WO2004113411A1 - Polyphosphonate flame retardant curing agent for epoxy resin - Google Patents
Polyphosphonate flame retardant curing agent for epoxy resin Download PDFInfo
- Publication number
- WO2004113411A1 WO2004113411A1 PCT/US2004/016459 US2004016459W WO2004113411A1 WO 2004113411 A1 WO2004113411 A1 WO 2004113411A1 US 2004016459 W US2004016459 W US 2004016459W WO 2004113411 A1 WO2004113411 A1 WO 2004113411A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- epoxy resin
- epoxy
- polyphosphonate
- composition
- curing agent
- Prior art date
Links
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 27
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 27
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 11
- 239000003063 flame retardant Substances 0.000 title description 6
- 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 description 5
- 239000000203 mixture Substances 0.000 claims abstract description 38
- 125000000732 arylene group Chemical group 0.000 claims abstract description 7
- 239000004593 Epoxy Substances 0.000 description 25
- 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 20
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 14
- 239000000047 product Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000000654 additive Substances 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- -1 arylenes diols Chemical class 0.000 description 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229920003986 novolac Polymers 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 229930185605 Bisphenol Natural products 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 230000037431 insertion Effects 0.000 description 3
- 238000003780 insertion Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 2
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 239000004594 Masterbatch (MB) Substances 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- VONWDASPFIQPDY-UHFFFAOYSA-N dimethyl methylphosphonate Chemical compound COP(C)(=O)OC VONWDASPFIQPDY-UHFFFAOYSA-N 0.000 description 2
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N methylimidazole Natural products CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 description 2
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- 150000005207 1,3-dihydroxybenzenes Chemical class 0.000 description 1
- 125000001989 1,3-phenylene group Chemical group [H]C1=C([H])C([*:1])=C([H])C([*:2])=C1[H] 0.000 description 1
- 150000005208 1,4-dihydroxybenzenes Chemical class 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- YYBGWBXKCAVMOJ-UHFFFAOYSA-N 3-cyclohexyl-2,4-dioxa-3$l^{5}-phosphabicyclo[3.3.1]nona-1(9),5,7-triene 3-oxide Chemical compound O1C(C=2)=CC=CC=2OP1(=O)C1CCCCC1 YYBGWBXKCAVMOJ-UHFFFAOYSA-N 0.000 description 1
- VWGKEVWFBOUAND-UHFFFAOYSA-N 4,4'-thiodiphenol Chemical compound C1=CC(O)=CC=C1SC1=CC=C(O)C=C1 VWGKEVWFBOUAND-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- JPYHHZQJCSQRJY-UHFFFAOYSA-N Phloroglucinol Natural products CCC=CCC=CCC=CCC=CCCCCC(=O)C1=C(O)C=C(O)C=C1O JPYHHZQJCSQRJY-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- HPUPGAFDTWIMBR-UHFFFAOYSA-N [methyl(phenoxy)phosphoryl]oxybenzene Chemical compound C=1C=CC=CC=1OP(=O)(C)OC1=CC=CC=C1 HPUPGAFDTWIMBR-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000005600 alkyl phosphonate group Chemical group 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical compound C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 description 1
- HECGKCOICWUUJU-UHFFFAOYSA-N bis(diphenylphosphanylmethyl)-phenylphosphane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CP(C=1C=CC=CC=1)CP(C=1C=CC=CC=1)C1=CC=CC=C1 HECGKCOICWUUJU-UHFFFAOYSA-N 0.000 description 1
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 229910001679 gibbsite Inorganic materials 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- YACKEPLHDIMKIO-UHFFFAOYSA-N methylphosphonic acid Chemical compound CP(O)(O)=O YACKEPLHDIMKIO-UHFFFAOYSA-N 0.000 description 1
- 239000012764 mineral filler Substances 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- QCDYQQDYXPDABM-UHFFFAOYSA-N phloroglucinol Chemical compound OC1=CC(O)=CC(O)=C1 QCDYQQDYXPDABM-UHFFFAOYSA-N 0.000 description 1
- 229960001553 phloroglucinol Drugs 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 239000012758 reinforcing additive Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- CYTQBVOFDCPGCX-UHFFFAOYSA-N trimethyl phosphite Chemical compound COP(OC)OC CYTQBVOFDCPGCX-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
-
- 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
- C08G59/62—Alcohols or phenols
- C08G59/621—Phenols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
- C08G59/4071—Curing agents not provided for by the groups C08G59/42 - C08G59/66 phosphorus containing compounds
-
- 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
- H05K1/032—Organic insulating material consisting of one material
- H05K1/0326—Organic insulating material consisting of one material containing O
Definitions
- the present invention relates to an epoxy resin composition that can be used, for example, in printed wiring boards for electronic applications. It represents a new embodiment, for example, over the type of flame retarded epoxy resin compositions described in PCT Patent Publication No. WO 03/029258 where an epoxy resin, which contained the type of polyphosphonate flame retardant additive that is also used in the epoxy resin compositions of the present invention, was cured in the presence of a methylimidazole curing catalyst.
