CN110527480A - A kind of 1-30 minutes multi-functional environment-protection adhesive - Google Patents
A kind of 1-30 minutes multi-functional environment-protection adhesive Download PDFInfo
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- CN110527480A CN110527480A CN201910801378.4A CN201910801378A CN110527480A CN 110527480 A CN110527480 A CN 110527480A CN 201910801378 A CN201910801378 A CN 201910801378A CN 110527480 A CN110527480 A CN 110527480A
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- 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
- C08G18/4081—Mixtures of compounds of group C08G18/64 with other macromolecular compounds
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- 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
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- 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
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- 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
- C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
- C08G18/6492—Lignin containing materials; Wood resins; Wood tars; Derivatives thereof
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- 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
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- 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
- C09J175/08—Polyurethanes from polyethers
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- 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
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/0812—Aluminium
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- 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
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/328—Phosphates of heavy metals
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- 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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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Abstract
The present invention discloses a kind of 1-30 minutes multi-functional environment-protection adhesive, it include following raw material: 10-15 parts of polyether polyol, 20-25 parts of crystalline polyester polyol, 5-10 parts of liquid non-crystalline polyester polyalcohol, 2-10 parts of solid amorphous polyester polyol, 20-25 parts of isocyanate-monomer, 15-20 parts of thermoplastic resin, 40-50 parts of modified rosin resin, 10-20 parts of natural plant gum, 2-3 parts of catalyst, 5-9 parts of graphene dispersion body, 5-9 parts of nanometer aluminium powder, 3-5 parts of trbasic zinc phosphate, 5-8 parts of curing agent, 5-8 parts of contracting agent.By using inventive formulation, the especially addition of curing agent and contracting agent, effectively promote the high initial bonding strength of product, curing rate faster, when solidification is shunk automatically to be realized and exempt from pressure maintaining, graphene dispersion body, nanometer aluminium powder, trbasic zinc phosphate are introduced simultaneously, it can effectively change adhesive thermal conductivity and electric conductivity as the heat dissipation and conductive compositions of adhesive, effectively be radiated to the object of gluing, it is vdiverse in function, meet the needs used.
Description
Technical field
The present invention relates to adhesive area technologies, refer in particular to a kind of 1-30 minutes multi-functional environment-protection adhesive.
Background technique
Polyurethane (PUR) hot melt adhesive refers to that using isocyanate groups be the base polyurethane prepolymer for use as of end group for base-material, then
Addition is not formed with the various additives to react, such as thermoplastic resin, filler, catalyst.Adhesive melts after heating,
Flowable scatter coated cools down after substrate surface, adherend bonding and forms gluing.Then since substrate surface contains minor amount of water
Divide or other are containing the moisture in compounds or air living for dialling hydrogen, chain extension is reacted with isocyanate groups, so that generating has friendship
Networking network, the big polymer of cohesive force further enhance bonding force.The main feature of PUR hot melt adhesive includes (1) moisture-curable,
No drying process, quick solidifying is easy to operate, can form rapid link.Subsequent cross-linking and curing reaction occurs under room temperature, final is viscous
Intensity is connect to greatly improve；(2) any organic solvent is free of, is environment-friendly adhesive；(3) it is easy to industrial automation, machinery
Change operation, improves productivity；(4) excellent water resistance, solvent resistance, chemical-resistance and resistance to low temperature.Due to
The many merits of PUR hot melt adhesive apply it more and more extensive, especially in fine electronics adhesive area.
PUR hot melt adhesive, solidification process are broadly divided into two steps, (1) physical solidification, i.e., are solid phase by liquid phase, by
Increase in cohesive force and generates solidification intensity；(2) chemosetting, i.e. isocyanate groups are reacted with water, form cross-linked structure, and
Generate solidification intensity.Generally, physical solidification intensity is relatively low, is no more than 0.5MPa, the physical solidification of existing product is strong on the market
Spend (10min shear strength) generally in 0.2MPa hereinafter, widget that can only be lighter to quality, plays locating effect, for
Structure is irregular, and resilience is more severe, and the bigger component of size can not form effective positioning bonding, it is necessary to carry out
Pressure maintaining can be only achieved scheduled adhesive effect, this just needs more pressure maintaining jig, the longer product stream turn-week phase, more
Process procedure increases cost, reduces efficiency, and initial adhesive strength is low, also be easy to cause from pressing workshop section to pressure maintaining workshop section
Product displacement, poor attachment is caused, so needing the initial adhesive strength of product.In addition, there are function for current PUR hot melt adhesive
The single problem of energy.
