CN111363120A - High-strength spraying polyurethane material containing reactive flame retardant and preparation method thereof - Google Patents
High-strength spraying polyurethane material containing reactive flame retardant and preparation method thereof Download PDFInfo
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- CN111363120A CN111363120A CN202010331066.4A CN202010331066A CN111363120A CN 111363120 A CN111363120 A CN 111363120A CN 202010331066 A CN202010331066 A CN 202010331066A CN 111363120 A CN111363120 A CN 111363120A
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- Prior art keywords
- component
- polyurethane material
- isocyanate
- diisocyanate
- flame retardant
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- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 36
- 239000000463 material Substances 0.000 title claims abstract description 36
- 239000004814 polyurethane Substances 0.000 title claims abstract description 34
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 34
- 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 33
- 238000005507 spraying Methods 0.000 title claims abstract description 10
- 238000002360 preparation method Methods 0.000 title claims description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 51
- 239000012948 isocyanate Substances 0.000 claims abstract description 43
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 43
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims abstract description 23
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229920005906 polyester polyol Polymers 0.000 claims abstract description 23
- 239000007921 spray Substances 0.000 claims abstract description 21
- 239000004970 Chain extender Substances 0.000 claims abstract description 17
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 10
- 238000007599 discharging Methods 0.000 claims description 10
- 239000006185 dispersion Substances 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 238000004806 packaging method and process Methods 0.000 claims description 10
- 239000002518 antifoaming agent Substances 0.000 claims description 7
- 239000007822 coupling agent Substances 0.000 claims description 7
- -1 polymethylene Polymers 0.000 claims description 7
- 230000003712 anti-aging effect Effects 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 239000005056 polyisocyanate Substances 0.000 claims description 5
- 229920001228 polyisocyanate Polymers 0.000 claims description 5
- 229920006389 polyphenyl polymer Polymers 0.000 claims description 5
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- PISLZQACAJMAIO-UHFFFAOYSA-N 2,4-diethyl-6-methylbenzene-1,3-diamine Chemical compound CCC1=CC(C)=C(N)C(CC)=C1N PISLZQACAJMAIO-UHFFFAOYSA-N 0.000 claims description 4
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 claims description 4
- 238000011049 filling Methods 0.000 claims description 4
- NNOZGCICXAYKLW-UHFFFAOYSA-N 1,2-bis(2-isocyanatopropan-2-yl)benzene Chemical compound O=C=NC(C)(C)C1=CC=CC=C1C(C)(C)N=C=O NNOZGCICXAYKLW-UHFFFAOYSA-N 0.000 claims description 3
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 claims description 3
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 3
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 3
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 3
- 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 description 3
- VZXPHDGHQXLXJC-UHFFFAOYSA-N 1,6-diisocyanato-5,6-dimethylheptane Chemical compound O=C=NC(C)(C)C(C)CCCCN=C=O VZXPHDGHQXLXJC-UHFFFAOYSA-N 0.000 claims description 2
- 229940008841 1,6-hexamethylene diisocyanate Drugs 0.000 claims description 2
- NWYDEWXSKCTWMJ-UHFFFAOYSA-N 2-methylcyclohexane-1,1-diamine Chemical compound CC1CCCCC1(N)N NWYDEWXSKCTWMJ-UHFFFAOYSA-N 0.000 claims description 2
- AOFIWCXMXPVSAZ-UHFFFAOYSA-N 4-methyl-2,6-bis(methylsulfanyl)benzene-1,3-diamine Chemical compound CSC1=CC(C)=C(N)C(SC)=C1N AOFIWCXMXPVSAZ-UHFFFAOYSA-N 0.000 claims description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 2
- QFAWAPOFKBIROP-UHFFFAOYSA-N n-benzhydrylbutan-2-amine Chemical compound C=1C=CC=CC=1C(NC(C)CC)C1=CC=CC=C1 QFAWAPOFKBIROP-UHFFFAOYSA-N 0.000 claims description 2
- 239000006097 ultraviolet radiation absorber Substances 0.000 claims description 2
- 239000002671 adjuvant Substances 0.000 claims 1
- 230000007797 corrosion Effects 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- 229920005862 polyol Polymers 0.000 description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- 150000003077 polyols Chemical class 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 239000004721 Polyphenylene oxide Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 229920000570 polyether Polymers 0.000 description 3
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 2
- 239000002250 absorbent Substances 0.000 description 2