- the composition of the present invention contains, as one essential component, an epoxy resin.
- This component is present at from about 50% to about 95%, by weight of the total weight of the composition.
- This component can be a non-halogen containing epoxy resin, such as a bisphenol A- type of epoxy resin, or other resins of this general type that have utility for the manufacture of printed wiring boards or other electronic substrate materials of that type (for example, bisphenol F epoxy, phenolic novolak epoxy, cresol novolak epoxy, and/or bisphenol A novolak epoxy resins) .
- a non-halogen containing epoxy resin such as a bisphenol A- type of epoxy resin, or other resins of this general type that have utility for the manufacture of printed wiring boards or other electronic substrate materials of that type (for example, bisphenol F epoxy, phenolic novolak epoxy, cresol novolak epoxy, and/or bisphenol A novolak epoxy resins) .
- Compatible mixtures of any of these resins may be employed, if desired.
- the polyphosphonate flame retardant curing agent that forms another essential additive of the compositions of the present invention is generally present at from about 5% to about 50%, by weight of the total weight of the composition, for example, from about 10% to about 35%, by weight.
- this polyphosphonate functions as the effective curing agent for the epoxy resin.
- This curing agent is an polyphosphonate composition having the formula: O O
- ⁇ V Y" is an arylene and "n" can range from about 2 to about 30.
- mixed arylenes diols and mixed alkylphosphonates can be used to prepare mixed products.
- This oligomeric or polymeric material has a phosphorus content of greater than about 10%, by weight.
- the polyphosphonate species in the composition comprise oligomers or polymers of this type that can either contain - OH end groups or not contain such end groups.
- the individual polyphosphonate species that contain -OH end groups can be monohydroxy or dihydroxy-substituted.
- the concentration of polyphosphonate species in the composition that contain hydroxy end groups can range from about 20% to about 100%, based upon the total number of termination ends ("chain ends") that potentially could hold such end groups, for example, from about 50% to about 100%.
- the number of OH terminal groups can be controlled by the ratio of arylene to phosphonate or by using end-capping agents such as triaryl phosphates. In the former case, if excess arylene- containing diol is used with the phosphonate reagent, for example, in making the polyphosphonate, there will be a higher hydroxyl content in the final product, and vice versa.
- the preferred R group is methyl, but can be lower alkyl .
- Arylene is meant any radical of a dihydric phenol.
- the dihydric phenol can have its two hydroxy groups in non- adjacent positions. Examples include the resorcinols; hydroquinones; and bisphenols, such as bisphenol A, bisphenol F, and 4, 4' -biphenol, phenolphthalein, 4,4'- thiodiphenol , or 4,4' -sulfonyldiphenol .
- a small amount of polyhydric phenol, such as a novolac or phloroglucinol with three or more hydroxyl groups therein can be included to increase the molecular weight.
- the Arylene group can be 1,3-phenylene, 1,4-phenylene, or a bisphenol diradical unit, but it is preferably 1,3-phenylene.
- the polyphosphonate curing agent for the epoxy resin composition of this invention can be made by any of several routes: (1) the reaction of an RP0C1 2 with HO-Aryl-OH or a salt thereof, where R is lower alkyl, preferably methyl; (2) the reaction of diphenyl alkylphosphonate , preferably methylphosphonate , with HO-Arylene-OH under transesterification conditions; (3) the reaction of an oligomeric phosphite with repeating units of the structure - OP (OR' ) -O-Arylene- with an Arbuzov rearrangement catalyst, where R' is lower alkyl, preferably methyl; or (4) the reaction of an oligomeric phosphite with the repeating units having the structure -OP (O-Ph) -O-Arylene with trimethyl phosphite and an Arbuzov catalyst or with dimethyl methylphosphonate with, optionally, an Arbuzov catalyst-.
