WO2015179232A1 - Halogen-free active ester curing agent compound for epoxy resins, flame retardant composition comprising same, articles made therefrom and method of making said compound - Google Patents
Halogen-free active ester curing agent compound for epoxy resins, flame retardant composition comprising same, articles made therefrom and method of making said compound Download PDFInfo
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- WO2015179232A1 WO2015179232A1 PCT/US2015/031049 US2015031049W WO2015179232A1 WO 2015179232 A1 WO2015179232 A1 WO 2015179232A1 US 2015031049 W US2015031049 W US 2015031049W WO 2015179232 A1 WO2015179232 A1 WO 2015179232A1
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- epoxy
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- 239000000203 mixture Substances 0.000 title claims abstract description 191
- 150000001875 compounds Chemical class 0.000 title claims abstract description 136
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 96
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 84
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 36
- 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 title claims abstract description 26
- 239000003063 flame retardant Substances 0.000 title claims description 20
- 150000002148 esters Chemical class 0.000 title claims description 17
- 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 description 14
- 238000004519 manufacturing process Methods 0.000 title abstract description 7
- 229920005989 resin Polymers 0.000 claims abstract description 55
- 239000011347 resin Substances 0.000 claims abstract description 55
- 229920001187 thermosetting polymer Polymers 0.000 claims abstract description 45
- 239000004593 Epoxy Substances 0.000 claims description 54
- 125000004432 carbon atom Chemical group C* 0.000 claims description 38
- 239000003054 catalyst Substances 0.000 claims description 28
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- CMLFRMDBDNHMRA-UHFFFAOYSA-N 2h-1,2-benzoxazine Chemical compound C1=CC=C2C=CNOC2=C1 CMLFRMDBDNHMRA-UHFFFAOYSA-N 0.000 claims description 24
- DWSWCPPGLRSPIT-UHFFFAOYSA-N benzo[c][2,1]benzoxaphosphinin-6-ium 6-oxide Chemical compound C1=CC=C2[P+](=O)OC3=CC=CC=C3C2=C1 DWSWCPPGLRSPIT-UHFFFAOYSA-N 0.000 claims description 20
- 239000002841 Lewis acid Substances 0.000 claims description 19
- 150000007517 lewis acids Chemical class 0.000 claims description 19
- 239000004971 Cross linker Substances 0.000 claims description 18
- 125000000217 alkyl group Chemical group 0.000 claims description 17
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 13
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- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 claims description 6
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- -1 e.g. Polymers 0.000 abstract description 43
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- 239000000243 solution Substances 0.000 description 25
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- 238000009472 formulation Methods 0.000 description 15
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 14
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- 239000000047 product Substances 0.000 description 13
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- 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 10
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- 239000000126 substance Substances 0.000 description 9
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- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 7
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- 238000007666 vacuum forming Methods 0.000 description 1
- 239000006200 vaporizer Substances 0.000 description 1
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 150000003738 xylenes Chemical class 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
- C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
- C08J5/244—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using glass fibres
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
- B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
- B32B5/26—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
- C08J5/249—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs characterised by the additives used in the prepolymer mixture
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
-
- 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
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K21/00—Fireproofing materials
- C09K21/06—Organic materials
- C09K21/12—Organic materials containing phosphorus
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
- B32B2260/02—Composition of the impregnated, bonded or embedded layer
- B32B2260/021—Fibrous or filamentary layer
- B32B2260/023—Two or more layers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
- B32B2260/04—Impregnation, embedding, or binder material
- B32B2260/046—Synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
- B32B2262/10—Inorganic fibres
- B32B2262/101—Glass fibres
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/306—Resistant to heat
- B32B2307/3065—Flame resistant or retardant, fire resistant or retardant
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2457/00—Electrical equipment
- B32B2457/08—PCBs, i.e. printed circuit boards
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
- C08J2363/04—Epoxynovolacs
Definitions
- the present invention relates to the field of flame retardants, specifically phosphorous- containing flame retardants for electronic applications such as printed wiring boards.
- Synthetic resins are widely used in both industrial and consumer electronics because of among other things, their chemical resistance, mechanical strength and electrical properties.
- synthetic resins can be used in electronics as protective films, adhesive materials and/or insulating materials, such as interlayer insulating films.
- the synthetic resins need to provide ease of handling and certain necessary physical, thermal, electrical insulation and moisture resistance properties.
- synthetic resins having a low dielectric constant, and a low moisture uptake as well as a high glass transition temperature (Tg) can be a desirable combination of properties for electronic applications.
- Synthetic resins can be flammable. As such, different approaches have been made to impart a desired level of flame resistance to synthetic resins, e.g., epoxy resin, where such approaches entail employing either halogen-free flame retardant compounds or halogen- containing flame retardant compounds. Halogenated compounds, however, are now undergoing additional scrutiny, and the various non-halogenated compounds available do not provide the desired level of flame retardancy to the synthetic resin. It would be desirable to provide a desired level of flame retardancy to a synthetic resin such as an epoxy resin while still maintaining a suitable combinations of properties for electronic applications.
- thermosetting resins e.g., epoxy resins
- Tg glass transition temperature
- halogen-free active ester curing agent for epoxy resins can be used interchangeably with “halogen-free curing agent for epoxy resins", “epoxy curing agent”, “curing agent for epoxy”, “epoxy resin curing agent” and “curing agent”, and the like.
- R 4 is selected from a bond, a divalent alkylene moiety containing from 1 to about 6 carbon atoms, more specifically from 1 to about 4 carbon atoms, more specifically isopropylene, and a sulphone;
- R 5 is not -OH, and provided that when R 2 is of the general formula (III) and any one or more of R, R l , and R 3 are -OH, then R 5 is not -OH, and provided that when R 3 is of the general formula (III) and any one or more of R, R l , and R 3 are -OH, then R 5 is not -OH; and,
- the compound of the formula (I) as described herein can function as a curing agent for curing thermosetting resins, e.g., epoxy resin, as described herein or in another embodiment as a flame retardant additive for thermoplastic resin compositions and/or formulations.
- Figure 1 is the Pressure Cooker Test (PCT) results of an epoxy laminate containing Composition A from the conditions of 30 minutes and 288°C solder bath as described in
- Figure 2 is a graph of a DSC at 10°C/minute for Composition B described in Example 5
- Figure 3 is a graph of the dynamic viscosity profile of a B-stage prepreg at a ramp rate of 5°C/minute in a rheometer of Composition B as described in Example 5.
- Figure 4 is a graph of the overlays of storage modulus, loss modulus and complex viscosity of a B-staged resin system in a rheometer of Composition B described in Example 5.
- Figure 5 is a graph of a Dynamic Mechanical Analysis measurement for the glass transition temperature for the laminate of Composition B as described in Example 5.
- Figure 6 is a graph of a Thermogravimetric Analysis for the laminate of Composition B as described in Example 5.
- the present invention is directed to compound(s), which can function as a halogen-free active ester curing agent(s) for thermoseting resins, e.g., epoxy resins, which cured epoxy resins can be employed in electronic applicatons while maintaining a low dielectric constant, and a low moisture uptake as well as a high glass transition temperature (Tg).
- thermoseting resins e.g., epoxy resins, which cured epoxy resins can be employed in electronic applicatons while maintaining a low dielectric constant, and a low moisture uptake as well as a high glass transition temperature (Tg).
- the compound(s) which function as a halogen-free active ester curing agent for thermosetting resins e.g., epoxy resins
- the products are in the absence of hydroxyl groups, such as secondary hydroxyl groups thus, avoiding the high water absorption and higher dielectric constant of conventional curing systems, which when reacted with epoxy the products therein contain such secondary hydroxyl groups.