- 230000002745 absorbent Effects 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- VOZKAJLKRJDJLL-UHFFFAOYSA-N 2,4-diaminotoluene Chemical compound CC1=CC=C(N)C=C1N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 description 1
- IBOFVQJTBBUKMU-UHFFFAOYSA-N 4,4'-methylene-bis-(2-chloroaniline) Chemical compound C1=C(Cl)C(N)=CC=C1CC1=CC=C(N)C(Cl)=C1 IBOFVQJTBBUKMU-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 239000004114 Ammonium polyphosphate Substances 0.000 description 1
- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical group CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 description 1
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 235000019826 ammonium polyphosphate Nutrition 0.000 description 1
- 229920001276 ammonium polyphosphate Polymers 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- ZQKXQUJXLSSJCH-UHFFFAOYSA-N melamine cyanurate Chemical compound NC1=NC(N)=NC(N)=N1.O=C1NC(=O)NC(=O)N1 ZQKXQUJXLSSJCH-UHFFFAOYSA-N 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- BXQLKGJCLJZZOP-UHFFFAOYSA-N methylsulfanylmethane;toluene Chemical compound CSC.CC1=CC=CC=C1 BXQLKGJCLJZZOP-UHFFFAOYSA-N 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920003225 polyurethane elastomer Polymers 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—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
-
- 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
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3225—Polyamines
- C08G18/3237—Polyamines aromatic
- C08G18/324—Polyamines aromatic containing only one aromatic ring
-
- 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
- C08G18/3855—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur
- C08G18/3863—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur containing groups having sulfur atoms between two carbon atoms, the sulfur atoms being directly linked to carbon atoms or other sulfur atoms
- C08G18/3865—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur containing groups having sulfur atoms between two carbon atoms, the sulfur atoms being directly linked to carbon atoms or other sulfur atoms containing groups having one sulfur atom between two carbon atoms
- C08G18/3868—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur containing groups having sulfur atoms between two carbon atoms, the sulfur atoms being directly linked to carbon atoms or other sulfur atoms containing groups having one sulfur atom between two carbon atoms the sulfur atom belonging to a sulfide group
-
- 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
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
-
- 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
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
- C08G18/4208—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups
-
- 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
- C08G18/50—Polyethers having heteroatoms other than oxygen
- C08G18/5021—Polyethers having heteroatoms other than oxygen having nitrogen
- C08G18/5024—Polyethers having heteroatoms other than oxygen having nitrogen containing primary and/or secondary amino groups
- C08G18/5027—Polyethers having heteroatoms other than oxygen having nitrogen containing primary and/or secondary amino groups directly linked to carbocyclic groups
-
- 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
- C08G18/6603—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6614—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6618—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
-
- 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/721—Two or more polyisocyanates not provided for in one single group C08G18/73 - C08G18/80
- C08G18/724—Combination of aromatic polyisocyanates with (cyclo)aliphatic polyisocyanates
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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
- C08G18/70—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
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/758—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing two or more cycloaliphatic rings
Abstract
The invention discloses a high-strength spraying polyurethane material containing a reactive flame retardant, which comprises a component A and a component B; the component A comprises the following components: isocyanate prepolymer synthesized from isocyanate and phthalic anhydride polyester polyol; the component B comprises the following components in percentage by weight: 0-30% of chain extender, 1-2% of auxiliary agent and 68-99% of amino-terminated benzene-containing oligomer; the volume ratio of the component A to the component B is 1: 0.8-1.5. The invention provides a high-strength spray polyurethane material containing a reactive flame retardant, which has high flame retardancy.
