CN118063837B - Preparation process of polyurethane foam material with flame retardant function - Google Patents
Preparation process of polyurethane foam material with flame retardant function Download PDFInfo
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- CN118063837B CN118063837B CN202410471879.1A CN202410471879A CN118063837B CN 118063837 B CN118063837 B CN 118063837B CN 202410471879 A CN202410471879 A CN 202410471879A CN 118063837 B CN118063837 B CN 118063837B
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- polyurethane foam
- flame retardant
- flame
- foam material
- polyurethane
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- 239000000463 material Substances 0.000 title claims abstract description 60
- 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 group 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 59
- 229920005830 Polyurethane Foam Polymers 0.000 title claims abstract description 37
- 239000011496 polyurethane foam Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000004793 Polystyrene Substances 0.000 claims abstract description 43
- 229920002223 polystyrene Polymers 0.000 claims abstract description 41
- 239000003063 flame retardant Substances 0.000 claims abstract description 40
- 239000002245 particle Substances 0.000 claims abstract description 40
- 229920002635 polyurethane Polymers 0.000 claims abstract description 36
- 239000004814 polyurethane Substances 0.000 claims abstract description 36
- 238000005187 foaming Methods 0.000 claims abstract description 22
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 42
- 238000006243 chemical reaction Methods 0.000 claims description 40
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- 239000001569 carbon dioxide Substances 0.000 claims description 16
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 15
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 13
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 12
- 239000003995 emulsifying agent Substances 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 9
- 239000003381 stabilizer Substances 0.000 claims description 9
- XDLGDTUOWIFMQC-UHFFFAOYSA-N 2,5-diiodobenzene-1,4-diol Chemical compound OC1=CC(I)=C(O)C=C1I XDLGDTUOWIFMQC-UHFFFAOYSA-N 0.000 claims description 8
- 238000007599 discharging Methods 0.000 claims description 8
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 8
- 238000000967 suction filtration Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 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
- CZHYKKAKFWLGJO-UHFFFAOYSA-N dimethyl phosphite Chemical compound COP([O-])OC CZHYKKAKFWLGJO-UHFFFAOYSA-N 0.000 claims description 7
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 7
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 7
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 7
- 235000011056 potassium acetate Nutrition 0.000 claims description 7
- 238000010898 silica gel chromatography Methods 0.000 claims description 7
- NWGKJDSIEKMTRX-AAZCQSIUSA-N Sorbitan monooleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O NWGKJDSIEKMTRX-AAZCQSIUSA-N 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 6
- QJPQVXSHYBGQGM-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 QJPQVXSHYBGQGM-UHFFFAOYSA-N 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- 239000011230 binding agent Substances 0.000 claims description 5
- 239000000706 filtrate Substances 0.000 claims description 5
- RBQRWNWVPQDTJJ-UHFFFAOYSA-N methacryloyloxyethyl isocyanate Chemical compound CC(=C)C(=O)OCCN=C=O RBQRWNWVPQDTJJ-UHFFFAOYSA-N 0.000 claims description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 3
- HVUMOYIDDBPOLL-XWVZOOPGSA-N Sorbitan monostearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O HVUMOYIDDBPOLL-XWVZOOPGSA-N 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- 238000013375 chromatographic separation Methods 0.000 claims description 2
- 239000000741 silica gel Substances 0.000 claims description 2
- 229910002027 silica gel Inorganic materials 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims 5
- 239000000178 monomer Substances 0.000 claims 5
- 229910052698 phosphorus Inorganic materials 0.000 claims 5
- 239000011574 phosphorus Substances 0.000 claims 5
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims 3
- 239000011630 iodine Substances 0.000 claims 3
- 229910052740 iodine Inorganic materials 0.000 claims 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims 2
- 239000007810 chemical reaction solvent Substances 0.000 claims 2
- 229920000642 polymer Polymers 0.000 claims 2
- OTABRXUCCNVFEN-UHFFFAOYSA-N acetic acid;triphenylphosphane Chemical compound CC(O)=O.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 OTABRXUCCNVFEN-UHFFFAOYSA-N 0.000 claims 1
- 229910052763 palladium Inorganic materials 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 abstract description 10
- 230000006835 compression Effects 0.000 abstract description 9
- 238000007906 compression Methods 0.000 abstract description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 7
- 229910052760 oxygen Inorganic materials 0.000 abstract description 7
- 239000001301 oxygen Substances 0.000 abstract description 7
- 229910019142 PO4 Inorganic materials 0.000 abstract description 5
