CN115521434B - 一种桦木醇基热塑性聚氨酯弹性体及其制备方法 - Google Patents
一种桦木醇基热塑性聚氨酯弹性体及其制备方法 Download PDFInfo
- Publication number
- CN115521434B CN115521434B CN202211149129.XA CN202211149129A CN115521434B CN 115521434 B CN115521434 B CN 115521434B CN 202211149129 A CN202211149129 A CN 202211149129A CN 115521434 B CN115521434 B CN 115521434B
- Authority
- CN
- China
- Prior art keywords
- betulinol
- polyurethane elastomer
- based thermoplastic
- thermoplastic polyurethane
- betulin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229920001971 elastomer Polymers 0.000 title claims abstract description 43
- 239000000806 elastomer Substances 0.000 title claims abstract description 43
- 239000004433 Thermoplastic polyurethane Substances 0.000 title claims abstract description 42
- 229920002803 thermoplastic polyurethane Polymers 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 235000018185 Betula X alpestris Nutrition 0.000 title description 3
- 235000018212 Betula X uliginosa Nutrition 0.000 title description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title description 2
- FVWJYYTZTCVBKE-ROUWMTJPSA-N betulin Chemical compound C1C[C@H](O)C(C)(C)[C@@H]2CC[C@@]3(C)[C@]4(C)CC[C@@]5(CO)CC[C@@H](C(=C)C)[C@@H]5[C@H]4CC[C@@H]3[C@]21C FVWJYYTZTCVBKE-ROUWMTJPSA-N 0.000 claims abstract description 83
- MVIRREHRVZLANQ-UHFFFAOYSA-N betulin Natural products CC(=O)OC1CCC2(C)C(CCC3(C)C2CC=C4C5C(CCC5(CO)CCC34C)C(=C)C)C1(C)C MVIRREHRVZLANQ-UHFFFAOYSA-N 0.000 claims abstract description 79
- JYDNKGUBLIKNAM-UHFFFAOYSA-N Oxyallobutulin Natural products C1CC(=O)C(C)(C)C2CCC3(C)C4(C)CCC5(CO)CCC(C(=C)C)C5C4CCC3C21C JYDNKGUBLIKNAM-UHFFFAOYSA-N 0.000 claims abstract description 42
- ZNUAKACHFYTNFX-UHFFFAOYSA-N Wallichenol Natural products CC12CCC(O)C(C)(C)C1CCC1(C)C2CCC2C3C(C(=C)CO)CCC3(C)CCC21C ZNUAKACHFYTNFX-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229920000642 polymer Polymers 0.000 claims abstract description 20
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 13
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 12
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims abstract description 8
- 239000003054 catalyst Substances 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 20
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 15
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 10