Summary of the invention
In view of this, more in view of the deficiencies of the prior art, the present invention aims to provide a kind of 1-30 minutes
Functional environment-friendly adhesive has the characteristics that high initial bonding strength, exempts from pressure maintaining, and vdiverse in function.
To achieve the above object, the present invention is using following technical solution:
A kind of 1-30 minutes multi-functional environment-protection adhesive, includes following raw material: 10-15 parts of polyether polyol, crystallization
20-25 parts of polyester polyol, 5-10 parts of liquid non-crystalline polyester polyalcohol, 2-10 parts of solid amorphous polyester polyol, isocyanide
20-25 parts of acid ester monomer, 15-20 parts of thermoplastic resin, 40-50 parts of modified rosin resin, 10-20 parts of natural plant gum, catalyst 2-3
Part, 5-9 parts of graphene dispersion body, 5-9 parts of nanometer aluminium powder, 3-5 parts of trbasic zinc phosphate, 5-8 parts of curing agent, 5-8 parts of contracting agent.
Preferably, the modified rosin resin is in preparation method: rosin resin being added into reaction kettle, then addition is urged
Agent, the amount of catalyst are the 0.2% of rosin resin quality, and control catalyst drips in 60min；Stirring is warming up to 110
DEG C, pentaerythrite is added, the mass ratio of pentaerythrite and rosin resin is 1:25, keeps temperature to be simultaneously condensed back 2 hours, obtains
Mixture A；The catalyst is tetraethylammonium bromide；The sodium bicarbonate of pentaerythrite quality 5% is added into mixed mixture A, it will
Temperature is reduced to 75 DEG C, after keeping the temperature 35min, the acrylic acid and sodium peroxydisulfate mixture of pentaerythrite quality 15% is added, by temperature
90 DEG C are raised to, 15min is stirred with 400r/min revolving speed, is further continued for heat preservation 15min, cooling discharging obtains modified rosin resin.
Preferably, the crystalline polyester polyol is at least 1,6 hexylene glycol esterdiol of poly- 1,6 adipic acid, poly- 1,6 adipic acid
One of Isosorbide-5-Nitrae butyl glycol ester diol, molecular weight 2000-4000.
Preferably, the liquid non-crystalline polyester polyalcohol is at least 1,6 adipic acids, phthalic acid, phthalic anhydride, new penta 2
The liquid non-crystalline polyester polyalcohol that one of alcohol, methyl pentanediol, diethylene glycol, diethylene glycol (DEG) acid are polymerized with alcohol, point
Son amount 1000-6000.
Preferably, the solid amorphous polyester polyol is at least 1,6 adipic acids, phthalic acid, phthalic anhydride, the last of the ten Heavenly stems two
The solid amorphous polyester polyol that one of acid, neopentyl glycol, hexylene glycol, diethylene glycol acid are polymerized with alcohol, molecule
Measure 1000-5000.
The present invention has obvious advantages and beneficial effects compared with the existing technology, specifically, by above-mentioned technical proposal
Known to:
By using the addition of inventive formulation, especially curing agent and contracting agent, the high initial bonding strength of product is effectively promoted, in 1-
Solidify in 30 minutes, curing rate faster, when solidification is shunk automatically to be realized and exempt from pressure maintaining, while introducing graphene dispersion body, nanometer
Aluminium powder, trbasic zinc phosphate can effectively change the thermal conductivity and electric conductivity of adhesive as the heat dissipation and conductive compositions of adhesive, right
The object of gluing is effectively radiated, vdiverse in function, meets the needs used.
Specific embodiment
Present invention discloses a kind of 1-30 minutes multi-functional environment-protection adhesive, and include following raw material: polyethers is more
First alcohol 10-15 parts, 20-25 parts of crystalline polyester polyol, 5-10 parts of liquid non-crystalline polyester polyalcohol, solid amorphous polyester
2-10 parts of polyalcohol, 20-25 parts of isocyanate-monomer, 15-20 parts of thermoplastic resin, 40-50 parts of modified rosin resin, natural plant gum
10-20 parts, 2-3 parts of catalyst, 5-9 parts of graphene dispersion body, 5-9 parts of nanometer aluminium powder, 3-5 parts of trbasic zinc phosphate, 5-8 parts of curing agent,
5-8 parts of contracting agent.