- 238000005452 bending Methods 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 5
- 239000010452 phosphate Substances 0.000 abstract description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052799 carbon Inorganic materials 0.000 abstract description 3
- 238000002485 combustion reaction Methods 0.000 abstract description 3
- 239000011159 matrix material Substances 0.000 abstract description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 33
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 21
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- KKUKTXOBAWVSHC-UHFFFAOYSA-N Dimethylphosphate Chemical compound COP(O)(=O)OC KKUKTXOBAWVSHC-UHFFFAOYSA-N 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- 239000003480 eluent Substances 0.000 description 7
- 238000010828 elution Methods 0.000 description 7
- 239000003208 petroleum Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 4
- 239000003431 cross linking reagent Substances 0.000 description 4
- MHCLJIVVJQQNKQ-UHFFFAOYSA-N ethyl carbamate;2-methylprop-2-enoic acid Chemical compound CCOC(N)=O.CC(=C)C(O)=O MHCLJIVVJQQNKQ-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 4
- 239000004433 Thermoplastic polyurethane Substances 0.000 description 3
- AJKZIPCWVAURSI-UHFFFAOYSA-N carbamic acid;2-methylprop-2-enoic acid Chemical compound NC(O)=O.CC(=C)C(O)=O AJKZIPCWVAURSI-UHFFFAOYSA-N 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 3
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- -1 polypropylene Polymers 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000012745 toughening agent Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/122—Hydrogen, oxygen, CO2, nitrogen or noble gases
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
- C08F230/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing phosphorus
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/06—CO2, N2 or noble gases
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2443/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium or a metal; Derivatives of such polymers
- C08J2443/02—Homopolymers or copolymers of monomers containing phosphorus
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Polyurethanes Or Polyureas (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to the technical field of polyurethane foam, and discloses a preparation process of a polyurethane foam material with a flame-retardant function, wherein a main chain of polystyrene flame-retardant particles contains a carbamate structural unit which is the same as polyurethane, so that the compatibility of the polystyrene flame-retardant particles and the polyurethane is improved, after foaming, the polystyrene flame-retardant particles are uniformly distributed in the polyurethane foam material respectively, and the rigid polystyrene particles play roles of supporting a polyurethane foam material framework, dispersing and transferring stress, so that the rebound performance, the compression performance and the bending strength of the polyurethane foam material are remarkably improved. The main chain of the polystyrene flame-retardant particles contains a large number of phosphate flame-retardant groups. The polyurethane foam material can catalyze and promote the matrix to be dehydrated during combustion to form a carbon layer, has a good flame retardant effect, and improves the limiting oxygen index and the flame retardant property of the polyurethane foam material.
Description
Technical Field
The invention relates to the technical field of polyurethane foam, in particular to a preparation process of a polyurethane foam material with a flame-retardant function.
Background
The polyurethane foam plastic has good elasticity, wear resistance and heat insulation performance, is a foam buffer material with excellent performance, and has wide application in the aspects of precision instruments, furniture products and the like. Improving the mechanical property of polyurethane foam and expanding the application field is a research hot spot. Moreover, the polyurethane foam plastic has no flame retardant property, is easy to burn, has a large potential safety hazard, and therefore needs to be subjected to flame retardant modification. The polystyrene rigid particles have good mechanical strength and toughness, can be used as a toughening agent, a flame retardant and the like, and can be widely applied to high polymer materials such as polyurethane, polypropylene and the like. Chinese patent CN111303548B discloses a PS/TPU supercritical foaming composite material and a preparation method thereof, wherein polystyrene, thermoplastic polyurethane elastomer, polysiloxane-polyurethane segmented copolymer and the like are used as main raw materials, and the prepared PS/TPU supercritical foaming composite material has the advantages of high tensile strength, good rebound resilience performance, good mechanical property and the like. However, the patent does not solve the problem of poor flame retardant properties of polyurethane foam materials.
Disclosure of Invention
The invention solves the problems that the polyurethane foaming material has lower strength and no flame retardant property.
