CN105969293B - A kind of double component solvent-free vegetable oil base adhesive - Google Patents
A kind of double component solvent-free vegetable oil base adhesive Download PDFInfo
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- CN105969293B CN105969293B CN201610510904.8A CN201610510904A CN105969293B CN 105969293 B CN105969293 B CN 105969293B CN 201610510904 A CN201610510904 A CN 201610510904A CN 105969293 B CN105969293 B CN 105969293B
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Classifications
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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
- C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
-
- 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/36—Hydroxylated esters of higher fatty acids
-
- 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
- C08G18/4288—Polycondensates having carboxylic or carbonic ester groups in the main chain modified by higher fatty oils or their acids or by resin acids
-
- 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—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
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/80—Masked polyisocyanates
- C08G18/8003—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen
- C08G18/8051—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/36
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a kind of double component solvent-free vegetable oil base adhesive, including A and two components of B；Component A includes：Modified vegetable oil, tackifying resin, coupling agent, filler, microcapsule expansion microballoon, chain extender；B component includes：The mixture of isocyanates or isocyanates and modified vegetable oil.The invention provides it is a kind of provide a kind of use safety, economy, curing rate it is moderate, it is soft or hard it is adjustable, initial cohesiveness is good, adhesion strength is big, water-tolerant, it is heat-resist, have a wide range of application, the double component solvent-free vegetable oil base adhesive of the excellent combination property of environmental protection.
Description
Technical field
The invention belongs to chemical field, and in particular to a kind of double component solvent-free vegetable oil base adhesive.
Background technology
Current adhesive based on oil-based solvent type, but because organic solvent that it contains it is most of it is inflammable and explosive, volatile,
Smell is big, pollution ambient influnence health.
Though Aqueous Adhesives are a kind of Environment-friendlyadhesive adhesives, Aqueous Adhesives are using water as basic medium, with drying
Time is long, poor to apolar surfaces bond effect, the shortcoming of poor water resistance.
Traditional adhesive is prepared using petroleum resources and synthetic chemical as raw material mostly, but with the exhaustion of petroleum resources
And the enhancing of people's environmental consciousness so that traditional adhesive receives certain limitation.Therefore renewable resource, biomaterial
Increasingly it is valued by people as industrial chemicals.
The content of the invention
It is an object of the invention to provide one kind using safety, economy, curing rate be moderate, soft or hard adjustable, tack
Can good, adhesion strength is big, water-tolerant, it is heat-resist, have a wide range of application, the two-component of the excellent combination property of environmental protection without
Solvent vegetable oil base adhesive.
This glue is double component solvent-free vegetable oil base adhesive, is liquid under normal temperature, it is not necessary to add organic solvent
It is diluted, it is when using that two components are well mixed with regard to the material to be pasted of Pasting according to quality proportioning.When not in use, by two
Person preserves respectively.
In order to solve the above technical problems, the technical solution adopted by the present invention is：
A kind of double component solvent-free vegetable oil base adhesive, the double component solvent-free vegetable oil base adhesive includes quality
Than for 1:2 to 5:1 two components of A and B：
Component A includes：
The modified vegetable oil of 30-90 parts by weight；
The tackifying resin of 10-60 parts by weight；
The coupling agent of 1-5 parts by weight；
The filler of 10-80 parts by weight；
The microcapsule expansion microballoon of 1-10 parts by weight；
The chain extender of 0-10 parts by weight；
Chain extender in component A can also be without.
The preparation method of component A is：
Prepare modified vegetable oil：It is 1 by mol ratio:3 to 2:1 vegetable oil and polyalcohol are with accounting for plant oil quality 0.1%-
1% acidic catalyst or base catalyst mixing, is warming up to 220 DEG C to 240 DEG C and maintains this temperature under nitrogen protection
Insulation 2 to 3 hours, is down to room temperature by reaction system and obtains modified vegetable oil；
The mixture of modified vegetable oil, tackifying resin, coupling agent and chain extender is stirred at 50 DEG C to 90 DEG C to 1 to 3 small
When, room temperature is down to, filler and microcapsule expansion microballoon is added, stirs and component A is made.
