CN107344975A - A kind of phosphazene compound containing polyacetylene, composition epoxy resin, plastic packaging material and composite metal substrate - Google Patents
A kind of phosphazene compound containing polyacetylene, composition epoxy resin, plastic packaging material and composite metal substrate Download PDFInfo
- Publication number
- CN107344975A CN107344975A CN201610293028.8A CN201610293028A CN107344975A CN 107344975 A CN107344975 A CN 107344975A CN 201610293028 A CN201610293028 A CN 201610293028A CN 107344975 A CN107344975 A CN 107344975A
- Authority
- CN
- China
- Prior art keywords
- unsubstituted
- substituted
- group
- phosphazene compound
- epoxy resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 45
- -1 phosphazene compound Chemical class 0.000 title claims abstract description 45
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 45
- 239000000203 mixture Substances 0.000 title claims abstract description 31
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 229920001197 polyacetylene Polymers 0.000 title claims abstract description 30
- 239000000758 substrate Substances 0.000 title claims abstract description 14
- 239000002131 composite material Substances 0.000 title claims abstract description 12
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 12
- 239000002184 metal Substances 0.000 title claims abstract description 12
- 239000005022 packaging material Substances 0.000 title claims abstract description 7
- 239000004033 plastic Substances 0.000 title claims abstract description 7
- 239000000463 material Substances 0.000 claims abstract description 25
- 125000001072 heteroaryl group Chemical group 0.000 claims description 17
- 125000001118 alkylidene group Chemical group 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
- 239000004411 aluminium Substances 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 8
- ZSTLPJLUQNQBDQ-UHFFFAOYSA-N azanylidyne(dihydroxy)-$l^{5}-phosphane Chemical compound OP(O)#N ZSTLPJLUQNQBDQ-UHFFFAOYSA-N 0.000 claims description 8
- 125000004437 phosphorous atom Chemical group 0.000 claims description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical group OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims description 6
- 125000003545 alkoxy group Chemical group 0.000 claims description 6
- 125000005587 carbonate group Chemical group 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 6
- 125000000000 cycloalkoxy group Chemical group 0.000 claims description 6
- 125000001424 substituent group Chemical group 0.000 claims description 6
- 238000006467 substitution reaction Methods 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 125000004104 aryloxy group Chemical group 0.000 claims description 5
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 claims description 5
- 239000011188 CEM-1 Substances 0.000 claims description 4
- 239000011190 CEM-3 Substances 0.000 claims description 4
- 101100257127 Caenorhabditis elegans sma-2 gene Proteins 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- 125000004171 alkoxy aryl group Chemical group 0.000 claims description 4
- 239000004020 conductor Substances 0.000 claims description 4
- 125000005114 heteroarylalkoxy group Chemical group 0.000 claims description 4
- 230000000269 nucleophilic effect Effects 0.000 claims description 4
- 229920002627 poly(phosphazenes) Polymers 0.000 claims description 3
- 229910000838 Al alloy Inorganic materials 0.000 claims description 2
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 2
- 229910000881 Cu alloy Inorganic materials 0.000 claims description 2
- 229910000640 Fe alloy Inorganic materials 0.000 claims description 2
- 239000004917 carbon fiber Substances 0.000 claims description 2
- 125000003262 carboxylic acid ester group Chemical group [H]C([H])([*:2])OC(=O)C([H])([H])[*:1] 0.000 claims description 2
- 239000000919 ceramic Substances 0.000 claims description 2
- 239000011152 fibreglass Substances 0.000 claims description 2
- 238000003754 machining Methods 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 2
- 125000000962 organic group Chemical group 0.000 claims description 2
- 229920000728 polyester Polymers 0.000 claims description 2
- 238000003825 pressing Methods 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims 1
- 125000002102 aryl alkyloxo group Chemical group 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
- 150000007942 carboxylates Chemical class 0.000 claims 1
- 150000003949 imides Chemical class 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000003063 flame retardant Substances 0.000 description 11
- 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 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 150000002118 epoxides Chemical class 0.000 description 7
- VOOLKNUJNPZAHE-UHFFFAOYSA-N formaldehyde;2-methylphenol Chemical compound O=C.CC1=CC=CC=C1O VOOLKNUJNPZAHE-UHFFFAOYSA-N 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 229910052736 halogen Inorganic materials 0.000 description 6
- 150000002367 halogens Chemical class 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 5
- DWSWCPPGLRSPIT-UHFFFAOYSA-N benzo[c][2,1]benzoxaphosphinin-6-ium 6-oxide Chemical compound C1=CC=C2[P+](=O)OC3=CC=CC=C3C2=C1 DWSWCPPGLRSPIT-UHFFFAOYSA-N 0.000 description 5
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- 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 description 4
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 4
- UXJHQBVRZUANLK-UHFFFAOYSA-N azanylidyne(dichloro)-$l^{5}-phosphane Chemical compound ClP(Cl)#N UXJHQBVRZUANLK-UHFFFAOYSA-N 0.000 description 4
- 239000000470 constituent Substances 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 150000001345 alkine derivatives Chemical class 0.000 description 3
- 125000002877 alkyl aryl group Chemical group 0.000 description 3
- 150000001555 benzenes Chemical group 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229940126062 Compound A Drugs 0.000 description 2
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- SMYKVLBUSSNXMV-UHFFFAOYSA-K aluminum;trihydroxide;hydrate Chemical compound O.[OH-].[OH-].[OH-].[Al+3] SMYKVLBUSSNXMV-UHFFFAOYSA-K 0.000 description 2
- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- 229940106691 bisphenol a Drugs 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- GPRDLRZMTVQCHM-UHFFFAOYSA-L magnesium;dihydroxide;hydrate Chemical compound O.[OH-].[OH-].[Mg+2] GPRDLRZMTVQCHM-UHFFFAOYSA-L 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 2
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- HGUFODBRKLSHSI-UHFFFAOYSA-N 2,3,7,8-tetrachloro-dibenzo-p-dioxin Chemical compound O1C2=CC(Cl)=C(Cl)C=C2OC2=C1C=C(Cl)C(Cl)=C2 HGUFODBRKLSHSI-UHFFFAOYSA-N 0.000 description 1
- BSYJHYLAMMJNRC-UHFFFAOYSA-N 2,4,4-trimethylpentan-2-ol Chemical compound CC(C)(C)CC(C)(C)O BSYJHYLAMMJNRC-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- 0 CC(C)[C@](C=C*)N(O)Oc1ccccc1 Chemical compound CC(C)[C@](C=C*)N(O)Oc1ccccc1 0.000 description 1
- BJUKPTQXHLYTCE-ARJAWSKDSA-N CC(C[O-]1)(C(/C=C\C=[IH])=[IH])[NH+]1Oc(cc1)ccc1NC1C=CC(O[NH+](C)[O-])=CC1 Chemical compound CC(C[O-]1)(C(/C=C\C=[IH])=[IH])[NH+]1Oc(cc1)ccc1NC1C=CC(O[NH+](C)[O-])=CC1 BJUKPTQXHLYTCE-ARJAWSKDSA-N 0.000 description 1
- KKZPDGTYKVSIMR-UHFFFAOYSA-N C[NH+]([O-])Oc1ccccc1 Chemical compound C[NH+]([O-])Oc1ccccc1 KKZPDGTYKVSIMR-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 238000004378 air conditioning Methods 0.000 description 1
- 125000005213 alkyl heteroaryl group Chemical group 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000002541 furyl group Chemical group 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 125000004446 heteroarylalkyl group Chemical group 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000000468 ketone group Chemical group 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 230000001473 noxious effect Effects 0.000 description 1
- 125000004043 oxo group Chemical group O=* 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- RDRCCJPEJDWSRJ-UHFFFAOYSA-N pyridine;1h-pyrrole Chemical class C=1C=CNC=1.C1=CC=NC=C1 RDRCCJPEJDWSRJ-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000013517 stratification Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/40—Introducing phosphorus atoms or phosphorus-containing groups
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
- B32B15/09—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyesters
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/14—Layered products comprising a layer of metal next to a fibrous or filamentary layer
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
- B32B9/04—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
-
- 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
- C07F9/6581—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 nitrogen atoms with or without oxygen or sulfur atoms, as ring hetero atoms
- C07F9/65812—Cyclic phosphazenes [P=N-]n, n>=3
- C07F9/65815—Cyclic phosphazenes [P=N-]n, n>=3 n = 3
-
- 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
- C08K5/5399—Phosphorus bound to nitrogen
-
- C—CHEMISTRY; METALLURGY
- 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
- C08L63/04—Epoxynovolacs
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
- B32B2262/10—Inorganic fibres
- B32B2262/101—Glass fibres
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Abstract
The invention provides a kind of phosphazene compound containing polyacetylene, composition epoxy resin, plastic packaging material and composite metal substrate, the phosphazene compound has the structure shown in Formulas I.The composite metal substrate being prepared by the composition epoxy resin containing the phosphazene compound has low-dielectric, good heat resistance, anti-flammability and mechanical performance, is a kind of material with larger economy and environmentally friendly friendly.
Description
Technical field
The present invention relates to the technical field of fire retardant matter, more particularly to a kind of phosphazene compound containing polyacetylene, epoxy
Resin combination, plastic packaging material and composite metal substrate.
Background technology
The family such as the electronic products such as mobile phone, computer, video camera, electronic game machine, air-conditioning, refrigerator, television image, sound equipment articles for use
With, office electric equipment products and the various products that use of other field, for safety, it is required for possessing different degrees of anti-flammability
Energy.
Traditional technology typically uses addition aluminium hydroxide hydrate, magnesium hydroxide hydrate etc. into material system to contain
The inorganic fire-retarded material such as the metal hydroxides of the crystallization water, and brominated bisphenol A, bmminated bisphenol-A type are added into material system
The method of the higher organic fire-resisting material of the content of halogen such as epoxy resin, product is set to reach required fire resistance or wait
Level.In order to improve the anti-flammability of these organic chemicals for containing halogen, such as antimony oxide is also usually added into system
Deng to the disagreeableness inorganic fire-retarded material of environment.
Halogen-containing fire retardant matter can produce the noxious material of no degradability or difficult degradation in burning, and (such as dioxin has
Machine halogen chemical substance), pollution environment, influence the mankind and animal health.
For the purpose of environmental protection, people replace chemical combination containing halogen using the not halogen-containing compound such as phosphorous, nitrogenous
Thing as fire retardant, particularly in electronics, electrically, on Electric Industrial, using the simple function with reactivity (in a molecule only
Have an active reactive group) flame-retardant composition, such as 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is (hereinafter referred to as
DOPO), it is more derivative compound using DOPO, addition or does not add aluminium hydroxide hydrate, magnesium hydroxide hydrate
To reach flame retardant effect.
