CN103694434A - Halogen-free reaction type flame retardant for polyurethane foam as well as preparation method and application thereof - Google Patents
Halogen-free reaction type flame retardant for polyurethane foam as well as preparation method and application thereof Download PDFInfo
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- CN103694434A CN103694434A CN201310692617.XA CN201310692617A CN103694434A CN 103694434 A CN103694434 A CN 103694434A CN 201310692617 A CN201310692617 A CN 201310692617A CN 103694434 A CN103694434 A CN 103694434A
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- polyurethane foam
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 114
- 229920005830 Polyurethane Foam Polymers 0.000 title claims abstract description 44
- 239000011496 polyurethane foam Substances 0.000 title claims abstract description 44
- 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 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 238000006757 chemical reactions by type Methods 0.000 title abstract 5
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 238000006683 Mannich reaction Methods 0.000 claims abstract description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 50
- 229910052736 halogen Inorganic materials 0.000 claims description 47
- 150000002367 halogens Chemical class 0.000 claims description 46
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 150000002148 esters Chemical class 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 239000012752 auxiliary agent Substances 0.000 claims description 12
- 239000003381 stabilizer Substances 0.000 claims description 10
- ZZVUWRFHKOJYTH-UHFFFAOYSA-N diphenhydramine Chemical compound C=1C=CC=CC=1C(OCCN(C)C)C1=CC=CC=C1 ZZVUWRFHKOJYTH-UHFFFAOYSA-N 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 7
- 125000005842 heteroatom Chemical group 0.000 claims description 7
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 229920000728 polyester Polymers 0.000 claims description 6
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims description 5
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 5
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 claims description 5
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical class [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 5
- 229920000570 polyether Polymers 0.000 claims description 5
- 150000005846 sugar alcohols Polymers 0.000 claims description 5
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims description 5
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 4
- 150000002334 glycols Chemical class 0.000 claims description 4
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 claims description 4
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- WZLFPVPRZGTCKP-UHFFFAOYSA-N 1,1,1,3,3-pentafluorobutane Chemical compound CC(F)(F)CC(F)(F)F WZLFPVPRZGTCKP-UHFFFAOYSA-N 0.000 claims description 3
- FRCHKSNAZZFGCA-UHFFFAOYSA-N 1,1-dichloro-1-fluoroethane Chemical compound CC(F)(Cl)Cl FRCHKSNAZZFGCA-UHFFFAOYSA-N 0.000 claims description 3
- BSYJHYLAMMJNRC-UHFFFAOYSA-N 2,4,4-trimethylpentan-2-ol Chemical compound CC(C)(C)CC(C)(C)O BSYJHYLAMMJNRC-UHFFFAOYSA-N 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 claims description 3
- 238000005187 foaming Methods 0.000 claims description 3
- MSSNHSVIGIHOJA-UHFFFAOYSA-N pentafluoropropane Chemical compound FC(F)CC(F)(F)F MSSNHSVIGIHOJA-UHFFFAOYSA-N 0.000 claims description 3
- 229920001228 polyisocyanate Polymers 0.000 claims description 3
- 239000005056 polyisocyanate Substances 0.000 claims description 3
- 229920006389 polyphenyl polymer Polymers 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical group CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 3
- 239000008096 xylene Substances 0.000 claims description 3
- 150000001298 alcohols Chemical class 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- DWSWCPPGLRSPIT-UHFFFAOYSA-N benzo[c][2,1]benzoxaphosphinin-6-ium 6-oxide Chemical compound C1=CC=C2[P+](=O)OC3=CC=CC=C3C2=C1 DWSWCPPGLRSPIT-UHFFFAOYSA-N 0.000 abstract description 35
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 18
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 3
- 229910052760 oxygen Inorganic materials 0.000 abstract description 3
- 239000001301 oxygen Substances 0.000 abstract description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 2
- 239000011574 phosphorus Substances 0.000 abstract description 2
- 150000003512 tertiary amines Chemical class 0.000 abstract description 2
- -1 alcohol amine Chemical class 0.000 abstract 2
- 241001115903 Raphus cucullatus Species 0.000 abstract 1
- 238000004321 preservation Methods 0.000 abstract 1
- 150000003141 primary amines Chemical class 0.000 abstract 1
- 238000009775 high-speed stirring Methods 0.000 description 14
- 239000000463 material Substances 0.000 description 10
- 238000010521 absorption reaction Methods 0.000 description 5
- 229920002635 polyurethane Polymers 0.000 description 5