The principle of method of modifying one：Vegetable oil is all the ester being condensed into by a glycerol molecule and three fatty acid molecules,
Namely fatty acid triglyceride.Vegetable oil-based polyols are prepared by alcoholysis reaction, can carry out polymerizeing instead with isocyanates
Should.Polyol viscosity prepared by this method is small, and mobility is more preferable.
The polyalcohol used in this method of modifying can be：Trihydroxylic alcohol (glycerine, butantriol etc.), tetrahydroxylic alcohol (erythrol,
Pentaerythrite etc.), other polyalcohols such as pentabasis alcohol (pentitol etc.).
(trihydroxylic alcohol, tetrahydroxylic alcohol are not limited to by taking trihydroxylic alcohol, tetrahydroxylic alcohol as an example), and the chemical equation of this method of modifying is such as
Under：
Trihydroxylic alcohol main chemical reactions equation is：
Tetrahydroxylic alcohol main chemical reactions equation is：
It is near again after reaction system, which is presented, becomes clear solution after stirring 1 to 3 hour during component A is prepared
Room temperature.
B component includes：
The isocyanates of 70-100 parts by weight；
The modified vegetable oil of 5-30 parts by weight；The modified vegetable oil of B component, selection is changed with the method for modifying of above-mentioned component A
Vegetable oil after property.
The preparation method of B component is：Isocyanates is heated to 50 DEG C to 90 DEG C, modified vegetable oil is added dropwise while stirring,
Reaction 2 to 4 hours, is down to room temperature and B component is made, or isocyanates directly is used as into B component.
The effect of isocyanates is to accelerate adhesive curing rate, strengthens sticking strength；By modified vegetable oil and isocyanide
Acid esters reacts pre-polymerization, can increase B component viscosity, and enhancing is just viscous, increases final sticking strength.
Preferably, another method of modifying for the modified vegetable oil that the present invention is used is on above-mentioned method of modifying basis
On, the obtained alcoholysis product of above-mentioned method of modifying is further reacted with binary acid, specific method is as follows：
Prepare modified vegetable oil：It is 1 by mol ratio:3 to 2:1 vegetable oil and polyalcohol are with accounting for plant oil quality 0.1%-
1% acidic catalyst or base catalyst mixing, is warming up to 220 DEG C to 240 DEG C and maintains this temperature under nitrogen protection
Insulation 2 to 3 hours, cools to 150 DEG C to 180 DEG C by reaction system and obtains alcoholysis product；It is 3 by mol ratio:1 to 1:2 alcoholysis
Product and binary acid are mixed with accounting for binary acid quality 0.1%-1% acidic catalyst, and 2 to 6 are reacted at 220 DEG C to 230 DEG C
Hour, treat that acid number reaches 20 to 3mgKOH/g, cool to 150 DEG C to 180 DEG C, vacuumizing makes water content≤0.05% be changed
Property vegetable oil.
Acid number represents a kind of index containing free acid in the organic substances such as grease type, polyesters, paraffin.Due to grease type
Material is water insoluble, and its acidity situation is reacted without pH indexs.But acid base neutralization titration method is utilized, titrate out neutralization 1g examinations
The milligram number of potassium hydroxide needed for sample, is exactly acid number.Such as, the 20mgKOH/g meanings are exactly to neutralize every gram of sample to need the KOH to be
20mg。
The principle being further modified：On the basis of method one, the vegetable oil-based polyols prepared and binary acid are entered
Row ester condensation reaction, the plant oil base PEPA prepared.Plant oil base PEPA prepared by this method, which has, to be divided
The characteristics of son amount is big, therefore the adhesive prepared is the characteristics of have more preferable toughness and bigger adhesion strength.
