CN112442079A - 一种含磷的反应型阻燃剂环氧树脂组合物、覆铜板及阻燃剂的制备方法 - Google Patents
一种含磷的反应型阻燃剂环氧树脂组合物、覆铜板及阻燃剂的制备方法 Download PDFInfo
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- CN112442079A CN112442079A CN201910804293.1A CN201910804293A CN112442079A CN 112442079 A CN112442079 A CN 112442079A CN 201910804293 A CN201910804293 A CN 201910804293A CN 112442079 A CN112442079 A CN 112442079A
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- flame retardant
- phosphorus
- reactive
- epoxy resin
- reactive flame
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 89
- 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 82
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 54
- 239000011574 phosphorus Substances 0.000 title claims abstract description 54
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 16
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 16
- 239000000203 mixture Substances 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title abstract description 20
- 150000001875 compounds Chemical class 0.000 claims abstract description 21
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000007259 addition reaction Methods 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 11
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 239000004841 bisphenol A epoxy resin Substances 0.000 claims description 4
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 4
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 3
- 125000001072 heteroaryl group Chemical group 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000004104 aryloxy group Chemical group 0.000 claims description 2
- 125000001589 carboacyl group Chemical group 0.000 claims description 2
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 2
- 125000004434 sulfur atom Chemical group 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 10
- 239000002131 composite material Substances 0.000 abstract description 9
- 230000000704 physical effect Effects 0.000 abstract description 6
- 125000003277 amino group Chemical group 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 2
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- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- 238000003756 stirring Methods 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 238000005160 1H NMR spectroscopy Methods 0.000 description 7
- 238000003760 magnetic stirring Methods 0.000 description 7
- 238000010992 reflux Methods 0.000 description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- 239000012074 organic phase Substances 0.000 description 6
- 238000010791 quenching Methods 0.000 description 6
- 230000000171 quenching effect Effects 0.000 description 6
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- -1 alcohol amine Chemical class 0.000 description 5
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- 230000000996 additive effect Effects 0.000 description 4
- 238000006757 chemical reactions by type Methods 0.000 description 4
- CZHYKKAKFWLGJO-UHFFFAOYSA-N dimethyl phosphite Chemical compound COP([O-])OC CZHYKKAKFWLGJO-UHFFFAOYSA-N 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000006467 substitution reaction Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 125000004093 cyano group Chemical group *C#N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 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 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000006683 Mannich reaction Methods 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 229920005830 Polyurethane Foam Polymers 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 2