The technical scheme of the invention is as follows: a preparation process of a polyurethane foaming material with a flame retardant function comprises the following steps:
adding water, styrene, 1, 4-di (methyl methacrylate) -2, 5-di (dimethyl phosphate) benzene, an emulsifying agent and a stabilizing agent into a flask, heating to 60-70 ℃, uniformly mixing, then dropwise adding an aqueous solution of potassium persulfate, reacting for 30-60min, then adding styrene, reacting for 2-3h, filtering after the reaction, placing the product into a Soxhlet extractor, and extracting with ethanol to obtain polystyrene flame-retardant particles.
Step two, adding polyurethane, polystyrene flame-retardant particles, water and sodium dodecyl benzene sulfonate into a high-pressure reaction kettle, uniformly mixing, and then introducing carbon dioxide, wherein the pressure in the reaction kettle is controlled to be 4-5MPa; heating to 120-125 deg.C, and maintaining pressure for 20-30min; introducing carbon dioxide; controlling the pressure in the reaction kettle to be 6-8MPa, maintaining the pressure for 30-40min for the second time, discharging the materials after pressure relief, washing the materials with water and drying the materials to obtain the polyurethane foaming material with the flame retardant function.
Wherein the weight ratio of the styrene, the 1, 4-di (methyl methacrylate) -2, 5-di (dimethyl phosphate) benzene, the potassium persulfate and the added styrene in the step one is 100 (240-450) (9-12) (400-600).
Wherein, in the first step, the emulsifier is any one of span 60 and span 80; the stabilizer is polyvinylpyrrolidone.
Wherein, the weight ratio of polyurethane to polystyrene flame-retardant particles in the second step is 100 (12-30).
Wherein, the preparation process of the 1, 4-bis (methyl methacrylate) -2, 5-bis (dimethyl phosphate) benzene in the step one is as follows:
Step a, introducing nitrogen into a flask, and adding a solvent, 2-isocyanatoethyl methacrylate and 1, 4-dihydroxy-2, 5-diiodobenzene, wherein the solvent is any one of 1, 4-dioxane, toluene and acetonitrile; the molar ratio of the methacrylic acid 2-isocyanic acid ethyl ester to the 1, 4-dihydroxyl-2, 5-diiodobenzene is (2.1-2.3): 1; heating to 70-100 ℃, reacting for 6-12h, concentrating the solution, and separating by silica gel column chromatography to obtain the 1, 4-di (methyl acrylic carbamate) -2, 5-diiodobenzene.
Step b, introducing nitrogen into the flask, adding tetrahydrofuran solvent, 1, 4-bis (carbamic acid ester methacrylate) -2, 5-diiodobenzene and dimethyl phosphite, uniformly mixing, and adding catalyst bis (triphenylphosphine) palladium acetate, cocatalyst potassium acetate and acid-binding agent triethylamine, wherein the molar ratio of 1, 4-bis (carbamic acid ester methacrylate) -2, 5-diiodobenzene, dimethyl phosphite, bis (triphenylphosphine) palladium acetate, potassium acetate and triethylamine is 1 (2-2.2): 0.035-0.042): 0.2-0.26): 2-2.2; stirring and reacting for 6-18h at 60-65 ℃, filtering, concentrating the filtrate, and then performing silica gel column chromatography to obtain 1, 4-di (methyl methacrylate) -2, 5-di (dimethyl phosphate) benzene.
The invention has the technical effects that: the 1, 4-di (methyl methacrylate) -2, 5-di (dimethyl phosphate) benzene prepared by the invention contains two alkenyl groups, and is used as a novel cross-linking agent to carry out cross-linking polymerization with styrene, thus obtaining novel rigid polystyrene flame-retardant particles; and (5) blending and foaming with polyurethane to obtain the polyurethane foaming material. The main chain of the polystyrene flame-retardant particles contains the same carbamate structural unit as polyurethane, so that the compatibility of the polystyrene flame-retardant particles and the polyurethane is improved, the polystyrene flame-retardant particles are uniformly and respectively distributed in the polyurethane foam material after foaming, the rigid polystyrene particles play roles in supporting the polyurethane foam material framework, dispersing and transferring stress, and the rebound performance, the compression performance and the bending strength of the polyurethane foam material are remarkably improved.
The main chain of the polystyrene flame-retardant particle contains a large number of phosphate flame-retardant groups. The polyurethane foam material can catalyze and promote the matrix to be dehydrated during combustion to form a carbon layer, has a good flame retardant effect, and improves the limiting oxygen index and the flame retardant property of the polyurethane foam material.
Detailed Description
In order to make the contents of the present invention more easily understood, the technical scheme of the present invention will be further described with reference to the specific embodiments, but the present invention is not limited thereto.
