CN118047926B - Preparation method of flame-retardant bio-based thermoplastic polyurethane elastomer - Google Patents
Preparation method of flame-retardant bio-based thermoplastic polyurethane elastomer Download PDFInfo
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- CN118047926B CN118047926B CN202410451900.1A CN202410451900A CN118047926B CN 118047926 B CN118047926 B CN 118047926B CN 202410451900 A CN202410451900 A CN 202410451900A CN 118047926 B CN118047926 B CN 118047926B
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- 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 title claims abstract description 55
- 239000003063 flame retardant Substances 0.000 title claims abstract description 55
- 239000004433 Thermoplastic polyurethane Substances 0.000 title claims abstract description 53
- 229920003225 polyurethane elastomer Polymers 0.000 title claims abstract description 42
- 229920006392 biobased thermoplastic Polymers 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims abstract description 55
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 claims abstract description 55
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims abstract description 55
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000002156 mixing Methods 0.000 claims abstract description 27
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 26
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 22
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 22
- BBRPAFVVQFWFAX-UHFFFAOYSA-N O1NC=CC2=C1C=CC=C2.N2=PN=PN=P2 Chemical compound O1NC=CC2=C1C=CC=C2.N2=PN=PN=P2 BBRPAFVVQFWFAX-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229920005862 polyol Polymers 0.000 claims abstract description 21
- 150000003077 polyols Chemical class 0.000 claims abstract description 21
- 239000000203 mixture Substances 0.000 claims abstract description 14
- PDCMTKJRBAZZHL-UHFFFAOYSA-N 5-aminobenzene-1,3-diol Chemical compound NC1=CC(O)=CC(O)=C1 PDCMTKJRBAZZHL-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000005058 Isophorone diisocyanate Substances 0.000 claims abstract description 11
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 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 abstract description 11
- 229920000909 polytetrahydrofuran Polymers 0.000 claims abstract description 11
- 238000001723 curing Methods 0.000 claims abstract description 9
- 238000001746 injection moulding Methods 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims description 63
- 239000002904 solvent Substances 0.000 claims description 51
- 238000001035 drying Methods 0.000 claims description 47
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 42
- 238000010438 heat treatment Methods 0.000 claims description 34
- 238000003756 stirring Methods 0.000 claims description 28
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 24
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 21
- 239000008367 deionised water Substances 0.000 claims description 21
- 229910021641 deionized water Inorganic materials 0.000 claims description 21
- 238000005406 washing Methods 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- FUGYGGDSWSUORM-UHFFFAOYSA-N 4-hydroxystyrene Chemical compound OC1=CC=C(C=C)C=C1 FUGYGGDSWSUORM-UHFFFAOYSA-N 0.000 claims description 20
- SJGXVPFYFQTPLK-UHFFFAOYSA-N 1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene-2,2,4,4,6,6-hexamine Chemical compound NP1(N)=NP(N)(N)=NP(N)(N)=N1 SJGXVPFYFQTPLK-UHFFFAOYSA-N 0.000 claims description 19
- 238000001816 cooling Methods 0.000 claims description 19
- CTSLXHKWHWQRSH-UHFFFAOYSA-N oxalyl chloride Chemical compound ClC(=O)C(Cl)=O CTSLXHKWHWQRSH-UHFFFAOYSA-N 0.000 claims description 18
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 18
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 150000001263 acyl chlorides Chemical class 0.000 claims description 16
- -1 hexanitrocyclotriphosphazene Chemical compound 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 12
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 claims description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 10
- UBIJTWDKTYCPMQ-UHFFFAOYSA-N hexachlorophosphazene Chemical compound ClP1(Cl)=NP(Cl)(Cl)=NP(Cl)(Cl)=N1 UBIJTWDKTYCPMQ-UHFFFAOYSA-N 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 9
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 9
- 238000002390 rotary evaporation Methods 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 7
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- 239000008096 xylene Substances 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 6
- 230000003213 activating effect Effects 0.000 claims description 5
- 238000009835 boiling Methods 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 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 3
- 229920002803 thermoplastic polyurethane Polymers 0.000 abstract description 15
- 229920001971 elastomer Polymers 0.000 abstract description 13
- 239000000806 elastomer Substances 0.000 abstract description 13
- 229920002635 polyurethane Polymers 0.000 abstract description 6
- 239000004814 polyurethane Substances 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 125000002252 acyl group Chemical group 0.000 abstract description 2
- 230000009435 amidation Effects 0.000 abstract description 2
- 238000007112 amidation reaction Methods 0.000 abstract description 2
- 238000005660 chlorination reaction Methods 0.000 abstract description 2
- 238000004821 distillation Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000010025 steaming Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000002028 Biomass Substances 0.000 description 3
- 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 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 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 description 3
- 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 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
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- 238000012986 modification Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 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
- CMLFRMDBDNHMRA-UHFFFAOYSA-N 2h-1,2-benzoxazine Chemical group C1=CC=C2C=CNOC2=C1 CMLFRMDBDNHMRA-UHFFFAOYSA-N 0.000 description 1
- 229920001661 Chitosan Polymers 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
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- 230000007547 defect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical group C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
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- 238000011160 research Methods 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
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- 239000008107 starch Substances 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention relates to the technical field of polyurethane and discloses a preparation method of a flame-retardant bio-based thermoplastic polyurethane elastomer. Acrylic acid modified rosin, 5-amino resorcinol and the like are used as raw materials, and the modified rosin polyol is obtained through acyl chlorination and amidation. Adding modified rosin polyol, isophorone diisocyanate and the like into polytetrahydrofuran ether glycol, uniformly mixing, curing, and injection molding to form a sheet to obtain the bio-based thermoplastic polyurethane elastomer. Finally adding the hexaDOPO benzoxazine cyclotriphosphazene flame retardant into the mixture, uniformly mixing the mixture, carrying out melt blending, tabletting and sample preparation to obtain the flame-retardant bio-based thermoplastic polyurethane elastomer. The thermoplastic polyurethane elastomer prepared by the invention has better environmental protection, heat resistance, flame retardance and other properties.
