CN115850641B - Flame-retardant modified polyurethane material and synthesis method thereof - Google Patents
Flame-retardant modified polyurethane material and synthesis method thereof Download PDFInfo
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- CN115850641B CN115850641B CN202211519388.7A CN202211519388A CN115850641B CN 115850641 B CN115850641 B CN 115850641B CN 202211519388 A CN202211519388 A CN 202211519388A CN 115850641 B CN115850641 B CN 115850641B
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- 239000004814 polyurethane Substances 0.000 title claims abstract description 72
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 72
- 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 68
- 239000003063 flame retardant Substances 0.000 title claims abstract description 65
- 239000000463 material Substances 0.000 title claims abstract description 57
- 238000001308 synthesis method Methods 0.000 title claims abstract description 9
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 28
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 20
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims abstract description 17
- 239000012975 dibutyltin dilaurate Substances 0.000 claims abstract description 17
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 10
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229920000570 polyether Polymers 0.000 claims abstract description 10
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims abstract description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 28
- 229910052757 nitrogen Inorganic materials 0.000 claims description 14
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 150000003384 small molecules Chemical class 0.000 claims description 13
- 238000001816 cooling Methods 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 238000007599 discharging Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- OSXYHAQZDCICNX-UHFFFAOYSA-N dichloro(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](Cl)(Cl)C1=CC=CC=C1 OSXYHAQZDCICNX-UHFFFAOYSA-N 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- 235000011187 glycerol Nutrition 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 3
- BSYJHYLAMMJNRC-UHFFFAOYSA-N 2,4,4-trimethylpentan-2-ol Chemical compound CC(C)(C)CC(C)(C)O BSYJHYLAMMJNRC-UHFFFAOYSA-N 0.000 claims description 3
- 238000009835 boiling Methods 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 2
- 239000012716 precipitator Substances 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims 1
- 230000000052 comparative effect Effects 0.000 description 7
- 239000000543 intermediate Substances 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 230000009286 beneficial effect Effects 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- LJUXFZKADKLISH-UHFFFAOYSA-N benzo[f]phosphinoline Chemical group C1=CC=C2C3=CC=CC=C3C=CC2=P1 LJUXFZKADKLISH-UHFFFAOYSA-N 0.000 description 3
- 239000004566 building material Substances 0.000 description 3
- 125000003700 epoxy group Chemical group 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000007142 ring opening reaction Methods 0.000 description 2
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical group NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910018557 Si O Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 125000006615 aromatic heterocyclic group Chemical group 0.000 description 1
- VBQRUYIOTHNGOP-UHFFFAOYSA-N benzo[c][2,1]benzoxaphosphinine 6-oxide Chemical group C1=CC=C2P(=O)OC3=CC=CC=C3C2=C1 VBQRUYIOTHNGOP-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000010382 chemical cross-linking Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
- C07F9/657163—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom
- C07F9/657172—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom the ring phosphorus atom and one oxygen atom being part of a (thio)phosphinic acid ester: (X = O, S)
-
- 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
- C08G18/3893—Low-molecular-weight compounds having heteroatoms other than oxygen containing silicon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4825—Polyethers containing two hydroxy groups
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention relates to the technical field of polyurethane and discloses a flame-retardant modified polyurethane material and a synthesis method thereof, wherein the flame-retardant modified polyurethane material comprises 50-70 parts of polyether glycol, 10-15 parts of toluene-2, 4-diisocyanate, 5-10 parts of dibutyltin dilaurate and 3-6 parts of micromolecular flame-retardant cross-linking agent.
Description
Technical Field
The invention relates to the technical field of polyurethane, in particular to a flame-retardant modified polyurethane material and a synthesis method thereof.
