CN114634607A - Preparation method of flame-retardant rigid polyurethane foam and prepared foam product - Google Patents
Preparation method of flame-retardant rigid polyurethane foam and prepared foam product Download PDFInfo
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 91
- 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 87
- 229920005830 Polyurethane Foam Polymers 0.000 title claims abstract description 44
- 239000011496 polyurethane foam Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000006260 foam Substances 0.000 title abstract description 6
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 22
- 229920000570 polyether Polymers 0.000 claims abstract description 22
- 229920005862 polyol Polymers 0.000 claims abstract description 22
- 150000003077 polyols Chemical class 0.000 claims abstract description 22
- 238000003756 stirring Methods 0.000 claims abstract description 21
- 239000003054 catalyst Substances 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229920000538 Poly[(phenyl isocyanate)-co-formaldehyde] Polymers 0.000 claims abstract description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000004088 foaming agent Substances 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 10
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 7
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000004327 boric acid Substances 0.000 claims abstract description 7
- 229910052796 boron Inorganic materials 0.000 claims abstract description 7
- 239000008367 deionised water Substances 0.000 claims abstract description 7
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 7
- KBXJHRABGYYAFC-UHFFFAOYSA-N octaphenylsilsesquioxane Chemical compound O1[Si](O2)(C=3C=CC=CC=3)O[Si](O3)(C=4C=CC=CC=4)O[Si](O4)(C=5C=CC=CC=5)O[Si]1(C=1C=CC=CC=1)O[Si](O1)(C=5C=CC=CC=5)O[Si]2(C=2C=CC=CC=2)O[Si]3(C=2C=CC=CC=2)O[Si]41C1=CC=CC=C1 KBXJHRABGYYAFC-UHFFFAOYSA-N 0.000 claims abstract description 7
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000005187 foaming Methods 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims abstract description 4
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 18
- VONWDASPFIQPDY-UHFFFAOYSA-N dimethyl methylphosphonate Chemical compound COP(C)(=O)OC VONWDASPFIQPDY-UHFFFAOYSA-N 0.000 claims description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 16
- 229910002804 graphite Inorganic materials 0.000 claims description 15
- 239000010439 graphite Substances 0.000 claims description 15
- BHTBHKFULNTCHQ-UHFFFAOYSA-H zinc;tin(4+);hexahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Zn+2].[Sn+4] BHTBHKFULNTCHQ-UHFFFAOYSA-H 0.000 claims description 15
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 13
- 239000012295 chemical reaction liquid Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 claims description 10
- FRCHKSNAZZFGCA-UHFFFAOYSA-N 1,1-dichloro-1-fluoroethane Chemical compound CC(F)(Cl)Cl FRCHKSNAZZFGCA-UHFFFAOYSA-N 0.000 claims description 9
- 239000012153 distilled water Substances 0.000 claims description 9
- 235000011056 potassium acetate Nutrition 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 8
- SVYKKECYCPFKGB-UHFFFAOYSA-N N,N-dimethylcyclohexylamine Chemical compound CN(C)C1CCCCC1 SVYKKECYCPFKGB-UHFFFAOYSA-N 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- 238000000967 suction filtration Methods 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 239000004604 Blowing Agent Substances 0.000 claims 1
- 238000005580 one pot reaction Methods 0.000 abstract description 3
- 238000001914 filtration Methods 0.000 abstract 1
- IXDZFGATLNCIOI-PBXRRBTRSA-N 1-deoxy-D-tagatose Chemical compound CC(=O)[C@@H](O)[C@@H](O)[C@H](O)CO IXDZFGATLNCIOI-PBXRRBTRSA-N 0.000 description 8
- 238000013329 compounding Methods 0.000 description 5
- 238000009413 insulation Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000005034 decoration Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- NDKGUMMLYBINOC-UHFFFAOYSA-N 1,2-dichloro-1-fluoroethane Chemical compound FC(Cl)CCl NDKGUMMLYBINOC-UHFFFAOYSA-N 0.000 description 1
- 229910015395 B-O-Si Inorganic materials 0.000 description 1
- 229910015403 B—O—Si Inorganic materials 0.000 description 1
- 229910002656 O–Si–O Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
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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
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0014—Use of organic additives
- C08J9/0038—Use of organic additives containing phosphorus