In electronic applications, usually used DOPO and novolac type epoxy resin, o-cresol formaldehyde epoxy resin, bisphenol-A
The high cost such as phenol aldehyde type epoxy resin, the product (abbreviation DOPO epoxy resin) of polyfunctional epoxy resin reaction, as covering copper
The epoxide resin material of plate purposes.These use the copper-clad plate manufactured by DOPO epoxy resin, have good fire resistance, but
There is the defects of many in cohesiveness, heat resistance, processability etc., be not suitable for manufacturing high multilayer, the Gao Ke that modern communicationses need
By property, high cohesiveness, excellent machinability product.Simultaneously because cost is higher, it is unfavorable for spreading to the low costs such as mobile phone and disappears
The civil goods such as power-consuming son field.
With the further raising of people's multiple stratification, high reliability request short to electronic product, small, thin, high, civilian consumption
The factor such as the popularization of electronics and increasingly severeer pollution pressure, there is an urgent need to good anti-flammability, resistance in market
The copper-clad plate material of hot, good mechanical performance and dielectric properties.
The content of the invention
In view of this, first aspect present invention provides a kind of phosphazene compound containing polyacetylene, described to contain polyacetylene
Phosphazene compound there is structure shown in Formulas I：
In Formula II, R is any organic group for meeting its chemical environment；X be-O- ,-S-,
In any one, Y is any inertia nucleophilic group for meeting its chemical environment；M is the phosphonitrile base M of ring three1, the phosphonitrile of ring more than four
Base M2, non-annularity polyphosphazene base M3In one kind and its any combination；C is the integer more than or equal to 1, and d is whole more than or equal to zero
Number, and 2 times of number of phosphorus atoms on c+d=M groups, n is 10-200 integer.
Preferably, R is substituted or unsubstituted straight-chain alkyl-sub, substituted or unsubstituted branched alkylidene, substitution or not
Substituted arlydene, substituted or unsubstituted inferior heteroaryl, substituted or unsubstituted alkylenearylene, substitution or not
Substituted arylidene alkylene, substituted or unsubstituted alkylidene inferior heteroaryl, substituted or unsubstituted inferior heteroaryl are sub-
Alkyl ,-R3-CONH-R4-、-R5-O-R6-、-R7-COO-R8-、-R9-NH-R10- or-R11-OOC-R12- in any one, its
Middle R3、R4、R5、R6、R7、R8、R9、R10、R11And R12It independently is substituted or unsubstituted straight-chain alkyl-sub, substitution or unsubstituted
Branched alkylidene, substituted or unsubstituted arlydene, substituted or unsubstituted inferior heteroaryl, substituted or unsubstituted Asia
Alkyl arylene, substituted or unsubstituted arylidene alkylene, substituted or unsubstituted alkylidene inferior heteroaryl or substitution
Or any one in unsubstituted inferior heteroaryl alkylidene.
Preferably, Y be substituted or unsubstituted alkoxy, it is substituted or unsubstituted cycloalkyloxy, substituted or unsubstituted
Aryloxy group, substituted or unsubstituted alkoxy aryl, substituted or unsubstituted heteroarylalkoxy, substituted or unsubstituted carboxylic acid
In ester group, substituted or unsubstituted carbonate group, substituted or unsubstituted sulfonate group or substituted or unsubstituted phosphonate group
Any one；The alkoxy, cycloalkyloxy, aryloxy group, alkoxy aryl, heteroarylalkoxy, carbonate group, sulphonic acid ester
The substituent of base or phosphonate group independently is straight or branched alkyl, alkoxy, cycloalkyloxy, aryl, aryloxy group, aryl alkane
In epoxide, heteroaryl, carboxylic acid ester groups, carbonate group, sulfonate group or phosphonate group any one or at least two combination,
The substituent does not contain reactive end-capping group.
In the present invention, the inertia nucleophilic group is also referred to as inertia end-capping group, refers to the performance under the conditions of popular response
It is more stable, the group of reaction is not continued to participate in；The reactive end-capping group refers to there is active chemical reactivity, can
The group of chemical reaction is participated in, carries not referring to containing OH ,-CN ,-NH in the present invention2、-SH、-COOH、-CHO、-CONH2Deng reaction
The group of property group.Due to Y in the present invention2For inertia nucleophilic group, therefore it is does not contain the reactive end-capping group
Group.
Preferably, M1Structure is：
M2Structure is：
Wherein, x is more than or equal to 4；
M3Structure is：
Wherein, y is more than or equal to 3；
Preferably, M includes at least 50wt%M1, at most 30wt%M2And at most 45wt%M3。
Preferably, the phosphazene compound containing polyacetylene is for one kind in the compound with following structure or extremely
Few two kinds combination：
Wherein M is the phosphonitrile base of ring three, n
For 10-200 integer.
In formula I, c is integer more than or equal to 1, and d is the integer more than or equal to zero, such as c can be but not
Be limited to 1,2,3,4,5,6,7,8,9 or 10, d can be but be not limited to 0,1,2,3,4,5,6,7,8,9 or 10, and a+b=M groups
2 times of upper number of phosphorus atoms, that is, ensure that phosphorus atoms reach the saturation state that chemical valence is pentavalent on M；N is 10-200 integer,
Such as n can be but be not limited to 10,13,15,18,20,22,25,28,30,35,40,45,50,55,60,65,70,75,80,
85th, 90,100,110,130,150,180 or 200.
In the structural formula (Formulas I) of phosphazene compound of the present invention, it should be understood that the group being connected with M is to connect
It is connected on M phosphorus atoms, i.e. M1、M2And M3The side base on phosphorus atoms in structure.Further illustrate, M1、M2And M3Structure
Two singly-bounds occurred on middle P atoms are not to be construed as two methyl, and two singly-bounds are merely representative of M1、M2And M3Pass through its P
Atom connects side base.