Description
Technical Field
The invention belongs to the technical field of materials, and particularly relates to a high-strength spraying polyurethane material containing a reactive flame retardant and a preparation method thereof.
Background
In the prior art, polyurethane materials are mostly flame-retardant by additive flame retardants or aqueous systems, and further, phosphorus-containing halogen-containing polyols are used as reactive flame retardants. With the development of social economy, higher requirements are put forward on the mechanical property and the corrosion resistance of the flame-retardant material in some application fields, such as national defense and military industry, petrochemical industry, engineering machinery, marine environment and the like. The traditional flame-retardant system has defects in mechanical property and corrosion resistance. Chinese patent CN201110119867.5 discloses a flame-retardant polyurethane composite material, which comprises a mixed system formed by 70-99 wt% of flame-retardant polyurethane and 1-30 wt% of blending type flame retardant; the blending type flame retardant is one or more of ammonium polyphosphate, melamine cyanurate, polysiloxane, graphene, carbon nano tubes, kaolin and montmorillonite, and the flame retardant polyurethane is a random copolymer consisting of polycarbonate units, polyether units and isocyanate units. The system contains a large amount of additive flame retardant and phosphorus-containing polyol, so that the corrosion resistance is reduced, and the service life is short in a severe environment. Chinese patent CN201310709700.3 discloses a spray-type flame-retardant antistatic polyurethane elastomer, wherein a component A is composed of 40-60 parts of isocyanate and 40-60 parts of phosphorus-containing flame-retardant polyol, a component B is composed of 0-30 parts of chain extender, 0-30 parts of polyether polyol, 10-75 parts of amine-terminated polyether, 0-30 parts of carbon nanotube slurry, 0-3 parts of pigment and 0-3 parts of auxiliary agent, and a large amount of phosphorus-containing polyol is added in the system, so that the corrosion resistance of the material is reduced, and the mechanical property is weaker.
Disclosure of Invention
The invention aims to provide a high-strength spray polyurethane material containing a reactive flame retardant, which has high flame retardancy.
The invention is realized by the following technical scheme:
one aspect of the present invention provides a high strength spray polyurethane material containing a reactive flame retardant, comprising a component a and a component B;
the component A comprises the following components: isocyanate prepolymer synthesized from isocyanate and phthalic anhydride polyester polyol;
the component B comprises the following components in percentage by weight: 0-30% of chain extender, 1-2% of auxiliary agent and 68-99% of amino-terminated benzene-containing oligomer;
the volume ratio of the component A to the component B is 1: 0.8-1.5.
Optionally, the isocyanate prepolymer has a — NCO (isocyanate) content of 10 to 18%.
Optionally, the isocyanate is one or more of polymethylene polyphenyl polyisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, 1, 6-hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, trimethyl hexamethylene diisocyanate, methylcyclohexyl diisocyanate, dicyclohexylmethane diisocyanate, and tetramethylxylylene diisocyanate.
Optionally, the molecular weight of the phthalic anhydride polyester polyol is 800-.
Optionally, the chain extender is one or more of diethyltoluenediamine, 4' -bis (sec-butylamino) -diphenylmethane, dimethylthiotoluenediamine, methylcyclohexanediamine, and 3,3' -dichloro-4, 4' -diaminodiphenylmethane.
Optionally, the auxiliary agent is at least one of a defoaming agent, a coupling agent, an anti-aging agent, an ultraviolet absorber and an anti-dripping agent.
Optionally, the amino-terminated benzene-containing oligomer is polytetramethylene ether glycol bis-p-aminobenzoate, and the molecular weight is 250-3000.
Optionally, the volume ratio of the isocyanate to the phthalic anhydride polyester polyol is 30: 70-70: 30.
