CN112442083A - Phosphorus-containing flame retardant with anhydride and preparation method and application thereof - Google Patents
Phosphorus-containing flame retardant with anhydride and preparation method and application thereof Download PDFInfo
- Publication number
- CN112442083A CN112442083A CN201910803119.5A CN201910803119A CN112442083A CN 112442083 A CN112442083 A CN 112442083A CN 201910803119 A CN201910803119 A CN 201910803119A CN 112442083 A CN112442083 A CN 112442083A
- Authority
- CN
- China
- Prior art keywords
- flame retardant
- phosphorus
- substituted
- unsubstituted
- containing flame
- 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.)
- Pending
Links
- 239000003063 flame retardant Substances 0.000 title claims abstract description 111
- 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 102
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 70
- 239000011574 phosphorus Substances 0.000 title claims abstract description 70
- 150000008064 anhydrides Chemical class 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- 239000004970 Chain extender Substances 0.000 claims abstract description 9
- 229920005989 resin Polymers 0.000 claims abstract description 9
- 239000011347 resin Substances 0.000 claims abstract description 9
- 239000000126 substance Substances 0.000 claims abstract description 9
- 125000002947 alkylene group Chemical group 0.000 claims description 40
- 150000008065 acid anhydrides Chemical class 0.000 claims description 15
- 125000000732 arylene group Chemical group 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 229920000647 polyepoxide Polymers 0.000 claims description 8
- 239000003822 epoxy resin Substances 0.000 claims description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 7
- 229920001225 polyester resin Polymers 0.000 claims description 7
- 239000004645 polyester resin Substances 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 229910052717 sulfur Inorganic materials 0.000 claims description 6
- 229920003180 amino resin Polymers 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 229920002379 silicone rubber Polymers 0.000 claims description 5
- 239000004945 silicone rubber Substances 0.000 claims description 5
- 125000004185 ester group Chemical group 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- 125000005549 heteroarylene group Chemical group 0.000 claims description 4
- 229920006122 polyamide resin Polymers 0.000 claims description 4
- 125000001072 heteroaryl group Chemical group 0.000 claims description 3
- 125000000962 organic group Chemical group 0.000 claims description 3
- 125000005568 organylene group Chemical group 0.000 claims description 3
- 229920000180 alkyd Polymers 0.000 claims description 2
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 2
- 229920005749 polyurethane resin Polymers 0.000 claims description 2
- 125000004434 sulfur atom Chemical group 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims 1
- 125000004417 unsaturated alkyl group Chemical group 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 12
- 239000000463 material Substances 0.000 abstract description 9
- 238000001556 precipitation Methods 0.000 abstract description 4
- 125000004018 acid anhydride group Chemical group 0.000 abstract description 3
- 229920002521 macromolecule Polymers 0.000 abstract description 3
- 239000000178 monomer Substances 0.000 abstract description 3
- 238000006116 polymerization reaction Methods 0.000 abstract description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 22
- 238000012360 testing method Methods 0.000 description 18
- 239000000203 mixture Substances 0.000 description 14
- 229960000583 acetic acid Drugs 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 12
- 239000012362 glacial acetic acid Substances 0.000 description 12
- 238000003756 stirring Methods 0.000 description 10
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- 239000004952 Polyamide Substances 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 229920002647 polyamide Polymers 0.000 description 6
- 229920000728 polyester Polymers 0.000 description 6
- 239000000654 additive Substances 0.000 description 5
- DWSWCPPGLRSPIT-UHFFFAOYSA-N benzo[c][2,1]benzoxaphosphinin-6-ium 6-oxide Chemical class C1=CC=C2[P+](=O)OC3=CC=CC=C3C2=C1 DWSWCPPGLRSPIT-UHFFFAOYSA-N 0.000 description 5
- 239000011521 glass Substances 0.000 description 4
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- -1 flame retardant compound Chemical class 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- SYIUWAVTBADRJG-UHFFFAOYSA-N 2H-pyran-2,6(3H)-dione Chemical compound O=C1CC=CC(=O)O1 SYIUWAVTBADRJG-UHFFFAOYSA-N 0.000 description 2
- 239000004114 Ammonium polyphosphate Substances 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 125000005237 alkyleneamino group Chemical group 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 235000019826 ammonium polyphosphate Nutrition 0.000 description 2
- 229920001276 ammonium polyphosphate Polymers 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
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 2
- 238000000113 differential scanning calorimetry Methods 0.000 description 2
- CZHYKKAKFWLGJO-UHFFFAOYSA-N dimethyl phosphite Chemical compound COP([O-])OC CZHYKKAKFWLGJO-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 125000000468 ketone group Chemical group 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- XVOUMQNXTGKGMA-OWOJBTEDSA-N (E)-glutaconic acid Chemical compound OC(=O)C\C=C\C(O)=O XVOUMQNXTGKGMA-OWOJBTEDSA-N 0.000 description 1
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-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
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- GGXNNMWBCDLFHJ-UHFFFAOYSA-N O(P(OC1=CC=CC=C1)(=O)OP(=O)(OC1=CC=CC=C1)OC1=CC=CC=C1)C1=CC=CC=C1.C=1(C(=CC=CC1)O)O Chemical compound O(P(OC1=CC=CC=C1)(=O)OP(=O)(OC1=CC=CC=C1)OC1=CC=CC=C1)C1=CC=CC=C1.C=1(C(=CC=CC1)O)O GGXNNMWBCDLFHJ-UHFFFAOYSA-N 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- HEDRZPFGACZZDS-MICDWDOJSA-N deuterated chloroform Substances [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 1
- LXCYSACZTOKNNS-UHFFFAOYSA-N diethoxy(oxo)phosphanium Chemical compound CCO[P+](=O)OCC LXCYSACZTOKNNS-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000002085 irritant Substances 0.000 description 1
- 231100000021 irritant Toxicity 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 230000001617 migratory effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- 125000004043 oxo group Chemical group O=* 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229960004063 propylene glycol Drugs 0.000 description 1
- 235000013772 propylene glycol Nutrition 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000004634 thermosetting polymer Substances 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 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 1
Classifications
-
- 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
- C07F9/655—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms
- C07F9/65515—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms the oxygen atom being part of a five-membered ring
- C07F9/65517—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms the oxygen atom being part of a five-membered ring condensed with carbocyclic rings or carbocyclic ring systems
