CN116813861B - Thermoplastic TPU prepared based on biological base and preparation process thereof - Google Patents
Thermoplastic TPU prepared based on biological base and preparation process thereof Download PDFInfo
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- CN116813861B CN116813861B CN202310723665.4A CN202310723665A CN116813861B CN 116813861 B CN116813861 B CN 116813861B CN 202310723665 A CN202310723665 A CN 202310723665A CN 116813861 B CN116813861 B CN 116813861B
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- flame retardant
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- 229920001169 thermoplastic Polymers 0.000 title claims abstract description 46
- 239000004416 thermosoftening plastic Substances 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 39
- 239000003063 flame retardant Substances 0.000 claims abstract description 119
- 229920005862 polyol Polymers 0.000 claims abstract description 98
- -1 flame retardant polyol Chemical class 0.000 claims abstract description 63
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 41
- 239000002994 raw material Substances 0.000 claims abstract description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 11
- DWSWCPPGLRSPIT-UHFFFAOYSA-N benzo[c][2,1]benzoxaphosphinin-6-ium 6-oxide Chemical compound C1=CC=C2[P+](=O)OC3=CC=CC=C3C2=C1 DWSWCPPGLRSPIT-UHFFFAOYSA-N 0.000 claims description 61
- 150000003077 polyols Chemical class 0.000 claims description 58
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 39
- 229930185605 Bisphenol Natural products 0.000 claims description 37
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 37
- 239000011574 phosphorus Substances 0.000 claims description 37
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 36
- 235000012424 soybean oil Nutrition 0.000 claims description 31
- 239000003549 soybean oil Substances 0.000 claims description 31
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 24
- 238000002156 mixing Methods 0.000 claims description 22
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 19
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 18
- 150000001875 compounds Chemical class 0.000 claims description 18
- WUMMIJWEUDHZCL-UHFFFAOYSA-N 3-prop-2-enyloxolane-2,5-dione Chemical compound C=CCC1CC(=O)OC1=O WUMMIJWEUDHZCL-UHFFFAOYSA-N 0.000 claims description 16
- 239000004970 Chain extender Substances 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 claims description 13
- 229940014800 succinic anhydride Drugs 0.000 claims description 13
- 229940043375 1,5-pentanediol Drugs 0.000 claims description 12
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 12
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 claims description 12
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 claims description 12
- PJUIMOJAAPLTRJ-UHFFFAOYSA-N monothioglycerol Chemical compound OCC(O)CS PJUIMOJAAPLTRJ-UHFFFAOYSA-N 0.000 claims description 10
- 239000012948 isocyanate Substances 0.000 claims description 9
- 150000002513 isocyanates Chemical class 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 238000006552 photochemical reaction Methods 0.000 claims description 8
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 7
- 238000007796 conventional method Methods 0.000 claims description 7
- UBIJTWDKTYCPMQ-UHFFFAOYSA-N hexachlorophosphazene Chemical compound ClP1(Cl)=NP(Cl)(Cl)=NP(Cl)(Cl)=N1 UBIJTWDKTYCPMQ-UHFFFAOYSA-N 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 6
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 5
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 4
- JMFRWRFFLBVWSI-NSCUHMNNSA-N coniferol Chemical compound COC1=CC(\C=C\CO)=CC=C1O JMFRWRFFLBVWSI-NSCUHMNNSA-N 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- LZFOPEXOUVTGJS-ONEGZZNKSA-N trans-sinapyl alcohol Chemical compound COC1=CC(\C=C\CO)=CC(OC)=C1O LZFOPEXOUVTGJS-ONEGZZNKSA-N 0.000 claims description 4
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 claims description 2
- FDYWJVHETVDSRA-UHFFFAOYSA-N 1,1-diisocyanatobutane Chemical compound CCCC(N=C=O)N=C=O FDYWJVHETVDSRA-UHFFFAOYSA-N 0.000 claims description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims description 2
- 229940035437 1,3-propanediol Drugs 0.000 claims 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 claims description 2
- LWRBVKNFOYUCNP-UHFFFAOYSA-N 2-methyl-1-(4-methylsulfanylphenyl)-2-morpholin-4-ylpropan-1-one Chemical compound C1=CC(SC)=CC=C1C(=O)C(C)(C)N1CCOCC1 LWRBVKNFOYUCNP-UHFFFAOYSA-N 0.000 claims description 2
- KYIMHWNKQXQBDG-UHFFFAOYSA-N N=C=O.N=C=O.CCCCCC Chemical compound N=C=O.N=C=O.CCCCCC KYIMHWNKQXQBDG-UHFFFAOYSA-N 0.000 claims description 2
- 235000019484 Rapeseed oil Nutrition 0.000 claims description 2
- RAWPGIYPSZIIIU-UHFFFAOYSA-N [benzoyl(phenyl)phosphoryl]-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)P(=O)(C=1C=CC=CC=1)C(=O)C1=CC=CC=C1 RAWPGIYPSZIIIU-UHFFFAOYSA-N 0.000 claims 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 claims description 2
- LZFOPEXOUVTGJS-UHFFFAOYSA-N cis-sinapyl alcohol Natural products COC1=CC(C=CCO)=CC(OC)=C1O LZFOPEXOUVTGJS-UHFFFAOYSA-N 0.000 claims description 2
- 229940119526 coniferyl alcohol Drugs 0.000 claims description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 2
- 229920000166 polytrimethylene carbonate Polymers 0.000 claims description 2
- 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 claims description 2
- 229920006392 biobased thermoplastic Polymers 0.000 claims 3
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 claims 1
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 claims 1
- 239000012957 2-hydroxy-2-methyl-1-phenylpropanone Substances 0.000 claims 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 1
- 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 abstract description 77
- 239000004433 Thermoplastic polyurethane Substances 0.000 abstract description 46
- 229920002803 thermoplastic polyurethane Polymers 0.000 abstract description 46
- 229920002635 polyurethane Polymers 0.000 abstract description 35
- 239000004814 polyurethane Substances 0.000 abstract description 35
- 230000000694 effects Effects 0.000 abstract description 22