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0066—Use of inorganic compounding ingredients
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0095—Mixtures of at least two compounding ingredients belonging to different one-dot groups
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
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- C08G2101/00—Manufacture of cellular products
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- C08G2110/00—Foam properties
- C08G2110/0025—Foam properties rigid
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- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
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- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
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- C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2483/04—Polysiloxanes
- C08J2483/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
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Abstract
A preparation method of flame-retardant rigid polyurethane foam and a prepared foam product are characterized by firstly adding 0.6-1 mol of boric acid and 0.1-0.3 mol of phenyltrimethoxysilane into 30-100 ml of ethanol, adding 0.1-0.3 ml of concentrated hydrochloric acid with the mass concentration of 37% as a catalyst, and adding N into the mixture2Heating to 75-90 ℃ under protection, reacting for 6-10 h, adding into 300-500 ml of deionized water, stirring for 10min, standing, filtering, and drying at 70-90 ℃ for 12-24 h to obtain boron-containing phenyl silsesquioxane (BPSQ flame retardant); adding a BPSQ flame retardant into polyether polyol 4110, uniformly mixing, adding a catalyst and a foaming agent, and uniformly stirring; and adding polymeric MDI polymethylene polyphenyl isocyanate, stirring and foaming to obtain the flame-retardant rigid polyurethane foam, and curing for 24-36 h. The preparation method can prepare the flame-retardant rigid polyurethane foam through one-step reaction, is simple and easy to realize industrialization, and the prepared rigid polyurethane foam has excellent flame retardant property and mechanical property.
Description
Technical Field
The invention relates to the technical field of flame retardant preparation methods, in particular to a preparation method of flame-retardant rigid polyurethane foam.
Background
The rigid polyurethane foam material has the advantages of light weight, high strength, excellent sound insulation and heat insulation performance and the like, and is widely applied to the industries of building external wall heat insulation, automobiles, furniture and the like. However, rigid polyurethane foams, which are typical organic polymer materials, are extremely flammable, severely limiting their range of use. In order to prepare flame-retardant rigid polyurethane foam materials, efficient flame-retardant polyurethane foam is prepared by adopting a mode of synergistic compounding of different flame retardants.
Disclosure of Invention
The invention aims to provide a preparation method of a flame-retardant rigid polyurethane foam and the flame-retardant rigid polyurethane foam prepared by the method.
In order to achieve the above object, the present invention provides the following technical solutions:
a preparation method of environment-friendly flame-retardant rigid polyurethane foam comprises the following steps:
(1) preparing a BPSQ flame retardant: adding 0.6-1 mol of boric acid and 0.1-0.3 mol of phenyltrimethoxysilane into 30-100 ml of ethanol, adding 0.1-0.3 ml of concentrated hydrochloric acid with the mass concentration of 37% as a catalyst, and adding N2Heating to 75-90 ℃ under protection, reacting for 6-10 h, cooling the reaction liquid to room temperature after the reaction is finished, adding the reaction liquid into 300-500 ml of deionized water, stirring for 10min, standing, and drying at 70-90 ℃ for 12-24 h after suction filtration to obtain boron-containing phenyl silsesquioxane (BPSQ flame retardant);
(2) adding a BPSQ flame retardant into polyether polyol 4110 at room temperature, uniformly mixing, adding a catalyst and a foaming agent, and uniformly stirring; and adding polymeric MDI polymethylene polyphenyl isocyanate, stirring and foaming to obtain the flame-retardant rigid polyurethane foam.
(3) And curing the flame-retardant rigid polyurethane foam for 24-36 h at room temperature.
Further, in the step (2), the BPSQ flame retardant and other flame retardants are compounded to form a flame retardant system, and then the flame retardant system is added into the polyether polyol 4110.
