurethane elastomer material comprises the following steps:
1) weighing a solvent and an unmodified lignin material, adding the unmodified lignin into the solvent, and then performing ultrasonic dispersion to obtain an unmodified lignin dispersion liquid, wherein the ratio of the unmodified lignin material to the solvent is 0.7 g: 15 mL; stirring and then carrying out ultrasonic dispersion to obtain lignin dispersion liquid.
2) Weighing a certain amount of dihydric alcohol, adding the dihydric alcohol into a three-neck flask, dehydrating at 115 ℃ in a vacuum state, and cooling to 80 ℃ after the dehydration;
3) introducing nitrogen, dissolving a certain amount of diisocyanate (hexamethylene diisocyanate) in a solvent, adding the solvent into dihydric alcohol, and performing reaction at 90 ℃ for 6 hours to obtain a mixed solution A; wherein the dosage ratio of the isocyanate to the solvent is 1g: 2 mL.
4) Adding the unmodified lignin dispersion liquid obtained in the step 1) into the mixed solution A obtained in the step 3), and stirring to uniformly disperse the unmodified lignin dispersion liquid into the mixed solution A to obtain a mixed solution B;
5) after reacting for 1h at 65 ℃, adding a certain amount of catalyst dibutyltin dilaurate into the system, reacting for 1h, adding a chain extender, and reacting for 4h to obtain the lignin-based thermoplastic polyurethane elastomer material. Wherein the mass part ratio of the catalyst, the modified lignin material and the chain extender is 0.3: 1: 5. the chain extender is a mixture of 1, 4-butanediol and 1, 6-hexamethylenediamine.
Referring to FIG. 1, it can be seen that 2230cm-1The disappearance of the peak of the isocyanate group indicates that the isocyanate group in the prepolymer is reacted completely without residual isocyanate group, and the synthesis of polyurethane can be determined.
Referring to fig. 2, it can be seen that the mechanical properties of the polyurethane composite material are improved after the lignin is added.
Referring to fig. 3, it can be seen that lignin modification was successful.
Referring to fig. 4, it can be seen that the modified lignin improves the mechanical properties of polyurethane.
Referring to fig. 5 (a) - (j), it can be seen that lignin aggregates in the polyurethane before and after modification.
The results show that the lignin carbamate with different contents has obvious influence on the mechanical properties of the lignin-based polyurethane elastomer. The appearance of the lignin carbamate sample is uniform, and the color of the sample becomes dark along with the increase of the content of the lignin carbamate. Compared with unmodified lignin, the modified lignin-containing carbamate has greatly improved dispersibility. The distribution of the lignin carbamate in the polyurethane matrix is observed by a scanning electron microscope. The lignin carbamate is uniformly dispersed in the polyurethane matrix. The homogeneous distribution of lignin urethane in the polyurethane matrix is mainly due to the entanglement effect caused by the long chain hanging of butane-based urethane and the hydrogen bonding between butyl carbamate and the polyurethane chain C ═ O. The results show that the lignin polyurethane is better compatible with the polyurethane matrix.
Claims (10)
1. The lignin-based thermoplastic polyurethane elastomer material is characterized by comprising the following raw materials in parts by weight:
2. the lignin-based thermoplastic polyurethane elastomer material according to claim 1, wherein the macrodiol is polycarbonate diol; the number average molecular weight of the macrodiol is 500-.
3. The lignin-based thermoplastic polyurethane elastomer material according to claim 1, wherein the diisocyanate is one or more of diphenylmethane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, and hexamethylene diisocyanate mixed in any ratio.
4. The lignin-based thermoplastic polyurethane elastomer material according to claim 1, wherein the modified lignin is prepared by the following steps:
a) adding a lignin material into a solvent, and then carrying out ultrasonic dispersion to obtain a lignin dispersion liquid;
b) under the condition of introducing nitrogen, dissolving aliphatic monoisocyanate in a solvent, and then adding the solvent into the lignin dispersion liquid to obtain a solution B;
c) adding a catalyst into the solution B, and then reacting for 3-8h at 60-85 ℃; and centrifuging, washing and drying to obtain the modified lignin.