- 239000011159 matrix material Substances 0.000 abstract description 9
- 239000000463 material Substances 0.000 abstract description 7
- 238000001556 precipitation Methods 0.000 abstract description 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 30
- 238000002485 combustion reaction Methods 0.000 description 22
- 238000001035 drying Methods 0.000 description 13
- 238000001914 filtration Methods 0.000 description 11
- 238000012360 testing method Methods 0.000 description 10
- 238000005406 washing Methods 0.000 description 8
- 239000000654 additive Substances 0.000 description 7
- 230000000996 additive effect Effects 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- 125000003700 epoxy group Chemical group 0.000 description 6
- 238000001125 extrusion Methods 0.000 description 6
- 238000005469 granulation Methods 0.000 description 6
- 230000003179 granulation Effects 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 125000005442 diisocyanate group Chemical group 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000000571 coke Substances 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 238000001746 injection moulding Methods 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 235000015112 vegetable and seed oil Nutrition 0.000 description 3
- 239000008158 vegetable oil Substances 0.000 description 3
- 238000007259 addition reaction Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000007142 ring opening reaction Methods 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 1
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 description 1
- HACRKYQRZABURO-UHFFFAOYSA-N 2-phenylethyl isocyanate Chemical compound O=C=NCCC1=CC=CC=C1 HACRKYQRZABURO-UHFFFAOYSA-N 0.000 description 1
- MGYGFNQQGAQEON-UHFFFAOYSA-N 4-tolyl isocyanate Chemical compound CC1=CC=C(N=C=O)C=C1 MGYGFNQQGAQEON-UHFFFAOYSA-N 0.000 description 1
- 241001391944 Commicarpus scandens Species 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- GZNJJEODYYLYSA-UHFFFAOYSA-N diethyl prop-2-enyl phosphate Chemical compound CCOP(=O)(OCC)OCC=C GZNJJEODYYLYSA-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 239000003000 extruded plastic Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- 239000004312 hexamethylene tetramine Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002991 molded plastic Substances 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000747 poly(lactic acid) Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3855—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur
- C08G18/3863—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur containing groups having sulfur atoms between two carbon atoms, the sulfur atoms being directly linked to carbon atoms or other sulfur atoms
- C08G18/3865—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur containing groups having sulfur atoms between two carbon atoms, the sulfur atoms being directly linked to carbon atoms or other sulfur atoms containing groups having one sulfur atom between two carbon atoms
- C08G18/3868—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur containing groups having sulfur atoms between two carbon atoms, the sulfur atoms being directly linked to carbon atoms or other sulfur atoms containing groups having one sulfur atom between two carbon atoms the sulfur atom belonging to a sulfide 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
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
-
- 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3878—Low-molecular-weight compounds having heteroatoms other than oxygen having phosphorus
- C08G18/3889—Low-molecular-weight compounds having heteroatoms other than oxygen having phosphorus having nitrogen in addition to phosphorus
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention relates to the technical field of polyurethane materials, in particular to a thermoplastic TPU prepared based on a biological base and a preparation process thereof. The thermoplastic TPU prepared on the basis of the biobase consists of the following raw materials: the flame retardant polyol adds flame retardant elements P, N to a molecular chain to achieve an overall flame retardant effect, so that the problems of dispersity and uniformity of a polyurethane matrix and the flame retardant are effectively solved, and compared with flame retardant polyurethane added with the flame retardant, the flame retardant polyurethane solves the problems of incompatibility and easy precipitation of the flame retardant and the matrix. The thermoplastic TPU prepared based on the biological base is flame-retardant polyurethane, and the mechanical property and the flame-retardant property of the polyurethane are improved.
Description
Technical Field
The invention relates to the technical field of polyurethane materials, in particular to a thermoplastic TPU prepared based on a biological base and a preparation process thereof.
Background
Thermoplastic polyurethane elastomers (TPU) are a class of polyurethanes that can be plasticized by heating and dissolved by the addition of solvents. TPU's have very wide application in modern production and life due to their excellent wear resistance, mechanical and rebound resilience, low temperature resistance, chemical resistance and structural designability. Currently, monomers used in TPU synthesis include diisocyanates and polyols, etc., the chemical structure of which often determines the final properties of the material. However, most of the monomers used for thermoplastic elastomer synthesis are derived from fossil fuels and belong to non-renewable resources. With the shortage of fossil raw materials and the increase of environmental pollution, the synthesis of polyurethane from renewable resources is widely focused in industry and academia, and especially the synthesis of polyurethane from bio-based polyols is a research hotspot in the current polymer field. Renewable resources useful in the synthesis of bio-based polyols include vegetable oils, polylactic acids, natural rubber and saccharide chemicals and derivatives thereof, among others, where vegetable oil-based polyols have received great attention due to their abundant sources, low cost, and excellent combination of properties.
