CN109651995A - One-component flame-retarded heat-conducting fluorine silicon modified polyurethane hot melt adhesive and preparation method thereof - Google Patents
One-component flame-retarded heat-conducting fluorine silicon modified polyurethane hot melt adhesive and preparation method thereof Download PDFInfo
- Publication number
- CN109651995A CN109651995A CN201811476161.2A CN201811476161A CN109651995A CN 109651995 A CN109651995 A CN 109651995A CN 201811476161 A CN201811476161 A CN 201811476161A CN 109651995 A CN109651995 A CN 109651995A
- Authority
- CN
- China
- Prior art keywords
- fluorine silicon
- hot melt
- melt adhesive
- parts
- polyacrylic acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- 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
- C09J175/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- 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
- C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- 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
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4202—Two or more polyesters of different physical or chemical nature
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- 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
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
- C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- 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
- C08G18/48—Polyethers
- C08G18/4804—Two or more polyethers of different physical or chemical nature
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- 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
- C08G18/48—Polyethers
- C08G18/4825—Polyethers containing two hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- 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
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- 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
- C08G18/63—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers
- C08G18/635—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers onto unsaturated polymers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Inorganic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention discloses a kind of one-component flame-retarded heat-conducting fluorine silicon modified polyurethane hot melt adhesive and preparation method thereof, feature is the polyether Glycols for including 1~40 part, 1~45 part of liquid polyesters dihydric alcohol, 1~50 part of flame retardant polyether polyol, 1~60 part of crystalline polyester dihydric alcohol, 1~50 part of polyacrylic acid fluorine silicon isocyanate copolymer, 1~50 part of isocyanates, 0.01~3 part of catalyst, 0.01~4 part of antioxidant, 0.1~5 part of silane coupling agent and 30~200 parts of heat filling.It is i.e. poly- (hexafluorobutyl acrylate-is random-methacryloxypropyl list sealing end dimethyl polysiloxane-is random-Isooctyl acrylate monomer-is random-isocyanatoethyl) that the present invention first synthesizes low-surface-energy polyacrylic acid fluorine silicon isocyanate copolymer, it is added in polyurethane prepolymer precursor reactant, efficiently synergistic effect, disperse heat filling, improves chemical resistance, heating conduction and flame retardant property.
Description
Technical field
The invention belongs to structure glue technical fields, and in particular to a kind of one-component flame-retarded heat-conducting fluorine silicon modified polyurethane hot melt
Glue and preparation method thereof, which are mainly applied to electronics and appliance industry, automobile industry, power battery assembling isostructuralism bonding necks
Domain.
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 surface,
It is cooled down after adherend bonding and forms excellent first adhesive property, then since substrate surface contains micro-moisture or other contain work
The compound for sprinkling hydrogen react with isocyano (- NCO) and chemical crosslink reaction occurs, thus generate with highly cross-linked network and
A kind of big structural bonding hot melt adhesive of cohesive force.
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, flame retardant property, the resistance to ag(e)ing of polyurethane hot melt adhesive coating
Energy is equal.
Summary of the invention
A kind of fluorinated silicone modified poly- ammonia of one-component flame-retarded heat-conducting is provided the purpose of the present invention is overcome the deficiencies in the prior art
Ester hot melt adhesive and preparation method thereof, due to one-component flame-retarded heat-conducting fluorine silicon modified polyurethane hot melt adhesive introduce fluorine silicon segment and
Reactive flame retardant, further high efficiency dispersion heat filling, can further be promoted polyurethane coating chemicals-resistant corrosive nature,
Flame retardant property, heating conduction, ageing-resistant performance etc..