- the -OH end groups, if attached to Arylene can be produced by having a controlled molar excess of the HO-Arylene-OH in the reaction media.
- the -OH end groups, if acid type (P- OH) can be formed by hydrolytic reactions . It is preferred that the end groups of the oligomers be mainly -Arylene-OH types .
- the epoxy resin composition of the present invention can contain optional additives like auxiliary flame retardant additive as well including the following types of materials: auxiliary curing catalysts, fiber and/or cloth reinforcing additives; mineral fillers, such as Al(OH) 3/ Mg(0H) 2 or silica; release agents; colorants; and the like.
- auxiliary flame retardant additive like auxiliary flame retardant additive as well including the following types of materials: auxiliary curing catalysts, fiber and/or cloth reinforcing additives; mineral fillers, such as Al(OH) 3/ Mg(0H) 2 or silica; release agents; colorants; and the like.
- Example 1 The aforementioned polyphosphonate curing agent (poly(m- phenylene methylphosphonate) (29.1 g) was mixed with 70.1 g of bisphenol A type epoxy (epoxy equivalent: 180) to prepare a master batch. A 10 g sample was removed from the master batch and was placed in a nitrogen-purged oven at 179°C. A sample was removed after ninety minutes and was cooled to room temperature. The Barkol hardness was than measured using Gl 934-1 meter. The sample was uniformly cured with a hardness of 28-29. The sample was submerged in acetone for twelve hours. No swelling or dissolution was observed.
- poly(m- phenylene methylphosphonate) 29.1 g
- bisphenol A type epoxy epoxy
- Comparative Example 2 A lOg sample of bisphenol A type epoxy (epoxy equivalent: 180) was placed the nitrogen-purged oven at 179°C for one hundred minutes. Sample did not cure or gel. It was a viscous liquid at room temperature and was completely soluble in acetone.
- FYROL PNX brand from Akzo Nobel was mixed with a bisphenol A di-epoxy resin (epoxy equivalent of 180) to form a mixture containing 70% of epoxy resin and 30% of FYROL PNX. Mixture was placed in the oven at 150°C for one and one half hours. It did not cure.
- a polyphosphonate which is the reaction product of dimethyl methylphosphonate, P 2 0 5 and ethylene oxide (FYROL HP brand from Akzo Nobel) with a hydroxyl number of 125mg KOH/g was mixed with a bisphenol A di-epoxy resin (epoxy equivalent 180) to form a mixture containing 70% of epoxy resin and 30% of the polyphosphonate. The mixture was placed in an oven at 150°C for one and one half hours. It did not cure.
- the epoxy insertion product as described in Example 7 was placed in the oven at 150°C for one hour and then the temperature was increased to 180°C over a period of one hour.
- the resulting cured epoxy composition had a BARKOL hardness of 32 (measured using Gl 934-1 meter) .
- the epoxy insertion product as described in Example 7 was dissolved in acetone and mixed with ATH to make a blend containing 62% ATH by weight and 38% of the epoxy composition.
- Acetone was evaporated under reduced pressure and resulting paste mixed well and cured at 150°C for one hour followed by a gradual temperature increase to 160°C over a period of thirty minutes.
- the resulting cured epoxy composition had a BARKOL hardness of 52.
- the epoxy insertion product as described in Example 7 dissolved in acetone and combined with 1000 ppm of methylimidazole and 1000 ppm of triphenyl phosphine. Acetone was evaporated under reduced pressure and sample cured at 138°C for one hour. The resulting cured epoxy composition had a BARKOL hardness of 25.
