CN115850641A - 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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- CN115850641A CN115850641A CN202211519388.7A CN202211519388A CN115850641A CN 115850641 A CN115850641 A CN 115850641A CN 202211519388 A CN202211519388 A CN 202211519388A CN 115850641 A CN115850641 A CN 115850641A
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- 239000004814 polyurethane Substances 0.000 title claims abstract description 75
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 75
- 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 70
- 239000003063 flame retardant Substances 0.000 title claims abstract description 66
- 239000000463 material Substances 0.000 title claims abstract description 62
- 238000001308 synthesis method Methods 0.000 title claims abstract description 11
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 29
- 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
- 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
- 150000003384 small molecules Chemical class 0.000 claims abstract description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 28
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 16
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 8
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 230000018044 dehydration Effects 0.000 claims description 6
- 238000006297 dehydration reaction Methods 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
- 238000007599 discharging Methods 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
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 238000004821 distillation Methods 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- 230000001376 precipitating effect Effects 0.000 claims description 3
- 239000012716 precipitator Substances 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 238000000967 suction filtration Methods 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
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 5
- 238000004132 cross linking Methods 0.000 abstract description 3
- 150000002009 diols Chemical class 0.000 abstract description 2
- 125000000524 functional group Chemical group 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 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
- 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
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000006872 improvement Effects 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
- 238000001556 precipitation 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
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000010382 chemical cross-linking Methods 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
- 238000010586 diagram Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000002329 infrared spectrum Methods 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
- 238000000034 method Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 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
- 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
- 238000006467 substitution reaction Methods 0.000 description 1
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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
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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
- C08G18/40—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 diol, 10-15 parts of toluene-2, 4-diisocyanate, 5-10 parts of dibutyltin dilaurate and 3-6 parts of a small-molecule flame-retardant cross-linking agent, and the prepared polyurethane material structure contains abundant phosphaphenanthrene flame-retardant functional groups by preparing the small-molecule flame-retardant cross-linking agent with a phosphaphenanthrene flame-retardant functional group and a hydroxyl active functional group in the structure, so that the flame-retardant property of the polyurethane material is effectively enhanced, and meanwhile, the cross-linking density of a molecular chain of the polyurethane material is improved by using the cross-linking agent, the density of the polyurethane material is improved, and the mechanical properties and the heat resistance of the polyurethane material such as impact strength are effectively enhanced.
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 with a Han carbamate group in a main chain structure, the application range of polyurethane is gradually widened along with the continuous development of material science, particularly in the field of building materials, building exterior wall insulation boards and the like prepared by taking polyurethane as a raw material are increasingly popular, but in recent years, the fire phenomenon of urban high-rise buildings is frequent, so that the requirement of people on the flame retardant property of the building materials is continuously improved, in order to meet the market demand, the polyurethane material is required to have good flame retardant property, but the molecular chain of the common polyurethane does not contain a functional group with the flame retardant function, so that the flame retardant property of the polyurethane material is not excellent, and as the building material, the temperature resistance and the mechanical property of the polyurethane also need to be enhanced to a certain degree.
Chinese patent with application number CN202010294313.8 discloses a flame retardant polyurethane material and a preparation method thereof, starting from the structural design of polyurethane, a nitrogen-containing heterocyclic structure is introduced into the molecular structure of the polyurethane material, the flame retardant and heat resistance of a polyurethane material product is effectively improved, meanwhile, an aromatic heterocyclic structure is introduced into the polyurethane structure, the rigidity and toughness of the material are effectively improved, so that the polyurethane is prepared by using different raw materials, excellent performance can be given to the polyurethane, but the patent uses more raw materials, which do not meet the requirements of actual production, so that the polyurethane is strong in use functionality, simple in components and beneficial to the preparation of the raw materials of actual production, on one hand, various functions of the polyurethane can be enhanced, and on the other hand, the polyurethane material is also beneficial to the further application.
Disclosure of Invention
The invention aims to provide a flame-retardant modified polyurethane material and a synthesis method thereof, wherein a small-molecular flame-retardant cross-linking agent with flame-retardant function is introduced by designing a polyurethane molecular chain, so that the problem of poor flame-retardant core performance of the polyurethane material is solved, and the heat resistance and the mechanical property of the polyurethane material are enhanced.