The modified rosin resin is in preparation method: rosin resin being added into reaction kettle, then adds catalyst, urges
The amount of agent is the 0.2% of rosin resin quality, and control catalyst drips in 60min；Stirring is warming up to 110 DEG C, and season is added
The mass ratio of penta tetrol, pentaerythrite and rosin resin is 1:25, keeps temperature and is condensed back 2 hours, obtains mixture A；
The catalyst is tetraethylammonium bromide；The sodium bicarbonate of pentaerythrite quality 5% is added into mixed mixture A, temperature is reduced
To 75 DEG C, after keeping the temperature 35min, the acrylic acid and sodium peroxydisulfate mixture of pentaerythrite quality 15% is added, temperature is raised to 90
DEG C, 15min is stirred with 400r/min revolving speed, is further continued for heat preservation 15min, cooling discharging obtains modified rosin resin.
The crystalline polyester polyol is at least 1,6 hexylene glycol esterdiol of poly- 1,6 adipic acid, poly- 1,6 adipic acid Isosorbide-5-Nitrae fourth two
One of alcohol esterdiol, molecular weight 2000-4000.The liquid non-crystalline polyester polyalcohol is at least 1,6 adipic acids, benzene
One of dioctyl phthalate, phthalic anhydride, neopentyl glycol, methyl pentanediol, diethylene glycol, diethylene glycol (DEG) acid and the liquid that alcohol is polymerized are non-
Crystalline polyester polyol, molecular weight 1000-6000.The solid amorphous polyester polyol is at least 1,6 adipic acids, benzene two
One of formic acid, phthalic anhydride, decanedioic acid, neopentyl glycol, hexylene glycol, diethylene glycol acid and the solid amorphous that alcohol is polymerized are poly-
Ester polyol, molecular weight 1000-5000.
When preparation, firstly, the polyether polyol, thermoplastic resin, modified rosin resin and natural plant gum are put into anti-
It answers in kettle, dissolution 2h is stirred under vacuum at 120-130 DEG C；Again by crystalline polyester polyol, liquid non-crystalline polyester polyalcohol, solid
Body non-crystalline polyester polyalcohol, graphene dispersion body, nanometer aluminium powder, trbasic zinc phosphate put into reaction kettle, in 120-130 DEG C of nitrogen item
Under part, be stirred under vacuum water removal 1h or more, until water content be no more than 500ppm, obtain mixed once material；It then will be described primary
Mixture warm is down to 80 DEG C, under a nitrogen atmosphere, the liquid of pure isocyanate-monomer molten in advance is added or has risen again
To the powder of the pure isocyanate-monomer of room temperature, it is stirred under vacuum reaction 2h at 80-100 DEG C, tests free NCO content, if
Undesirable, the reaction was continued, until free NCO content meets the requirements, obtains secondary mixed material；Then, by the catalysis
Agent, curing agent and contracting agent under a nitrogen atmosphere, are added in the secondary mixed material, are stirred under vacuum 15-30min, are obtained
Exempt from pressure maintaining multi-functional environment-protection adhesive.
With multiple embodiments, invention is further described in detail below:
Embodiment 1:
A kind of 1-30 minutes multi-functional environment-protection adhesive, includes following raw material: 10 parts of polyether polyol, crystallization are poly-
20 parts of ester polyol, 5 parts of liquid non-crystalline polyester polyalcohol, 2 parts of solid amorphous polyester polyol, isocyanate-monomer 20
Part, 15 parts of thermoplastic resin, 40 parts of modified rosin resin, 10 parts of natural plant gum, 2 parts of catalyst, graphene dispersion body 5 part, nanometer
5 parts of aluminium powder, 3 parts of trbasic zinc phosphate, 5 parts of curing agent, 5 parts of contracting agent.
The modified rosin resin is in preparation method: rosin resin being added into reaction kettle, then adds catalyst, urges
The amount of agent is the 0.2% of rosin resin quality, and control catalyst drips in 60min；Stirring is warming up to 110 DEG C, and season is added
The mass ratio of penta tetrol, pentaerythrite and rosin resin is 1:25, keeps temperature and is condensed back 2 hours, obtains mixture A；
The catalyst is tetraethylammonium bromide；The sodium bicarbonate of pentaerythrite quality 5% is added into mixed mixture A, temperature is reduced
To 75 DEG C, after keeping the temperature 35min, the acrylic acid and sodium peroxydisulfate mixture of pentaerythrite quality 15% is added, temperature is raised to 90
DEG C, 15min is stirred with 400r/min revolving speed, is further continued for heat preservation 15min, cooling discharging obtains modified rosin resin.