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Epoxy Resins (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US10/557,812 US7910665B2 (en) | 2004-05-19 | 2004-05-19 | Composition of epoxy resin and epoxy-reactive polyphosphonate |
| JP2006533410A JP2007502904A (ja) | 2003-05-22 | 2004-05-19 | ポリエキシ樹脂用ポリホスホネート難燃硬化剤 |
| CA002525856A CA2525856A1 (en) | 2003-05-22 | 2004-05-19 | Polyphosphonate flame retardant curing agent for epoxy resin |
| EP04776110A EP1625171A1 (en) | 2003-05-22 | 2004-05-19 | Polyphosphonate flame retardant curing agent for epoxy resin |
| TW093130123A TWI356839B (en) | 2004-05-19 | 2004-10-05 | Polyphosphonate flame retardant curing agent for e |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US47265403P | 2003-05-22 | 2003-05-22 | |
| US60/472,654 | 2003-05-22 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2004113411A1 true WO2004113411A1 (en) | 2004-12-29 |
Family
ID=33539043
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/US2004/016459 WO2004113411A1 (en) | 2003-05-22 | 2004-05-19 | Polyphosphonate flame retardant curing agent for epoxy resin |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP1625171A1 (enrdf_load_stackoverflow) |
| JP (1) | JP2007502904A (enrdf_load_stackoverflow) |
| KR (1) | KR20060019547A (enrdf_load_stackoverflow) |
| CN (1) | CN1795223A (enrdf_load_stackoverflow) |
| CA (1) | CA2525856A1 (enrdf_load_stackoverflow) |
| WO (1) | WO2004113411A1 (enrdf_load_stackoverflow) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010051182A1 (en) * | 2008-10-29 | 2010-05-06 | Icl-Ip America Inc. | Phosphorus-containing flame retardant epoxy resin composition, prepeg and laminate thereof |
| US20110132646A1 (en) * | 2009-06-12 | 2011-06-09 | Icl-Ip America Inc. | Flame retardant epoxy resin composition, prepreg and laminate thereof |
| EP2655384A4 (en) * | 2010-12-22 | 2014-04-16 | Frx Polymers Inc | OLIGOMER PHOSPHONATES AND COMPOSITIONS COMPRISING THE SAME |
| EP2716718A4 (en) * | 2011-06-03 | 2015-04-15 | Frx Polymers Inc | FIRE-RESISTANT RESIN, METAL-BASED BASE LAMINATE FOR A FLEXIBLE FITTED PCB WITH THIS COMPOSITION, COVER AND ADHESIVE FILM FOR FLEXIBLE FITTED PCBS AND FLEXIBLE FITTED LADDER PLATE |
| US10167377B2 (en) | 2013-01-22 | 2019-01-01 | Frx Polymers, Inc. | Phosphorus containing epoxy compounds and compositions therefrom |
| US11359047B2 (en) | 2017-09-13 | 2022-06-14 | Hexion Inc. | Epoxy resin systems |
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| KR101469270B1 (ko) * | 2011-12-30 | 2014-12-08 | 제일모직주식회사 | 폴리포스포네이트 공중합체, 그 제조 방법 및 이를 포함하는 난연성 열가소성 수지 조성물 |
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| CN105801814B (zh) | 2014-12-29 | 2018-05-04 | 广东生益科技股份有限公司 | 一种无卤热固性树脂组合物及使用它的预浸料和印制电路用层压板 |
| CN105330824A (zh) * | 2015-12-09 | 2016-02-17 | 西安元创化工科技股份有限公司 | 一种用于环氧树脂的阻燃固化剂及其制备方法 |
| TWI620785B (zh) * | 2016-08-10 | 2018-04-11 | Taiwan Union Technology Corporation | 樹脂組成物、及使用該樹脂組成物所製得之預浸漬片、金屬箔積層板及印刷電路板 |
| TWI620763B (zh) * | 2017-04-27 | 2018-04-11 | Taiwan Union Technology Corporation | 樹脂組成物、及使用該樹脂組成物所製得之預浸漬片、金屬箔積層板及印刷電路板 |
| CN107903383A (zh) * | 2017-11-22 | 2018-04-13 | 吉林省高性能复合材料制造业创新中心有限公司 | 中低温固化环氧树脂及其制备方法与在大小丝束碳纤维环氧复合传动轴中的应用 |
| CN107778456A (zh) * | 2017-11-22 | 2018-03-09 | 吉林省高性能复合材料制造业创新中心有限公司 | 中低温固化环氧树脂及其制备方法与在大丝束碳纤维环氧复合传动轴中的应用 |
| CN109705530B (zh) * | 2018-12-29 | 2021-06-04 | 广东生益科技股份有限公司 | 热固性树脂组合物及含有它的预浸料、层压板和高频电路基板 |