Another aspect of the present invention provides a method for preparing a high-strength spray polyurethane material containing a reactive flame retardant, comprising the steps of:
preparing a component A: reacting phthalic anhydride polyester polyol with isocyanate to obtain a component A;
preparing a component B: adding the chain extender, the amino-terminated benzene-containing oligomer and the auxiliary agent into a dispersion machine, dispersing for 15-60 min by using the dispersion machine, discharging and packaging to obtain a component B;
mixing: and mixing the component A and the component B in proportion to obtain the spray polyurethane material.
Optionally, the preparation of the component A comprises the following steps:
heating phthalic anhydride polyester polyol to the temperature of 100-120 ℃, vacuumizing, dehydrating for 1-2 hours, filling nitrogen, cooling to room temperature, adding metered isocyanate, heating to the temperature of 60-90 ℃, preserving heat, stirring, reacting for 2-5 hours, cooling to the temperature of 40-50 ℃, discharging, and packaging to obtain the component A.
The invention has the beneficial effects that:
1. the invention provides a high-strength spray polyurethane material containing a reactive flame retardant, which has high flame retardancy.
2. The formula of the embodiment of the invention does not contain an additive flame retardant, a conventional phosphorus-nitrogen flame retardant system and the like, and meets the flame retardant requirement mainly by improving the benzene content in the material, so that the flame retardant material has excellent mechanical property, chemical resistance and corrosion resistance.
3. The invention adopts bi-component spraying, the reaction speed is faster, and the construction efficiency is high. The anti-dripping agent is added, so that the dripping phenomenon during combustion is reduced, and the flame retardant property is improved. The invention has no solvent system, environmental protection and no pollution.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the present invention, and not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, belong to the scope of the present invention.
Example 1
The embodiment 1 of the invention provides a high-strength spraying polyurethane material containing a reactive flame retardant, which comprises a component A and a component B;
the component A comprises the following components: isocyanate prepolymer synthesized from isocyanate and phthalic anhydride polyester polyol;
the component B comprises the following components in percentage by weight: 20% of chain extender, 1% of auxiliary agent and 79% of amino-terminated benzene-containing oligomer;
the volume ratio of the component A to the component B is 1: 0.8.
the isocyanate prepolymer had an-NCO (isocyanate) content of 10%.
The isocyanate is polymethylene polyphenyl polyisocyanate.
The molecular weight of the phthalic anhydride polyester polyol is 1000.
The chain extender is diethyltoluenediamine.
The auxiliary agent comprises: defoaming agent, coupling agent, anti-aging agent, ultraviolet absorbent and anti-dripping agent. The defoaming agent, the coupling agent, the anti-aging agent, the ultraviolet absorbent and the anti-dripping agent are respectively as follows: BYK067A, KH560, Irganox1010, TinuvinP, Dyneon TMMM5935 EF.
The amino-terminated benzene-containing oligomer is polytetramethylene ether glycol bis-p-aminobenzoate, and the molecular weight is 888.
The volume ratio of the isocyanate to the phthalic anhydride polyester polyol is 30: 70.
A preparation method of a high-strength spray polyurethane material containing a reactive flame retardant comprises the following steps:
preparing a component A: heating phthalic anhydride polyester polyol to 100 ℃, vacuumizing, dehydrating for 1 hour, charging nitrogen, cooling to room temperature, then adding metered isocyanate, heating to 60 ℃, preserving heat and stirring, reacting for 2 hours to generate isocyanate prepolymer, then cooling to 40 ℃, discharging and packaging to obtain the component A;
preparing a component B: sequentially adding a chain extender, an amino-terminated benzene-containing oligomer and an auxiliary agent, dispersing for 15min by using a high-speed dispersion machine at a dispersion rate of 400r/min, discharging and packaging to obtain a component B;
mixing: and mixing the component A and the component B in proportion to obtain the spray polyurethane material.