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 229920002866 paraformaldehyde Polymers 0.000 description 4
- 239000004814 polyurethane Substances 0.000 description 4
- 239000006260 foam Substances 0.000 description 3
- 125000000623 heterocyclic group Chemical group 0.000 description 3
- 230000002688 persistence Effects 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 229930040373 Paraformaldehyde Natural products 0.000 description 2
- 150000002169 ethanolamines Chemical class 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- GRZJZRHVJAXMRR-UHFFFAOYSA-N 1-cyclohexyl-2-phenylbenzene Chemical group C1CCCCC1C1=CC=CC=C1C1=CC=CC=C1 GRZJZRHVJAXMRR-UHFFFAOYSA-N 0.000 description 1
- 229910001369 Brass Inorganic materials 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- XADCESSVHJOZHK-UHFFFAOYSA-N Meperidine Chemical compound C=1C=CC=CC=1C1(C(=O)OCC)CCN(C)CC1 XADCESSVHJOZHK-UHFFFAOYSA-N 0.000 description 1
- 0 O=*1OC(CCC=C2)=C2c2ccccc12 Chemical compound O=*1OC(CCC=C2)=C2c2ccccc12 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000006261 foam material Substances 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 239000012774 insulation material Substances 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical group C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 1
- 125000002743 phosphorus functional group Chemical group 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 235000019587 texture Nutrition 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3878—Low-molecular-weight compounds having heteroatoms other than oxygen having phosphorus
- C08G18/3889—Low-molecular-weight compounds having heteroatoms other than oxygen having phosphorus having nitrogen in addition to phosphorus
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
- C07F9/657163—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom
- C07F9/657172—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom the ring phosphorus atom and one oxygen atom being part of a (thio)phosphinic acid ester: (X = O, S)
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—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
-
- 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
- C08G2110/00—Foam properties
- C08G2110/0025—Foam properties rigid
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Polyurethanes Or Polyureas (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a halogen-free reaction type flame retardant for polyurethane foam as well as a preparation method and an application thereof. The halogen-free reaction type flame retardant is prepared through a Mannich reaction of 9,10-dihdro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), alcohol amine and formaldehyde; the structural formula of the halogen-free reaction type flame retardant is as shown in the specification; the alcohol amine and the formaldehyde are introduced to the DOPO flame retardant structure through a DODO reaction; the cost of the flame retardant is reduced; the synthesized halogen-free reaction type flame retardant contains active hydroxyl, flame retardant nitrogen and phosphorus, and primary amine or tertiary amine and has relatively high reaction activity; as rigid benzene rings are applied to the flame retardant type polyurethane foam, the flame retardant type polyurethane foam has relatively high flame retardance, the strength and the flame retardance durability of the flame retardant type polyurethane foam are improved, and the oxygen index can reach 23-28%. The flame retardant type polyurethane foam has wide application prospect in buildings, heat preservation fields and certain special occasions.
Description
Technical field
The invention belongs to Halogen phosphorus flame retardant technical field, relate generally to non-halogen reacting fire-retardant agent and synthetic method thereof and the application in flame-retardant hard polyurethane foam.
Background technology
9,10-dihydro-9-oxy is assorted-and 10-phospho hetero phenanthrene-10-oxide compound is a kind of good Flame Retardants for Polyurethane Foam, can be applied in polyurethane foam heat insulation material, 9, mix-10-phospho hetero phenanthrene-10-oxide compound (DOPO) of 10-dihydro-9-oxy and derivative thereof are owing to containing cyclohexyl biphenyl and phenanthrene ring structure in molecular structure, particularly side phosphorus group is introduced in the mode of ring-type O=P-O key, than general, organophosphate thermostability and the chemical stability of Cheng Huan are not high, flame retardant properties is better.DOPO and derivative thereof can be used as response type and additive flame retardant, and synthetic fire retardant Halogen, smokeless, nontoxic, does not move, and flame retardant properties is lasting.Can be used for the multiple macromolecular material fire-retardant finish such as linear polyester, polymeric amide, epoxy resin, urethane.External be widely used in the fire-retardant of the materials such as pressure layer, circuit card in plastics electronics for, brass.