Description
Technical Field
The invention relates to the technical field of polyurethane, in particular to a preparation method of a flame-retardant bio-based thermoplastic polyurethane elastomer.
Background
The thermoplastic polyurethane elastomer is polyurethane which can be plasticized by heating and dissolved by adding a solvent, has excellent wear resistance, low temperature resistance and other excellent performances, and is widely applied in modern production and life. However, polyurethane elastomers are very easy to burn and have great fire safety hazards in the application process, so that the improvement of the flame retardant property of the polyurethane elastomer is attracting a great deal of attention from researchers. 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) is a flame retardant intermediate, has excellent flame retardant property and is widely applied.
Biomass resources have the advantages of easy acquisition, regeneration and the like, and common biomass resources include starch, chitosan, natural vegetable oil and the like. Rosin is a natural resource with abundant sources and low price, and is widely applied to the fields of paint, paper making, soap and the like. Most of the monomers for polyurethane synthesis belong to fossil fuels, belong to non-renewable resources, and with shortage of fossil fuels and aggravation of environmental pollution, development of use of bio-based polyols for polyurethane synthesis is a hot spot of current research.
For example, patent publication number CN115521434B discloses a betulin-based thermoplastic polyurethane elastomer and a preparation method thereof, the invention uses hydroxyl-terminated polymer, diisocyanate, betulin solution and the like as raw materials, and the prepared betulin-based thermoplastic polyurethane elastomer has better mechanical properties, but does not improve the flame retardant property and heat resistance.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a preparation method of a flame-retardant bio-based thermoplastic polyurethane elastomer, and the prepared thermoplastic polyurethane has better environmental protection, flame retardance and heat resistance.
The preparation method of the flame retardant bio-based thermoplastic polyurethane elastomer comprises the following steps:
(1) Adding acrylic acid modified rosin into a dichloromethane solvent, adding oxalyl chloride into the dichloromethane solvent, reacting for 2-5 hours at 20-30 ℃, after the reaction is finished, performing rotary evaporation, washing with deionized water, and drying to obtain acrylic acid modified rosin acyl chloride;
(2) Under the condition of nitrogen, adding acrylic acid modified rosin acyl chloride and 5-amino resorcinol into a xylene solvent, stirring and dispersing, heating to 120-140 ℃, reacting for 1-3h, cooling to room temperature after the reaction is finished, washing with deionized water, and drying to obtain modified rosin polyol;
(3) Adding polytetrahydrofuran ether glycol, modified rosin polyol, isophorone diisocyanate and an organotin catalyst into a reaction kettle, uniformly mixing, placing into a nitrogen-protected oven at 120 ℃ for curing for 3-6 hours, cooling to room temperature after the reaction is finished, crushing into particles, and performing injection molding at 190 ℃ to obtain a bio-based thermoplastic polyurethane elastomer;
(4) Adding hexaDOPO benzoxazine cyclotriphosphazene flame retardant into the bio-based thermoplastic polyurethane elastomer, uniformly mixing, placing into a torque rheometer for melt blending, drying in an oven at 100-110 ℃ for 5-10h, and then placing into a flat vulcanizing machine at 145 ℃ and 42kPa for tabletting and sample preparation to obtain the flame-retardant bio-based thermoplastic polyurethane elastomer.
Preferably, in the step (1), the molar ratio of the acrylic modified rosin to the oxalyl chloride is 1: (1.125-1.15).