-
- 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
- C07F9/655—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms
- C07F9/65515—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms the oxygen atom being part of a five-membered ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
- C07F9/657163—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom
- C07F9/657172—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom the ring phosphorus atom and one oxygen atom being part of a (thio)phosphinic acid ester: (X = O, S)
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- 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
- C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
- C08G59/423—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof containing an atom other than oxygen belonging to a functional groups to C08G59/42, carbon and hydrogen
-
- 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
- C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
- C08G59/4238—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof heterocyclic
-
- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/692—Polyesters containing atoms other than carbon, hydrogen and oxygen containing phosphorus
- C08G63/6924—Polyesters containing atoms other than carbon, hydrogen and oxygen containing phosphorus derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/6928—Polycarboxylic acids and polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
-
- 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
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/42—Polyamides containing atoms other than carbon, hydrogen, oxygen, and 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Fireproofing Substances (AREA)
Abstract
The invention provides a phosphorus-containing flame retardant with anhydride, and a preparation method and application thereof. The phosphorus-containing flame retardant with anhydride provided by the invention can be used as a reaction monomer or a chain extender to participate in the polymerization reaction of macromolecules, and finally, the phosphorus-containing group of the flame retardant provided by the invention exists in a macromolecular material in the form of a chemical bond, so that the phenomenon of micromolecule precipitation does not exist, and the phosphorus-containing group cannot be dissolved in water and precipitated; namely, the phosphorus-containing flame retardant provided by the invention can realize permanent flame retardance. And the acid anhydride group carried by the resin can participate in the preparation of various resins, and the application range is wide.
Description
Technical Field
The invention belongs to the technical field of flame retardants, and relates to a phosphorus-containing flame retardant with anhydride and a preparation method and application thereof.
Background
The application range of the polymer materials is wider and wider, but the general polymer materials are usually flammable. Thermoplastic and thermosetting polymers (e.g., polyamides, polyesters, epoxies, and polyurethanes) require the use of flame retardants in many applications because of their flammability. Generally, halogenated compounds (more specifically, aromatic polybrominated compounds) have been used as flame retardant additives in polymers. It is generally believed that these products inhibit the radical gas phase reaction in the flame when they are ignited. This makes halogenated flame retardants very common additives for different types of polymeric materials.
However, the traditional halogen flame retardant generates more smoke and releases irritant and corrosive gases during combustion, so that the environment is polluted and the human health is harmed; the european union has banned the use of halogen flame retardants in 2006. The establishment of a novel efficient, halogen-free and nontoxic flame retardant system has become a new direction of flame retardant scientific research.
There are many organophosphorus compounds shown in the prior art to impart flame retardancy to polymers. Most phosphorus-containing flame retardants provide flame retardant activity through a combination of gas phase and condensed phase reactions, polymer carbonization promotion, and char formation. On one hand, although the addition type flame retardant has the characteristic of flame retardance, the addition type flame retardant has mobility and part of the flame retardant is easily dissolved in water, so that the flame retardance of the material is gradually weakened, and the migrated micromolecules easily pollute the environment; on the other hand, the processing of polymeric materials often requires high temperature environments, possibly to temperatures above 200 ℃, above which the flame retardant tends to decompose or to participate in certain side reactions, losing its flame retardant properties and also affecting the mechanical properties of the material.
CN105713043A discloses a DOPO derivative flame retardant, one molecular compound of which comprises two molecules of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, which has better flame retardant property as a flame retardant and can bear the processing temperature of more than 200 ℃, but when the DOPO derivative flame retardant is applied to a composition system, the phenomenon of micromolecule precipitation still exists.
Therefore, there is a need to develop a new flame retardant compound that can truly achieve environmental protection and flame retardancy.
Disclosure of Invention
The invention aims to provide a phosphorus-containing flame retardant with anhydride, and a preparation method and application thereof. The phosphorus-containing flame retardant with anhydride provided by the invention can be used as a reaction monomer or a chain extender to participate in the polymerization reaction of macromolecules, and finally, the phosphorus-containing group of the flame retardant provided by the invention exists in a macromolecular material in the form of a chemical bond, so that the phenomenon of micromolecule precipitation does not exist, and the phosphorus-containing group cannot be dissolved in water and precipitated; namely, the phosphorus-containing flame retardant provided by the invention can realize permanent flame retardance. And the acid anhydride group carried by the resin can participate in the preparation of various resins, and the application range is wide.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides an anhydride-bearing phosphorus-containing flame retardant having the structure shown in formula I:
wherein Z is1、Z2Each independently is preferably a phosphorus-containing group.
M1Selected from linear alkylene, branched alkylene or arylene.
M2Selected from any organic group that satisfies the chemical environment.
Y1、Y2Each independently is preferably an inert group, a sulfur atom, an oxygen atom or-H.
X1Selected from any organylene group that satisfies a chemical environment.
g. h is preferably an integer of 0 to 5, and g and h are not 0 at the same time.
e is an integer from 0 to 100, such as 2, 5, 10, 20, 30, 40, 50, 60, 70, 80, 90, and the like.
Preferably, Z1、Z2Each independently preferably
R1Is methyl or ethyl.