Chinese patent application number 202211431891.7 discloses a bio-based flame retardant polyurethane and a preparation method thereof. The preparation method of the bio-based flame retardant polyurethane comprises the following steps: enabling allyl diethyl phosphate to react with 3-mercapto-1, 2-propylene glycol to prepare phosphorus-containing flame-retardant polyol, and enabling vegetable oil to react with 3-mercapto-1, 2-propylene glycol to prepare bio-based polyol; and reacting the phosphorus-containing flame-retardant polyol, the bio-based polyol and diisocyanate to prepare the bio-based flame-retardant polyurethane. Although the bio-based flame-retardant polyurethane prepared by the method has good flame-retardant effect, the mechanical property is poor, the service life of the polyurethane is influenced when the bio-based flame-retardant polyurethane is used in an extremely severe environment, and the bio-based flame-retardant polyurethane is easy to break or damage, so that a preparation method of the polyurethane material with high flame-retardant effect and good mechanical property is required to be developed, and the application range and the service life of the polyurethane material are enlarged.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a thermoplastic TPU prepared based on a biological base and a preparation process thereof.
In order to solve the technical problems, the invention adopts the following technical scheme:
a thermoplastic TPU prepared based on biobased, consisting of the following raw materials: bio-based polyols, flame retardant polyols, isocyanates, catalysts, and chain extenders.
Preferably, the thermoplastic TPU prepared on the basis of biobases consists of the following raw materials in parts by weight: 40-80 parts of bio-based polyol, 5-15 parts of flame retardant polyol, 20-40 parts of isocyanate, 2-5 parts of catalyst and 7-14 parts of chain extender.
The bio-based polyol is any one of rapeseed oil polyol and soybean oil polyol.
The preparation method of the soybean oil polyol comprises the following steps: adding soybean oil, 3-mercapto-1, 2-propanediol and photoinitiator into a photochemical reaction instrument, stirring at room temperature, and reacting under ultraviolet light to obtain soybean oil-based polyol.
Preferably, the preparation method of the soybean oil polyol comprises the following steps: adding 8-14 parts by weight of soybean oil, 5-10 parts by weight of 3-mercapto-1, 2-propanediol and 0.05-0.2 part by weight of photoinitiator into a photochemical reaction instrument, stirring for 20-50min at room temperature and rotating speed of 300-500rpm, reacting for 3-8h under ultraviolet light, purifying with ethyl acetate, washing for 3-6 times with saturated sodium chloride, drying with anhydrous magnesium sulfate, and distilling under reduced pressure to obtain soybean oil-based polyol.
The photoinitiator is any one of 2-hydroxy-2-methyl-1-phenylpropion, 2-methyl-2- (4-morpholinyl) -1- [4- (methylthio) phenyl ] -1-propanone, 1-hydroxycyclohexylphenyl ketone, dibenzoylphenyl phosphine oxide and thiopropoxy thioxanthone.
The catalyst is any one of dibutyl tin diacetate, dibutyl tin dilaurate and stannous octoate.
The isocyanate is any one of 2,2' -diphenylmethane diisocyanate, phenethyl isocyanate, p-phenylene diisocyanate, butane diisocyanate, hexane diisocyanate and p-toluene isocyanate.
The chain extender is any one of bio-based 1, 3-propanediol, diethylene glycol, bio-based 1, 4-butanediol, bio-based 1, 5-pentanediol, hexamethylenetetramine, coumarol, coniferyl alcohol and sinapyl alcohol.
The bio-based polyurethane belongs to inflammable materials, the Limiting Oxygen Index (LOI) of the common TPU is only about 19%, combustion is extremely easy to occur, and secondary combustion and the like are caused by dripping of molten drops along with release of heat and smoke in the combustion process. The application of the flame retardant modified TPU in the fields with high fire safety requirements of parts such as automobiles, cables and the like is influenced, and the flame retardant modified TPU is very important. In order to solve the above problems, bio-based polyurethane can be generally rendered flame retardant by adding a flame retardant. The reactive flame retardant or the additive flame retardant is added in the process of synthesizing the polymer in a physical doping mode, but the additive flame retardant is large in addition amount, easy to separate out, poor in compatibility with polyurethane and capable of affecting the mechanical property of the material, but the reactive flame retardant is more efficient by taking the dispersion degree and uniformity of the polyurethane matrix and the flame retardant into consideration by participating in the reactive flame retardant. Compared with the traditional flame-retardant polyurethane added with the flame retardant, the flame-retardant polyurethane not only solves the problems of incompatibility and easy precipitation of the flame retardant and a matrix, but also improves the flame retardant property and the mechanical property of the polyurethane.
Specific reaction mechanism: s1, taking DOPO and allyl succinic anhydride as main raw materials, carrying out addition reaction on P-H in the DOPO and C=C double bond in the allyl succinic anhydride under the heating condition to obtain succinic anhydride grafted DOPO, adding diethanolamine-D4 for reaction, and carrying out reaction and addition reaction on anhydride and N-H in the diethanolamine-D4 to obtain a derivative of DOPO; s2, bisphenol S and hexachloro-triphosphazene are taken as main raw materials, acetone is taken as a solvent, phosphorus-containing bisphenol compound is obtained through stirring reaction, epoxy chloropropane is added to introduce epoxy groups, and phosphorus-containing bisphenol compound glycidyl ether is obtained; s3, taking a derivative of DOPO and the phosphorous bisphenol compound glycidyl ether as a reaction raw material, and taking N, N-dimethylformamide as a reaction solvent, and grafting the phosphorous bisphenol compound glycidyl ether into DOPO through a condensation reaction to obtain the flame retardant polyol.