In order to achieve the above object, the technical solution of one-component flame-retarded heat-conducting fluorine silicon modified polyurethane hot melt adhesive of the invention
It is achieved in that it is characterized by comprising 1~40 part of polyether Glycols, 1~45 part of liquid polyesters dihydric alcohol, 1~50
The flame retardant polyether polyol, 1~60 part of crystalline polyester dihydric alcohol, 1~50 part of polyacrylic acid fluorine silicon isocyanates of part are total
Polymers, 1~50 part of isocyanates, 0.01~3 part of catalyst, 0.01~4 part of antioxidant, 0.1~5 part silane coupled
Agent and 30~200 parts of heat filling, are mass fraction above；The chemistry of the polyacrylic acid fluorine silicon isocyanate copolymer
Structure is: poly- (hexafluorobutyl acrylate-is random-and methacryloxypropyl list sealing end dimethyl polysiloxane-is random-propylene
The different monooctyl ester-of acid is random-isocyanatoethyl) i.e. P(HFMA-r-EHAPDMS-r-EHA-r-ICEMA) and, polyacrylic acid
The number-average molecular weight of fluorine silicon isocyanate copolymer 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 any group of polyadipate -1,4-butanediol esterdiol (PMA) one or more
It closes；
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 preparation method of one-component flame-retarded heat-conducting fluorine silicon modified polyurethane hot melt adhesive of the invention
Technical solution be achieved in that it is characterized in that preparation step is as follows:
Step 1: synthesis polyacrylic acid fluorine silicon isocyanate copolymer
1~45 part of hexafluorobutyl acrylate HFMA, 1~45 part of methacryloxypropyl list are blocked into the poly- silicon oxygen of dimethyl
Alkane MAPDMS, 1~90 part of Isooctyl acrylate monomer EHA and 1~20 part of isocyanatoethyl ICEMA are dissolved in 50
In~300 parts of toluene, 40~110 DEG C are controlled in, under nitrogen protection, 0.1~4 part of thermal initiator peroxidating 2- second is added
Polymerization reaction 2~50 hours, after rotary evaporation removes toluene, it is total to obtain polyacrylic acid fluorine silicon isocyanates for base caproic acid tert-pentyl ester
Polymers, the number-average molecular weight of polyacrylic acid fluorine silicon isocyanate copolymer are 1000~50000；
Step 2: synthesis one-component flame-retarded heat-conducting fluorine silicon modified polyurethane hot melt adhesive
By 1~40 part of polyether Glycols, 1~45 part of liquid polyesters dihydric alcohol, 1~50 part of flame retardant polyether polyol, 1~
60 parts of crystalline polyester dihydric alcohol, 0.01~3 part of catalyst, 30~200 parts of heat filling and 0.01~4 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 1~50 part isocyanates and 1~50 part
Polyacrylic acid fluorine silicon isocyanate copolymer carries out polymerization reaction 1~20 hour, and sampling analysis polymerizate NCO% content reaches
1%~3%, tested viscosity reaches 5000~40000 mPa.s at 100 DEG C, and 0.1~5 part of silane coupling agent is added, and obtains single group
Part flame-retarded heat-conducting fluorine silicon modified polyurethane hot melt adhesive, is mass fraction above.
In the technical scheme, in step 1 methacryloxypropyl list sealing end dimethyl polysiloxane MAPDMS number
Average molecular weight is 1000, No. CAS: 146632-07-7.
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 present invention solves heat filling dispersion problem, the low-surface-energy polyacrylic acid fluorine silicon isocyanate copolymer of synthesis
The bulk viscosity of glue can be reduced, thermal conductivity is improved by heat filling high efficiency dispersion in base polyurethane prepolymer for use as；
2, the present invention solves traditional reaction type polyurethane hot-melt adhesive chemical resistance, flame retardant property, ageing-resistant performance etc. no
The defect of foot improves the poly- ammonia of response type by introducing fluorine silicon segment and reactive flame retardant in base polyurethane prepolymer for use as
Ester hot melt adhesive chemical resistance, flame retardant property 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 adhesive and applies
The flow leveling of glue, 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 one-component flame-retarded heat-conducting fluorine silicon modified polyurethane hot melt adhesive, is prepared by the following steps to obtain:
Step 1: synthesis polyacrylic acid fluorine silicon isocyanate copolymer
5 parts of hexafluorobutyl acrylate HFMA, 10 parts of methacryloxypropyl list are blocked into dimethyl polysiloxane
MAPDMS, 40 parts of Isooctyl acrylate monomer EHA and 7 parts of isocyanatoethyl ICEMA are dissolved in 50 parts of toluene
In, 90 DEG C are controlled in, under nitrogen protection, 3.7 parts of thermal initiator peroxidating 2 ethyl hexanoic acid tert-pentyl ester, polymerization reaction is added
8 hours, after rotary evaporation removes toluene, obtain polyacrylic acid fluorine silicon isocyanate copolymer, polyacrylic acid fluorine silicon isocyanates
The chemical structure of copolymer is: poly- (hexafluorobutyl acrylate-is random-and methacryloxypropyl list blocks the poly- silicon oxygen of dimethyl
Alkane-is random-and Isooctyl acrylate monomer-is random-isocyanatoethyl) i.e. P(HFMA-r-EHAPDMS-r-EHA-r-
ICEMA), the number-average molecular weight of polyacrylic acid fluorine silicon isocyanate copolymer is 4700；Methacryloxypropyl list sealing end two
The number-average molecular weight of methyl polysiloxane MAPDMS is 1000, No. CAS: 146632-07-7.