Pay attention to, M1、M2In the expression of structural formula, occur symbol "" it is only that one kind of " ring-type " structure is shown
Meaning.
In the present invention, substituted or unsubstituted straight chained alkyl or branched alkyl be preferably substituted or unsubstituted C1~
C12 (such as C1, C2, C3, C4, C5, C6, C7, C8, C9, C10 or C11) straight chained alkyls or branched alkyl, further preferred C1~
C8 straight chained alkyls or branched alkyl, it is methyl when carbon number is 1, when carbon number is 2, as ethyl.
Substituted or unsubstituted cycloalkyl be preferably substituted or unsubstituted C3~C12 (such as C4, C5, C6, C7, C8,
C9, C10 or C11) cycloalkyl.
Substituted or unsubstituted aryl be preferably phenyl, benzyl, naphthyl, Deng.
Substituted or unsubstituted heteroaryl is five yuan or six membered heteroaryl, the heteroaryl be containing hetero atom (such as O,
S, N etc.) aromatic radical, preferably substituted or unsubstituted furyl or pyridine radicals.
Substituted or unsubstituted aryl alkyl is preferably C7-C13 (such as C8, C9, C10, C11 or C12) aryl alkyl.
Substituted or unsubstituted alkylaryl is preferably C7-C13 (such as C8, C9, C10, C11 or C12) alkylaryl.
Substituted or unsubstituted heteroaryl alkyl is preferably C7-C13 (such as C8, C9, C10, C11 or C12) heteroaryl alkane
Base.
Substituted or unsubstituted miscellaneous alkyl aryl is preferably C7-C13 (such as C8, C9, C10, C11 or C12) alkyl heteroaryl
Base.
Substituted or unsubstituted straight-chain alkyl-sub be preferably C1-C12 (such as C2, C3, C4, C5, C6, C7, C8, C9,
C10 or C11) straight-chain alkyl-sub.
Substituted or unsubstituted branched alkylidene be preferably C1-C12 (such as C2, C3, C4, C5, C6, C7, C8, C9,
C10 or C11) branched alkylidene.
Substituted or unsubstituted arlydene is preferably C6-C13 (such as C7, C8, C9, C10, C11 or C12) arlydene.
Substituted or unsubstituted inferior heteroaryl is preferably C5-C13 (such as C6, C7, C8, C9, C10, C11 or C12)
Inferior heteroaryl.
Substituted or unsubstituted alkylenearylene is preferably C7-C13 (such as C8, C9, C10, C11 or C12) alkylene
Base arlydene.
Substituted or unsubstituted arylidene alkylene is preferably C7-C13 (such as C8, C9, C10, C11 or C12) alkylene
Base arlydene.
Substituted or unsubstituted alkylidene inferior heteroaryl is preferably C6-C13 (such as C7, C8, C9, C10, C11 or C12)
Alkylidene inferior heteroaryl.
Substituted or unsubstituted inferior heteroaryl alkylidene is preferably C6-C13 (such as C7, C8, C9, C10, C11 or C12)
Inferior heteroaryl alkylidene.
Term " substituted " used in the present invention refer to any one or more hydrogen atoms on specified atom by selected from
The substituent substitution of designated groups, condition is that the specified atom is no more than normal valency, and the result substituted is to produce stabilization
Compound.When substituent is oxo group or ketone group (i.e.=O), then 2 hydrogen atoms on atom are substituted.Ketone substitutes
Base is not present on aromatic rings." stable compound " be refer to it is sufficiently strong strongly from reactant mixture separation to effective
Purity is simultaneously configured to compounds effective.
In the present invention, M is the phosphonitrile base M of ring three1, the phosphonitrile base M of ring more than four2Or non-annularity polyphosphazene base M3In one kind
Or at least two combination.
Preferably, M includes at least 50wt%M1, at most 30wt%M2And at most 45wt%M3。
In the present invention, M1Content is at least 50wt%, i.e. M1Content can be 50wt~100wt%, M1For main body into
Point.Work as M1When content is 100wt%, then M is not contained2And M3.The typical but non-limiting M of the present invention1Content can be
50wt%, 51wt%, 55wt%, 58wt%, 60wt%, 65wt%, 70wt%, 74wt%, 75wt%, 80wt%, 85wt%,
90wt%, 92wt%, 95wt%, 98wt% or 100wt%.
In the present invention, M2Content is at most 30wt%, that is, is referred to, M2Content can be 0~30wt%.Work as M2Content is
During 0wt%, that is, refer to, do not contain M2.The typical but non-limiting M of the present invention2Content can be 0wt%, 2wt%, 5wt%,
8wt%, 11wt%, 14wt%, 16wt%, 17wt%, 19wt%, 20wt%, 22wt%, 25wt%, 27wt%, 28wt% or
29wt%.
In the present invention, M3Content is at most 45wt%, that is, is referred to, M3Content can be 0~45wt%.Work as M3Content is
During 0wt%, that is, refer to, do not contain M3.The typical but non-limiting M of the present invention3Content can be 0wt%, 2wt%, 5wt%,
8wt%, 10wt%, 12wt%, 14wt%, 16wt%, 18wt%, 20wt%, 23wt%, 25wt%, 27wt%, 28wt%,
30wt%, 32wt%, 35wt%, 38wt%, 40wt%, 43wt% or 45wt%.