- LXCYSACZTOKNNS-UHFFFAOYSA-N diethoxy(oxo)phosphanium Chemical compound CCO[P+](=O)OCC LXCYSACZTOKNNS-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
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 2
- 239000011496 polyurethane foam Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 125000000547 substituted alkyl group Chemical group 0.000 description 2
- 125000003107 substituted aryl group Chemical group 0.000 description 2
- WJKHJLXJJJATHN-UHFFFAOYSA-N triflic anhydride Chemical compound FC(F)(F)S(=O)(=O)OS(=O)(=O)C(F)(F)F WJKHJLXJJJATHN-UHFFFAOYSA-N 0.000 description 2
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 2
- 229940008841 1,6-hexamethylene diisocyanate Drugs 0.000 description 1
- XIRDTMSOGDWMOX-UHFFFAOYSA-N 3,4,5,6-tetrabromophthalic acid Chemical group OC(=O)C1=C(Br)C(Br)=C(Br)C(Br)=C1C(O)=O XIRDTMSOGDWMOX-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- UNJUEMDTKUZHPU-UHFFFAOYSA-N N=C=O.CC(C)C1=CC=CC(C(C)C)=C1 Chemical compound N=C=O.CC(C)C1=CC=CC(C(C)C)=C1 UNJUEMDTKUZHPU-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- QHWKHLYUUZGSCW-UHFFFAOYSA-N Tetrabromophthalic anhydride Chemical compound BrC1=C(Br)C(Br)=C2C(=O)OC(=O)C2=C1Br QHWKHLYUUZGSCW-UHFFFAOYSA-N 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- ZTOMUSMDRMJOTH-UHFFFAOYSA-N glutaronitrile Chemical compound N#CCCCC#N ZTOMUSMDRMJOTH-UHFFFAOYSA-N 0.000 description 1
- UBIJTWDKTYCPMQ-UHFFFAOYSA-N hexachlorophosphazene Chemical compound ClP1(Cl)=NP(Cl)(Cl)=NP(Cl)(Cl)=N1 UBIJTWDKTYCPMQ-UHFFFAOYSA-N 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 239000012433 hydrogen halide Substances 0.000 description 1
- 229910000039 hydrogen halide Inorganic materials 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical group CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 description 1
- HNHVTXYLRVGMHD-UHFFFAOYSA-N n-butyl isocyanate Chemical compound CCCCN=C=O HNHVTXYLRVGMHD-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- SUSQOBVLVYHIEX-UHFFFAOYSA-N phenylacetonitrile Chemical compound N#CCC1=CC=CC=C1 SUSQOBVLVYHIEX-UHFFFAOYSA-N 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 125000003003 spiro group Chemical group 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
Classifications
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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
- C07F9/547—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)
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- 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
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/40—Esters thereof
- C07F9/4003—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
- C07F9/4006—Esters of acyclic acids which can have further substituents on alkyl
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- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/40—Esters thereof
- C07F9/4003—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
- C07F9/4006—Esters of acyclic acids which can have further substituents on alkyl
- C07F9/4009—Esters containing the structure (RX)2P(=X)-alk-N...P (X = O, S, Se)
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- 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
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/40—Esters thereof
- C07F9/4071—Esters thereof the ester moiety containing a substituent or a structure which is considered as characteristic
- C07F9/4075—Esters with hydroxyalkyl compounds