Preferably, in the step (2), the molar ratio of the acrylic modified rosin acyl chloride to the 5-amino resorcinol is 1: (1.4-1.5).
Preferably, in the step (3), the mass ratio of polytetrahydrofuran ether glycol, modified rosin polyol, isophorone diisocyanate and organotin catalyst is (0.15-1.5): (0.15-1.5): 1: (0.00003-0.0001).
Preferably, in the step (4), the mass ratio of the bio-based thermoplastic polyurethane elastomer to the hexaDOPO benzoxazine cyclotriphosphazene flame retardant is 100: (5-30).
Preferably, in the step (4), the rotor speed of the torque rheometer is 20-30r/min, and the 4 temperature areas are 170 ℃, 172 ℃, 175 ℃ and 180 ℃.
Preferably, in the step (4), the preparation method of the hexaDOPO benzoxazine cyclotriphosphazene flame retardant is as follows:
S1, adding hexachlorocyclotriphosphazene and p-nitrophenol into an acetonitrile solvent, stirring and dispersing, adding potassium carbonate into the mixture, heating to 80-90 ℃, reacting for 5-12h, and carrying out reduced pressure distillation and drying after the reaction is finished to obtain hexanitrocyclotriphosphazene;
S2, adding reduced iron powder and 30-38% of concentrated hydrochloric acid into 70-80% of ethanol solution, heating, boiling and activating for 20-40min, and adding hexanitrocyclotriphosphazene into the mixture, wherein the mole ratio of the reduced iron powder to the hexanitrocyclotriphosphazene is (18-20): 1, reacting for 5-10 hours at 75-85 ℃, cooling to room temperature after the reaction is finished, filtering, distilling to remove solvent, and drying to obtain hexaaminocyclotriphosphazene;
S3, adding DOPO into a toluene solvent, stirring and dispersing, adding 4-vinyl phenol and azodiisobutyronitrile into the mixture, heating to 80-90 ℃, reacting for 6-12 hours, removing the solvent by rotary evaporation after the reaction is finished, and drying to obtain DOPO-containing phenol;
S4, adding hexaamino cyclotriphosphazene, DOPO-containing phenol and 35-40% formaldehyde aqueous solution into dioxane solvent, stirring and dispersing, heating to 90-100 ℃, reacting for 5-12h, decompressing and distilling after the reaction is finished, washing with deionized water, and drying to obtain the hexaDOPO benzoxazine cyclotriphosphazene flame retardant.
Preferably, in the step S1, the molar ratio of hexachlorocyclotriphosphazene, p-nitrophenol and potassium carbonate is 1: (7-7.5): (15-16).
Preferably, in the step S3, the molar ratio of DOPO, 4-vinylphenol, azobisisobutyronitrile is (0.8-1.2): 1: (0.01-0.02).
Preferably, in the step S4, the molar ratio of hexaaminocyclotriphosphazene to DOPO-group-containing phenol is 1:10.
Reaction mechanism: according to the invention, hexa-chloro-cyclotriphosphazene, p-nitrophenol and iron powder are used as raw materials, hexa-amino-cyclotriphosphazene is obtained through reaction, DOPO, 4-vinyl phenol, hexa-amino-cyclotriphosphazene and the like are used as raw materials, and the hexa-DOPO benzoxazine cyclotriphosphazene flame retardant is obtained through reaction. Acrylic acid modified rosin, 5-amino resorcinol and the like are used as raw materials, and the modified rosin polyol is obtained through acyl chlorination and amidation. Adding modified rosin polyol, isophorone diisocyanate and the like into polytetrahydrofuran ether glycol, uniformly mixing, curing, and injection molding to form a sheet to obtain the bio-based thermoplastic polyurethane elastomer. Finally adding the hexaDOPO benzoxazine cyclotriphosphazene flame retardant into the mixture, uniformly mixing the mixture, carrying out melt blending, tabletting and sample preparation to obtain the flame-retardant bio-based thermoplastic polyurethane elastomer.
The beneficial effects are that: the flame-retardant bio-based thermoplastic polyurethane elastomer prepared by the invention contains phosphorus element, the phosphorus element is heated to form phosphoric acid and polyphosphoric acid, the dehydration and carbonization of the material are promoted, in addition, the oxygen acid of the phosphorus is in a glass shape and can be covered on the surface of a combustion material to form a non-volatile film, so that the flame-retardant bio-based thermoplastic polyurethane elastomer plays a role in isolating oxygen. The nitrogen element contained in the flame retardant glass can be heated to generate flame retardant gas, so that the concentration of inflammable gas in the air is diluted, the flame retardant aim is achieved, and the benzoxazine structure contained in the flame retardant glass can be heated to generate a cross-linked network structure, so that the heat resistance of the flame retardant glass is improved.