In the present invention, M1、M2And M3Mass percent sum is 100%.
If M1Content is less than 50wt%, or M2It is more than 30wt%, then in use with the reacted product of epoxy resin
Heat resistance, water resistance and mechanical performance etc. will be damaged must performance；M3Content comprise up to the 45% of phosphazenium groups gross mass.
If exceeding the content, would be possible in use with the reacted product of epoxy resin because viscosity is excessive, inconvenient for use, with
And its performance is set the bad result such as to suffer damage because molecular weight is excessive.
Second aspect, the invention provides a kind of preparation method of the phosphazene compound containing polyacetylene, methods described is
Nucleophilic substitution is carried out using the polyacetylene with active reactive group and phosphonitrile chloride and is prepared described to contain poly- second
The phosphazene compound of alkynes.
The active reactive group is hydroxyl, sulfydryl, amino or carboxylic acid group etc., the poly- second with active reactive group
Alkynes can be but be not limited to Those skilled in the art can be according to the synthetic method of prior art
These above-mentioned polyacetylene compounds are prepared using known raw material, or can be commercially available.
In the present invention nucleophilic substitution is carried out using the polyacetylene with active reactive group and phosphonitrile chloride.From
And polyacetylene is connected on M.We can carry phosphonitrile chloride and only an activity first during real reaction
Nucleopilic reagent (such as the methanol or sodium methoxide) reaction of group so that the end-capping group in connection on a part of P of M groups, and
Afterwards by will with the polyacetylene with active reactive group again with phosphonitrile chloride react, so as to obtain target such as Formulas I institute
The phosphazene compound shown.
The third aspect, the present invention provide a kind of conductive material, and the conductive material contains polyacetylene comprising described above
Phosphazene compound.The described phosphazene compound containing polyacetylene has relatively low dielectric constant, and it is good can to assign material
Electric conductivity.
5th aspect, the present invention provide a kind of ring with good heat resistance, good mechanical performance and low-dielectric energy
Epoxy resin composition.
The above-mentioned phosphazene compound containing polyacetylene is included in the composition epoxy resin.
Above-mentioned composition epoxy resin can be according to being actually needed as plastic packaging material and pre-impregnated sheet.
Another aspect of the present invention provides a kind of plastic packaging material, and it includes above-mentioned composition epoxy resin.
Another aspect of the present invention provides a kind of pre-impregnated sheet, and it is impregnated with or be coated on base by composition epoxy resin described above
Material forms.
Preferably, the base material can be fiberglass substrate, polyester base material, polyimide base material, ceramic base material or carbon
Fiber base material etc..
In the present invention, it is not particularly limited for the concrete technology condition for being impregnated with or being coated with." pre-impregnated sheet " is also this area
" bonding sheet " known to technical staff.
A kind of composite metal substrate, it is by least one such as above-mentioned pre-impregnated sheet by carrying out surface metal-clad weight successively
Folded, pressing forms.
Preferably, the material of the surface metal-clad is the alloy of aluminium, copper, iron and its any combination.
Preferably, the composite metal substrate is that CEM-1 copper-clad plates, CEM-3 copper-clad plates, FR-4 copper-clad plates, FR-5 cover copper
Any one in plate, CEM-1 aluminium bases, CEM-3 aluminium bases, FR-4 aluminium bases or FR-5 aluminium bases.
A kind of wiring board, formed in the Surface Machining circuit of above-mentioned composite metal substrate.
The composition epoxy resin forms the coating with good flame-retardance energy by being solidificated on composite metal substrate,
Wiring board heat resistance, good mechanical performance and low-dielectric energy can be improved.
Above-mentioned term " ××× base or group ", which refers to, sloughs one or more hydrogen atoms in ××× molecular structure of compounds
Or remaining part after other atoms or atomic group.
Relative to prior art, the invention has the advantages that：
Composition epoxy resin is prepared by the use of the phosphazene compound for containing polyacetylene as curing agent in the present invention, utilizes
The dielectric constant (1GHz) for the copper-clad plate that said composition is prepared is 3.21-3.32, and dielectric loss (1GHz) is 0.004-
0.005, Tg can reach 165 DEG C and more than, T- peel strengths can reach 2.1kg/mm2More than and, interlaminar strength can reach
1.85kg/mm2More than and, saturated water absorption can reach less than 0.19%, heat decomposition temperature can reach 410 DEG C and more than, bending
Intensity can reach 12.3kg/mm2More than and, flammability (UL-94) reaches V-0 ranks, therefore provided by the invention contains poly- second
The copper-clad plate that the phosphazene compound of alkynes is prepared has low dielectric, high heat-resisting and good mechanical performance and fire resistance.
Embodiment
Technical scheme is further illustrated with reference to embodiment.
Embodiment 1
The present embodiment phosphazene compound has following structure：
Preparation method is as follows：
Hexachlorocyclotriph,sphazene 1mol, acetone 200ml, first are put into three mouthfuls of 2000ml glass reactors with agitating device
Sodium alkoxide 5mol, stir, while leading to nitrogen, be warming up to 60 DEG C, instill 20% sodium hydroxide solution 621g with 60min, keep
60 DEG C of temperature, 8 hours of stirring reaction, then add(wherein n is about
10) 1mol, continue reaction 8 hours, after reaction, with inorganic constituents and moisture in the method removal system of physics, distill system
Middle solvent, the phosphazene compound 1mol containing polyacetylene is obtained, this purpose product is named as A.