Background
Polyurethane is a synthetic high polymer material containing carbamate groups in a main chain structure, along with the continuous development of material science, the application range of polyurethane is gradually wide, and especially in the field of building materials, building external wall insulation boards prepared by taking polyurethane as a raw material are increasingly popular, but in recent years, the fire disaster occurrence of urban high-rise buildings frequently causes the continuous improvement of the requirement of people on the flame retardant property of the building materials, and in order to meet the market demand, the polyurethane material is required to have good flame retardant property, but the common polyurethane molecular chain does not contain functional groups with flame retardant function, so the flame retardant property of the polyurethane material is not excellent, and as the building materials, the temperature resistance and the mechanical property of the polyurethane are also required to be enhanced to a certain extent.
The Chinese patent with the application number of CN202010294313.8 discloses a flame-retardant polyurethane material and a preparation method thereof, and the nitrogen-containing heterocyclic structure is introduced into the molecular structure of the polyurethane material from the structural design of the polyurethane, so that the flame retardance and the heat resistance of polyurethane material products are effectively improved, and meanwhile, the aromatic heterocyclic structure is introduced into the polyurethane structure, so that the rigidity and the toughness of the material are effectively improved, and the polyurethane can be prepared by using different raw materials, so that the excellent performance of the polyurethane can be endowed, but the raw materials used in the patent are more and do not meet the requirements of actual production, so that the polyurethane is prepared by using the raw materials which are strong in functionality, simple in components and beneficial to actual production, on one hand, the functions of the polyurethane can be enhanced, and on the other hand, the polyurethane material is also beneficial to further application.
Disclosure of Invention
The invention aims to provide a flame-retardant modified polyurethane material and a synthesis method thereof, wherein a small-molecule flame-retardant cross-linking agent with flame-retardant function is introduced into a polyurethane molecular chain by designing the polyurethane molecular chain, so that the problem of poor flame-retardant performance of the polyurethane material is solved, and the heat resistance and mechanical properties of the polyurethane material are enhanced.
The aim of the invention can be achieved by the following technical scheme:
the flame-retardant modified polyurethane material comprises the following raw materials in parts by weight: 50-70 parts of polyether glycol, 10-15 parts of toluene-2, 4-diisocyanate, 5-10 parts of dibutyltin dilaurate and 3-6 parts of small-molecule flame retardant cross-linking agent;
the structural formula of the small molecule flame retardant cross-linking agent is shown as follows:
further, the synthesis method of the small molecule flame retardant cross-linking agent comprises the following steps:
mixing diphenyl dichlorosilane with 1, 4-dioxane, adding 1, 3-diglycidyl ether glycerol, stirring uniformly, placing the system at 70-80 ℃ for 4-12 hours, removing low-boiling substances after gas is exhausted, distilling under reduced pressure, pouring out the product, filtering to separate solid, washing with deionized water, and vacuum drying to obtain an intermediate;
II, dissolving the intermediate and 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide in an organic solvent, mechanically stirring uniformly, introducing nitrogen to remove air in the system, raising the temperature of the system for reaction, cooling the product to room temperature, and placing the product in a precipitator for precipitation for 2-4 times to obtain the micromolecular flame-retardant cross-linking agent.
According to the technical scheme, the diphenyl dichlorosilane structure contains S i-C l bonds, can react with hydroxyl functional groups in the 1, 3-diglycidyl ether glycerin structure to generate intermediates containing abundant epoxy groups, and under the high-temperature condition, the P-H bonds in the 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide structure can perform ring-opening addition reaction with the epoxy groups in the intermediate structure, so that the generated product structure contains abundant phosphaphenanthrene groups and hydroxyl generated by ring opening of the epoxy groups, and can participate in the polymerization reaction process of polyurethane, namely the micromolecular flame retardant cross-linking agent.
Further, in the step I, the molar ratio of the diphenyl dichlorosilane to the 1, 3-diglycidyl ether glycerin is 1:2-3.
Further, in the step I, the temperature during vacuum drying is 50-60 ℃ and the time is 2-6h.
Further, in the step II, the organic solvent is any one of tetrahydrofuran, N-dimethylformamide and N, N-dimethylacetamide.
Further, in the step II, the temperature of the reaction is 80-90 ℃, and the reaction is stirred for 6-18h under the protection of nitrogen.