The rosin prepared by the method is a cheap and easily available biomass resource, the environment-friendly performance of the rosin can be improved when the rosin is applied to thermoplastic polyurethane, and the rigidity and the thermal stability of a polyurethane material can be improved by a ternary phenanthrene ring rigid structure contained in the rosin. The thermoplastic polyurethane elastomer prepared by the invention has better environmental protection, heat resistance, flame retardance and other properties.
Drawings
FIG. 1 is a preparation route diagram of hexaaminocyclotriphosphazene of the invention;
FIG. 2 is a scheme for the preparation of DOPO-containing phenol according to the present invention.
Detailed Description
The technical scheme of the invention is further described through the specific embodiments. The examples are presented to facilitate a better understanding of the invention and are not intended to limit the invention in any way.
The preparation method of the acrylic modified rosin comprises the following steps: to 200g of rosin, 38g of acrylic acid was added, the temperature was raised to 250℃and the reaction was carried out for 2.5 hours, after the completion of the reaction, the mixture was cooled to room temperature, whereby an acrylic acid-modified rosin was obtained.
Example 1: (1) Adding 20mmol of hexachlorocyclotriphosphazene and 150mmol of p-nitrophenol into an acetonitrile solvent, stirring and dispersing, adding 300mmol of potassium carbonate into the mixture, heating to 90 ℃, reacting for 6 hours, and carrying out reduced pressure distillation and drying after the reaction is finished to obtain hexanitrocyclotriphosphazene;
(2) Adding 200mmol of reduced iron powder and 35% of concentrated hydrochloric acid into 70% ethanol solution, heating, boiling and activating for 30min, adding 10mmol of hexanitrocyclotriphosphazene into the solution, reacting at 85 ℃ for 5h, cooling to room temperature after the reaction is finished, filtering, distilling to remove solvent, and drying to obtain hexaaminocyclotriphosphazene;
(3) Adding 600mmol of DOPO into a toluene solvent, stirring and dispersing, adding 500mmol of 4-vinyl phenol and 8mmol of azodiisobutyronitrile, heating to 85 ℃, reacting for 12 hours, removing the solvent by rotary evaporation after the reaction is finished, and drying to obtain DOPO-containing phenol;
(4) Adding 20mmol of hexaamino cyclotriphosphazene, 200mmol of DOPO-containing phenol and 40% formaldehyde aqueous solution into a dioxane solvent, stirring and dispersing, heating to 95 ℃, reacting for 12 hours, decompressing and distilling after the reaction is finished, washing with deionized water, and drying to obtain the hexaDOPO benzoxazine cyclotriphosphazene flame retardant;
(5) Adding 40mmol of acrylic acid modified rosin into a dichloromethane solvent, adding 45mmol of oxalyl chloride into the dichloromethane solvent, reacting for 5 hours at 30 ℃, steaming in a rotary manner after the reaction is finished, washing with deionized water, and drying to obtain acrylic acid modified rosin acyl chloride;
(6) Under the condition of nitrogen, adding 20mmol of acrylic acid modified rosin acyl chloride and 30mmol of 5-aminoresorcinol into a xylene solvent, stirring and dispersing, heating to 130 ℃, reacting for 3 hours, cooling to room temperature after the reaction is finished, washing with deionized water, and drying to obtain modified rosin polyol;
(7) Adding 18g of polytetrahydrofuran ether glycol, 1.8g of modified rosin polyol, 12g of isophorone diisocyanate and 0.00036g of organotin catalyst into a reaction kettle, uniformly mixing, placing into a nitrogen-protected oven at 120 ℃, curing for 6 hours, cooling to room temperature after the reaction is finished, crushing into particles, and performing injection molding at 190 ℃ to obtain a bio-based thermoplastic polyurethane elastomer;
(8) Adding 2.5g of hexaDOPO benzoxazine cyclotriphosphazene flame retardant into 50g of biological thermoplastic polyurethane elastomer, uniformly mixing, placing into a torque rheometer, and melt blending, wherein the rotor speed of the torque rheometer is 20r/min,4 temperature areas are 170 ℃, 172 ℃, 175 ℃, 180 ℃, drying in a 110 ℃ oven for 10 hours, and then placing into a flat vulcanizing machine under the conditions of 145 ℃ and 42kPa for tabletting and sample preparation to obtain the flame retardant biological thermoplastic polyurethane elastomer.