Preferably, said M1Selected from the group consisting of C1-C30 linear or branched alkylene, C6-C30 arylene, and C5-C7 heteroarylene, more preferably C1-C5 linear alkylene, C3-C5 branched alkylene, or phenyl, still more preferably C1-C3 linear alkylene, C3 branched alkylene, or phenyl.
The C1-C30 can be C2, C4, C6, C8, C10, C12, C14, C16, C18, C20, C22, C24, C26, C28 and the like.
The C6-C30 can be C8, C10, C12, C14, C16, C18, C20, C22, C24, C26, C28 and the like.
The C5-C7 may be C6 or the like.
The C1-C5 linear alkylene group may be methylene, ethylene, propylene, butylene, etc.
The C3-C5 may be C3, C4, C5, etc.
The C1-C3 may be C1, C2, C3, etc.
Preferably, said M2Selected from N, S, C1-C30 straight chain or branched chain alkyl, C6-C30 aryl, C5-C7 heteroaryl,
Wherein R is2、R3、R4、R5、R6、R7、R8、R9Each independently of the others is preferably a linear or branched alkylene group having from C1 to C10, L2、Y2、Z2Is connected to R2、R3、R4、R5、R6、R7、R8、R9N, m, i, k are each independently preferably an integer from 0 to 100, such as 2, 5, 10, 20, 30, 40, 50, 60, 70, 80, 90, etc.
The C1-C30 can be C2, C4, C6, C8, C10, C12, C14, C16, C18, C20, C22, C24, C26, C28 and the like.
The C6-C30 can be C8, C10, C12, C14, C16, C18, C20, C22, C24, C26, C28 and the like.
The C5-C7 may be C6 or the like.
Preferably, Y1、Y2Each independently is preferably-H or ═ O.
Preferably, said X1Selected from N, S, substituted or unsubstituted C1-C30 linear or branched alkylene, substituted or unsubstituted C6-C30 arylene, substituted or unsubstituted C5-C7 heteroarylene, substituted or unsubstituted C1-C30 alkyleneamine, substituted or unsubstituted C1-C30 alkyleneacyl, substituted or unsubstituted C1-C30 alkyleneester, substituted or unsubstituted C6-C30 alkyleneamine, substituted or unsubstituted C6-C30 aryleneacyl or C6-C30 aryleneester, further preferably substituted or unsubstituted C1-C5 linear or branched alkylene, substituted or unsubstituted C1-C5 alkyleneamine, substituted or unsubstituted C1-C5 alkyleneacyl or substituted or unsubstituted C1-C5 alkyleneester, further preferably-NH-R-, -R '-NH-, -R' -O-, -RV-C (O) -, substituted or unsubstituted C1-C5 linear or branched alkylene, wherein, R, R', R ", RVEach independently is preferably a substituted or unsubstituted C1-C10 straight or branched chain alkylene group.
The term "substituted" as used herein means that any one or more hydrogen atoms on the designated atom is replaced with a substituent selected from the designated group, provided that the designated atom does not exceed a normal valence and that the result of the substitution is a stable compound. When the substituent is an oxo group or a keto group (i.e., ═ O), then 2 hydrogen atoms on the atom are substituted. The ketone substituent is absent on the aromatic ring. By "stable compound" is meant a compound that can be isolated from a reaction mixture sufficiently robustly to an effective purity and formulated to be effective.
The C1-C30 can be C2, C4, C6, C8, C10, C12, C14, C16, C18, C20, C22, C24, C26, C28 and the like.
The C6-C30 can be C8, C10, C12, C14, C16, C18, C20, C22, C24, C26, C28 and the like.
The C5-C7 may be C6 or the like.
The C1-C5 may be C1, C2, C3, C4, C5, etc.
The following description is merely an explanation of structures such as alkyleneamino groups, and R does not particularly denote any meaning.
The alkyleneamino group refers to-R-NH-, wherein R is alkylene.
The alkylene acyl refers to-R-C (O) -, wherein R is alkylene.
The alkylene ester group means-R-COO-wherein R represents an alkylene group.
The arylene amine group means-Ar-NH-, wherein Ar represents an arylene group.
The aryleneacyl group means-Ar-C (O) -, wherein Ar represents an arylene group.
The arylene ester group means-Ar-COO-in which Ar represents an arylene group.
Preferably, said R is2、R3、R4、R5、R6、R7、R8、R9Independently of one another, these are preferably C1-C6 straight-chain or branched alkylene groups.
Preferably, n, m, i, k are each independently preferably an integer from 0 to 30, such as 1,2, 4, 6, 8, 10, 12, 14, 16, 18, 20, 22, 24, 26, 28, and the like.
Preferably, the phosphorus-containing flame retardant with acid anhydride has a structure shown in formula II:
wherein M is1Selected from linear alkylene of C1-C3 (e.g., C1, C2, C3, etc.), branched alkylene of C3, or phenyl.
M2Selected from N, -NH-RTStraight chain or branched chain alkyl of C1-C6,
Wherein R isTIs a linear or branched alkyl group of C1-C6 (e.g., C2, C3, C4, C5, etc.), R2、R3、R4、R5、R6、R7、R8、R9Each independently is preferably a C1-C6 (e.g., C2, C3, C4, C5, etc.) straight or branched chain alkylene group, and each of n, m, i, k independently is preferably an integer of 0 to 30, such as 1,2, 4, 6, 8, 10, 12, 14, 16, 18, 20, 22, 24, 26, 28, etc.
R1Is methyl or ethyl.
RPSelected from substituted or unsubstituted C1-C10 (e.g., C2, C3, C4, C5, C6, C7, C8, C9, etc.) straight or branched chain alkylene groups.