The preparation method of the flame retardant polyol comprises the following steps:
S1, uniformly mixing an N, N-dimethylformamide solution of DOPO and a chloroform solution of allyl succinic anhydride, and performing a heating reaction to obtain succinic anhydride grafted DOPO; dissolving the succinic anhydride grafted DOPO in toluene, and adding diethanolamine-D4 to react to obtain a derivative of DOPO;
S2, uniformly mixing bisphenol S, triethylamine and acetone, adding hexachloro-triphosphazene for reaction, and then adding triethylamine and methanol for continuous reaction to obtain a phosphorus-containing bisphenol compound; uniformly mixing a phosphorus-containing bisphenol compound with acetone, adding epichlorohydrin, stirring, and then adding a sodium hydroxide aqueous solution for reaction to obtain phosphorus-containing bisphenol compound glycidyl ether;
s3, under the protection of nitrogen, mixing and reacting the derivative of DOPO, the glycidyl ether of the phosphorus-containing bisphenol compound and N, N-dimethylformamide to obtain the flame retardant polyol.
According to the invention, the derivative of DOPO with flame retardant effect is grafted with the phosphorous bisphenol compound glycidyl ether to obtain the flame retardant polyol, the flame retardant polyol can participate in the reaction of isocyanate and chain extender as the bio-based polyol, and the phosphorous flame retardant polyol and the bio-based polyol are grafted onto a molecular chain through esterification with diisocyanate, so that the flame retardant element P is added onto the molecular chain to obtain the polyurethane with flame retardant property. The DOPO derivative prepared in the S1 contains DOPO with flame retardant effect of polyhydroxy groups, carboxyl groups and P elements, the phosphorus-containing bisphenol compound glycidyl ether prepared in the S2 contains epoxy groups and P, the carboxyl groups in the derivative DOPOD in the S3 and the epoxy groups in the phosphorus-containing bisphenol compound glycidyl ether carry out ring opening reaction, the phosphorus-containing bisphenol compound glycidyl ether is effectively grafted into the DOPO derivative, and finally the polyhydroxy and P flame retardant polyol is obtained.
The flame retardant polyol prepared by the invention not only contains DOPO, but also has more excellent flame retardant performance compared with the DOPO flame retardant containing P and having flame retardant elements. Specifically, during combustion, the thermoplastic TPU prepared based on the biological base can be cracked to generate phosphoric acid molecules, and capture free radicals required by combustion reaction, so that flame retardant effect is exerted; and secondly, the thermoplastic TPU prepared based on the biological base is dehydrated and carbonized during combustion, so that the generation of combustible gas can be avoided, and meanwhile, a coke layer is formed on the surface of a combustion object to isolate the combustion environment, so that the further flame retardant effect is achieved.
The thermoplastic TPU prepared based on the biological base is flame-retardant polyurethane, and the flame-retardant element P, N is added to a molecular chain to achieve the overall flame-retardant effect, so that the problems of dispersity and uniformity of a polyurethane matrix and a flame retardant are effectively solved.
Preferably, the preparation method of the flame retardant polyol comprises the following steps:
s1, dissolving DOPO in N, N-dimethylformamide to prepare 1-2wt% DOPO solution, and dissolving allyl succinic anhydride in chloroform to prepare 0.5-1.5wt% allyl succinic anhydride solution; uniformly mixing 30-60 parts by weight of DOPO solution and 30-60 parts by weight of allyl succinic anhydride solution, reacting for 3-6 hours at 110-140 ℃ and 300-500rpm, cooling to room temperature, filtering, washing and drying to obtain succinic anhydride grafted DOPO; dissolving 3-7 parts by weight of succinic anhydride grafted DOPO in 80-160 parts by weight of toluene, adding 2-3 parts by weight of diethanolamine-D4, reacting for 4-8 hours at 65-85 ℃ and 300-500rpm, cooling to room temperature, extracting with ethyl acetate, retaining supernatant, distilling under reduced pressure, and drying to obtain a DOPO derivative;
S2, uniformly mixing 15-30 parts by weight of bisphenol S, 8-13 parts by weight of triethylamine and 200-400 parts by weight of acetone, adding 10-18 parts by weight of hexachlorophosphazene, reacting for 10-20 hours at 20-35 ℃ and 300-500rpm, adding 15-25 parts by weight of triethylamine and 5-15 parts by weight of methanol, continuing to react for 15-25 hours, filtering to keep filtrate, and distilling under reduced pressure to remove solvent to obtain phosphorus-containing bisphenol compound; mixing 8-14 parts by weight of phosphorus-containing bisphenol compound and 80-160 parts by weight of acetone uniformly, adding 20-40 parts by weight of epichlorohydrin, stirring for 5-12min at 500-800rpm, adding 20-40 parts by weight of 8-12wt% sodium hydroxide aqueous solution, reacting for 2-5h at 40-50 ℃ under 300-500rpm, filtering, washing and drying to obtain phosphorus-containing bisphenol compound glycidyl ether;
S3, under the protection of nitrogen, mixing 3-6 parts by weight of the DOPO derivative, 5-10 parts by weight of the phosphorus-containing bisphenol compound glycidyl ether and 80-180 parts by weight of N, N-dimethylformamide, placing the mixture at 110-140 ℃ for reaction for 5-8 hours at 500-800rpm, distilling under reduced pressure, and drying to obtain the flame retardant polyol.
According to the preparation process of the thermoplastic TPU based on the bio-based preparation, bio-based polyol, flame retardant polyol, isocyanate, catalyst and chain extender are uniformly mixed, and a double-screw extruder is adopted for extrusion granulation by a conventional method to obtain the thermoplastic TPU based on the bio-based preparation.