The purpose of the invention can be realized by the following technical scheme:
a 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 micromolecular flame-retardant cross-linking agent;
the structural formula of the micromolecule flame-retardant cross-linking agent is as follows:
further, the synthesis method of the small molecule flame-retardant cross-linking agent comprises the following steps:
i, mixing diphenyldichlorosilane and 1, 4-dioxane, adding 1, 3-diglycidyl ether glycerol, uniformly stirring, placing the system at 70-80 ℃, preserving heat for 4-12h, removing low-boiling-point substances by reduced pressure distillation after gas is exhausted, pouring out products, carrying out suction filtration to separate solids, washing by using deionized water, and carrying out vacuum drying to obtain an intermediate;
II, dissolving the intermediate and 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide in an organic solvent, uniformly stirring by a machine, introducing nitrogen to remove air in the system, raising the temperature of the system for reaction, cooling the product to room temperature, and precipitating the product in a precipitator for 2-4 times to obtain the micromolecule flame retardant crosslinking agent.
According to the technical scheme, the diphenyl dichlorosilane structure contains Si-Cl bonds, and can react with hydroxyl functional groups in a 1, 3-diglycidyl ether glycerol structure to generate an intermediate containing rich epoxy groups, the P-H bonds in a 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide structure can perform ring-opening addition reaction with the epoxy groups in the intermediate structure under a high-temperature condition, the generated product structure contains rich phosphaphenanthrene groups, and simultaneously contains hydroxyl groups generated by ring opening of the epoxy groups, so that the product can participate in the polymerization reaction process of polyurethane, namely the micromolecule flame-retardant cross-linking agent.
Further, in the step I, the molar ratio of the diphenyl dichlorosilane to the 1, 3-diglycidyl ether glycerol is 1.
Further, in the step I, the temperature is 50-60 ℃ during vacuum drying, 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 reaction temperature is 80-90 ℃, and the stirring is carried out for 6-18h under the protection of nitrogen.
Further, in step II, the precipitant is methanol.
The synthesis method of the flame-retardant modified polyurethane material comprises the following steps:
adding vacuum dehydrated polyether diol 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 4-6h under the protection of nitrogen, adding the micromolecule flame-retardant cross-linking agent and the rest dibutyltin dilaurate into the system, continuously reacting for 2-3h, 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 micromolecule flame-retardant cross-linking agent is prepared to participate in the polymerization process of polyurethane, and under the action of the cross-linking agent, the cross-linking density of a polyurethane molecular chain 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, on the other hand, the improvement of the density can enable the polyurethane material to have higher impact resistance, and is beneficial to further application of the polyurethane material.
(2) The micromolecule flame-retardant cross-linking agent prepared by the invention contains abundant phosphaphenanthrene functional flame-retardant functional groups and hydroxyl functional groups, because the phosphaphenanthrene functional groups can generate phosphorus oxyacid with the function of catalyzing carbon formation by burning, the surface of the polyurethane material can be promoted to form a carbon layer, and the burning is prevented from continuing, so that the polyurethane material can have excellent flame-retardant property and cross-linking density by adding a small amount of micromolecule flame-retardant cross-linking agent, and the micromolecule flame-retardant cross-linking agent contains silicon element, inorganic materials such as silicon dioxide generated by burning and the like can be attached to the carbon layer, the strength of the carbon layer is enhanced, the flame-retardant property of the polyurethane material is prevented from being reduced due to collapse of the carbon layer, in addition, the flame retardant exists in a chemical cross-linking mode and the polyurethane structure, and the phenomenon that the compatibility of the flame retardant and the polyurethane is poor and the precipitation phenomenon can be avoided.