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- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/40—Esters thereof
- C07F9/4071—Esters thereof the ester moiety containing a substituent or a structure which is considered as characteristic
- C07F9/4087—Esters with arylalkanols
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- 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
- C08G59/44—Amides
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- 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
- C08G59/504—Amines containing an atom other than nitrogen belonging to the amine group, carbon and hydrogen
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Abstract
本发明提供了一种含磷的反应型阻燃剂环氧树脂组合物、覆铜板及阻燃剂的制备方法,所述含磷的反应型阻燃剂由带有‑P‑H反应基团的化合物与含有碳氮不饱和键的化合物通过加成反应得到;本发明提供的含磷的反应型阻燃剂结构新颖,应用范围广,结构中含有活性氨基,能够参与到复合材料的反应中,使得复合材料的稳定性增强,阻燃性提高,并且不会受到水等因素的影响,同时具有良好的物理性能和强度,应用前景良好。
Description
技术领域
本发明属于阻燃剂领域,涉及一种含磷的反应型阻燃剂环氧树脂组合物、覆铜板及阻燃剂的制备方法。
背景技术
聚氨酯材料所用的阻燃剂分为添加型阻燃剂和反应型阻燃剂两大类。添加型阻燃剂因为良好的阻燃效果和相对简单的生产工艺已被大量应用于聚氨酯阻燃的实际生产中,但其添加量较大、易析出和产品性能下降等问题制约其进一步的应用。反应型阻燃剂因在聚氨酯原料异氰酸酯和聚醚多元醇中引入磷等阻燃元素,使聚氨酯复合材料具有较好的阻燃性能和力学性能。
CN103694434A公开了一种用于聚氨酯泡沫的无卤反应型阻燃剂及其制备方法和应用,无卤反应型阻燃剂,由9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物(DOPO),醇胺和甲醛反应通过Mannich反应制得,结构式为无卤反应型阻燃剂采用Mannich反应把醇胺和甲醛引入到DOPO阻燃剂结构中,降低了阻燃剂的成本,合成的无卤反应型阻燃剂含有活性羟基及阻燃氮、磷元素,并含有伯胺或者叔胺,反应活性较高,刚性苯环用于阻燃型聚氨酯泡沫,具有较高的阻燃性,并增加泡沫的强度和阻燃持久性,氧指数可以达到23~28%。在建筑、保温及一些特殊的场合具有广泛的应用前景。但是此方法合成收率较低,经济效益较差。
CN105646813A公开了一种应用于聚氨酯材料的反应型阻燃剂及其制备方法。所述阻燃剂为含有溴、磷和氮三种阻燃元素的四溴邻苯二甲酸(2-羟乙基膦酸二乙酯亚甲基)胺基单-2-乙酯,具体制备步骤为,首先向反应容器中加入反应物四溴苯酐、N,N-二(2-羟乙基)氨基亚甲基膦酸二乙酯和溶剂;搅拌至四溴苯酐完全溶解,在搅拌条件下升温至60-120℃,反应2-12小时,合成TBPAHM;反应结束后,降温至50℃以下,过滤,蒸馏回收溶剂,得到粘稠状的TBPAHM。这种方法提供的阻燃剂含有卤素,影响其性能。
CN105061511A公开了一种桥连环磷腈反应型阻燃剂及其制备方法,以六氯环三磷腈为原料,通过刚性结构将两个磷腈环桥连,再通过与苯胺发生取代反应而获得。两种新型阻燃剂具有高刚性、大空间位阻、多活性点、磷氮元素的含量高等特点,并且具有极好的热稳定性,可作为反应型阻燃剂应用于环氧树脂中,由于不含卤素,燃烧时不会释放出卤化氢等有毒气体,符合当前阻燃剂绿色环保的发展趋势。但是此方法制备过程较为复杂,收率较低,不利于大规模生产应用。
目前,现有的含磷的反应型阻燃剂都存在制备过程较为复杂、物理性能、稳定性和阻燃性偏低的问题,如何开发一种新型的反应型阻燃剂对于应用具有重要的意义。
发明内容
针对现有技术的不足,本发明的目的在于提供一种含磷的反应型阻燃剂环氧树脂组合物、覆铜板及阻燃剂的制备方法,以解决现有的含磷阻燃剂制备过程复杂,收率较低且阻燃性、稳定性较差的问题。
为达此目的,本发明采用以下技术方案:
第一方面,本发明提供了一种含磷的反应型阻燃剂,所述含磷的反应型阻燃剂由带有-P-H反应基团的化合物与含有碳氮不饱和键的化合物通过加成反应得到。
本发明提供的含磷的反应型阻燃剂结构新颖,应用范围广。结构中含有活性氨基,能够参与到复合材料的反应中,使得复合材料的稳定性增强,阻燃性提高,并且不会受到水等因素的影响,同时具有良好的物理性能和强度,应用前景良好。
优选地,所述带有-P-H反应基团的化合物具有如式I所示结构:
其中,所述X为VI主族元素或不存在,L1、L2各自独立地优选为烷基、环烷基、芳基、杂芳基、烷氧基、烷基酰基或芳基氧基,或L1和L2连接成环。
优选地,所述X为氧原子或硫原子,进一步优选氧原子。
优选地,所述L1、L2各自独立地优选为C1-C5的烷氧基、C6-C9的芳基或C6-C9的芳基氧基,或L1和L2连接成环。
其中,C1-C5可以是C1、C2、C3、C4或C5等,C6-C9可以是C6、C7、C8或C9等。
示例性地,带有-P-H反应基团的化合物可以是9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物(DOPO)、亚磷酸二甲酯、亚磷酸二乙酯或亚磷酸二苯酯等等。
优选地,所述含有碳氮不饱和键的化合物为含有异氰酸酯基的化合物和/或含有氰基的化合物。
在本发明中,所述烷基可以是直链烷基、也可以是带有支链的烷基,可以是环状的、螺环的等等结构。本发明所述芳基可以是苯、萘、蒽、菲等等结构的芳香族化合物,杂芳基指的是含有硫、氮、氧的原子的具有芳香性的化合物。
本发明所述取代指的是通过任意的取代基将烷基或芳基等基团进行取代,其中取代基可以是羟基、氨基、羧基、氰基等等本领域技术人员所熟知的官能团。
第二方面,本发明提供了一种如第一方面所述的含磷的反应型阻燃剂的制备方法,所述制备方法为将带有-P-H反应基团的化合物与含有碳氮不饱和键的化合物发生加成反应得到所述含磷的反应型阻燃剂。
第三方面,本发明提供了一种环氧树脂组合物,所述环氧树脂组合按重量份计包括以下组分:第一方面所述的含磷的反应型阻燃剂20~40份,双酚A型环氧树脂80~120份,2-甲基咪唑0.2~1份。
第四方面,本发明提供了一种覆铜板,所述覆铜板包括如第三方面所述的环氧树脂组合物。
相对于现有技术,本发明具有以下有益效果:
本发明提供的含磷的反应型阻燃剂结构新颖,应用范围广。结构中含有活性氨基,能够参与到复合材料的反应中,使得复合材料的稳定性增强,阻燃性提高,并且不会受到水等因素的影响,同时具有良好的物理性能和强度,避免了现有的阻燃剂的析出现象,应用前景良好,适于工业化生产。
具体实施方式
下面通过具体实施方式来进一步说明本发明的技术方案。本领域技术人员应该明了,所述实施例仅仅是帮助理解本发明,不应视为对本发明的具体限制。
实施例1
本实施例提供一种含磷的反应型阻燃剂,结构如下:
制备方法:
在配有磁力搅拌、温度计的三口烧瓶中加入4mol亚磷酸二甲酯和1mol的戊二腈以及50mL乙醇,搅拌下,冰水浴控制温度在5℃以下,滴加2mol三氟甲磺酸酐,逐渐升温回流,继续反应1h,减压蒸馏得到上述结构的反应型阻燃剂。
1H NMR(400MHz,DMSO-d6)δ3.42(d,J=10.8Hz,24H),2.61(s,4H),1.82(t,J=7.8Hz,4H),1.28(p,J=7.8Hz,2H).