Example 2: (1) Adding 20mmol of hexachlorocyclotriphosphazene and 140mmol of p-nitrophenol into an acetonitrile solvent, stirring and dispersing, adding 320mmol of potassium carbonate into the mixture, heating to 85 ℃, reacting for 12 hours, and carrying out reduced pressure distillation and drying after the reaction is finished to obtain hexanitrocyclotriphosphazene;
(2) 180mmol of reduced iron powder and 35% of concentrated hydrochloric acid are added into 80% ethanol solution, heated, boiled and activated for 40min, 10mmol of hexanitrocyclotriphosphazene is added into the solution, the reaction is carried out for 10h at 80 ℃, after the reaction is finished, the solution is cooled to room temperature, filtered, distilled to remove the solvent, and dried, thus obtaining hexaaminocyclotriphosphazene;
(3) Adding 500mmol of DOPO into a toluene solvent, stirring and dispersing, adding 500mmol of 4-vinyl phenol and 10mmol of azodiisobutyronitrile, heating to 85 ℃, reacting for 12 hours, removing the solvent by rotary evaporation after the reaction is finished, and drying to obtain DOPO-containing phenol;
(4) Adding 20mmol of hexaamino cyclotriphosphazene, 200mmol of DOPO-containing phenol and 40% formaldehyde aqueous solution into a dioxane solvent, stirring and dispersing, heating to 95 ℃, reacting for 12 hours, decompressing and distilling after the reaction is finished, washing with deionized water, and drying to obtain the hexaDOPO benzoxazine cyclotriphosphazene flame retardant;
(5) Adding 40mmol of acrylic acid modified rosin into a dichloromethane solvent, adding 45mmol of oxalyl chloride into the dichloromethane solvent, reacting for 5 hours at 25 ℃, steaming in a rotary manner after the reaction is finished, washing with deionized water, and drying to obtain acrylic acid modified rosin acyl chloride;
(6) Under the condition of nitrogen, adding 20mmol of acrylic acid modified rosin acyl chloride and 30mmol of 5-aminoresorcinol into a xylene solvent, stirring and dispersing, heating to 125 ℃, reacting for 3 hours, cooling to room temperature after the reaction is finished, washing with deionized water, and drying to obtain modified rosin polyol;
(7) Adding 15g of polytetrahydrofuran ether glycol, 4.8g of modified rosin polyol, 12g of isophorone diisocyanate and 0.0012g of organotin catalyst into a reaction kettle, uniformly mixing, placing into a nitrogen-protected oven at 120 ℃, curing for 5 hours, cooling to room temperature after the reaction is finished, crushing into particles, and performing injection molding at 190 ℃ to obtain a bio-based thermoplastic polyurethane elastomer;
(8) Adding 5g of hexaDOPO benzoxazine cyclotriphosphazene flame retardant into 50g of bio-based thermoplastic polyurethane elastomer, uniformly mixing, placing into a torque rheometer, and melt blending, wherein the rotor speed of the torque rheometer is 25r/min,4 temperature areas are 170 ℃, 172 ℃, 175 ℃, 180 ℃, drying in an oven at 105 ℃ for 10 hours, and then placing into a flat vulcanizing machine at 145 ℃ and 42kPa for tabletting and sample preparation to obtain the flame-retardant bio-based thermoplastic polyurethane elastomer.
Example 3: (1) Adding 20mmol of hexachlorocyclotriphosphazene and 150mmol of p-nitrophenol into an acetonitrile solvent, stirring and dispersing, adding 320mmol of potassium carbonate into the mixture, heating to 80 ℃, reacting for 12 hours, and carrying out reduced pressure distillation and drying after the reaction is finished to obtain hexanitrocyclotriphosphazene;
(2) Adding 200mmol of reduced iron powder and 38% of concentrated hydrochloric acid into 80% ethanol solution, heating, boiling and activating for 40min, adding 10mmol of hexanitrocyclotriphosphazene into the solution, reacting at 85 ℃ for 5h, cooling to room temperature after the reaction is finished, filtering, distilling to remove solvent, and drying to obtain hexaaminocyclotriphosphazene;
(3) Adding 600mmol of DOPO into a toluene solvent, stirring and dispersing, adding 500mmol of 4-vinyl phenol and 10mmol of azodiisobutyronitrile, heating to 90 ℃, reacting for 12 hours, removing the solvent by rotary evaporation after the reaction is finished, and drying to obtain DOPO-containing phenol;
(4) Adding 20mmol of hexaamino cyclotriphosphazene, 200mmol of DOPO-containing phenol and 40% formaldehyde aqueous solution into a dioxane solvent, stirring and dispersing, heating to 100 ℃, reacting for 5 hours, decompressing and distilling after the reaction is finished, washing with deionized water, and drying to obtain the hexaDOPO benzoxazine cyclotriphosphazene flame retardant;
(5) Adding 40mmol of acrylic acid modified rosin into a dichloromethane solvent, adding 45mmol of oxalyl chloride into the dichloromethane solvent, reacting for 5 hours at 30 ℃, steaming in a rotary manner after the reaction is finished, washing with deionized water, and drying to obtain acrylic acid modified rosin acyl chloride;
(6) Under the condition of nitrogen, adding 20mmol of acrylic acid modified rosin acyl chloride and 30mmol of 5-aminoresorcinol into a xylene solvent, stirring and dispersing, heating to 125 ℃, reacting for 3 hours, cooling to room temperature after the reaction is finished, washing with deionized water, and drying to obtain modified rosin polyol;
(7) Adding 9.8g of polytetrahydrofuran ether glycol, 10g of modified rosin polyol, 12g of isophorone diisocyanate and 0.001g of organotin catalyst into a reaction kettle, uniformly mixing, placing into a nitrogen-protected oven at 120 ℃, curing for 5 hours, cooling to room temperature after the reaction is finished, crushing into particles, and performing injection molding at 190 ℃ to obtain a bio-based thermoplastic polyurethane elastomer;
(8) Adding 10g of hexaDOPO benzoxazine cyclotriphosphazene flame retardant into 50g of bio-based thermoplastic polyurethane elastomer, uniformly mixing, placing into a torque rheometer, and melt blending, wherein the rotor speed of the torque rheometer is 25r/min,4 temperature areas are 170 ℃, 172 ℃, 175 ℃,180 ℃, drying in an oven at 105 ℃ for 10 hours, and then placing into a flat vulcanizing machine at 145 ℃ and 42kPa for tabletting and sample preparation to obtain the flame-retardant bio-based thermoplastic polyurethane elastomer.