Y1、Y2Each independently is preferably-H or ═ O.
g. h is preferably 0, 1 or 2, and g and h are not 0 at the same time.
e is an integer from 0 to 20, e.g., 1,2, 4, 6, 8, 10, 12, 14, 16, 18, 19, etc., and f is 0 or 1.
The invention does not limit the preparation method of the phosphorus-containing flame retardant with anhydride, and any preparation method capable of obtaining the compound of the invention can be adopted, and the preparation method is exemplified as follows:
in a second aspect, the present invention provides a method for preparing a phosphorus-containing flame retardant with an acid anhydride according to the first aspect, comprising the steps of:
the phosphorus-containing flame retardant with the anhydride is obtained by the addition reaction of a compound containing a-P-H bond and a compound containing an unsaturated bond and/or a cyclic group.
Or, contains-P-L-COH- (A)1)2The hydroxyl of the compound (A) and the available reactive groups of other compounds react to obtain the phosphorus-containing flame retardant with anhydride;
wherein L is absent or selected from any organylene group that satisfies a chemical environment.
A1May be H or selected from any organic group that satisfies the chemical environment.
In the present invention, the reactive group carried by the other compound may be a group reactive with a hydroxyl group such as an amine group, a carboxyl group, an ester group, or the like, and may be reacted with dehydration, dealcoholization, or the like.
In a third aspect, the present invention provides the use of a phosphorus-containing flame retardant with an acid anhydride according to the first aspect for the preparation of a polyester resin, an amino resin, an alkyd resin or a silicone rubber resin.
In a fourth aspect, the present invention provides a chain extender comprising the phosphorus-containing flame retardant with an acid anhydride of the first aspect.
The chain extender of the present invention may be the phosphorus-containing flame retardant with an acid anhydride described in the first aspect as a whole, or may be a combination thereof with another acid anhydride or carboxylic acid.
Preferably, the chain extender is applied to polyester resin, polyurethane resin, amino resin or silicone rubber.
When the chain extender is applied to the preparation of resin, the flame-retardant polyester resin, flame-retardant polyurethane, flame-retardant amino resin or flame-retardant silicone rubber can be obtained finally.
In a fifth aspect, the present invention provides an epoxy resin curing agent comprising the anhydride-containing phosphorus-containing flame retardant of the first aspect.
Compared with the prior art, the invention has the following beneficial effects:
the phosphorus-containing flame retardant with anhydride provided by the invention can be used as a reaction monomer or a chain extender to participate in the polymerization reaction of macromolecules, and finally, the phosphorus-containing group of the flame retardant provided by the invention exists in a macromolecular material in the form of a chemical bond, so that the phenomenon of micromolecule precipitation does not exist, and the phosphorus-containing group cannot be dissolved in water and precipitated; namely, the phosphorus-containing flame retardant provided by the invention can realize permanent flame retardance. And the acid anhydride group carried by the resin can participate in the preparation of various resins, and the application range is wide.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Preparation example 1
A phosphorus-containing flame retardant with anhydride has the following structure:
the preparation method comprises the following steps:
50mL of glacial acetic acid, 0.5mol of dimethyl phosphite and 0.5mol of cis-4-cyclohexene-1, 2-dicarboxylic anhydride are put into a three-port 200mL glass reactor with a stirring device under nitrogen atmosphere and stirred, 0.5mmol of Pb catalyst is dissolved in 20mL of glacial acetic acid at the stirring temperature of 60 ℃, then the mixture is added into a reaction system in a dropwise manner and reacts for 12h, and then the product is separated, so that the phosphorus-containing flame retardant with the structure is obtained.
1H NMR(CDCl3,400MHz,TMS):δ＝3.40-3.45(d,6H，-P-O-CH3),2.92-2.95(m,1H,-P-CH-CH2-CH-),2.52-2.60(m,1H,-CH-CH-),1.80-1.82(m,1H,-P-CH-),1.43-1.66(m,6H,-CH2-).
Preparation example 2
A phosphorus-containing flame retardant with anhydride has the following structure:
the preparation method comprises the following steps:
adding 1mol of tetrahydrophthalic anhydride, 1mol of diethyl phosphite and 500mL of glacial acetic acid into a reaction kettle, and stirring and uniformly mixing at 65 ℃ under the protection of nitrogen; then dropwise adding 1mmol of glacial acetic acid solution of platinum catalyst into the reaction kettle, and continuing to react for 15 h; separating and purifying the product to obtain the target product with the structure.
1H NMR(CDCl3,400MHz,TMS):δ＝3.78-4.05(m,4H,-P-CH2-),2.92-2.95(m,1H,-P-CH-CH2-CH-),2.52-2.60(m,1H,-CH-CH-),1.80-1.82(m,1H,-P-CH-),1.35-1.66(m,12H,-CH2-,-CH3).
Preparation example 3
A phosphorus-containing flame retardant with anhydride has the following structure:
the preparation method comprises the following steps:
50mL of glacial acetic acid, 0.5mol of dimethyl phosphite and 0.5mol of maleic anhydride are put into a three-port 200mL glass reactor with a stirring device under nitrogen atmosphere and stirred, 0.5mmol of Pb catalyst is dissolved in 20mL of glacial acetic acid at the stirring temperature of 60 ℃, then the mixture is added into a reaction system in a dropwise manner and reacts for 12 hours, and then a product is separated, so that the phosphorus-containing flame retardant with the structure is obtained.
1H NMR(CDCl3,400MHz,TMS):δ＝4.12-4.16(t,1H,-CH-),3.40-3.45(d,6H，-P-O-CH3),3.38-3.42(d,2H,-CH2-).