Of course, it is not necessary for any product in which the invention is practiced to achieve all of the above-described advantages at the same time.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a schematic diagram of a structure according to the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In the following examples, the synthesis method of the small molecule flame retardant cross-linking agent is as follows:
mixing 10g of diphenyldichlorosilane and 1, 4-dioxane, adding 18g of 1, 3-diglycidyl ether glycerol, uniformly stirring, placing the system at 75 ℃, keeping the temperature for 8 hours, removing low-boiling-point substances by reduced pressure distillation after gas is exhausted, pouring out products, carrying out suction filtration to separate solids, washing by using deionized water, and carrying out vacuum drying at 50 ℃ for 4 hours to obtain an intermediate;
II, dissolving 5g of the intermediate and 16g of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide in tetrahydrofuran, mechanically stirring uniformly, introducing nitrogen to remove air in a system, raising the temperature of the system to 90 ℃, stirring for 12 hours under the protection of nitrogen, cooling a product to room temperature, placing the product in a methanol precipitator for precipitation for 3 times to obtain the micromolecule flame retardant cross-linking agent, wherein the structure is as follows:
FIG. 1 is an infrared spectrum of a small molecular flame-retardant cross-linking agent, wherein 3456cm -1 Characteristic absorption peak of hydroxyl at 2859cm -1 A P-O stretching vibration peak at 1284cm -1 Peak of stretching vibration at P = O, 1031cm -1 Is located at the stretching vibration peak of Si-O, 803cm -1 The absorption vibration peak of the benzene ring is shown.
Example 1
Preparation of flame-retardant modified polyurethane material
50 parts of polyether glycol subjected to vacuum dehydration and 10 parts of toluene-2, 4-diisocyanate are put into a reactor and uniformly mixed, 3 parts of dibutyltin dilaurate are dropwise added, the temperature of the system is raised to 60 ℃, the reaction is carried out for 4 hours under the protection of nitrogen, 3 parts of micromolecule flame-retardant cross-linking agent and 2 parts of dibutyltin dilaurate are put into the system and continuously reacted for 2 hours, and after the reaction is finished, the product is cooled to room temperature, and the material is discharged, so that the flame-retardant modified polyurethane material is obtained.
Example 2
Preparation of flame-retardant modified polyurethane material
Putting 55 parts of polyether glycol subjected to vacuum dehydration 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, putting 4 parts of micromolecule 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
60 parts of polyether glycol subjected to vacuum dehydration and 14 parts of toluene-2, 4-diisocyanate are put into a reactor and uniformly mixed, 5.5 parts of dibutyltin dilaurate are dropwise added, the temperature of the system is raised to 65 ℃, the reaction is carried out for 5 hours under the protection of nitrogen, 5 parts of micromolecule flame-retardant cross-linking agent and 3 parts of dibutyltin dilaurate are put into the system and continuously reacted for 3 hours, and after the reaction is finished, the product is cooled to room temperature, and the material is discharged, so that the flame-retardant modified polyurethane material is obtained.
Example 4
Preparation of flame-retardant modified polyurethane material
Putting 70 parts of polyether glycol subjected to vacuum dehydration and 15 parts of toluene-2, 4-diisocyanate 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, putting 6 parts of micromolecule flame-retardant cross-linking agent and 4 parts of dibutyltin dilaurate into the system, continuously reacting for 3 hours, and after the reaction is finished, cooling the product to room temperature, and discharging to obtain the flame-retardant modified polyurethane material.
Comparative example 1
Preparation of polyurethane materials
Putting 55 parts of polyether glycol subjected to vacuum dehydration 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, putting 4 parts of pentaerythritol cross-linking agent and 2.5 parts of dibutyltin dilaurate into the system, continuously reacting for 2 hours, and after the reaction is finished, cooling the product to room temperature, and discharging to obtain the flame-retardant modified polyurethane material.
