TW201910344A - 一種低極性本徵阻燃樹脂及其製備方法和應用 - Google Patents

一種低極性本徵阻燃樹脂及其製備方法和應用 Download PDF

Info

Publication number
TW201910344A
TW201910344A TW106143785A TW106143785A TW201910344A TW 201910344 A TW201910344 A TW 201910344A TW 106143785 A TW106143785 A TW 106143785A TW 106143785 A TW106143785 A TW 106143785A TW 201910344 A TW201910344 A TW 201910344A
Authority
TW
Taiwan
Prior art keywords
resin
preparation
scope
item
reaction
Prior art date
Application number
TW106143785A
Other languages
English (en)
Other versions
TWI660966B (zh
Inventor
蘇民社
Original Assignee
大陸商廣東生益科技股份有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 大陸商廣東生益科技股份有限公司 filed Critical 大陸商廣東生益科技股份有限公司
Publication of TW201910344A publication Critical patent/TW201910344A/zh
Application granted granted Critical
Publication of TWI660966B publication Critical patent/TWI660966B/zh

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F299/00Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
    • C08F299/02Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
    • C08F299/022Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polycondensates with side or terminal unsaturations
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00Layered products comprising a layer of metal
    • B32B15/04Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00Layered products comprising a layer of metal
    • B32B15/14Layered products comprising a layer of metal next to a fibrous or filamentary layer
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00Layered products comprising a layer of metal
    • B32B15/20Layered products comprising a layer of metal comprising aluminium or copper
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/02Layered products essentially comprising sheet glass, or glass, slag, or like fibres in the form of fibres or filaments
    • B32B17/04Layered products essentially comprising sheet glass, or glass, slag, or like fibres in the form of fibres or filaments bonded with or embedded in a plastic substance
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/04Layered products comprising a layer of synthetic resin as impregnant, bonding, or embedding substance
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00Layered 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
    • B32B5/02Layered 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 structural features of a fibrous or filamentary layer
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00Layered 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
    • B32B5/02Layered 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 structural features of a fibrous or filamentary layer
    • B32B5/024Woven fabric
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00Layered 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
    • B32B5/22Layered 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
    • B32B5/24Layered 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
    • B32B5/26Layered 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
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07FACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02Phosphorus compounds
    • C07F9/547Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6564Heterocyclic 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
    • C07F9/6571Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
    • C07F9/657163Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom
    • C07F9/657172Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom the ring phosphorus atom and one oxygen atom being part of a (thio)phosphinic acid ester: (X = O, S)
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07FACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02Phosphorus compounds
    • C07F9/547Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6564Heterocyclic 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
    • C07F9/6571Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
    • C07F9/6574Esters of oxyacids of phosphorus
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07FACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02Phosphorus compounds
    • C07F9/547Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6564Heterocyclic 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
    • C07F9/6571Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
    • C07F9/6574Esters of oxyacids of phosphorus
    • C07F9/65744Esters of oxyacids of phosphorus condensed with carbocyclic or heterocyclic rings or ring systems
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F279/00Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
    • C08F279/02Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/08Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
    • C08F290/14Polymers provided for in subclass C08G
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/12Unsaturated polyimide precursors
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G8/00Condensation polymers of aldehydes or ketones with phenols only
    • C08G8/28Chemically modified polycondensates
    • C08G8/36Chemically modified polycondensates by etherifying
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00Processes of treating or compounding macromolecular substances
    • C08J3/24Crosslinking, e.g. vulcanising, of macromolecules
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C08J5/241Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
    • C08J5/244Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using glass fibres
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C08J5/249Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs characterised by the additives used in the prepolymer mixture
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/34Silicon-containing compounds
    • C08K3/36Silica
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/49Phosphorus-containing compounds
    • C08K5/51Phosphorus bound to oxygen
    • C08K5/53Phosphorus bound to oxygen bound to oxygen and to carbon only
    • C08K5/5313Phosphinic compounds, e.g. R2=P(:O)OR'
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00Use of ingredients characterised by shape
    • C08K7/02Fibres or whiskers
    • C08K7/04Fibres or whiskers inorganic
    • C08K7/14Glass
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/04Condensation polymers of aldehydes or ketones with phenols only
    • C08L61/06Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
    • C08L61/14Modified phenol-aldehyde condensates
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08L9/06Copolymers with styrene
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J161/00Adhesives based on condensation polymers of aldehydes or ketones; Adhesives based on derivatives of such polymers
    • C09J161/04Condensation polymers of aldehydes or ketones with phenols only
    • C09J161/06Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
    • C09J161/14Modified phenol-aldehyde condensates
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K21/00Fireproofing materials
    • C09K21/06Organic materials
    • C09K21/12Organic materials containing phosphorus
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K21/00Fireproofing materials
    • C09K21/14Macromolecular materials
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00Layers arrangement
    • B32B2250/022 layers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00Layers arrangement
    • B32B2250/40Symmetrical or sandwich layers, e.g. ABA, ABCBA, ABCCBA
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2260/00Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/02Composition of the impregnated, bonded or embedded layer
    • B32B2260/021Fibrous or filamentary layer
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2260/00Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/04Impregnation, embedding, or binder material
    • B32B2260/046Synthetic resin
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/10Inorganic fibres
    • B32B2262/101Glass fibres
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00Properties of the layers or laminate
    • B32B2307/20Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • B32B2307/206Insulating
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00Properties of the layers or laminate
    • B32B2307/30Properties of the layers or laminate having particular thermal properties
    • B32B2307/306Resistant to heat
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00Properties of the layers or laminate
    • B32B2307/30Properties of the layers or laminate having particular thermal properties
    • B32B2307/306Resistant to heat
    • B32B2307/3065Flame resistant or retardant, fire resistant or retardant
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2309/00Characterised by the use of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08J2309/06Copolymers with styrene
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00Properties
    • C08L2201/02Flame or fire retardant/resistant
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00Properties
    • C08L2201/08Stabilised against heat, light or radiation or oxydation
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00Applications
    • C08L2203/20Applications use in electrical or conductive gadgets
    • C08L2203/206Applications use in electrical or conductive gadgets use in coating or encapsulating of electronic parts
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/05Polymer mixtures characterised by other features containing polymer components which can react with one another
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2312/00Crosslinking
    • C08L2312/04Crosslinking with phenolic resin