- the halogen-free active ester curing agent(s) described herein can be used as a flame retardant additive in thermoplastic compositions and/or formulations while maintainig optimal properties of the thermoplastic material.
- compound(s) which can be used as the curing agent compound for curing thermosetting resins is wherein the compound is selected from any one or more of the formulae (IV)-(VIII): wherein DOPO and R* are as defined herein and R 6 is an alkyl of from 1 to about 6 carbon atoms;
- DOPO and R* are as defined herein and R 6 is an alkyl of from 1 to about 6 carbon atoms, more specifically from 1 to about 4 carbon atoms, and most specifically from 1 to about 3 carbon atoms;
- DOPO and R* are as defined herein;
- DOPO and R* are as defined herein;
- formulae (VI)-(VIII) can be such wherein one or both of the -CH2-DOPO moieties on the right hand side of the structure are not present.
- the compound which can be used as the curing agent compound for curing thermosetting resins is of the general formula (IX):
- the compound(s) which can be used as the curing agent compound for curing thermosetting resins e.g., epoxy resin (e.g., the halogen-free active ester curing agent for epoxy resins described herein) can be a phosphorus containing compound such as those having at least one active ester group(s) per molecule, or one phenolic group and one active ester group(s) per molecule and a phosphorus content of at least 4 wt-percent. And more preferably the phosphorus containing compounds are those having at least two active ester groups per molecule and phosphorus content of 6%.
- epoxy resin e.g., the halogen-free active ester curing agent for epoxy resins described herein
- the phosphorus containing compounds are those having at least two active ester groups per molecule and phosphorus content of 6%.
- the compounds (I) and/or (IV)-(IX) described herein meet these requirements and are preferably substantially free (or completely free) of bromine atoms, and more preferably substantially free (or completely free) of halogen atoms.
- Compounds (I) and/or (IV)-(IX) described herein may also be used as a non-reactive additive, such as when used with a thermoplastic or other thermosetting systems, e.g., other than epoxy.
- Compound (I) and/or (IV)- (IX) noted above can be used a charring agent to provide an insulating layer of char at elevated temperatures for thermoplastic formulations and for thermosetting formulations.
- active ester refers to an aromatic ester that can react with epoxy according to the following scheme:
- R as defined here for the above scheme can be a linear or branched alkyl of from 1 to 6 carbon atoms or a non-substituted phenyl or a substituted phenyl containing up to about 12 carbon atoms, wherein the substituted phenyl can be substituted with a linear or branched alkyl of from 1 to 6 carbon atoms.
- compositions and/or formulations obtainable by reacting, blending or mixing Compound (I), and/or the related compounds (IV)-(IX) with other components such as a thermosetting resin or a thermoplastic material or a mixture of a thermosetting resin and a thermoplastic material to form various ignition resistant compounds, compositions or formulations useful in various applications such as prepregs, laminates, coatings, molding articles and composite products.
- Another embodiment herein is directed to phosphorous-containing epoxy resin curable formulations comprising (i) Compound (I), and/or the related compounds (IV)-(IX) (ii) an epoxy resin or a mixture of epoxy resins, (iii) optionally, a co-crosslinker, (iv) optionally, a curing catalyst, and (v) optionally, a Lewis acid.
- a curable flame-resistant epoxy resin composition comprising (i) the above phosphorus-containing compound (e.g., Compound (I), and/or (IV)-(IX)), (ii) optionally, a benzoxazine-containing compound, (iii) a crosslinkable epoxy resin or a blend of two or more epoxy resins having more than one epoxy group per molecule, (iv) optionally a co-crosslinker and, (v) optionally, a curing catalyst to obtain a curable flame resistant epoxy resin composition.
- Such curable flame resistant epoxy resin compositions may be used to make prepregs, which prepregs may be used to make laminates and circuit boards useful in the electronics industry.
- the epoxy resin composition may also be used to coat metallic foils such as copper foils to make resin coated copper foils for so called build-up technology.
- the phosphorus-containing compounds (Compounds (I), and/or (IV)-(IX) described herein), and derivatives thereof, may also be combined with at least one thermoplastic resin to make an ignition-resistant thermoplastic composition.
- the phosphorus-containing compounds, (Compounds (I), and/or (IV)-(IX) described herein) and derivatives thereof, may also be combined with at least one thermoplastic resin and thermosetting systems (epoxy and curing agents) to make a hybrid ignition-resistant
- thermoplastic containing thermosetting composition thermoplastic containing thermosetting composition
- Epoxy resin composition Ignition Resistant Epoxy Resin Composition (Epoxy resin composition)
- the phosphorus-containing compound (I) , and/or (IV)-(IX) described herein as well in one embodiment, combinations thereof, may be used, as one component, of a curable (crosslinkable) phosphorus- containing flame resistant epoxy resin composition.
- the curable phosphorus-containing flame-resistant epoxy resin composition comprises (i) the phosphorus-containing compound, Compound (I), and/or (IV)-(IX) described herein, (ii) at least one epoxy resin such as those selected from halogen-free epoxies, phosphorus-free epoxies, and phosphorus-containing epoxies and mixtures thereof, including, but not limited to DEN 438, DER 330 Epon 164 (DEN and DER are trademarks of The Dow Chemical Company), epoxy functional polyoxazolidone containing compounds, cycloaliphatic epoxies, GMA/styrene copolymers, and the reaction product of DEN 438 and DOPO resins; and optionally (iii) at least one co-crosslinker, and optionally one or more of a curing catalyst, a Lewis acid, an inhibitor, and a benzoxazine-containing compound.
- epoxy resin such as those selected from halogen-free e
- the curable phosphorous containing flame resistant epoxy resin composition optionally may contain at least one additional crosslinkable epoxy resin or a blend of two or more epoxy resins other than and different from component (ii) above.
- the curable phosphorous-containing flame resistant epoxy resin composition may also optionally contain at least one curing catalyst and at least one inhibitor. All of the above components may be blended or mixed together in any order to form the curable phosphorus-containing flame-resistant epoxy resin composition.
- the curable phosphorous-containing flame resistant epoxy resin compositions prepared according to the present invention may be used to make prepregs, which, in turn, may be used to make laminates and circuit boards useful in the electronics industry.
- the phosphorous- containing flame resistant epoxy resin compositions may also be used to coat metallic foils such as copper foils to make resin coated copper foils for so called build-up technology.
- R is substituted or unsubstituted aromatic, aliphatic, cycloaliphatic or heterocyclic group having a valence of "q", where "q” preferably has an average value of from 1 to less than about 8.
- the polyepoxide compounds useful in the present invention include the diglycidyl ethers of the following compounds: resorcinol, catechol, hydroquinone, bisphenol, bisphenol A, bisphenol AP (l,l-bis(4-hydroxylphenyl)-l -phenyl ethane), bisphenol F, bisphenol K, phenol-formaldehyde novolac resins, alkyi substituted phenol-formaldehyde resins, phenol- hydroxybenzaldehyde resins, cresol-hydroxybenzaldehyde resins, dicyclopentadiene-phenol resins, dicyclopentadiene-substituted phenol resins tetramethylbiphenol, and any combinations thereof.
- polyepoxide compounds useful in the present invention include a diglycidyl ether of bisphenol A having an epoxy equivalent weight (EEW) between 177 and 189 sold by The Dow Chemical Company under the trademark D.E.R. 330; the halogen-free epoxy- terminated polyoxazolidone resins, phosphorus element containing compounds; cycloaliphatic epoxies; and copolymers of glycidyl methacrylate ethers and styrene.