Preparation example 4
A phosphorus-containing flame retardant with anhydride has the following structure:
the preparation method comprises the following steps:
adding 1mol of DOPO, 1mol of cis-4-cyclohexene-1, 2-dicarboxylic anhydride and 50mL of glacial acetic acid into a three-neck flask with a magnetic stirring thermometer, adding a glacial acetic acid solution dissolved with 1mmol of Pb catalyst into a reaction system in a dropwise manner at a stirring speed of 50 ℃, reacting for 12h, and separating a product to obtain the reactive flame retardant with the structure.
1H NMR(CDCl3400MHz, TMS). delta. DELTA.6.94-7.64 (m,8H, ph-H),2.92-2.95(m,2H, -CH-) attached to the anhydride group, 1.80-1.82(m,1H, -P-CH-),1.51-1.74(m,6H,-CH2-).
Preparation example 5
A phosphorus-containing flame retardant with anhydride has the following structure:
the preparation method comprises the following steps:
50mL of glacial acetic acid, 0.5mol of DOPO and 0.5mol of maleic anhydride are put into a three-port 200mL glass reactor with a stirring device under nitrogen atmosphere and stirred, 0.5mmol of Pb catalyst is dissolved in 20mL of glacial acetic acid at the stirring temperature of 60 ℃, then the mixture is added into a reaction system in a dropwise manner and reacts for 12 hours, and then the product is separated, so that the phosphorus-containing flame retardant with the structure is obtained.
1H NMR(CDCl3,400MHz,TMS):δ＝6.94-7.64(m,8H,ph-H),4.12-4.16(t,1H,-CH-),3.38-3.42(d,2H,-CH2-).
Preparation example 6
A phosphorus-containing flame retardant with anhydride has the following structure:
the preparation method comprises the following steps:
(1) under the nitrogen atmosphere, 2mol of glutaconic acid, 300mL of toluene and 20mL of 1mol/L hydrochloric acid solution are put into a three-port 500mL glass reactor with a stirring device and a water separator device, heated to reflux, reacted for 12h, and then the solvent is removed to obtain the glutaconic anhydride.
(2) Adding 1mol of glutaconic anhydride, 1mol of DOPO and 50mL of glacial acetic acid into a reaction kettle, heating to 80 ℃ under the condition of stirring, then dropwise adding glacial acetic acid solution of 1mmol of Pb catalyst into the reaction system, and reacting for 24 hours; separating and purifying to obtain the target product.
1H NMR(CDCl3,400MHz,TMS):δ＝6.94-7.64(m,8H,ph-H),2.92-2.95(d,4H,-C 2H-CH-C 2H-),2.25-2.30(m,1H,-CH-).
The phosphorus-containing flame retardant with anhydride prepared by the invention is applied to the preparation of polyester resin:
examples 1 to 6
A polyester composition is prepared by the following steps:
a polyester composition was prepared by mixing 60 parts by weight of maleic anhydride, 10 parts by weight of a phosphorus-containing flame retardant, 10 parts by weight of ethylene glycol, 10 parts by weight of 1, 2-propanediol, 50 parts by weight of poly (1, 4-cyclohexylenedimethylene) terephthalate, and 10 parts by weight of polyethylene terephthalate.
In the examples, the phosphorus-containing flame retardant was the phosphorus-containing flame retardant of the acid anhydride provided in preparation examples 1 to 6.
Comparative example 1
The only difference from example 1 is that the phosphorus containing flame retardant was replaced by maleic anhydride.
Comparative example 2
On the basis of comparative example 1, 10 parts by weight of ammonium polyphosphate was added.
Comparative example 3
On the basis of comparative example 1, 40 parts by weight of ammonium polyphosphate was added.
Performance testing
The resin compositions provided in examples 1 to 6 and comparative examples 1 to 3 were subjected to a performance test by the following method:
(1) combustibility: testing according to UL-94 vertical burning test standard;
(2) tensile strength and elongation: the test is carried out according to the specification of GB/T1040-;
(3) flame retardant stability: the polyester composition was boiled in water for 2 hours and dried to measure its flammability again.
The results of the tests on the examples and comparative examples are shown in Table 1:
TABLE 1
| Sample (I) | Combustibility | Tensile strength/MPa | Elongation at break/% | Combustibility after immersion in water |
| Example 1 | V-0 | 25.7 | 82 | V-0 |
| Example 2 | V-0 | 25.1 | 84 | V-0 |
| Example 3 | V-0 | 27.8 | 78 | V-0 |
| Example 4 | V-0 | 31.4 | 85 | V-0 |
| Example 5 | V-0 | 33.8 | 95 | V-0 |
| Example 6 | V-0 | 33.1 | 90 | V-0 |
| Comparative example 1 | V-2 | 20.1 | 50 | V-2 |
| Comparative example 2 | V-1 | 21.5 | 38 | V-2 |
| Comparative example 3 | V-0 | 24.3 | 29 | V-2 |
As can be seen from the examples and performance tests, the phosphorus-containing flame retardant with anhydride provided by the invention can participate in the preparation of the polyester composition, and the phosphorus-containing flame retardant with anhydride can enhance the mechanical property of polyester due to the existence of the phosphorus-containing flame retardant as a molecular chain segment, wherein the tensile strength is more than 25.1MPa and can reach more than 30.0MPa at most; meanwhile, the flame retardant property of the material can reach V-0 level, and the phosphorus-containing flame retardant provided by the invention has good flame retardant stability, and the flame retardant property can not be reduced because the flame retardant is dissolved in water in operations such as washing and the like.
The phosphorus-containing flame retardant with anhydride prepared by the invention is applied to the preparation of polyamide resin:
examples 7 to 12
A polyamide composition comprises the following components:
100 parts of hexamethylene diamine, 50 parts of reactive flame retardant, 61060 parts of nylon, 6640 parts of nylon, 5 parts of vinyl triethoxysilane and 20 parts of glass fiber.
The reactive flame retardants used in examples 7 to 12 were, in order, the phosphorus-containing flame retardants with acid anhydride provided in preparation examples 1 to 6.