Example 1
The flask was purged with nitrogen, 300mL of acetonitrile solvent, 92mmol of ethyl methacrylate, 40mmol of 1, 4-dihydroxy-2, 5-diiodobenzene were added, the mixture was heated to 70℃and reacted for 12 hours, the solution was concentrated, and the eluent was ethyl acetate and petroleum ether, followed by gradient elution to obtain 1, 4-bis (urethane methacrylate) -2, 5-diiodobenzene. The preparation reaction formula is as follows:
Into the flask, 100mL of tetrahydrofuran solvent, 10mmol of 1, 4-bis (carbamate methacrylate) -2, 5-diiodobenzene and 20mmol of dimethyl phosphite are added, after the mixture is uniformly mixed, 0.42mmol of catalyst bis (triphenylphosphine) palladium acetate, 2.6mmol of promoter potassium acetate and 22mmol of acid-binding agent triethylamine are added, the mixture is heated to 60 ℃, the mixture is stirred and reacted for 12 hours, suction filtration is carried out, after the filtrate is concentrated, silica gel column chromatography separation is carried out, the eluent is ethyl acetate and petroleum ether, and gradient elution is carried out, thus obtaining 1, 4-bis (carbamate methacrylate) -2, 5-bis (dimethyl phosphate) benzene. The preparation reaction formula is as follows:
500mL of water, 5g of styrene, 12g of 1, 4-bis (carbamate) 2, 5-bis (dimethyl phosphate) benzene, 5g of emulsifier span 80 and 3.5g of stabilizer polyvinylpyrrolidone are added into a flask, heated to 60 ℃, evenly mixed, added with 5mL of aqueous solution containing 0.45g of potassium persulfate dropwise, reacted for 30min, then added with 20g of styrene again, reacted for 3h, filtered by suction after the reaction, and the product is placed into a Soxhlet extractor and extracted by ethanol, thus obtaining polystyrene flame-retardant particles.
100G of polyurethane, 12g of polystyrene flame-retardant particles, 140mL of water and 0.4g of sodium dodecyl benzene sulfonate are added into a high-pressure reaction kettle, carbon dioxide is introduced after uniform mixing, and the pressure in the reaction kettle is controlled to be 4MPa; heating to 125 ℃, and maintaining the pressure for 20min; introducing carbon dioxide; controlling the pressure in the reaction kettle to be 8MPa, maintaining the pressure for 30min for the second time, releasing pressure, discharging, washing with water, and drying to obtain the polyurethane foaming material with the flame retardant function.
Example 2
Introducing nitrogen into the flask, adding 200mL of toluene solvent, 81mmol of ethyl methacrylate and 40mmol of 1, 4-dihydroxy-2, 5-diiodobenzene, heating to 100 ℃, reacting for 6 hours, concentrating the solution, separating by silica gel column chromatography, and performing gradient elution on the eluent of ethyl acetate and petroleum ether to obtain 1, 4-di (methyl methacrylate) -2, 5-diiodobenzene; the structural formula is as follows:。
The flask is filled with nitrogen, 80mL of tetrahydrofuran solvent, 10mmol of 1, 4-di (methyl acrylic carbamate) -2, 5-diiodobenzene and 21mmol of dimethyl phosphite are added, after the mixture is uniformly mixed, 0.38mmol of catalyst bis (triphenylphosphine) palladium acetate, 2.4mmol of promoter potassium acetate and 21mmol of acid-binding agent triethylamine are added, the mixture is heated to 60 ℃, the mixture is stirred and reacted for 18h, suction filtration is carried out, after the filtrate is concentrated, silica gel column chromatographic separation is carried out, the eluent is ethyl acetate and petroleum ether, and gradient elution is carried out, thus obtaining 1, 4-di (methyl acrylic carbamate) -2, 5-di (dimethyl phosphate) benzene.
700ML of water, 5g of styrene, 18g of 1, 4-bis (carbamate) 2, 5-bis (dimethyl phosphate) benzene, 6g of emulsifier span 60 and 4.4g of stabilizer polyvinylpyrrolidone are added into a flask, heated to 70 ℃, 5mL of aqueous solution containing 0.52g of potassium persulfate is dropwise added after uniform mixing for reaction for 30min, then 25g of styrene is added for reaction for 2h, suction filtration is carried out after the reaction, and the product is placed into a Soxhlet extractor for extraction by ethanol, thus obtaining polystyrene flame-retardant particles.