Example 2
The embodiment 2 of the invention provides a high-strength spraying polyurethane material containing a reactive flame retardant, which comprises a component A and a component B;
the component A comprises the following components: isocyanate prepolymer synthesized from isocyanate and phthalic anhydride polyester polyol;
the component B comprises the following components in percentage by weight: 30% of chain extender, 2% of auxiliary agent and 68% of amino-terminated benzene-containing oligomer;
the volume ratio of the component A to the component B is 1: 1.5.
the isocyanate prepolymer had an-NCO (isocyanate) content of 18%.
The isocyanate comprises: polymethylene polyphenyl polyisocyanate and dicyclohexyl methane diisocyanate in the ratio of 1: 1.
The molecular weight of the phthalic anhydride polyester polyol is 3000.
The chain extender is dimethyl-sulfur-based toluene diamine.
The auxiliary agent comprises: defoaming agent, coupling agent and anti-aging agent. The defoaming agent, the coupling agent and the anti-aging agent are respectively adopted as follows: BYK067A, KH560 and Irganox 1010.
The amino-terminated benzene-containing oligomer is polytetramethylene ether glycol bis-p-aminobenzoate and has a molecular weight of 488.
The volume ratio of the isocyanate to the phthalic anhydride polyester polyol is 70: 30.
A preparation method of a high-strength spray polyurethane material containing a reactive flame retardant comprises the following steps:
preparing a component A: heating phthalic anhydride polyester polyol to 120 ℃, vacuumizing, dehydrating for 2 hours, filling nitrogen, cooling to room temperature, then adding metered isocyanate, heating to 90 ℃, preserving heat, stirring, reacting for 5 hours to generate isocyanate prepolymer, then cooling to 50 ℃, discharging, and packaging to obtain the component A;
preparing a component B: sequentially adding a chain extender, an amino-terminated benzene-containing oligomer and an auxiliary agent, dispersing for 15min by using a high-speed dispersion machine at a dispersion rate of 400r/min, discharging and packaging to obtain a component B;
mixing: and mixing the component A and the component B in proportion to obtain the spray polyurethane material.
Example 3
Embodiment 3 of the present invention provides a high strength spray polyurethane material containing a reactive flame retardant, comprising a component a and a component B;
the component A comprises the following components: isocyanate prepolymer synthesized from isocyanate and phthalic anhydride polyester polyol;
the component B comprises the following components in percentage by weight: 5% of chain extender, 2% of assistant and 93% of amino-terminated benzene-containing oligomer;
the volume ratio of the component A to the component B is 1: 1.
the isocyanate prepolymer had an-NCO (isocyanate) content of 15%.
The isocyanate comprises: polymethylene polyphenyl polyisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, xylylene diisocyanate, methylcyclohexyl diisocyanate, dicyclohexylmethane diisocyanate, tetramethylxylylene diisocyanate.
The molecular weight of the phthalic anhydride polyester polyol is 2000.
The chain extender is diethyl toluene diamine, dimethyl sulfur toluene diamine and methyl cyclohexane diamine.
The auxiliary agent comprises: defoaming agent and coupling agent.
The amino-terminated benzene-containing oligomer is: polytetramethylene ether glycol bis-p-aminobenzoate, molecular weight 1238.
The volume ratio of the isocyanate to the phthalic anhydride polyester polyol is 50: 50.
A preparation method of a high-strength spray polyurethane material containing a reactive flame retardant comprises the following steps:
preparing a component A: heating phthalic anhydride polyester polyol to 110 ℃, vacuumizing, dehydrating for 1.5 hours, filling nitrogen, cooling to room temperature, adding metered isocyanate, heating to 80 ℃, preserving heat, stirring, reacting for 3 hours to generate an isocyanate prepolymer, cooling to 45 ℃, discharging, and packaging to obtain the component A;
preparing a component B: sequentially adding a chain extender, an amino-terminated benzene-containing oligomer and an auxiliary agent, dispersing for 15min by using a high-speed dispersion machine at a dispersion rate of 400r/min, discharging and packaging to obtain a component B;
mixing: and mixing the component A and the component B in proportion to obtain the spray polyurethane material.
The experimental results are as follows:
the embodiment of the invention is subjected to experimental tests, and the experimental results are as follows:
the foregoing is considered as illustrative of the preferred embodiments of the invention and is not to be construed as limiting the invention in any way. Although the present invention has been described with reference to the preferred embodiments, it is not intended to be limited thereto. Therefore, any simple modification, equivalent change and modification made to the above embodiments according to the technical spirit of the present invention should fall within the protection scope of the technical scheme of the present invention, unless the technical spirit of the present invention departs from the content of the technical scheme of the present invention.
Claims (10)
1. A high-strength spraying polyurethane material containing reactive flame retardant is characterized by comprising a component A and a component B;
the component A comprises the following components: isocyanate prepolymer synthesized from isocyanate and phthalic anhydride polyester polyol;
the component B comprises the following components in percentage by weight: 0-30% of chain extender, 1-2% of auxiliary agent and 68-99% of amino-terminated benzene-containing oligomer;
the volume ratio of the component A to the component B is 1: 0.8-1.5.
2. A spray polyurethane material according to claim 1, characterised in that the isocyanate prepolymer has a-NCO (isocyanate) content of 10-18%.
3. The spray polyurethane material of claim 1, wherein the isocyanate is one or more of polymethylene polyphenyl polyisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, 1, 6-hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, trimethylhexamethylene diisocyanate, methylcyclohexyl diisocyanate, dicyclohexylmethane diisocyanate, tetramethylxylylene diisocyanate.
4. The spray polyurethane material of claim 1, wherein the phthalic anhydride polyester polyol has a molecular weight of 800-.
5. A spray polyurethane material according to claim 1, characterised in that the chain extender is one or more of diethyltoluenediamine, 4' -bis (sec-butylamino) -diphenylmethane, dimethylthiotoluenediamine, methylcyclohexanediamine, 3' -dichloro-4, 4' -diaminodiphenylmethane.
6. The spray polyurethane material of claim 1, wherein the adjuvant is at least one of an antifoaming agent, a coupling agent, an anti-aging agent, an ultraviolet absorber, and an anti-dripping agent.
7. The spray polyurethane material of claim 1, wherein the amino-terminated benzene-containing oligomer is polytetramethylene ether glycol bis-p-aminobenzoate having a molecular weight of 250-3000.
8. The spray polyurethane material of claim 1, wherein the volume ratio of the isocyanate to the phthalic anhydride polyester polyol is 30:70 to 70: 30.
9. A preparation method of a high-strength spraying polyurethane material containing a reactive flame retardant is characterized by comprising the following steps:
preparing a component A: reacting phthalic anhydride polyester polyol with isocyanate to obtain a component A;
preparing a component B: adding the chain extender, the amino-terminated benzene-containing oligomer and the auxiliary agent into a dispersion machine, dispersing for 15-60 min by using the dispersion machine, discharging and packaging to obtain a component B;
mixing: and mixing the component A and the component B in proportion to obtain the spray polyurethane material.
10. The preparation method of the high-strength spraying polyurethane material containing the reactive flame retardant is characterized in that the preparation of the component A comprises the following steps:
heating phthalic anhydride polyester polyol to the temperature of 100-120 ℃, vacuumizing, dehydrating for 1-2 hours, filling nitrogen, cooling to room temperature, adding metered isocyanate, heating to the temperature of 60-90 ℃, preserving heat, stirring, reacting for 2-5 hours, cooling to the temperature of 40-50 ℃, discharging, and packaging to obtain the component A.
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| CN112940593A (en) * | 2021-02-05 | 2021-06-11 | 青岛理工大学 | Anti-fragment composite coating aiming at engineering blasting and construction process |
| CN114045104A (en) * | 2021-12-29 | 2022-02-15 | 师海峰 | Preparation method of flame-retardant high-performance flexible explosion-proof coating |
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