CN115651150A - Water glass filled modified flame-retardant polyurethane foam and preparation method thereof - Google Patents
Water glass filled modified flame-retardant polyurethane foam and preparation method thereof Download PDFInfo
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- CN115651150A CN115651150A CN202211242068.1A CN202211242068A CN115651150A CN 115651150 A CN115651150 A CN 115651150A CN 202211242068 A CN202211242068 A CN 202211242068A CN 115651150 A CN115651150 A CN 115651150A
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- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical class 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 72
- 229920005830 Polyurethane Foam Polymers 0.000 title claims abstract description 65
- 239000011496 polyurethane foam Substances 0.000 title claims abstract description 65
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 235000019353 potassium silicate Nutrition 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title abstract description 14
- 239000003063 flame retardant Substances 0.000 claims abstract description 67
- 239000000463 material Substances 0.000 claims abstract description 50
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 44
- 229920000570 polyether Polymers 0.000 claims abstract description 44
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229920005862 polyol Polymers 0.000 claims abstract description 36
- 150000003077 polyols Chemical class 0.000 claims abstract description 36
- 239000006260 foam Substances 0.000 claims abstract description 26
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 23
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 23
- 239000002994 raw material Substances 0.000 claims abstract description 17
- 239000004964 aerogel Substances 0.000 claims abstract description 15
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 13
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 11
- 239000003381 stabilizer Substances 0.000 claims abstract description 8
- 238000004519 manufacturing process Methods 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims description 27
- -1 polyoxypropylene Polymers 0.000 claims description 26
- 229920001296 polysiloxane Polymers 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 238000005187 foaming Methods 0.000 claims description 12
- 229920006389 polyphenyl polymer Polymers 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 11
- 239000004965 Silica aerogel Substances 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 8
- 239000004111 Potassium silicate Substances 0.000 claims description 7
- 239000004115 Sodium Silicate Substances 0.000 claims description 7
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 claims description 7
- 229910052913 potassium silicate Inorganic materials 0.000 claims description 7
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000004094 surface-active agent Substances 0.000 claims description 4
- 239000012970 tertiary amine catalyst Substances 0.000 claims description 3
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 2
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims description 2
- 229920002472 Starch Polymers 0.000 claims description 2
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 2
- 229930006000 Sucrose Natural products 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- PAZHGORSDKKUPI-UHFFFAOYSA-N lithium metasilicate Chemical compound [Li+].[Li+].[O-][Si]([O-])=O PAZHGORSDKKUPI-UHFFFAOYSA-N 0.000 claims description 2
- 229910052912 lithium silicate Inorganic materials 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 2
- 229920001451 polypropylene glycol Polymers 0.000 claims description 2
- 239000000600 sorbitol Substances 0.000 claims description 2
- 239000008107 starch Substances 0.000 claims description 2
- 235000019698 starch Nutrition 0.000 claims description 2
- 239000005720 sucrose Substances 0.000 claims description 2
- 229920002635 polyurethane Polymers 0.000 abstract description 25
- 239000004814 polyurethane Substances 0.000 abstract description 25
- 229910052736 halogen Inorganic materials 0.000 abstract description 7
- 150000002367 halogens Chemical class 0.000 abstract description 7
- 239000000126 substance Substances 0.000 abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 12
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical group [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 11
- 229920003023 plastic Polymers 0.000 description 9
- 239000004033 plastic Substances 0.000 description 9
- AXFVIWBTKYFOCY-UHFFFAOYSA-N 1-n,1-n,3-n,3-n-tetramethylbutane-1,3-diamine Chemical compound CN(C)C(C)CCN(C)C AXFVIWBTKYFOCY-UHFFFAOYSA-N 0.000 description 7
- 238000005303 weighing Methods 0.000 description 7