Comparative example 4
The difference from example 7 is that the phosphorus-containing flame retardant with anhydride is replaced by adipic acid.
Comparative example 5
50 parts by weight of benzenediol tetraphenyl diphosphate were added on the basis of comparative example 4.
Performance testing
The polyamide compositions provided in examples 7 to 12 and comparative examples 4 to 5 were subjected to the following property tests:
(1) combustibility: testing according to UL-94 vertical burning test standard;
(2) tensile strength: the test is carried out according to the specification of GB/T1040-;
(3) flame retardant stability: the polyamide composition was boiled in water for 2 hours and dried to measure its flammability again.
(4) Mobility: the polyamide composition was baked at 150 ℃ for 2 hours and the weight difference percentage before and after baking was measured.
The test results are shown in table 2:
TABLE 2
The embodiment and the performance test show that the phosphorus-containing flame retardant with anhydride can participate in the preparation of polyamide resin, and the phosphorus-containing flame retardant exists as a molecular chain segment, so that the mechanical property of polyamide is not influenced, wherein the tensile strength is more than 118MPa and can reach more than 150 MPa; meanwhile, the flame retardant property of the material can reach V-0 level, and the phosphorus-containing flame retardant provided by the invention has good flame retardant stability, and the flame retardant property can not be reduced because the flame retardant is dissolved in water in operations such as washing and the like.
The phosphorus-containing flame retardant with anhydride prepared by the invention is used as an epoxy resin flame-retardant curing agent, and comprises the following components in percentage by weight:
examples 13 to 18
An epoxy resin composition, which consists of the following components:
100 parts of bisphenol A type epoxy resin (the epoxy equivalent is 450g/eq), 30 parts of flame-retardant curing agent, if the curing agent is complemented, the curing agent is complemented by dicyandiamide, and 0.5 part of 2-methylimidazole.
The flame retardant curing agents used in examples 13 to 18 were phosphorus-containing flame retardants with acid anhydride provided in preparation examples 1 to 6 in this order.
Comparative example 6
The only difference from example 13 is that 30 parts by weight of the flame retardant curing agent was replaced with a dicyandiamide curing agent in an amount sufficient for the epoxy resin to be cured.
Comparative examples 7 to 8
30 parts by weight (comparative example 7) and 45 parts by weight (comparative example 8) of triphenyl phosphate as a flame retardant were added to the case of comparative example 6.
Performance testing
The epoxy resin compositions provided in examples 13 to 18 and comparative examples 6 to 8 were prepared into copper clad laminates according to a known conventional method, and the following tests were carried out:
(1)Tg: differential Scanning Calorimetry (DSC) according to the DSC method defined in IPC-TM-650 at 2.4.25;
(2) dielectric constant (Dk) and dielectric loss factor (Df): testing the dielectric constant Dk and the dielectric loss Df of the board by adopting an SPDR method under the frequency of 10 GHz;
(3) combustibility: testing according to UL-94 vertical burning test standard;
(4) flame retardant stability: soaking the copper-clad plate in water for 1h, drying and measuring the combustibility of the copper-clad plate again;
(5) mobility: and baking the copper-clad plate at 150 ℃ for 2h, and testing the weight difference percentage before and after baking.
The results of the tests on examples 13-18 and comparative examples 6-8 are shown in Table 3:
TABLE 3
The embodiment and the performance test show that the copper-clad plate prepared by the phosphorus-containing flame retardant with anhydride provided by the invention has excellent performance, wherein the glass transition temperature is more than 161 ℃, the dielectric constant is less than 3.89(10GHz), the lowest dielectric constant can be less than 3.40(10GHz), the dielectric loss is less than 0.0078(10GHz), and the lowest dielectric loss can be less than 0.0040(10 GHz). The comparison between the embodiment and the comparative example shows that the additive flame retardant can affect the glass transition temperature, the peel strength and other properties of the copper-clad plate, and the additive flame retardant has a migratory type and part of additive flame retardant is soluble in water, so that the flame retardant stability is extremely poor.
The applicant states that the present invention is illustrated by the above examples of the phosphorus-containing flame retardant with acid anhydride and the preparation method and application thereof, but the present invention is not limited to the above detailed method, i.e. it does not mean that the present invention must be implemented by relying on the above detailed method. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (10)
1. A phosphorus-containing flame retardant with anhydride, characterized in that the phosphorus-containing flame retardant with anhydride has a structure shown in formula I:
wherein Z is1、Z2Each independently selected from phosphorus-containing groups;
M1selected from linear alkylene, branched alkylene or arylene;
M2selected from any organic group that satisfies a chemical environment;
Y1、Y2each independently selected from an inert group, a sulfur atom, an oxygen atom, or-H;
X1selected from any organylene group that satisfies a chemical environment;
g. h is independently selected from an integer of 0-5, and g and h are not 0 at the same time;
e is an integer of 0 to 100.
2. The phosphorus-containing flame retardant with acid anhydride according to claim 1, wherein Z is1、Z2Each independently preferably
R1Is any of saturated or unsaturated alkyl, aryl or heteroaryl, and is more preferably methyl, ethyl or phenyl.
3. The phosphorus-containing flame retardant with acid anhydride according to claim 1 or 2, wherein M is1Selected from the group consisting of C1-C30 linear or branched alkylene, C6-C30 arylene, and C5-C7 heteroarylene, more preferably C1-C5 linear alkylene, C3-C5 branched alkylene, or phenyl, still more preferably C1-C3 linear alkylene, C3 branched alkylene, or phenyl.