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 10
- 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 10
- 239000012948 isocyanate Substances 0.000 claims description 7
- 150000002513 isocyanates Chemical class 0.000 claims description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 5
- 239000004814 polyurethane Substances 0.000 abstract description 16
- 229920002635 polyurethane Polymers 0.000 abstract description 15
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 239000002861 polymer material Substances 0.000 abstract description 2
- 230000002194 synthesizing effect Effects 0.000 abstract description 2
- 229920003225 polyurethane elastomer Polymers 0.000 description 10
- 239000002994 raw material Substances 0.000 description 9
- 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 description 6
- 239000000463 material Substances 0.000 description 6
- 229920005862 polyol Polymers 0.000 description 6
- 150000003077 polyols Chemical class 0.000 description 6
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 5
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 239000002028 Biomass Substances 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 description 2
- BFMYDTVEBKDAKJ-UHFFFAOYSA-L disodium;(2',7'-dibromo-3',6'-dioxido-3-oxospiro[2-benzofuran-1,9'-xanthene]-4'-yl)mercury;hydrate Chemical compound O.[Na+].[Na+].O1C(=O)C2=CC=CC=C2C21C1=CC(Br)=C([O-])C([Hg])=C1OC1=C2C=C(Br)C([O-])=C1 BFMYDTVEBKDAKJ-UHFFFAOYSA-L 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- -1 polyhexamethylene adipate Polymers 0.000 description 2
- 229920006264 polyurethane film Polymers 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 description 1
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 description 1
- BSYJHYLAMMJNRC-UHFFFAOYSA-N 2,4,4-trimethylpentan-2-ol Chemical compound CC(C)(C)CC(C)(C)O BSYJHYLAMMJNRC-UHFFFAOYSA-N 0.000 description 1
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 1
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 description 1
- 239000004970 Chain extender Substances 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 229920002121 Hydroxyl-terminated polybutadiene Polymers 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229920005830 Polyurethane Foam Polymers 0.000 description 1