The obtained alcoholysis product of above-mentioned method of modifying and the further reactive chemistry equation of binary acid are as follows：
Preferably, the double component solvent-free vegetable oil base adhesive, the modified vegetable oil is selected from modified soybean oil, changed
Property palm oil, modified peanut oil, modified linseed oil, modified colza, modified cottonseed oil, modified castor oil, in modified tung oil
It is one or more of.
There are environmental protection and energy saving using modified vegetable oil synthetic adhesive, while vegetable oil has longer fat-based
Carbochain, the binding agent of preparation has stronger water resistance, and the binding agent prepared with vegetable oil is had baked tensile strength height, got angry
Measure small, the advantages of mobility is moderate.Baked tensile strength is high：Glue-line intensity is big, pastes intensity just big；Gas forming amount is small：In preparation process
Produce and produced almost without gas, it is small to pasting performance impact；Mobility：Mobility is moderate, and adhesive is easy to coating.
Preferably, the double component solvent-free vegetable oil base adhesive, the acidic catalyst be sulfuric acid, sulfonic acid, hydrochloric acid,
Copper chloride or zinc chloride；Base catalyst is sodium hydroxide, potassium hydroxide, Kocide SD, organic base.
Organic base is aminated compounds, the alkaline metal salt (sodium methoxide, potassium ethoxide, potassium tert-butoxide) of alcohol, metal alkyl lithium
Compound (butyl lithium, phenyl lithium), amido lithium compound (lithium diisopropyl amido, the silicon amido lithium of methyl two).
Preferably, the double component solvent-free vegetable oil base adhesive, the tackifying resin is aliphatic hydrocarbon resins or virtue
Fragrant hydrocarbon resins.
Aliphatic hydrocarbon resins：C5 resins, C9 resins, copolymerized petroleum resin, hydrogenated petroleum resin, pentadiene oil tree
Fat.
Arene resin：Rosin, rosin modified phenolic resin, terpene resin, terpenes-styrene resin, terpenes phenolic aldehyde
Resin, phenolic resin, rosin modified phenolic resin, coumarone indene resin etc..
Add the effect of tackifying resin：Tackifying resin, which has, plays the effect such as enhancing, hardening, moistening, moisture-proof, can be effective
Strengthen initial bonding strength of the adhesive to material surface, and improve bonding force etc., extend the working life and sticky holding phase of adhesive, increase
Strong permeability etc..
Preferably, the double component solvent-free vegetable oil base adhesive, the coupling agent is silane coupler, titanate esters idol
Join agent or aluminate coupling agent.
Silane coupler：Vinyl trichlorosilane, VTES；
Titanate coupling agent：Isopropyl three (dioctylphyrophosphoric acid acyloxy) titanate esters, the coupling of monoalkoxy type titanate esters
Agent, tetra isopropyl two (dioctyl phosphito acyloxy) titanate esters；
Aluminate coupling agent：Distearyl acyl-oxygen isopropyl Aluminate.
Add the effect of coupling agent：Coupling modifier is that occur chemical coupling reaction in particle surface, and particle surface is through coupling
Good compatibility can be produced after agent processing with organic matter.Chemically reacted or physics bag by coupling agent and inorganic filler
The method such as cover, filler surface is become lipophile by hydrophily, combined closely so as to reach with polymer, make the strong of material
Degree, cohesion, electrical property, hydrophobicity, ageing resistace etc. are significantly improved.
Preferably, the double component solvent-free vegetable oil base adhesive, the filler is filler：Carbonate, silicate
Class, oxide-based, Sulfates, hydroxide or metal simple-substance.