Further, in the step II, the precipitating agent is methanol.
The synthesis method of the flame-retardant modified polyurethane material specifically comprises the following steps:
adding polyether glycol dehydrated in vacuum and toluene-2, 4-diisocyanate into a reactor, uniformly mixing, dropwise adding dibutyltin dilaurate, raising the temperature of the system to 60-70 ℃, reacting for 4-6 hours under the protection of nitrogen, adding a micromolecular flame retardant cross-linking agent and the rest dibutyltin dilaurate into the system, continuously reacting for 2-3 hours, cooling the product to room temperature after the reaction is finished, and discharging to obtain the flame retardant modified polyurethane material.
The invention has the beneficial effects that:
(1) According to the invention, the micromolecular flame retardant cross-linking agent is prepared and participates in the polymerization process of polyurethane, and under the action of the cross-linking agent, the cross-linking density of polyurethane molecular chains is greatly improved, so that the density of the polyurethane material is improved, on one hand, the improvement of the density is beneficial to enhancing the heat resistance of the polyurethane material, and on the other hand, the improvement of the density can enable the polyurethane material to have higher impact resistance, and is beneficial to the further application of the polyurethane material.
(2) The small-molecule flame-retardant cross-linking agent prepared by the invention contains rich phosphaphenanthrene functional flame-retardant functional groups and hydroxyl functional groups, and phosphorus oxyacids with a carbon-forming catalytic effect can be generated by burning the phosphaphenanthrene groups, so that the surface of a polyurethane material can be promoted to form a carbon layer, and continuous burning is prevented, therefore, the polyurethane material has excellent flame-retardant performance and cross-linking density by adding a small amount of small-molecule flame-retardant cross-linking agent, and the small-molecule flame-retardant cross-linking agent contains silicon elements, inorganic materials such as silicon dioxide generated by burning can be attached to the carbon layer, so that the strength of the carbon layer is enhanced, the flame-retardant performance of the polyurethane material is prevented from being reduced due to collapse of the carbon layer, and in addition, the flame retardant exists in a chemical cross-linking mode with the polyurethane structure, so that the phenomenon that the flame retardant has poor compatibility with polyurethane and precipitation occurs can be avoided.
Of course, it is not necessary for any one product to practice the invention to achieve all of the advantages set forth above at the same time.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed for the description of the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is an infrared spectrum of a small molecule flame retardant cross-linking agent in an embodiment of the invention.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In the following examples, the synthesis method of the small molecule flame retardant cross-linking agent comprises the following steps:
mixing 10g of diphenyl dichlorosilane with 1, 4-dioxane, adding 18g of 1, 3-diglycidyl ether glycerol, stirring uniformly, placing the system at 75 ℃, preserving the temperature for 8 hours, removing low-boiling substances by reduced pressure distillation after the gas is exhausted, pouring out the product, filtering and separating the solid, washing with deionized water, and vacuum drying at 50 ℃ for 4 hours to obtain an intermediate;
II, dissolving 5g of intermediate and 16g of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide in tetrahydrofuran, mechanically stirring uniformly, introducing nitrogen to remove air in the system, raising the temperature of the system to 90 ℃, stirring for 12 hours under the protection of nitrogen, cooling the product to room temperature, and placing the product in a methanol precipitant to precipitate for 3 times to obtain the micromolecular flame retardant cross-linking agent, wherein the structure is as follows:
FIG. 1 is an infrared spectrum of a small molecule flame retardant cross-linking agent, 3456cm in length -1 Characteristic absorption peak at hydroxyl group, 2859cm -1 The position is a P-O telescopic vibration peak of 1284cm -1 The stretching vibration peak of P=O is 1031cm -1 The position is a stretching vibration peak of Si-O, 803cm -1 The absorption vibration peak of benzene ring is shown.