Step 2: synthesis one-component flame-retarded heat-conducting fluorine silicon modified polyurethane hot melt adhesive
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 7320,70 parts of crystalline polyester dihydric alcohol of aluminium oxide, 0.6 part of phosphoric acid and 0.9 part
Irgasfos 168 mixing after, calorify 150 DEG C, carry out mechanical dispersion, vacuumize water removal 1 hour, until the moisture content of mixture contains
Amount is lower than 280ppm, cools down in 75 DEG C, under nitrogen protection, 40 parts of 4,4 '-diisocyanate of modified diphenylmethane-is added
Desmodur CD-C(MDI performed polymer) and 15 parts of step 1 synthesis polyacrylic acid fluorine silicon isocyanate copolymer, polymerize
Reaction 3 hours, sampling analysis polymerizate NCO% content reaches 2.3%, and viscosity reaches 7560 mPa.s, 2 parts of silane is added
Coupling agent ND-42 obtains one-component flame-retarded heat-conducting fluorine silicon modified polyurethane hot melt adhesive, is above mass fraction.Polyoxygenated third
The number-average molecular weight of enediol PPG is 1000, polyethylene glycol adipate glycol PEA, and number-average molecular weight 500 is used
Brookfield DV-C digital viscometer viscosity, test setting temperature are 100 DEG C.
Embodiment two
It is a kind of one-component flame-retarded heat-conducting fluorine silicon modified polyurethane hot melt adhesive, is prepared by the following steps to obtain:
Step 1: synthesis polyacrylic acid fluorine silicon isocyanate copolymer
10 parts of hexafluorobutyl acrylate HFMA, 20 parts of methacryloxypropyl list are blocked into dimethyl polysiloxane
MAPDMS, 50 parts of Isooctyl acrylate monomer EHA and 8 parts of isocyanatoethyl ICEMA are dissolved in 120 parts of toluene
In, 100 DEG C are controlled in, under nitrogen protection, 3 parts of thermal initiator peroxidating 2 ethyl hexanoic acid tert-pentyl ester, polymerization reaction 9 is added
Hour, after rotary evaporation removes toluene, polyacrylic acid fluorine silicon isocyanate copolymer is obtained, polyacrylic acid fluorine silicon isocyanates is total
The chemical structure of polymers is: poly- (hexafluorobutyl acrylate-is random-and methacryloxypropyl list blocks dimethyl polysiloxane-
Randomly-Isooctyl acrylate monomer-is random-isocyanatoethyl) i.e. P(HFMA-r-EHAPDMS-r-EHA-r-
ICEMA), the number-average molecular weight of polyacrylic acid fluorine silicon isocyanate copolymer is 8800；Methacryloxypropyl list sealing end two
The number-average molecular weight of methyl polysiloxane MAPDMS is 1000, No. CAS: 146632-07-7.