Example 4: (1) Adding 20mmol of hexachlorocyclotriphosphazene and 140mmol of p-nitrophenol into an acetonitrile solvent, stirring and dispersing, adding 320mmol of potassium carbonate into the mixture, heating to 85 ℃, reacting for 12 hours, and carrying out reduced pressure distillation and drying after the reaction is finished to obtain hexanitrocyclotriphosphazene;
(2) Adding 200mmol of reduced iron powder and 38% of concentrated hydrochloric acid into 80% ethanol solution, heating, boiling and activating for 40min, adding 10mmol of hexanitrocyclotriphosphazene into the solution, reacting at 80 ℃ for 10h, cooling to room temperature after the reaction is finished, filtering, distilling to remove solvent, and drying to obtain hexaaminocyclotriphosphazene;
(3) Adding 400mmol of DOPO into a toluene solvent, stirring and dispersing, adding 500mmol of 4-vinyl phenol and 10mmol of azodiisobutyronitrile, heating to 90 ℃, reacting for 12 hours, removing the solvent by rotary evaporation after the reaction is finished, and drying to obtain DOPO-containing phenol;
(4) Adding 20mmol of hexaamino cyclotriphosphazene, 200mmol of DOPO-containing phenol and 40% formaldehyde aqueous solution into a dioxane solvent, stirring and dispersing, heating to 95 ℃, reacting for 12 hours, decompressing and distilling after the reaction is finished, washing with deionized water, and drying to obtain the hexaDOPO benzoxazine cyclotriphosphazene flame retardant;
(5) Adding 40mmol of acrylic acid modified rosin into a dichloromethane solvent, adding 45mmol of oxalyl chloride into the dichloromethane solvent, reacting for 4 hours at 30 ℃, steaming in a rotary manner after the reaction is finished, washing with deionized water, and drying to obtain acrylic acid modified rosin acyl chloride;
(6) Under the condition of nitrogen, adding 20mmol of acrylic acid modified rosin acyl chloride and 28mmol of 5-aminoresorcinol into a xylene solvent, stirring and dispersing, heating to 130 ℃, reacting for 3 hours, cooling to room temperature after the reaction is finished, washing with deionized water, and drying to obtain modified rosin polyol;
(7) Adding 4.8g of polytetrahydrofuran ether glycol, 15g of modified rosin polyol, 12g of isophorone diisocyanate and 0.001g of organotin catalyst into a reaction kettle, uniformly mixing, placing into a nitrogen-protected oven at 120 ℃, curing for 4 hours, cooling to room temperature after the reaction is finished, crushing into particles, and performing injection molding at 190 ℃ to obtain a bio-based thermoplastic polyurethane elastomer;
(8) Adding 12g of hexaDOPO benzoxazine cyclotriphosphazene flame retardant into 50g of bio-based thermoplastic polyurethane elastomer, uniformly mixing, placing into a torque rheometer, and melt blending, wherein the rotor speed of the torque rheometer is 30r/min,4 temperature areas are 170 ℃, 172 ℃, 175 ℃,180 ℃, drying in a 110 ℃ oven for 10 hours, and then placing into a flat vulcanizing machine under the conditions of 145 ℃ and 42kPa for tabletting and sample preparation to obtain the flame-retardant bio-based thermoplastic polyurethane elastomer.