实施例2
本实施例提供一种含磷的反应型阻燃剂,结构如下:
制备方法:
在配有磁力搅拌、温度计的三口烧瓶中加入2mol的DOPO和1mol的2,4-甲苯二异氰酸酯以及100mL甲苯,搅拌下,滴加2mol四氯化钛,回流反应6h,盐酸淬灭反应,水洗后有机相后,蒸干溶剂得到含磷的反应型阻燃剂。
1H NMR(400MHz,DMSO-d6)δ13.87(s,1H),9.46(s,1H),8.04–7.14(m,20H),2.20(d,J=1.0Hz,3H).
实施例3
本实施例提供一种含磷的反应型阻燃剂,结构如下:
制备方法:
在配有磁力搅拌、温度计的三口烧瓶中加入1mol的亚磷酸二甲酯和1mol的2,6-二异丙基苯异氰酸酯以及200mL甲苯,搅拌下,滴加1mol四氯化钛,回流反应4h,盐酸淬灭反应,水洗后有机相后,蒸干溶剂得到含磷的反应型阻燃剂。
1H NMR(400MHz,DMSO-d6)δ7.28–7.07(m,3H),3.78(d,J=10.9Hz,6H),2.80(m,2H),1.10(d,J=6.8Hz,12H).
实施例4
本实施例提供一种含磷的反应型阻燃剂,结构如下:
制备方法:
在配有磁力搅拌、温度计的三口烧瓶中加入2mol的DOPO和1mol的1,6-己二异氰酸酯以及200mL甲苯,搅拌下,滴加1mol四氯化钛,回流反应3h,盐酸淬灭反应,水洗后有机相后,蒸干溶剂得到含磷的反应型阻燃剂。
1H NMR(400MHz,DMSO-d6)δ9.77(s,1H),8.04–7.16(m,17H),3.06(t,J=7.4Hz,4H),1.63–1.52(m,4H),1.44–1.34(m,4H).
实施例5
本实施例提供一种含磷的反应型阻燃剂,结构如下:
制备方法:
在配有磁力搅拌、温度计的三口烧瓶中加入1mol的亚磷酸二甲酯和1mol的正丁基异氰酸酯以及100mL甲苯,搅拌下,滴加1mol四氯化钛,回流反应2h,盐酸淬灭反应,水洗后有机相后,蒸干溶剂得到含磷的反应型阻燃剂。
1H NMR(400MHz,DMSO-d6)δ8.54(s,1H),3.78(d,J=10.9Hz,6H),3.06(t,J=7.6Hz,2H),1.48(p,J=7.7Hz,2H),1.35–1.22(m,2H),0.88(t,J=6.5Hz,3H).
实施例6
本实施例提供一种含磷的反应型阻燃剂,结构如下:
制备方法:
在配有磁力搅拌、温度计的三口烧瓶中加入2mol的亚磷酸二苯酯和1mol的2,6-甲苯二异氰酸酯以及250mL甲苯,搅拌下,滴加2mol四氯化钛,回流反应2h,盐酸淬灭反应,水洗后有机相后,蒸干溶剂得到含磷的反应型阻燃剂。
1H NMR(400MHz,DMSO-d6)δ10.99(s,1H),10.85(s,1H),7.76(d,J=7.6Hz,2H),7.44–7.12(m,22H),2.33(s,3H).