- 229920002334 Spandex Polymers 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- TVXBFESIOXBWNM-UHFFFAOYSA-N Xylitol Natural products OCCC(O)C(O)C(O)CCO TVXBFESIOXBWNM-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000005489 elastic deformation Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 239000002649 leather substitute Substances 0.000 description 1
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 229920006306 polyurethane fiber Polymers 0.000 description 1
- 239000011496 polyurethane foam Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical class [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000004759 spandex Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000012815 thermoplastic material Substances 0.000 description 1
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 1
- 239000000811 xylitol Substances 0.000 description 1
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 description 1
- 229960002675 xylitol Drugs 0.000 description 1
- 235000010447 xylitol Nutrition 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- 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
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
-
- 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
-
- 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
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
-
- 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
-
- 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
- C08G18/7621—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring being toluene diisocyanate including isomer mixtures
-
- 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
本发明公开了一种桦木醇基热塑性聚氨酯弹性体,属于生物基高分子材料技术领域,桦木醇作为一种二羟基化合物,其分子结构中分布的羟基能够为合成桦木醇基聚氨酯提供基础,具体的,该桦木醇基热塑性聚氨酯弹性体的制备方法为:(1)利用羟基封端聚合物和二异氰酸酯以及催化剂反应得到聚氨酯预聚体;(2)向步骤(1)得到的聚氨酯预聚体中加入桦木醇溶液,反应得到所述的桦木醇基热塑性聚氨酯弹性体,所述的桦木醇基热塑性聚氨酯弹性体性能可调节范围大,拉伸模量为7.2‑173MPa,拉伸强度为1.6‑16.0MPa,断裂伸长率为84‑1100%。
Description
技术领域
本发明涉及生物基高分子材料技术领域,具体涉及一种桦木醇基热塑性聚氨酯弹性体及其制备方法。
背景技术
聚氨基甲酸酯简称聚氨酯(PU),是以氨基甲酸酯键为重复单元的一种通用的高分子化合物。聚氨酯一般是由二元或多元异氰酸酯与聚醚多元醇或聚酯多元醇经过聚加成反应而得的。最早的聚氨酯是由德国拜尔博士于19世纪30年代发明的聚氨酯纤维(氨纶纤维),经过80多年的发展,随着原料结构的多样化,聚氨酯材料的性能可调性更加广阔,并且其产品形式的多元性更加丰富,例如,泡沫、合成皮革、粘合剂、纤维、弹性体、涂料等。聚氨酯弹性体具有良好的弹性、韧性、尺寸稳定性,以及良好的耐油、耐磨、耐低温、耐老化的特性,且具有一定的生物相容性,聚氨酯弹性体已经逐渐走进了我们生活的方方面面,是合成聚氨酯材料中的重要品类之一。