Further, the hydroxyl value of the polyether polyol 4110 is 400-500 mgKOH/g, the viscosity at 25 ℃ is 2500-4000 mPa.s, and the water content is less than or equal to 0.15%, so that the polyether polyol 4110 has a promoting effect on the foaming and flame-retardant properties of the final flame-retardant rigid polyurethane foam.
Further, the catalyst is one or a mixture of several of potassium acetate solution with the mass concentration of 30%, pentamethyldiethylenetriamine and N, N-dimethylcyclohexylamine.
Further, the foaming agent is distilled water or/and 1-fluoro-1, 1-dichloroethane.
Further, the other flame retardant is one or more of SiB, tris- (3-DOPO-2-hydroxy-propyl) -1,3, 5-triazine-2, 4, 6-trione, dimethyl methylphosphonate, aluminum hydroxide, expandable graphite and zinc hydroxystannate.
The flame-retardant rigid polyurethane foam product prepared by the method comprises the following components in parts by weight: 411060-100 parts of polyether polyol, 0-10 parts of tris- (3-DOPO-2-hydroxy-propyl) -1,3, 5-triazine-2, 4, 6-trione, 15-35 parts of dimethyl methylphosphonate, 5-25 parts of expandable graphite, 3-15 parts of zinc hydroxystannate, 2-10 parts of BPSQ flame retardant, 5-20 parts of aluminum hydroxide, 4-8 parts of catalyst, 10-25 parts of foaming agent and 120-150 parts of polymeric MDI polymethylene polyphenyl isocyanate.
Further, the flame-retardant rigid polyurethane foam product prepared by the method comprises the following components in parts by weight: 411080-90 parts of polyether polyol, 2-8 parts of tris- (3-DOPO-2-hydroxy-propyl) -1,3, 5-triazine-2, 4, 6-trione, 20-30 parts of dimethyl methylphosphonate, 10-20 parts of expandable graphite, 5-10 parts of zinc hydroxystannate, 5-10 parts of BPSQ flame retardant, 10-20 parts of aluminum hydroxide, 4-8 parts of catalyst, 10-25 parts of foaming agent and 120-140 parts of polymeric MDI polymethylene polyphenyl isocyanate.
The preparation method can prepare the flame-retardant rigid polyurethane foam through one-step reaction, is simple and easy to realize industrialization, and the prepared rigid polyurethane foam has excellent flame retardant property and mechanical property.
Drawings
FIG. 1 shows the chemical structure of the BPSQ flame retardant prepared by the present invention.
Detailed Description
The present invention will be further illustrated with reference to the following examples.
The preparation method of the environment-friendly flame-retardant rigid polyurethane foam comprises the following steps:
(1) preparing a BPSQ flame retardant: adding 0.6-1 mol of boric acid and 0.1-0.3 mol of phenyltrimethoxysilane into 30-100 ml of ethanol, adding 0.1-0.3 ml of 37 mass percent concentrated hydrochloric acid serving as a catalyst, and adding N2Heating to 75 deg.C under protectionReacting at the temperature of 90 ℃ below zero for 6-10 h, cooling the reaction liquid to room temperature after the reaction is finished, then adding the reaction liquid into 300-500 ml of deionized water, stirring for 10min, standing, and drying at the temperature of 70-90 ℃ for 12-24 h after suction filtration to obtain the boron-containing phenyl silsesquioxane (BPSQ flame retardant). The chemical structural formula of the BPSQ flame retardant BPSQ is shown in figure 1, wherein O-Si-O, B-O-Si and an aromatic ring structure have good char forming property, which is beneficial to improving the carbon residue of rigid polyurethane foam and improving the flame retardant property of the polyurethane foam.