实施例7
本实施例提供一种含磷的反应型阻燃剂,结构如下:
制备方法:
在配有磁力搅拌、温度计的三口烧瓶中加入2mol的亚磷酸二乙酯和1mol的苯乙腈以及250mL甲苯,搅拌下,滴加2mol四氯化钛,回流反应2h,盐酸淬灭反应,水洗后有机相后,蒸干溶剂得到含磷的反应型阻燃剂。
1H NMR(400MHz,DMSO-d6)δ7.40–7.15(m,5H),3.98(dp,J=12.5,8.1Hz,4H),3.73–3.60(m,4H),3.21(s,2H),2.60(s,2H),1.36(t,J=8.0Hz,12H).
将实施例1-7中提供的含磷的反应型阻燃剂应用到环氧树脂组合物中,分别对应于环氧树脂组合物1-7,具体包括以下组分:含磷的反应型阻燃剂30份,双酚A型环氧树脂100份,2-甲基咪唑1份,如果含磷的反应型阻燃剂固化效果不足,使用双氰胺补足。
对比例1
本对比例与上述环氧树脂组合物的区别在于,将含磷的反应型阻燃剂完全替换为双氰胺固化剂。
对比例2
本对比例与对比例1的区别在于,添加阻燃剂磷酸三苯酯30份。
对比例3
本对比例与对比例1的区别在于,添加阻燃剂磷酸三苯酯45份。
性能测试
将环氧树脂组合物1-7和对比例1-3提供的环氧树脂组合物按照公知的常规方法制备得到覆铜板,进行如下测试:
(1)Tg:差示扫描量热法(DSC),按照IPC-TM-650中2.4.25所规定的DSC方法进行测定;
(2)层间剥离强度PS:按照IPC-TM-650 2.4.8方法中“热应力后”实验条件,测试板材的剥离强度;
(3)介电常数(Dk)和介电损耗因子(Df):采用SPDR法,在10GHz频率下,测试板材的介电常数Dk和介电损耗Df;
(5)燃烧性:按照UL-94垂直燃烧测试标准进行测试;
(6)阻燃稳定性:将覆铜板在水中浸泡1h后,干燥再次测量其燃烧性;
(7)迁移性:将覆铜板在150℃下烘烤2h,测试烘烤前后的重量差百分比。
测试结果见表1:
表1
由上述表1中的结果可知,采用本发明提供的含磷的反应型阻燃剂制备得到的覆铜板的性能较优异,其中,玻璃化转变温度在173℃以上,剥离强度在0.75N/mm以上,介电常数在3.66(10GHz)以下,介电损耗在0.0078(10GHz)以下。
与对比例的对比可知,采用添加型阻燃剂,会影响覆铜板的稳定性和物理性能,而且阻燃性也有所下降,而本发明提供的含磷的反应型阻燃剂阻燃性好的同时阻燃稳定性优异。
由本发明提供的实施例之间的化合物对比可知,不同结构的化合物表现出不同的物理性能和稳定性,但都具有良好的阻燃性。
申请人声明,本发明通过上述实施例来说明本发明的含磷的反应型阻燃剂环氧树脂组合物、覆铜板及阻燃剂的制备方法,但本发明并不局限于上述详细方法,即不意味着本发明必须依赖上述详细方法才能实施。所属技术领域的技术人员应该明了,对本发明的任何改进,对本发明产品各原料的等效替换及辅助成分的添加、具体方式的选择等,均落在本发明的保护范围和公开范围之内。
Claims (9)
1.一种含磷的反应型阻燃剂,其特征在于,所述含磷的反应型阻燃剂由带有-P-H反应基团的化合物与含有碳氮不饱和键的化合物通过加成反应得到。
3.根据权利要求2所述的含磷的反应型阻燃剂,其特征在于,所述X优选为氧原子或硫原子,进一步优选为氧原子。
4.根据权利要求2或3所述的含磷的反应型阻燃剂,其特征在于,所述L1、L2各自独立地优选为C1-C5的烷氧基、C6-C9的芳基或C6-C9的芳基氧基,或L1和L2连接成环。
7.根据权利要求1-6中任一项所述的含磷的反应型阻燃剂的制备方法,其特征在于,所述制备方法为将带有-P-H反应基团的化合物与含有碳氮不饱和键的化合物发生加成反应得到所述含磷的反应型阻燃剂。
8.一种环氧树脂组合物,其特征在于,所述环氧树脂组合按重量份计包括以下组分:权利要求1-6中任一项所述的含磷的反应型阻燃剂20~40份,双酚A型环氧树脂80~120份,2-甲基咪唑0.2~1份。
9.一种覆铜板,其特征在于,所述覆铜板包括如权利要求8所述的环氧树脂组合物。
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