The crystalline polyester polyol is 1,6 hexylene glycol esterdiol of poly- 1,6 adipic acid, molecular weight 2000-4000.It is described
Liquid non-crystalline polyester polyalcohol is the liquid non-crystalline polyester polyalcohol that 1,6 adipic acids and alcohol are polymerized, molecular weight 1000-
6000.The solid amorphous polyester polyol is the solid amorphous polyester polyol that 1,6 adipic acids and alcohol are polymerized,
Molecular weight 1000-5000.
When preparation, firstly, the polyether polyol, thermoplastic resin, modified rosin resin and natural plant gum are put into anti-
It answers in kettle, dissolution 2h is stirred under vacuum at 120 DEG C；It is again that crystalline polyester polyol, liquid non-crystalline polyester polyalcohol, solid is non-
Crystalline polyester polyol, graphene dispersion body, nanometer aluminium powder, trbasic zinc phosphate put into reaction kettle, under 120 DEG C of condition of nitrogen gas, very
Sky stirring water removal 1h or more, until water content be no more than 500ppm, obtain mixed once material；Then by the mixed once material temperature
80 DEG C are down to, under a nitrogen atmosphere, the liquid of pure isocyanate-monomer molten in advance is added or has risen again to room temperature
The powder of pure isocyanate-monomer is stirred under vacuum reaction 2h at 80 DEG C, tests free NCO content, if it does not meet the requirements, after
Continuous reaction obtains secondary mixed material until free NCO content meets the requirements；Then, by the catalyst, curing agent and receipts
Contracting agent under a nitrogen atmosphere, is added in the secondary mixed material, is stirred under vacuum 15min, and pressure maintaining multi-functional environment-protection is exempted from acquisition
Adhesive.
Embodiment 2:
A kind of 1-30 minutes multi-functional environment-protection adhesive, includes following raw material: 15 parts of polyether polyol, crystallization are poly-
25 parts of ester polyol, 10 parts of liquid non-crystalline polyester polyalcohol, 10 parts of solid amorphous polyester polyol, isocyanate-monomer 25
Part, 20 parts of thermoplastic resin, 40 parts of modified rosin resin, 10 parts of natural plant gum, 2 parts of catalyst, graphene dispersion body 5 part, nanometer
5 parts of aluminium powder, 3 parts of trbasic zinc phosphate, 5 parts of curing agent, 5 parts of contracting agent.
The modified rosin resin is in preparation method: rosin resin being added into reaction kettle, then adds catalyst, urges
The amount of agent is the 0.2% of rosin resin quality, and control catalyst drips in 60min；Stirring is warming up to 110 DEG C, and season is added
The mass ratio of penta tetrol, pentaerythrite and rosin resin is 1:25, keeps temperature and is condensed back 2 hours, obtains mixture A；
The catalyst is tetraethylammonium bromide；The sodium bicarbonate of pentaerythrite quality 5% is added into mixed mixture A, temperature is reduced
To 75 DEG C, after keeping the temperature 35min, the acrylic acid and sodium peroxydisulfate mixture of pentaerythrite quality 15% is added, temperature is raised to 90
DEG C, 15min is stirred with 400r/min revolving speed, is further continued for heat preservation 15min, cooling discharging obtains modified rosin resin.
The crystalline polyester polyol is poly- 1,6 adipic acid Isosorbide-5-Nitrae butyl glycol ester diols, molecular weight 2000-4000.It is described
Liquid non-crystalline polyester polyalcohol is the liquid non-crystalline polyester polyalcohol that phthalic anhydride and alcohol are polymerized, molecular weight 1000-6000.
The solid amorphous polyester polyol is the solid amorphous polyester polyol that phthalic acid and alcohol are polymerized, molecular weight
1000-5000。
When preparation, firstly, the polyether polyol, thermoplastic resin, modified rosin resin and natural plant gum are put into anti-
It answers in kettle, dissolution 2h is stirred under vacuum at 130 DEG C；It is again that crystalline polyester polyol, liquid non-crystalline polyester polyalcohol, solid is non-
Crystalline polyester polyol, graphene dispersion body, nanometer aluminium powder, trbasic zinc phosphate put into reaction kettle, under 130 DEG C of condition of nitrogen gas, very
Sky stirring water removal 1h or more, until water content be no more than 500ppm, obtain mixed once material；Then by the mixed once material temperature
80 DEG C are down to, under a nitrogen atmosphere, the liquid of pure isocyanate-monomer molten in advance is added or has risen again to room temperature
The powder of pure isocyanate-monomer is stirred under vacuum reaction 2h at 100 DEG C, tests free NCO content, if it does not meet the requirements,
The reaction was continued, until free NCO content meets the requirements, obtains secondary mixed material；Then, by the catalyst, curing agent and
Contracting agent under a nitrogen atmosphere, is added in the secondary mixed material, is stirred under vacuum 15-30min, it is multi-functional that pressure maintaining is exempted from acquisition
Environment-friendly adhesive.