目前,聚氨酯材料的制备大多以石油基原料为主,大量石化资源的使用造成了严重的资源消耗以及环境问题,生物质资源代替石油基资源用于聚氨酯的制备成为主流。如公开号为CN113929858A的中国专利文献公开了一种生物基聚氨酯材料的制备方法,该发明以淀粉基聚醚多元醇和石油基多元醇制备混合多元醇作为原料之一,采用一步全水发泡法制备生物基聚氨酯泡沫;公开号CN109776746A的中国专利文献公开了一种生物基阻燃聚氨酯及其制备方法,该发明以含磷双官能单体DOMF与二异氰酸酯反应形成线性聚合物,然后引入生物基多元醇作为网络节点,形成生物基网络结构阻燃聚氨酯,其中,DOMF为9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物与生物基原料5-羟甲基糠醛的加成产物,生物基多元醇采用丙三醇、木糖醇等。
桦木醇又称白桦酯醇,广泛存在于桦木树皮中,是一种重要的天然产物,能够从丰富的植物资源中获得,可应用于食品、化妆品及医药等行业,利用桦木醇来制备生物基聚氨酯材料,具有较高的实际推广价值,为促进生物基聚氨酯材料的发展提供一定的贡献。
发明内容
本发明提供了一种桦木醇基热塑性聚氨酯弹性体,利用可再生的且绿色环保的生物质原料桦木醇制备得到,该桦木醇基热塑性聚氨酯弹性体的性能可调节范围大,力学性能好,可重复加工。
具体采用的技术方案如下:
本发明提供了一种桦木醇基热塑性聚氨酯弹性体,所述的桦木醇基热塑性聚氨酯弹性体的结构式为:
式中,n为正整数,n为5-12,BE为桦木醇残基,DI为二异氰酸酯残基,R为羟基封端聚合物和二异氰酸酯反应所形成的聚合物残基。
桦木醇作为一种二羟基化合物,其分子结构中分布的羟基能够为合成桦木醇基聚氨酯提供基础,且桦木醇分子结构中的脂肪环可以为聚合物提供一定的刚性,利用桦木醇制备得到的桦木醇基热塑性聚氨酯弹性体,具有绿色环保、可持续、应用潜力好等一系列优点。
本发明中的桦木醇基热塑性聚氨酯弹性体硬段包括桦木醇残基和异氰酸酯残基,软段包括聚合物结构,优选的,所述的桦木醇基热塑性聚氨酯弹性体中,硬段含量为20-60%;当硬段含量较高时(>60%),产物刚性大,质脆,几乎没有弹性形变;当硬段含量较低时(<20%),产物力学性能变化不明显,和预聚体的性能一致甚至更差,主要因为桦木醇的空间位阻阻碍了聚氨酯分子量的进一步增大。
进一步优选的,所述的桦木醇基热塑性聚氨酯弹性体中,硬段含量为30-50%,此范围制备的聚氨酯弹性体力学性能较好,满足后续相关应用。
本发明还提供了所述的桦木醇基热塑性聚氨酯弹性体的制备方法,包括以下步骤:
(1)利用羟基封端聚合物和二异氰酸酯以及催化剂反应得到聚氨酯预聚体;
(2)向步骤(1)得到的聚氨酯预聚体中加入桦木醇溶液,反应得到所述的桦木醇基热塑性聚氨酯弹性体。
考虑到产品聚氨酯弹性体的性能,本发明采用分步法而不是一锅法来制备所述的桦木醇基热塑性聚氨酯弹性体,有助于提高产品聚氨酯弹性体的分子量。
在制备桦木醇基热塑性聚氨酯弹性体的过程中,羟基封端聚合物、桦木醇和桦木醇的溶剂等均需要进行除水处理后再进行反应。
优选的,所述的桦木醇溶液中,溶剂选自氯仿、甲苯、环己烷、四氢呋喃、二氯甲烷、丙酮和2-丁酮中的至少一种。
进一步优选的,所述的桦木醇溶液为桦木醇的氯仿溶液或桦木醇的四氢呋喃溶液,氯仿和四氢呋喃沸点较低,利于后处理过程。
优选的,所述的羟基封端聚合物包括聚乙二醇、聚四氢呋喃、聚己内酯二醇、端羟基聚丁二烯和聚己二酸己二醇酯中至少一种,所述的羟基封端聚合物的数均分子量为500-2000。
所述的二异氰酸酯包括二苯基甲烷二异氰酸酯、异佛尔酮二异氰酸酯、六亚甲基二异氰酸酯、对苯二异氰酸酯、1,5-萘二异氰酸酯、甲苯二异氰酸酯和二环己基二异氰酸酯中的至少一种。
所述的催化剂为胺类化合物或有机金属化合物,包括但不限于三亚乙基二胺、三乙胺、二月桂酸二丁基锡、辛酸亚锡、异辛酸锌等。
以桦木醇与羟基封端聚合物的羟基含量计算,基于总羟基含量的异氰酸酯指数为1.0-1.1。
优选的,所述的羟基封端聚合物为聚四氢呋喃,主要充当聚氨酯主链的软段部分;所述的二异氰酸酯为六亚甲基二异氰酸酯(HDI)、甲苯二异氰酸酯(TDI)或二苯基甲烷二异氰酸酯(MDI);以桦木醇与羟基封端聚合物的羟基含量计算,基于总羟基含量的异氰酸酯指数为1.05;桦木醇存在刚性的多环结构,脂肪链的HDI和具有芳香环的TDI、MDI以及聚四氢呋喃可以在上述条件下按照不同使用场景或要求动态调节来制备不同性能的产品。
优选的,步骤(1)的反应温度为60-80℃,反应时间为10-40min;步骤(2)的反应温度为60-120℃,反应时间为60-180min。
本发明中桦木醇基热塑性聚氨酯弹性体的可调节范围大,所述的桦木醇基热塑性聚氨酯弹性体的拉伸模量为7.2-173MPa,拉伸强度为1.6-16.0MPa,断裂伸长率为84-1100%。
与现有技术相比,本发明的有益效果在于:
(1)本发明利用了可再生的且绿色环保的生物质原料桦木醇制备得到了桦木醇基热塑性聚氨酯弹性体,该弹性体为热塑性材料,可以进行重复加工;
(2)本发明中的桦木醇基热塑性聚氨酯弹性体的性能可调节范围大,能够通过调控聚合物主链的软硬段比例,得到一系列具有不同性能范围的产物,从而满足用户对产品性能的不同要求。
附图说明
图1为所述的桦木醇基热塑性聚氨酯弹性体的合成过程示意图。
图2为实施例1和实施例3中的桦木醇基热塑性聚氨酯弹性体的拉伸性能曲线图。
具体实施方式
下面结合实施例和附图,进一步阐明本发明。应理解,这些实施例仅用于说明本发明,而不用于限制本发明的范围。