The invention has the beneficial effects that: the thermoplastic TPU prepared based on the biological base is prepared by adopting the phosphorus-containing and nitrogen-containing flame retardant polyol and the biological base polyol to participate in the diisocyanate reaction at the same time, the raw materials of the polyurethane prepared by the biological base polyol are from renewable resources, the thermoplastic TPU prepared by the flame retardant polyol is environment-friendly, not only is phosphorus element, nitrogen element and sulfur element with flame retardant effect introduced, but also phosphoric acid molecules can be produced by cracking during combustion so as to play a flame retardant effect, and the release of a large amount of toxic smoke in the combustion process is avoided; meanwhile, the bio-based polyurethane is dehydrated and carbonized during combustion, and a coke layer isolating the combustion environment is formed on the surface of the combustion object, so that the flame retardant effect can be further improved. The thermoplastic TPU prepared based on the biological base is flame-retardant polyurethane, and the flame-retardant element P, N is added to a molecular chain to achieve the overall flame-retardant effect, so that the problems of dispersity and uniformity of a polyurethane matrix and a flame retardant are effectively solved.
Detailed Description
The above summary of the present invention is described in further detail below in conjunction with the detailed description, but it should not be understood that the scope of the above-described subject matter of the present invention is limited to the following examples.
Example 1
The thermoplastic TPU prepared on the basis of the biobase is composed of the following raw materials in parts by weight: 70 parts of bio-based polyol, 30 parts of 2,2' -diphenylmethane diisocyanate, 4 parts of dibutyltin diacetate and 10 parts of chain extender 1, 5-pentanediol.
The bio-based polyol is a soybean oil polyol; the preparation method of the soybean oil polyol comprises the following steps: 10 parts by weight of soybean oil, 8 parts by weight of 3-mercapto-1, 2-propanediol and 0.1 part by weight of 2-hydroxy-2-methyl-1-phenylpropionic acid are added into a photochemical reaction instrument, stirred for 30min at room temperature and rotating speed of 400rpm, reacted for 5h under ultraviolet light, purified by ethyl acetate, washed by saturated sodium chloride for 4 times, dried by anhydrous magnesium sulfate and distilled under reduced pressure to obtain soybean oil-based polyol.
The preparation process of the thermoplastic TPU based on bio-based preparation comprises the following steps: 70 parts by weight of bio-based polyol, 30 parts by weight of 2,2' -diphenylmethane diisocyanate and 4 parts by weight of dibutyltin diacetate, 10 parts by weight of chain extender 1, 5-pentanediol are uniformly mixed, and extrusion granulation is carried out by a double screw extruder by a conventional method to obtain the thermoplastic TPU prepared based on bio-base.
Example 2
The thermoplastic TPU prepared on the basis of the biobase is composed of the following raw materials in parts by weight: 60 parts of bio-based polyol, 10 parts of flame retardant polyol, 30 parts of 2,2' -diphenylmethane diisocyanate, 4 parts of dibutyltin diacetate and 10 parts of chain extender 1, 5-pentanediol.
The bio-based polyol is a soybean oil polyol; the preparation method of the soybean oil polyol comprises the following steps: 10 parts by weight of soybean oil, 8 parts by weight of 3-mercapto-1, 2-propanediol and 0.1 part by weight of 2-hydroxy-2-methyl-1-phenylpropionic acid are added into a photochemical reaction instrument, stirred for 30min at room temperature and rotating speed of 400rpm, reacted for 5h under ultraviolet light, purified by ethyl acetate, washed by saturated sodium chloride for 4 times, dried by anhydrous magnesium sulfate and distilled under reduced pressure to obtain soybean oil-based polyol.
The preparation method of the flame retardant polyol comprises the following steps:
S1, dissolving DOPO in N, N-dimethylformamide to prepare 1.5wt% DOPO solution, and dissolving allyl succinic anhydride in chloroform to prepare 0.8wt% allyl succinic anhydride solution; uniformly mixing 50 parts by weight of DOPO solution and 50 parts by weight of allyl succinic anhydride solution, reacting at 130 ℃ and 400rpm for 5 hours, cooling to room temperature, filtering, washing and drying to obtain succinic anhydride grafted DOPO; 5 parts by weight of the succinic anhydride grafted DOPO are dissolved in 100 parts by weight of toluene, 2.4 parts by weight of diethanolamine-D4 are added, the mixture is reacted for 6 hours at 75 ℃ and 400rpm, cooled to room temperature, extracted with ethyl acetate, the supernatant is reserved, distilled under reduced pressure and dried, and the flame retardant polyol is obtained.
The preparation process of the thermoplastic TPU based on bio-based preparation comprises the following steps: 60 parts by weight of bio-based polyol, 10 parts by weight of flame retardant polyol, 30 parts by weight of 2,2' -diphenylmethane diisocyanate and 4 parts by weight of dibutyltin diacetate, 10 parts by weight of chain extender 1, 5-pentanediol are uniformly mixed, and extrusion granulation is carried out by a double screw extruder by a conventional method to obtain the thermoplastic TPU prepared based on bio-base.
Example 3
The thermoplastic TPU prepared on the basis of the biobase is composed of the following raw materials in parts by weight: 60 parts of bio-based polyol, 10 parts of flame retardant polyol, 30 parts of 2,2' -diphenylmethane diisocyanate, 4 parts of dibutyltin diacetate and 10 parts of chain extender 1, 5-pentanediol.
The bio-based polyol is a soybean oil polyol; the preparation method of the soybean oil polyol comprises the following steps: 10 parts by weight of soybean oil, 8 parts by weight of 3-mercapto-1, 2-propanediol and 0.1 part by weight of 2-hydroxy-2-methyl-1-phenylpropionic acid are added into a photochemical reaction instrument, stirred for 30min at room temperature and rotating speed of 400rpm, reacted for 5h under ultraviolet light, purified by ethyl acetate, washed by saturated sodium chloride for 4 times, dried by anhydrous magnesium sulfate and distilled under reduced pressure to obtain soybean oil-based polyol.