Polyurethane foam is the current insulating heat insulating material of performance the best in the world, also be good sound-proof material, in energy-conserving and environment-protective, require today of more and more paying attention to, polyurethane foam is widely used in refrigerator, roof, top ceiling, body of wall, freezer, floor etc. as lagging material.But the density of polyurethane foam is smaller, there is a lot of cavernous structures, compare more easily burning with non-foam material, during burning, emit a large amount of heat and poisonous smog, affect people's healthy and life security.Therefore thermotolerance, the flame retardant type of hard polyurethane foams, become the important technical indicator of polyurethane foamed material.A large amount of rules have been put into effect in every country and area, and the flame retardant properties of regulation polyurethane foamed material must reach certain standard could produce, and the appearance of various rules has advanced the development of polyurethane flame-proof technology greatly.
Traditional fire retardant is divided into the fire retardant of linear fire retardant and heterocyclic, the thermostability of linear fire retardant is little, the Heat stability is good of the fire retardant that contains the ring texturees such as phenyl ring, heterocycle, be applied to the flame retardant properties that not only improves macromolecular material in macromolecular material, and the thermostability of raising macromolecular material, the fire retardant that therefore contains heterocyclic has better flame retardant properties.
The investigator of every country has carried out a large amount of research to DOPO, but because DOPO cost is high, limited the application of DOPO fire retardant, by add alcohol amine structure on DOPO molecule, can greatly reduce the cost of fire retardant, and the existence of phenyl ring has strengthened thermostability and flame retardant resistance, the existence of amino and hydroxyl makes fire retardant to have good compatibility with other polyol components, and with isocyanate reaction, ignition-proof element being attached in polyurethane molecular structure goes, has greatly improved fire-retardant persistence.
Summary of the invention
The technical problem solving: in order to improve flame retardant resistance and the fire-retardant persistence of polyurethane foam, the invention provides a kind of non-halogen reacting fire-retardant agent and its preparation method and application, adopt Mannich reaction, hydramine and formaldehyde are incorporated into 9, in mix-10-phospho hetero phenanthrene-10-oxide compound (DOPO) fire retardant structure of 10-dihydro-9-oxy, reduced the cost of fire retardant, and synthetic non-halogen reacting fire-retardant agent is applied in hard polyaminoester flame-retardant foam, and preparation technology is simple.
Technical scheme:
Non-halogen reacting fire-retardant agent for polyurethane foam, is obtained by 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, hydramine and formaldehyde reaction, and structural formula is as follows:
The preparation method of the described non-halogen reacting fire-retardant agent for polyurethane foam, step is: by 9, mix-10-phospho hetero phenanthrene-10-oxide compound of 10-dihydro-9-oxy, hydramine and formaldehyde in molar ratio 1:0.8:0.8-1:1.2:1.2 are reacted and are obtained by Mannich, described Mannich reaction conditions is 80-100 ℃, and the reaction times is 4-6h; React the complete water of removing in solution.
The application of described non-halogen reacting fire-retardant agent in flame-retardant hard polyurethane foam, first combination polyvalent alcohol, non-halogen reacting fire-retardant agent and auxiliary agent are mixed under the condition stirring, and then under the condition stirring, stir 10～20s with isocyanic ester, during foaming, the ratio that is 1.2～2.5 in the mol ratio of NCO/OH preparation, rotating speed 2000～3000r/min, pours in mould, slaking 48h; Each raw material is counted with mass parts: 100 parts of combination polyvalent alcohols; 130 parts of isocyanic ester; 1～25 part of non-halogen reacting fire-retardant agent; Auxiliary agent is: 1～2 part of polyurethane foam stabilizer, 1～2 part of tin class catalyzer, 1～2 part, water, 10～30 parts of whipping agents.
Described tin class catalyzer is: di-n-butyltin dilaurate.
Described polyurethane foam stabilizer is silicon type suds-stabilizing agent.
Described isocyanic ester is tolylene diisocyanate, Xylene Diisocyanate or polymethine polyphenyl polyisocyanate.
Described whipping agent is choosing any one kind of them or the multiple mixture with arbitrary proportion in HCFC-141b, pentamethylene, iso-pentane, HFC-245fa or HFC-365mfc.
Described combination polyvalent alcohol is 40 parts of rosin polyester polyhydric-alcohols, (4110) 60 parts of polyether glycols.
Beneficial effect:
1, non-halogen reacting fire-retardant agent adopts Mannich reaction, hydramine and formaldehyde are incorporated into 9, in mix-10-phospho hetero phenanthrene-10-oxide compound (DOPO) fire retardant structure of 10-dihydro-9-oxy, synthetic non-halogen reacting fire-retardant agent contains activity hydroxy and combination polyvalent alcohol has good consistency, has improved the stability in storage of combination material.