Step 2: synthesis one-component flame-retarded heat-conducting fluorine silicon modified polyurethane hot melt adhesive
By 20 parts of polytetrahydrofuran ether glycol PTMG, 25 parts of polyadipate -1,6- hexylene glycol esterdiol PHA, 30 parts of resistance
Combustible polyether glycol WANOL FR-312,40 parts of 7360,90 parts of graphite of crystalline polyester dihydric alcohol, 0.4 part of three ethyl alcohol
After amine and the mixing of 1 part of irgasfos 168,140 DEG C are calorified, mechanical dispersion is carried out, vacuumizes water removal 2.5 hours, until mixing
The water content of object is lower than 280ppm, cools down in 70 DEG C, under nitrogen protection, 40 parts of modified diphenylmethane -4,4 '-two is added
Isocyanates Desmodur CD-C(MDI performed polymer) and the synthesis of 25 parts of step 1 the copolymerization of polyacrylic acid fluorine silicon isocyanates
Object carries out polymerization reaction 3 hours, and sampling analysis polymerizate NCO% content reaches 2.4%, and viscosity reaches 12800 mPa.s, adds
Enter 3 parts of silane coupling agent ND-42, obtains one-component flame-retarded heat-conducting fluorine silicon modified polyurethane hot melt adhesive, be above mass parts
Number.The number-average molecular weight of polytetrahydrofuran ether glycol PTMG is 2000, and the number of polyadipate -1,6- hexylene glycol esterdiol PHA is equal
Molecular weight is 1000, and with Brookfield DV-C digital viscometer viscosity, test setting temperature is 100 DEG C.
Embodiment three
It is a kind of one-component flame-retarded heat-conducting fluorine silicon modified polyurethane hot melt adhesive, is prepared by the following steps to obtain:
Step 1: synthesis polyacrylic acid fluorine silicon isocyanate copolymer
20 parts of hexafluorobutyl acrylate HFMA, 10 parts of methacryloxypropyl list are blocked into dimethyl polysiloxane
MAPDMS, 60 parts of Isooctyl acrylate monomer EHA and 10 parts of isocyanatoethyl ICEMA are dissolved in 140 parts of first
In benzene, 95 DEG C are controlled in, under nitrogen protection, 2.5 parts of thermal initiator peroxidating 2 ethyl hexanoic acid tert-pentyl ester is added, polymerization is anti-
It answers 10 hours, after rotary evaporation removes toluene, obtains polyacrylic acid fluorine silicon isocyanate copolymer, polyacrylic acid fluorine silicon isocyanic acid
The chemical structure of ester copolymer is: poly- (hexafluorobutyl acrylate-is random-and methacryloxypropyl list blocks the poly- silicon of dimethyl
Oxygen alkane-is random-and Isooctyl acrylate monomer-is random-isocyanatoethyl) i.e. P(HFMA-r-EHAPDMS-r-EHA-r-
ICEMA), the number-average molecular weight of polyacrylic acid fluorine silicon isocyanate copolymer is 15400；Methacryloxypropyl list sealing end two
The number-average molecular weight of methyl polysiloxane MAPDMS is 1000, No. CAS: 146632-07-7.
Step 2: synthesis one-component flame-retarded heat-conducting fluorine silicon modified polyurethane hot melt adhesive
15 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 7360,120 parts of calcium carbonate of crystalline polyester dihydric alcohol, 0.8 part of 2,2- dimorpholine
After base Anaesthetie Ether and the mixing of 1.5 parts of antioxidant 1010,150 DEG C are calorified, mechanical dispersion is carried out, it is small to vacuumize water removal 3
When, until the water content of mixture is lower than 280ppm, cool down in 80 DEG C, under nitrogen protection, 45 parts of modification hexichol is added
Methane -4,4 '-diisocyanate Desmodur CD-C(MDI performed polymer) and 35 parts of step 1 synthesis polyacrylic acid fluorine silicon it is different
Cyanic acid ester copolymer carries out polymerization reaction 6 hours, and sampling analysis polymerizate NCO% content reaches 2.4%, and viscosity reaches 17807
2 parts of silane coupling agent ND-42 is added in mPa.s, obtains one-component flame-retarded heat-conducting fluorine silicon modified 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 setting temperature is 100 DEG C.