The preparation method of the flame retardant polyol comprises the following steps:
S1, dissolving DOPO in N, N-dimethylformamide to prepare 1.5wt% DOPO solution, and dissolving allyl succinic anhydride in chloroform to prepare 0.8wt% allyl succinic anhydride solution; uniformly mixing 50 parts by weight of DOPO solution and 50 parts by weight of allyl succinic anhydride solution, reacting at 130 ℃ and 400rpm for 5 hours, cooling to room temperature, filtering, washing and drying to obtain succinic anhydride grafted DOPO; dissolving 5 parts by weight of succinic anhydride grafted DOPO in 100 parts by weight of toluene, adding 2.4 parts by weight of diethanolamine-D4, reacting at 75 ℃ and 400rpm for 6 hours, cooling to room temperature, extracting with ethyl acetate, retaining an upper layer liquid, distilling under reduced pressure, and drying to obtain a derivative of DOPO;
S2, uniformly mixing 25 parts by weight of bisphenol S, 10 parts by weight of triethylamine and 300 parts by weight of acetone, adding 15 parts by weight of hexachloro-triphosphazene, reacting at 30 ℃ and 400rpm for 16 hours, adding 20 parts by weight of triethylamine and 10 parts by weight of methanol, continuing to react for 20 hours, filtering to keep filtrate, and distilling under reduced pressure to remove solvent to obtain a phosphorus-containing bisphenol compound; uniformly mixing 10 parts by weight of phosphorus-containing bisphenol compound with 100 parts by weight of acetone, adding 30 parts by weight of epichlorohydrin, stirring for 10min at 600rpm, adding 30 parts by weight of 10wt% sodium hydroxide aqueous solution, reacting for 3h at 45 ℃ and 400rpm, filtering, washing and drying to obtain phosphorus-containing bisphenol compound glycidyl ether;
S3, under the protection of nitrogen, 5 parts by weight of the DOPO derivative, 8 parts by weight of the phosphorus-containing bisphenol compound glycidyl ether and 100 parts by weight of N, N-dimethylformamide are mixed, and the mixture is reacted for 6 hours at 130 ℃ and 600rpm, distilled under reduced pressure and dried to obtain the flame retardant polyol.
The preparation process of the thermoplastic TPU based on bio-based preparation comprises the following steps:
60 parts by weight of bio-based polyol, 10 parts by weight of flame retardant polyol, 30 parts by weight of 2,2' -diphenylmethane diisocyanate and 4 parts by weight of dibutyltin diacetate, 10 parts by weight of chain extender 1, 5-pentanediol are uniformly mixed, and extrusion granulation is carried out by a double screw extruder by a conventional method to obtain the thermoplastic TPU prepared based on bio-base.
Example 4
The thermoplastic TPU prepared on the basis of the biobase is composed of the following raw materials in parts by weight: 60 parts of bio-based polyol, 10 parts of flame retardant polyol, 30 parts of 2,2' -diphenylmethane diisocyanate, 4 parts of dibutyltin diacetate and 10 parts of bio-based 1, 5-pentanediol.
The bio-based polyol is a soybean oil polyol; the preparation method of the soybean oil polyol comprises the following steps: 10 parts by weight of soybean oil, 8 parts by weight of 3-mercapto-1, 2-propanediol and 0.1 part by weight of 2-hydroxy-2-methyl-1-phenylpropionic acid are added into a photochemical reaction instrument, stirred for 30min at room temperature and rotating speed of 400rpm, reacted for 5h under ultraviolet light, purified by ethyl acetate, washed by saturated sodium chloride for 4 times, dried by anhydrous magnesium sulfate and distilled under reduced pressure to obtain soybean oil-based polyol.
The preparation method of the flame retardant polyol comprises the following steps:
S1, dissolving DOPO in N, N-dimethylformamide to prepare 1.5wt% DOPO solution, and dissolving allyl succinic anhydride in chloroform to prepare 0.8wt% allyl succinic anhydride solution; uniformly mixing 50 parts by weight of DOPO solution and 50 parts by weight of allyl succinic anhydride solution, reacting at 130 ℃ and 400rpm for 5 hours, cooling to room temperature, filtering, washing and drying to obtain succinic anhydride grafted DOPO; dissolving 5 parts by weight of succinic anhydride grafted DOPO in 100 parts by weight of toluene, adding 2.4 parts by weight of diethanolamine-D4, reacting at 75 ℃ and 400rpm for 6 hours, cooling to room temperature, extracting with ethyl acetate, retaining an upper layer liquid, distilling under reduced pressure, and drying to obtain a derivative of DOPO;
s2, uniformly mixing 25 parts by weight of bisphenol S, 10 parts by weight of triethylamine and 300 parts by weight of acetone, adding 15 parts by weight of hexachloro-triphosphazene, reacting at 30 ℃ and 400rpm for 16 hours, adding 20 parts by weight of triethylamine and 10 parts by weight of methanol, continuing to react for 20 hours, filtering to keep filtrate, and distilling under reduced pressure to remove solvent to obtain a phosphorus-containing bisphenol compound;
S3, under the protection of nitrogen, mixing 5 parts by weight of the DOPO derivative, 8 parts by weight of the phosphorus bisphenol compound and 100 parts by weight of N, N-dimethylformamide, reacting at 130 ℃ and 600rpm for 6 hours, distilling under reduced pressure, and drying to obtain the flame retardant polyol.
The preparation process of the thermoplastic TPU based on bio-based preparation comprises the following steps: 60 parts by weight of bio-based polyol, 10 parts by weight of flame retardant polyol, 30 parts by weight of 2,2' -diphenylmethane diisocyanate and 4 parts by weight of dibutyltin diacetate, 10 parts by weight of chain extender 1, 5-pentanediol are uniformly mixed, and extrusion granulation is carried out by a double screw extruder by a conventional method to obtain the thermoplastic TPU prepared based on bio-base.
