KR20160043195A - Organic Phosphorus Flame-Resistant Curing Agents And Methods thereof - Google Patents
Organic Phosphorus Flame-Resistant Curing Agents And Methods thereof Download PDFInfo
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- KR20160043195A KR20160043195A KR1020140136721A KR20140136721A KR20160043195A KR 20160043195 A KR20160043195 A KR 20160043195A KR 1020140136721 A KR1020140136721 A KR 1020140136721A KR 20140136721 A KR20140136721 A KR 20140136721A KR 20160043195 A KR20160043195 A KR 20160043195A
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- curing agent
- phosphorus
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- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 68
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 68
- 239000011574 phosphorus Substances 0.000 title claims abstract description 68
- 238000000034 method Methods 0.000 title claims abstract description 44
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 26
- -1 amine compound Chemical class 0.000 claims abstract description 126
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 58
- 238000006243 chemical reaction Methods 0.000 claims abstract description 37
- 150000001875 compounds Chemical class 0.000 claims abstract description 30
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 14
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims abstract description 9
- 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 claims description 61
- 239000003063 flame retardant Substances 0.000 claims description 59
- 238000004519 manufacturing process Methods 0.000 claims description 26
- 150000001412 amines Chemical class 0.000 claims description 22
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 20
- LXCYSACZTOKNNS-UHFFFAOYSA-N diethoxy(oxo)phosphanium Chemical compound CCO[P+](=O)OCC LXCYSACZTOKNNS-UHFFFAOYSA-N 0.000 claims description 19
- 125000004432 carbon atom Chemical group C* 0.000 claims description 18
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 claims description 14
- IMUDHTPIFIBORV-UHFFFAOYSA-N aminoethylpiperazine Chemical compound NCCN1CCNCC1 IMUDHTPIFIBORV-UHFFFAOYSA-N 0.000 claims description 14
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 13
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 13
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 10
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 claims description 10
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 claims description 10
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims description 10
- 150000002576 ketones Chemical class 0.000 claims description 9
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 6
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 5
- WTFAGPBUAGFMQX-UHFFFAOYSA-N 1-[2-[2-(2-aminopropoxy)propoxy]propoxy]propan-2-amine Chemical compound CC(N)COCC(C)OCC(C)OCC(C)N WTFAGPBUAGFMQX-UHFFFAOYSA-N 0.000 claims description 5
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 5
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 5
- RTWNYYOXLSILQN-UHFFFAOYSA-N methanediamine Chemical compound NCN RTWNYYOXLSILQN-UHFFFAOYSA-N 0.000 claims description 5
- 229920000570 polyether Polymers 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- BVXOPEOQUQWRHQ-UHFFFAOYSA-N dibutyl phosphite Chemical compound CCCCOP([O-])OCCCC BVXOPEOQUQWRHQ-UHFFFAOYSA-N 0.000 claims description 4
- CZHYKKAKFWLGJO-UHFFFAOYSA-N dimethyl phosphite Chemical compound COP([O-])OC CZHYKKAKFWLGJO-UHFFFAOYSA-N 0.000 claims description 4
- NFORZJQPTUSMRL-UHFFFAOYSA-N dipropan-2-yl hydrogen phosphite Chemical compound CC(C)OP(O)OC(C)C NFORZJQPTUSMRL-UHFFFAOYSA-N 0.000 claims description 4
- 125000003282 alkyl amino group Chemical group 0.000 claims description 3
- 125000005264 aryl amine group Chemical group 0.000 claims description 3
- 239000008199 coating composition Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 3
- 150000003018 phosphorus compounds Chemical class 0.000 claims description 2
- LMYSNFBROWBKMB-UHFFFAOYSA-N 4-[2-(dipropylamino)ethyl]benzene-1,2-diol Chemical compound CCCN(CCC)CCC1=CC=C(O)C(O)=C1 LMYSNFBROWBKMB-UHFFFAOYSA-N 0.000 claims 2
- JLBSVDZUWJLOCF-GTWSWNCMSA-N DDM-838 Chemical compound C1CCCNC(=O)C1NC(=O)CC(C)OC(=O)C(CCCCNC(=O)\C=C/CCCCCCCCCCCCCCCCC)NC(=O)C(N=1)(C)COC=1C1=CC=CC=C1O JLBSVDZUWJLOCF-GTWSWNCMSA-N 0.000 claims 2
- CDXVUROVRIFQMV-UHFFFAOYSA-N oxo(diphenoxy)phosphanium Chemical compound C=1C=CC=CC=1O[P+](=O)OC1=CC=CC=C1 CDXVUROVRIFQMV-UHFFFAOYSA-N 0.000 claims 2
- 239000004593 Epoxy Substances 0.000 abstract description 23
- 239000007789 gas Substances 0.000 abstract description 3
- 206010000369 Accident Diseases 0.000 abstract 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 abstract 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 abstract 1
- 230000015556 catabolic process Effects 0.000 abstract 1
- 238000006731 degradation reaction Methods 0.000 abstract 1
- 238000001723 curing Methods 0.000 description 55
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 239000002131 composite material Substances 0.000 description 5
- 239000003822 epoxy resin Substances 0.000 description 5
- 229920000647 polyepoxide Polymers 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000004809 thin layer chromatography Methods 0.000 description 5
- 239000000654 additive Substances 0.000 description 4
- 230000032683 aging Effects 0.000 description 4
- 230000008034 disappearance Effects 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- 229920003319 Araldite® Polymers 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- KUMNEOGIHFCNQW-UHFFFAOYSA-N diphenyl phosphite Chemical compound C=1C=CC=CC=1OP([O-])OC1=CC=CC=C1 KUMNEOGIHFCNQW-UHFFFAOYSA-N 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000009408 flooring Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 2
- 239000012796 inorganic flame retardant Substances 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- QOHMWDJIBGVPIF-UHFFFAOYSA-N n',n'-diethylpropane-1,3-diamine Chemical compound CCN(CC)CCCN QOHMWDJIBGVPIF-UHFFFAOYSA-N 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 239000012744 reinforcing agent Substances 0.000 description 2
- 239000002341 toxic gas Substances 0.000 description 2
- KVGZZAHHUNAVKZ-UHFFFAOYSA-N 1,4-Dioxin Chemical compound O1C=COC=C1 KVGZZAHHUNAVKZ-UHFFFAOYSA-N 0.000 description 1
- HVCFCNAITDHQFX-UHFFFAOYSA-N 1-cyclopropylethanone Chemical compound CC(=O)C1CC1 HVCFCNAITDHQFX-UHFFFAOYSA-N 0.000 description 1
- VNRLFQGYFLCRMU-UHFFFAOYSA-N 2-piperazin-1-ylethanamine Chemical compound NCCN1CCNCC1.NCCN1CCNCC1 VNRLFQGYFLCRMU-UHFFFAOYSA-N 0.000 description 1
- JPWAHXRRIWJSKT-UHFFFAOYSA-N C=1(C(=C(C(=CC1)N)N)C)C.C=1(C(=C(C(=CC1)N)C)N)C Chemical compound C=1(C(=C(C(=CC1)N)N)C)C.C=1(C(=C(C(=CC1)N)C)N)C JPWAHXRRIWJSKT-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- XUYGNGMQMDMYHW-UHFFFAOYSA-N benzene-1,3-diamine Chemical compound NC1=CC=CC(N)=C1.NC1=CC=CC(N)=C1 XUYGNGMQMDMYHW-UHFFFAOYSA-N 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012757 flame retardant agent Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
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- 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
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/22—Amides of acids of phosphorus
-
- 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
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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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
- C08G59/4071—Curing agents not provided for by the groups C08G59/42 - C08G59/66 phosphorus containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2
- C08K5/5333—Esters of phosphonic acids
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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Abstract
Description
본 발명은 유기 인계 난연성 경화제 및 그의 제조 방법에 관한 것으로서, 보다 구체적으로는, 기존 에폭시 또는 우레탄용 경화제로 사용되는 아민계 화합물에 인 (P) 을 포함하는 화합물을 반응시킴으로써, 인 (P) 에 의해 난연성이 추가된 유기 인계 난연성 경화제 및 그의 제조 방법에 관한 것이다. The present invention relates to an organophosphorus flame retardant curing agent and a process for producing the same. More specifically, the present invention relates to an organophosphorus flame retardant curing agent and a method for producing the phosphorus (P) Based flame-retardant curing agent and a method for producing the same.
에폭시 수지는 분자 내에 에폭시기를 갖는 열경화성 수지의 총칭으로, 내열성, 전기 절연성, 접착성 등이 뛰어나다. 단독으로 사용되는 경우는 거의 없고 무기물과의 융화력이 좋기 때문에 실리카와 산화티탄 같은 충전제, 보강제 등과 조합하여 사용하는 경우가 많다. 에폭시 수지는 이들 경화제와 충전제, 보강제의 차이에 따라 물성이 크게 달라지기 때문에 폭넓은 용도가 개발되고 있다. 현재 가장 많이 보급되고 있는 형태는 비스페놀 A (bisphenol A, 2,2-bis(4'-oxyphenol)propane) 와 에피크롤히드린 (epichlorohydrin, ECH) 을 수산화나트륨의 존재 하에서 반응시킨 축합물로, 이를 분자량 300 ~ 4000의 제1차 수지 (프레폴리머) 라고 하며 총 수요의 약 90% 를 차지하고 있다.The epoxy resin is a generic term of a thermosetting resin having an epoxy group in a molecule and is excellent in heat resistance, electrical insulation, adhesiveness and the like. They are rarely used alone, and they are often used in combination with a filler such as silica and titanium oxide, a reinforcing agent or the like because of its good fusion strength with an inorganic material. Epoxy resins are widely used because their properties vary greatly depending on the difference between these curing agents, fillers and reinforcing agents. Currently, the most popular form is a condensate obtained by reacting bisphenol A (2,2-bis (4'-oxyphenol) propane) and epichlorohydrin (ECH) in the presence of sodium hydroxide. It is called the first resin (prepolymer) with a molecular weight of 300 ~ 4000, which accounts for about 90% of total demand.