Example IV
It is a kind of one-component flame-retarded heat-conducting fluorine silicon modified polyurethane hot melt adhesive, is prepared by the following steps to obtain:
Step 1: synthesis polyacrylic acid fluorine silicon isocyanate copolymer
20 parts of hexafluorobutyl acrylate HFMA, 30 parts of methacryloxypropyl list are blocked into dimethyl polysiloxane
MAPDMS, 80 parts of Isooctyl acrylate monomer EHA and 15 parts of isocyanatoethyl ICEMA are dissolved in 150 parts of first
In benzene, 100 DEG C are controlled in, under nitrogen protection, 1 part of thermal initiator peroxidating 2 ethyl hexanoic acid tert-pentyl ester is added, polymerization is anti-
It answers 8 hours, after rotary evaporation removes toluene, obtains polyacrylic acid fluorine silicon isocyanate copolymer, polyacrylic acid fluorine silicon isocyanic acid
The chemical structure of ester copolymer is: poly- (hexafluorobutyl acrylate-is random-and methacryloxypropyl list blocks the poly- silicon of dimethyl
Oxygen alkane-is random-and Isooctyl acrylate monomer-is random-isocyanatoethyl) i.e. P(HFMA-r-EHAPDMS-r-EHA-r-
ICEMA), the number-average molecular weight of polyacrylic acid fluorine silicon isocyanate copolymer is 24000；Methacryloxypropyl list sealing end two
The number-average molecular weight of methyl polysiloxane MAPDMS is 1000, No. CAS: 146632-07-7.
Step 2: synthesis one-component flame-retarded heat-conducting fluorine silicon modified polyurethane hot melt adhesive
By 30 parts of polyoxypropyleneglycol PPG, 10 parts of polyadipate -1,4-butanediol esterdiol PMA, 45 parts fire-retardant poly-
Ethoxylated polyhydric alcohol WANOL FR-312,50 parts of 7380,140 parts of aluminium hydroxide of crystalline polyester dihydric alcohol, 0.9 part of three second
After hydramine and the mixing of 1 part of irgasfos 168,150 DEG C are calorified, mechanical dispersion is carried out, vacuumizes water removal 2 hours, until mixing
The water content of object is lower than 280ppm, cools down in 90 DEG C, under nitrogen protection, 50 parts of modified diphenylmethane -4,4 '-two is added
Isocyanates Desmodur CD-C(MDI performed polymer) and the synthesis of 45 parts of step 1 the copolymerization of polyacrylic acid fluorine silicon isocyanates
Object carries out polymerization reaction 3 hours, and sampling analysis polymerizate NCO% content reaches 2.7%, and viscosity reaches 26520 mPa.s, adds
Enter 1 part of silane coupling agent ND-42, obtains one-component flame-retarded heat-conducting fluorine silicon modified polyurethane hot melt adhesive, be above mass parts
Number.The number-average molecular weight of polyoxypropyleneglycol PPG is 4000, polyadipate -1,4-butanediol esterdiol PMA equal molecule of number
Amount is 2000, and with Brookfield DV-C digital viscometer viscosity, test setting temperature is 100 DEG C.
Performance test
Universal method of the present invention referring to current hot melt adhesive, the one-component flame-retarded heat-conducting fluorine silicon that the four kinds of above embodiments are obtained
Modified polyurethane hot melt adhesive carry out melt viscosity, the open hour, shore hardness, elongation at break, shear strength, oxygen index (OI) and and
The energy of resistance to acidity of oil index test.Melt viscosity is tested referring to HG/T3660-1999 standard, is arranged 100 DEG C.Open hour ginseng
It is tested according to ASTM D4497-1994 (2004) method.Shore hardness is tested referring to GB-T2411-2008 standard.It is disconnected
Elongation is split to be tested referring to GB/T30776-2014 standard.Shear strength is tested referring to GB/T7124-2004 standard.
Oxygen index (OI) is measured using GB/T5454-1997 " textile combustion performance test-oxygen index method ".Chemical resistance index tool
Body test method is to prepare sample after sample places solidification in 72 hours with reference to test shear strength method to be soaked in sample
Oleic acid (purity 98%) solution 24 hours is taken out sample, is placed under 85 DEG C and 85% relative humidity conditions, it is small to carry out aging 1000
Shi Hou, then carry out shear strength test.Thermal coefficient is tested with reference to ASTMD5470 standard.All test datas compare feelings
Condition is see the following table 1.