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • General Chemical & Material Sciences (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Textile Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Phenolic Resins Or Amino Resins (AREA)
  • Fireproofing Substances (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

本發明提供一種低極性本徵阻燃樹脂及其製備方法和應用。前述低極性本徵阻燃樹脂具有式I所示結構,其係基於酚類化合物或樹脂,經烯丙基醚化、重排及含磷基團封端三步反應製備得到,其分子式中不含有極性的羥基、並且分子結構穩定,極性低、反應活性高,在應用加工過程中不會產生極性羥基,避免二次羥基對於其產物性能的影響,該樹脂在提高介電性能同時,依舊帶有可交聯反應基團,使固化後耐高溫性能無顯著變化,引入含磷封端基團,使得樹脂具有本徵阻燃性能,將其用於覆金屬箔層壓板製備中有利於降低覆金屬箔層壓板的介電常數及介電損耗,並具有較高耐高溫性能,提高阻燃性,使覆金屬箔層壓板具有良好的綜合性能,應用前景廣闊。

Description

一種低極性本徵阻燃樹脂及其製備方法和應用
本發明屬於熱固性樹脂技術領域,關於一種低極性本徵阻燃樹脂及其製備方法和應用。
高性能熱固性樹脂以其優異的耐熱性、阻燃性、耐候性、電絕緣性,良好的力學性能及尺寸穩定性等特點,被廣泛應用於航空航太、軌道交通、電力絕緣、微電子封裝等領域複合材料之樹脂基體、耐高溫絕緣材料及膠黏劑等。常用的高性能熱固性樹脂有環氧樹脂、酚醛樹脂、雙馬來醯亞胺樹脂等,但上述樹脂存在著脆性導致材料抗衝擊能力不足,樹脂分子結構極性大導致介電常數及損耗偏高等弱點,從而限制其在某些領域之推廣應用,對熱固性樹脂改性研究一直係材料工作者關注的研究課題。
近年來,以雙馬來醯亞胺樹脂為代表的耐高溫熱固性樹脂,越來越多用於航空航太雷達天線罩,軌道交通電路絕緣材料及微電子電路板等領域。隨著上述產業的迅速發展,電磁發射功率及頻率不斷增大,對材料之透波、絕緣性能要求日益提高,普通耐高溫熱固性樹脂由於介電常數及損耗偏高,其透波絕緣性能已經不能滿足雷達、絕緣材料及微 電子電路板之設計要求。因此,如何降低樹脂極性,進而降低介電常數及損耗一直係研究人員關注的技術瓶頸問題。
合成新結構單體或樹脂係降低介電常數及損耗之可行方法。CN104311756A公開一種含矽雙馬來醯亞胺樹脂,含矽基團之引入可將介電常數降低至3.0以下。CN104479130A公開一種含氟結構之新型雙馬來醯亞胺單體,顯著降低雙馬來醯亞胺樹脂之介電常數及損耗。但是,上述新型結構雙馬來醯亞胺單體合成工藝複雜、成本高,難以批量製備及應用。此外,藉由其他樹脂共聚改性係改善熱固性樹脂絕緣性能的重要方法之一。CN101338032A公開採用氰酸酯改性雙馬來醯亞胺樹脂,製備預浸料,複合材料介電常數及損耗顯著降低。然而,該方法對於改善樹脂介電性能雖有一定的效果,但程度有限,距離應用尚有一定的差距。
阻燃性能係複合材料重要性能之一,然而隨著環保法規日益嚴格,含溴阻燃劑逐漸退出訊息電子領域,取而代之的係含磷、含氮等新型阻燃劑。但是,為達到理想阻燃效果,上述阻燃劑加入量普遍較大,加入後複合材料耐高溫、力學強度有顯著影響。因此,研製開發具有本徵阻燃之基體樹脂係今後發展趨勢。
因此,於本領域中,期望得到一種低極性之本徵阻燃樹脂材料以降低其固化物之介電常數及損耗,增強阻燃性能,並同時保持覆銅板之其他方面的優良性能。
針對先前技術的不足,本發明之目的在於提供一種低極性本徵阻燃樹脂及其製備方法和應用。本發明之樹脂不含有極性基團(例如羥基)、分子極性低、反應活性高,降低其固化物之介電常數及損耗,樹脂結構中之烯丙基結構實現交聯固化,保證固化後之力學強度,並且可以保證固化物具有優良的耐熱性能,同時該樹脂結構中帶有阻燃性含磷結構,使其具有優異的本徵阻燃效果。
為達到此發明目的,本發明採用以下技術手段:一方面,本發明提供一種低極性本徵阻燃樹脂,前述低極性本徵阻燃樹脂具有如下式I所示之結構: 其中,R為直鏈或支鏈烷基,、-O-、;X及Y獨立地為氫、烯丙基、直鏈烷 基、支鏈烷基中的任意一種或至少兩種之組合;A為含磷封端基團,n為1-20的整數。
於本發明所記載之低極性本徵阻燃樹脂中,前述低極性係指不含有極性基團,尤其係不含有羥基基團,使得樹脂具有較低的極性, 克服通用熱固性樹脂極性大導致之高頻介電常數及損耗高之缺陷,同時可透過該結構中之烯丙基結構實現交聯固化,保證固化後之力學強度,並使得固化物具有優良的耐熱性能,同時,該樹脂中含有阻燃性含磷結構,使其具有優異的本徵阻燃效果。
理想地,前述R為C1-C6(例如C1、C2、C3、C4、C5或C6)之直鏈烷基或C3-C6(例如C3、C4、C5或C6)支鏈烷基,具體而 言可以為-CH2-、等。
理想地,R為-CH2-、、-O-或 ,n為1-20的整數,X 及Y獨立地為氫、烯丙基、直鏈烷基、支鏈烷基中的任意一種或至少兩種之組合,A為含磷封端基團。
於本發明中,n為1-20的整數,例如n可以為1、2、3、4、5、6、7、8、9、10、11、12、13、14、15、16、17、18、19或20。