Example 1
Preparation of flame-retardant modified polyurethane material
Adding 50 parts of polyether glycol and 10 parts of toluene-2, 4-diisocyanate which are dehydrated in vacuum into a reactor, uniformly mixing, dropwise adding 3 parts of dibutyltin dilaurate, raising the temperature of the system to 60 ℃, reacting for 4 hours under the protection of nitrogen, adding 3 parts of micromolecular flame retardant cross-linking agent and 2 parts of dibutyltin dilaurate into the system, continuously reacting for 2 hours, cooling the product to room temperature after the reaction is finished, and discharging to obtain the flame retardant modified polyurethane material.
Example 2
Preparation of flame-retardant modified polyurethane material
Adding 55 parts of polyether glycol dehydrated in vacuum and 12 parts of toluene-2, 4-diisocyanate into a reactor, uniformly mixing, dropwise adding 4.5 parts of dibutyltin dilaurate, raising the temperature of the system to 65 ℃, reacting for 5 hours under the protection of nitrogen, adding 4 parts of micromolecular flame retardant cross-linking agent and 2.5 parts of dibutyltin dilaurate into the system, continuously reacting for 2 hours, cooling the product to room temperature after the reaction is finished, and discharging to obtain the flame retardant modified polyurethane material.
Example 3
Preparation of flame-retardant modified polyurethane material
Adding 60 parts of polyether glycol dehydrated in vacuum and 14 parts of toluene-2, 4-diisocyanate into a reactor, uniformly mixing, dropwise adding 5.5 parts of dibutyltin dilaurate, raising the temperature of the system to 65 ℃, reacting for 5 hours under the protection of nitrogen, adding 5 parts of micromolecular flame retardant cross-linking agent and 3 parts of dibutyltin dilaurate into the system, continuously reacting for 3 hours, cooling the product to room temperature after the reaction is finished, and discharging to obtain the flame retardant modified polyurethane material.
Example 4
Preparation of flame-retardant modified polyurethane material
Adding 70 parts of polyether glycol and 15 parts of toluene-2, 4-diisocyanate which are dehydrated in vacuum into a reactor, uniformly mixing, dropwise adding 6 parts of dibutyltin dilaurate, raising the temperature of the system to 70 ℃, reacting for 6 hours under the protection of nitrogen, adding 6 parts of micromolecular flame retardant cross-linking agent and 4 parts of dibutyltin dilaurate into the system, continuously reacting for 3 hours, cooling the product to room temperature after the reaction is finished, and discharging to obtain the flame retardant modified polyurethane material.
Comparative example 1
Preparation of polyurethane materials
Adding 55 parts of polyether glycol dehydrated in vacuum and 12 parts of toluene-2, 4-diisocyanate into a reactor, uniformly mixing, dropwise adding 4.5 parts of dibutyltin dilaurate, raising the temperature of the system to 65 ℃, reacting for 5 hours under the protection of nitrogen, adding 4 parts of pentaerythritol cross-linking agent and 2.5 parts of dibutyltin dilaurate into the system, continuously reacting for 2 hours, cooling the product to room temperature after the reaction is finished, and discharging to obtain the flame-retardant modified polyurethane material.
Performance detection
Referring to national standard GB/T1043.2-2018, impact performance tests were conducted on polyurethane materials prepared in examples 1-4 and comparative example 1 of the present invention using a JBW-300B type impact tester; referring to national standard GB/T2406-2009, limiting oxygen index tests were carried out on polyurethane materials prepared in examples 1-4 and comparative example 1 of the present invention using JF-3 type limiting oxygen index instrument; polyurethane materials prepared in examples 1 to 4 and comparative example 1 of the present invention were prepared by taking 0.5g, placing the materials in a SAT200 thermogravimetric analyzer, setting a heating rate of 10 ℃/min, heating from 25 ℃ to 600 ℃ under the protection of nitrogen, recording initial decomposition temperature, and evaluating heat resistance, wherein the test results are shown in the following table:
as is clear from the table, the polyurethane materials prepared in examples 1 to 4 of the present invention have higher impact resistance and flame retardance because of higher values of limiting oxygen index, and in addition, the initial decomposition temperature is higher, which means that the polyurethane materials have stronger heat resistance, whereas the polyurethane materials prepared in comparative example 1 have lower limiting oxygen index, presumably because pentaerythritol which does not contain flame retardance is used as a crosslinking agent, and thus the flame retardance is poorer.