Performance detection
Referring to the national standard GB/T1043.2-2018, a JBW-300B type impact tester is used for carrying out an impact performance test on the polyurethane materials prepared in the embodiments 1-4 and the comparative example 1 of the invention; with reference to the national standard GB/T2406-2009, a JF-3 type limit oxygen index instrument is used for carrying out limit oxygen index tests on polyurethane materials prepared in the embodiments 1-4 and the comparative example 1 of the invention; 0.5g of the polyurethane materials prepared in inventive examples 1 to 4 and comparative example 1 were placed in an SAT200 thermogravimetric analyzer at a temperature rise rate of 10 ℃/min from 25 ℃ to 600 ℃ under nitrogen protection, the initial decomposition temperature was recorded, and the heat resistance was evaluated, and the test results are shown in the following table:
as is apparent from the table, the polyurethane materials prepared in examples 1 to 4 of the present invention have high values of impact strength and limiting oxygen index, and thus have high impact resistance and flame retardancy, and further, the initial decomposition temperature is high, indicating high heat resistance, while the polyurethane material prepared in comparative example 1 has a low limiting oxygen index, presumably because pentaerythritol having no flame retardancy is used as a crosslinking agent, and thus has poor flame retardancy.
With reference to the national standard GB/T2048-1996, UL-94 vertical burning tests were performed on the polyurethane materials prepared in examples 1-4 of the present invention and comparative example 1, and the test results are shown in the following table:
as can be seen from the table, the polyurethane materials prepared in the examples 1 to 4 of the invention have the flame retardant rating of V-0 grade and have excellent flame retardant property, while the polyurethane material prepared in the comparative example 1 has the flame retardant rating of V-2 grade and therefore has poor flame retardant property.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean 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 invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer 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. Moreover, various embodiments or examples and features of various embodiments or examples described in this specification can be combined and combined by one skilled in the art without being mutually inconsistent.
The foregoing is merely exemplary and illustrative of the principles of the present invention and various modifications, additions and substitutions of the specific embodiments described herein may be made by those skilled in the art without departing from the principles of the present invention or exceeding the scope of the claims set forth herein.
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 micromolecule flame-retardant cross-linking agent;
the structural formula of the micromolecule flame-retardant cross-linking agent is as follows:
2. the flame-retardant modified polyurethane material as claimed in claim 1, wherein the synthesis method of the small-molecule flame-retardant cross-linking agent comprises the following steps:
mixing diphenyldichlorosilane and 1, 4-dioxane, adding 1, 3-diglycidyl ether glycerol, uniformly stirring, placing the system at 70-80 ℃, preserving heat for 4-12h, removing low-boiling-point substances by reduced pressure distillation after gas is exhausted, pouring out products, carrying out suction filtration to separate solids, washing by using deionized water, and carrying out vacuum drying to obtain an intermediate;
and II, dissolving the intermediate and 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide in an organic solvent, uniformly stirring by a machine, introducing nitrogen to remove air in a system, raising the temperature of the system to react, cooling a product to room temperature, and precipitating the product in a precipitator for 2-4 times to obtain the micromolecule flame-retardant crosslinking agent.
3. The flame-retardant modified polyurethane material according to claim 2, wherein in step I, the molar ratio of the diphenyldichlorosilane to the 1, 3-diglycidyl ether glycerol is 1.
4. The flame-retardant modified polyurethane material as claimed in claim 2, wherein in step I, the temperature during vacuum drying is 50-60 ℃ and the time is 2-6h.
5. The flame-retardant modified polyurethane material as claimed in claim 2, wherein in step ii, the organic solvent is any one of tetrahydrofuran, N-dimethylformamide and N, N-dimethylacetamide.
6. The flame-retardant modified polyurethane material as claimed in claim 2, wherein in step II, the reaction temperature is 80-90 ℃, and the mixture is stirred for 6-18h under the protection of nitrogen.
7. The flame-retardant modified polyurethane material as claimed in claim 2, wherein in step II, the precipitating agent is methanol.
8. The synthesis method of the flame-retardant modified polyurethane material as claimed in claim 1, wherein the synthesis method specifically comprises the following steps:
and (2) putting the polyether glycol subjected to vacuum dehydration and toluene-2, 4-diisocyanate into a reactor, uniformly mixing, dropwise adding part of dibutyltin dilaurate, raising the temperature of the system to 60-70 ℃, reacting for 4-6h under the protection of nitrogen, putting the micromolecule flame-retardant cross-linking agent and the rest dibutyltin dilaurate into the system, continuously reacting for 2-3h, 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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| CN116655883A (en) | 2023-08-29 |
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