Proton nmr spectra sign is carried out to obtained compound A, it is as a result as follows：
1H NMR(CDCl3,500MHz):δ ppm 6.6 (m, phenyl ring on hydrogen), 5.0 (s,On
Hydrogen), 3.9 (m, Ph-OCH 2CH2CH2-),3.4(m,-OCH 3),1.9(m,Ph-OCH2CH2CH 2-),1.7(m,Ph-
OCH2CH 2CH2-)。
The position of infrared spectrum characteristic peak：The characteristic absorption peak 1217cm of P=N keys in phosphazene backbone-1, P- in phosphazene backbone
N 874cm-1, the absworption peak 2995cm- of methyl ether1, P-O-C key absworption peaks 1035cm-1, contraposition substituted benzene ring 827cm-1, C=C
Absworption peak 1470cm-1。
Using above-mentioned phosphazene compound A 70g as fire retardant, the linear phenol-aldehyde resin that phenolic hydroxyl equivalent is 105g/eq is added
Curing agent 105g, add the o-cresol formaldehyde epoxy resin 200g that epoxide equivalent is 200g/eq, curing accelerator 2-methylimidazole
0.2g, prepare composition epoxy resin.It is made and is met according to general copper-clad plate production process using the composition epoxy resin
The standard copper-clad plate sample of the standards such as national standard, UL, a copper-clad plates are named as, test the performance of a copper-clad plates, its result is in table -1
Represent.
Embodiment 2
The present embodiment phosphazene compound has following structure：
Preparation method is as follows：
Hexachlorocyclotriph,sphazene 1mol, acetone 200ml, first are put into three mouthfuls of 2000ml glass reactors with agitating device
Sodium alkoxide 3mol, stir, while leading to nitrogen, be warming up to 60 DEG C, instill 20% sodium hydroxide solution 621g with 60min, keep
60 DEG C of temperature, 5 hours of stirring reaction, then add(wherein n is about
10) 3mol, reaction 8 hours is continued, after reaction, with inorganic constituents and moisture in the method removal system of physics, distill system
Middle solvent, the phosphazene compound 1mol containing polyacetylene is obtained, this purpose product is named as B.
Proton nmr spectra sign is carried out to obtained compound B, it is as a result as follows：
1H NMR(CDCl3,500MHz):δppm 5.2(s,Upper hydrogen), 3.40 (m, OCH 3),2.3
(m,OCO-CH 2CH2CH2CH2-),1.9(m,OCO-CH2CH2CH2CH 2-),1.6(m,OCO-CH2CH 2CH2CH2-),1.3(m,
OCO-CH2CH2CH 2CH2-)。
The position of infrared spectrum characteristic peak：The characteristic absorption peak 1217cm of P=N keys in phosphazene backbone-1, P- in phosphazene backbone
N 874cm-1, the absworption peak 2995cm- of methyl ether1, P-O-C key absworption peaks 1035cm-1, C=C absworption peak 1470cm-1。
Using above-mentioned phosphazene compound B 70g as fire retardant, the linear phenol-aldehyde resin that phenolic hydroxyl equivalent is 105g/eq is added
Curing agent 105g, add the o-cresol formaldehyde epoxy resin 200g that epoxide equivalent is 200g/eq, curing accelerator 2-methylimidazole
0.2g, prepare composition epoxy resin.Then it is made using the composition epoxy resin according to general copper-clad plate production process
Meet the standard copper-clad plate sample of the standards such as national standard, UL, be named as b copper-clad plates, test the performance of b copper-clad plates, its result table-
Represented in 1.
Embodiment 3
The present embodiment phosphazene compound has following structure：
Preparation method is as follows：
Hexachlorocyclotriph,sphazene 1mol, acetone 200ml, first are put into three mouthfuls of 2000ml glass reactors with agitating device
Sodium alkoxide 5mol, stir, while leading to nitrogen, be warming up to 60 DEG C, instill 20% sodium hydroxide solution 621g with 60min, keep
60 DEG C of temperature, 6 hours of stirring reaction, then add the polyacetylene raw material with carboxyl(its
Middle n is about 10) 1mol, continues reaction 8 hours, after reaction, with inorganic constituents and moisture in the method removal system of physics, distillation
Fall solvent in system, obtain the phosphazene compound 1mol containing polyacetylene, this purpose product is named as C.
Proton nmr spectra sign is carried out to obtained compound C, it is as a result as follows：
1H NMR(CDCl3,500MHz):ppm 8.0(m,-CONH-), 7.5-7.8 (m, phenyl ring on hydrogen), 5.8 (s,Upper hydrogen), 4.4 (m ,-COCH-),3.4(m,-OCH 3),3.1(s,-CH(CH3)2),1.1(m,-CH
(CH 3)2)。
The position of infrared spectrum characteristic peak：The characteristic absorption peak 1217cm of P=N keys in phosphazene backbone-1, P- in phosphazene backbone
N 874cm-1, the absworption peak 2995cm- of methyl ether1, P-O-C key absworption peaks 1035cm-1, contraposition substituted benzene ring 827cm-1, C=C
Absworption peak 1470cm-1。
Using above-mentioned phosphazene compound C 70g as fire retardant, the linear phenol-aldehyde resin that phenolic hydroxyl equivalent is 105g/eq is added
Curing agent 105g, add the o-cresol formaldehyde epoxy resin 200g that epoxide equivalent is 200g/eq, curing accelerator 2-methylimidazole
0.2g, prepare composition epoxy resin.It is made and is met according to general copper-clad plate production process using the composition epoxy resin
The standard copper-clad plate sample of the standards such as national standard, UL, c copper-clad plates are named as, test the performance of c copper-clad plates, its result is in table -1
Represent.