- XLUBVTJUEUUZMR-UHFFFAOYSA-B silicon(4+);tetraphosphate Chemical compound [Si+4].[Si+4].[Si+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XLUBVTJUEUUZMR-UHFFFAOYSA-B 0.000 description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 5
- 229910052698 phosphorus Inorganic materials 0.000 description 5
- 239000011574 phosphorus Substances 0.000 description 5
- 230000035807 sensation Effects 0.000 description 5
- 239000000779 smoke Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 4
- HVCNXQOWACZAFN-UHFFFAOYSA-N 4-ethylmorpholine Chemical compound CCN1CCOCC1 HVCNXQOWACZAFN-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000004088 foaming agent Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 229920002994 synthetic fiber Polymers 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- URAYPUMNDPQOKB-UHFFFAOYSA-N triacetin Chemical compound CC(=O)OCC(OC(C)=O)COC(C)=O URAYPUMNDPQOKB-UHFFFAOYSA-N 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 1
- SVYKKECYCPFKGB-UHFFFAOYSA-N N,N-dimethylcyclohexylamine Chemical compound CN(C)C1CCCCC1 SVYKKECYCPFKGB-UHFFFAOYSA-N 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910008051 Si-OH Inorganic materials 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- 229910006358 Si—OH Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000010382 chemical cross-linking Methods 0.000 description 1
- 238000006757 chemical reactions by type Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 229960002887 deanol Drugs 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- 239000012972 dimethylethanolamine Substances 0.000 description 1
- 239000012971 dimethylpiperazine Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 235000019439 ethyl acetate Nutrition 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000004872 foam stabilizing agent Substances 0.000 description 1
- 239000001087 glyceryl triacetate Substances 0.000 description 1
- 235000013773 glyceryl triacetate Nutrition 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 229910001853 inorganic hydroxide Inorganic materials 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- RLQWHDODQVOVKU-UHFFFAOYSA-N tetrapotassium;silicate Chemical compound [K+].[K+].[K+].[K+].[O-][Si]([O-])([O-])[O-] RLQWHDODQVOVKU-UHFFFAOYSA-N 0.000 description 1
- 239000012974 tin catalyst Substances 0.000 description 1
- 229960002622 triacetin Drugs 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
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Abstract
The invention discloses a water glass filled modified flame-retardant polyurethane foam and a preparation method thereof, wherein the water glass filled modified flame-retardant polyurethane foam is prepared from the following raw materials in parts by weight: 90-120 parts of polyether polyol, 100-150 parts of polyisocyanate, 2-10 parts of foam stabilizer, 0.5-3.0 parts of foam catalyst, 50-160 parts of water glass and 1-12 parts of silicon dioxide aerogel. According to the invention, the water glass and the silicon dioxide aerogel are used as the flame-retardant raw materials of the polyurethane foam, so that the flame retardant is uniformly doped in the polyurethane in a physical and chemical doping manner, the flame-retardant property of the polyurethane material can be effectively improved, the addition of the water glass can reduce the consumption of the raw materials so as to save the raw materials, compared with the traditional halogen-containing flame-retardant polyurethane, the production cost of the flame-retardant polyurethane can be obviously reduced, and the flame-retardant polyurethane has a wide application value.
Description
Technical Field
The invention belongs to the technical field of polyurethane foam, and particularly relates to water glass filled modified flame-retardant polyurethane foam and a preparation method thereof.
Background
The polyurethane material is a synthetic material which is rapidly raised after five general plastics are used, and the traditional polyurethane material is expensive, inflammable and quick to burn when meeting fire, and can generate a large amount of black smoke and toxic and harmful gases. Because of light weight, low heat conductivity coefficient and large expansion coefficient, the polyurethane foam is widely applied to the fields of gap filling, wall heat preservation, building sound insulation and material shock absorption, and is called one of the polymer synthetic materials with the fastest global development and the widest application.
The oxygen index of the polyurethane is only about 14-17%, and the polyurethane belongs to inflammable materials. Polyurethane foam can release a large amount of smoke and toxic small-molecule gas during combustion, so that air pollution is caused, and the polyurethane foam causes great harm to human bodies after being inhaled, thereby greatly limiting the application range of the polyurethane foam.