Embodiment 3:
A kind of 1-30 minutes multi-functional environment-protection adhesive, includes following raw material: 15 parts of polyether polyol, crystalline polyester
25 parts of polyalcohol, 10 parts of liquid non-crystalline polyester polyalcohol, 10 parts of solid amorphous polyester polyol, isocyanate-monomer 25
Part, 20 parts of thermoplastic resin, 50 parts of modified rosin resin, 20 parts of natural plant gum, 3 parts of catalyst, graphene dispersion body 9 part, nanometer
9 parts of aluminium powder, 5 parts of trbasic zinc phosphate, 8 parts of curing agent, 8 parts of contracting agent.
The modified rosin resin is in preparation method: rosin resin being added into reaction kettle, then adds catalyst, urges
The amount of agent is the 0.2% of rosin resin quality, and control catalyst drips in 60min；Stirring is warming up to 110 DEG C, and season is added
The mass ratio of penta tetrol, pentaerythrite and rosin resin is 1:25, keeps temperature and is condensed back 2 hours, obtains mixture A；
The catalyst is tetraethylammonium bromide；The sodium bicarbonate of pentaerythrite quality 5% is added into mixed mixture A, temperature is reduced
To 75 DEG C, after keeping the temperature 35min, the acrylic acid and sodium peroxydisulfate mixture of pentaerythrite quality 15% is added, temperature is raised to 90
DEG C, 15min is stirred with 400r/min revolving speed, is further continued for heat preservation 15min, cooling discharging obtains modified rosin resin.
The crystalline polyester polyol is 1,6 hexylene glycol esterdiol of poly- 1,6 adipic acid, molecular weight 2000-4000.It is described
Liquid non-crystalline polyester polyalcohol is the liquid non-crystalline polyester polyalcohol that phthalic anhydride and alcohol are polymerized, molecular weight 1000-6000.
The solid amorphous polyester polyol is the solid amorphous polyester polyol that phthalic anhydride and alcohol are polymerized, molecular weight less
1000-5000。
When preparation, firstly, the polyether polyol, thermoplastic resin, modified rosin resin and natural plant gum are put into anti-
It answers in kettle, dissolution 2h is stirred under vacuum at 125 DEG C；It is again that crystalline polyester polyol, liquid non-crystalline polyester polyalcohol, solid is non-
Crystalline polyester polyol, graphene dispersion body, nanometer aluminium powder, trbasic zinc phosphate put into reaction kettle, under 125 DEG C of condition of nitrogen gas, very
Sky stirring water removal 1h or more, until water content be no more than 500ppm, obtain mixed once material；Then by the mixed once material temperature
80 DEG C are down to, under a nitrogen atmosphere, the liquid of pure isocyanate-monomer molten in advance is added or has risen again to room temperature
The powder of pure isocyanate-monomer is stirred under vacuum reaction 2h at 90 DEG C, tests free NCO content, if it does not meet the requirements, after
Continuous reaction obtains secondary mixed material until free NCO content meets the requirements；Then, by the catalyst, curing agent and receipts
Contracting agent under a nitrogen atmosphere, is added in the secondary mixed material, is stirred under vacuum 20min, and pressure maintaining multi-functional environment-protection is exempted from acquisition
Adhesive.
Embodiment 4:
A kind of 1-30 minutes multi-functional environment-protection adhesive, includes following raw material: 13 parts of polyether polyol, crystallization are poly-
23 parts of ester polyol, 8 parts of liquid non-crystalline polyester polyalcohol, 6 parts of solid amorphous polyester polyol, isocyanate-monomer 23
Part, 7 parts of graphene dispersion body, is received 18 parts of thermoplastic resin, 45 parts of modified rosin resin, 15 parts of natural plant gum, 2.5 parts of catalyst
Rice 8 parts of aluminium powder, 4 parts of trbasic zinc phosphate, 7 parts of curing agent, 6 parts of contracting agent.