Example 5: (1) Adding 20mmol of hexachlorocyclotriphosphazene and 150mmol of p-nitrophenol into an acetonitrile solvent, stirring and dispersing, adding 320mmol of potassium carbonate into the mixture, heating to 85 ℃, reacting for 12 hours, and carrying out reduced pressure distillation and drying after the reaction is finished to obtain hexanitrocyclotriphosphazene;
(2) 180mmol of reduced iron powder and 36% of concentrated hydrochloric acid are added into 80% ethanol solution, heated, boiled and activated for 30min, 10mmol of hexanitrocyclotriphosphazene is added into the solution, the reaction is carried out for 10h at 80 ℃, after the reaction is finished, the solution is cooled to room temperature, filtered, distilled to remove the solvent, and dried, thus obtaining hexaaminocyclotriphosphazene;
(3) Adding 400mmol of DOPO into a toluene solvent, stirring and dispersing, adding 500mmol of 4-vinyl phenol and 8mmol of azodiisobutyronitrile, heating to 85 ℃, reacting for 12 hours, removing the solvent by rotary evaporation after the reaction is finished, and drying to obtain DOPO-containing phenol;
(4) Adding 20mmol of hexaamino cyclotriphosphazene, 200mmol of DOPO-containing phenol and 40% formaldehyde aqueous solution into a dioxane solvent, stirring and dispersing, heating to 100 ℃, reacting for 10 hours, decompressing and distilling after the reaction is finished, washing with deionized water, and drying to obtain the hexaDOPO benzoxazine cyclotriphosphazene flame retardant;
(5) Adding 40mmol of acrylic acid modified rosin into a dichloromethane solvent, adding 46mmol of oxalyl chloride into the dichloromethane solvent, reacting for 4 hours at 30 ℃, steaming in a rotary manner after the reaction is finished, washing with deionized water, and drying to obtain acrylic acid modified rosin acyl chloride;
(6) Under the condition of nitrogen, adding 20mmol of acrylic acid modified rosin acyl chloride and 30mmol of 5-aminoresorcinol into a xylene solvent, stirring and dispersing, heating to 130 ℃, reacting for 3 hours, cooling to room temperature after the reaction is finished, washing with deionized water, and drying to obtain modified rosin polyol;
(7) Adding 1.8g of polytetrahydrofuran ether glycol, 18g of modified rosin polyol, 12g of isophorone diisocyanate and 0.0012g of organotin catalyst into a reaction kettle, uniformly mixing, placing into a nitrogen-protected oven at 120 ℃, curing for 5 hours, cooling to room temperature after the reaction is finished, crushing into particles, and performing injection molding at 190 ℃ to obtain a bio-based thermoplastic polyurethane elastomer;
(8) Adding 15g of hexaDOPO benzoxazine cyclotriphosphazene flame retardant into 50g of bio-based thermoplastic polyurethane elastomer, uniformly mixing, placing into a torque rheometer, and melt blending, wherein the rotor speed of the torque rheometer is 25r/min,4 temperature areas are 170 ℃, 172 ℃, 175 ℃,180 ℃, drying in a 110 ℃ oven for 10 hours, and then placing into a flat vulcanizing machine under the conditions of 145 ℃ and 42kPa for tabletting and sample preparation to obtain the flame-retardant bio-based thermoplastic polyurethane elastomer.
Comparative example 1: the difference between this comparative example and example 1 is that: in step (8), the hexaDOPO benzoxazine cyclotriphosphazene flame retardant is not contained.
An oxygen index tester was used to test the oxygen index of the thermoplastic polyurethane elastomer.
A vertical burn tester was used to test the vertical burn rating of the thermoplastic polyurethane elastomer.
Table 1: flame retardant Property test results of examples and comparative examples
As can be seen from Table 1, the thermoplastic polyurethane elastomer prepared by the present invention has excellent flame retardant properties.
The heat resistance of the polyurethane elastomer was tested using a thermogravimetric analyzer, with a temperature rise rate of 10 ℃/min.
Table 2: results of heat resistance test of examples and comparative examples
As can be seen from Table 2, the thermoplastic polyurethane elastomer prepared by the invention has better heat resistance.
The tensile strength of the thermoplastic polyurethane elastomer was tested with reference to GB/T528-2009.
The Shore A hardness of the polyurethane elastomer was tested with reference to GB/531.1-2009.
Table 3: mechanical property test results of examples and comparative examples
As can be seen from Table 3, the thermoplastic polyurethane elastomer prepared by the invention has better mechanical properties.