The addition of the flame retardant is an effective method for improving the flame retardant property of polyurethane foam, and the conventional preparation of flame retardant polyurethane mainly comprises the addition of melamine, phosphate, inorganic hydroxide and other addition type flame retardants, phosphorus-containing halogen-containing reaction type flame retardants and the like. However, the traditional flame retardant has some problems at present, the halogen-containing phosphorus-containing flame retardant has the problem of serious environmental pollution, and the common additive flame retardant has the problems of large addition amount, high price and the like, so that the practical production and application requirements are difficult to meet.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art described above. Therefore, the invention provides the water glass filled modified flame-retardant polyurethane foam and the preparation method thereof, and the water glass and the silicon dioxide aerogel are used as flame-retardant raw materials of the polyurethane foam, so that the flame retardant is uniformly doped in the polyurethane in a physical and chemical doping manner, and the flame retardant property of the polyurethane material can be effectively improved; in addition, the addition of the water glass can reduce the usage amount of raw materials so as to save the raw materials, and compared with the traditional halogen-containing phosphorus-containing flame retardant, the halogen-containing flame retardant polyurethane can obviously reduce the production cost of the flame retardant polyurethane, and has wide application value.
According to one aspect of the invention, a flame-retardant polyurethane foam is provided, which is prepared from the following raw materials in parts by weight: 90-120 parts of polyether polyol, 100-150 parts of polyisocyanate, 2-10 parts of foam stabilizer, 0.5-3.0 parts of foam catalyst, 50-160 parts of water glass and 1-12 parts of silica aerogel.
In some preferred embodiments of the present invention, the water glass is used in an amount of 80 to 120 parts.
In some embodiments of the invention, the feedstock further comprises a water glass curing agent. Further, the amount of the water glass curing agent is 2-10 parts. The water glass curing agent can further adjust the curing speed and enhance the foam strength.
In some embodiments of the invention, the polyether polyol is a polyoxypropylene polyol, having a hydroxyl number of 350-650mg KOH/g, and a functionality of 3-5.
In some embodiments of the present invention, the polyether polyol is selected from at least one of a glycerol polyether polyol, a sorbitol polyether polyol, a pentaerythritol polyether polyol, a sucrose polyether polyol, a starch polyether polyol, or an amine polyether polyol.
In some embodiments of the invention, the polyisocyanate is a polymethylene polyphenyl polyisocyanate having an average functionality of 2.5 to 3.0 and a viscosity of 100 to 1000 mPas at 25 ℃.
In some embodiments of the invention, the water glass is at least one of a sodium silicate solution (sodium water glass), a potassium silicate solution (potassium water glass), or a lithium silicate solution (lithium water glass) with a modulus between 2.0 and 5.0. Further, the concentration of the water glass is 35.2-45 Baume degrees.
In some embodiments of the present invention, the foam stabilizing agent is selected from at least one of a silicone surfactant, a polyether-modified polysiloxane, or a non-silicone surfactant.
In some embodiments of the present invention, the foam catalyst is selected from at least one of a tertiary amine catalyst or an organotin catalyst. Further, the tertiary amine catalyst is at least one selected from the group consisting of N, N-dimethylcyclohexylamine, tetramethylethylenediamine, tetramethylbutanediamine, N' -dimethylpiperazine, triethylenediamine, triethanolamine, dimethylethanolamine, dimethylbenzylamine, N-ethylmorpholine, pentamethyldiethylenetriamine and triethylamine. Further, the organic tin catalyst is stannous octoate.
In some embodiments of the invention, the silica aerogel has a particle size of 10 to 60 μm.
In some embodiments of the invention, the water glass curing agent is selected from at least one of silicon phosphate, sodium phosphate, aluminum tripolyphosphate, glyceryl triacetate, or ethyl acetate.