4. The anhydride-bearing phosphorus-containing flame retardant according to any one of claims 1 to 3, wherein M is the same as M2Selected from N, S, C1-C30 straight chain or branched chain alkyl, C6-C30 aryl, C5-C7 heteroaryl,
Wherein R is2、R3、R4、R5、R6、R7、R8、R9Each independently of the others is preferably a linear or branched alkylene group having from C1 to C10, L2、Y2、Z2Is connected to R2、R3、R4、R5、R6、R7、R8、R9N, m, i, k are each independently preferably an integer from 0 to 100;
preferably, Y1、Y2Each independently is preferably-H or ═ O.
5. The anhydride-bearing phosphorus-containing flame retardant of any one of claims 1 to 4, wherein X is1Selected from N, S, substituted or unsubstituted C1-C30 linear or branched alkylene, substituted or unsubstituted C6-C30 arylene, substituted or unsubstituted C5-C7 heteroarylene, substituted or unsubstituted C1-C30 alkyleneamine, substituted or unsubstituted C1-C30 alkyleneacyl, substituted or unsubstituted C1-C30 alkyleneester, substituted or unsubstituted C6-C30 aryleneamine, substituted or unsubstituted C6-C30 aryleneacyl or C6-C30 aryleneester, further preferably substituted or unsubstituted C1-C5 linear or branched alkylene, substituted or unsubstituted C1-C5 alkyleneamine, substituted or unsubstituted C1-C5 linear or branched alkyleneAlkyleneacyl or substituted or unsubstituted alkylene ester group of C1-C5, more preferably-NH-R-, -R' -NH-, -R "-O-, -R ″V-C (O) -, substituted or unsubstituted C1-C5 linear or branched alkylene, wherein, R, R', R ", RVEach independently is preferably a substituted or unsubstituted C1-C10 straight or branched chain alkylene group.
6. The anhydride-bearing phosphorus-containing flame retardant of any one of claims 1 to 5, wherein R is2、R3、R4、R5、R6、R7、R8、R9Each independently is preferably a linear or branched alkylene group of C1 to C6;
preferably, n, m, i, k are each independently preferably an integer from 0 to 30.
7. The anhydride-bearing phosphorus-containing flame retardant of any of claims 1 to 6, wherein the anhydride-bearing phosphorus-containing flame retardant preferably has a structure according to formula II:
wherein M is1Selected from C1-C3 linear alkylene, C3 branched alkylene or phenyl;
M2selected from N, -NH-RTStraight chain or branched chain alkyl of C1-C6,
Wherein R isTIs a linear or branched alkyl group of C1-C6, R2、R3、R4、R5、R6、R7、R8、R9Each independently is preferably a C1-C6 linear or branched alkylene group, and n, m, i, k each independently is preferably an integer of 0-30;
R1is methyl or ethyl;
RPa linear or branched alkylene group selected from substituted or unsubstituted C1-C10;
Y1、Y2each independently is preferably-H or ═ O;
g. h is preferably 0, 1 or 2 independently of one another, and g and h are not 0 at the same time;
e is an integer of 0 to 20.
8. Use of the phosphorus-containing flame retardant with an acid anhydride according to any one of claims 1 to 7 for the preparation of a polyester resin, a polyamide resin, an amino resin, a polyester resin, an alkyd resin or a silicone rubber resin.
9. A chain extender comprising the phosphorus-containing flame retardant with an acid anhydride of any one of claims 1 to 7;
preferably, the chain extender is applied to polyester resin, polyurethane resin, polyamide resin, amino resin, or silicone rubber.
10. An epoxy resin curing agent comprising the phosphorus-containing flame retardant with an acid anhydride according to any one of claims 1 to 7.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910803119.5A CN112442083A (en) | 2019-08-28 | 2019-08-28 | Phosphorus-containing flame retardant with anhydride and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910803119.5A CN112442083A (en) | 2019-08-28 | 2019-08-28 | Phosphorus-containing flame retardant with anhydride and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112442083A true CN112442083A (en) | 2021-03-05 |
Family
ID=74741659
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910803119.5A Pending CN112442083A (en) | 2019-08-28 | 2019-08-28 | Phosphorus-containing flame retardant with anhydride and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112442083A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112940224A (en) * | 2021-03-08 | 2021-06-11 | 西北工业大学 | Reactive flame retardant, preparation method thereof and epoxy resin-anhydride system flame retardant material |
| CN116023663A (en) * | 2023-01-09 | 2023-04-28 | 无锡东润电子材料科技有限公司 | Phosphorus-nitrogen-containing polysiloxane and preparation method and application thereof |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008303260A (en) * | 2007-06-06 | 2008-12-18 | Chisso Corp | Flame retardant, and curable composition using the same |
| WO2011080306A2 (en) * | 2009-12-31 | 2011-07-07 | Chemische Fabrik Budenheim Kg | Flame retardant composition for thermoplastic molding compounds |
| CN102134304A (en) * | 2011-03-03 | 2011-07-27 | 沈阳化工大学 | Reactive type phosphoric epoxy resin flame retardant and preparation method thereof |
| CN102617840A (en) * | 2012-03-28 | 2012-08-01 | 江苏恒力化纤股份有限公司 | Polyester industrial yarn solid-phase polymerization flame-retarding chain extender and preparing method thereof |
| CN106750183A (en) * | 2016-12-06 | 2017-05-31 | 沈阳化工大学 | A kind of DOPO modified anhydrides ethoxyline resin antiflaming curing agent and preparation method thereof |
| WO2018062475A1 (en) * | 2016-09-30 | 2018-04-05 | 株式会社クラレ | Copolymer composition having phosphonate group |
| CN109336927A (en) * | 2018-10-26 | 2019-02-15 | 洪湖市泰科技有限公司 | A kind of preparation method of phosphine system reactive flame retardant monomer |
| CN109721710A (en) * | 2018-07-27 | 2019-05-07 | 武汉工程大学 | A kind of new compound DOPO-MA and its synthetic method |