2, synthetic non-halogen reacting fire-retardant agent is applied in flame-retardant hard polyurethane foam, owing to containing 2 rigidity phenyl ring in molecule, has improved mechanical property and the thermostability of foam.
3, hydramine and formaldehyde are synthesized in DOPO fire retardant, reduced the cost of fire retardant, non-halogen reacting fire-retardant agent of the present invention contains fire-retardant nitrogen, phosphoric, there is good fire-retardant synergy, and contain primary amine or tertiary amine, reactive behavior is higher, and the flame retarded polyurethane-foam of preparation has higher flame retardant resistance and fire-retardant persistence; Oxygen index can reach 23～28%.In building, insulation and some special occasions, be with a wide range of applications.
Accompanying drawing explanation
Fig. 1 is the infrared spectrogram of non-halogen reacting fire-retardant agent.
As seen from the figure: 3301cm
-1place for-NH and-vibration absorption peak of OH; 2870cm
-1stretching vibration absorption peak for methylene radical; 1593cm
-1, 1455cm
-1place is the vibration absorption peak of P-Ph; 1150cm
-1, 1245cm
-1place is the absorption peak of P=O; 1030cm
-1place is the charateristic avsorption band of middle P-O-C and O-C-O; 890cm
-1vibration absorption peak for P-O-Ph.
Embodiment
With specific embodiment, be described further below: in the present invention all raw materials be all commercially available, if in following examples without specializing, be all mass parts.
The present invention carries out a series of modification to 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) and obtains the agent of DOPO derivative non-halogen reacting fire-retardant.Obtained non-halogen reacting fire-retardant agent and polyvalent alcohol, isocyanic ester and other auxiliary agent foam and make flame-retardant hard polyurethane foam; Major programme comprises the content of following two aspects.
One, the method for the DOPO derivative non-halogen reacting fire-retardant agent described in preparation
Adopt structurally-modified method, the method of the DOPO derivative non-halogen reacting fire-retardant agent that preparation is described, adopt Mannich reaction, hydramine and formaldehyde are incorporated into 9, in mix-10-phospho hetero phenanthrene-10-oxide compound (DOPO) fire retardant structure of 10-dihydro-9-oxy, obtain the agent of DOPO derivative non-halogen reacting fire-retardant, reaction equation is:
Method for making is more specifically, in mass parts: (37%wt) formalin of 100～110 mass parts DOPO, 30～50 mass parts monoethanolamines or diethanolamine, 40～60 mass parts or 15～20 mass parts paraformaldehydes are mixed, in the environment of logical nitrogen, be heated to 80～100 ℃ of temperature, reaction 4～6h, reacting the complete water of removing in solution can obtain.
Two, composition and the preparation of DOPO derivative non-halogen reacting fire-retardant agent flame-retardant hard polyurethane foam:
1, the composition of combination polyvalent alcohol, by mass parts:
(1) rosin polyester polyhydric-alcohol is 40 parts, (4110) 60 parts of polyether glycols; (Jiangsu Qiang Lin bioenergy Materials Co., Ltd).
(2) catalyzer is 1～2 part, is generally tin class catalyzer, is selected from di-n-butyltin dilaurate and similar catalyzer.
(3) polyurethane foam stabilizer is 1～2 part, is mainly silicon type suds-stabilizing agent, suds-stabilizing agent AK8805, AK8815, AK8812, AK8809 etc. that dolantin Shi Chuan company produces; Germany Sa company: B8464, B8481, B8474, B8471, B8481 etc.Suds-stabilizing agent can be one of above-mentioned, can be also the composite arbitrarily of two or more.
(4) whipping agent is 10～30 parts: HCFC-141b, pentamethylene, iso-pentane, HFC-245fa, HFC-365mfc etc. choose any one kind of them or the multiple mixture with arbitrary proportion.
(5) water is 1～2 part
2, formula and the preparation of DOPO derivative non-halogen reacting fire-retardant agent flame-retardant hard polyurethane foam:
Preparation formula, the performance test results of DOPO derivative non-halogen reacting fire-retardant agent flame-retardant hard polyurethane foam see attached list 1, subordinate list 2.Take combination polyvalent alcohol and isocyanic ester is main raw material, and during foaming, the ratio that is 1.2～2.5 in the mol ratio of NCO/OH preparation obtains.Concrete operations are as follows: first combination polyvalent alcohol, the non-halogen reacting fire-retardant agent of DOPO derivative and auxiliary agent are mixed under the condition of high-speed stirring, under the condition of high-speed stirring, stir 10～20s with isocyanic ester again, rotating speed 2000～3000r/min, pours in mould, slaking 48h.