(2) Adding a BPSQ flame retardant into polyether polyol 4110 at room temperature; or compounding the BPSQ flame retardant with other flame retardants to form a flame retardant system, and then adding the flame retardant system into polyether polyol 4110; after mixing uniformly, adding a catalyst and a foaming agent, and stirring uniformly; and adding polymeric MDI polymethylene polyphenyl isocyanate, stirring and foaming to obtain the flame-retardant rigid polyurethane foam. The other flame retardant is one or more of SiB, tri- (3-DOPO-2-hydroxy-propyl) -1,3, 5-triazine-2, 4, 6-Trione (TGD), dimethyl methyl phosphonate (DMMP), aluminum hydroxide, expandable graphite and zinc hydroxystannate. The catalyst is preferably one or a mixture of more of potassium acetate solution (KAc) with the mass concentration of 30%, pentamethyldiethylenetriamine (AM-1) and N, N-Dimethylcyclohexylamine (DMCHA). The foaming agent is preferably one or two of distilled water and 1-fluoro-1, 1-dichloroethane (HCFC-141 b).
(3) And curing the flame-retardant rigid polyurethane foam for 24-36 h at room temperature. The curing time is measured from the time the product has fully foamed.
The flame-retardant rigid polyurethane foam prepared by the method comprises the following components in parts by weight: 411060-100 parts of polyether polyol, 0-10 parts of tris- (3-DOPO-2-hydroxy-propyl) -1,3, 5-triazine-2, 4, 6-Trione (TGD), 15-35 parts of dimethyl methyl phosphonate (DMMP), 5-25 parts of expandable graphite, 3-15 parts of zinc hydroxystannate, 2-10 parts of BPSQ flame retardant, 5-20 parts of aluminum hydroxide, 4-8 parts of catalyst, 10-25 parts of foaming agent and 120-150 parts of polymeric MDI polymethylene polyphenyl isocyanate. More preferably, the components comprise, by weight, 411080-90 parts of polyether polyol, 2-8 parts of TGD, 20-30 parts of DMMP, 10-20 parts of expandable graphite, 5-10 parts of zinc hydroxystannate, 5-10 parts of BPSQ flame retardant, 10-20 parts of aluminum hydroxide, 4-8 parts of catalyst, 10-25 parts of foaming agent and 120-140 parts of polymeric MDI polymethylene polyphenyl isocyanate.
The present invention does not require a reaction vessel, and a reaction vessel known to those skilled in the art may be used.
Example 1
The preparation method comprises the following steps:
(1) preparing a BPSQ flame retardant: 0.6mol of boric acid and 0.1mol of phenyltrimethoxysilane are added into 50ml of ethanol, 0.1ml of concentrated hydrochloric acid with the mass concentration of 37% is added as a catalyst, and N is added2Raising the temperature to 80 ℃ under protection and reacting for 7 h. After the reaction is finished, cooling the reaction liquid to room temperature, then adding the reaction liquid into 500ml of deionized water, stirring for 10min, standing, and drying at 70 ℃ for 24h after suction filtration to obtain boron-containing phenyl silsesquioxane, namely the BPSQ flame retardant;
(2) 411084 g of polyether polyol, 0.56g of a 30% potassium acetate solution by mass, 0.48g of pentamethyldiethylenetriamine, 1.68g of N, N-dimethylcyclohexylamine, 1.08g of distilled water, 18g of HCFC-141b, 8g of TGD, 26g of DMMP, 12g of aluminum hydroxide, 20g of expandable graphite, 3g of zinc hydroxystannate, 5g of BPSQ and 130g of polymeric MDI polymethylene polyphenyl isocyanate are weighed respectively. Under the condition of room temperature, compounding a BPSQ flame retardant with aluminum hydroxide, expandable graphite and zinc hydroxystannate to form a flame retardant system, adding the flame retardant system into polyether polyol 4110, uniformly mixing, adding a potassium acetate solution, pentamethyldiethylenetriamine, N-dimethylcyclohexylamine, a flame retardant, distilled water, HCFC-141b, TGD and DMMP, mixing and stirring for 90s at the rotating speed of 2000r/min, adding polymeric MDI polymethylene polyphenyl isocyanate, quickly stirring for 10s to obtain flame-retardant rigid polyurethane foam, pouring the rigid polyurethane foam into a mold, and curing for 24h at room temperature to obtain freely foamed foam.