| CN109897222A (en) * | 2017-12-11 | 2019-06-18 | 广东广山新材料股份有限公司 | A kind of reactive flame retardant and its preparation method and application |
-
2019
- 2019-08-28 CN CN201910803119.5A patent/CN112442083A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008303260A (en) * | 2007-06-06 | 2008-12-18 | Chisso Corp | Flame retardant, and curable composition using the same |
| WO2011080306A2 (en) * | 2009-12-31 | 2011-07-07 | Chemische Fabrik Budenheim Kg | Flame retardant composition for thermoplastic molding compounds |
| CN102134304A (en) * | 2011-03-03 | 2011-07-27 | 沈阳化工大学 | Reactive type phosphoric epoxy resin flame retardant and preparation method thereof |
| CN102617840A (en) * | 2012-03-28 | 2012-08-01 | 江苏恒力化纤股份有限公司 | Polyester industrial yarn solid-phase polymerization flame-retarding chain extender and preparing method thereof |
| WO2018062475A1 (en) * | 2016-09-30 | 2018-04-05 | 株式会社クラレ | Copolymer composition having phosphonate group |
| CN106750183A (en) * | 2016-12-06 | 2017-05-31 | 沈阳化工大学 | A kind of DOPO modified anhydrides ethoxyline resin antiflaming curing agent and preparation method thereof |
| CN109897222A (en) * | 2017-12-11 | 2019-06-18 | 广东广山新材料股份有限公司 | A kind of reactive flame retardant and its preparation method and application |
| CN109721710A (en) * | 2018-07-27 | 2019-05-07 | 武汉工程大学 | A kind of new compound DOPO-MA and its synthetic method |
| CN109336927A (en) * | 2018-10-26 | 2019-02-15 | 洪湖市泰科技有限公司 | A kind of preparation method of phosphine system reactive flame retardant monomer |
Non-Patent Citations (3)
| Title |
|---|
| PENG LIU 等: "Preparation, characterization and properties of a halogen-free phosphorous flame-retarded poly(butylene terephthalate) composite based on a DOPO derivative", 《JOURNAL OF APPLIED POLYMER SCIENCE》 * |
| XUEJUANYANG 等: "Study on synthesis of novel phosphorus-containing flame retardant epoxy curing agents from renewable resources and the comprehensive properties of their combined cured products", 《PROGRESS IN ORGANIC COATINGS》 * |
| 朱思巧 等: "含磷阻燃环氧树脂固化剂研究进展", 《化工新型材料》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112940224A (en) * | 2021-03-08 | 2021-06-11 | 西北工业大学 | Reactive flame retardant, preparation method thereof and epoxy resin-anhydride system flame retardant material |
| CN116023663A (en) * | 2023-01-09 | 2023-04-28 | 无锡东润电子材料科技有限公司 | Phosphorus-nitrogen-containing polysiloxane and preparation method and application thereof |
| CN116023663B (en) * | 2023-01-09 | 2023-12-29 | 无锡东润电子材料科技有限公司 | Phosphorus-nitrogen-containing polysiloxane and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Lin et al. | Novel phosphorus-containing epoxy resins Part I. Synthesis and properties | |
| Wang et al. | Synthesis and properties of phosphorus‐containing epoxy resins by novel method | |
| CN103709717B (en) | Ethylene benzyl is etherified DOPO compound resins composition and preparation and application | |
| US6441067B1 (en) | Phosphorus-containing compounds and their use in flame retardance | |
| CN106986893B (en) | Phosphorus-containing compound and method for producing same | |
| CN112442073A (en) | Phosphorus-containing reactive flame retardant and preparation method and application thereof | |
| CN108503842B (en) | Poly (phenylphosphonate-amide) flame retardant, preparation method thereof and application thereof in polyester | |
| US5773533A (en) | Epoxy resin reacted with carboxy-functional phosphinic or phosphonic acid and hardener | |
| CN112442083A (en) | Phosphorus-containing flame retardant with anhydride and preparation method and application thereof | |
| CN113429770A (en) | Preparation method of efficient flame-retardant modified unsaturated polyester resin | |
| CN112442088A (en) | Phosphorus-containing flame retardant with carboxyl and preparation method and application thereof | |
| CN112442077A (en) | Phosphorus-containing flame retardant with reactive groups and preparation method and application thereof | |
| CN112442072A (en) | Reactive flame retardant with carboxylic acid or anhydride group, and preparation method and application thereof | |
| CN114409827B (en) | Synthesis and performance of transparent epoxy resin material with high flame retardant performance based on chitosan derivative | |
| CN113402712B (en) | Phosphorus-containing ladder-shaped polysiloxane and preparation method and application thereof | |
| CN112521418B (en) | Sulfhydryl-containing phosphorus-containing flame retardant and preparation method and application thereof | |
| CN112442067A (en) | Phosphorus-nitrogen-containing flame retardant with hydroxyl and preparation method and application thereof | |
| CN112442071B (en) | Phosphorus-containing reactive flame retardant, high-molecular flame retardant, preparation method and application | |
| CN109929098B (en) | Polymer, preparation method thereof and urushiol-based phosphorus-containing flame-retardant pressure-sensitive adhesive | |
| CN112442069A (en) | Phosphorus-containing flame retardant with amido, preparation method and application thereof | |
| CN108484881B (en) | Halogen-free flame-retardant epoxy resin and synthetic method thereof | |
| CN112480373A (en) | Flame-retardant epoxy resin composition and preparation method and application thereof | |
| CN112442162A (en) | Phosphorus-containing flame retardant with hydroxyl and preparation method and application thereof | |
| CN112480372B (en) | Phosphorus-containing compound with amino group, epoxy resin composition, preparation method and application | |
| CN112442212A (en) | Phosphorus-containing reactive flame retardant and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210305 |