The invention also provides a preparation method of the flame-retardant polyurethane foam, which comprises the following steps:
(1) Mixing and stirring polyether polyol, a foam catalyst, a foam stabilizer and silicon dioxide aerogel to obtain a first mixed material;
(2) Adding water glass into the first mixed material, and stirring to obtain a second mixed material;
(3) And mixing the polyisocyanate and the second mixed material, stirring, pouring the mixed material into a mould for natural foaming after the mixed material is consistent in color and begins to foam, and heating for reaction and curing to obtain the flame-retardant polyurethane foam.
In some embodiments of the present invention, in the step (1), the polyether polyol, the foam catalyst, the foam stabilizer and the silica aerogel are mixed and stirred for 1 to 2min.
In some embodiments of the invention, in the step (2), the first mixture and the water glass are mixed and stirred for 3-5min until the system is free from granular sensation and milky white observed by naked eyes.
In some embodiments of the invention, in step (3), the stirring time is 30 to 60s.
In some embodiments of the present invention, in the step (3), the natural foaming time is 40 to 60s.
In some embodiments of the invention, in step (3), the temperature of the heating is 75-85 ℃.
In some embodiments of the invention, in step (3), the aging time is 20 to 28 hours.
In some embodiments of the present invention, when the raw material includes a water glass curing agent, the preparation method is as follows:
s1: mixing and stirring polyether polyol, a foam catalyst, a foam stabilizer and silicon dioxide aerogel to obtain a first mixed material; adding water glass into the first mixed material, and stirring to obtain a second mixed material;
s2: mixing and stirring polyisocyanate and a water glass curing agent to obtain a third mixed material;
s3: and mixing and stirring the second mixed material and the third mixed material, pouring the mixed material into a mould for natural foaming after the mixed material is consistent in color and begins to foam, and heating, reacting and curing to obtain the flame-retardant polyurethane foam.
According to a preferred embodiment of the present invention, at least the following advantages are provided:
1. the water glass filled modified flame-retardant rigid polyurethane foam can reach the fire-retardant grades of vertical UL94V-0 and horizontal UL94 HB through detection, and compared with halogen-containing phosphorus-containing flame-retardant polyurethane foam, the water glass filled modified flame-retardant rigid polyurethane foam is novel, environment-friendly and economical.
2. The carbon dioxide generated by the reaction of the polyisocyanate and the water in the water glass not only can be used as a chemical foaming agent for polyurethane foaming, but also can be used as a curing agent for the water glass. The water consumption is continuously reduced along with the reaction of polyisocyanate and water, and the reaction of a water glass curing agent and water, so that the water of a sodium silicate (potassium, lithium and the like) hydrosol system is continuously reduced, free silicate is dehydrated to generate more Si-OH water-soluble silica gel, si-OH is dehydrated to form-Si-O-Si-dehydrated association complex and crystal water-containing metasilicate, the water glass starts to be cured when reaching the critical solid content, and the dehydrated association complex, the crystal water-containing metasilicate and a polyurethane crosslinking structure form a three-dimensional solid structure together after the water glass is completely cured. A large amount of reaction heat can be released in the polyurethane curing reaction process, redundant water is evaporated into gaseous water vapor, the occurrence of foam core burning and high heat release danger caused by the curing reaction heat is reduced, and the polyurethane curing reaction device is particularly suitable for being used in the underground heat preservation and insulation environment of a coal mine.
3. The invention uses the low-density and low-thermal conductivity silica aerogel which is not only used as a filler for reducing the thermal conductivity of polyurethane foam, but also is a cross-linking point of a three-dimensional solid structure of water glass and polyurethane. The chemical main components of the silicon dioxide aerogel are similar to that of water glass, a part of the aerogel and the water glass are combined to form a physical cross-linking point, hydroxyl on the surface of a part of the aerogel reacts with polyisocyanate to form a chemical cross-linking point, and the last part of the aerogel is freely dispersed in the polyurethane foam, so that the mechanical strength of the water glass filled modified rigid polyurethane foam is improved by the three components.