桦木醇采购于陕西绿晟源生物制品制造有限公司,纯度98%;
实施例或对比例中,异氰酸酯指数是以桦木醇与羟基封端聚合物的总羟基含量计算的;制得的桦木醇基热塑性聚氨酯弹性体需进行溶液铺膜或者热压得到片材后,再进行性能测试。
实施例1
(1)以摩尔份数计,称取10份聚四氢呋喃(数均分子量为850),在80℃下抽真空除水,然后加入21份甲苯二异氰酸酯(异氰酸酯指数1.05),搅拌10min至其分散均匀,然后加入痕量的二月桂酸二丁基锡,在60℃下反应20min,得到聚氨酯预聚体;
(2)称取25份的四氢呋喃溶液,加入活化后的分子筛除水;称取10份桦木醇粉末,在80℃下抽真空除水;然后将处理好的桦木醇粉末加入除水后的四氢呋喃溶液中充分溶解得到桦木醇溶液;再将桦木醇溶液加入到步骤(1)的聚氨酯预聚体中(硬段含量为50%),并在80℃下反应120min(加装冷凝回流装置),得到所述的桦木醇基热塑性聚氨酯弹性体(合成过程示意图如图1所示)。
将桦木醇基热塑性聚氨酯弹性体剪裁成哑铃状拉伸样条,在万能式样拉伸机上进行测试,拉伸性能曲线图如图2所示,该桦木醇基热塑性聚氨酯弹性体具有173MPa的模量,16.0MPa拉伸强度,440%的断裂伸长率。
实施例2
将10份的聚四氢呋喃替换为20份的聚四氢呋喃,21份甲苯二异氰酸酯替换为31.5份(异氰酸酯指数仍为1.05),其他参数和方法与实施例1相同,得到硬段含量为40%的桦木醇基热塑性聚氨酯弹性体。
经与实施例1相同的方法测试其各项性能时发现,本实施例中桦木醇基热塑性聚氨酯弹性体具有30.9MPa的模量,2.22MPa拉伸强度,97%的断裂伸长率。
实施例3
将10份的聚四氢呋喃替换为15份的聚四氢呋喃,10份的桦木醇粉末替换为5份(异氰酸酯指数仍为1.05),其他参数和方法与实施例1相同,得到硬段含量为30%的桦木醇基热塑性聚氨酯弹性体。
经与实施例1相同的方法测试其各项性能时发现,该桦木醇基热塑性聚氨酯弹性体(拉伸性能曲线图如图2所示)具有17.5MPa的模量,6.14MPa拉伸强度,1100%的断裂伸长率;断裂伸长率有明显提高。
实施例4
将甲苯二异氰酸酯替换为六亚甲基二异氰酸酯,其他参数和方法与实施例1相同,得到桦木醇基热塑性聚氨酯弹性体。
经与实施例1相同的方法测试其各项性能时发现,本实施例中桦木醇基聚氨酯弹性体具有7.2MPa的模量,1.64MPa拉伸强度,524.2%的断裂伸长率。
实施例5
将甲苯二异氰酸酯替换为二苯基甲烷二异氰酸酯,其他参数和方法分别对应的与实施例1相同,并调整原料的摩尔份数,分别制备硬段含量分别为50%、40%和30%的桦木醇基热塑性聚氨酯弹性体。
经与实施例1相同的方法测试其各项性能时发现,将二异氰酸酯换为二苯基甲烷二异氰酸酯后,硬段含量为30%-50%的桦木醇基聚氨酯弹性体具有30.9-57.9MPa的模量,1.99-2.33MPa拉伸强度,84-270%的断裂伸长率。
实施例6
将25份的四氢呋喃溶液替换为30份的氯仿溶液,其他参数和方法与实施例1相同,得到桦木醇基热塑性聚氨酯弹性体。
经与实施例1相同的方法测试其各项性能时发现,本实施例中桦木醇基热塑性聚氨酯弹性体具有173MPa的模量,15.8MPa拉伸强度,420%的断裂伸长率。
对比例1
按照实施例1的制备方法,调整原料的摩尔份数,设置产品聚氨酯弹性体中硬段含量为70%,虽然可以成功制备聚氨酯薄膜,但是质脆易碎,无法测试力学性能。同样的,按照实施例1的制备方法,调整原料的摩尔份数,设置聚氨酯中硬段含量小于20%时,由于软段含量较高和桦木醇扩链剂的较大位阻结构,使得氢键无序度增大,微相分离程度低,故产物较软甚至变粘,性能较差。
对比例2
按照实施例1的制备方法,其中步骤(2)中不加入四氢呋喃溶液(直接向反应容器中加入桦木醇粉末),反应时间由120min替换为40min,其他参数和方法与实施例1相同,得到桦木醇基热塑性聚氨酯弹性体。
本对比例所制备的桦木醇基聚氨酯弹性体薄膜中存在桦木醇粉末颗粒(分散性差),经与实施例1相同的方法测试其性能时发现,本对比例中桦木醇基热塑性聚氨酯弹性体只具有10.5MPa的模量,1.65MPa拉伸强度,74%的断裂伸长率;其力学性能相对于实施例1大幅下降。
以上所述的实施例对本发明的技术方案进行了详细说明,应理解的是以上所述的仅为本发明的具体实施例,并不用于限制本发明,凡在本发明的原则范围内所做的任何修改、补充或类似方式替代等,均应包含在本发明的保护范围之内。
Claims (3)
1.一种桦木醇基热塑性聚氨酯弹性体的制备方法,其特征在于,包括以下步骤:
(1)利用羟基封端聚合物和二异氰酸酯以及催化剂反应得到聚氨酯预聚体;所述的羟基封端聚合物为聚四氢呋喃,数均分子量为500-2000;所述的二异氰酸酯为甲苯二异氰酸酯;
(2)向步骤(1)得到的聚氨酯预聚体中加入桦木醇溶液,反应得到所述的桦木醇基热塑性聚氨酯弹性体;所述的桦木醇溶液为桦木醇的氯仿溶液或桦木醇的四氢呋喃溶液;
步骤(2)的反应温度为60-120℃,反应时间为60-180min;
所述的桦木醇基热塑性聚氨酯弹性体的结构式为:
式中,n为5-12的正整数,BE为桦木醇残基,DI为二异氰酸酯残基,R为聚四氢呋喃和二异氰酸酯反应所形成的聚合物残基;
所述的桦木醇基热塑性聚氨酯弹性体中,硬段含量为20-60%;
所述的桦木醇基热塑性聚氨酯弹性体的拉伸模量为7.2-173MPa,拉伸强度为1.6-16.0MPa,断裂伸长率为84-1100%。