Each embodiment specific performance of table 1 tests control case
It can be seen that the one-component flame-retarded heat-conducting fluorine silicon modified polyurethane hot melt adhesive of the invention synthesized with excellent from the data of table 1
Good chemicals-resistant 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 (4)
1. a kind of one-component flame-retarded heat-conducting fluorine silicon modified polyurethane hot melt adhesive, it is characterised in that including 1~40 part of polyethers binary
Alcohol, 1~45 part of liquid polyesters dihydric alcohol, 1~50 part of flame retardant polyether polyol, 1~60 part of crystalline polyester dihydric alcohol,
1~50 part of polyacrylic acid fluorine silicon isocyanate copolymer, 1~50 part of isocyanates, 0.01~3 part of catalyst, 0.01
~4 parts of antioxidant, 0.1~5 part of silane coupling agent and 30~200 parts of heat filling, are mass fraction above；It is described
The chemical structure of polyacrylic acid fluorine silicon isocyanate copolymer is: poly- (hexafluorobutyl acrylate-is random-methacryloxypropyl third
Base list block dimethyl polysiloxane-it is random-Isooctyl acrylate monomer-is random-isocyanatoethyl) i.e. P(HFMA-
R-EHAPDMS-r-EHA-r-ICEMA), the number-average molecular weight of polyacrylic acid fluorine silicon isocyanate copolymer is 1000~50000.
2. one-component flame-retarded heat-conducting fluorine silicon modified 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 any group of polyadipate -1,4-butanediol esterdiol (PMA) one or more
It closes；
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 preparation method of one-component flame-retarded heat-conducting fluorine silicon modified polyurethane hot melt adhesive, it is characterised in that preparation step is such as
Under:
Step 1: synthesis polyacrylic acid fluorine silicon isocyanate copolymer
1~45 part of hexafluorobutyl acrylate HFMA, 1~45 part of methacryloxypropyl list are blocked into the poly- silicon oxygen of dimethyl
Alkane MAPDMS, 1~90 part of Isooctyl acrylate monomer EHA and 1~20 part of isocyanatoethyl ICEMA are dissolved in 50
In~300 parts of toluene, temperature control is in 40~110 DEG C, under nitrogen protection, 0.1~4 part of thermal initiator peroxidating 2- second is added
Polymerization reaction 2~50 hours, after rotary evaporation removes toluene, it is total to obtain polyacrylic acid fluorine silicon isocyanates for base caproic acid tert-pentyl ester
Polymers, the number-average molecular weight of polyacrylic acid fluorine silicon isocyanate copolymer are 1000~50000；
Step 2: synthesis one-component flame-retarded heat-conducting fluorine silicon modified polyurethane hot melt adhesive
By 1~40 part of polyether Glycols, 1~45 part of liquid polyesters dihydric alcohol, 1~50 part of flame retardant polyether polyol, 1~
60 parts of crystalline polyester dihydric alcohol, 0.01~3 part of catalyst, 30~200 parts of heat filling and 0.01~4 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 1~50 part isocyanates and 1~50 part
Polyacrylic acid fluorine silicon isocyanate copolymer carries out polymerization reaction 1~20 hour, and sampling analysis polymerizate NCO% content reaches
1%~3%, tested viscosity reaches 5000~40000 mPa.s at 100 DEG C, and 0.1~5 part of silane coupling agent is added, and obtains single group
Part flame-retarded heat-conducting fluorine silicon modified polyurethane hot melt adhesive, is mass fraction above.