4. The invention can achieve good flame-retardant effect, because: (1) The silicate can change the decomposition reaction process and direction of the polyurethane foam, reduce the generation of combustible substances (carbon monoxide, acetonitrile, acrylonitrile, pyridine and the like), inhibit the flame combustion of the polyurethane and promote the generation of more carbon layers on the surface of the polyurethane; (2) When exposed fire occurs, the metasilicate with the crystal water can be quickly decomposed into water vapor to take away heat and generate anhydrous silicate, so that the surface temperature of the product can be reduced and the oxygen concentration on the surface can be diluted. The anhydrous silicate forms a glassy melt at a higher temperature, and covers the surfaces of the polyurethane and the carbon layer, so that the carbon layer is more compact, and the compact carbon layer structure is favorable for heat insulation, air isolation and smoke release reduction, and achieves efficient flame retardance and smoke suppression performance.
5. The invention prepares the economic and environment-friendly flame retardant polyurethane foam by adopting the water glass solution as the flame retardant and the foaming agent, the flame retardant water glass is an important raw material in the alkali-activated industrial waste residue cementing material, the price is low, the preparation is easy, the flame retardant is used as the flame retardant, the flame retardant performance of the foamed plastic can be obviously improved, the consumption of the polyether polyol raw material can be reduced, the production cost can be effectively reduced, the use of halogen-containing and phosphorus-containing flame retardant is avoided, the environmental protection requirement is met, and the application prospect is wide.
Drawings
The invention is further described with reference to the following figures and examples, in which:
FIG. 1 is a graph comparing 15s ignition and 45s ignition of a polyurethane foam obtained in example 2 of the present invention;
FIG. 2 is a test chart of the infrared spectrum of the polyurethane foam obtained in example 2 of the present invention;
FIG. 3 is a graph showing the spectrum of the polyurethane foam obtained in example 2 of the present invention.
Detailed Description
The concept and technical effects of the present invention will be clearly and completely described below in conjunction with the embodiments to fully understand the objects, features and effects of the present invention. It is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments, and those skilled in the art can obtain other embodiments without inventive effort based on the embodiments of the present invention, and all embodiments are within the protection scope of the present invention.
Example 1
The embodiment prepares the flame-retardant polyurethane foam, which is prepared from the following raw materials in parts by weight: 100 parts of polyether polyol (the hydroxyl value is 450mg KOH/g, the functionality is 4), 110 parts of polymethylene polyphenyl polyisocyanate, 10 parts of polyether modified polysiloxane, 1.5 parts of tetramethyl butanediamine, 1 part of stannous octoate, 100 parts of potassium silicate solution (40 Baume degree) and 3 parts of 15-micron silicon dioxide aerogel.
The preparation method comprises the following specific steps:
(1) Putting 100 parts of polyether polyol into a disposable plastic container, sequentially adding 1 part of stannous octoate, 1.5 parts of tetramethylbutanediamine, 10 parts of polyether modified polysiloxane and 3 parts of 15-micron silicon dioxide aerogel, and quickly stirring for 1-2min until uniformly mixing to obtain a white material system;
(2) Weighing 100 parts of potassium silicate solution into a white material system, and stirring for 3-5min until the system is observed by naked eyes to have no granular sensation and be in a milky white state, thereby obtaining a flame-retardant white material system;
(3) Weighing 110 parts of polymethylene polyphenyl polyisocyanate into a flame-retardant white material system, stirring at a high speed for 40-55s, quickly pouring the prepolymer into a mould for natural foaming for 40-60s when the color of the prepolymer is consistent and slightly expanded, and finally putting the prepolymer into an oven at 80 ℃ for reaction and curing for 24h to obtain the flame-retardant polyurethane foam.