The foregoing description is only a preferred embodiment of the present invention, and the present invention is not limited thereto, but it is to be understood that modifications and equivalents of some of the technical features described in the foregoing embodiments may be made by those skilled in the art, although the present invention has been described in detail with reference to the foregoing embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (5)
1. The preparation method of the flame-retardant bio-based thermoplastic polyurethane elastomer is characterized by comprising the following steps of:
(1) Adding acrylic acid modified rosin into a dichloromethane solvent, adding oxalyl chloride into the dichloromethane solvent, reacting for 2-5 hours at 20-30 ℃, after the reaction is finished, performing rotary evaporation, washing with deionized water, and drying to obtain acrylic acid modified rosin acyl chloride;
(2) Under the condition of nitrogen, adding acrylic acid modified rosin acyl chloride and 5-amino resorcinol into a xylene solvent, stirring and dispersing, heating to 120-140 ℃, reacting for 1-3h, cooling to room temperature after the reaction is finished, washing with deionized water, and drying to obtain modified rosin polyol;
(3) Adding polytetrahydrofuran ether glycol, modified rosin polyol, isophorone diisocyanate and an organotin catalyst into a reaction kettle, uniformly mixing, placing into a nitrogen-protected oven at 120 ℃ for curing for 3-6 hours, cooling to room temperature after the reaction is finished, crushing into particles, and performing injection molding at 190 ℃ to obtain a bio-based thermoplastic polyurethane elastomer;
(4) Adding a hexaDOPO benzoxazine cyclotriphosphazene flame retardant into the bio-based thermoplastic polyurethane elastomer, wherein the mass ratio of the hexaDOPO benzoxazine cyclotriphosphazene flame retardant to the bio-based thermoplastic polyurethane elastomer is 100: (5-30), uniformly mixing, placing in a torque rheometer, carrying out melt blending, drying in an oven at 100-110 ℃ for 5-10h, then placing in a flat vulcanizing machine at 145 ℃ and 42kPa for tabletting and sample preparation to obtain the flame-retardant bio-based thermoplastic polyurethane elastomer, wherein the preparation method of the hexaDOPO benzoxazine cyclotriphosphazene flame retardant comprises the following steps:
S1, adding hexachlorocyclotriphosphazene and p-nitrophenol into an acetonitrile solvent, stirring and dispersing, and then adding potassium carbonate into the acetonitrile solvent, wherein the molar ratio of hexachlorocyclotriphosphazene to p-nitrophenol to potassium carbonate is 1: (7-7.5): (15-16), heating to 80-90 ℃, reacting for 5-12h, distilling under reduced pressure after the reaction is finished, and drying to obtain hexanitrocyclotriphosphazene;
S2, adding reduced iron powder and 30-38% of concentrated hydrochloric acid into 70-80% of ethanol solution, heating, boiling and activating for 20-40min, and adding hexanitrocyclotriphosphazene into the mixture, wherein the mole ratio of the reduced iron powder to the hexanitrocyclotriphosphazene is (18-20): 1, reacting for 5-10 hours at 75-85 ℃, cooling to room temperature after the reaction is finished, filtering, distilling to remove solvent, and drying to obtain hexaaminocyclotriphosphazene;
s3, adding DOPO into a toluene solvent, stirring and dispersing, and then adding 4-vinyl phenol and azobisisobutyronitrile, wherein the molar ratio of DOPO to 4-vinyl phenol to azobisisobutyronitrile is (0.8-1.2): 1: (0.01-0.02), heating to 80-90 ℃, reacting for 6-12h, removing the solvent by rotary evaporation after the reaction is finished, and drying to obtain DOPO-containing phenol;
S4, adding hexaaminocyclotriphosphazene, DOPO-group-containing phenol and 35-40% formaldehyde aqueous solution into a dioxane solvent, wherein the mole ratio of the hexaaminocyclotriphosphazene to the DOPO-group-containing phenol is 1:10, stirring and dispersing, heating to 90-100 ℃, reacting for 5-12h, after the reaction is finished, distilling under reduced pressure, washing with deionized water, and drying to obtain the hexaDOPO benzoxazine cyclotriphosphazene flame retardant.
2. The method for preparing a flame retardant bio-based thermoplastic polyurethane elastomer according to claim 1, wherein in the step (1), the molar ratio of the acrylic acid modified rosin to the oxalyl chloride is 1: (1.125-1.15).
3. The method for preparing a flame retardant bio-based thermoplastic polyurethane elastomer according to claim 1, wherein in the step (2), the molar ratio of the acrylic acid modified rosin acyl chloride to the 5-amino resorcinol is 1: (1.4-1.5).
4. The method for preparing a flame retardant bio-based thermoplastic polyurethane elastomer according to claim 1, wherein in the step (3), the mass ratio of polytetrahydrofuran ether glycol, modified rosin polyol, isophorone diisocyanate, and organotin catalyst is (0.15-1.5): (0.15-1.5): 1: (0.00003-0.0001).
5. The method for preparing a flame retardant bio-based thermoplastic polyurethane elastomer according to claim 1, wherein in the step (4), the rotational speed of the rotor of the torque rheometer is 20-30r/min, and the 4 temperature zones are 170 ℃, 172 ℃, 175 ℃ and 180 ℃.
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