- EW epoxy equivalent weight
- Preferred polyepoxide compounds include epoxy novolacs, such as D.E.N. 438 or D.E.N. 439 (trademarks of The Dow Chemical Company); cresole epoxy novolacs such as QUATREX 3310, 3410 and 3710 available from Ciba Geigy; trisepoxy compounds, such as TACTIX 742 (trademark of Ciba Geigy Corporation of Basel, Switzerland); epoxidized bisphenol A novolacs, dicyclopentadiene phenol epoxy novolacs; glycidyl ethers of
- the most preferred epoxy compounds are epoxy novolac resins (sometimes referred to as epoxidized novolac resins, a term which is intended to embrace both epoxy phenol novolac resins and epoxy cresol novolac resins).
- Epoxy novolac resins (including epoxy cresol novolac resins) are readily commercially available, for example under the trade names D.E.N, (trademark of The Do Chemical Company), and QUATREX and TACTiX 742 (trademarks of Ciba Geigy).
- Preferred compounds of the type mentioned above have epoxy equivalent between 150- 400 and most preferably from 160-300 and molecular weight above 500 and most preferable between 700-2500.
- the polyepoxide useful in the present invention is preferably substantially free (or completely free) of bromine atoms, and more preferably substantially free (or completely free) of halogen atoms.
- polyepoxides that are useful in the present invention and that are substantially free of halogen atoms are the phosphorus-containing epoxy resins such as those which are the reaction products of an epoxy compound containing at least two epoxy groups and a reactive phosphorus-containing compound such as 3,4,5,6-dibenzo-l,2- oxaphosphane-2-oxide (DOP), or 10-(2',5'-dihydroxyphenyl)-9,10-dihydro-9-oxa-10- phosphaphenanthrene-10-o- xide (DOP-HQ).
- DOP 3,4,5,6-dibenzo-l,2- oxaphosphane-2-oxide
- DOP-HQ 10-(2',5'-dihydroxyphenyl)-9,10-dihydro-9-oxa-10- phosphaphenanthrene-10-o- xide
- thermoset composition and the hybrid composition is such that the final formulation of epoxy, any optional phosphorous containing epoxy, compound of the general formula (I) and/or (IV)-(IX) in the amounts described herein, and any other components in the amounts described herein or known to those skilled in the art, is such that the total phosphorous content of the composition is from 1 weight percent to about 5 weight percent, more specifically from about 2 to about 3.5 weight percent.
- the amount of epoxy to be commensurate with such other components so as to have a final phosphorous content as described above.
- the amount of such phosphorus containing epoxy in the final composition can vary from 0-90 parts, preferably 20-80 parts and most preferably from 30-50 parts based on 100 parts of epoxy resin.
- the amounts of epoxy resin described herein can in one non-limiting embodiment be the amounts of the thermoplastic resin in the thermoplastic composition described herein, the thermoset resin in the thermoset composition described herein and the combined amount of resins in the hybrid composition described herein.
- flame retardant effective amount of the compound (I) and/or (IV)- (IX) which can be used as the compound for curing epoxy resin herein in the curable epoxy resin composition described herein will vary depending on the specific epoxy resin and the specific compound being employed as well as specific parameters of processing as are known by those skilled in the art.
- flame retardant effective amount of the compound (I) and/or compound (IV)-(IX) which can be used for curing epoxy resin is from about 10 to about 150 parts by weight per 100 parts of the epoxy resin, more specifically from about 30 to about 100 parts by weight per 100 parts of the epoxy resin and most specifically from about 50 to about 70 parts by weight per 100 parts of the epoxy resin.
- compositions herein will have from 1.0% P to about 5% P in the final composition.
- the above stated amounts of compound (I) and/or (IV)-(IX) can be the amounts of compound (I) and/or (IV)- (IX) used in any of the epoxy resin composition, the thermoplastic composition, the thermoset composition and the hybrid composition described herein.
- a phosphorous-containing flame resistant epoxy resin compositions may be formed by blending (i) the phosphorus-containing product, Compound (I) and/or
- the phosphorous-containing flame resistant epoxy resin compositions may be formed by blending (i) an epoxidized Compound (I) and/or
- the phosphorous-containing flame resistant epoxy resin compositions may, optionally, contain at least one crosslinkable epoxy resin other than the crosslinkable phosphorus-containing epoxy compounds in (ii) above. In one embodiment herein it will be understood that the term
- crosslinkable in crosslinkable phosphorus-containing epoxy compound is understood to be a phosphorous-containing epoxy compound which has more than 2 epoxy functionalities, as would be understood by those skilled in the art.
- any number of co- crosslinking agents may optionally also be used.
- Suitable co-crosslinkers that may optionally be present in combination with the phosphorus-containing epoxy compounds according to the present invention include, for example, are the multifunctional co-crosslinkers as are known to those in the art.
- The-co-crosslinkers include, for example, copolymers of styrene and maleic anhydride having a molecular weight (M w ) in the range of from 1,500 to 50,000 and an anhydride content of more than 15 percent.
- SMA 1000, SMA 2000, and SMA 3000 and SMA 4000 having styrene-maleic anhydride ratios of 1:1, 2:1, 3:1 and 4:1, respectively, and having molecular weights ranging from 6,000 to 15,000, which are available from Elf Atochem S.A.
- hydroxyl- containing compounds such as those represented by the following Formula (XI):
- R is hydrogen or an alkyl group having from 1 to 20, preferably from 1 to 10, and more preferably 1 to 5 carbon atoms and "t” is an integer of from 0 to 20, preferably from 1 to 10, and more preferably from 2 to 5.
- Another example includes SD1708 (from Momentive): Viscosity at 150°C, 2200-3800 cps Softening Pt: 110°C; HRJ 13399 ( from SI Group): Specific Gravity 1.20, Softening Pt: 90- 105; HRJ12952 ( from SI Group): Specific Gravity 1.25, Softening Pt: 97-107; FRJ425 (from SI Group): Specific Gravity 1.24, Softening Pt: 112-118; BRJ 473 liquid (from SI Group): Specific Gravity 1.10, Brookfield viscosity: 1000-4500 cps.
- co-crosslinker that is suitable in the compositions described herein are active ester phenolic resins with general formula (XII):
- R is hydrogen, a aliphatic moiety of from 1 to 10 carbon atoms, or phenyl or a substituted phenyl
- R 10 is an aliphatic moiety of from 1 to 4 carbon atoms, or a phenyl or a substituted phenyl group.
- EPICLON HPC- 8000-65T available from DIC corporation, Japan.
- phenolic functional materials which are suitable as co-crosslinker include compounds which form a phenolic crosslinking agent having a functionality of at least 2 upon heating. Some examples of these compounds are benzoxazine groups-containing compounds. Examples of compounds which form a phenolic crosslinking agent upon heating include phenolic species obtained from heating benzoxazine, for example as illustrated in the following chemical equation:
- u is greater than 1 and preferably up to about 100,000; and wherein “R 11 " and “R 12 " may be, independently and separately, the same or different of a hydrogen, an allyl group from 1 to about 10 carbon atoms, such as methyl, a 6 to 20 carbon atom aromatic group such as phenyl or a 4 to 20 carbon atom cycloaliphatic group such as cyclohexane.
- Examples of the above compounds also include benzoxazine of phenolphthalein.