Example 2
The embodiment prepares the flame-retardant polyurethane foam, which is prepared from the following raw materials in parts by weight: 100 parts of polyether polyol, the hydroxyl value of which is 450mg KOH/g, and the functionality of which is 4), 110 parts of polymethylene polyphenyl polyisocyanate, 10 parts of polyether modified polysiloxane, 1.5 parts of N-ethyl morpholine, 1 part of stannous octoate, 100 parts of sodium silicate solution (40 Baume degrees) and 3 parts of 50-micron silicon dioxide aerogel, and 2 parts of silicon phosphate.
The preparation method comprises the following specific steps:
(1) Putting 100 parts of polyether polyol into a disposable plastic container, sequentially adding 1 part of stannous octoate, 1.5 parts of N-ethyl morpholine, 10 parts of polyether modified polysiloxane and 3 parts of 50-micron silica aerogel, and quickly stirring for 1-2min until uniformly mixing to obtain a white material system;
(2) Placing 110 parts of polymethylene polyphenyl polyisocyanate into a disposable plastic container, adding 2 parts of silicon phosphate, and rapidly stirring for 10-15s to obtain a black material system;
(3) Weighing 100 parts of sodium silicate solution into a white material system, and stirring for 3-5min until the system is free from granular sensation and is in a milky white state when observed by naked eyes to obtain a flame-retardant white material system;
(4) And (3) pouring the flame-retardant white material system obtained in the step (3) into the black material system obtained in the step (2), stirring at a high speed for 40-55s, quickly pouring the prepolymer into a mould for natural foaming for 40-60s when the color of the prepolymer is consistent and slightly expanded, and finally putting the prepolymer into an oven at 80 ℃ for reaction and curing for 24h to obtain the flame-retardant polyurethane foam.
Example 3
The embodiment prepares the flame-retardant polyurethane foam, which is prepared from the following raw materials in parts by weight: 100 parts of polyether polyol (hydroxyl value is 450mg KOH/g, functionality is 4), 110 parts of polymethylene polyphenyl polyisocyanate, 10 parts of polyether modified polysiloxane, 1.5 parts of triethanolamine, 1 part of stannous octoate, 100 parts of sodium silicate solution (40 Baume degrees), 3 parts of 50-micron silicon dioxide aerogel and 4 parts of silicon phosphate.
The preparation method comprises the following specific steps:
(1) Putting 100 parts of polyether polyol into a disposable plastic container, sequentially adding 1 part of stannous octoate, 1.5 parts of triethanolamine, 10 parts of polyether modified polysiloxane and 3 parts of 50-micron silicon dioxide aerogel, and quickly stirring for 1-2min until uniformly mixing to obtain a white material system;
(2) Placing 110 parts of polymethylene polyphenyl polyisocyanate into a disposable plastic container, adding 4 parts of silicon phosphate, and rapidly stirring for 10-15s to obtain a black material system;
(3) Weighing 100 parts of sodium silicate solution into a white material system, and stirring for 3-5min until the system is free from granular sensation and is in a milky white state when observed by naked eyes to obtain a flame-retardant white material system;
(4) And (3) pouring the flame-retardant white material system obtained in the step (3) into the black material system obtained in the step (2), stirring at a high speed for 40-55s, quickly pouring the prepolymer into a mould for natural foaming for 40-60s when the color of the prepolymer is consistent and slightly expanded, and finally putting the prepolymer into an oven at 80 ℃ for reaction and curing for 24h to obtain the flame-retardant polyurethane foam.
Comparative example 1
The comparative example prepared a common polyurethane foam, which was different from example 1 mainly in that the potassium silicate solution and silica aerogel were not added, and specifically prepared from the following raw materials in parts by weight: 100 parts of polyether polyol (hydroxyl value is 450mg KOH/g, and functionality is 4), 110 parts of polymethylene polyphenyl polyisocyanate, 3 parts of polyether modified polysiloxane, 1.5 parts of tetramethyl butanediamine, 1 part of stannous octoate and 2 parts of water.