4. the preparation method of one-component flame-retarded heat-conducting fluorine silicon modified polyurethane hot melt adhesive according to claim 3, feature
The number-average molecular weight for being methacryloxypropyl list sealing end dimethyl polysiloxane MAPDMS in step 1 is 1000, CAS
Number: 146632-07-7.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811476161.2A CN109651995A (en) | 2018-12-04 | 2018-12-04 | One-component flame-retarded heat-conducting fluorine silicon modified polyurethane hot melt adhesive and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811476161.2A CN109651995A (en) | 2018-12-04 | 2018-12-04 | One-component flame-retarded heat-conducting fluorine silicon modified polyurethane hot melt adhesive and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109651995A true CN109651995A (en) | 2019-04-19 |
Family
ID=66112406
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811476161.2A Withdrawn CN109651995A (en) | 2018-12-04 | 2018-12-04 | One-component flame-retarded heat-conducting fluorine silicon modified polyurethane hot melt adhesive and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109651995A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116572608A (en) * | 2023-05-10 | 2023-08-11 | 山东仁丰特种材料股份有限公司 | Copper-clad plate and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN1901942A (en) * | 2003-12-30 | 2007-01-24 | 庄臣及庄臣视力保护公司 | Antimicrobial contact lenses and methods for their production |
| 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 |
-
2018
- 2018-12-04 CN CN201811476161.2A patent/CN109651995A/en not_active Withdrawn
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN1901942A (en) * | 2003-12-30 | 2007-01-24 | 庄臣及庄臣视力保护公司 | Antimicrobial contact lenses and methods for their production |
| 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 |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116572608A (en) * | 2023-05-10 | 2023-08-11 | 山东仁丰特种材料股份有限公司 | Copper-clad plate and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111019589B (en) | Two-component polyurethane adhesive, preparation method thereof and application thereof in soft package battery | |
| CN103524703B (en) | A preparation method of a polyurethane/epoxy resin composite material | |
| EP2547744A2 (en) | Silane moisture curable hot melts | |
| CN101280061A (en) | Synthetic method of organosilicon polyurethane-acrylic ester ternary composite ionomer emulsion | |
| CN109679561A (en) | Graphene oxide modified flame-retardant fluorine-silicon polyurethane hot melt adhesive and preparation method thereof | |
| CN109852320A (en) | Graphene oxide modified fluoride-containing flame retardant polyurethane hot melt adhesive and preparation method thereof | |
| CN109651994A (en) | Ageing-resistant performance excellent flame damp solidifying polyurethane hot melt adhesive and preparation method thereof | |
| CN109679559A (en) | The excellent damp solidifying polyurethane hot melt adhesive and preparation method thereof of oil resistance | |
| CN105061714A (en) | Synthetic method and application of silicon alkane terminated polyurethane prepolymer | |
| CN110845983A (en) | Epoxy modified polyurethane hot melt adhesive and preparation method thereof | |
| CN109852322A (en) | Thermally conductive reaction-type flame-retarding polyurethane hot melt of one-component and preparation method thereof | |
| CN109651992A (en) | The excellent moisture-curable flame retardant polyurethane hot melt adhesive and preparation method thereof of weather resistance | |
| CN109651995A (en) | One-component flame-retarded heat-conducting fluorine silicon modified polyurethane hot melt adhesive and preparation method thereof | |
| CN109679560A (en) | Thermally conductive organic-silicon-modified flame retardant polyurethane hot melt adhesive of moisture-curable and preparation method thereof | |
| CN109609078A (en) | Organic-silicon-modified flame retardant polyurethane hot melt adhesive of wet-cured type and preparation method thereof | |
| CN109852323A (en) | Organic-silicon-modified one-component reaction type polyurethane hot-melt adhesive and preparation method thereof | |
| CN109651991A (en) | Wet-cured type organic silicon modified polyurethane hot melt adhesive and preparation method thereof | |
| CN109651996A (en) | High thermal conductivity flame retardant polyurethane hot melt adhesive and preparation method thereof | |
| CN109679562A (en) | Novel moisture-curable flame retardant polyurethane hot melt adhesive and preparation method thereof | |
| CN109679563A (en) | Graphene oxide modified flame-retardant damp solidifying polyurethane hot melt adhesive and preparation method thereof | |
| CN109486463A (en) | Flame-retarded heat-conducting damp solidifying polyurethane hot melt adhesive and preparation method thereof | |
| CN109609077A (en) | Organic-silicon-modified reaction-type flame-retarding polyurethane hot melt and preparation method thereof | |
| CN109679565A (en) | Thermally conductive fluorine richness flame retardant polyurethane hot melt adhesive and preparation method thereof | |
| KR20160090290A (en) | Double-sided adhesive sheet and method for producing double-sided adhesive sheet | |
| CN109666437A (en) | Oil resistance excellent flame damp solidifying polyurethane hot melt adhesive and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WW01 | Invention patent application withdrawn after publication |
Application publication date: 20190419 |
|
| WW01 | Invention patent application withdrawn after publication |