100G of polyurethane, 22g of polystyrene flame-retardant particles, 160mL of water and 0.6g of sodium dodecyl benzene sulfonate are added into a high-pressure reaction kettle, carbon dioxide is introduced after uniform mixing, and the pressure in the reaction kettle is controlled to be 5MPa; heating to 120 ℃, and maintaining the pressure for 30min; introducing carbon dioxide; controlling the pressure in the reaction kettle to be 6MPa, maintaining the pressure for 40min for the second time, releasing pressure, discharging, washing with water, and drying to obtain the polyurethane foaming material with the flame retardant function.
Example 3
Into the flask, nitrogen is introduced, 200mL of 1, 4-dioxane solvent, 81mmol of 2-isocyanatoethyl methacrylate and 40mmol of 1, 4-dihydroxy-2, 5-diiodobenzene are added, the mixture is heated to 80 ℃ and reacted for 6 hours, the solution is concentrated, silica gel column chromatography is carried out, the eluent is ethyl acetate and petroleum ether, and gradient elution is carried out, thus obtaining the 1, 4-di (methacrylic acid carbamate) -2, 5-diiodobenzene.
To the flask, 80mL of tetrahydrofuran solvent, 10mmol of 1, 4-bis (urethane methacrylate) -2, 5-diiodobenzene and 20mmol of dimethyl phosphite are added, after the mixture is uniformly mixed, 0.35mmol of catalyst bis (triphenylphosphine) palladium acetate, 2mmol of catalyst promoter potassium acetate and 20mmol of acid-binding agent triethylamine are added, the mixture is heated to 65 ℃, stirred and reacted for 6 hours, suction filtration is carried out, after the filtrate is concentrated, silica gel column chromatography separation is carried out, the eluent is ethyl acetate and petroleum ether, and gradient elution is carried out, thus obtaining 1, 4-bis (urethane methacrylate) -2, 5-bis (dimethyl phosphate) benzene.
700ML of water, 5g of styrene, 22.5g of 1, 4-bis (methyl methacrylate) -2, 5-bis (dimethyl phosphate) benzene, 6g of emulsifier span 80 and 5g of stabilizer polyvinylpyrrolidone are added into a flask, heated to 70 ℃, 5mL of aqueous solution containing 0.6g of potassium persulfate is dropwise added after uniform mixing for reaction for 60min, then 30g of styrene is added again for reaction for 3h, suction filtration is carried out after reaction, and the product is placed into a Soxhlet extractor for extraction by ethanol, thus obtaining polystyrene flame-retardant particles.
100G of polyurethane, 30g of polystyrene flame-retardant particles, 160mL of water and 0.8g of sodium dodecyl benzene sulfonate are added into a high-pressure reaction kettle, carbon dioxide is introduced after uniform mixing, and the pressure in the reaction kettle is controlled to be 5MPa; heating to 120 ℃, and maintaining the pressure for 20min; introducing carbon dioxide; controlling the pressure in the reaction kettle to be 8MPa, maintaining the pressure for 30min for the second time, releasing pressure, discharging, washing with water, and drying to obtain the polyurethane foaming material with the flame retardant function.
Comparative example 1
100G of polyurethane, 140mL of water and 0.4g of sodium dodecyl benzene sulfonate are added into a high-pressure reaction kettle, carbon dioxide is introduced after uniform mixing, and the pressure in the reaction kettle is controlled to be 4MPa; heating to 125 ℃, and maintaining the pressure for 20min; introducing carbon dioxide; controlling the pressure in the reaction kettle to be 8MPa, maintaining the pressure for 30min for the second time, discharging the materials after pressure relief, washing the materials with water and drying the materials to obtain the polyurethane foaming material.
Comparative example 2
The flask was purged with nitrogen, 300mL of acetonitrile solvent, 92mmol of ethyl methacrylate, 40mmol of 1, 4-dihydroxy-2, 5-diiodobenzene were added, the mixture was heated to 70℃and reacted for 12 hours, the solution was concentrated, and the eluent was ethyl acetate and petroleum ether, followed by gradient elution to obtain 1, 4-bis (urethane methacrylate) -2, 5-diiodobenzene.