5. The lignin-based thermoplastic polyurethane elastomer material according to claim 4, wherein the solvent in step a) is tetrahydrofuran; the dosage ratio of the lignin material to the solvent is 0.1-1 g: 3-30 mL;
in the step b), the solvent is tetrahydrofuran, the aliphatic monoisocyanate is methyl diisocyanate or diphenylmethane diisocyanate, and the dosage ratio of the aliphatic monoisocyanate to the solvent is 0.1-1 g: 0.3-3 mL;
the using amount of the catalyst in the step c) is 0.5 percent of the total mass of the lignin and the aliphatic monoisocyanate; the catalyst is organic bismuth catalyst, organic tin catalyst or titanate catalyst.
6. A preparation method of a lignin-based thermoplastic polyurethane elastomer material is characterized by comprising the following steps:
1) weighing 58-73 parts of macromolecular dihydric alcohol, 11-17 parts of diisocyanate, 0.04-2.5 parts of lignin or modified lignin, 4-7 parts of chain extender and 0.1-0.5 part of catalyst according to parts by weight;
adding lignin or modified lignin into a solvent, and then carrying out ultrasonic dispersion to obtain a lignin dispersion liquid;
2) dissolving diisocyanate in a solvent under the condition of introducing nitrogen, then adding the diisocyanate into the dehydrated macromolecular dihydric alcohol, and reacting for 1-2h at the temperature of 60-100 ℃ to obtain a mixed solution A;
3) adding a catalyst into the mixed solution A, reacting for 1-2h at 60-85 ℃, then adding a chain extender, and reacting for 4-8 h to obtain a mixed solution B;
adding the lignin dispersion liquid obtained in the step 1) into the mixed solution B, and uniformly stirring to obtain the lignin-based thermoplastic polyurethane elastomer material.
7. The method for preparing the lignin-based thermoplastic polyurethane elastomer material according to claim 6, wherein the macrodiol is polycarbonate diol; the number average molecular weight of the macrodiol is 500-;
the diisocyanate is one or more than two of diphenylmethane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, toluene diisocyanate and hexamethylene diisocyanate which are mixed in any proportion.
8. The method for preparing the lignin-based thermoplastic polyurethane elastomer material according to claim 6, wherein the modified lignin is prepared by the following steps:
a) adding a lignin material into a solvent, and then performing ultrasonic dispersion to obtain a lignin dispersion liquid, namely a solution A, wherein the ratio of the unmodified lignin material to the solvent is 0.1-1 g: 3-30 mL;
b) under the condition of introducing nitrogen, dissolving aliphatic monoisocyanate in a solvent, and then adding the solution into the solution A to obtain a solution B;
c) adding a catalyst into the solution B, and then reacting for 3-8h at 60-85 ℃; and centrifuging, washing and drying to obtain the modified lignin.
9. The method for preparing the lignin-based thermoplastic polyurethane elastomer material according to claim 8, wherein the solvent in step a) is tetrahydrofuran; the dosage ratio of the unmodified lignin material to the solvent is 0.1-1 g: 3-30 mL;
in the step b), the solvent is tetrahydrofuran, the aliphatic monoisocyanate is methyl diisocyanate or diphenylmethane diisocyanate, and the dosage ratio of the aliphatic monoisocyanate to the solvent is 0.1-1 g: 0.3-3 mL;
the using amount of the catalyst in the step c) is 0.5 percent of the total mass of the lignin and the aliphatic monoisocyanate; the catalyst is organic bismuth catalyst, organic tin catalyst or titanate catalyst.
10. The method for preparing the lignin-based thermoplastic polyurethane elastomer material according to claim 6, wherein the solvent in the step 1) is tetrahydrofuran; the ratio of the lignin or the modified lignin to the solvent is 0.1-1 g: 3-30 mL;
in the step 2), the solvent is tetrahydrofuran, and the using amount ratio of diisocyanate to the solvent is 0.1-1 g: 0.3-3 mL;
the catalyst in the step 3) is an organic bismuth catalyst, an organic tin catalyst or a titanate catalyst; the chain extender is one or more than two of 1, 4-butanediol, 1, 6-hexanediamine, trimethylolpropane, triethanolamine and boron trifluoride triethanolamine mixed in any proportion.
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