- benzoxazine of bisphenol- A benzoxazine of bisphenol-F
- benzoxazine of phenol novolac benzoxazine of phenol novolac
- a mixture of these compounds and Formula (XI) may also be used in the present invention.
- Non-limiting examples of commercial benzoxazines from Huntsman include examples such as Bisphenol A benzoxazine (MT35600) ; Bisphenol F benzoxazine (MT35700) Phenolphthalein benzoxazine (MT35800); Thiodiphenol benzoxazine (MT35900) and,
- the co-crosslinker is present in an amount to crosslink of less than 50 percent of the stoichiometric amount needed to cure the thermosetting resin, e.g., the epoxy resin, is more preferably less than about 40 % amount needed to cure the thermosetting resin, e.g., epoxy resin and most preferably less than about 35 % amount needed to cure the thermosetting resin, e.g., epoxy resin.
- Any of the curable compositions of the present invention described herein may comprise a curing catalyst.
- Suitable curing catalyst (catalyst) materials useful in the present invention include compounds containing amine, phosphine, ammonium, phosphonium, arsonium or sulfonium moieties or mixtures thereof. Particularly preferred catalysts are heterocyclic nitrogen-containing compounds.
- the catalysts (as distinguished from co-crosslinkers) preferably contain on average no more than about 1 active hydrogen moiety per molecule.
- Active hydrogen moieties include hydrogen atoms bonded to an amine group, a phenolic hydroxyl group, or a carboxylic acid group.
- the amine and phosphine moieties in catalysts are preferably tertiary amine or phosphine moieties; and the ammonium and phosphonium moieties are preferably quaternary ammonium and phosphonium moieties.
- tertiary amines that may be used as catalysts are those mono- or polyamines having an open-chain or cyclic structure which have all of the amine hydrogen replaced by suitable substituents, such as hydrocarbyl radicals, and preferably aliphatic, cycloaliphatic or aromatic radicals.
- Examples of these amines include, among others, l,8-diazabicyclo(5.4.0)undec-7-en (DBU), methyl diethanol amine, triethylamine, tributylamine, dimethyl benzylamine, triphenylamine, tricyclohexyl amine, pyridine and quinoline.
- DBU l,8-diazabicyclo(5.4.0)undec-7-en
- Preferred amines are the trialkyl, tricycloalkyl and triaryl amines, such as triethylamine, triphenylamine, tri-(2,3- dimethylcyclohexyl)amine, and the alkyl dialkanol amines, such as methyl diethanol amines and the trialkanolamines such as triethanolamine
- Weak tertiary amines for example, amines that in aqueous solutions give a pH less than 10 in aqueous solutions of 1 M concentration, are particularly preferred.
- Especially preferred tertiary amine catalysts are benzyldimethylamine and tris-(dimethylaminomethyl)phenol.
- heterocyclic nitrogen- containing catalysts include heterocyclic secondary and tertiary amines or nitrogen-containing catalysts which can be employed herein include, for example, imidazoles, benzimidazoles, imidazolidines, imidazolines, oxazoles, pyrroles, thiazoles, pyridines, pyrazines, morpholines, pyridazines, pyrimidines, pyrrolidines, pyrazoles, quinoxalines, quinazolines, phthalozines, quinolines, purines, indazoles, indoles, indolazines, phenazines, phenarsazines, phenothiazines, pyrrolines, indolines, piperidines, piperazines and combinations thereof.
- alkyl-substituted imidazoles 2,5-chloro-4-ethyl imidazole; and phenyl-substituted imidazoles, and mixtures thereof.
- N-methylimidazole 2-methylimidazole; 2-ethyl-4-methylimidazole; 1,2- dimethylimidazole; and 2-methylimidazole and mixtures thereof.
- 2- phenylimidazole is 2- phenylimidazole.
- the amount of curing catalyst used depends on the molecular weight of the catalyst, the activity of the catalyst and the speed at which the polymerization is intended to proceed.
- the curing catalyst is used in an amount of from 0.01 parts per 100 parts of resin (p.h.r.) to about 1.0 p.h.r., more specifically, from about 0.01 p.h.r. to about 0.5 p.h.r. and, most specifically, from about 0.1 p.h.r. to about 0.5 p.h.r.
- a Lewis acid is also employed in any of the curable epoxy resin compositions of the present invention described herein, especially when the catalyst is particularly a heterocyclic nitrogen-containing compound.
- the Lewis acids useful in the present invention include for example one or a mixture of two or more haiides, oxides, hydroxides and alkoxides of zinc, tin, titanium, cobalt, manganese, iron, silicon, aluminum, and boron, for example Lewis acids of boron, and anhydrides of Lewis acids of boron, for example boric acid, metaboric acid, optionally substituted boroxines (such as trimethoxyboroxine), optionally substituted oxides of boron, alkyl borates, boron haiides, zinc haiides (such as zinc chloride) and other Lewis acids that tend to have a relatively weak conjugate base.
- Lewis acids of boron for example boric acid, metaboric acid, optionally substituted boroxines (such as trimethoxyboroxine), optionally substituted oxides of boron, alkyl borates, boron haiides, zinc haiides (such as zinc chloride) and other Lewis acids that tend to have a relatively weak conjug
- the Lewis acid is a Lewis acid of boron, or an anhydride of a Lewis acid of boron, for example boric acid, metaboric acid, an optionally substituted boroxine (such as trimethoxy boroxine, trimethyl boroxine or triethyl boroxine), an optionally substituted oxide of boron, or an alkyl borate.
- a Lewis acid of boron for example boric acid, metaboric acid, an optionally substituted boroxine (such as trimethoxy boroxine, trimethyl boroxine or triethyl boroxine), an optionally substituted oxide of boron, or an alkyl borate.
- the most preferred Lewis acid is boric acid.
- the Lewis acids and amines can be combined before mixing into the formulation or by mixing with the catalyst in situ, to make a curing catalyst combination.
- the amount of the Lewis acid employed is preferably at least 0.1 mole of Lewis acid per mole of heterocyclic nitrogen compound, more preferably at least 0.3 mole of Lewis acid per mole of heterocyclic nitrogen-containing compound.
- the curable compositions of the present invention may optionally have boric acid and/or maleic acid present as a cure inhibitor.
- the curing agent is preferably a polyamine or polyamide.
- the amount of cure inhibitor will be known by those skilled in the art.
- the curable compositions of the present invention may also optionally contain one or more additional flame retardant additives including, for example, red phosphorus, encapsulated red phosphorus or liquid or solid phosphorus-containing compounds, for example, "EXOLIT OP 930", EXOLIT OP 910 from Clariant GmbH and ammonium polyphosphate such as "EXOLIT 700" from Clariant GmbH, a phosphite, or phosphazenes; nitrogen-containing fire retardants and/or synergists, for example melamines, melem, cyanuric acid, isocyanuric acid and derivatives of those nitrogen-containing compounds; halogenated flame retardants and halogenated epoxy resins (especially brominated epoxy resins); synergistic phosphorus-halogen containing chemicals or compounds containing salts of organic acids; inorganic metal hydrates such as Sb 2 0 , SbaOj, aluminum trihydroxide and magnesium hydroxide such as "ZEROGEN 30" from Martin
- the phosphorus-containing flame retardants are preferably present in amounts such that the total phosphorus content of the epoxy resin composition is from 0.2 wt. percent to 5 wt. percent.
- the curable compositions of the present invention may also optionally contain other additives of a generally conventional type including for example, stabilizers, other organic or inorganic additives, pigments, wetting agents, flow modifiers, UV light blockers, and fluorescent additives. These additives can be present in amounts of from 0 to 5 weight-percent and is preferably present in amounts less than 3 weight percent.
- the flame resistant epoxy resin is preferably free of bromine atoms, and more preferably free of halogen atoms.
- compositions described above are useful for making coating formulations, encapsulation, composites, and adhesives, molding, bonding sheets, and laminated plates.
- the compositions of the present invention can be used to make composite materials by techniques well-known in the industry, such as by pultrusion, molding, encapsulation, or coating.
- a coating formulation may comprise (i) Compound (I), and/or Compounds (IV)-(IX) (ii) a solid epoxy resin, and (iii) a hardener such as an amine or phenolic hardener.
- a hardener such as an amine or phenolic hardener.
- the amounts of hardener will be known by those skilled in the art.
- the present invention is particularly useful for making B-staged prepregs, laminates, bonding sheets, and resin coated copper foils by well known techniques in the industry.
- Thermoplastic resin composition Ignition-Resistant Thermoplastic Resins (Thermoplastic resin composition)
- the phosphorus-containing product, Compound (I), and/or Compounds (IV)-(IX) are used to make phosphorus-containing ignition resistant thermoplastic resins.
- a halogen-free ignition-resistant thermoplastic resin composition are obtainable by blending (i) the phosphorus-containing compound, Compound (I), and/or Compounds (IV)-(IX) according to the present invention with (ii) at least one thermoplastic resin, and optionally any one or more of the optional components described for the thermosetting (e.g., epoxy) resin composition described herein.
- thermoplastic polymers include, but are not limited to, polymers produced from vinyl aromatic monomers and hydrogenated versions thereof, including both diene and aromatic hydrogenated versions, including aromatic hydrogenation, such as styrene-butadiene block copolymers, polystyrene (including high impact polystyrene), acrylonitrile-butadiene-styrene (ABS) copolymers, and styrene-acrylonitrile copolymers (SAN); polycarbonate (PC), ABS/PC compositions, polyethylene terephthalate, epoxy resins, hydroxy phenoxy ether polymers (PHE), ethylene vinyl alcohol copolymers, ethylene acrylic acid copolymers, polyolefin carbon monoxide interpolymers, chlorinated polyethylene, polyolefins (for example, ethylene polymers and propylene polymers, such as polyethylene, polypropylene, and copolymers of ethylene and/or propylene with each other or with an alpha-ole
- thermoplastic polymers are well-known by those skilled in the art, as well as methods for making them.
- the thermoplastic polymer is a rubber-modified
- monovinylidene aromatic polymer produced by polymerizing a vinyl aromatic monomer in the presence of a dissolved elastomer or rubber.
- thermoplastic polymer or polymer blend is employed in the halogen-free ignition resistant polymer compositions of the present invention in amounts of at least 35 parts by weight, preferably at least 40 parts by weight, more preferably at least 45 parts by weight, and most preferably at least 50 parts by weight based on 100 parts by weight of the halogen-free ignition resistant polymer composition of the present invention.
- the thermoplastic polymer component is employed in amounts less than or equal to 99 parts by weight, preferably less than or equal to 95 parts by weight, more preferably less than or equal to about 90 parts by weight, and most preferably less than or equal to about 85 parts by weight based on 100 parts by weight of the halogen-free ignition resistant polymer composition of the present invention.
- the halogen-free ignition resistant polymer composition of the present invention comprises Compound (I) and/or Compounds (IV) -(IX) with a blend of two thermoplastic polymers wherein at least one of the thermoplastic polymers is for example a polyphenylene ether.
- Polyphenylene ethers are made by a variety of well known catalytic and non-catalytic processes from corresponding phenols or reactive derivatives thereof.
- the polyphenylene ether resin is preferably employed in the halogen-free ignition resistant polymer compositions of the present invention in amounts of at least 5 parts by weight, preferably 10 part by weight, more preferably at least 12 parts by weight, more preferably at least 15 parts by weight, and most preferably at least 18 parts by weight to 30 parts by weight, preferably to 28 parts by weight, more preferably to 25 parts by weight, based on 100 parts by weight of the halogen-free ignition resistant polymer composition of the present invention.
- the thermoplastic and polyphenylene ether polymer can be prepared as a blend prior to incorporation into the composition of the present invention, or each polymer can be incorporated individually.
- compositions of the present invention may include other additives such as modifiers that include compounds containing functionalities which will enhance the mechanical properties of the composition and are compatible with the thermoplastic resin.
- modifiers such as compounds containing functionalities which will enhance the mechanical properties of the composition and are compatible with the thermoplastic resin.
- such functionalities might include, but are not limited to, butadienes, styrene-maleic anhydrides, polybutadiene-maleic anhydride copolymers, carboxylic acid terminated butadienes, and carboxylic acid functionalized polystyrenes. Any combination of modifiers can be used in modifying the phosphorus element- containing epoxy compounds.
- the amount of Compound (I), and/or Compounds (IV)-(IX) used in the ignition resistant thermoplastic polymer composition of the present invention is typically at least 1 weight-percent, generally at least 5 weight-percent, preferably at least 10, more preferably at least 15, and most preferably at least 20, weight-percent and less than 50, preferably less than 45, more preferably less than 40 and most preferably less than 35, weight-percent, based on the total weight of the ignition resistant polymer composition.
- thermoplastic resin compositions herein can contain any of the components and or ranges of amounts of components described herein for the thermosetting composition, the epoxy resin composition, or the hybrid compositions and vice-versa and of the thermoplastic composition, i.e., any of the components and or amounts of the components of the thermoplastic composition described herein can be used in any of the thermosetting composition, the epoxy resin composition, or the hybrid compositions described herein.
- Preparation of the ignition resistant thermoplastic polymer composition of the present invention can be accomplished by any suitable mixing means known in the art, including dry blending the individual components and subsequently melt mixing, either directly in the extruder used to make the finished article or pre-mixing in a separate extruder. Dry blends of the compositions can also be directly injection molded without pre-melt mixing.
- the ignition resistant thermoplastic polymer composition of this invention can be formed or molded using conventional techniques such as compression molding, injection molding, gas assisted injection molding, calendaring, vacuum forming, thermoforming, extrusion and/or blow molding, alone or in combination.
- the ignition resistant thermoplastic polymer composition can also be formed, spun, or drawn into films, fibers, multi-layer laminates or extruded sheets, or can be compounded with one or more organic or inorganic substances, on any machine suitable for such purpose.
- thermoplastic compositions of the present invention can be utilized in the preparation of foam.
- the ignition resistant thermoplastic polymer composition is extruded into foam by melt processing it with a blowing agent to form a foamable mixture, extruding said foamable mixture through an extrusion die to a region of reduced pressure and allowing the foamable mixture to expand and cool.
- Conventional foam extrusion equipment such as screw extruders, twin screw extruders and accumulating extrusion apparatus can be used.
- the halogen-free ignition resistant thermoplastic polymer composition of the present invention may optionally include, in addition to Compound (I), and/or Compounds (IV)-(IX) other phosphorus- containing compounds.
- thermoplastic composition of the present invention may also include other flame retardant additives which can be phosphorus or non-phosphorus materials as described above.
- the amount of optional phosphorus-containing compounds, other than Compound (I), and/or Compounds (IV) -(IX) and/or the optional flame retardant additives used in the composition of the present invention may be from 0 up to 30 weight percent.
- the amount of optional phosphorus-containing component, other than Compound (I), and/or Compounds (IV)- (IX) when present, is preferably at least 1 weight-percent and preferably up to 30 weight-percent based on the total weight of the thermoplastic resin.
- the amount of component, Compound (I), and/or Compounds (IV)-(IX) is preferably at least 5 weight-percent and preferably up to 20 weight-percent, based on the total weight of the thermoplastic resin.
- the ignition resistant thermoplastic resin is preferably substantially free of bromine atoms, and more preferably completely free of halogen atoms.
- thermoplastic polymer compositions of the present invention are useful to fabricate numerous useful articles and parts.
- Some of the articles which are particularly well suited include television cabinets, computer monitors, related printer housings which typically requires to have excellent flammability ratings.
- Other applications include automotive and small appliances.
- Thermosetting composition (Thermosetting composition)
- the phosphorus-containing product, Compound (I), and/or Compounds (IV)-(IX) is used to make a phosphorus-containing ignition resistant thermosetting composition, e.g., in one non-limiting embodiment wherein the thermoset polymer is in addition to or other than epoxy.
- a halogen-free ignition-resistant thermosetting composition is obtainable by blending (i) the phosphorus-containing compound, Compound (I), and/or Compounds (IV)-(IX) according to the present invention with (ii) at least one thermosetting system.
- thermosetting systems are epoxy, polyurethane, polyisocyanates, benzoxazine ring- containing compounds, unsaturated resin systems containing double or triple bonds, polycyanate ester, bismaleimide, triazine, bismaleimide and mixtures thereof.
- thermoset resin compositions herein can contain any of the components and or ranges of amounts of such components described herein for the curable epoxy resin composition, the thermoplastic composition or the hybrid compositions and vice- versa and of the thermoset resin composition, i.e., any of the components and or amounts of the components of the thermoset composition described herein can be used in any of the epoxy composition, the thermoplastic resin composition, or the hybrid compositions described herein.
- the phosphorus-containing product, Compound (I), and/or Compounds (IV)-(IX) is used to make phosphorus-containing ignition resistant hybrid resin system that contains both a thermoplastic and a thermosetting system.
- hybrid ignition-resistant thermoplastic and thermosetting compositions are obtainable by blending (i) the phosphorus-containing compound, Compound (I), and/or
- thermoplastic resins are polyphenylene oxide (PPO), mixtures thereof, and others as described above.
- thermosetting systems are epoxy, polyurethane, polyisocyanates, benzoxazine ring-containing compounds, unsaturated resin systems containing double or triple bonds, polycyanate ester, bismaleimide, triazine,
- the hybrid ignition-resistant thermoplastic and thermosetting composition can contain any of the optional components and amounts thereof described in the subject disclosure.
- the amount of thermoplastic resin in the hybrid composition can be from about 20 to about 95 and preferably from about 30 to about 80, while the amount of thermoset resin can be from about 10 to about 20 and more preferably from about 30 to about 40 wherein said amounts are based on the total amount of thermoplastic and thermoset resin employed.
- the hybrid resin compositions herein can contain any of the components and or ranges of amounts of components described herein for the the epoxy resin composition, the thermosetting resin composition or the thermoplastic resin composition and vice-versa any of the epoxy resin composition, the thermosetting resin composition and the thermoplastic resin composition can contain any of the components and or amounts of the components of the hybrid resin
- the article herein can be used in lead free soldering applications and electronic devices, e.g., printed wiring board applications, specifically the article can be a prepreg and/or a laminate.
- a laminate and/or a prepreg that contains any one or more of the compositions described herein.
- a printed wiring board optionally a multilayer printed wiring board, comprising one or more prepreg(s) and/or a laminate (e.g., either uncured, partially cured or completely cured) wherein said prepreg(s) and/or laminate comprise any one or more of the compositions described herein.
- a printed wiring board comprising a prepreg and/or a laminate wherein said prepreg and/or laminate comprises any one of the compositions described herein.
- Partial curing as used herein can comprise any level of curing, short of complete cure, and will vary widely depending on the specific materials and conditions of manufacture as well as the desired end-use applications.
- the article herein can further comprise a copper foil.
- the article can comprise a printed wiring board.
- an FR-4 laminate which comprises a prepreg and/or laminate of the invention.
- a printed circuit board comprising an FR-4 laminate, wherein the FR-4 laminate comprises a prepreg or laminate of the invention.
- a process of making a laminate that contains any of the compositions described herein comprises impregnating the respective composition(s) into a filler material, e.g., a glass fiber mat to form a prepreg, followed by processing the prepreg at elevated temperature and/or pressure to promote partial cure to a B- stage and then laminating two or more of said prepregs to form said laminate.
- a filler material e.g., a glass fiber mat
- said prepreg can be used in the applications described herein, e.g., printed wiring boards.
- any of the compositions described herein are useful for making a prepreg and/or laminate with a good balance of laminate properties and thermal stability, such as one or more of high T g (i.e. above 130°C), Ta of 330°C and above, t 28 8 of 5 minutes and above, a flame resistance rating of V-0, good toughness, and good adhesion to copper foil.
- T ⁇ j has become one of the most important parameters, because the industry is changing to lead-free solders which melt at higher temperature than traditional tin- lead solders.
- compositions described herein can be used in other applications, e.g., encapsulants for electronic elements, protective coatings, structural adhesives, structural and/or decorative composite materials in amounts as deemed necessary depending on the particular application.
- thermosetting resins e.g., epoxy resins
- 2,4,6-tris-morpholinomethyl-l,3-dihydroxybenzene is reacted with 10-ethoxy-10H-9- oxa-10-phospha-phenanthrene (DOP-OEt) and also acetic anhydride to form 2,4,6-tris-DOPO- 1 ,3-dihydroxybenzene.
- DOP-OEt 10-ethoxy-10H-9- oxa-10-phospha-phenanthrene
- the method of making the halogen-free active ester curing agent of formula (1) and/or (I V)-(IX) herein can comprise reacting any substituted hydroxyaromatic Mannich-base with any carboxylic anhydride and an alkoxylated phospha- phenanthrene compound in the presence of a hydrocarbon solvent to produce compounds of the general formula (I) and/or (IV)- (IX).
- the method of making the halogen-free active ester curing agent of formula (I) and/or (IV)-(IX) herein can comprise the following general reaction mechanism:
- substituted hydroxyaromatic Mannich-base the carboxylic anhydride and the DOP- O-alkyl are defined in various non-limiting embodiments below.
- the substituted hydroxyaromatic Mannich-base is selected from one or more of the general formulae (A) and/or (B):
- R and R are each independently 1 to 12 carbon atom-containing linear or branched alkyl radicals such as the non-limiting examples of methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, isopentyl, hexyl, heptyl, 3-heptyl, octyl, 2- ethylhexyl, nonyl, decyl, undecyl, ddecyl, 2-ethylbutyl, 1-methylbutyl, 1 -rnethylpentyl, 1,3- dimethylbutyl, 1,1,3,3-tetramethylbutyl, 1 -trimethylhexyl, isoheptyl, 1 -methylheptyl, 1,1,3- trimefhylhexyl and 1-methylundecyl, and R 3 is hydrogen, -OH,
- each R ! is independently selected from morpholine, piperazine, ] -Methylpiperazine, piperidine, pyrrolidine and 2-Pyrrolidinone;
- R 3 is, hydrogen, ⁇ OH or an alkyl group of from 1 to 6 carbon atoms, more specifically from 1 to about 4 carbon atoms.
- the carboxylic anhydride may be derived from any carboxylic acid.
- examples of such anhydrides are acetic anhydride, succinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydiophthalic anhydride, as well as hexahydrophthalic anhydride.
- DOP-O-Alkyl is selected from the general formulae (C):
- R 1 is a linear or branched alkyl group containing from I to 8 carbon atoms, more specifically from 1 to about 4 carbon atoms; each of R 2 -R 9 is independently a hydrogen atom or a hydrocarbyl group that may contain on or more heteroatrom such as O, S, N, P or Si provided that not more than 3 of R 2 - R 5 '" are hydrogen atoms, and each of R ⁇ R 9
- R 1* is hydrogen, a linear or branched alkyl group of from 1 to 8 carbon atoms, more specifically from 1 to about 4 carbon atoms.
- each R* is independently an aliphatic moiety of from 1 to 10 carbon atoms, or phenyl or a substituted phenyl of up to about 12 carbon atoms.
- the solvent o-xylene indicated in the reaction mechanism above is one embodiment of the invention although the solvent can be any organic, preferably aprotic, solvent.
- the solvent may be polar or non-polar.
- Exemplary of polar aprotic solvents are dimethyl formamide, dimethyl acetamide and N-methylpyrrolidone.
- Preferred solvents are aprotic and non-polar, conveniently aliphatic hydrocarbons, typically heptane, octane, cyclohexane, decalin, mineral oil distillates, such as petroleum ether, ligroin, kerosene, aromatic hydrocarbons such as benzene, toluene, or xylenes, or mixtures of said solvents.
- the amounts of (A) and/or (B), carboxylic anhydride, and (C) are used in equimolar amounts but an excess of up to 20%, preferably up to 10% of one or more of (A) and/or (B), carboxylic anhydride and (C) can be useful.
- the reaction temperature of the above reaction mechanism range from room temperature (e.g., 25°C) up to about 200°C, preferably from 50°C to about 140°C and most preferably from 60°C to about 120°C.
- CDCI 3 , ⁇ , ppm 7.90-7.84 (m, 2H), 7.60-7.48 (m, 2H), 7.37-7.25 (m, 2H), 7.19-7.10 (m, 2H); 31 P NMR (121 MHz, CDCI 3 , ppm): 134.
- DOPO-OEt (8.9 g, 36.8 mmol) synthesized as in Step 2, and 2,4,6- ⁇ 3 ⁇ ⁇ 1 ⁇ 1-1,3- dihydroxybenzene (5 g, 12.26 mmol) synthesized as in Step 3 were dissolved in o-xylene and heated to 80 °C.
- acetic anhydride (3.75 g, 36.8 mmol) was added drop wise.
- the resulting clear solution was heated to reflux under a nitrogen atmosphere.
- the progress of the reaction was monitored by 31 P NMR, which showed that after - 8-10 hours the reaction was near completion.
- the solvent was removed under reduced pressure and the resulting solid was dissolved in DCM and the solution was washed with 1M HC1 four times.
- the organic layer was dried over MgS0 4 and the DCM was removed under vacuum.
- the product was a white solid (11.2 g. 31 P NMR (121 MHz, CDC1 3 , ppm : 29-35 (m).
- DOP-OEt (6-Ethoxy-6H-dibenz[c,e][l,2]-oxaphosphorin): DOP-C1 (741 g, 3.1 mole) was dissolved in anhydrous xylene (400 mL) to get a homogenous solution. To this solution, triethylamine (353 g, 3.5 mole) was added under nitrogen atmosphere. To this triethylamine-DOP-Cl solution ethanol (161.0 g, 3.5 mole) was added slowly. A white ppt.
- Vaporizer temperature 250°C
- composition A Composition A
- composition A synthesized in Example 2 was explored as a co-curing agent for the epoxy laminate application
- the composition A together with phenolic novolac was used to cure multi-functional epoxy resins DEN 438 and EPON 164. All the materials information is listed in Table 1.
- a varnish formulation was prepared therefrom which had a phosphorous content of 3.0 % and the composition contents are shown in Table 2. The prepared varnish is yellow in color. Table 1.
- a circular stack of 4 prepregs with a diameter of 25 mm was placed between disposable aluminum (Al) plates to study the rheological behavior of the B-stage prepreg by electrically heating the resin to 225°C at 5°C/min in an AR2000ex Rheometer.
- a continuous controlled strain condition within the linear viscoelastic region of the prepreg was maintained along with the normal force control that accounts for volume changes occurring in the resin with change in temperature.
- the final curing temperature for the laminate was selected above 179°C. Based on the rheology curve, the curing cycle was designed to obtain a good wetting of the glass cloth. At 120-122°C the complex viscosity of the prepreg was at its lowest value and a 50 psi pressure was applied at this minimum viscosity point. The pressure was increased in small steps from 130-160°C and a maximum pressure of 500 psi was applied at 190°C.
- a laminate was made by stacking together 8 prepregs with a copper foil on the top and bottom of the prepreg stack. The assembly was placed between two stainless steel plates and into a hydraulic press with four sheets of kraft paper below and above the plates.
- the 8 prepregs were compression molded in the hydraulic press following the cure cycle mentioned above by linearly heating the press to 195°C and the final laminate was isothermally maintained at 195°C for 90 minutes with a pressure of 500 psi and later post-cured the compressed laminate at 21 °C for 15 minutes.
- the post-curing was performed because a final plateau was observed in the storage modulus after 215°C.
- the resultant laminate showed a high resin flow and the thickness of the final laminate was from 1.05-1.10 mm (without copper).
- the laminate was rated as a strong V-0 with a maximum burn time of 4 seconds by following ASTM D3801-10 standard using an Atlas UL-94 burning chamber (V-0 being the highest possible rating).
- the thermal decomposition temperature of the composite at 5 weight% loss is 365°C as measured by Thermogravinietric Analysis (TGA) at a heating rate of 5°C/min in an inert atmosphere of nitrogen.
- TGA Thermogravin
- Composition A was used as a curing agent together with phenolic novolac (SD-1708) to cure multi-functional epoxy resins DEN 438 and EPON 164.
- the varnish formulation had phosphorus content of 2.7 % P and is shown in Table 4. The solids content was maintained at 66.67 % with the addition of Dowanol.
- the varnish had a gel time of 368 seconds at 171°C.
- a DSC heating run with 10°C/min up to 300°C was conducted to study the curing behavior of the varnish. The maximum exotherm occurs at 204°C for the varnish formulation shown in Table 4.
- Prepregs were made with this varnish and dried at 165°C for 4 ⁇ 0" (four minutes), which gave a resin flow close to 14.0 %. Also, the resin content was controlled to be over 45 - 52 %, which is determined through the difference in weight between the glass fabric and the prepreg.
- the prepreg gel time was determined by collecting the fusible, thermoplastic resin by crushing the prepreg in a zip-lock bag. The collected resin was placed on the hot-plate at 171°C and the gel time determined. The prepreg properties are shown in the table 5 below:
- a circular stack of 4 prepregs with a diameter of 25 mm was placed between disposable Aluminum (Al) plates to study the rheological behavior of the resin by electrically heating to 200°C at 5°C/min in an AR2000ex Rheometer.
- the onset of gelation occurs at around 110°C and the cross-linking of the epoxy resin was evident with the rapid increase in complex viscosity at around 175°C.
- the curing cycle was designed to obtain a good wetting of the glass-fiber.
- Small initial pressure of 10-20 psi was applied at close to 90-100°C for wetting the glass-fiber and pressure was increased in small increments between 135°C-174°C.
- Small drop (2-8 pressure units) in pressure was observed while the pressure was raised from 50 to 200 psi in the temperature range of 135-174°C.
- 200 psi was applied at 195°C and the laminate was isothermally cured for 90 minutes.
- the epoxy laminate containing Composition A was ranked as V-0 with a maximum burn time of 7 seconds.
- the glass transition temperature (Tg) of the multilayer laminate was determined to be 176°C by Dynamic Mechanical Analysis (DMA) in a single-cantilever mode at a ramp rate of 3°C/min.
- the thermal decomposition temperature of the composite at 5 weight% loss is 412°C as measured by Thermogravimetric Analysis (TGA) at a heating rate of 10°C/min in an inert atmosphere of nitrogen.
- PCT Pressure Cooker Test
- Laminate preparation with Composition B Laminate preparation with Composition B
- Composition B as curing agent
- Composition B was used as a curing agent together with phenolic novolac (SD-1708) to cure multi-functional epoxy resins DEN 438 and EPON 164.
- the varnish formulation had phosphorus content of 2.7 % P and is shown in Table 6. The solids content was maintained at 63.90 % with the addition of Dowanol.
- the varnish had a gel time of 360 seconds at 171°C.
- a DSC heating run with 10°C/min up to 300°C was conducted to study the curing behavior of the varnish. The result is shown in Figure 2, which shows that the maximum exotherm occurs at 204°C.
- Prepregs were made with this varnish and dried at 165°C for 2'40", which gives a resin flow close to 7.0-10.0 %. Also, the resin content was controlled to be over 30 - 35 %, which is determined through the difference in weight between the glass fabric and the prepreg.
- the prepreg gel time was determined by collecting the fusible, thermoplastic resin by crushing the prepreg in a zip-lock bag. The collected resin was placed on the hot-plate at 171°C and the gel time determined.
- the prepreg properties are shown in the table 6 below:
- FIG. 1 shows the complex viscosity profile of the prepreg with rise in temperature of the B-staged resin system in an oscillatory testing mode.
- Figure 4 shows the overlay curves for the storage modulus (G'), loss modulus (G") and complex viscosity (] ⁇ [) of the B-staged resin system. Based on the Figures 2, 3 and 4, the curing cycle was designed to obtain a good wetting of the glass cloth.
- a low initial pressure of 10 psi was applied at 90-92°C (the complex viscosity of the prepreg was around 17530-15750 pa-s) and sufficient to wet the glass fabric as studied during the preparation of various experimental epoxy laminates.
- Subsequent 20 psi pressure was applied at 109-110°C and the pressure was maintained at 20 psi until 130°C.
- the pressure was again raised to 50 psi at 130°C and 75 psi once the press reached 146°C.
- a pressure of 100 psi was applied at 166°C and finally a pressure of 220 psi was applied at 195°C.
- the press was maintained at 220 psi and 195°C isothermaliy for 90 minutes.
- the laminate showed a good resin flow and the thickness of the final laminate was close to 1.3 mm (without copper). The laminate was rated as a strong V-0 with a maximum burn time of 7 seconds.
- the glass transition temperature of the laminate was 159°C using the DMA method with 3°C/min heating rate as shown in Figure 5.
- PCT pressure cooker test
- the water uptake after 30 minutes was 0.071 and 0.085 weight% respectively.
- 4 out of 4 samples passed the 20 seconds soldering bath dip test at 288°C.
- the thermal decomposition of the composite is also shown in Figure 6.
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US201462001239P | 2014-05-21 | 2014-05-21 | |
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Cited By (8)
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CN107033329A (zh) * | 2017-04-12 | 2017-08-11 | 武汉理工大学 | 一种无卤阻燃环氧固化剂及其制备方法 |
EP3211035A4 (en) * | 2015-12-28 | 2018-01-10 | Shengyi Technology Co., Ltd. | Epoxy resin composition as well as prepreg and laminated board using the same |
US10208156B2 (en) | 2014-12-26 | 2019-02-19 | Shengyi Technology Co., Ltd. | Epoxy resin composition, prepreg and laminate using same |
US10696844B2 (en) | 2014-02-25 | 2020-06-30 | Shengyi Technology Co., Ltd. | Halogen-free flame retardant type resin composition |
WO2021068304A1 (zh) * | 2019-10-10 | 2021-04-15 | 苏州巨峰电气绝缘系统股份有限公司 | 一种含磷活性酯化合物及其制备方法 |
US11001759B2 (en) | 2018-01-04 | 2021-05-11 | Taiwan Union Technology Corporation | Resin composition, and pre-preg, metal-clad laminate, and printed circuit board prepared using the same |
TWI728781B (zh) * | 2020-04-21 | 2021-05-21 | 穗曄實業股份有限公司 | 熱固型樹脂組成物 |
CN116813861A (zh) * | 2023-06-19 | 2023-09-29 | 温州东润新材料科技有限公司 | 一种基于生物基制备的热塑性tpu及其制备工艺 |
Families Citing this family (1)
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CN114656749B (zh) * | 2020-12-23 | 2024-03-29 | 广东生益科技股份有限公司 | 一种热固性树脂组合物及其应用 |
Citations (1)
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WO2011081664A1 (en) * | 2009-12-30 | 2011-07-07 | Dow Global Technologies Inc. | Thermosetting monomers and compositions containing phosphorus and cyanato groups |
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- 2015-05-15 WO PCT/US2015/031049 patent/WO2015179232A1/en active Application Filing
- 2015-05-19 TW TW104115889A patent/TW201609781A/zh unknown
Patent Citations (1)
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WO2011081664A1 (en) * | 2009-12-30 | 2011-07-07 | Dow Global Technologies Inc. | Thermosetting monomers and compositions containing phosphorus and cyanato groups |
Cited By (11)
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US10696844B2 (en) | 2014-02-25 | 2020-06-30 | Shengyi Technology Co., Ltd. | Halogen-free flame retardant type resin composition |
US10208156B2 (en) | 2014-12-26 | 2019-02-19 | Shengyi Technology Co., Ltd. | Epoxy resin composition, prepreg and laminate using same |
EP3211035A4 (en) * | 2015-12-28 | 2018-01-10 | Shengyi Technology Co., Ltd. | Epoxy resin composition as well as prepreg and laminated board using the same |
US10544255B2 (en) | 2015-12-28 | 2020-01-28 | Shengyi Technology Co., Ltd. | Epoxy resin composition, prepreg and laminate prepared therefrom |
CN107033329A (zh) * | 2017-04-12 | 2017-08-11 | 武汉理工大学 | 一种无卤阻燃环氧固化剂及其制备方法 |
CN107033329B (zh) * | 2017-04-12 | 2019-05-24 | 武汉理工大学 | 一种无卤阻燃环氧固化剂及其制备方法 |
US11001759B2 (en) | 2018-01-04 | 2021-05-11 | Taiwan Union Technology Corporation | Resin composition, and pre-preg, metal-clad laminate, and printed circuit board prepared using the same |
WO2021068304A1 (zh) * | 2019-10-10 | 2021-04-15 | 苏州巨峰电气绝缘系统股份有限公司 | 一种含磷活性酯化合物及其制备方法 |
TWI728781B (zh) * | 2020-04-21 | 2021-05-21 | 穗曄實業股份有限公司 | 熱固型樹脂組成物 |
CN116813861A (zh) * | 2023-06-19 | 2023-09-29 | 温州东润新材料科技有限公司 | 一种基于生物基制备的热塑性tpu及其制备工艺 |
CN116813861B (zh) * | 2023-06-19 | 2024-04-23 | 温州东润新材料科技有限公司 | 一种基于生物基制备的热塑性tpu及其制备工艺 |
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