500ML of water, 5g of styrene, 12g of 1, 4-di (methyl acrylic carbamate) -2, 5-diiodobenzene, 5g of emulsifier span 80 and 3.5g of stabilizer polyvinylpyrrolidone are added into a flask, heated to 60 ℃, evenly mixed, then added with 5mL of aqueous solution containing 0.45g of potassium persulfate dropwise, reacted for 30min, then added with 20g of styrene again, reacted for 3h, suction filtered, and the product is placed in a Soxhlet extractor and extracted by ethanol, thus obtaining polystyrene particles.
100G of polyurethane, 12g of polystyrene particles, 140mL of water and 0.4g of sodium dodecyl benzene sulfonate are added into a high-pressure reaction kettle, carbon dioxide is introduced after uniform mixing, and the pressure in the reaction kettle is controlled to be 4MPa; heating to 125 ℃, and maintaining the pressure for 20min; introducing carbon dioxide; controlling the pressure in the reaction kettle to be 8MPa, maintaining the pressure for 30min for the second time, discharging the materials after pressure relief, washing the materials with water and drying the materials to obtain the polyurethane foaming material.
Comparative example 3
500ML of water, 5g of styrene, 12g of divinylbenzene, 5g of emulsifier span 80 and 3.5g of stabilizer polyvinylpyrrolidone are added into a flask, heated to 60 ℃, evenly mixed, then 5mL of aqueous solution containing 0.45g of potassium persulfate is added dropwise for reaction for 30min, then 20g of styrene is added for reaction for 3h, suction filtration is carried out after the reaction, and the product is placed into a Soxhlet extractor and extracted by ethanol, thus obtaining polystyrene particles.
100G of polyurethane, 12g of polystyrene particles, 140mL of water and 0.4g of sodium dodecyl benzene sulfonate are added into a high-pressure reaction kettle, carbon dioxide is introduced after uniform mixing, and the pressure in the reaction kettle is controlled to be 4MPa; heating to 125 ℃, and maintaining the pressure for 20min; introducing carbon dioxide; controlling the pressure in the reaction kettle to be 8MPa, maintaining the pressure for 30min for the second time, discharging the materials after pressure relief, washing the materials with water and drying the materials to obtain the polyurethane foaming material.
The rebound resilience performance of the polyurethane foaming material is tested according to the GB/T6670-2008 method by adopting a falling ball rebound resilience meter. The compression performance was tested according to the method GB/T8813-2020, the compression rate was 2mm/min, and the compression stress at 10% deformation was tested. The bending strength GB/T8812.2-2007 method was tested. Limiting oxygen index was tested according to GB/T2406-2009 method.
Table 1 polyurethane foam performance test.
As is clear from the above table, the comparative example 1 is a common polyurethane foam material, which has low rebound performance, compression performance and bending strength, limited oxygen index of only 19.4% and poor flame retardant performance, without adding polystyrene flame retardant particles. In examples 1-3, rigid polystyrene flame retardant particles were added, and the main chain of the polystyrene flame retardant particles contained urethane structural units identical to those of polyurethane [ (]) The compatibility of the polystyrene flame-retardant particles and polyurethane is improved, the polystyrene flame-retardant particles are uniformly and respectively distributed in the polyurethane foam material after foaming, the rigid polystyrene particles play roles of supporting the polyurethane foam material framework, dispersing and transferring stress, and the rebound performance, the compression performance and the bending strength of the polyurethane foam material are remarkably improved. And the main chain of the polystyrene flame-retardant particles contains a large number of phosphate flame-retardant groups. The polyurethane foam material can catalyze and promote the matrix to be dehydrated during combustion to form a carbon layer, has a good flame retardant effect, and improves the limiting oxygen index of the polyurethane foam material; up to 28.6%.
Compared with the example 1, the comparative example 2 uses 1, 4-di (methyl acrylic carbamate) -2, 5-diiodobenzene as a cross-linking agent, and polystyrene particles obtained by cross-linking polymerization of the cross-linking agent and styrene also contain carbamate structural units, so that the compatibility with polyurethane is good, and the mechanical properties such as compression of polyurethane foaming materials are obviously improved. However, the polystyrene particles do not contain phosphate flame retardant groups, the limiting oxygen index of the polyurethane foam material is low, and the flame retardant property is poor.