Referring to national standard GB/T2048-1996, the polyurethane materials prepared in examples 1 to 4 and comparative example 1 of the present invention were subjected to UL-94 vertical burning test, and the test results are shown in the following table:
as can be seen from the table, the polyurethane materials prepared in examples 1 to 4 of the present invention have a flame retardant rating of V-0, and have excellent flame retardant properties, whereas the polyurethane material prepared in comparative example 1 has a flame retardant rating of V-2, and thus has poor flame retardant properties.
In the description of the present specification, a description referring to terms "one embodiment," "some embodiments," "examples," "specific examples," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms are not necessarily directed to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, the different embodiments or examples described in this specification and the features of the different embodiments or examples may be combined and combined by those skilled in the art without contradiction.
The foregoing is merely illustrative and explanatory of the principles of the invention, as various modifications and additions may be made to the specific embodiments described, or similar thereto, by those skilled in the art, without departing from the principles of the invention or beyond the scope of the appended claims.
Claims (8)
1. The flame-retardant modified polyurethane material is characterized by comprising the following raw materials in parts by weight: 50-70 parts of polyether glycol, 10-15 parts of toluene-2, 4-diisocyanate, 5-10 parts of dibutyltin dilaurate and 3-6 parts of small-molecule flame retardant cross-linking agent;
the structural formula of the small molecule flame retardant cross-linking agent is shown as follows:
2. the flame-retardant modified polyurethane material according to claim 1, wherein the synthesis method of the small molecule flame-retardant cross-linking agent comprises the following steps:
mixing diphenyl dichlorosilane with 1, 4-dioxane, adding 1, 3-diglycidyl ether glycerol, stirring uniformly, placing the system at 70-80 ℃ for 4-12 hours, removing low-boiling substances after gas is exhausted, distilling under reduced pressure, pouring out the product, filtering to separate solid, washing with deionized water, and vacuum drying to obtain an intermediate;
II, dissolving the intermediate and 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide in an organic solvent, mechanically stirring uniformly, introducing nitrogen to remove air in the system, raising the temperature of the system for reaction, cooling the product to room temperature, and placing the product in a precipitator for precipitation for 2-4 times to obtain the micromolecular flame-retardant cross-linking agent.
3. The flame retardant modified polyurethane material of claim 2, wherein in step i, the molar ratio of diphenyldichlorosilane to 1, 3-diglycidyl ether glycerin is 1:2-3.
4. The flame retardant modified polyurethane material of claim 2, wherein in step i, the temperature is 50-60 ℃ and the time is 2-6 hours during vacuum drying.
5. The flame-retardant modified polyurethane material according to claim 2, wherein in the step ii, the organic solvent is any one of tetrahydrofuran, N-dimethylformamide, and N, N-dimethylacetamide.
6. The flame retardant modified polyurethane material of claim 2, wherein in step ii, the reaction temperature is 80-90 ℃, and the reaction is stirred for 6-18 hours under nitrogen protection.
7. The flame retardant modified polyurethane material of claim 2, wherein in step ii, the precipitant is methanol.
8. A method for synthesizing the flame-retardant modified polyurethane material according to claim 1, which is characterized in that the method specifically comprises the following steps:
adding polyether glycol dehydrated in vacuum and toluene-2, 4-diisocyanate into a reactor, uniformly mixing, dripping part of dibutyltin dilaurate, raising the temperature of the system to 60-70 ℃, reacting for 4-6 hours under the protection of nitrogen, adding a micromolecular flame retardant cross-linking agent and the rest dibutyltin dilaurate into the system, continuously reacting for 2-3 hours, cooling the product to room temperature after the reaction is finished, and discharging to obtain the flame retardant modified polyurethane material.
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