The selection of isocyanic ester: tolylene diisocyanate, Xylene Diisocyanate, polymethine polyphenyl polyisocyanate (PAPI), preferred PAPI, the PM-200 that trade names are Yantai Wanhua Polyurethane Co., Ltd.
Embodiment 1
Take 110 mass parts DOPO, 30 mass parts thanomins, 15 mass parts paraformaldehydes and mix, in the environment of logical nitrogen, be heated to 90 ℃ of temperature, reaction 4h, reacts the complete water of removing in solution and can obtain non-halogen reacting fire-retardant agent.Then according to table 1, fill a prescription, first combination polyvalent alcohol, the non-halogen reacting fire-retardant agent of DOPO derivative and auxiliary agent are mixed under the condition of high-speed stirring, then under the condition of high-speed stirring, stir 10～20s with isocyanic ester, rotating speed 2000～3000r/min, pour in mould slaking 48h into.
Embodiment 2
(37%wt) formalin that takes 100 mass parts DOPO, 35 mass parts monoethanolamines, 35 mass parts mixes, in the environment of logical nitrogen, be heated to 80 ℃ of temperature, reaction 5h, reacts the complete water of removing in solution and can obtain non-halogen reacting fire-retardant agent.Then according to table 1, fill a prescription, first combination polyvalent alcohol, the non-halogen reacting fire-retardant agent of DOPO derivative and auxiliary agent are mixed under the condition of high-speed stirring, then under the condition of high-speed stirring, stir 10～20s with isocyanic ester, rotating speed 2000～3000r/min, pour in mould slaking 48h into.
Embodiment 3
The paraformaldehyde that takes 105 mass parts DOPO, 45 mass parts diethanolamine, 15 mass parts mixes, and in the environment of logical nitrogen, is heated to 90 ℃ of temperature, and reaction 5h, reacts the complete water of removing in solution and can obtain non-halogen reacting fire-retardant agent.Then according to table 1, fill a prescription, first combination polyvalent alcohol, the non-halogen reacting fire-retardant agent of DOPO derivative and auxiliary agent are mixed under the condition of high-speed stirring, then under the condition of high-speed stirring, stir 10～20s with isocyanic ester, rotating speed 2000～3000r/min, pour in mould slaking 48h into.
Embodiment 4
(37%wt) formalin that takes 108 mass parts DOPO, 53 mass parts diethanolamine, 41 mass parts mixes, in the environment of logical nitrogen, be heated to 100 ℃ of temperature, reaction 6h, reacts the complete water of removing in solution and can obtain non-halogen reacting fire-retardant agent (Fig. 1).Then according to table 1, fill a prescription, first combination polyvalent alcohol, the non-halogen reacting fire-retardant agent of DOPO derivative and auxiliary agent are mixed under the condition of high-speed stirring, then under the condition of high-speed stirring, stir 10～20s with isocyanic ester, rotating speed 2000～3000r/min, pour in mould slaking 48h into.
Embodiment 5
The paraformaldehyde that takes 108 mass parts DOPO, 53 mass parts diethanolamine, 15 mass parts mixes, and in the environment of logical nitrogen, is heated to 100 ℃ of temperature, and reaction 6h, reacts the complete water of removing in solution and can obtain non-halogen reacting fire-retardant agent.Then according to table 1, fill a prescription, first combination polyvalent alcohol, the non-halogen reacting fire-retardant agent of DOPO derivative and auxiliary agent are mixed under the condition of high-speed stirring, then under the condition of high-speed stirring, stir 10～20s with isocyanic ester, rotating speed 2000～3000r/min, pour in mould slaking 48h into.
Embodiment 6
(37%wt) formalin that takes 105 mass parts DOPO, 30 mass parts thanomins, 35 mass parts mixes, in the environment of logical nitrogen, be heated to 90 ℃ of temperature, reaction 4h, reacts the complete water of removing in solution and can obtain non-halogen reacting fire-retardant agent.Then according to table 1, fill a prescription, first combination polyvalent alcohol, the non-halogen reacting fire-retardant agent of DOPO derivative and auxiliary agent are mixed under the condition of high-speed stirring, then under the condition of high-speed stirring, stir 10～20s with isocyanic ester, rotating speed 2000～3000r/min, pour in mould slaking 48h into.