The preparation method comprises the following specific steps:
(1) Putting 100 parts of polyether polyol into a disposable plastic container, sequentially adding 1 part of stannous octoate, 1.5 parts of tetramethylbutanediamine, 3 parts of polyether modified polysiloxane and 2 parts of water, and quickly stirring for 1-2min until the materials are uniformly mixed to obtain a white material system;
(2) Weighing 110 parts of polymethylene polyphenyl polyisocyanate into a white material system, stirring at a high speed for 15-35s, pouring the prepolymer into a mould for natural foaming for 40-60s when the color of the prepolymer is consistent and slightly expanded, and finally putting the prepolymer into an oven at 80 ℃ for reaction and curing for 24h to prepare the common polyurethane foam.
Comparative example 2
The comparative example prepared a flame retardant polyurethane foam, which differs from example 1 mainly in that no silica aerogel was added, and was specifically made from the following raw materials in parts by weight: 100 parts of polyether polyol (hydroxyl value is 450mg KOH/g, functionality is 4), 110 parts of polymethylene polyphenyl polyisocyanate, 10 parts of polyether modified polysiloxane, 1.5 parts of tetramethyl butanediamine, 1 part of stannous octoate and 100 parts of potassium silicate solution (40 Baume degrees).
The preparation method comprises the following specific steps:
(1) Putting 100 parts of polyether polyol into a disposable plastic container, sequentially adding 1 part of stannous octoate, 1.5 parts of tetramethylbutanediamine and 10 parts of polyether modified polysiloxane, and rapidly stirring for 1-2min until uniformly mixing to obtain a white material system;
(2) Weighing 110 parts of potassium silicate solution into a white material system, and stirring for 3-5min until the system has no granular sensation and is in a milky white state to obtain a flame-retardant white material system;
(3) Weighing 110 parts of polymethylene polyphenyl polyisocyanate into a flame-retardant white material system, stirring at a high speed for 40-55s, quickly pouring the prepolymer into a mould for natural foaming for 40-60s when the color of the prepolymer is consistent and slightly expanded, and finally putting the prepolymer into an oven at 80 ℃ for reaction and curing for 24h to obtain the flame-retardant polyurethane foam.
Test examples
The polyurethane foams of the examples and comparative examples were tested for compressive strength in the horizontal and vertical directions of foaming according to the GB/T8813-2008 standard.
The polyurethane foams of the examples and comparative examples were subjected to thermal conductivity tests in accordance with the standard GB/T10294-2008.
The polyurethane foams of the examples and comparative examples were subjected to the foaming ratio test in accordance with the standard GB/T21558-2008.
The polyurethane foams of the examples and comparative examples were subjected to density tests in accordance with the standard GB/T6343.
The polyurethane foams of the examples and comparative examples were subjected to horizontal and vertical direction burning tests in accordance with the standard GB/T2408-2008.
TABLE 1 Performance index of the polyurethane foams of the examples and comparative examples
As can be seen from Table 1, in examples 1 to 3, by constructing an inorganic water glass flame-retardant system, the flame-retardant grade reaches V-0 grade under the UL94 standard of vertical test combustion time, the flame-retardant polyurethane foam has excellent flame retardance, and the thermal conductivity and the compressive strength are equivalent to those of the common polyurethane foam prepared in comparative example 1; examples 2 and 3 have higher strength than example 1 by adding more silicon phosphate as a water glass curing agent; comparative example 2, which only added water glass and no silica aerogel, was inferior to example 1 in mechanical properties, thermal conductivity and flame retardancy.
FIG. 1 is a graph comparing 15s ignition and 45s ignition of the polyurethane foam obtained in example 2 of the present invention. As can be seen from FIG. 1, when the flame-retardant polyurethane foam is continuously ignited for 15s by using an alcohol lamp, the whole foam has no relatively obvious ignition and ignition tendency, the bottom of the foam is directly changed from light yellow to black, and the smoke generated by combustion is very little; when the flame-retardant polyurethane foam is continuously ignited for 45s, the foam still does not catch fire and burn completely, the polyurethane which can be contacted with the outermost layer is burned and blackened, the whole volume does not cause great loss, and meanwhile, the phenomenon of molten drops does not occur in the foam block which is ignited in the burning process, so that the flame-retardant polyurethane foam has excellent flame-retardant and smoke-suppression performances.