The modified rosin resin is in preparation method: rosin resin being added into reaction kettle, then adds catalyst, urges
The amount of agent is the 0.2% of rosin resin quality, and control catalyst drips in 60min；Stirring is warming up to 110 DEG C, and season is added
The mass ratio of penta tetrol, pentaerythrite and rosin resin is 1:25, keeps temperature and is condensed back 2 hours, obtains mixture A；
The catalyst is tetraethylammonium bromide；The sodium bicarbonate of pentaerythrite quality 5% is added into mixed mixture A, temperature is reduced
To 75 DEG C, after keeping the temperature 35min, the acrylic acid and sodium peroxydisulfate mixture of pentaerythrite quality 15% is added, temperature is raised to 90
DEG C, 15min is stirred with 400r/min revolving speed, is further continued for heat preservation 15min, cooling discharging obtains modified rosin resin.
The crystalline polyester polyol is 1,6 hexylene glycol esterdiol of poly- 1,6 adipic acid, molecular weight 2000-4000.It is described
Liquid non-crystalline polyester polyalcohol is at least the liquid non-crystalline polyester polyalcohol that neopentyl glycol and alcohol are polymerized, molecular weight
1000-6000.The solid amorphous polyester polyol is the solid amorphous polyester polyols that decanedioic acid and alcohol are polymerized
Alcohol, molecular weight 1000-5000.
When preparation, firstly, the polyether polyol, thermoplastic resin, modified rosin resin and natural plant gum are put into anti-
It answers in kettle, dissolution 2h is stirred under vacuum at 123 DEG C；It is again that crystalline polyester polyol, liquid non-crystalline polyester polyalcohol, solid is non-
Crystalline polyester polyol, graphene dispersion body, nanometer aluminium powder, trbasic zinc phosphate put into reaction kettle, under 125 DEG C of condition of nitrogen gas, very
Sky stirring water removal 1h or more, until water content be no more than 500ppm, obtain mixed once material；Then by the mixed once material temperature
80 DEG C are down to, under a nitrogen atmosphere, the liquid of pure isocyanate-monomer molten in advance is added or has risen again to room temperature
The powder of pure isocyanate-monomer is stirred under vacuum reaction 2h at 85 DEG C, tests free NCO content, if it does not meet the requirements, after
Continuous reaction obtains secondary mixed material until free NCO content meets the requirements；Then, by the catalyst, curing agent and receipts
Contracting agent under a nitrogen atmosphere, is added in the secondary mixed material, is stirred under vacuum 15-30min, and pressure maintaining multi-functional ring is exempted from acquisition
Protect adhesive.
Embodiment 5:
A kind of 1-30 minutes multi-functional environment-protection adhesive, includes following raw material: 12 parts of polyether polyol, crystallization are poly-
21 parts of ester polyol, 6 parts of liquid non-crystalline polyester polyalcohol, 4 parts of solid amorphous polyester polyol, isocyanate-monomer 21
Part, 7 parts of graphene dispersion body, is received 16 parts of thermoplastic resin, 42 parts of modified rosin resin, 12 parts of natural plant gum, 2.2 parts of catalyst
Rice 6 parts of aluminium powder, 3.5 parts of trbasic zinc phosphate, 6 parts of curing agent, 7 parts of contracting agent.
The modified rosin resin is in preparation method: rosin resin being added into reaction kettle, then adds catalyst, urges
The amount of agent is the 0.2% of rosin resin quality, and control catalyst drips in 60min；Stirring is warming up to 110 DEG C, and season is added
The mass ratio of penta tetrol, pentaerythrite and rosin resin is 1:25, keeps temperature and is condensed back 2 hours, obtains mixture A；
The catalyst is tetraethylammonium bromide；The sodium bicarbonate of pentaerythrite quality 5% is added into mixed mixture A, temperature is reduced
To 75 DEG C, after keeping the temperature 35min, the acrylic acid and sodium peroxydisulfate mixture of pentaerythrite quality 15% is added, temperature is raised to 90
DEG C, 15min is stirred with 400r/min revolving speed, is further continued for heat preservation 15min, cooling discharging obtains modified rosin resin.
The crystalline polyester polyol is one of poly- 1,6 adipic acid Isosorbide-5-Nitrae butyl glycol ester diols, molecular weight 2000-
4000.The liquid non-crystalline polyester polyalcohol is the liquid non-crystalline polyester polyalcohol that diethylene glycol and alcohol are polymerized, point
Son amount 1000-6000.The solid amorphous polyester polyol is that the solid amorphous that neopentyl glycol and alcohol are polymerized is poly-
Ester polyol, molecular weight 1000-5000.