Embodiment 4
The present embodiment phosphazene compound has following structure：
Hexachlorocyclotriph,sphazene 1mol, acetone 200ml, methanol are put into three mouthfuls of 2000ml glass reactors with agitating device
Sodium 5mol, stir, while leading to nitrogen, be warming up to 60 DEG C, instill 20% sodium hydroxide solution 621g with 60min, kept for 60 DEG C
Temperature, 8 hours of stirring reaction, then add the polyacetylene raw material with carboxyl
(n is about 20) 1mol, continue reaction 5 hours, after reaction, with inorganic constituents and moisture in the method removal system of physics, distillation
Fall solvent in system, obtain the phosphazene compound 1mol containing polyacetylene, this purpose product is named as D.
Proton nmr spectra sign is carried out to obtained compound D, it is as a result as follows：
1H NMR(CDCl3,500MHz):δ ppm 7.4-8.0 (m, phenyl ring on hydrogen) 5.2 (s,On
Hydrogen), 3.40 (m, OCH 3),2.3(d,-CH2CH2CH2CH 2COO-),2.0(d,-CH 2CH2CH2CH2COO-),1,6(d,-
CH2CH2CH 2CH2COO-),1.3(d,-CH2CH 2CH2CH2COO-)。
The position of infrared spectrum characteristic peak：The characteristic absorption peak 1217cm of P=N keys in phosphazene backbone-1, P- in phosphazene backbone
N 874cm-1, the absworption peak 2995cm- of methyl ether1, P-O-C key absworption peaks 1035cm-1, contraposition substituted benzene ring 827cm-1, C=C
Absworption peak 1470cm-1。
Using above-mentioned phosphazene compound D 70g as fire retardant, the linear phenol-aldehyde resin that phenolic hydroxyl equivalent is 105g/eq is added
Curing agent 105g, add the o-cresol formaldehyde epoxy resin 200g that epoxide equivalent is 200g/eq, curing accelerator 2-methylimidazole
0.2g, prepare composition epoxy resin.It is made and is met according to general copper-clad plate production process using the composition epoxy resin
The standard copper-clad plate sample of the standards such as national standard, UL, d copper-clad plates are named as, test the performance of d copper-clad plates, its result is in table -1
Represent.
Comparative example 1
Epoxide equivalent is 200g/eq o-cresol formaldehyde epoxy resin 200g, adds the line that phenolic hydroxyl equivalent is 105g/eq
Type phenolic resin curative 105g and hexaphenoxycyclotriphosphazene 70g and 0.2g as fire retardant 2-methylimidazole, system
Standby composition epoxy resin.It is made using the composition epoxy resin according to general copper-clad plate production process and meets national standard, UL
Etc. the standard copper-clad plate sample e of standard, the properties for covering copper e represent in table -1.
Comparative example 2
Epoxide equivalent is 200g/eq o-cresol formaldehyde epoxy resin 200g, and adding has such as the resinification of formula (1) structure
Compound 220g, ester equivalent are 220g/eq and hexaphenoxycyclotriphosphazene 70g and 0.2g as fire retardant pyridine azoles, are made
Standby composition epoxy resin.It is made using the composition epoxy resin according to general copper-clad plate production process and meets national standard, UL
Etc. the standard copper-clad plate sample f of standard, the properties for covering copper f represent in table -1.
Embodiment and the test result of comparative example are as shown in following table -1 (in view of specific method of testing has been people in the art
Known to member, method is no longer described in detail at this).
Table -1
The test data of above table, show phosphazene compound and its derivative of the present invention when use is in epoxy resin cure
When in system and other systems, there is good anti-flammability, its solidfied material has good heat resistance, water resistance, cohesiveness, machine
Tool performance and electrical property.
Applicant states that the present invention illustrates the phosphazene compound of the present invention and its application, but this by above-described embodiment
Invention is not limited to above-described embodiment, that is, does not mean that the present invention has to rely on above-described embodiment and could implemented.Affiliated technology
The technical staff in field is it will be clearly understood that any improvement in the present invention, to the equivalence replacement and auxiliary of each raw material of product of the present invention
The addition of composition, selection of concrete mode etc., within the scope of all falling within protection scope of the present invention and disclosing.
Claims (10)
1. a kind of phosphazene compound containing polyacetylene, it is characterised in that the phosphazene compound containing polyacetylene has Formulas I
Shown structure：
In Formulas I, R is any organic group for meeting its chemical environment；X be-O- ,-S-,In
Any one, Y is any inertia nucleophilic group for meeting its chemical environment；M is the phosphonitrile base M of ring three1, the phosphonitrile base of ring more than four
M2, non-annularity polyphosphazene base M3In one kind and its any combination；C is the integer more than or equal to 1, and d is whole more than or equal to zero
Number, and 2 times of number of phosphorus atoms on c+d=M groups, n is 10-200 integer.