2.根据权利要求1所述的桦木醇基热塑性聚氨酯弹性体的制备方法,其特征在于,以桦木醇与羟基封端聚合物的羟基含量计算,基于总羟基含量的异氰酸酯指数为1.0-1.1。
3.根据权利要求1所述的桦木醇基热塑性聚氨酯弹性体的制备方法,其特征在于,步骤(1)的反应温度为60-80℃,反应时间为10-40min。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202211149129.XA CN115521434B (zh) | 2022-09-20 | 2022-09-20 | 一种桦木醇基热塑性聚氨酯弹性体及其制备方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202211149129.XA CN115521434B (zh) | 2022-09-20 | 2022-09-20 | 一种桦木醇基热塑性聚氨酯弹性体及其制备方法 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN115521434A CN115521434A (zh) | 2022-12-27 |
CN115521434B true CN115521434B (zh) | 2023-11-03 |
Family
ID=84699816
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202211149129.XA Active CN115521434B (zh) | 2022-09-20 | 2022-09-20 | 一种桦木醇基热塑性聚氨酯弹性体及其制备方法 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN115521434B (zh) |
Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2001288222A (ja) * | 2000-04-06 | 2001-10-16 | Kyokuto Kobunshi Kk | ベチュリンから得られるポリマー及びその製造法 |
JP2010090385A (ja) * | 2009-11-30 | 2010-04-22 | Kyokuto Kobunshi Kk | ベチュリンから得られるポリマー及びその製造法 |
JP2013082929A (ja) * | 2012-12-14 | 2013-05-09 | Masayoshi Tabata | ベチュリンから得られるポリマー及びその製造法 |
CN105294970A (zh) * | 2015-11-24 | 2016-02-03 | 深圳光华伟业股份有限公司 | 一种生物基热塑性聚氨酯弹性体材料及其的制备方法 |
CN110079207A (zh) * | 2019-04-29 | 2019-08-02 | 青岛必福高分子科技有限公司 | 一种水泥基墙地面用高硬度水性涂料及其一遍薄涂成型的施工方法 |
CN111808292A (zh) * | 2020-07-10 | 2020-10-23 | 浙江旭川树脂有限公司 | 一种桦木醇基耐水解阻燃性聚酯多元醇及其制备方法 |
CN112292434A (zh) * | 2018-06-25 | 2021-01-29 | 汉高股份有限及两合公司 | 基于可再生原料的包装粘合剂 |
CN112839976A (zh) * | 2018-10-15 | 2021-05-25 | 汉高股份有限及两合公司 | 包含生物基聚酯多元醇的热熔粘合剂组合物 |
CN115093530A (zh) * | 2022-07-27 | 2022-09-23 | 旭川化学(苏州)有限公司 | 一种生物基阻燃热塑性聚氨酯弹性体及其制备方法 |
-
2022
- 2022-09-20 CN CN202211149129.XA patent/CN115521434B/zh active Active
Patent Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2001288222A (ja) * | 2000-04-06 | 2001-10-16 | Kyokuto Kobunshi Kk | ベチュリンから得られるポリマー及びその製造法 |
JP2010090385A (ja) * | 2009-11-30 | 2010-04-22 | Kyokuto Kobunshi Kk | ベチュリンから得られるポリマー及びその製造法 |
JP2013082929A (ja) * | 2012-12-14 | 2013-05-09 | Masayoshi Tabata | ベチュリンから得られるポリマー及びその製造法 |
CN105294970A (zh) * | 2015-11-24 | 2016-02-03 | 深圳光华伟业股份有限公司 | 一种生物基热塑性聚氨酯弹性体材料及其的制备方法 |
CN112292434A (zh) * | 2018-06-25 | 2021-01-29 | 汉高股份有限及两合公司 | 基于可再生原料的包装粘合剂 |
CN112839976A (zh) * | 2018-10-15 | 2021-05-25 | 汉高股份有限及两合公司 | 包含生物基聚酯多元醇的热熔粘合剂组合物 |