제1차 수지는 원료의 배합조건에 따라 기름 모양의 것에서 연화점이 160 ℃ 에 가까운 고체 모양의 것까지 얻을 수 있기 때문에 용도에 따라 반응조건을 선택한다. 제1차 수지에 m-페닐렌다이아민 (m-phenylenediamine) 등의 아민, 프탈산무수물 등의 경화제인 산을 첨가하면 에폭시기의 고리열림 및 하이드록시기와의 반응이 일어나 다리결합이 이루어져 경화제의 종류나 반응조건에 따라 각각 성질이 다른 수지가 생긴다. 또한, 에폭시 수지는 굽힘 강도·굳기 등의 기계적 성질이 우수하다. 경화 시에 휘발성 물질의 발생 및 부피의 수축이 없고, 경화할 때는 재료면에 큰 접착력을 가진다. 가연성·내약품성이 크지만 강한 산과 강한 염기에는 약간 침식된다. 안료를 첨가함으로써 마음대로 착색할 수 있고, 또 내일광성도 크다. 제품의 최고 사용온도는 80℃ 정도로 낮다. 주형·매입·봉입 등 뛰어난 가공성을 보인다. 따라서 에폭시 수지는 도료, 전기전자용 절연재료, 접착제, 주형품 재료, 염화비닐수지의 안정제 등의 폭 넓은 용도에 사용되고 있다. Depending on the blending conditions of the raw materials, the first resin can be obtained in an oil-like form and a solid form having a softening point close to 160 ° C, so the reaction conditions are selected depending on the application. When an acid such as an amine such as m-phenylenediamine or an anhydride such as phthalic anhydride is added to the first resin, the ring opening of the epoxy group and the reaction with the hydroxy group occur to form a bridge bond, Depending on the reaction conditions, resins of different properties are produced. The epoxy resin is excellent in mechanical properties such as bending strength and hardness. There is no generation of volatile substances and shrinkage of volume at the time of curing, and a large adhesive force is given to the material surface when curing. Flammability and chemical resistance are high, but are slightly eroded by strong acid and strong base. The pigment can be colored at will by adding pigments, and the tomorrow's light is also great. The maximum operating temperature of the product is as low as 80 ℃. It shows excellent workability such as mold, burying and filling. Therefore, epoxy resins are used in a wide range of applications such as paints, insulating materials for electric and electronic devices, adhesives, mold materials, and stabilizers for vinyl chloride resins.
일례로 일반적으로 공공건물 지하 바닥, 아파트 지하 바닥, 대형할인마트 주차장 바닥, 공공건물 현장 바닥, 공장 현장 바닥 등은 에폭시로 되어 있다. 그러나 에폭시 바닥재의 경우 유기화합물로 되어 있어 화재가 발생할 경우 유독가스 발생 등을 유발할 수 있다. 특히 공장 바닥에서 화재가 발생할 경우 규모가 매우 클 가능성이 있고 아파트나 공공 건물 지하에 화재가 발생할 경우 2차 피해까지 발생할 수 있다. 그럼에도 불구하고 현재 건축용 바닥재의 경우 일반적으로 난연 처리를 하지 않거나 무기계 난연제 또는 브롬계 난연제를 섞는 수준에 불과한 것이 현실이다.For example, in general, underground floors of public buildings, underground floors of apartments, floors of large discount marts, floors of public buildings, floor of factories are made of epoxy. However, since the epoxy flooring is made of an organic compound, it can cause toxic gas generation when a fire occurs. Especially, when a fire occurs on the floor of a factory, it can be very large. Secondary damage can occur if a fire occurs in an apartment or a public building. Nevertheless, in the case of architectural flooring, it is a reality that the flame retardant treatment is not generally performed, or only the inorganic flame retardant or the brominated flame retardant is mixed.
무기계 난연제의 경우 난연성을 나타내기 위해서는 과량을 사용하여야 하나, 이 경우 에폭시 특성 감소 및 성형성에 문제가 된다. 또한 브롬계 난연제의 경우, 화재 발생시 다이옥신의 발생으로 인한 환경오염 및 유독가스 발생으로 인한 인명피해를 초래하므로 비할로겐계로의 대체가 요구된다. 특히, 인체에 유해한 가스가 배출되지 않는 인계 난연제의 개발이 요구된다.In case of the inorganic flame retardant, an excess amount should be used in order to exhibit flame retardancy. However, in this case, there is a problem in reduction of the epoxy property and moldability. In addition, in the case of a brominated flame retardant, a substitution of a halogen-free flame retardant agent is required because it causes damage to the human body due to environmental pollution and toxic gas generation due to the generation of dioxin in the event of a fire. In particular, development of a phosphorus flame retardant that does not release harmful gases to the human body is required.
이와 관련하여, 대한민국 특허출원공개공보 KR 2013-0106909 A 에는 아미노기 함유 인산에스테르 난연제 및 그 제조방법이 기재되어 있으나, 상기 문헌의 난연제는 첨가형 구조로서, 에폭시 수지 등과 직접적으로 반응하여 경화시킬 수 있는 경화제의 역할을 하지 못하여, 에폭시와 혼합하였을 때 에폭시의 물성을 감소시킨다는 단점이 있다.In this connection, Korean Patent Application Laid-Open Publication No. 2013-0106909 A discloses an amino group-containing phosphoric acid ester flame retardant and a method for producing the flame retardant, and the flame retardant of the above document is an addition type structure. The flame retardant is a curing agent capable of reacting directly with an epoxy resin, It has the disadvantage of reducing the physical properties of the epoxy when mixed with the epoxy.
이에, 본 발명자들은 첨가형으로 난연을 내는 방식이 아닌 경화제에 직접 난연성을 부여한 경화제를 제조하여, 기존의 무기계 첨가 또는 할로겐계 난연제 첨가 방식으로 사용된 에폭시 경화 방법에 비해 에폭시의 물성 또는 특성의 감소 없이 친환경적인 방법으로 난연 효과를 나타낼 수 있도록 실험을 거듭한 끝에 본 발명을 완성하게 되었으며, 본 발명에 따른 경화제는 에폭시 또는 에폭시 복합재료에도 사용될 수 있다.Thus, the present inventors have found that a curing agent which imparts direct flame retardancy to a curing agent, which is not a flame retardant addition type, is manufactured and compared with an epoxy curing method which is used in the conventional inorganic addition or halogen flame retardant addition method, The present inventors have completed the present invention based on the results of repeated experiments to exhibit a flame retardant effect in an environmentally friendly manner, and the curing agent according to the present invention can also be used in an epoxy or epoxy composite material.
본 발명은 상기와 같은 종래 기술의 문제점을 해결하기 위한 것으로 무기계 첨가형 난연제 대신 유기 인계 변성 아민을 제조함으로써, 이 후 에폭시 또는 에폭시 복합재료 등과 반응시 상온에서도 경화되는 효과를 나타낼 뿐만 아니라, 우수한 난연 효과도 나타내는 유기 인계 난연성 경화제 및 이의 제조 방법을 제공하는데 목적이 있다. SUMMARY OF THE INVENTION The present invention has been made to solve the problems of the prior art as described above, and it is an object of the present invention to provide an organophosphorous modified amine instead of an inorganic additive type flame retardant to thereby exhibit an effect of curing at room temperature upon reaction with an epoxy or epoxy composite material, And an object of the present invention is to provide a method for producing the flame retardant.
상기한 목적을 달성하기 위하여, 본 발명은, ⅰ) 아민계 화합물과 포르말린 또는 포름알데히드를 반응시켜 얻어진 반응 결과물과, ⅱ) 인계 화합물을 반응시켜 제조되는 유기 인계 난연성 경화제를 제공한다.In order to achieve the above object, the present invention provides an organophosphorus flame retardant curing agent produced by the reaction of i) a reaction product obtained by reacting an amine compound with formalin or formaldehyde, and ii) a phosphorus compound.
또한, 본 발명은, ⅰ) 아민계 화합물과, ⅱ) 하이드록시기를 포함하는 인계 화합물을 반응시켜 제조되는 유기 인계 난연성 경화제를 제공한다.The present invention also provides an organophosphorus flame retardant curing agent produced by reacting i) an amine compound and ii) a phosphorus compound containing a hydroxy group.
또한, 본 발명은, ⅰ) 아민계 화합물과 인계 화합물을 혼합한 후, ⅱ) 케톤계 화합물과 반응시켜 제조되거나; 또는 ⅰ) 아민계 화합물과 케톤계 화합물을 반응시켜 얻어진 반응 결과물과, ⅱ) 인계 화합물을 반응시켜 제조되는 유기 인계 난연성 경화제를 제공한다.The present invention also relates to a process for the preparation of a compound of formula (I), which comprises: i) mixing an amine compound with a phosphorus compound, and ii) reacting with a ketone compound; Or an organic phosphorus-based flame-retardant curing agent prepared by reacting a reaction product obtained by i) reacting an amine-based compound with a ketone-based compound and ii) a phosphorus compound.
본 발명의 일 구현예에 있어서, 본 발명에 따른 유기 인계 난연성 경화제는 하기 화학식 1로 표시될 수 있다.In one embodiment of the present invention, the organophosphorus flame retardant curing agent according to the present invention can be represented by the following general formula (1).
하기 화학식 1로 표시되는 유기 인계 난연성 경화제:An organophosphorus flame retardant curing agent represented by the following formula (1)
[화학식 1][Chemical Formula 1]
(식 중, R1 및 R2 는 각각 독립적으로, 1 내지 8 개의 탄소수를 가진 알킬기 또는 6 내지 12 개의 탄소수를 가진 아릴기이고;(Wherein R 1 and R 2 are each independently an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 12 carbon atoms;
R3 은 1 내지 10 개의 탄소수를 가진 알킬아민기 또는 6 내지 10 개의 탄소수를 가진 아릴아민기이며, R3 에는 2 개 내지 10 개의 아민이 포함되고, 상기 2 개 내지 10 개의 아민 중 적어도 1 개 내지 3 개의 아민은 말단에 위치하고;R 3 is an alkylamine group having 1 to 10 carbon atoms or an arylamine group having 6 to 10 carbon atoms, R 3 contains 2 to 10 amines and at least one of the 2 to 10 amines To three amines are located at the ends;
R4 및 R5 는 각각 독립적으로, 수소, 1 내지 8 개의 탄소수를 가진 알킬기, 또는 6 내지 12 개의 탄소수를 가진 아릴기이고;R 4 and R 5 are each independently hydrogen, an alkyl group having 1 to 8 carbon atoms, or an aryl group having 6 to 12 carbon atoms;
n 은 0 초과 3 이하의 범위를 갖는다.)n ranges from more than 0 to less than 3).
본 발명의 일 구현예에 있어서, 상기 아민계 화합물은, 에틸렌 디아민 (ethylenediamine, EDA), 디에틸렌트리아민 (diethylenetriamine, DETA), 트리에틸렌테트라아민 (triethylenetetraamine, TETA), 테트라에틸렌펜타민 (tetraethylenepentamine, TEPA), 디프로펜디아민 (diprophenediaming, DPDA), 디에틸아미노프로필아민 (diethylaminopropylamine, DEPA), 헥사메틸렌디아민 (hexamethylenediamine, HMDA), m-크실렌디아민 (m-xylenediamine, MXDA), N-아미노에틸피페라진 (N-aminoethylpiperazine, AEPA), 라미론 C-260 (Lamiron C-260), 아랄다이트 HY-964 (araldite HY-964), 메탄디아민 (methanediamine), 이소포론디아민 (isophoronediamine, IPDA), sho-amine, m-페닐렌디아민 (m-phenylenediamine), 디아미노디페닐메탄 (diaminodiphenylmethane), 디아미노디페닐설폰 (diaminodiphenylsulfone) 및 JEFFAMINE® D-230 폴리에테르아민 (polyetheramine) 으로 이루어진 군으로부터 선택될 수 있다.In one embodiment of the present invention, the amine compound is selected from the group consisting of ethylenediamine (EDA), diethylenetriamine (DETA), triethylenetetraamine (TETA), tetraethylenepentamine TEPA), diprophenediamine (DPDA), diethylaminopropylamine (DEPA), hexamethylenediamine (HMDA), m-xylenediamine (MXDA), N-aminoethylpiperazine N-aminoethylpiperazine (AEPA), Lamiron C-260, Araldite HY-964, methanediamine, isophoronediamine (IPDA), sho be selected from -amine, m- phenylenediamine (m-phenylenediamine), diaminodiphenyl methane (diaminodiphenylmethane), diaminodiphenyl sulfone group consisting of (diaminodiphenylsulfone), and JEFFAMINE ® D-230 polyether amine (polyetheramine) There.
본 발명의 일 구현예에 있어서, 상기 인계 화합물은, 디메틸포스파이트, 디에틸포스파이트, 디이소프로필포스파이트, 디부틸포스파이트 및 디페닐포스파이트로 이루어진 군으로부터 선택될 수 있다.In one embodiment of the present invention, the phosphorus compound may be selected from the group consisting of dimethyl phosphite, diethyl phosphite, diisopropyl phosphite, dibutyl phosphite, and diphenyl phosphite.
본 발명의 일 구현예에 있어서, 상기 하이드록시기를 포함하는 인계 화합물은, 하이드록시메틸디에틸포스포네이트 (hydroxymethyldiethylphosphonate), 하이드록시메틸디메틸포스포네이트 (hydroxymethyldimethylphosphonate), 하이드록시메틸디이소프로필포스포네이트 (hydroxymethyldiisopropylphosphonate), 하이드록시메틸디부틸포스포네이트 (hydroxymethyldibutylphosphonate) 및 하이드록시메틸디페닐포스포네이트 (hydroxymethyldiphenylphosphonate) 로 이루어진 군으로부터 선택될 수 있다.In one embodiment of the present invention, the phosphorus-containing compound having a hydroxy group is selected from the group consisting of hydroxymethyldiethylphosphonate, hydroxymethyldimethylphosphonate, hydroxymethyldiisopropylphosphate, Hydroxymethyldibutylphosphonate, hydroxymethyldiphenylphosphonate, hydroxymethyldibutylphosphonate, and hydroxymethyldiphenylphosphonate. The hydroxymethyldibutylphosphonate may be selected from the group consisting of hydroxymethyldisopropylphosphonate, hydroxymethyldibutylphosphonate, and hydroxymethyldiphenylphosphonate.
본 발명의 일 구현예에 있어서, 상기 케톤계 화합물은 아세톤일 수 있다.In one embodiment of the present invention, the ketone-based compound may be acetone.
또한, 본 발명은, ⅰ) 아민계 화합물에 포르말린 또는 포름알데히드를 혼합하여 반응시키는 단계; 및 ⅱ) 상기 반응 후 생성된 물을 제거하고 인계 화합물을 혼합하여 반응시키는 단계를 포함하는 유기 인계 난연성 경화제의 제조 방법을 제공한다.The present invention also relates to a process for the production of a compound of formula (I), comprising the steps of: i) reacting an amine compound with formalin or formaldehyde; And ii) removing water produced after the reaction and mixing the phosphorus compound and reacting the phosphorus compound to produce an organophosphorus flame retardant curing agent.
본 발명의 일 구현예에 있어서, 상기 ⅰ) 단계의 포르말린 또는 포름알데히드는 아민계 화합물 1 당량 당 0.5 내지 3 당량으로 혼합될 수 있다.In one embodiment of the present invention, the formalin or formaldehyde of step (i) may be mixed in an amount of 0.5 to 3 equivalents per equivalent of the amine compound.
본 발명의 일 구현예에 있어서, 상기 ⅱ) 단계에서의 인계 화합물은 아민계 화합물 1 당량 당 0.5 내지 3 당량으로 혼합될 수 있다.In one embodiment of the present invention, the phosphorus compound in step ii) may be mixed in an amount of 0.5 to 3 equivalents per equivalent of the amine compound.
또한, 본 발명은, 아민계 화합물에 하이드록시기를 포함하는 인계 화합물을 혼합하여 반응시키는 단계를 포함하는 유기 인계 난연성 경화제의 제조 방법을 제공한다.The present invention also provides a method for producing an organophosphorus flame retardant curing agent comprising the step of mixing and reacting an amine compound with a phosphorus compound containing a hydroxy group.
또한, 본 발명은, ⅰ) 아민계 화합물과 인계 화합물을 혼합하는 단계; 및 ⅱ) 상기 혼합물과 케톤계 화합물을 반응시키는 단계를 포함하는 유기 인계 난연성 경화제의 제조 방법을 제공한다.The present invention also relates to a process for preparing a phosphorus-containing compound, comprising the steps of: i) mixing an amine compound and a phosphorus compound; And ii) reacting the mixture with a ketone-based compound to produce an organic phosphorus-based flame-retardant curing agent.
또한, 본 발명은, ⅰ) 아민계 화합물과 케톤계 화합물을 반응시키는 단계; 및 ⅱ) 상기 반응 결과물과 인계 화합물을 반응시키는 단계를 포함하는 유기 인계 난연성 경화제의 제조 방법을 제공한다.The present invention also relates to a process for the production of i) a process comprising the steps of: i) reacting an amine compound with a ketone compound; And ii) reacting the reaction product with a phosphorus compound to produce an organophosphorus flame retardant curing agent.
본 발명의 일 구현예에 있어서, 상기 인계 화합물은 아민계 화합물 1 당량 당 0.5 내지 3 당량으로 혼합될 수 있다.In one embodiment of the present invention, the phosphorus compound may be mixed in an amount of 0.5 to 3 equivalents per equivalent of the amine compound.
본 발명의 일 구현예에 있어서, 상기 케톤계 화합물은 아민계 화합물 1 당량 당 0.5 내지 3 당량으로 혼합될 수 있다.In one embodiment of the present invention, the ketone compound may be mixed in an amount of 0.5 to 3 equivalents per equivalent of the amine compound.
또한, 본 발명은, 본 발명에 따른 유기 인계 난연성 경화제를 포함하는 도료 조성물을 제공한다.In addition, the present invention provides a coating composition comprising an organophosphorus flame retardant curing agent according to the present invention.
본 발명은 유기 인계 난연성 경화제 및 이의 제조 방법을 제공하며, 본 발명에 따른 유기 인계 난연성 경화제는, a) ⅰ) 아민계 화합물과 포르말린 또는 포름알데히드를 반응시켜 얻어진 반응 결과물과 ⅱ) 인계 화합물을 반응시켜 제조되거나; 또는 b) ⅰ) 아민계 화합물과 ⅱ) 하이드록시기를 포함하는 인계 화합물을 반응시켜 제조되거나; 또는 c) ⅰ) 아민계 화합물과 인계 화합물을 혼합한 후, ⅱ) 케톤계 화합물과 반응시켜 제조되거나, ⅰ) 아민계 화합물과 케톤계 화합물을 반응시켜 얻어진 반응 결과물과, ⅱ) 인계 화합물을 반응시켜 제조될 수 있다.The present invention provides an organophosphorus flame retardant curing agent and a method for producing the same, wherein the organophosphorus flame retardant curing agent according to the present invention comprises a) a reaction product obtained by i) reacting an amine compound with formalin or formaldehyde, and ii) ≪ / RTI > Or b) by reacting i) an amine compound and ii) a phosphorus compound comprising a hydroxy group; Or c) a reaction product obtained by mixing i) an amine compound and a phosphorus compound, ii) reacting the compound with a ketone compound, or ii) reacting the reaction product obtained by reacting an amine compound with a ketone compound, and ii) .
따라서, 이러한 방법으로 수득된 유기 인계 난연성 경화제는 기존 아민계 경화제에 인이 부가되어 있는 형태를 가짐으로써, 기존 경화 방법 그대로 실온에서 경화제로서 사용될 수 있을 뿐만 아니라, 부가된 인으로 인하여 우수한 난연성을 나타내므로, 기존의 무기계 첨가 또는 할로겐계 난연제 첨가 방식으로 사용된 에폭시 경화 방법에 비해 에폭시의 물성 또는 특성의 감소 없이 친환경적인 방법으로 난연 효과를 얻을 수 있는 장점이 있다.Therefore, the organophosphorus flame retardant curing agent obtained by this method has a form in which phosphorus is added to the existing amine curing agent, so that it can be used not only as a curing agent at room temperature but also with excellent flame retardancy The flame retardant effect can be obtained in an environmentally friendly manner without decreasing the physical properties or properties of the epoxy as compared with the conventional epoxy curing method using the inorganic additive or the halogen flame retardant addition method.
즉, 본 발명의 유기 인계 난연성 경화제를 이용함으로써, 에폭시 또는 에폭시 복합재료에 난연제를 첨가하는 방식이 아닌 경화제에 직접 난연성을 부여하는 방식을 통해, 에폭시 또는 에폭시 복합재료와 혼합하였을 때 에폭시 또는 에폭시 복합재료의 물성 감소 없이 우수한 난연성을 가지도록 할 수 있다. That is, by using the organophosphorus flame retardant curing agent of the present invention, the flame retardant is not added to the epoxy or epoxy composite material, but the flame retardancy is imparted directly to the curing agent. When the epoxy or epoxy composite material is mixed with epoxy or epoxy composite It is possible to obtain excellent flame retardancy without reducing the physical properties of the material.
또한 본 발명의 유기 인계 난연성 경화제를 이용함으로써, 에폭시와 반응시 상온에서도 경화가 이루어지도록 할 수 있고, 우수한 난연성까지 갖도록 함으로써 화재 등의 상황에서 유해한 가스가 배출되지 않는 친환경 특성을 가지도록 할 수 있다.Further, by using the organophosphorus flame retardant curing agent of the present invention, curing can be carried out even at room temperature when reacted with epoxy, and excellent flame retardancy can be obtained, so that eco-friendly properties in which harmful gas is not discharged in the event of fire or the like can be obtained .
도 1 내지 도 7은 본 발명의 유기 인계 난연성 경화제의 제조 과정을 예시한 것이다. 1 to 7 illustrate a process for producing the organic phosphorus-based flame retardant of the present invention.
이하 본 발명을 상세하게 설명한다.Hereinafter, the present invention will be described in detail.
본 발명은, ⅰ) 아민계 화합물과 포르말린 또는 포름알데히드를 반응시켜 얻어진 반응 결과물과, ⅱ) 인계 화합물을 반응시켜 제조되는 유기 인계 난연성 경화제에 관한 것이다.The present invention relates to an organophosphorus flame retardant curing agent prepared by i) reacting a reaction product obtained by reacting an amine compound with formalin or formaldehyde and ii) reacting a phosphorus compound.
또한, 본 발명은, ⅰ) 아민계 화합물과, ⅱ) 하이드록시기를 포함하는 인계 화합물을 반응시켜 제조되는 유기 인계 난연성 경화제에 관한 것이다.The present invention also relates to an organophosphorus flame retardant curing agent prepared by reacting i) an amine compound and ii) a phosphorus compound containing a hydroxy group.
또한, 본 발명은, ⅰ) 아민계 화합물과 인계 화합물을 혼합한 후, ⅱ) 케톤계 화합물과 반응시켜 제조되는 유기 인계 난연성 경화제에 관한 것이다.The present invention also relates to an organophosphorus flame retardant curing agent prepared by i) mixing an amine compound and a phosphorus compound, and then ii) reacting with a ketone compound.
또한, 본 발명은, ⅰ) 아민계 화합물과 케톤계 화합물을 반응시켜 얻어진 반응 결과물과, ⅱ) 인계 화합물을 반응시켜 제조되는 유기 인계 난연성 경화제에 관한 것이다.The present invention also relates to an organophosphorus flame retardant curing agent produced by reacting i) a reaction product obtained by reacting an amine compound with a ketone compound, and ii) a phosphorus compound.
본 발명의 일 구현예에 있어서, 본 발명에 따른 유기 인계 난연성 경화제는 하기 화학식 1로 표시될 수 있다.In one embodiment of the present invention, the organophosphorus flame retardant curing agent according to the present invention can be represented by the following general formula (1).
하기 화학식 1로 표시되는 유기 인계 난연성 경화제:An organophosphorus flame retardant curing agent represented by the following formula (1)
[화학식 1][Chemical Formula 1]
(식 중, R1 및 R2 는 각각 독립적으로, 1 내지 8 개의 탄소수를 가진 알킬기 또는 6 내지 12 개의 탄소수를 가진 아릴기이고;(Wherein R 1 and R 2 are each independently an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 12 carbon atoms;
R3 은 1 내지 10 개의 탄소수를 가진 알킬아민기 또는 6 내지 10 개의 탄소수를 가진 아릴아민기이며, R3 에는 2 개 내지 10 개의 아민이 포함되고, 상기 2 개 내지 10 개의 아민 중 적어도 1 개 내지 3 개의 아민은 말단에 위치하고;R 3 is an alkylamine group having 1 to 10 carbon atoms or an arylamine group having 6 to 10 carbon atoms, R 3 contains 2 to 10 amines and at least one of the 2 to 10 amines To three amines are located at the ends;
R4 및 R5 는 각각 독립적으로, 수소, 1 내지 8 개의 탄소수를 가진 알킬기, 또는 6 내지 12 개의 탄소수를 가진 아릴기이고;R 4 and R 5 are each independently hydrogen, an alkyl group having 1 to 8 carbon atoms, or an aryl group having 6 to 12 carbon atoms;
n 은 0 초과 3 이하의 범위를 갖는다.)
n ranges from more than 0 to less than 3).
또한, 본 발명에 따른 유기 인계 난연성 경화제의 제조 방법으로서, 비제한적으로 하기의 세 가지 제조 방법이 가능하며, 제조 방법에 대하여 다음과 같이 상세하게 설명한다.
Further, as a method for producing the organic phosphorus-based flame retardant curing agent according to the present invention, the following three production methods are possible without limitation, and the production method will be described in detail as follows.
a) 첫번째 제조 방법으로서, ⅰ) 아민계 화합물에 포르말린 또는 포름알데히드를 혼합하여 반응시키는 단계; 및 ⅱ) 상기 반응 후 생성된 물을 제거하고 인계 화합물을 혼합하여 반응시키는 단계를 포함하는 유기 인계 난연성 경화제의 제조 방법이 있다.a) a first process comprising the steps of: i) reacting an amine compound with formalin or formaldehyde; And ii) removing water produced after the reaction and mixing the phosphorus compound and reacting the phosphorus compound to produce an organic phosphorus-based flame-retardant curing agent.
b) 두번째 제조 방법으로서, 아민계 화합물에 하이드록시기를 포함하는 인계 화합물을 혼합하여 반응시키는 단계를 포함하는 유기 인계 난연성 경화제의 제조 방법이 있다. b) As a second production method, there is a method for producing an organophosphorus flame retardant curing agent comprising a step of mixing and reacting an amine compound with a phosphorus compound containing a hydroxy group.
c) 세번째 제조 방법으로서, ⅰ) 아민계 화합물과 인계 화합물을 혼합하는 단계; 및 ⅱ) 상기 혼합물과 케톤계 화합물을 반응시키는 단계를 포함하는 유기 인계 난연성 경화제의 제조 방법이 있으며, 또다른 세번째 제조 방법으로서, ⅰ) 아민계 화합물과 케톤계 화합물을 반응시키는 단계; 및 ⅱ) 상기 반응 결과물과 인계 화합물을 반응시키는 단계를 포함하는 유기 인계 난연성 경화제의 제조 방법이 있다.
c) a third process comprising: i) mixing an amine compound and a phosphorus compound; And ii) reacting the mixture with a ketone-based compound. The third method comprises: i) reacting an amine-based compound with a ketone-based compound; And ii) reacting the reaction product with a phosphorus compound to produce an organophosphorus flame retardant curing agent.
상기 a) 방법의 일 구현예로서, 에틸렌디아민에 먼저 포르말린을 반응시키고, 생성된 물을 제거한 후 디에틸포스파이트를 첨가함으로써, 유기 인계 난연성 경화제를 제조하는 방법이 가능하다.As an embodiment of the method a), it is possible to produce an organophosphorus flame retardant curing agent by reacting formaldehyde first with ethylenediamine, removing the produced water, and then adding diethylphosphite.
상기 b) 방법의 일 구현예로서, 하이드록시메틸디에틸포스포네이트와 에틸렌디아민을 반응시킴으로써 유기 인계 난연성 경화제를 제조하는 방법이 가능하다.As an embodiment of the method b), a method of producing an organophosphorus flame retardant curing agent by reacting hydroxymethyldiethylphosphonate with ethylenediamine is possible.
상기 c) 방법의 일 구현예로서, N-아미노에틸피페라진과 디에틸포스파이트를 혼합한 후, 아세톤을 반응시킴으로써 유기 인계 난연성 경화제를 제조하는 방법이 가능하다.As an embodiment of the c) method, it is possible to produce an organophosphorus flame retardant curing agent by mixing N-aminoethylpiperazine and diethylphosphite and then reacting with acetone.
상기 a) 내지 c) 방법 모두는 같은 목적 화합물을 제조할 수 있는 방법으로, 본 발명은 에틸렌디아민과 같은 아민계 화합물과 인계 화합물을 반응시켜 유기 인계 변성 아민 화합물을 제조하는데 특징이 있다.
All the above methods a) to c) are methods for preparing the same target compound. The present invention is characterized in that an amine-based compound such as ethylenediamine is reacted with a phosphorus-based compound to produce an organophosphorus-modified amine compound.
본 발명의 일 구현예에 있어서, 상기 a) 방법에서 포르말린 또는 포름알데히드는 아민계 화합물 1 당량 당 0.5 내지 3 당량으로 혼합될 수 있으며, 인계 화합물은 아민계 화합물 1 당량 당 0.5 내지 3 당량으로 혼합될 수 있다.In one embodiment of the present invention, in the method a), the formalin or formaldehyde may be mixed in an amount of 0.5 to 3 equivalents per equivalent of the amine compound, and the phosphorus compound may be mixed in an amount of 0.5 to 3 equivalents per equivalent of the amine compound .
본 발명의 일 구현예에 있어서, 상기 c) 방법에서 케톤계 화합물은 아민계 화합물 1 당량 당 0.5 내지 3 당량으로 혼합될 수 있으며, 인계 화합물은 아민계 화합물 1 당량 당 0.5 내지 3 당량으로 혼합될 수 있다.In one embodiment of the present invention, in the method c), the ketone compound may be mixed at 0.5 to 3 equivalents per equivalent of the amine compound, and the phosphorus compound may be mixed at 0.5 to 3 equivalents per equivalent of the amine compound .
상기 a) 방법 또는 c) 방법에서, 인계 화합물로는 디메틸포스파이트, 디에틸포스파이트, 디이소프로필포스파이트, 디부틸포스파이트와 같은 알킬포스파이트 또는 디페닐포스파이트와 같은 방향족포스파이트 등이 사용될 수 있으나, 이에 제한되는 것은 아니다.In the above a) or c) method, phosphorus compounds include alkyl phosphites such as dimethyl phosphite, diethyl phosphite, diisopropyl phosphite, dibutyl phosphite, or aromatic phosphites such as diphenyl phosphite and the like But is not limited thereto.
상기 a) 방법 또는 c) 방법에서, 아민계 화합물로는 에틸렌 디아민 (ethylenediamine, EDA), 디에틸렌트리아민 (diethylenetriamine, DETA), 트리에틸렌테트라아민 (triethylenetetraamine, TETA), 테트라에틸렌펜타민 (tetraethylenepentamine, TEPA), 디프로펜디아민 (diprophenediaming, DPDA), 아미노에틸피페라진(N-aminoethylpiperazine, AEP), 이소포론디아민(Isophorone diamine, IPDA), 헥사메틸렌디아민 (hexamethylenediamine, HMDA), m-크실렌디아민 (m-xylenediamine, MXDA), 라미론 C-260 (Lamiron C-260), 아랄다이트 HY-964 (araldite HY-964), 메탄디아민 (methanediamine), sho-amine, m-페닐렌디아민 (m-phenylenediamine), 디아미노디페닐메탄 (diaminodiphenylmethane, DDM) , 디아미노디페닐설폰 (diaminodiphenylsulfone, DDS) 및 JEFFAMINE D-230® 폴리에테르아민 (polyetheramine) 과 같은 아민 등이 사용될 수 있으나, 이에 제한되는 것은 아니다.In the a) or c) method, examples of the amine compound include ethylenediamine (EDA), diethylenetriamine (DETA), triethylenetetramine (TETA), tetraethylenepentamine TEPA), diprophenediamine (DPDA), N-aminoethylpiperazine (AEP), isophorone diamine (IPDA), hexamethylenediamine (HMDA), m-xylenediamine -xylenediamine, MXDA), Lamiron C-260, Araldite HY-964, methanediamine, sho-amine, m-phenylenediamine ), diaminodiphenyl methane (diaminodiphenylmethane, DDM), diaminodiphenyl sulfone (diaminodiphenylsulfone, DDS) and JEFFAMINE D-230 ® polyether amines (but the number of the amine to be used, such as polyetheramine), but is not limited thereto.
상기 c) 방법에서, 케톤계 화합물로는 아세톤, 메틸에틸케톤 (methyl ethyl ketone), 메틸이소부틸케톤 (methyl isobutyl ketone), 시클로프로필메틸케톤 (cyclopropyl methyl ketone) 등이 사용될 수 있으나, 이에 제한되는 것은 아니다.As the ketone compound, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopropyl methyl ketone, and the like may be used in the above c) It is not.
상기 b) 방법에서는 인계 화합물은 아민계 화합물 1 당량 당 0.5 내지 3 당량으로 혼합될 수 있다. In the method b), the phosphorus compound may be mixed with 0.5 to 3 equivalents per equivalent of the amine compound.
상기 b) 방법에서, 인계 화합물로는 하이드록시메틸디에틸포스포네이트 (hydroxymethyldiethylphosphonate), 하이드록시메틸디메틸포스포네이트 (hydroxymethyldimethylphosphonate), 하이드록시메틸디이소프로필포스포네이트 (hydroxymethyldiisopropylphosphonate), 하이드록시메틸디부틸포스포네이트 (hydroxymethyldibutylphosphonate) 또는 하이드록시메틸디페닐포스포네이트 (hydroxymethyldiphenylphosphonate) 등이 사용될 수 있으나, 이에 제한되는 것은 아니다.In the above method b), as the phosphorus compound, hydroxymethyldiethylphosphonate, hydroxymethyldimethylphosphonate, hydroxymethyldiisopropylphosphonate, hydroxymethyldiisopropylphosphonate, But are not limited to, hydroxymethyldibutylphosphonate or hydroxymethyldiphenylphosphonate. The term " hydroxymethyldibutylphosphonate "
상기 b) 방법에서, 아민계 화합물로는 에틸렌 디아민 (ethylenediamine, EDA), 디에틸렌트리아민 (diethylenetriamine, DETA), 트리에틸렌테트라아민 (triethylenetetraamine, TETA), 테트라에틸렌펜타민 (tetraethylenepentamine, TEPA), 디프로펜디아민 (diprophenediaming, DPDA), 아미노에틸피페라진(N-aminoethylpiperazine, AEP), 이소포론디아민(Isophorone diamine, IPDA), 헥사메틸렌디아민 (hexamethylenediamine, HMDA), m-크실렌디아민 (m-xylenediamine, MXDA), 라미론 C-260 (Lamiron C-260), 아랄다이트 HY-964 (araldite HY-964), 메탄디아민 (methanediamine), sho-amine, m-페닐렌디아민 (m-phenylenediamine), 디아미노디페닐메탄 (diaminodiphenylmethane, DDM) , 디아미노디페닐설폰 (diaminodiphenylsulfone, DDS) 및 JEFFAMINE® D-230 폴리에테르아민 (polyetheramine) 과 같은 고분자형 아민 등이 사용될 수 있으나, 이에 제한되는 것은 아니다.
In the method b), as the amine compound, ethylenediamine (EDA), diethylenetriamine (DETA), triethylenetetraamine (TETA), tetraethylenepentamine (TEPA) Such as diprophenediamine (DPDA), N-aminoethylpiperazine (AEP), isophorone diamine (IPDA), hexamethylenediamine (HMDA), m-xylenediamine ), Lamiron C-260, araldite HY-964, methanediamine, sho-amine, m-phenylenediamine, diamino diphenylmethane (diaminodiphenylmethane, DDM), diaminodiphenyl sulfone (diaminodiphenylsulfone, DDS) and JEFFAMINE ® D-230 polyether amine, but can be used include polymeric amine, such as (polyetheramine), but is not limited thereto.
상기 a) 방법 내지 c) 방법에서 당량비는 개시된 수치로만 제한되는 것은 아니나, 당량비가 3 초과로 올라갈 경우 점도의 증가가 나타나 사용하기 어려운 점이 있다. In the methods a) to c), although the equivalence ratio is not limited to the disclosed values, it is difficult to use because the viscosity increases when the equivalent ratio exceeds 3.
상기 a) 방법 내지 c) 방법은 -10 ~ 80 ℃ 에서도 제조가 가능하나, 바람직하게는 -10 ℃ ~ 30 ℃ 에서 제조하는 것이 색상의 변색 없이 제조가 가능하다는 장점이 있다. 그러나 용도에 따라 색상 및 점도에 문제가 없는 경우, 0 ~ 80 ℃ 의 반응온도에서 제조될 수 있다.
The methods a) to c) can be carried out at -10 to 80 ° C, but preferably at -10 ° C to 30 ° C. However, if there is no problem in color and viscosity depending on the application, it can be produced at a reaction temperature of 0 to 80 ° C.
하기 반응식은 본 발명의 유기 인계 난연성 경화제의 제조 과정을 예시한 것으로써, 하기의 제조 방법이 본 발명에 따른 유기 인계 난연성 경화제의 제조 방법을 한정하는 것은 아니다.
The following reaction formula illustrates the production process of the organophosphorus flame retardant curing agent of the present invention, and the following production method does not limit the method for producing the organophosphorus flame retardant curing agent according to the present invention.
반응식 a)Scheme a)
반응식 b)Scheme b)
반응식 c)Scheme c)
또한, 본 발명에 따른 유기 인계 난연성 경화제를 포함하는 도료 조성물을 제조할 수 있다. 도료에 사용되는 첨가제로는 습윤 분산제, 방부제, 소포제, 도막조제, pH 조절제, 증점제, 가소제, 건조 촉진제 등이 포함되나, 이에 제한되는 것은 아니다. 또한, 당업계에서 사용되고 있는 첨가제를 본 발명에서도 사용할 수 있다. 그 종류 및 사용량은 각각 다르므로 구체적으로 명시하지는 않으나, 그 종류 및 사용량이 제한되는 것은 아니다.
Further, a coating composition containing the organophosphorus-based flame retardant according to the present invention can be produced. Additives used in paints include, but are not limited to, wetting and dispersing agents, preservatives, defoamers, film formers, pH adjusting agents, thickeners, plasticizers, drying promoters and the like. In addition, additives used in the art can be used in the present invention. The type and amount of use thereof are different from each other, so that the kind and amount thereof are not limited.
이하, 실시예를 통하여 본 발명을 더욱 상세히 설명하고자 한다. 이들 실시예는 오로지 본 발명을 예시하기 위한 것으로서, 본 발명의 범위가 이들 실시예에 의해 제한되는 것으로 해석되지는 않는 것은 당업계에서 통상의 지식을 가진 자에게 있어서 자명할 것이다.
Hereinafter, the present invention will be described in more detail with reference to Examples. It is to be understood by those skilled in the art that these examples are for illustrative purposes only and that the scope of the present invention is not construed as being limited by these examples.
실시예Example
[실시예 1] 경화제의 제조 1[Example 1] Production of curing agent 1
20 L 반응기에 DETA (디에틸렌트리아민; diethylenetriamine) 5.5 kg 을 넣고 20 ℃ 이하로 유지하면서 35% 포르말린 4.6 kg 을 첨가한다. 반응 종결 후 반응기 내부온도를 40 ~ 60 ℃ 로 유지하면서, 생성된 물을 진공으로 제거해준다. 이 후, 반응기 내부온도를 30 ℃ 이하로 유지하면서, 반응액에 디에틸포스파이트 7.36 kg 을 첨가한다. 이 때 발열되므로 아이스배쓰 (ice bath) 를 이용하여 온도를 조절한다. 첨가 후 약 1 시간 숙성시킨 후, 미량의 수분 제거를 위해 감압 농축을 한다. 최종 제품은 12.9 kg 으로, 95% 의 수율로서 얻을 수 있었다.Add 5.5 kg of DETA (diethylenetriamine) to a 20 L reactor and add 4.6 kg of 35% formalin while keeping it below 20 ° C. After completion of the reaction, the produced water is removed under vacuum while maintaining the internal temperature of the reactor at 40 to 60 ° C. Thereafter, 7.36 kg of diethylphosphite is added to the reaction solution while maintaining the internal temperature of the reactor at 30 占 폚 or lower. Temperature is controlled by using an ice bath because heat is generated at this time. After the addition, the mixture is aged for about 1 hour and then concentrated under reduced pressure to remove a trace amount of water. The final product, 12.9 kg, was obtained with a yield of 95%.
[실시예 2] 경화제의 제조 2[Example 2] Production of curing agent 2
500 mL 반응기에 EDA (에틸렌디아민; ethylenediamine) 140 g 을 넣고 20 ℃ 이하로 유지하면서 35% 포르말린 200 g 을 첨가한다. 반응 종결 후 반응기 내부온도를 40 ~ 60 ℃ 로 유지하면서, 생성된 물을 진공으로 제거해준다. 이 후, 반응기 내부온도를 30 ℃ 이하로 유지하면서, 반응액에 디에틸포스파이트 322 g 을 첨가한다. 이 때 발열되므로 아이스배쓰를 이용하여 온도를 조절한다. 첨가 후 약 1 시간 숙성시킨 후, 미량의 수분 제거를 위해 감압 농축을 한다. 최종 제품은 475 g 으로, 97% 의 수율로서 얻을 수 있었다.
In a 500-mL reactor, add 140 g of EDA (ethylenediamine) and add 200 g of 35% formalin while keeping the temperature below 20 ° C. After completion of the reaction, the produced water is removed under vacuum while maintaining the internal temperature of the reactor at 40 to 60 ° C. Thereafter, 322 g of diethylphosphite is added to the reaction solution while maintaining the internal temperature of the reactor at 30 占 폚 or lower. At this time, the temperature is controlled by using an ice bath because heat is generated. After the addition, the mixture is aged for about 1 hour and then concentrated under reduced pressure to remove a trace amount of water. The final product was 475 g, 97% yield.
[실시예 3] 경화제의 제조 3[Example 3] Production of curing agent 3
500 mL 반응기에 MXDA (m-크실렌디아민; m-xylenediamine) 100 g 을 넣고 20 ℃ 이하로 유지하면서 35% 포르말린 63g 을 첨가한다. 반응 종결 후 반응기 내부온도를 40 ~ 60 ℃ 로 유지하면서, 생성된 물을 진공으로 제거해준다. 이 후, 반응기 내부온도를 30 ℃ 이하로 유지하면서, 반응액에 디에틸포스파이트 102 g 을 첨가한다. 이 때 발열되므로 아이스배쓰를 이용하여 온도를 조절한다. 첨가 후 약 1 시간 숙성시킨 후, 미량의 수분 제거를 위해 감압 농축을 한다. 최종 제품은 205 g 으로, 95% 의 수율로서 얻을 수 있었다.
Add 100 g of MXDA (m-xylenediamine) to a 500 mL reactor and add 63 g of 35% formalin while keeping the temperature below 20 ° C. After completion of the reaction, the produced water is removed under vacuum while maintaining the internal temperature of the reactor at 40 to 60 ° C. Thereafter, 102 g of diethylphosphite is added to the reaction solution while maintaining the internal temperature of the reactor at 30 占 폚 or lower. At this time, the temperature is controlled by using an ice bath because heat is generated. After the addition, the mixture is aged for about 1 hour and then concentrated under reduced pressure to remove a trace amount of water. The final product, 205 g, was obtained in a yield of 95%.
[실시예 4] 경화제의 제조 4[Example 4] Production of curing agent 4
500 mL 반응기에 EDA 100 g 을 넣고 0 ℃ 이하로 유지한다. 하이드록시메틸디에틸포스포네이트 (hydroxymethyldiethylphosphonate; DEP-OH) 364 g 을, 10 ℃ 가 넘지 않도록 아이스배쓰를 이용하여 반응기 온도를 유지하면서 첨가한다. 첨가 완료 후, 약 1 시간 동안 교반 숙성하면서 반응을 완료시킨다.In a 500 mL reactor, add 100 g of EDA and keep below 0 ° C. 364 g of hydroxymethyldiethylphosphonate (DEP-OH) is added while maintaining the temperature of the reactor using an ice bath so as not to exceed 10 캜. After completion of the addition, the reaction is completed while stirring and aging for about 1 hour.
반응이 완료된 것은, TLC (thin layer chromatography) 를 통해 DEP-OH 가 사라진 것을 확인함으로써 알 수 있다. 반응이 완결되면 반응으로 생성된 물을 감압 농축하여 제거한다. 생성된 화합물은 420 g 으로, 97% 의 수율로서 수득하였다.The reaction was completed by confirming the disappearance of DEP-OH by TLC (thin layer chromatography). When the reaction is completed, the water produced by the reaction is concentrated under reduced pressure to remove it. The resulting compound was obtained in 420 g, 97% yield.
[실시예 5] 경화제의 제조 5[Example 5] Production of curing agent 5
500 mL 반응기에 EDA 100 g 을 넣고 0 ℃ 이하로 유지한다. 하이드록시메틸디에틸포스포네이트 (DEP-OH) 476 g 을, 10 ℃ 가 넘지 않도록 아이스배쓰를 이용하여 반응기 온도를 유지하면서 첨가한다. 첨가 완료 후, 약 1 시간 동안 교반 숙성하면서 반응을 완료시킨다.In a 500 mL reactor, add 100 g of EDA and keep below 0 ° C. 476 g of hydroxymethyl diethylphosphonate (DEP-OH) are added while maintaining the reactor temperature using an ice bath so that the temperature does not exceed 10 캜. After completion of the addition, the reaction is completed while stirring and aging for about 1 hour.
반응이 완료된 것은 TLC 를 통해 DEP-OH 가 사라진 것을 확인함으로써 알 수 있다. 반응이 완결되면 반응으로 생성된 물을 감압 농축하여 제거한다. 생성된 화합물은 520 g 으로, 97% 의 수율로서 수득하였다.
The reaction was completed by confirming the disappearance of DEP-OH via TLC. When the reaction is completed, the water produced by the reaction is concentrated under reduced pressure to remove it. The resulting compound was obtained in 520 g, 97% yield.
[실시예 6] 경화제의 제조 6[Example 6] Production of curing agent 6
500 mL 반응기에 DETA 100 g 을 넣고 0 ℃ 이하로 유지한다. 하이드록시메틸디에틸포스포네이트 (DEP-OH) 212 g 을, 10 ℃ 가 넘지 않도록 아이스배쓰를 이용하여 반응기 온도를 유지하면서 첨가한다. 첨가 완료 후, 약 1 시간 동안 교반 숙성하면서 반응을 완료시킨다.In a 500 mL reactor, add 100 g of DETA and keep it below 0 ° C. 212 g of hydroxymethyldiethylphosphonate (DEP-OH) are added to the reaction mixture while maintaining the reactor temperature using an ice bath so as not to exceed 10 ° C. After completion of the addition, the reaction is completed while stirring and aging for about 1 hour.
반응이 완료된 것은 TLC 를 통해 DEP-OH 가 사라진 것을 확인함으로써 알 수 있다. 반응이 완결되면 반응으로 생성된 물을 감압 농축하여 제거한다. 생성된 화합물은 284 g 으로, 97% 의 수율로서 수득하였다.The reaction was completed by confirming the disappearance of DEP-OH via TLC. When the reaction is completed, the water produced by the reaction is concentrated under reduced pressure to remove it. The resulting compound was 284 g, 97% yield.
[실시예 7] 경화제의 제조 7[Example 7] Production of curing agent 7
500 mL 반응기에 N-아미노에틸피페라진 (N-aminoethylpiperazine;NAEP) 100 g 을 넣고 0 ℃ 이하로 유지한다. 하이드록시메틸디에틸포스포네이트 (DEP-OH) 130 g 을, 40 ℃ 가 넘지 않도록 아이스배쓰를 이용하여 반응기 온도를 유지하면서 첨가한다. 첨가 완료 후, 약 1 시간 동안 교반 숙성하면서 반응을 완료시킨다.Add 100 g of N-aminoethylpiperazine (NAEP) to a 500 mL reactor and keep it below 0 ° C. 130 g of hydroxymethyl diethylphosphonate (DEP-OH) was added at an excess of 40 C using an ice bath while maintaining the reactor temperature. After completion of the addition, the reaction is completed while stirring and aging for about 1 hour.
반응이 완료된 것은 TLC 를 통해 DEP-OH 가 사라진 것을 확인함으로써 알 수 있다. 반응이 완결되면 반응으로 생성된 물을 제거하기 위하여 톨루엔 50 g 을 투입하여 진공하에 공비화합물로 제거한다. 생성된 화합물은 207 g 으로, 95% 의 수율로서 수득하였다.The reaction was completed by confirming the disappearance of DEP-OH via TLC. When the reaction is complete, 50 g of toluene is added to remove the water generated by the reaction, and the reaction mixture is removed with an azeotropic compound under vacuum. The resulting compound was obtained in a yield of 95% at 207 g.
[실시예 8] 경화제의 제조 8[Example 8] Production of curing agent 8
500 mL 반응기에 NAEP (N-aminoethylpiperazine) 100 g 과 디에틸포스파이트 107 g 을 넣은 후 30 ∼ 40 ℃ 로 승온한다. 이후 아세톤 50 g 을 적가한다. 적가시 반응 온도는 50 ∼ 60 ℃ 이하로 유지한다. 적가가 완료되면 50 ∼ 60 ℃ 를 유지하면서 추가로 3 ∼ 4 시간 동안 교반한다. 교반 후 디에틸포스파이트가 TLC상 완전히 사라지면 반응을 종료한다. 반응이 종결되면 반응에서 생긴 물을 톨루엔 70 g 을 넣고 공비하여 제거한다. 생성된 화합물은 231 g 으로, 97% 의 수율로서 수득하였다.100 g of NAEP (N-aminoethylpiperazine) and 107 g of diethylphosphite are placed in a 500 mL reactor, and the temperature is raised to 30 to 40 ° C. Then, 50 g of acetone is added dropwise. The desired visible reaction temperature is maintained at 50 to 60 ° C or lower. When the dropwise addition is completed, the mixture is further stirred for 3 to 4 hours while maintaining the temperature at 50 to 60 ° C. After stirring, the reaction is terminated when the diethylphosphite completely disappears on the TLC. When the reaction is completed, 70 g of toluene is added to the water produced in the reaction and the mixture is azeotropically removed. The resulting compound was obtained in 231 g, 97% yield.
이제까지 본 발명에 대하여 그 바람직한 실시예들을 중심으로 살펴보았다. 본 발명이 속하는 기술 분야에서 통상의 지식을 가진 자는 본 발명이 본 발명의 본질적인 특성에서 벗어나지 않는 범위에서 변형된 형태로 구현될 수 있음을 이해할 수 있을 것이다. 그러므로 개시된 실시예들은 한정적인 관점이 아니라 설명적인 관점에서 고려되어야 한다. 본 발명의 범위는 전술한 설명이 아니라 특허청구범위에 나타나 있으며, 그와 동등한 범위 내에 있는 모든 차이점은 본 발명에 포함된 것으로 해석되어야 할 것이다. The present invention has been described with reference to the preferred embodiments. It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims. Therefore, the disclosed embodiments should be considered in an illustrative rather than a restrictive sense. The scope of the present invention is defined by the appended claims rather than by the foregoing description, and all differences within the scope of equivalents thereof should be construed as being included in the present invention.
Claims (23)
[화학식 1]
(식 중, R1 및 R2 는 각각 독립적으로, 1 내지 8 개의 탄소수를 가진 알킬기 또는 6 내지 12 개의 탄소수를 가진 아릴기이고;
R3 은 1 내지 10 개의 탄소수를 가진 알킬아민기 또는 6 내지 10 개의 탄소수를 가진 아릴아민기이며, R3 에는 2 개 내지 10 개의 아민이 포함되고, 상기 2 개 내지 10 개의 아민 중 적어도 1 개 내지 3 개의 아민은 말단에 위치하고;
R4 및 R5 는 각각 독립적으로, 수소, 1 내지 8 개의 탄소수를 가진 알킬기, 또는 6 내지 12 개의 탄소수를 가진 아릴기이고;
n 은 0 초과 3 이하의 범위를 갖는다.)An organophosphorus flame retardant curing agent represented by the following formula (1)
[Chemical Formula 1]
(Wherein R 1 and R 2 are each independently an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 12 carbon atoms;
R 3 is an alkylamine group having 1 to 10 carbon atoms or an arylamine group having 6 to 10 carbon atoms, R 3 contains 2 to 10 amines and at least one of the 2 to 10 amines To three amines are located at the ends;
R 4 and R 5 are each independently hydrogen, an alkyl group having 1 to 8 carbon atoms, or an aryl group having 6 to 12 carbon atoms;
n ranges from more than 0 to less than 3).
상기 아민계 화합물은, 에틸렌 디아민 (ethylenediamine, EDA), 디에틸렌트리아민 (diethylenetriamine, DETA), 트리에틸렌테트라아민 (triethylenetetraamine, TETA), 테트라에틸렌펜타민 (tetraethylenepentamine, TEPA), 디프로펜디아민 (diprophenediaming, DPDA), 아미노에틸피페라진(N-aminoethylpiperazine, AEP), 이소포론디아민(Isophorone diamine, IPDA), 헥사메틸렌디아민 (hexamethylenediamine, HMDA), m-크실렌디아민 (m-xylenediamine, MXDA), 라미론 C-260 (Lamiron C-260), 아랄다이트 HY-964 (araldite HY-964), 메탄디아민 (methanediamine), sho-amine, m-페닐렌디아민 (m-phenylenediamine), 디아미노디페닐메탄 (diaminodiphenylmethane, DDM), 디아미노디페닐설폰 (diaminodiphenylsulfone, DDS) 및 JEFFAMINE® D-230 폴리에테르아민 (polyetheramine) 으로 이루어진 군으로부터 선택되는 것을 특징으로 하는 유기 인계 난연성 경화제.5. The method according to any one of claims 1 to 4,
The amine compound may be selected from the group consisting of ethylenediamine (EDA), diethylenetriamine (DETA), triethylenetetraamine (TETA), tetraethylenepentamine (TEPA), diprophenediamine , DPDA), N-aminoethylpiperazine (AEP), isophorone diamine (IPDA), hexamethylenediamine (HMDA), m-xylenediamine (MXDA), lamellone C (HY-964), methanediamine, sho-amine, m-phenylenediamine, diaminodiphenylmethane , DDM), diaminodiphenyl sulfone (diaminodiphenylsulfone, DDS) and JEFFAMINE ® D-230 polyether amine (an organic phosphorus flame retardant curing agent, characterized in that the polyetheramine) selected from the group consisting of.
상기 인계 화합물은, 디메틸포스파이트, 디에틸포스파이트, 디이소프로필포스파이트, 디부틸포스파이트 및 디페닐포스파이트로 이루어진 군으로부터 선택되는 것을 특징으로 하는 유기 인계 난연성 경화제.The method of claim 1, 3, or 4,
Wherein said phosphorus compound is selected from the group consisting of dimethyl phosphite, diethyl phosphite, diisopropyl phosphite, dibutyl phosphite, and diphenyl phosphite.
상기 인계 화합물은, 하이드록시메틸디에틸포스포네이트 (hydroxymethyldiethylphosphonate), 하이드록시메틸디메틸포스포네이트 (hydroxymethyldimethylphosphonate), 하이드록시메틸디이소프로필포스포네이트 (hydroxymethyldiisopropylphosphonate), 하이드록시메틸디부틸포스포네이트 (hydroxymethyldibutylphosphonate) 및 하이드록시메틸디페닐포스포네이트 (hydroxymethyldiphenylphosphonate) 로 이루어진 군으로부터 선택되는 것을 특징으로 하는 유기 인계 난연성 경화제.3. The method of claim 2,
The phosphorus compound may be at least one selected from the group consisting of hydroxymethyldiethylphosphonate, hydroxymethyldimethylphosphonate, hydroxymethyldiisopropylphosphonate, hydroxymethyldibutylphosphonate hydroxymethyldibutylphosphonate, hydroxymethyldibutylphosphonate, and hydroxymethyldiphenylphosphonate. < RTI ID = 0.0 > 11. < / RTI >
상기 케톤계 화합물은 아세톤인 것을 특징으로 하는 유기 인계 난연성 경화제.The method according to claim 3 or 4,
Wherein the ketone-based compound is acetone.
ⅱ) 상기 반응 후 생성된 물을 제거하고 인계 화합물을 혼합하여 반응시키는 단계를 포함하는 유기 인계 난연성 경화제의 제조 방법.I) mixing the amine compound with formalin or formaldehyde to react; And
Ii) removing water generated after the reaction and mixing phosphorus compounds to react them.
ⅱ) 상기 혼합물과 케톤계 화합물을 반응시키는 단계를 포함하는 유기 인계 난연성 경화제의 제조 방법.I) mixing an amine compound and a phosphorus compound; And
Ii) reacting the mixture with a ketone-based compound to produce an organic phosphorus-based flame-retardant curing agent.
ⅱ) 상기 반응 결과물과 인계 화합물을 반응시키는 단계를 포함하는 유기 인계 난연성 경화제의 제조 방법.I) reacting an amine compound with a ketone compound; And
Ii) reacting the reaction product with a phosphorus compound to produce an organophosphorus flame retardant curing agent.
상기 아민계 화합물은, 에틸렌 디아민 (ethylenediamine, EDA), 디에틸렌트리아민 (diethylenetriamine, DETA), 트리에틸렌테트라아민 (triethylenetetraamine, TETA), 테트라에틸렌펜타민 (tetraethylenepentamine, TEPA), 디프로펜디아민 (diprophenediaming, DPDA), 아미노에틸피페라진(N-aminoethylpiperazine, AEP), 이소포론디아민(Isophorone diamine, IPDA), 헥사메틸렌디아민 (hexamethylenediamine, HMDA), m-크실렌디아민 (m-xylenediamine, MXDA), 라미론 C-260 (Lamiron C-260), 아랄다이트 HY-964 (araldite HY-964), 메탄디아민 (methanediamine), sho-amine, m-페닐렌디아민 (m-phenylenediamine), 디아미노디페닐메탄 (diaminodiphenylmethane, DDM), 디아미노디페닐설폰 (diaminodiphenylsulfone, DDS) 및 JEFFAMINE® D-230 폴리에테르아민 (polyetheramine) 으로 이루어진 군으로부터 선택되는 것을 특징으로 하는 방법.14. The method according to any one of claims 10 to 13,
The amine compound may be selected from the group consisting of ethylenediamine (EDA), diethylenetriamine (DETA), triethylenetetraamine (TETA), tetraethylenepentamine (TEPA), diprophenediamine , DPDA), N-aminoethylpiperazine (AEP), isophorone diamine (IPDA), hexamethylenediamine (HMDA), m-xylenediamine (MXDA), lamellone C (HY-964), methanediamine, sho-amine, m-phenylenediamine, diaminodiphenylmethane , DDM), diaminodiphenyl sulfone (diaminodiphenylsulfone, DDS) and JEFFAMINE ® D-230 polyether amine (characterized in that the polyetheramine) selected from the group consisting of.
상기 인계 화합물은, 디메틸포스파이트, 디에틸포스파이트, 디이소프로필포스파이트, 디부틸포스파이트 및 디페닐포스파이트로 이루어진 군으로부터 선택되는 것을 특징으로 하는 방법.14. The method according to claim 10, 12 or 13,
Wherein said phosphorus compound is selected from the group consisting of dimethyl phosphite, diethyl phosphite, diisopropyl phosphite, dibutyl phosphite and diphenyl phosphite.
상기 인계 화합물은, 하이드록시메틸디에틸포스포네이트, 하이드록시메틸디메틸포스포네이트, 하이드록시메틸디이소프로필포스포네이트, 하이드록시메틸디부틸포스포네이트 및 하이드록시메틸디페닐포스포네이트로 이루어진 군으로부터 선택되는 것을 특징으로 하는 방법.12. The method of claim 11,
The phosphorus compound may be at least one selected from the group consisting of hydroxymethyl diethyl phosphonate, hydroxymethyl dimethyl phosphonate, hydroxymethyl diisopropyl phosphonate, hydroxymethyl dibutyl phosphonate, and hydroxymethyl diphenyl phosphonate ≪ / RTI >
상기 ⅰ) 단계의 포르말린 또는 포름알데히드는 아민계 화합물 1 당량 당 0.5 내지 3 당량으로 혼합되는 것을 특징으로 하는 방법.11. The method of claim 10,
Characterized in that the formalin or formaldehyde of step (i) is mixed in an amount of 0.5 to 3 equivalents per equivalent of the amine compound.
상기 ⅱ) 단계에서의 인계 화합물은 아민계 화합물 1 당량 당 0.5 내지 3 당량으로 혼합되는 것을 특징으로 하는 방법.11. The method of claim 10,
Wherein the phosphorus compound in step ii) is mixed in an amount of 0.5 to 3 equivalents per equivalent of the amine compound.
상기 인계 화합물은 아민계 화합물 1 당량 당 0.5 내지 3 당량으로 혼합되는 것을 특징으로 하는 방법.12. The method of claim 11,
Wherein the phosphorus compound is mixed at 0.5 to 3 equivalents per equivalent of the amine compound.
상기 케톤계 화합물은 아세톤인 것을 특징으로 하는 방법.The method according to claim 12 or 13,
Wherein the ketone-based compound is acetone.
상기 케톤계 화합물은 아민계 화합물 1 당량 당 0.5 내지 3 당량으로 혼합되는 것을 특징으로 하는 방법.The method according to claim 12 or 13,
Wherein the ketone compound is mixed at 0.5 to 3 equivalents per equivalent of the amine compound.
상기 인계 화합물은 아민계 화합물 1 당량 당 0.5 내지 3 당량으로 혼합되는 것을 특징으로 하는 방법.The method according to claim 12 or 13,
Wherein the phosphorus compound is mixed at 0.5 to 3 equivalents per equivalent of the amine compound.
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CN114163647A (en) * | 2021-12-17 | 2022-03-11 | 厦门大学 | Biomass polybenzimidazole epoxy flame-retardant curing agent and preparation method and application thereof |
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CN112442167A (en) * | 2019-08-28 | 2021-03-05 | 广东广山新材料股份有限公司 | Reactive flame retardant and preparation method and application thereof |
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