2. the phosphazene compound according to claim 1 containing polyacetylene, it is characterised in that R is substituted or unsubstituted
Straight-chain alkyl-sub, substituted or unsubstituted branched alkylidene, substituted or unsubstituted arlydene, substituted or unsubstituted Asia are miscellaneous
Aryl, substituted or unsubstituted alkylenearylene, substituted or unsubstituted arylidene alkylene, substitution or it is unsubstituted
Alkylidene inferior heteroaryl, substituted or unsubstituted inferior heteroaryl alkylidene ,-R3-CONH-R4-、-R5-O-R6-、-R7-COO-
R8-、-R9-NH-R10- or-R11-OOC-R12- in any one, wherein R3、R4、R5、R6、R7、R8、R9、R10、R11And R12It is independent
Ground is substituted or unsubstituted straight-chain alkyl-sub, substituted or unsubstituted branched alkylidene, substituted or unsubstituted arlydene, taken
Generation or unsubstituted inferior heteroaryl, substituted or unsubstituted alkylenearylene, substituted or unsubstituted arlydene are sub-
It is any one in alkyl, substituted or unsubstituted alkylidene inferior heteroaryl or substituted or unsubstituted inferior heteroaryl alkylidene
Kind；
Preferably, Y is substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyloxy, substituted or unsubstituted fragrant oxygen
Base, substituted or unsubstituted alkoxy aryl, substituted or unsubstituted heteroarylalkoxy, substituted or unsubstituted carboxylate
In base, substituted or unsubstituted carbonate group, substituted or unsubstituted sulfonate group or substituted or unsubstituted phosphonate group
Any one；The alkoxy, cycloalkyloxy, aryloxy group, alkoxy aryl, heteroarylalkoxy, carbonate group, sulfonate group
Or the substituent of phosphonate group independently is straight or branched alkyl, alkoxy, cycloalkyloxy, aryl, aryloxy group, arylalkoxy
In base, heteroaryl, carboxylic acid ester groups, carbonate group, sulfonate group or phosphonate group any one or at least two combination, institute
State substituent and do not contain reactive end-capping group；
Preferably, M1Structure is：
M2Structure is：
Wherein, x is more than or equal to 4；
M3Structure is：
Wherein, y is more than or equal to 3；
Preferably, M includes at least 50wt%M1, at most 30wt%M2And at most 45wt%M3。
3. the phosphazene compound according to claim 1 or 2 containing polyacetylene, it is characterised in that described to contain polyacetylene
Phosphazene compound be for one kind in the compound with following structure or at least two combination：
Wherein M is the phosphonitrile base of ring three, n
For 10-200 integer.
4. a kind of conductive material, it is characterised in that the conductive material includes containing as any one of claim 1-3
The phosphazene compound of polyacetylene.
5. a kind of composition epoxy resin, it is characterised in that the composition epoxy resin is included as any in claim 1-3
The phosphazene compound containing polyacetylene described in.
6. a kind of plastic packaging material, it is characterised in that include the composition epoxy resin described in claim 5.
7. a kind of pre-impregnated sheet, it is characterised in that it is impregnated with or be coated on base by composition epoxy resin as claimed in claim 5
Material forms.
8. prepreg according to claim 7, it is characterised in that the base material is fiberglass substrate, polyester base material, gathered
Acid imide base material, ceramic base material or carbon fiber base material.
9. a kind of composite metal substrate, it is characterised in that it is passed through by an at least pre-impregnated sheet as claimed in claims 6 or 7
Surface metal-clad is carried out successively, overlapping, pressing forms；
Preferably, the material of the surface metal-clad is the alloy of aluminium, copper, iron and its any combination；
Preferably, the composite metal substrate be CEM-1 copper-clad plates, CEM-3 copper-clad plates, FR-4 copper-clad plates, FR-5 copper-clad plates,
Any one in CEM-1 aluminium bases, CEM-3 aluminium bases, FR-4 aluminium bases or FR-5 aluminium bases.
10. a kind of wiring board, it is characterised in that formed in the Surface Machining circuit of the composite metal substrate described in claim 9.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610293028.8A CN107344975A (en) | 2016-05-04 | 2016-05-04 | A kind of phosphazene compound containing polyacetylene, composition epoxy resin, plastic packaging material and composite metal substrate |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610293028.8A CN107344975A (en) | 2016-05-04 | 2016-05-04 | A kind of phosphazene compound containing polyacetylene, composition epoxy resin, plastic packaging material and composite metal substrate |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103756257A (en) * | 2013-12-27 | 2014-04-30 | 广东生益科技股份有限公司 | Thermosetting epoxy resin composition and use thereof |
| CN104140559A (en) * | 2013-05-10 | 2014-11-12 | 信汇科技有限公司 | Application of cyclophosphazene compound in preparation of resin as fire retardant |
| CN104892898A (en) * | 2015-05-12 | 2015-09-09 | 广东广山新材料有限公司 | Phosphorus-nitrogen epoxy resin with bisphenol S radicals, flame-retardant composition, composite metal substrate |
| CN105348563A (en) * | 2014-12-09 | 2016-02-24 | 广东广山新材料有限公司 | Flame-retardant compound, flame-retardant epoxy resin and flame-retardant composition |
-
2016
- 2016-05-04 CN CN201610293028.8A patent/CN107344975A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104140559A (en) * | 2013-05-10 | 2014-11-12 | 信汇科技有限公司 | Application of cyclophosphazene compound in preparation of resin as fire retardant |
| CN103756257A (en) * | 2013-12-27 | 2014-04-30 | 广东生益科技股份有限公司 | Thermosetting epoxy resin composition and use thereof |
| CN105348563A (en) * | 2014-12-09 | 2016-02-24 | 广东广山新材料有限公司 | Flame-retardant compound, flame-retardant epoxy resin and flame-retardant composition |
| CN104892898A (en) * | 2015-05-12 | 2015-09-09 | 广东广山新材料有限公司 | Phosphorus-nitrogen epoxy resin with bisphenol S radicals, flame-retardant composition, composite metal substrate |
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Application publication date: 20171114 |