理想地,X及Y獨立地為C1-C21(例如C1、C2、C3、C4、C5、C6、C7、C8、C9、C10、C11、C12、C13、C14、C15、C16、C17、C18、C19、C20或C21)之直鏈烷基或C3-C21(例如C3、C4、C5、C6、C7、C8、C9、C10、C11、C12、C13、C14、C15、C16、C17、C18、C19、C20或C21)支鏈烷基。
理想地,A為含有DOPO結構之基團,理想為中的任意一種。
理想地,前述低極性本徵阻燃樹脂為具有如下式A至式E所示結構之化合物中的任意一種或至少兩種之組合:
其中n為1-20的整數。
另一方面,本發明提供如上述之低極性本徵阻燃樹脂之製備方法,前述方法包含以下步驟:
(1)式II所示酚類化合物或酚類樹脂與烯丙基化試劑反應得到式III所示烯丙基醚化樹脂,示例反應式如下:
(2)在保護性氣體保護下,將式III所示烯丙基醚化樹脂加熱,發生分子內重排反應得到式IV所示烯丙基化酚類樹脂;
(3)式IV所示烯丙基化酚類樹脂與含磷封端試劑發生反應,得到式I所示低極性本徵阻燃樹脂; 其中,R1為直鏈或支鏈烷基,、-O-、;R2為直鏈或支鏈烷基,、 -O-、;R3為直鏈或 支鏈烷基,、-O-、;R為直鏈或支鏈烷基,、 -O-或;X及Y獨立地 為氫、烯丙基、直鏈烷基、支鏈烷基中的任意一種或至少兩種之組合;A為含磷封端基團,n為1-20的整數。
於本發明中,步驟(2)之重排步驟中,當R2時,包含其中的烯丙醚 基會發生重排之情況,導致在式IV所示烯丙基化酚類樹脂之中間單元R3中含有由於重排而產生烯丙基,進而在產物式I所示低極性樹脂之R單元中包含由於重排而產生之烯丙基,本發明為了表述簡潔未將該烯丙基直接表示至R3及R的相應結構中,而僅由X來代表苯環上所有之取代基,然而在此闡明此處X包含由於重排而產生之烯丙基,若在重排反應前R2,苯環上帶有其他取代 基X,於步驟(2)之重排反應後,則在R3的結構中X可以表示重排產生之烯丙基及反應前的 其他取代基之組合。當然於步驟(2)之重排步驟中,亦包含R2時,R2單元中烯丙醚基 不發生重排反應之情況,此時,反應後R3以及產物R中的X與反應前式 III所示烯丙基醚化樹脂中R2中之X基團相同。
理想地,步驟(1)所記載之酚類化合物或酚類樹脂為酚、二元酚、多元酚或其衍生樹脂,理想為苯酚、鄰甲酚、雙酚A、雙酚F、四甲基雙酚A、酚醛樹脂、鄰甲酚酚醛樹脂或環戊二烯酚醛樹脂中的任意一種或至少兩種之組合。
理想地,前述烯丙基化試劑為烯丙基矽醇、烯丙基氯、烯丙基溴、烯丙基碘或烯丙基胺中的任意一種或至少兩種之組合。
理想地,前述酚類化合物或酚類樹脂中酚羥基與烯丙基化試劑中烯丙基之莫耳比為1:(0.3~1.2),例如1:0.3、1:0.4、1:0.5、1:0.6、1:0.7、1:0.8、1:0.9、1:1、1:1.1或1:1.2。
理想地,步驟(1)所記載之反應於鹼性物質存在下進行,前述鹼性物質理想為氫氧化鈉、氫氧化鉀、碳酸鈉或碳酸鉀中的任意一種或至少兩種之組合。
理想地,前述鹼性物質與步驟(1)所記載之酚類化合物或酚類樹脂中所含酚羥基之莫耳比為(0.3~1.4):1,例如0.3:1、0.4:1、0.5:1、0.6:1、0.7:1、0.8:1、0.9:1、1:1、1.1:1、1.2:1、1.3:1或1.4:1。
理想地,步驟(1)所記載之反應於相轉移催化劑存在下進行。
理想地,前述相轉移催化劑為季銨鹽類相轉移催化劑,理想為四丁基氯化銨、四丁基溴化銨、苄基三乙基氯化銨、四丁基硫酸氫銨、三辛基甲基氯化銨、十二烷基三甲基氯化銨或十四烷基溴三甲基氯化銨中的任意一種或至少兩種之組合。
理想地,前述相轉移催化劑之加入量為步驟(1)所記載之酚類化合物或酚類樹脂質量的0.1~5%,例如0.1%、0.3%、0.5%、0.8%、1%、1.3%、1.5%、1.8%、2%、2.3%、2.5%、2.8%、3%、3.3%、3.5%、3.8%、4%、4.3%、4.5%、4.8%或5%。
理想地,步驟(1)所記載之反應的溶劑為醇類溶劑、芳香烴溶劑或酮類溶劑中的任意一種或至少兩種之組合,理想為乙醇、丙醇、丁醇、甲苯或二甲苯中的任意一種或至少兩種之組合。
理想地,前述溶劑之加入量為步驟(1)所記載之酚類化合物或酚類樹脂質量的2~5倍,例如2倍、2.3倍、2.5倍、2.8倍、3倍、3.3倍、3.5倍、3.8倍、4倍、4.3倍、4.5倍、4.8倍或5倍。
理想地,步驟(1)所記載之反應的溫度為60~90℃,例如60℃、63℃、65℃、68℃、70℃、75℃、78℃、80℃、85℃、88℃或90℃。
理想地,步驟(1)所記載之反應的時間為4~6小時,例如4小時、4.3小時、4.5小時、4.8小時、5小時、5.2小時、5.5小時、5.8小時或6小時。
理想地,步驟(2)所記載之保護性氣體為氮氣或氬氣。
理想地,步驟(2)所記載之加熱為加熱至180~220℃,例如180℃、185℃、190℃、195℃、200℃、205℃、210℃、215℃或220℃。
理想地,步驟(2)所記載之反應的時間為4~6小時,例如4小時、4.3小時、4.5小時、4.8小時、5小時、5.2小時、5.5小時、5.8小時或6小時。
理想地,步驟(3)所記載之含磷封端試劑為9,10-二氫-9-氧雜-10-膦菲-10-氧化物、9,10-二氫-9-氧雜-10-膦菲-10-氧化物、2-(6H-二苯並(c,e)(1,2)-5-氧雜-6-膦醯雜-6-苯基-1,4-對苯二酚、2-(6H-二苯並(c,e)(1,2)-5-氧雜-6-膦醯雜-6-苯基-4-苯酚、2-(6H-二苯並(c,e)(1,2)-5-氧雜-6-膦醯雜-6-苯基-3-苯酚、2-(6H-二苯並(c,e)(1,2)-5-氧雜-6-膦醯雜-6-苯基-4-苯甲醇或2-(6H-二苯並(c,e)(1,2)-5-氧雜-6-膦醯雜-6-苯基-3-苯甲醇中的任意一種或至少兩種之組合。