Example 2
The preparation method comprises the following steps:
(1) preparing a BPSQ flame retardant: 0.8mol of boric acid and 0.3mol of phenyltrimethoxysilane were added to 100ml of ethanol, and 0.3ml of a mass concentration was added37% concentrated hydrochloric acid as catalyst in N2Raising the temperature to 75 ℃ under protection and reacting for 10 h. After the reaction is finished, cooling the reaction liquid to room temperature, then adding the reaction liquid into 400ml of deionized water, stirring for 10min, standing, and drying at 80 ℃ for 20h after suction filtration to obtain boron-containing phenyl silsesquioxane, namely the BPSQ flame retardant;
(2) 411054 g of polyether polyol, 0.82g of potassium acetate solution with the mass concentration of 30%, 0.32g of pentamethyldiethylenetriamine, 2.12g of N, N-dimethylcyclohexylamine, 2g of distilled water, 15g of HCFC-141b, 4g of TGD, 26g of DMMP, 25g of aluminum hydroxide, 30g of expandable graphite, 6g of zinc hydroxystannate, 4g of BPSQ and 140g of polymeric MDI polymethylene polyphenyl isocyanate are weighed respectively. Under the condition of room temperature, compounding a BPSQ flame retardant with aluminum hydroxide, expandable graphite and zinc hydroxystannate to form a flame retardant system, adding the flame retardant system into polyether polyol 4110, uniformly mixing, adding a potassium acetate solution, pentamethyldiethylenetriamine, N-dimethylcyclohexylamine, a flame retardant, distilled water, HCFC-141b, TGD and DMMP, mixing and stirring for 90s at the rotating speed of 2000r/min, adding polymeric MDI polymethylene polyphenyl isocyanate, quickly stirring for 10s to obtain flame-retardant rigid polyurethane foam, pouring the rigid polyurethane foam into a mold, and curing for 24h at room temperature to obtain freely foamed foam.
Example 3
(1) Preparing a BPSQ flame retardant: adding 1mol of boric acid and 0.2mol of phenyltrimethoxysilane into 80ml of ethanol, adding 0.2ml of concentrated hydrochloric acid with the mass concentration of 37 percent as a catalyst, and reacting in N2Raising the temperature to 90 ℃ under protection and reacting for 6 h. After the reaction is finished, cooling the reaction liquid to room temperature, then adding the reaction liquid into 300ml of deionized water, stirring for 10min, standing, and drying at 90 ℃ for 12h after suction filtration to obtain boron-containing phenyl silsesquioxane, namely the BPSQ flame retardant;
411064 g of polyether polyol, 0.6g of potassium acetate solution with the mass concentration of 30%, 0.48g of pentamethyldiethylenetriamine, 1.8g of N, N-dimethylcyclohexylamine, 1.5g of distilled water, 6g of HCFC-141b, 25g of DMMP, 25g of expandable graphite, 4g of zinc hydroxystannate, BPSQ6g and 150g of polymeric MDI polymethylene polyphenyl isocyanate are weighed respectively. Under the condition of room temperature, compounding a BPSQ flame retardant with expandable graphite and zinc hydroxystannate to form a flame retardant system, adding the flame retardant system into polyether polyol 4110, uniformly mixing, adding a potassium acetate solution, pentamethyldiethylenetriamine, N-dimethylcyclohexylamine, the flame retardant system, distilled water, HCFC-141b, TGD and DMMP, mixing and stirring for 90s at the rotating speed of 2000r/min, adding polymeric MDI polymethylene polyphenyl isocyanate, quickly stirring for 10s, and pouring into a mold. After curing at room temperature for 24h, a free-foaming foam was obtained.
The products prepared in examples 1-3 were tested for flame retardant and physical properties, and the results are shown in Table 1.
TABLE 1 flame retardancy and mechanical Property test results for products prepared in examples 1-3
As can be seen from Table 1, the rigid polyurethane foams prepared in examples 1, 2 and 3 have significantly improved LOI, significantly reduced total heat release THR and total smoke release TSR, indicating significantly improved flame retardancy, but maintained apparent densities of 43kg/m3The processing and use of the material will not be affected below.