| CN112480373A (zh) * | 2019-09-11 | 2021-03-12 | 广东广山新材料股份有限公司 | 一种阻燃性环氧树脂组合物及其制备方法和应用 |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001019746A (ja) * | 1999-07-09 | 2001-01-23 | Asahi Denka Kogyo Kk | 難燃性エポキシ樹脂組成物 |
| WO2003029258A1 (en) * | 2001-10-04 | 2003-04-10 | Akzo Nobel N.V. | Oligomeric, hydroxy-terminated phosphonates |
| WO2004044054A1 (en) * | 2002-11-08 | 2004-05-27 | Akzo Nobel N.V. | Epoxy resin composition containing reactive flame retardant phosphonate oligomer and filler |
| WO2004060957A1 (de) * | 2003-01-07 | 2004-07-22 | Bakelite Ag | Phosphormodifiziertes epoxidharz |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1180178A (ja) * | 1997-09-12 | 1999-03-26 | Hitachi Chem Co Ltd | リン含有フェノール末端オリゴマー及びその製造法 |
| JP2002363259A (ja) * | 2001-06-04 | 2002-12-18 | Mitsubishi Gas Chem Co Inc | 難燃性樹脂組成物 |
-
2004
- 2004-05-19 CA CA002525856A patent/CA2525856A1/en not_active Abandoned
- 2004-05-19 EP EP04776110A patent/EP1625171A1/en not_active Withdrawn
- 2004-05-19 KR KR1020057022045A patent/KR20060019547A/ko not_active Ceased
- 2004-05-19 JP JP2006533410A patent/JP2007502904A/ja active Pending
- 2004-05-19 CN CNA2004800140798A patent/CN1795223A/zh active Pending
- 2004-05-19 WO PCT/US2004/016459 patent/WO2004113411A1/en active Application Filing
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001019746A (ja) * | 1999-07-09 | 2001-01-23 | Asahi Denka Kogyo Kk | 難燃性エポキシ樹脂組成物 |
| WO2003029258A1 (en) * | 2001-10-04 | 2003-04-10 | Akzo Nobel N.V. | Oligomeric, hydroxy-terminated phosphonates |
| WO2004044054A1 (en) * | 2002-11-08 | 2004-05-27 | Akzo Nobel N.V. | Epoxy resin composition containing reactive flame retardant phosphonate oligomer and filler |
| WO2004060957A1 (de) * | 2003-01-07 | 2004-07-22 | Bakelite Ag | Phosphormodifiziertes epoxidharz |
Non-Patent Citations (1)
| Title |
|---|
| PATENT ABSTRACTS OF JAPAN vol. 2000, no. 16 8 May 2001 (2001-05-08) * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010051182A1 (en) * | 2008-10-29 | 2010-05-06 | Icl-Ip America Inc. | Phosphorus-containing flame retardant epoxy resin composition, prepeg and laminate thereof |
| US20110132646A1 (en) * | 2009-06-12 | 2011-06-09 | Icl-Ip America Inc. | Flame retardant epoxy resin composition, prepreg and laminate thereof |
| EP2655384A4 (en) * | 2010-12-22 | 2014-04-16 | Frx Polymers Inc | OLIGOMER PHOSPHONATES AND COMPOSITIONS COMPRISING THE SAME |
| US8779041B2 (en) | 2010-12-22 | 2014-07-15 | Frx Polymers, Inc. | Oligomeric phosphonates and compositions including the same |
| EP2716718A4 (en) * | 2011-06-03 | 2015-04-15 | Frx Polymers Inc | FIRE-RESISTANT RESIN, METAL-BASED BASE LAMINATE FOR A FLEXIBLE FITTED PCB WITH THIS COMPOSITION, COVER AND ADHESIVE FILM FOR FLEXIBLE FITTED PCBS AND FLEXIBLE FITTED LADDER PLATE |
| US10167377B2 (en) | 2013-01-22 | 2019-01-01 | Frx Polymers, Inc. | Phosphorus containing epoxy compounds and compositions therefrom |
| US11359047B2 (en) | 2017-09-13 | 2022-06-14 | Hexion Inc. | Epoxy resin systems |
| CN115260453A (zh) * | 2017-09-13 | 2022-11-01 | 瀚森公司 | 环氧树脂体系 |
| CN115260453B (zh) * | 2017-09-13 | 2023-10-03 | 瀚森公司 | 环氧树脂体系 |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2007502904A (ja) | 2007-02-15 |
| CN1795223A (zh) | 2006-06-28 |
| KR20060019547A (ko) | 2006-03-03 |
| CA2525856A1 (en) | 2004-12-29 |
| EP1625171A1 (en) | 2006-02-15 |
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