Comparative example 3 polystyrene particles obtained by crosslinking and polymerizing conventional divinylbenzene as a crosslinking agent with styrene, which do not contain urethane structural units, have poor compatibility with polyurethane, and the polystyrene particles after foaming are difficult to uniformly distribute in a polyurethane foaming material, so that the effect of improving mechanical properties such as compression of the material is poor. And the polystyrene particles do not contain phosphate flame retardant groups, the limiting oxygen index of the polyurethane foam material is low, and the flame retardant property is poor.
It will be understood that the application has been described in terms of several embodiments, and that various changes and equivalents may be made to these features and embodiments by those skilled in the art without departing from the spirit and scope of the application. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the application without departing from the essential scope thereof. Therefore, it is intended that the application not be limited to the particular embodiment disclosed, but that the application will include all embodiments falling within the scope of the appended claims.
Claims (9)
1. The preparation process of the polyurethane foaming material with the flame retardant function is characterized by comprising the following steps of:
Adding water, styrene, a phosphorus-containing polymeric monomer, an emulsifier and a stabilizer into a flask, heating to 60-70 ℃, uniformly mixing, then dropwise adding an aqueous solution of potassium persulfate, reacting for 30-60min, then adding styrene, reacting for 2-3h, and performing suction filtration after the reaction, and extracting by a Soxhlet extractor to obtain polystyrene flame-retardant particles;
The chemical structural formula of the phosphorus-containing polymerized monomer is as follows:
；
Step two, adding polyurethane, polystyrene flame-retardant particles, water and sodium dodecyl benzene sulfonate into a high-pressure reaction kettle, uniformly mixing, and then introducing carbon dioxide, wherein the pressure in the reaction kettle is controlled to be 4-5MPa; heating to 120-125 deg.C, and maintaining pressure for 20-30min; introducing carbon dioxide; controlling the pressure in the reaction kettle to be 6-8MPa, maintaining the pressure for 30-40min for the second time, discharging the materials through pressure relief, washing and drying to obtain the polyurethane foaming material with the flame retardant function.
2. The preparation process of the polyurethane foam material with the flame retardant function according to claim 1, wherein the weight ratio of the styrene, the phosphorus-containing polymer monomer, the potassium persulfate and the added styrene in the step one is 100 (240-450): 9-12): 400-600.
3. The process for preparing a polyurethane foam material with flame retardant function according to claim 1, wherein the emulsifier in the first step is any one of span 60 and span 80; the stabilizer is polyvinylpyrrolidone.
4. The process for preparing the polyurethane foam material with the flame retardant function according to claim 1, wherein the weight ratio of polyurethane to polystyrene flame retardant particles in the second step is 100 (12-30).
5. The process for preparing polyurethane foam materials with flame retardant function according to claim 1, wherein the process for preparing the phosphorus-containing polymer monomer in the step one is as follows:
step a, introducing nitrogen into a flask, adding a reaction solvent, 2-isocyanatoethyl methacrylate and 1, 4-dihydroxy-2, 5-diiodobenzene, heating to 70-100 ℃, reacting for 6-12h, concentrating the solution, and separating by silica gel column chromatography to obtain an intermediate containing iodine;
And b, introducing nitrogen into the flask, adding tetrahydrofuran solvent, iodine-containing intermediate and dimethyl phosphite, uniformly mixing, adding catalyst bis (triphenylphosphine) palladium acetate, cocatalyst potassium acetate and acid-binding agent triethylamine, stirring for reaction, carrying out suction filtration, concentrating filtrate, and carrying out silica gel column chromatographic separation to obtain the phosphorus-containing polymerized monomer.
6. The process for preparing a polyurethane foam having a flame retardant function according to claim 5, wherein the molar ratio of 2-isocyanatoethyl methacrylate to 1, 4-dihydroxy-2, 5-diiodobenzene in the step a is (2.1-2.3): 1.
7. The process for preparing the polyurethane foam material with the flame retardant function according to claim 5, wherein the reaction solvent in the step a is any one of 1, 4-dioxane, toluene and acetonitrile.
8. The process for preparing the polyurethane foam material with the flame retardant function according to claim 5, wherein the molar ratio of the iodine-containing intermediate, the dimethyl phosphite, the palladium bis (triphenylphosphine) acetate, the potassium acetate and the triethylamine in the step b is 1 (2-2.2): (0.035-0.042): (0.2-0.26): (2-2.2).
9. The process for preparing a polyurethane foam having a flame retardant function according to claim 5, wherein the reaction in the step b is performed at a temperature of 60 to 65 ℃ for 6 to 18 hours.
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