理想地,步驟(3)所記載之式IV所示烯丙基化酚類樹脂中酚羥基與含磷封端試劑中含磷封端基之莫耳比為1:(1~1.2),例如1:1、1:1.05、1:1.1、1:1.15或1:1.2。使得反應得到的樹脂分子結構中酚羥基均被含磷封端基封端,從而使樹脂中無極性羥基基團。
理想地,步驟(3)所記載之反應於鹼性物質存在下進行。
理想地,前述鹼性物質為無機鹼或有機鹼,理想為氫氧化鈉、氫氧化鉀、碳酸鈉、碳酸鉀、三乙胺或吡啶中的任意一種或至少兩種之組合。
理想地,前述鹼性物質與式IV所示烯丙基化酚類樹脂中酚羥基之莫耳比為(1~1.4):1,例如1:1、1.05:1、1.1:1、1.15:1、1.2:1、1.25:1、1.3:1、1.35:1或1.4:1。
理想地,步驟(3)所記載之反應於四氯化碳存在下進行。
理想地,前述四氯化碳與步驟(3)所記載之式IV所示烯丙基化酚類樹脂中酚羥基莫耳比為(1~2):1,例如1:1、1.1:1、1.2:1、1.3:1、1.4:1、1.5:1、1.6:1、1.7:1、1.8:1、1.9:1或2:1。
理想地,步驟(3)所記載之反應的溶劑為鹵代烴類溶劑,理想為一氯甲烷、二氯甲烷、三氯甲烷或二氯乙烷中的任意一種或至少兩種之組合。
理想地,前述溶劑之加入量為步驟(3)所記載之烯丙基化酚類樹脂質量的2~5倍,例如2倍、2.3倍、2.5倍、2.8倍、3倍、3.3倍、3.5倍、3.8倍、4倍、4.3倍、4.5倍、4.8倍或5倍。
理想地,步驟(3)所記載之反應的溫度為0~30℃,例如0℃、3℃、5℃、8℃、10℃、15℃、18℃、20℃、25℃、28℃或30℃,10℃為佳。
理想地,步驟(3)所記載之反應的時間為4~6小時,例如4小時、4.3小時、4.5小時、4.8小時、5小時、5.2小時、5.5小時、5.8小時或6小時。
藉由本發明之方法製備得到的樹脂中不含有極性之羥基、並且分子結構穩定,具有分子極性低、反應活性高之特點,在其應用的加工過程中亦不會產生極性羥基,避免產生之二次羥基對於其產物之性能的影響,此外以含磷封端基封端,賦予樹脂本徵阻燃性能。
另一方面,本發明提供如上述之低極性本徵阻燃樹脂在樹脂複合材料製備中的應用。
本發明之低極性本徵阻燃樹脂可用於樹脂複合材料中基體樹脂的組分之一,能夠與環氧樹脂、雙馬來醯亞胺樹脂等其他熱固性樹脂共交聯固化,顯著降低樹脂介電常數及介電損耗。
於本發明中,前述樹脂複合材料可以為航空航太透波複合 材料、電力絕緣材料、電子封裝用樹脂複合材料以及覆銅板用樹脂複合材料等。
另一方面,本發明提供如上述之低極性本徵阻燃樹脂在電子封裝材料製備中的應用。
本發明之低極性本徵阻燃樹脂由於具有分子極性低、反應活性高之特點,亦可應用於微電子領域封裝膠黏劑、灌封樹脂等材料之製備。
另一方面,本發明提供如上述之低極性本徵阻燃樹脂在覆金屬箔層壓板製備中的應用。
本發明所記載之低極性本徵阻燃樹脂可用於樹脂複合材料中基體樹脂的組分之一,能夠與環氧樹脂、雙馬來醯亞胺樹脂等其他熱固性樹脂共交聯固化,顯著降低樹脂介電常數及介電損耗,將其用於覆金屬箔層壓板製備中有利於降低覆金屬箔層壓板之介電常數及介電損耗,提高耐熱性能,同時,該樹脂中含有阻燃性含磷結構,使得覆金屬箔層壓板具有優異的阻燃效果。
與先前技術相比,本發明具有如下功效:本發明之樹脂中不含有極性之羥基、並且分子結構穩定,具有分子極性低、反應活性高之特點,在其應用的加工過程中亦不會產生極性羥基,避免產生之二次羥基對於其產物之性能的影響,因此該樹脂在提高介電性能同時,依舊帶有可交聯反應基團,使得固化後耐高溫性能無顯著變化, 引入含磷封端基團,使得樹脂具有本徵阻燃性能,該樹脂可用於樹脂複合材料中基體樹脂的組分之一,能夠與環氧樹脂、雙馬來醯亞胺樹脂等其他熱固性樹脂共交聯固化,顯著降低樹脂介電常數及介電損耗,將其用於覆金屬箔層壓板製備中有利於降低覆金屬箔層壓板之介電常數及介電損耗,並具有較高的耐高溫性能,同時提高覆金屬箔層壓板之阻燃性,使得覆金屬箔層壓板具有良好的綜合性能,並且可推廣用於電子封裝膠黏劑、灌封樹脂等,應用前景廣闊。
【圖1】為實施例1製備得到的低極性本徵阻燃樹脂之紅外光譜圖。
下面藉由具體實施方式來進一步說明本發明之技術手段。所屬技術領域中具有通常知識者應該明瞭,下述實施例僅係幫助理解本發明,不應視為對本發明之具體限制。
實施例1
於本實施例中,藉由以下方法製備低極性本徵阻燃樹脂,包含以下步驟:
(1)三口反應瓶中加入188g丙酮,將228g雙酚A加入反應瓶中,攪拌溶解後,加入106g碳酸鈉。緩慢滴加153g氯丙烯溶液,接著升溫反應4小時後停止反應。過濾,除去大部分溶劑,洗滌,再除去殘留的溶劑及水,即得到雙酚A二烯丙基醚。
(2)將步驟(1)製備的134g雙酚A二烯丙基醚放入反應瓶中,加熱進行重排反應6小時,降溫出料,得到棕色黏稠液體即二烯丙基雙酚A。
(3)三口瓶中通惰性氣體保護,加入300g二氯甲烷,將步驟2製備的134g二烯丙基雙酚A放入反應瓶中,攪拌溶解後,加入40g氫氧化鈉,並加入152g四氯化碳。緩慢滴加230g 2-(6H-二苯並(c,e)(1,2)-5-氧雜-6-膦醯雜-6-苯基-4-苯酚,反應4小時,停止反應,加入氫氧化鈉水溶液洗滌至中性,再洗滌數次,除去殘留的溶劑及水,即得到含磷酯化二烯丙基雙酚A,即前述低極性本徵阻燃樹脂,其結構如下所示:
對該實施例製備得到的含磷酯化二烯丙基雙酚A之紅外光譜圖如圖1(圖1中T%表示%透過率)所示,可以看出,3300-3500cm-1處之羥基結構已經消失,不含有極性之羥基基團,使分子極性顯著降低。
實施例2
於本實施例中,藉由以下方法製備低極性本徵阻燃樹脂,包含以下步驟:
(1)三口反應瓶中加入300g正丁醇,將114g線型酚醛樹脂加入反應瓶中,攪拌溶解後,加入56g氫氧化鉀。緩慢滴加153g溴丙烯溶液,接著升溫反應4小時後停止反應。過濾,洗滌,再除去殘留的溶劑及水,即得到烯丙基醚化酚醛樹脂。
(2)將步驟(1)製備的141g烯丙基醚化酚醛樹脂放入反應瓶中, 加熱進行重排反應4小時,降溫出料,得到棕色黏稠液體即烯丙基酚醛樹脂。
(3)三口瓶中通惰性氣體保護,加入350g二氯甲烷,將步驟2製備的141g二烯丙基雙酚A放入反應瓶中,攪拌溶解後,加入72g三乙胺,並加入152g四氯化碳。待溫度降至30℃以下後,緩慢滴加230g 2-(6H-二苯並(c,e)(1,2)-5-氧雜-6-膦醯雜-6-苯基-4-苯酚,反應4小時,停止反應,加入氫氧化鈉水溶液洗滌至中性,再洗滌數次,除去殘留的溶劑及水,即得到含磷酯化烯丙基酚醛樹脂,即前述低極性本徵阻燃樹脂,其Mn為1300,其結構如下所示:
實施例3
於本實施例中,藉由以下方法製備低極性本徵阻燃樹脂,包含以下步驟:
(1)三口反應瓶中加入250g甲苯,將118g鄰甲酚酚醛樹脂加入反應瓶中,攪拌溶解後,加入100g氫氧化鈉水溶液(濃度40%),再加入1g四丁基溴化銨。待溫度恆定後,緩慢滴加153g氯丙烯溶液,接著升溫反 應4小時後停止反應,洗滌,再除去溶劑,即得到烯丙基醚化鄰甲酚酚醛樹脂。
(2)將步驟(1)製備的159g烯丙基醚化鄰甲酚酚醛樹脂放入反應瓶中,加熱進行重排反應4小時,降溫出料,得到深棕色半固體為烯丙基鄰甲酚酚醛樹脂。
(3)三口瓶中通惰性氣體保護,加入350g二氯甲烷,將步驟2製備的159g二烯丙基雙酚A放入反應瓶中,攪拌溶解後,加入103g吡啶,並加入152g四氯化碳。緩慢滴加230g 2-(6H-二苯並(c,e)(1,2)-5-氧雜-6-膦醯雜-6-苯基-3-苯酚,反應4小時,停止反應,加入氫氧化鈉水溶液洗滌至中性,再洗滌數次,除去殘留的溶劑及水,即得到含磷酯化烯丙基鄰甲酚酚醛樹脂,即前述低極性本徵阻燃樹脂,Mn為1200。
實施例4
於本實施例中,藉由以下方法製備低極性本徵阻燃樹脂,包含以下步驟:
(1)三口反應瓶中加入250g甲苯,將118g環戊二烯酚醛樹脂加入反應瓶中,攪拌溶解後,加入100g氫氧化鈉水溶液(濃度40%),再加入1g四丁基溴化銨。緩慢滴加153g烯丙基矽醇,接著升溫反應4小時後停 止反應,洗滌,再除去溶劑,即得到烯丙基醚化環戊二烯酚醛樹脂。
(2)將步驟(1)製備的159g烯丙基醚化環戊二烯酚醛樹脂放入反應瓶中,加熱進行重排反應4小時,降溫出料,得到深棕色半固體為烯丙基環戊二烯酚醛樹脂。
(3)三口瓶中通惰性氣體保護,加入350g二氯甲烷,將步驟2製備的159g二烯丙基雙酚A放入反應瓶中,攪拌溶解後,加入103g吡啶,並加入152g四氯化碳。緩慢滴加230g 2-(6H-二苯並(c,e)(1,2)-5-氧雜-6-膦醯雜-6-苯基-4-苯甲醇,反應4小時,停止反應,加入氫氧化鈉水溶液洗滌至中性,再洗滌數次,除去殘留的溶劑及水,即得到含磷酯化烯丙基環戊二烯酚醛樹脂,即前述低極性本徵阻燃樹脂,其結構如下所示,其Mn為1280。
實施例5
將80重量份的液體丁苯樹脂Ricon100,20重量份的實施例1製備的含磷酯化二烯丙基雙酚A,85重量份的二氧化矽(525),6.5重量份的引發劑DCP混合,用溶劑甲苯調至合適的黏度,攪拌混合均勻,使填料均一 地分散在樹脂中,製得膠液。用1080玻璃纖維布浸漬以上膠液,接著烘乾去掉溶劑後製得半固化片。將八張已製成的半固化片相疊合,在其兩側壓覆1oz(盎司)厚度之銅箔,在壓機中進行2小時固化,固化壓力為50Kg/cm2,固化溫度為190℃,得到覆銅板。
實施例6
與實施例5的區別僅在於將實施例1製備得到的含磷酯化二烯丙基雙酚A替換為實施例2製備得到的含磷酯化烯丙基酚醛樹脂。
實施例7
與實施例5的區別僅在於將實施例1製備得到的含磷酯化二烯丙基雙酚A替換為實施例3製備得到的含磷酯化烯丙基鄰甲酚酚醛樹脂。
實施例8
與實施例5的區別僅在於將實施例1製備得到的含磷酯化二烯丙基雙酚A替換為實施例4製備得到的含磷酯化烯丙基環戊二烯酚醛樹脂。
比較例1
將80重量份的液體丁苯樹脂Ricon100,85重量份的二氧化矽(525),5.8重量份的引發劑DCP混合,用溶劑甲苯調至合適的黏度,攪拌混合均勻,使填料均一地分散在樹脂中,製得膠液。用1080玻璃纖維布浸漬以上膠液,接著烘乾去掉溶劑後製得半固化片。將八張已製成的半固化片相疊合,在其兩側壓覆1oz(盎司)厚度之銅箔,在壓機中進行2小時固化,固化壓力為50Kg/cm2,固化溫度為190℃,得到覆銅板。
實施例6~10以及比較例1所應用到的原料來源如表1所示,製備得到的覆銅板之物性資料如表2所示。
由表2可知,本發明製備得到的低極性本徵阻燃性樹脂可以使得覆銅板具有較低的介電常數及介電損耗,具有較佳的耐高溫性能以及阻燃性能。
申請人聲明,本發明藉由上述實施例來說明本發明之低極性本徵阻燃樹脂及其製備方法和應用,但本發明並不侷限於上述實施例,即不意味著本發明必須依賴上述實施例才能實施。所屬技術領域中具有通常知識者應該明瞭,對本發明的任何改進,對本發明所選用原料的均等置換及輔助成分之添加、具體方式之選擇等,均落在本發明的保護範圍及公開範圍之內。

Claims (28)

  1. 一種低極性本徵阻燃樹脂,其特徵係,前述低極性本徵阻燃樹脂具有如下式I所示之結構: 其中,R為直鏈或支鏈烷基, 、-O-、 ;X及Y獨立地為氫、烯丙基、直鏈烷 基、支鏈烷基中的任意一種或至少兩種之組合;A為含磷封端基團,n為1-20的整數。
  2. 如申請專利範圍第1項所記載之低極性本徵阻燃樹脂,其中,R為-CH 2-、 、-O-或 ,n為1-20的整數,X及Y獨立地為氫、烯 丙基、直鏈烷基、支鏈烷基中的任意一種或至少兩種之組合,A為含磷封端基團。
  3. 如申請專利範圍第2項所記載之低極性本徵阻燃樹脂,其中,A為含有DOPO結構之基團。
  4. 如申請專利範圍第3項所記載之低極性本徵阻燃樹脂,其中,A為 中的任意一種。
  5. 如申請專利範圍第2項所記載之低極性本徵阻燃樹脂,其中,前述低極性本徵阻燃樹脂為具有如下式A至式E所示結構之化合物中的任意一種或至少兩種之組合: 且n為1-20的整數。
  6. 如申請專利範圍第1至5項中任一項所記載之低極性本徵阻燃樹脂之製備方法,其中,前述方法包含以下步驟:(1)式II所示酚類化合物或酚類樹脂與烯丙基化試劑反應得到式III所示烯丙基醚化樹脂,反應式如下: (2)在保護性氣體保護下,將式III所示烯丙基醚化樹脂加熱,發生分子內重排反應得到式IV所示烯丙基化酚類樹脂; (3)式IV所示烯丙基化酚類樹脂與含磷封端試劑發生反應,得到式I所示低極性本徵阻燃樹脂; 且,R 1為直鏈或支鏈烷基, 、-O-、 ;R 2為直鏈或支鏈烷基, 、 -O-、 ;R 3為直鏈或 支鏈烷基, 、-O-、 ;R為直鏈或支鏈烷基, 、 -O-、 ;X及Y獨立 地為氫、烯丙基、直鏈烷基、支鏈烷基中的任意一種或至少兩種之組 合;A為含磷封端基團,n為1-20的整數。
  7. 如申請專利範圍第6項所記載之製備方法,其中,步驟(1)所記載之酚類化合物或酚類樹脂為酚、二元酚、多元酚或其等之衍生樹脂;前述烯丙基化試劑為烯丙基矽醇、烯丙基氯、烯丙基溴、烯丙基碘或烯丙基胺中的任意一種或至少兩種之組合;前述酚類化合物或酚類樹脂與烯丙基化試劑之莫耳比為1:(0.3~1.2)。
  8. 如申請專利範圍第7項所記載之製備方法,其中,步驟(1)所記載之酚類化合物或酚類樹脂為苯酚、鄰甲酚、雙酚A、雙酚F、四甲基雙酚A、酚醛樹脂、鄰甲酚酚醛樹脂或環戊二烯酚醛樹脂中的任意一種或至少兩種之組合。
  9. 如申請專利範圍第7項所記載之製備方法,其中,步驟(1)所記載之反應於鹼性物質存在下進行;前述鹼性物質與步驟(1)所記載之酚類化合物或酚類樹脂中所含酚羥基之莫耳比為(0.3~1.4):1。
  10. 如申請專利範圍第9項所記載之製備方法,其中,前述鹼性物質為氫氧化鈉、氫氧化鉀、碳酸鈉或碳酸鉀中的任意一種或至少兩種之組合。
  11. 如申請專利範圍第6至10項中任一項所記載之製備方法,其中,步驟(1)所記載之反應於相轉移催化劑存在下進行;前述相轉移催化劑之加入量為步驟(1)所記載之酚類化合物或酚類樹脂質量的0.1~5%。
  12. 如申請專利範圍第11項所記載之製備方法,其中,前述相轉移催化劑為季銨鹽類相轉移催化劑。
  13. 如申請專利範圍第12項所記載之製備方法,其中,前述相轉移催化劑為四丁基氯化銨、四丁基溴化銨、苄基三乙基氯化銨、四丁基硫酸氫銨、三辛基甲基氯化銨、十二烷基三甲基氯化銨或十四烷基溴三甲基氯化銨中的任意一種或至少兩種之組合。
  14. 如申請專利範圍第11項所記載之製備方法,其中,步驟(1)所記載之反應的溶劑為醇類溶劑、芳香烴溶劑或酮類溶劑中的任意一種或至少兩種之組合;前述溶劑之加入量為步驟(1)所記載之酚類化合物或酚類樹脂質量的2~5倍。
  15. 如申請專利範圍第14項所記載之製備方法,其中,步驟(1)所記載之反應的溶劑為乙醇、丙醇、丁醇、甲苯或二甲苯中的任意一種或至少兩種之組合。
  16. 如申請專利範圍第11項所記載之製備方法,其中,步驟(1)所記載之反應的溫度為60~90℃;步驟(1)所記載之反應的時間為4~6小時。
  17. 如申請專利範圍第6至10項中任一項所記載之製備方法,其中,步驟(2)所記載之保護性氣體為氮氣或氬氣;步驟(2)所記載之加熱為加熱至180~220℃;步驟(2)所記載之反應的時間為4~6小時。
  18. 如申請專利範圍第6至10項中任一項所記載之製備方法,其中,步驟(3)所記載之含磷封端試劑為9,10-二氫-9-氧雜-10-膦菲-10-氧化物、9,10-二氫-9-氧雜-10-膦菲-10-氧化物、2-(6H-二苯並(c,e)(1,2)-5-氧雜-6-膦 醯雜-6-苯基-1,4-對苯二酚、2-(6H-二苯並(c,e)(1,2)-5-氧雜-6-膦醯雜-6-苯基-4-苯酚、2-(6H-二苯並(c,e)(1,2)-5-氧雜-6-膦醯雜-6-苯基-3-苯酚、2-(6H-二苯並(c,e)(1,2)-5-氧雜-6-膦醯雜-6-苯基-4-苯甲醇或2-(6H-二苯並(c,e)(1,2)-5-氧雜-6-膦醯雜-6-苯基-3-苯甲醇中的任意一種或至少兩種之組合;步驟(3)所記載之式IV所示烯丙基化酚類樹脂中酚羥基與含磷封端試劑中含磷封端基之莫耳比為1:(1~1.2)。
  19. 如申請專利範圍第18項所記載之製備方法,其中,步驟(3)所記載之反應於鹼性物質存在下進行;前述鹼性物質與式IV所示烯丙基化酚類樹脂中酚羥基之莫耳比為(1~1.4):1。
  20. 如申請專利範圍第19項所記載之製備方法,其中,前述鹼性物質為無機鹼或有機鹼。
  21. 如申請專利範圍第20項所記載之製備方法,其中,前述鹼性物質為氫氧化鈉、氫氧化鉀、碳酸鈉、碳酸鉀、三乙胺或吡啶中的任意一種或至少兩種之組合。
  22. 如申請專利範圍第18項所記載之製備方法,其中,步驟(3)所記載之反應於四氯化碳存在下進行;前述四氯化碳與步驟(3)所記載之式IV所示烯丙基化酚類樹脂中酚羥基莫耳比為(1~2):1。
  23. 如申請專利範圍第18項所記載之製備方法,其中,步驟(3)所記載之反應的溶劑為鹵代烴類溶劑;前述溶劑之加入量為步驟(3)所記載之烯丙基化酚類樹脂質量的2~5 倍。
  24. 如申請專利範圍第23項所記載之製備方法,其中,步驟(3)所記載之反應的溶劑為一氯甲烷、二氯甲烷、三氯甲烷或二氯乙烷中的任意一種或至少兩種之組合。
  25. 如申請專利範圍第18項所記載之製備方法,其中,步驟(3)所記載之反應的溫度為0~30℃;步驟(3)所記載之反應的時間為4~6小時。
  26. 如申請專利範圍第1至5項中任一項所記載之低極性本徵阻燃樹脂於樹脂複合材料製備中之應用。
  27. 如申請專利範圍第1至5項中任一項所記載之低極性本徵阻燃樹脂於電子封裝材料製備中之應用。
  28. 如申請專利範圍第1至5項中任一項所記載之低極性本徵阻燃樹脂於覆金屬箔層壓板製備中之應用。
TW106143785A 2017-07-26 2017-12-13 一種低極性本徵阻燃樹脂及其製備方法和應用 TWI660966B (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
??201710618308.6 2017-07-26
CN201710618308.6A CN109306044A (zh) 2017-07-26 2017-07-26 一种低极性本征阻燃树脂及其制备方法和应用

Publications (2)

Publication Number Publication Date
TW201910344A true TW201910344A (zh) 2019-03-16
TWI660966B TWI660966B (zh) 2019-06-01

Family

ID=65039973

Family Applications (1)

Application Number Title Priority Date Filing Date
TW106143785A TWI660966B (zh) 2017-07-26 2017-12-13 一種低極性本徵阻燃樹脂及其製備方法和應用

Country Status (7)

Country Link
US (1) US20200208057A1 (zh)
EP (1) EP3660028A4 (zh)
JP (1) JP6802390B2 (zh)
KR (1) KR102292464B1 (zh)
CN (1) CN109306044A (zh)
TW (1) TWI660966B (zh)
WO (1) WO2019019483A1 (zh)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117261378B (zh) * 2023-11-23 2024-01-23 四川烈火胜服科技有限公司 一种防火隔热复合面料及其在消防服中的应用

Family Cites Families (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5356250A (en) * 1976-11-02 1978-05-22 Toyobo Co Ltd Polyeser composition
US4678849A (en) * 1986-02-21 1987-07-07 Ciba-Geigy Corporation Heat-curable mixture containing substituted bicyclo(2.2.1)hept-5-ene-2,3-dicarboximide and polymaleimide
US4923928A (en) * 1988-02-18 1990-05-08 Basf Aktiengesellschaft Thermosetting bismaleimide resin composition containing an adduct of a propenylphenol and an epoxy compound
JP2690761B2 (ja) * 1988-11-25 1997-12-17 三田工業株式会社 電子写真感光体
JPH08188638A (ja) * 1995-01-11 1996-07-23 Hitachi Ltd 樹脂封止型半導体装置並びにその製造方法
CN100526351C (zh) * 2006-07-10 2009-08-12 中国科学院化学研究所 一种热固性树脂组合物及其制备方法
CN101338032A (zh) 2008-08-20 2009-01-07 中国科学院长春应用化学研究所 一种双马树脂改性氰酸酯预浸料的制备方法
CN101974156B (zh) * 2010-09-03 2011-12-28 苏州生益科技有限公司 无卤阻燃预聚物及其制备和在覆铜板中的应用
JP5860239B2 (ja) * 2011-07-28 2016-02-16 丸菱油化工業株式会社 難燃性樹脂組成物
KR101252063B1 (ko) * 2011-08-25 2013-04-12 한국생산기술연구원 알콕시실릴기를 갖는 에폭시 화합물, 이의 제조 방법, 이를 포함하는 조성물과 경화물 및 이의 용도
TWI544011B (zh) * 2013-05-17 2016-08-01 明和化成股份有限公司 含磷之酚樹脂 、其製造方法及其用途
CN103709717B (zh) * 2013-12-17 2017-10-20 中山台光电子材料有限公司 乙烯苄基醚化‑dopo化合物树脂组合物及制备和应用
WO2016029453A1 (en) * 2014-08-29 2016-03-03 Blue Cube Ip Llc Halogen-free and flame retardant compositions with low thermal expansion for high density printed wiring boards
CN104447869B (zh) * 2014-10-27 2019-03-01 复旦大学 一种含dopo且分子结构不对称的双马来酰亚胺、其制备方法及在制备复合树脂中的应用
CN104311756B (zh) 2014-11-07 2018-07-10 中国科学院上海有机化学研究所 含硅双马来酰亚胺树脂及其制备
CN104961895A (zh) * 2014-11-24 2015-10-07 西安元创化工科技股份有限公司 一种阻燃双马来酰亚胺树脂
CN104479130B (zh) 2014-12-02 2017-02-22 中国科学院化学研究所 一种含氟低介电损耗的双马来酰亚胺树脂及其制备方法和应用
CN104877134B (zh) * 2015-05-28 2017-04-05 苏州生益科技有限公司 无卤阻燃聚酰亚胺树脂组合物及使用其制作的半固化片及层压板
CN104861652B (zh) * 2015-05-28 2017-05-10 苏州生益科技有限公司 一种热固性树脂组合物及使用其制作的半固化片及层压板
CN105037723B (zh) * 2015-06-26 2017-07-07 苏州生益科技有限公司 一种无卤阻燃预聚物及使用其制作的半固化片及层压板
CN106366128B (zh) * 2015-07-24 2019-05-07 中山台光电子材料有限公司 膦菲类化合物及其制备方法和应用
TWI546319B (zh) * 2015-09-25 2016-08-21 台光電子材料股份有限公司 含磷聚苯醚樹脂及其製法、含磷聚苯醚預聚物之製法、樹脂組成物及其應用
CN108546493B (zh) * 2016-07-31 2020-09-18 鹤山市欧克特电子科技有限公司 一种环氧树脂涂料及其应用
CN106543228B (zh) * 2016-10-25 2018-07-17 北京工商大学 一种含磷杂菲基团的烷基次膦酸盐衍生物阻燃剂及其制备方法

Also Published As

Publication number Publication date
KR102292464B1 (ko) 2021-08-23
TWI660966B (zh) 2019-06-01
EP3660028A1 (en) 2020-06-03
CN109306044A (zh) 2019-02-05
EP3660028A4 (en) 2021-05-05
WO2019019483A1 (zh) 2019-01-31
JP6802390B2 (ja) 2020-12-16
US20200208057A1 (en) 2020-07-02
KR20200016346A (ko) 2020-02-14
JP2020517773A (ja) 2020-06-18

Similar Documents

Publication Publication Date Title
CN108250675B (zh) 一种含磷活性酯及其无卤组合物与覆铜箔基板
JP2016532759A (ja) 熱硬化性樹脂組成物及びその用途
CN111393594B (zh) 一种活性酯树脂及其树脂组合物
CN105348742B (zh) 含三聚氰胺型苯并噁嗪树脂的热固性树脂组合物、半固化片及层压板
KR102282600B1 (ko) 열경화성 수지 조성물, 이로 제조된 프리프레그, 금속박 적층판 및 고주파 회로기판
CN103980704A (zh) 用于高频高速基板的无卤树脂组合物、半固化片及层压板
CN104109347A (zh) 一种无卤热固性树脂组合物、半固化片及层压板
TWI658095B (zh) 一種熱固性樹脂組合物、由其製作之半固化片、覆金屬箔層壓板及高頻電路板
TWI548667B (zh) A halogen-free thermosetting resin composition, and a prepreg for use and a laminate for printed circuit
CN114634708B (zh) 一种树脂组合物、使用其的半固化片与覆铜箔层压板
WO2016107068A1 (zh) 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
CN103965588A (zh) 无卤热固性树脂组合物、半固化片及层压板
TWI660966B (zh) 一種低極性本徵阻燃樹脂及其製備方法和應用
TWI662051B (zh) 一種低極性樹脂及其製備方法和應用
TWI662050B (zh) 一種低極性樹脂及其製備方法和應用
TWI658046B (zh) 一種熱固性樹脂組合物、由其製作之半固化片、覆金屬箔層壓板及高頻電路板
TWI596155B (zh) Halogen-free thermosetting resin composition and prepreg and printed circuit laminate using the same
TWI548666B (zh) A halogen-free thermosetting resin composition and a prepreg using the same, and a laminate for printed circuit
KR20180009556A (ko) 난연성 및 전기적 특성이 우수한 난연 화합물 및 이의 조성물

Legal Events

Date Code Title Description
MM4A Annulment or lapse of patent due to non-payment of fees