Example 5
The thermoplastic TPU prepared on the basis of the biobase is composed of the following raw materials in parts by weight: 60 parts of bio-based polyol, 10 parts of flame retardant, 30 parts of 2,2' -diphenylmethane diisocyanate, 4 parts of dibutyltin diacetate and 10 parts of chain extender 1, 5-pentanediol.
The bio-based polyol is a soybean oil polyol; the preparation method of the soybean oil polyol comprises the following steps: 10 parts by weight of soybean oil, 8 parts by weight of 3-mercapto-1, 2-propanediol and 0.1 part by weight of 2-hydroxy-2-methyl-1-phenylpropionic acid are added into a photochemical reaction instrument, stirred for 30min at room temperature and rotating speed of 400rpm, reacted for 5h under ultraviolet light, purified by ethyl acetate, washed by saturated sodium chloride for 4 times, dried by anhydrous magnesium sulfate and distilled under reduced pressure to obtain soybean oil-based polyol.
The preparation method of the flame retardant comprises the following steps:
S1, uniformly mixing 25 parts by weight of bisphenol S, 10 parts by weight of triethylamine and 300 parts by weight of acetone, adding 15 parts by weight of hexachloro-triphosphazene, reacting at 30 ℃ and 400rpm for 16 hours, adding 20 parts by weight of triethylamine and 10 parts by weight of methanol, continuing to react for 20 hours, filtering to keep filtrate, and distilling under reduced pressure to remove solvent to obtain a phosphorus-containing bisphenol compound; uniformly mixing 10 parts by weight of phosphorus-containing bisphenol compound with 100 parts by weight of acetone, adding 30 parts by weight of epichlorohydrin, stirring for 10min at 600rpm, adding 30 parts by weight of 10wt% sodium hydroxide aqueous solution, reacting for 3h at 45 ℃ and 400rpm, filtering, washing and drying to obtain phosphorus-containing bisphenol compound glycidyl ether;
S2, under the protection of nitrogen, 5 parts by weight of DOPO, 8 parts by weight of the phosphorous bisphenol compound glycidyl ether and 100 parts by weight of N, N-dimethylformamide are mixed, and the mixture is placed at 130 ℃ and 600rpm for reaction for 6 hours, distilled under reduced pressure and dried to obtain the flame retardant polyol.
The preparation process of the thermoplastic TPU based on bio-based preparation comprises the following steps: 60 parts by weight of bio-based polyol, 10 parts by weight of flame retardant, 30 parts by weight of 2,2' -diphenylmethane diisocyanate and 4 parts by weight of dibutyltin diacetate, 10 parts by weight of chain extender 1, 5-pentanediol are uniformly mixed, and extrusion granulation is carried out by a double screw extruder by a conventional method to obtain the thermoplastic TPU prepared based on bio-base.
Test example 1
Mechanical property test: determination of Plastic tensile Property Using national Standard GB/T1040.2-2006 section 2: test conditions for molded and extruded plastics. The thermoplastic TPU prepared on the basis of the biological base prepared in the example is injection molded by an injection molding machine, and a type II sample is adopted, wherein the test temperature is 25 ℃, and the stretching rate is 250mm/min. Each group was provided with 5 replicates and averaged, the results are shown in table 1.
TABLE 1 results of thermoplastic TPU mechanical test prepared based on biobased
| Tensile strength, MPa | Elongation at break% | |
| Example 1 | 50.8 | 576 |
| Example 3 | 53.4 | 609 |
Test example 2
Flame retardant performance test: determination of the Combustion behavior by the oxygen index method for plastics, section 2, with reference to the national Standard GB/T2406.2-2009: room temperature test thermoplastic TPU prepared in the examples based on bio-based preparation was injection molded using an injection molding machine and then oxygen index was measured. Sample size: the test specimen was 100mm in length, 10mm in width and 4mm in thickness, adjusted at 23℃and 50% humidity for 90 hours, and a scribe line was marked at 50mm of the specimen. Parallel to the 5 groups, the average was taken and the results are shown in Table 2.
Vertical burn (UL-94) test: the thermoplastic TPU prepared in the examples based on the biobased preparation was injection molded with an injection molding machine with reference to GB/T2408-2008 "determination of the Combustion Properties of plastics horizontal and vertical methods", and then vertical combustion determination was carried out, using test method B: vertical combustion (V). Sample size: 125mm in length, 13mm in width and 3mm in thickness. Each group of samples was tested in duplicate and the results averaged and are shown in table 2.