FIG. 2 and FIG. 3 are an infrared spectrum test chart and an energy spectrum test chart, respectively, of the polyurethane foam obtained in example 2 of the present invention. As can be seen from the figure, the flame-retardant polyurethane foam has an absorption peak of 1094cm in addition to the characteristic absorption peak of polyurethane itself -1 Has an Si-O-Si stretching vibration peak of 3427cm -1 A sharper OH stretching vibration peak appears, which shows that the water glass forms a silica chemical bond after being cured, and a small amount of water still exists in the system after the flame retardant polyurethane is cured and forms an intramolecular hydrogen bond. The presence of the silicon-containing compound in the flame retarded polyurethane foam is also confirmed by the energy spectrum test pattern.
The embodiments of the present invention have been described in detail with reference to the accompanying drawings, but the present invention is not limited to the above embodiments, and various changes can be made within the knowledge of those skilled in the art without departing from the gist of the present invention. Furthermore, the embodiments of the present invention and the features of the embodiments may be combined with each other without conflict.
Claims (10)
1. The flame-retardant polyurethane foam is characterized by being prepared from the following raw materials in parts by weight: 90-120 parts of polyether polyol, 100-150 parts of polyisocyanate, 2-10 parts of foam stabilizer, 0.5-3.0 parts of foam catalyst, 50-160 parts of water glass and 1-12 parts of silica aerogel.
2. The flame retardant polyurethane foam of claim 1, wherein the feedstock further comprises a water glass curing agent.
3. The flame retardant polyurethane foam of claim 1, wherein the polyether polyol is a polyoxypropylene polyol having a hydroxyl number of 350-650mg KOH/g and a functionality of 3-5.
4. The flame retardant polyurethane foam of claim 1, wherein the polyether polyol is selected from at least one of glycerol polyether polyol, sorbitol polyether polyol, pentaerythritol polyether polyol, sucrose polyether polyol, starch polyether polyol, or amine polyether polyol.
5. The flame-retardant polyurethane foam according to claim 1, wherein the polyisocyanate is polymethylene polyphenyl polyisocyanate, has an average functionality of 2.5 to 3.0, and has a viscosity of 100 to 1000 mPa-s at 25 ℃.
6. The flame retarded polyurethane foam according to claim 1 wherein said water glass is at least one of a sodium silicate solution, a potassium silicate solution, or a lithium silicate solution and has a modulus between 2.0 and 5.0.
7. The flame-retardant polyurethane foam according to claim 1, wherein the foam stabilizer is at least one selected from the group consisting of a silicone surfactant, a polyether-modified polysiloxane, and a non-silicone surfactant.
8. The flame retarded polyurethane foam according to claim 1 wherein the foam catalyst is selected from at least one of a tertiary amine catalyst or an organotin catalyst.
9. The flame retardant polyurethane foam according to claim 1, wherein the silica aerogel has a particle size of 10 to 60 μm.
10. A process for preparing a flame retarded polyurethane foam according to any of claims 1 to 9, comprising the steps of:
(1) Mixing and stirring polyether polyol, a foam catalyst, a foam stabilizer and silicon dioxide aerogel to obtain a first mixed material;
(2) Adding water glass into the first mixed material, and stirring to obtain a second mixed material;
(3) And mixing the polyisocyanate and the second mixed material, stirring, pouring the mixed material into a mould for natural foaming after the mixed material is consistent in color and begins to foam, and heating for reaction and curing to obtain the flame-retardant polyurethane foam.
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Cited By (1)
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| CN116948390A (en) * | 2023-09-21 | 2023-10-27 | 赢胜节能集团股份有限公司 | Composite heat-insulating material based on aluminum silicate fibers |
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