The formula (mass parts) of table 1DOPO derivative non-halogen reacting fire-retardant agent flame-retardant hard polyurethane foam
| Embodiment | 1 | 2 | 3 | 4 | 5 | 6 |
| Rosin polyester polyhydric- |
40 | 40 | 40 | 40 | 40 | 40 |
| Polyether glycol (4110) | 60 | 60 | 60 | 60 | 60 | 60 |
| The fire retardant that the present invention is synthetic | 2 | 6 | 11 | 16 | 20 | 25 |
| AK8805 | 2.0 | 2.0 | 2.0 | 2.0 | 2.0 | 2.0 |
| Di-n-butyltin dilaurate | 1.5 | 1.6 | 1.8 | 1.5 | 1.5 | 1.6 |
| Water | 1.0 | 0.9 | 1.5 | 1.6 | 1.0 | 1.7 |
| Pentamethylene | 25 | 25 | 25 | 25 | 25 | 25 |
| NCO/OH（MDI） | 1.4 | 1.6 | 1.8 | 2.0 | 1.8 | 1.7 |
Wherein, combination polyvalent alcohol: 40 parts of rosin polyester polyhydric-alcohols, (4110) 60 parts of polyether glycols; (Jiangsu Qiang Lin bioenergy Materials Co., Ltd)
The product performance of table 2 flame retarded polyurethane-foam (testing method is with reference to national standard)
Mensuration shows: flame retarded polyurethane-foam prepared by the DOPO derivative non-halogen reacting fire-retardant agent preparing with the present invention, there is good mechanical property, thermostability and flame retardant resistance, synthetic DOPO derivative non-halogen reacting fire-retardant agent is for flame-retardant hard polyurethane foam, have higher flame retardant resistance, oxygen index can reach 23～28%.Can in higher temperature environment, use, heat insulation effect is improved, and has saved the energy.Embodiment 4 and 5 is better, and particularly flame retardant properties and mechanical property are taken into account.
Claims (8)
1. for the non-halogen reacting fire-retardant agent of polyurethane foam, it is characterized in that being obtained by 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, hydramine and formaldehyde reaction, structural formula is as follows:
Described in claim 1 for the preparation method of the non-halogen reacting fire-retardant agent of polyurethane foam, it is characterized in that step is: by 9, mix-10-phospho hetero phenanthrene-10-oxide compound of 10-dihydro-9-oxy, hydramine and formaldehyde in molar ratio 1:0.8:0.8-1:1.2:1.2 are reacted and are obtained by Mannich, described Mannich reaction conditions is 80-100 ℃, and the reaction times is 4-6h; React the complete water of removing in solution.
3. the application of non-halogen reacting fire-retardant agent in flame-retardant hard polyurethane foam described in claim 1, it is characterized in that: first combination polyvalent alcohol, non-halogen reacting fire-retardant agent and auxiliary agent are mixed under the condition stirring, and then under the condition stirring, stir 10～20s with isocyanic ester, during foaming, the ratio that is 1.2～2.5 in the mol ratio of NCO/OH preparation, rotating speed 2000～3000r/min, pours in mould, slaking 48h; Each raw material is counted with mass parts: 100 parts of combination polyvalent alcohols; 130 parts of isocyanic ester; 1～25 part of non-halogen reacting fire-retardant agent; Auxiliary agent is: 1～2 part of polyurethane foam stabilizer, 1～2 part of tin class catalyzer, 1～2 part, water, 10～30 parts of whipping agents.
4. the application of non-halogen reacting fire-retardant agent in flame-retardant hard polyurethane foam according to claim 3, is characterized in that described tin class catalyzer is: di-n-butyltin dilaurate.
5. the application of non-halogen reacting fire-retardant agent in flame-retardant hard polyurethane foam according to claim 3, is characterized in that described polyurethane foam stabilizer is silicon type suds-stabilizing agent.
6. the application of Flame Retardants for Polyurethane Foam in flame-retardant hard polyurethane foam according to claim 3, is characterized in that described isocyanic ester is tolylene diisocyanate, Xylene Diisocyanate or polymethine polyphenyl polyisocyanate.
7. the application of Flame Retardants for Polyurethane Foam in flame-retardant hard polyurethane foam according to claim 3, is characterized in that described whipping agent is choosing any one kind of them or the multiple mixture with arbitrary proportion in HCFC-141b, pentamethylene, iso-pentane, HFC-245fa or HFC-365mfc.
8. the application of Flame Retardants for Polyurethane Foam in flame-retardant hard polyurethane foam according to claim 3, is characterized in that described combination polyvalent alcohol is 40 parts of rosin polyester polyhydric-alcohols, (4110) 60 parts of polyether glycols.
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