CN110079207A (zh) * | 2019-04-29 | 2019-08-02 | 青岛必福高分子科技有限公司 | 一种水泥基墙地面用高硬度水性涂料及其一遍薄涂成型的施工方法 |
CN111808292A (zh) * | 2020-07-10 | 2020-10-23 | 浙江旭川树脂有限公司 | 一种桦木醇基耐水解阻燃性聚酯多元醇及其制备方法 |
CN115093530A (zh) * | 2022-07-27 | 2022-09-23 | 旭川化学(苏州)有限公司 | 一种生物基阻燃热塑性聚氨酯弹性体及其制备方法 |
Non-Patent Citations (3)
Title |
---|
Betulin-Constituted Multiblock Amphiphiles for Broad-Spectrum Protein Resistance;Ye Chen etc.;《ACS Appl. Mater. Interfaces》;第10卷;第6593-6600页 * |
Carbon Dioxide Adsorption in Betulin-Based Micro- and Macroporous Polyurethanes;Jekaterina Jeromenok etc.;《ChemistryOpen》;第2卷(第1期);第17-20页 * |
李绍雄等.《聚氨酯树脂及其应用》.化学工业出版社,2002,(第1版),第266-267页. * |
Also Published As
Publication number | Publication date |
---|---|
CN115521434A (zh) | 2022-12-27 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN105399917B (zh) | 一种有机硅改性热塑性聚氨酯弹性体及其制备方法 | |
KR100916490B1 (ko) | 폴리트리메틸렌 에테르 글리콜로부터의 폴리우레탄 및폴리우레탄-우레아 탄성체 | |
CN110627985B (zh) | 一种聚乳酸基热塑性聚氨酯弹性体材料及其制备方法 | |
CN101130597B (zh) | 一种耐溶剂型聚氨酯弹性体的合成方法 | |
CN109438653A (zh) | 一种生物型热塑性聚氨酯弹性体及其制备方法 | |
EP0316150B1 (en) | Thermosetting urethane elastomer | |
CN102181136A (zh) | 一种聚醚型聚氨酯弹性体增韧聚乳酸合金及其制备方法 | |
CN112126036A (zh) | 基于二硫键的生物基可降解交联自修复聚氨酯及其制备方法 | |
EP3632958B1 (en) | Method for producing a biopolyether polyol, biopolyether polyol, and biopolyurethane resin | |
Głowińska et al. | Eco-friendly route for thermoplastic polyurethane elastomers with bio-based hard segments composed of bio-glycol and mixtures of aromatic–aliphatic and aliphatic–aliphatic diisocyanate | |
CN105037676B (zh) | 一种低压缩永久变形的ppdi基聚氨酯弹性体及其制备方法 | |
CN115109220A (zh) | 一种耐水解热塑性聚氨酯弹性体材料的制备方法 | |
CN113045730A (zh) | 一种基于生物基的混炼型聚氨酯橡胶及制备方法与应用 | |
CN115521434B (zh) | 一种桦木醇基热塑性聚氨酯弹性体及其制备方法 | |
CN109929500B (zh) | 制备聚氨酯热熔胶的方法、聚氨酯热熔胶及加工制品 | |
CN115403740A (zh) | 一种可生物降解二氧化碳基聚氨酯树脂及其制备方法 | |
WO2007080929A1 (ja) | ポリオキサレートウレタン | |
JP3587051B2 (ja) | 軟質ポリウレタンフォームの製造方法 | |
CN110669199A (zh) | 高频筛用聚氨酯弹性体及其制备方法 | |
CN111848918B (zh) | 一种血管支架用可生物降解聚氨酯及其合成方法 | |
CN117801214A (zh) | 一种强度高耐磨型热塑性聚氨酯弹性体及其制备方法和用途 | |
WO2023153398A1 (ja) | プレポリマー組成物、ポリウレタン樹脂、弾性成形品およびプレポリマー組成物の製造方法 | |
CN117986522A (zh) | 热塑性聚氨酯弹性体及其制备方法和应用 | |
KR20090070023A (ko) | 가소제를 함유하지 않은 카렌다 가공성이 우수한 무가소제저경도 열가소성 폴리우레탄 수지 조성물 | |
CN116284659A (zh) | 一种高强度乳酸基生物可降解弹性体材料 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |