CN109679565A - Thermally conductive fluorine richness flame retardant polyurethane hot melt adhesive and preparation method thereof - Google Patents
Thermally conductive fluorine richness flame retardant polyurethane hot melt adhesive and preparation method thereof Download PDFInfo
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- CN109679565A CN109679565A CN201811476166.5A CN201811476166A CN109679565A CN 109679565 A CN109679565 A CN 109679565A CN 201811476166 A CN201811476166 A CN 201811476166A CN 109679565 A CN109679565 A CN 109679565A
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- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
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- C09J175/06—Polyurethanes from polyesters
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- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
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- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
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- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
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- C08G18/40—High-molecular-weight compounds
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- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
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- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/7862—Nitrogen containing cyano groups or aldimine or ketimine groups
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
- C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
- C08G18/794—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aromatic isocyanates or isothiocyanates
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- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
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- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
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Abstract
The invention discloses a kind of thermally conductive fluorine richness flame retardant polyurethane hot melt adhesive and preparation method thereof, feature be the polyether Glycols for including 1~30 part, 1~40 part of liquid polyesters dihydric alcohol, 1~50 part of flame retardant polyether polyol, 1~60 part of crystalline polyester dihydric alcohol, 1~60 part containing isocyanate-modified polyacrylic acid fluorinated copolymer, 1~60 part of isocyanates, 0.01~3 part of catalyst, 0.01~3 part of antioxidant, 0.1~4 part of silane coupling agent and 40~200 parts of heat filling.The present invention first synthesizes poly- (hexafluorobutyl acrylate-is random-acrylonitrile-is random-butyl acrylate-is random-isocyanatoethyl), it is added in polyurethane prepolymer precursor reactant, heat filling is further added, low-surface-energy fluoro-acrylate copolymer plays peptizaiton for heat filling high efficiency dispersion in base polyurethane prepolymer for use as, fluoro-acrylate copolymer segment and reactive flame retardant are introduced in base polyurethane prepolymer for use as simultaneously, formula efficiently acts synergistically, and improves the comprehensive chemical resistance of polyurethane hot melt, heating conduction and flame retardant property.
Description
Technical field
The invention belongs to structure glue technical fields, and in particular to a kind of thermally conductive fluorine richness flame retardant polyurethane hot melt adhesive and its system
Preparation Method, which are mainly applied to electronics and appliance industry, power battery assembling, automobile industry isostructuralism to be bonded field.
Background technique
Polyurethane hot melt be a new generation can provide superior adhesion can structure glue, it is to be with polyurethane prepolymer
Material of main part is equipped with a hot melt adhesive prepared by various auxiliary agents.Polyurethane hot melt is easy to use, environmentally friendly, and performance again can be with
Solvent-based thermal melten gel compares favourably.Nearly ten years, polyurethane hot melt is obtained in the high-end fields such as electronics and appliance industry, automobile industry
It is fast-developing and be widely used.Polyurethane hot melt can be divided into thermoplastic polyurethane elastomer hot melt adhesive by cured form difference
And reactive polyurethane hot melt.Reactive polyurethane hot melt can be divided into response type and enclosed type by its principle of solidification difference.
Reaction type polyurethane hot-melt adhesive (PUR) is a kind of one pack system hot melt adhesive, is melted after heating, and flows scatter coated in substrate table
Face cools down after adherend bonding and forms excellent first adhesive property, then due to substrate surface contain micro-moisture or other
Compound containing active hydrogen reacts with isocyano (- NCO) and chemical crosslink reaction occurs, so that generating has highly cross-linked net
A kind of structural bonding hot melt adhesive of network and cohesive force greatly.
Reaction type polyurethane hot-melt adhesive has technically obtained unprecedented development at present, mainly around high-adhesive-strength, eutectic
Body viscosity, open hour reprocess and the progress performances such as cured form are optimized and revised.Chinese patent discloses one kind entitled " one
The application for a patent for invention of kind of reactive hot melt adhesive ", application number is 201480080313.0, is prepared a kind of with reprocessing
Removable polyurethane-hot melt adhesive, more suitable for high-end electronic product scope application.Chinese patent also discloses a kind of name
Referred to as the application for a patent for invention of " solvent-free damp solidifying polyurethane hot-melt adhesive composition ", application number are
201180047316.0, prepare a kind of quick polyurethane-hot melt for establishing adhesive property polyacrylate and polyester preparation of low toxicity
Viscose binder.In order to improve the cured form of reaction type polyurethane hot-melt adhesive, it is that " one kind has that Chinese patent, which discloses a kind of title,
The application for a patent for invention of machine silicon modified polyurethane sealant ", application number are 201710271725.8, prepare a kind of organosilicon and change
Property polyurethane sealant, with silane coupling agent replace isocyano (- NCO), be more suitable for applying under high humidity environment.Currently, reaction
The research and development technology of type polyurethane hot melt adhesive meets different type high-end electronic product scope application in fast development.Response type is poly-
Although urethane hot melt adhesive can form highly cross-linked network after hardening, it is thermally conductive, fire-retardant etc. that there is also chemicals-resistant burn intos
Performance deficiency problem.This main cause is most of reaction type polyurethane hot-melt adhesives to improve its initial cohesiveness, be joined big
The non-reacted thermoplasticity thickening resin of amount or polynary acrylic copolymer.These non-reaction system thickening resins can not participate in solid
Metaplasia is at cross-linked network, to easily reduce chemicals-resistant corrosive nature, heat resistance, the resistance to ag(e)ing of polyurethane hot melt adhesive coating
Energy is equal.
Heat-conducting glue is exclusively used in the bonding and conductive force of electronic and electrical equipment material.Currently, mainly have heat-conducting organic silica gel,
Thermally conductive epoxy glue and heat-conduction polyurethane glue.Heat-conducting organic silica gel has excellent heat-resisting and ageing-resistant performance, but to the attached of substrate
Put forth effort compared to weaker.Thermally conductive epoxy glue is very big to the bonding force of substrate, but deposits that hardness is big after hardening and brittleness is too strong.It is thermally conductive poly-
Urethane glue has excellent adhesive force and flexibility, can reach good damping and conductive force.Heat-conduction polyurethane glue is usually set
It is calculated as two-component, using mixed process, in order to quickly defoam, a large amount of silicon class defoaming agents is added and are quickly defoamed.Defoaming agent
Because that can not participate in reacting, coating surface, polluted product is easily precipitated.
Summary of the invention
A kind of thermally conductive fluorine richness flame retardant polyurethane hot melt adhesive is provided the purpose of the present invention is overcome the deficiencies in the prior art
And preparation method thereof, since thermally conductive fluorine richness flame retardant polyurethane hot melt adhesive introduces fluorine-containing groups, reactive flame retardant and thermally conductive
Filler can further promote chemicals-resistant corrosive nature, flame retardant property, heating conduction of polyurethane coating etc..
In order to achieve the above object, the technical solution of thermally conductive fluorine richness flame retardant polyurethane hot melt adhesive of the invention is such reality
It is existing, it is characterised in that including 1~30 part of polyether Glycols, 1~40 part of liquid polyesters dihydric alcohol, 1~50 part fire-retardant
Polyether polyol, 1~60 part of crystalline polyester dihydric alcohol, 1~60 part of the fluorine-containing copolymerization containing isocyanate-modified polyacrylic acid
Object, 1~60 part of isocyanates, 0.01~3 part of catalyst, 0.01~3 part of antioxidant, 0.1~4 part of silane coupling agent
It is above mass fraction with 40~200 parts of heat filling；It is described containing isocyanate-modified polyacrylic acid fluorinated copolymer
Chemical structure is: poly- (hexafluorobutyl acrylate-is random-and acrylonitrile-is random-and butyl acrylate-is random-methacrylic acid isocyanide
Base ethyl ester) i.e. P(HFMA-r-AN-r-BA-r-ICEMA), the equal molecule of number containing isocyanate-modified polyacrylic acid fluorinated copolymer
Amount is 1000~50000.
In the technical scheme, the polyether Glycols are polyoxypropyleneglycol of the number-average molecular weight 500~4000
One or two kinds of any combination of PPG or polytetrahydrofuran ether glycol PTMG；
The liquid polyesters dihydric alcohol be number-average molecular weight 200~2000 polyethylene glycol adipate glycol PEA, gather oneself two
Acid -1,6- hexylene glycol esterdiol PHA or polyadipate -1,4-butanediol esterdiol PMA one or more any combination；
The flame retardant polyether polyol is the WANOL FR-130, WANOL of Wanhua Chemical Group Co., Ltd.'s production
One or two kinds of any combination of FR-212 or WANOL FR-312；
The crystalline polyester dihydric alcohol is to win 7380 one or more of wound Degussa model 7320, model 7360 and model
Any combination；
The isocyanates is modified diphenylmethane -4,4 '-diisocyanate Desmodur CD-C(MDI performed polymer)；
The catalyst is one or more kinds of any groups of triethanolamine, 2,2- dimorpholine base Anaesthetie Ether and phosphoric acid
It closes；
The antioxidant is one or both of 168 and 1010 any combination；
The silane coupling agent is anilinomethyl triethoxysilane ND-42；
The heat filling is one or more kinds of any combination of aluminium oxide, graphite, aluminium hydroxide and calcium carbonate, thermally conductive
Packing material size is 0.1~5 μm.
In order to achieve the above object, the technical solution of thermally conductive fluorine richness flame retardant polyurethane hot melt adhesive preparation method of the invention
It is achieved in that preparation method is characterized in that:
Step 1: synthesis contains isocyanate-modified polyacrylic acid fluorinated copolymer
By 1~40 part of hexafluorobutyl acrylate HFMA, 1~50 part of acrylonitrile AN, 1~50 part of butyl acrylate BA and 1
~20 parts of isocyanatoethyl ICEMA is dissolved in 50~200 parts of toluene, 40~110 DEG C is controlled in, in nitrogen
Under gas shielded, 0.1~4 part of thermal initiator peroxidating 2 ethyl hexanoic acid tert-pentyl ester is added, polymerization reaction 2~50 hours, rotates
After evaporation removes toluene, obtains and contain isocyanate-modified polyacrylic acid fluorinated copolymer, contain containing isocyanate-modified polyacrylic acid
The number-average molecular weight of fluo-copolymer is 1000~50000；
Step 2: thermally conductive fluorine richness flame retardant polyurethane hot melt adhesive is synthesized
By 1~30 part of polyether Glycols, 1~40 part of liquid polyesters dihydric alcohol, 1~50 part of flame retardant polyether polyol, 1~
60 parts of crystalline polyester dihydric alcohol, 40~200 parts of heat filling, 0.01~3 part of catalyst and 0.01~3 part of antioxygen
After agent mixing, 120~150 DEG C are calorified, carries out mechanical dispersion, vacuumizes water removal about 1~3 hour, until the moisture content of mixture
Content is lower than 280ppm, cools down in 70~100 DEG C, under nitrogen protection, be added 1~60 part isocyanates and 1~60 part
Containing isocyanate-modified polyacrylic acid fluorinated copolymer, carry out polymerization reaction 1~10 hour, sampling analysis polymerizate NCO% contains
Amount reaches 1%~3%, and tested viscosity reaches 5000~50000 mPa.s at 100 DEG C, and 0.1~4 part of silane coupling agent is added, obtains
Thermally conductive fluorine richness flame retardant polyurethane hot melt adhesive is obtained, is above mass fraction.
In the technical scheme, with Brookfield DV-C digital viscometer viscosity.
Compared with prior art, the present invention have following advantages and effects
1, the work of dispersing agent can be played due to the low-surface-energy of fluorine element containing isocyanate-modified polyacrylic acid fluorinated copolymer
With promotion heat filling dispersibility in hot melt colloid reduces the Viscosity of colloid, improves the thermal conductivity of heat filling；
2, the present invention is improved by introducing fluorine-containing groups, reactive flame retardant and heat filling in base polyurethane prepolymer for use as
Reaction type polyurethane hot-melt adhesive chemical resistance, flame retardant property, heating conduction and ageing-resistant performance；
3, thickening resin acrylic copolymer random polycondensation is introduced base polyurethane prepolymer for use as by the present invention, is improved thickening resin and is gathered
The compatibility of urethane, further the deficiencies of solving the problems, such as reaction type polyurethane hot-melt adhesive chemical resistance.
4, the present invention solves the problems, such as that traditional reaction type polyurethane hot-melt adhesive is poor to substrate wet performance, improves hot melt
The flow leveling of glue sizing, packaging and Process of Applying Glue are not likely to produce bubble.
Specific embodiment
Below with reference to embodiment, the present invention is described in further detail, and embodiments of the present invention are not limited thereto.
Number involved in following embodiment is mass fraction.
Embodiment one
It is a kind of thermally conductive fluorine richness flame retardant polyurethane hot melt adhesive, is prepared by the following steps to obtain:
Step 1: synthesis contains isocyanate-modified polyacrylic acid fluorinated copolymer
By 10 parts of hexafluorobutyl acrylate HFMA, 30 parts of acrylonitrile AN, 10 parts of butyl acrylate BA and 5 parts of methyl-prop
Olefin(e) acid isocyano group ethyl ester ICEMA is dissolved in 70 parts of toluene, is controlled in 95 DEG C, under nitrogen protection, 2.5 parts of heat is added and draws
Agent peroxidating 2 ethyl hexanoic acid tert-pentyl ester is sent out, polymerization reaction 15 hours, after rotary evaporation removes toluene, acquisition changed containing isocyanates
Property polyacrylic acid fluorinated copolymer, the number-average molecular weight containing isocyanate-modified polyacrylic acid fluorinated copolymer be 6200, change
Learning structure is: poly- (hexafluorobutyl acrylate-is random-and acrylonitrile-is random-and butyl acrylate-is random-methacrylic acid isocyano group
Ethyl ester) i.e. P(HFMA-r-AN-r-BA-r-ICEMA).
Step 2: thermally conductive fluorine richness flame retardant polyurethane hot melt adhesive is synthesized
10 parts of polyoxypropyleneglycol PPG, 15 parts of polyethylene glycol adipate glycol PEA, 25 parts of flame retarding polyether is more
First alcohol WANOL FR-130,30 parts of 7320,50 parts of crystalline polyester dihydric alcohol of heat filling aluminium oxide, 0.3 part of phosphoric acid
After 0.5 part of irgasfos 168 mixing, 150 DEG C are calorified, mechanical dispersion is carried out, vacuumizes water removal 1 hour, until mixture
Water content be lower than 280ppm, cool down in 75 DEG C, under nitrogen protection, 35 parts of modified diphenylmethane -4 be added, 4 '-two is different
Cyanate Desmodur CD-C(MDI performed polymer) and the synthesis of 25 parts of step 1 is fluorine-containing total containing isocyanate-modified polyacrylic acid
Polymers carries out polymerization reaction 5 hours, and sampling analysis polymerizate NCO% content reaches 1.4%, and viscosity reaches 12400 mPa.s,
1.5 parts of silane coupling agent ND-42 is added, obtains thermally conductive fluorine richness flame retardant polyurethane hot melt adhesive, is above mass fraction.It is poly-
The number-average molecular weight of propylene oxide glycol PPG is 1000, and the number-average molecular weight of polyethylene glycol adipate glycol PEA is 500, is used
Brookfield DV-C digital viscometer viscosity, test temperature are set as 100 DEG C.
Embodiment two
It is a kind of thermally conductive fluorine richness flame retardant polyurethane hot melt adhesive, is prepared by the following steps to obtain:
Step 1: synthesis contains isocyanate-modified polyacrylic acid fluorinated copolymer
By 20 parts of hexafluorobutyl acrylate HFMA, 10 parts of acrylonitrile AN, 35 parts of butyl acrylate BA and 10 parts of methyl
Acrylic acid isocyano group ethyl ester ICEMA is dissolved in 100 parts of toluene, is controlled in 100 DEG C, under nitrogen protection, is added 1.8 parts
Thermal initiator peroxidating 2 ethyl hexanoic acid tert-pentyl ester polymerization reaction 15 hours, after rotary evaporation removes toluene, obtains and contains isocyanic acid
Ester modified polyacrylic acid fluorinated copolymer, the number-average molecular weight containing isocyanate-modified polyacrylic acid fluorinated copolymer are 11300,
Its chemical structure is: poly- (hexafluorobutyl acrylate-is random-and acrylonitrile-is random-butyl acrylate-is random-and methacrylic acid is different
Cyanaoethyl methacrylate) i.e. P(HFMA-r-AN-r-BA-r-ICEMA).
Step 2: thermally conductive fluorine richness flame retardant polyurethane hot melt adhesive is synthesized
By 10 parts of polytetrahydrofuran ether glycol PTMG, 15 parts of polyadipate -1,6- hexylene glycol esterdiol PHA, 40 parts of resistance
Combustible polyether glycol WANOL FR-312,30 parts of 7360,70 parts of crystalline polyester dihydric alcohol of heat filling graphite, 0.5 part
Triethanolamine and the mixing of 0.9 part of irgasfos 168 after, calorify 140 DEG C, carry out mechanical dispersion, it is small to vacuumize water removal 2.5
When, until the water content of mixture is lower than 280ppm, cool down in 70 DEG C, under nitrogen protection, 35 parts of modification hexichol is added
Methane -4,4 '-diisocyanate Desmodur CD-C(MDI performed polymer) and the synthesis of 30 parts of step 1 containing isocyanate-modified
Polyacrylic acid fluorinated copolymer carries out polymerization reaction 4 hours, and sampling analysis polymerizate NCO% content reaches 2.1%, and viscosity reaches
To 17540 mPa.s, 3 parts of silane coupling agent ND-42 is added, obtains thermally conductive fluorine richness flame retardant polyurethane hot melt adhesive, it is above equal
For mass fraction.The number-average molecular weight of polytetrahydrofuran ether glycol PTMG is 2000, polyadipate -1,6- hexylene glycol esterdiol
The number-average molecular weight of PHA is 1000, and with Brookfield DV-C digital viscometer viscosity, test temperature is set as 100
℃。
Embodiment three
It is a kind of thermally conductive fluorine richness flame retardant polyurethane hot melt adhesive, is prepared by the following steps to obtain:
Step 1: synthesis contains isocyanate-modified polyacrylic acid fluorinated copolymer
By 30 parts of hexafluorobutyl acrylate HFMA, 40 parts of acrylonitrile AN, 20 parts of butyl acrylate BA and 10 parts of methyl
Acrylic acid isocyano group ethyl ester ICEMA is dissolved in 140 parts of toluene, is controlled in 95 DEG C, under nitrogen protection, is added 1.2 parts
Thermal initiator peroxidating 2 ethyl hexanoic acid tert-pentyl ester polymerization reaction 12 hours, after rotary evaporation removes toluene, obtains and contains isocyanic acid
Ester modified polyacrylic acid fluorinated copolymer, the number-average molecular weight containing isocyanate-modified polyacrylic acid fluorinated copolymer are 16850,
Its chemical structure is: poly- (hexafluorobutyl acrylate-is random-and acrylonitrile-is random-butyl acrylate-is random-and methacrylic acid is different
Cyanaoethyl methacrylate) i.e. P(HFMA-r-AN-r-BA-r-ICEMA).
Step 2: thermally conductive fluorine richness flame retardant polyurethane hot melt adhesive is synthesized
25 parts of polyoxypropyleneglycol PPG, 15 parts of polyethylene glycol adipate glycol PEA, 40 parts of flame retarding polyether is more
First alcohol WANOL FR-212,50 parts of 7360,110 parts of crystalline polyester dihydric alcohol of heat filling aluminium hydroxide, 0.4 part
After 2,2- dimorpholine base Anaesthetie Ethers and the mixing of 1.2 parts of antioxidant 1010,150 DEG C are calorified, mechanical dispersion is carried out, taken out true
Sky water removal 3 hours cools down until the water content of mixture is lower than 280ppm in 80 DEG C, under nitrogen protection, is added 40 parts
Modified diphenylmethane -4,4 '-diisocyanate Desmodur CD-C(MDI performed polymer) and 35 parts of step 1 synthesis contain isocyanide
Acid esters modified polyacrylic acid fluorinated copolymer carries out polymerization reaction 6 hours, and sampling analysis polymerizate NCO% content reaches
2.3%, viscosity reaches 31230 mPa.s, and 3.5 parts of silane coupling agent ND-42 is added, obtains thermally conductive fluorine richness flame retardant polyurethane
Hot melt adhesive is mass fraction above.The number-average molecular weight of polyoxypropyleneglycol PPG is 3000, polyethylene glycol adipate
The number-average molecular weight of glycol PEA is 1500, and with Brookfield DV-C digital viscometer viscosity, test temperature is set as
100℃。
Example IV
It is a kind of thermally conductive fluorine richness flame retardant polyurethane hot melt adhesive, is prepared by the following steps to obtain:
Step 1: synthesis contains isocyanate-modified polyacrylic acid fluorinated copolymer
By 40 parts of hexafluorobutyl acrylate HFMA, 10 parts of acrylonitrile AN, 40 parts of butyl acrylate BA and 15 parts of methyl
Acrylic acid isocyano group ethyl ester ICEMA is dissolved in 180 parts of toluene, is controlled in 100 DEG C, under nitrogen protection, is added 1.0 parts
Thermal initiator peroxidating 2 ethyl hexanoic acid tert-pentyl ester polymerization reaction 7 hours, after rotary evaporation removes toluene, obtains and contains isocyanic acid
Ester modified polyacrylic acid fluorinated copolymer, the number-average molecular weight containing isocyanate-modified polyacrylic acid fluorinated copolymer are 24000,
Its chemical structure is: poly- (hexafluorobutyl acrylate-is random-and acrylonitrile-is random-butyl acrylate-is random-and methacrylic acid is different
Cyanaoethyl methacrylate) i.e. P(HFMA-r-AN-r-BA-r-ICEMA).
Step 2: thermally conductive fluorine richness flame retardant polyurethane hot melt adhesive is synthesized
By 10 parts of polyoxypropyleneglycol PPG, 20 parts of polyadipate -1,4-butanediol esterdiol PMA, 45 parts fire-retardant poly-
Ethoxylated polyhydric alcohol WANOL FR-312,45 parts of 7380,150 parts of crystalline polyester dihydric alcohol of heat filling calcium carbonate, 0.8 part
Triethanolamine and the mixing of 1.5 parts of irgasfos 168 after, calorify 150 DEG C, carry out mechanical dispersion, vacuumize water removal 2 hours,
Until the water content of mixture is lower than 280ppm, cool down in 90 DEG C, under nitrogen protection, 50 parts of modification hexichol first is added
Alkane -4,4 '-diisocyanate Desmodur CD-C(MDI performed polymer) and the synthesis of 50 parts of step 1 containing isocyanate-modified poly-
Acrylic acid fluorinated copolymer carries out polymerization reaction 3 hours, and sampling analysis polymerizate NCO% content reaches 2.3%, and viscosity reaches
3.5 parts of silane coupling agent ND-42 is added in 43520 mPa.s, obtains thermally conductive fluorine richness flame retardant polyurethane hot melt adhesive, above equal
For mass fraction.The number-average molecular weight of polyoxypropyleneglycol PPG is 3000, and the number of polyethylene glycol adipate glycol PEA is equal
Molecular weight is 1500, and with Brookfield DV-C digital viscometer viscosity, test temperature is set as 100 DEG C.
Performance test
Universal method of the present invention referring to current hot melt adhesive, the fire-retardant poly- ammonia of thermally conductive fluorine richness that the four kinds of above embodiments are obtained
Ester hot melt adhesive carry out melt viscosity, the open hour, shore hardness, elongation at break, shear strength, oxygen index (OI) and with resistance to acidity of oil
It can index test.Melt viscosity is tested referring to HG/T3660-1999 standard, selects No. 27 rotors, is arranged 100 DEG C.It is open
Time is tested referring to ASTM D4497-1994 (2004) method.Shore hardness is surveyed referring to GB-T2411-2008 standard
Examination.Elongation at break is tested referring to GB/T30776-2014 standard.Shear strength is carried out referring to GB/T7124-2004 standard
Test.Oxygen index (OI) is measured using GB/T5454-1997 " textile combustion performance test-oxygen index method ".Chemical resistance
The specific test method of index is that sample is prepared with reference to test shear strength method, after sample places solidification in 72 hours, by sample
It is soaked in oleic acid (purity 98%) solution 24 hours, takes out sample, be placed under 85 DEG C and 85% relative humidity conditions, carry out aging
After 1000 hours, then carry out shear strength test.Thermal coefficient is tested with reference to ASTMD5470 standard.All test datas
Comparative situation is see the following table 1.
Each embodiment specific performance of table 1 tests control case
Can be seen that the thermally conductive fluorine richness flame retardant polyurethane hot melt adhesive that the present invention synthesizes from the data of table 1 has excellent resistance toization
Product ageing properties, heating conduction and flame retardant property.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (3)
1. a kind of thermally conductive fluorine richness flame retardant polyurethane hot melt adhesive, it is characterised in that including 1~30 part of polyether Glycols, 1~40
Liquid polyesters dihydric alcohol, 1~50 part of the flame retardant polyether polyol, 1~60 part of crystalline polyester dihydric alcohol, 1~60 part of part
Containing isocyanate-modified polyacrylic acid fluorinated copolymer, 1~60 part of isocyanates, 0.01~3 part of catalyst, 0.01~
3 parts of antioxidant, 0.1~4 part of silane coupling agent and 40~200 parts of heat filling, are mass fraction above；It is described to contain
The chemical structure of isocyanate-modified polyacrylic acid fluorinated copolymer is: poly- (hexafluorobutyl acrylate-is random-acrylonitrile-nothing
Rule-butyl acrylate-is random-isocyanatoethyl) i.e. P(HFMA-r-AN-r-BA-r-ICEMA) and, contain isocyanic acid
The number-average molecular weight of ester modified polyacrylic acid fluorinated copolymer is 1000~50000.
2. thermally conductive fluorine richness flame retardant polyurethane hot melt adhesive according to claim 1, it is characterised in that:
The polyether Glycols are polyoxypropyleneglycol PPG or polytetrahydrofuran ether two of the number-average molecular weight 500~4000
One or two kinds of any combination of alcohol PTMG；
The liquid polyesters dihydric alcohol be number-average molecular weight 200~2000 polyethylene glycol adipate glycol PEA, gather oneself two
Acid -1,6- hexylene glycol esterdiol PHA or polyadipate -1,4-butanediol esterdiol PMA one or more any combination；
The flame retardant polyether polyol is the WANOL FR-130, WANOL of Wanhua Chemical Group Co., Ltd.'s production
One or two kinds of any combination of FR-212 or WANOL FR-312；
The crystalline polyester dihydric alcohol is to win 7380 one or more of wound Degussa model 7320, model 7360 and model
Any combination；
The isocyanates is modified diphenylmethane -4,4 '-diisocyanate Desmodur CD-C(MDI performed polymer)；
The catalyst is one or more kinds of any groups of triethanolamine, 2,2- dimorpholine base Anaesthetie Ether and phosphoric acid
It closes；
The antioxidant is one or both of 168 and 1010 any combination；
The silane coupling agent is anilinomethyl triethoxysilane ND-42；
The heat filling is one or more kinds of any combination of aluminium oxide, graphite, aluminium hydroxide and calcium carbonate, thermally conductive
Packing material size is 0.1~5 μm.
3. a kind of thermally conductive fluorine richness flame retardant polyurethane hot melt adhesive preparation method, preparation method are characterized in that:
Step 1: synthesis contains isocyanate-modified polyacrylic acid fluorinated copolymer
By 1~40 part of hexafluorobutyl acrylate HFMA, 1~50 part of acrylonitrile AN, 1~50 part of butyl acrylate BA and 1
~20 parts of isocyanatoethyl ICEMA is dissolved in 50~200 parts of toluene, 40~110 DEG C is controlled in, in nitrogen
Under gas shielded, 0.1~4 part of thermal initiator peroxidating 2 ethyl hexanoic acid tert-pentyl ester is added, polymerization reaction 2~50 hours, rotates
After evaporation removes toluene, obtains and contain isocyanate-modified polyacrylic acid fluorinated copolymer, contain containing isocyanate-modified polyacrylic acid
The number-average molecular weight of fluo-copolymer is 1000~50000；
Step 2: thermally conductive fluorine richness flame retardant polyurethane hot melt adhesive is synthesized
By 1~30 part of polyether Glycols, 1~40 part of liquid polyesters dihydric alcohol, 1~50 part of flame retardant polyether polyol, 1~
60 parts of crystalline polyester dihydric alcohol, 40~200 parts of heat filling, 0.01~3 part of catalyst and 0.01~3 part of antioxygen
After agent mixing, 120~150 DEG C are calorified, carries out mechanical dispersion, vacuumizes water removal about 1~3 hour, until the moisture content of mixture
Content is lower than 280ppm, cools down in 70~100 DEG C, under nitrogen protection, be added 1~60 part isocyanates and 1~60 part
Containing isocyanate-modified polyacrylic acid fluorinated copolymer, carry out polymerization reaction 1~10 hour, sampling analysis polymerizate NCO% contains
Amount reaches 1%~3%, and tested viscosity reaches 5000~50000 mPa.s at 100 DEG C, and 0.1~4 part of silane coupling agent is added, obtains
Thermally conductive fluorine richness flame retardant polyurethane hot melt adhesive is obtained, is above mass fraction.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111334226A (en) * | 2019-12-31 | 2020-06-26 | 武汉长盈鑫科技有限公司 | Heat-conducting adhesive with low glass transition temperature and preparation method thereof |
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| CN1845943A (en) * | 2003-06-09 | 2006-10-11 | 国家淀粉及化学投资控股公司 | Moisture curing reactive polyurethane hot melt adhesives modified with acrylic polymers |
| CN102504752A (en) * | 2011-11-30 | 2012-06-20 | 山东北方现代化学工业有限公司 | Room-temperature moisture-curable single-component flame-retardant polyurethane sealant |
| CN105601797A (en) * | 2015-12-31 | 2016-05-25 | 徐宪 | Environment-friendly fluorine-containing nanometer positive ion acrylic ester polymer emulsion and preparation method thereof |
| CN105670550A (en) * | 2016-03-31 | 2016-06-15 | 东莞新能源科技有限公司 | Heat-conducting adhesive and secondary battery containing heat-conducting adhesive |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1845943A (en) * | 2003-06-09 | 2006-10-11 | 国家淀粉及化学投资控股公司 | Moisture curing reactive polyurethane hot melt adhesives modified with acrylic polymers |
| CN102504752A (en) * | 2011-11-30 | 2012-06-20 | 山东北方现代化学工业有限公司 | Room-temperature moisture-curable single-component flame-retardant polyurethane sealant |
| CN105601797A (en) * | 2015-12-31 | 2016-05-25 | 徐宪 | Environment-friendly fluorine-containing nanometer positive ion acrylic ester polymer emulsion and preparation method thereof |
| CN105670550A (en) * | 2016-03-31 | 2016-06-15 | 东莞新能源科技有限公司 | Heat-conducting adhesive and secondary battery containing heat-conducting adhesive |
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| CN111334226A (en) * | 2019-12-31 | 2020-06-26 | 武汉长盈鑫科技有限公司 | Heat-conducting adhesive with low glass transition temperature and preparation method thereof |
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