When preparation, firstly, the polyether polyol, thermoplastic resin, modified rosin resin and natural plant gum are put into anti-
It answers in kettle, dissolution 2h is stirred under vacuum at 128 DEG C；It is again that crystalline polyester polyol, liquid non-crystalline polyester polyalcohol, solid is non-
Crystalline polyester polyol, graphene dispersion body, nanometer aluminium powder, trbasic zinc phosphate put into reaction kettle, under 122 DEG C of condition of nitrogen gas, very
Sky stirring water removal 1h or more, until water content be no more than 500ppm, obtain mixed once material；Then by the mixed once material temperature
80 DEG C are down to, under a nitrogen atmosphere, the liquid of pure isocyanate-monomer molten in advance is added or has risen again to room temperature
The powder of pure isocyanate-monomer is stirred under vacuum reaction 2h at 92 DEG C, tests free NCO content, if it does not meet the requirements, after
Continuous reaction obtains secondary mixed material until free NCO content meets the requirements；Then, by the catalyst, curing agent and receipts
Contracting agent under a nitrogen atmosphere, is added in the secondary mixed material, is stirred under vacuum 18min, and pressure maintaining multi-functional environment-protection is exempted from acquisition
Adhesive.
Embodiment 6:
A kind of 1-30 minutes multi-functional environment-protection adhesive, includes following raw material: 14 parts of polyether polyol, crystallization are poly-
24 parts of ester polyol, 9 parts of liquid non-crystalline polyester polyalcohol, 9 parts of solid amorphous polyester polyol, isocyanate-monomer 24
Part, 8 parts of graphene dispersion body, is received 18 parts of thermoplastic resin, 49 parts of modified rosin resin, 19 parts of natural plant gum, 2.8 parts of catalyst
Rice 8 parts of aluminium powder, 4 parts of trbasic zinc phosphate, 7 parts of curing agent, 7.5 parts of contracting agent.
The modified rosin resin is in preparation method: rosin resin being added into reaction kettle, then adds catalyst, urges
The amount of agent is the 0.2% of rosin resin quality, and control catalyst drips in 60min；Stirring is warming up to 110 DEG C, and season is added
The mass ratio of penta tetrol, pentaerythrite and rosin resin is 1:25, keeps temperature and is condensed back 2 hours, obtains mixture A；
The catalyst is tetraethylammonium bromide；The sodium bicarbonate of pentaerythrite quality 5% is added into mixed mixture A, temperature is reduced
To 75 DEG C, after keeping the temperature 35min, the acrylic acid and sodium peroxydisulfate mixture of pentaerythrite quality 15% is added, temperature is raised to 90
DEG C, 15min is stirred with 400r/min revolving speed, is further continued for heat preservation 15min, cooling discharging obtains modified rosin resin.
The crystalline polyester polyol is at least 1,6 hexylene glycol esterdiol of poly- 1,6 adipic acid, poly- 1,6 adipic acid Isosorbide-5-Nitrae fourth two
One of alcohol esterdiol, molecular weight 2000-4000.The liquid non-crystalline polyester polyalcohol is at least 1,6 adipic acids, benzene
One of dioctyl phthalate, phthalic anhydride, neopentyl glycol, methyl pentanediol, diethylene glycol, diethylene glycol (DEG) acid and the liquid that alcohol is polymerized are non-
Crystalline polyester polyol, molecular weight 1000-6000.The solid amorphous polyester polyol is at least 1,6 adipic acids, benzene two
One of formic acid, phthalic anhydride, decanedioic acid, neopentyl glycol, hexylene glycol, diethylene glycol acid and the solid amorphous that alcohol is polymerized are poly-
Ester polyol, molecular weight 1000-5000.
When preparation, firstly, the polyether polyol, thermoplastic resin, modified rosin resin and natural plant gum are put into anti-
It answers in kettle, dissolution 2h is stirred under vacuum at 120-130 DEG C；Again by crystalline polyester polyol, liquid non-crystalline polyester polyalcohol, solid
Body non-crystalline polyester polyalcohol, graphene dispersion body, nanometer aluminium powder, trbasic zinc phosphate put into reaction kettle, in 120-130 DEG C of nitrogen item
Under part, be stirred under vacuum water removal 1h or more, until water content be no more than 500ppm, obtain mixed once material；It then will be described primary
Mixture warm is down to 80 DEG C, under a nitrogen atmosphere, the liquid of pure isocyanate-monomer molten in advance is added or has risen again
To the powder of the pure isocyanate-monomer of room temperature, it is stirred under vacuum reaction 2h at 80-100 DEG C, tests free NCO content, if
Undesirable, the reaction was continued, until free NCO content meets the requirements, obtains secondary mixed material；Then, by the catalysis
Agent, curing agent and contracting agent under a nitrogen atmosphere, are added in the secondary mixed material, are stirred under vacuum 15-30min, are obtained
Exempt from pressure maintaining multi-functional environment-protection adhesive.
Design focal point of the invention is: by using the addition of inventive formulation, especially curing agent and contracting agent, effectively
The high initial bonding strength for promoting product, the solidification in 1-30 minute, curing rate faster, shrink realization automatically and exempt from pressure maintaining, together by when solidification
When introduce graphene dispersion body, nanometer aluminium powder, trbasic zinc phosphate, can be used as the heat dissipation and conductive compositions of adhesive, effectively change glue
The thermal conductivity and electric conductivity of stick effectively radiate to the object of gluing, vdiverse in function, meet the needs used.
The technical principle of the invention is described above in combination with a specific embodiment.These descriptions are intended merely to explain of the invention
Principle, and shall not be construed in any way as a limitation of the scope of protection of the invention.Based on the explanation herein, the technology of this field
Personnel can associate with other specific embodiments of the invention without creative labor, these modes are fallen within
Within protection scope of the present invention.
Claims (5)
1. a kind of 1-30 minutes multi-functional environment-protection adhesive, it is characterised in that: include following raw material: polyether polyol
10-15 parts, 20-25 parts of crystalline polyester polyol, 5-10 parts of liquid non-crystalline polyester polyalcohol, solid amorphous polyester polyol
2-10 parts, 20-25 parts of isocyanate-monomer, 15-20 parts of thermoplastic resin, 40-50 parts of modified rosin resin, natural plant gum 10-20
Part, 2-3 parts of catalyst, 5-9 parts of graphene dispersion body, 5-9 parts of nanometer aluminium powder, 3-5 parts of trbasic zinc phosphate, 5-8 parts of curing agent, contracting agent
5-8 parts.
2. a kind of 1-30 minutes multi-functional environment-protection adhesive as described in claim 1, it is characterised in that: the modified rosin tree
Rouge is in preparation method: rosin resin being added into reaction kettle, then adds catalyst, the amount of catalyst is rosin resin quality
0.2%, control catalyst dripped in 60min；Stirring is warming up to 110 DEG C, and pentaerythrite, pentaerythrite and rosin is added
The mass ratio of resin is 1:25, keeps temperature and is condensed back 2 hours, obtains mixture A；The catalyst is tetraethyl bromination
Ammonium；The sodium bicarbonate of pentaerythrite quality 5% is added into mixed mixture A, temperature is reduced to 75 DEG C, after keeping the temperature 35min, is added
The acrylic acid and sodium peroxydisulfate mixture for entering pentaerythrite quality 15%, are raised to 90 DEG C for temperature, with the stirring of 400r/min revolving speed
15min, is further continued for heat preservation 15min, and cooling discharging obtains modified rosin resin.
3. a kind of 1-30 minutes multi-functional environment-protection adhesive as described in claim 1, it is characterised in that: the crystalline polyester is more
First alcohol is at least one of 1,6 hexylene glycol esterdiol of poly- 1,6 adipic acid, poly- 1,6 adipic acid Isosorbide-5-Nitrae butyl glycol ester diol, molecule
Amount is 2000-4000.
4. a kind of 1-30 minutes multi-functional environment-protection adhesive as described in claim 1, it is characterised in that: the liquid is noncrystalline
Polyester polyol be at least 1,6 adipic acids, phthalic acid, phthalic anhydride, neopentyl glycol, methyl pentanediol, diethylene glycol, in diethylene glycol (DEG)
A kind of liquid non-crystalline polyester polyalcohol that is polymerized with alcohol of acid, molecular weight 1000-6000.
5. a kind of 1-30 minutes multi-functional environment-protection adhesive as described in claim 1, it is characterised in that: the non-knot of the solid
Brilliant polyester polyol be at least 1,6 adipic acids, phthalic acid, phthalic anhydride, decanedioic acid, neopentyl glycol, hexylene glycol, in diethylene glycol
A kind of solid amorphous polyester polyol that acid is polymerized with alcohol, molecular weight 1000-5000.
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Application publication date: 20191203 |