As can be seen from the above examples, the preparation method provided by the invention has simple steps and is easy to operate, and the flame-retardant rigid polyurethane foam with good flame retardant property can be obtained through one-step reaction.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (8)
1. The preparation method of the flame-retardant rigid polyurethane foam is characterized by comprising the following steps:
(1) preparing a BPSQ flame retardant: 0.6-1 mol of boric acid and 0.1-0.3 mol of phenyltrimethoxysilane are added into 30-100 ml of ethanol, and 0.1-0.3 ml of concentrated hydrochloric acid with mass concentration of 37% is added to be used asCatalyst in N2Heating to 75-90 ℃ under protection, reacting for 6-10 h, cooling the reaction liquid to room temperature after the reaction is finished, adding the reaction liquid into 300-500 ml of deionized water, stirring for 10min, standing, and drying at 70-90 ℃ for 12-24 h after suction filtration to obtain boron-containing phenyl silsesquioxane (BPSQ flame retardant);
(2) adding a BPSQ flame retardant into polyether polyol 4110 at room temperature, uniformly mixing, adding a catalyst and a foaming agent, and uniformly stirring; then adding polymeric MDI polymethylene polyphenyl isocyanate, stirring and foaming to obtain flame-retardant rigid polyurethane foam;
(3) and curing the flame-retardant rigid polyurethane foam for 24-36 h at room temperature.
2. The method for preparing a flame retardant rigid polyurethane foam according to claim 1, wherein in the step (2), the BPSQ flame retardant and other flame retardants are compounded to form a flame retardant system, and then the flame retardant system is added into the polyether polyol 4110.
3. The method for preparing a flame retardant rigid polyurethane foam according to claim 1 or 2, wherein the polyether polyol 4110 has a hydroxyl value of 400 to 500mgKOH/g, a viscosity of 2500 to 4000mPa s at 25 ℃, and a water content of 0.15% or less.
4. The method for preparing a flame-retardant rigid polyurethane foam according to claim 1 or 2, wherein the catalyst is one or a mixture of potassium acetate solution with a mass concentration of 30%, pentamethyldiethylenetriamine and N, N-dimethylcyclohexylamine.
5. The method for preparing a flame retardant rigid polyurethane foam according to claim 1 or 2, wherein the blowing agent is distilled water or/and 1-fluoro-1, 1-dichloroethane.
6. The method as claimed in claim 2, wherein the other flame retardant is one or more of SiB, tris- (3-DOPO-2-hydroxy-propyl) -1,3, 5-triazine-2, 4, 6-trione, dimethyl methylphosphonate, aluminum hydroxide, expandable graphite and zinc hydroxystannate.
7. The flame retarded rigid polyurethane foam product prepared by the process of claim 6 wherein the flame retarded rigid polyurethane foam comprises the following components in parts by weight: 411060-100 parts of polyether polyol, 0-10 parts of tris- (3-DOPO-2-hydroxy-propyl) -1,3, 5-triazine-2, 4, 6-trione, 15-35 parts of dimethyl methylphosphonate, 5-25 parts of expandable graphite, 3-15 parts of zinc hydroxystannate, 2-10 parts of BPSQ flame retardant, 5-20 parts of aluminum hydroxide, 4-8 parts of catalyst, 10-25 parts of foaming agent and 120-150 parts of polymeric MDI polymethylene polyphenyl isocyanate.
8. The flame retarded rigid polyurethane foam product prepared by the process of claim 6 wherein the flame retarded rigid polyurethane foam comprises the following components in parts by weight: 411080-90 parts of polyether polyol, 2-8 parts of tris- (3-DOPO-2-hydroxy-propyl) -1,3, 5-triazine-2, 4, 6-trione, 20-30 parts of dimethyl methylphosphonate, 10-20 parts of expandable graphite, 5-10 parts of zinc hydroxystannate, 5-10 parts of BPSQ flame retardant, 10-20 parts of aluminum hydroxide, 4-8 parts of catalyst, 10-25 parts of foaming agent and 120-140 parts of polymeric MDI polymethylene polyphenyl isocyanate.
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