TABLE 2 flame retardant Property test results of thermoplastic TPU prepared based on biobased
| LOI(％) | UL-94 rating | |
| Example 1 | 19.3 | V-2 |
| Example 2 | 25.6 | V-1 |
| Example 3 | 31.6 | V-0 |
| Example 4 | 27.3 | V-0 |
| Example 5 | 23.8 | V-1 |
From the results, the thermoplastic TPU prepared based on the biological base has good flame retardant effect, and the mechanical property is effectively improved. In the embodiment 1 of the present invention, the reactive flame retardant or the additive flame retardant is not added, the derivative of the partially reactive flame retardant DOPO is added in the embodiment 2, the completely reactive flame retardant polyol prepared by the specific method of the present invention is added in the embodiment 3, the mixture of the derivative of the partially reactive flame retardant DOPO and the additive flame retardant phosphorus bisphenol compound is added in the embodiment 4, the additive flame retardant phosphorus bisphenol compound and DOPO are only added in the embodiment 5, and the completely reactive flame retardant polyol prepared in the embodiment 3 not only contains DOPO, but also has flame retardant elements containing P, and has more excellent flame retardant performance compared with the DOPO flame retardant of single P element. Specifically, during combustion, the thermoplastic TPU prepared based on the biological base can be cracked to generate phosphoric acid molecules, and capture free radicals required by combustion reaction, so that flame retardant effect is exerted; and secondly, the thermoplastic TPU prepared based on the biological base is dehydrated and carbonized during combustion, so that the generation of combustible gas can be avoided, and meanwhile, a coke layer is formed on the surface of a combustion object to isolate the combustion environment, so that the further flame retardant effect is achieved. The flame retardant effect of comparative examples 3 to 4, example 4 is significantly inferior to that of example 3, because the phosphorus-containing bisphenol compound prepared in example 4 has no epoxy group, only the phosphorus-containing bisphenol compound cannot react with carboxyl groups in the derivative of DOPO, the phosphorus-containing bisphenol compound cannot be effectively grafted into the derivative of DOPO, and the phosphorus-containing bisphenol compound and the derivative of DOPO are simply mixed, so that the flame retardant effect of DOPO and the flame retardant effect of the phosphorus-containing bisphenol compound cannot be synergistically enhanced. It can be seen from examples 3 and 5 that the effect of the additive flame retardant alone is not at all as good as that of the completely reactive flame retardant polyol of example 3, because the additive flame retardant has poor compatibility with the matrix polyurethane, and at the same time, cannot react with isocyanate as a reaction raw material, cannot be well dispersed in the matrix, and affects the flame retardant effect thereof. The DOPO derivative prepared in the S1 contains DOPO with flame retardant effect of polyhydroxy groups, carboxyl groups and P elements, the phosphorus-containing bisphenol compound glycidyl ether prepared in the S2 contains epoxy groups and P, the carboxyl groups in the derivative DOPOD in the S3 and the epoxy groups in the phosphorus-containing bisphenol compound glycidyl ether carry out ring opening reaction, the phosphorus-containing bisphenol compound glycidyl ether is effectively grafted into the DOPO derivative, and finally the polyhydroxy and P flame retardant polyol is obtained. The prepared flame retardant polyol and bio-based polyol are simultaneously taken as raw materials to participate in the reaction, and flame retardant elements P, N are added to a molecular chain to achieve the overall flame retardant effect, so that the problems of dispersity and uniformity of a polyurethane matrix and the flame retardant are effectively solved.
Claims (8)
1. A thermoplastic TPU prepared on a biobasis, characterized by being composed of the following raw materials: a bio-based polyol, a flame retardant polyol, isocyanate, a catalyst, and a chain extender;
The preparation method of the flame retardant polyol comprises the following steps:
S1, uniformly mixing an N, N-dimethylformamide solution of DOPO and a chloroform solution of allyl succinic anhydride, and performing a heating reaction to obtain succinic anhydride grafted DOPO; dissolving the succinic anhydride grafted DOPO in toluene, and adding diethanolamine-D4 to react to obtain a derivative of DOPO;
S2, uniformly mixing bisphenol S, triethylamine and acetone, adding hexachloro-triphosphazene for reaction, and then adding triethylamine and methanol for continuous reaction to obtain a phosphorus-containing bisphenol compound; uniformly mixing a phosphorus-containing bisphenol compound with acetone, adding epichlorohydrin, stirring, and then adding a sodium hydroxide aqueous solution for reaction to obtain phosphorus-containing bisphenol compound glycidyl ether;
s3, under the protection of nitrogen, mixing and reacting the derivative of DOPO, the glycidyl ether of the phosphorus-containing bisphenol compound and N, N-dimethylformamide to obtain the flame retardant polyol.
2. The biobased prepared thermoplastic TPU of claim 1, wherein said biobased polyol is any one of rapeseed oil polyol, soybean oil polyol.
3. The bio-based thermoplastic TPU of claim 2, wherein said soybean oil polyol is prepared by the following process: adding soybean oil, 3-mercapto-1, 2-propanediol and photoinitiator into a photochemical reaction instrument, stirring at room temperature, and reacting under ultraviolet light to obtain soybean oil-based polyol.
4. A bio-based prepared thermoplastic TPU according to claim 3 wherein said photoinitiator is any of 2-hydroxy-2-methyl-1-phenyl-propanone, 2-methyl-2- (4-morpholinyl) -1- [4- (methylthio) phenyl ] -1-propanone, 1-hydroxycyclohexylphenyl-methanone, dibenzoylphenylphosphine oxide, thiopropyloxythioxanthone.
5. The biobased thermoplastic TPU of claim 1, wherein said catalyst is any one of dibutyltin diacetate, dibutyltin dilaurate, stannous octoate.
6. The biobased thermoplastic TPU of claim 1, wherein said isocyanate is any one of 2,2' -diphenylmethane diisocyanate, p-phenylene diisocyanate, butane diisocyanate, hexane diisocyanate.
7. The biobased prepared thermoplastic TPU of claim 1, wherein said chain extender is any one of biobased 1, 3-propanediol, diethylene glycol, biobased 1, 4-butanediol, biobased 1, 5-pentanediol, coumaryl alcohol, coniferyl alcohol, and sinapyl alcohol.
8. The process for the preparation of a thermoplastic TPU based on bio-based preparation according to any of the claims 1-7 comprising the steps of: and uniformly mixing the bio-based polyol, the flame retardant polyol, the isocyanate and the catalyst, and extruding and granulating by adopting a double-screw extruder by adopting a conventional method to obtain the thermoplastic TPU prepared on the basis of the bio-based.
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| CN116813861A (en) | 2023-09-29 |
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