Carbonate：Precipitated calcium carbonate, powdered whiting, calcite in powder etc.；
Silicates：Talcum powder, mica powder, kaolin etc.；
It is oxide-based：White carbon, calcium oxide, aluminum oxide, titanium dioxide etc.；
Sulfates：Ultra-fine barium sulfate, land plaster, lithopone etc.；
Hydroxide：Sierozem power, aluminium hydroxide etc.；
Metal simple-substance：Aluminium powder, iron powder, copper powder etc.；
Add the effect of filler：1st, intensity is pasted in toughened and reinforced effect, enhancing；2nd, play a part of physical crosslinking, strengthen
Adhesive ageing resistance, strengthens glue-line intensity；3rd, cost is reduced.
Preferably, the double component solvent-free vegetable oil base adhesive, the wall shell of the microcapsule expansion microballoon is natural
A diameter of 10 after high polymer material, semi-synthetic high polymer material or fully synthetic high polymer material, microcapsule expansion microsphere expansion
To 210 microns.
Microcapsule expansion microballoon：Microcapsules refer to a kind of with polymeric shell wall and miniature vessel or packing material.Microcapsules are made
Grain technology is exactly by solid, liquid or gas entrapment, sealed up for safekeeping in a kind of microencapsulation as a kind of skill of solia particle product
Art.Microcapsule expansion microballoon refers to the solia particle after the gasification substance in polymeric shell wall.
On microcapsule expansion microballoon referring to document：Cai Tao, wangdan, the technology of preparing of the microcapsules such as Song Zhixiang and its state
Interior application progress [J] chemical propellants and macromolecule, 2010,8 (2):20-25.Microcapsule expansion microballoon used in this patent is text
Particulate after the heating expansion of microcapsules described in offering.Specific method is：Microcapsules are heated 5 minutes extremely at 100 DEG C to 200 DEG C
60 minutes i.e. available.
Expandable microspheres are easier to mix with component A relative to inorganic filler, bigger with expandable microspheres reinforcement adhesive intensity,
Specific surface area is big, adds a small amount of microballoon, and adhesive just can reach required viscosity, it is to avoid high amount of inorganic filler is to adhesive intensity
Influence.
The wall shell of microcapsule expansion microballoon：Wall shell is usually natural macromolecular material, semi-synthetic high polymer material, fully synthetic
High polymer material.
Natural macromolecular material：Sodium alginate, zein, chitosan etc.；
Semi-synthetic high polymer material：Carboxymethyl cellulose, methylcellulose, ethyl cellulose etc.；
Fully synthetic high polymer material：Polyethylene glycol, polyvinyl alcohol, polyamide, polyacrylamide, polyurethane, poly- methyl-prop
Olefin(e) acid etc..
Preferably, the double component solvent-free vegetable oil base adhesive, the chain extender be polyalcohols, alicyclic ring alcohols,
Aromatic alcohols, alcamines or Diamines.
Polyalcohols：Ethylene glycol, propane diols, 1,4- butanediols, diglycol, glycerine, trimethylolpropane etc.；
Alicyclic ring alcohols：1,4- cyclohexanediols, hydrogenated bisphenol A；
Aromatic alcohols：Dimethylenebenzene glycol, hydroquinones bis-beta-hydroxyethyl ether, resorcinol hydroxy ether；
Alcamines：Diethanol amine, triethanolamine, methyl diethanolamine；
Diamines：Diethyl toluene diamine, 3,5- dimethythiotoluene diamines.
Add the effect of chain extender：1st, polyurethane reaction system can be made promptly to carry out chain extension and crosslinking；2nd, whole anti-
Answer in material system, isocyanate systems are constituted with stronger response competition probability, reaction system can be extremely efficient adjusted
Reaction speed；Some of chain extension agent molecule characteristic group structure can be introduced into polyurethane polymer backbone, can be to poly- ammonia
Some performances of ester produce certain influence.
Preferably, the double component solvent-free vegetable oil base adhesive, the isocyanates is the isocyanide of diphenyl methane two
Acid esters, toluene di-isocyanate(TDI), poly methylene poly phenyl poly isocyanate, IPDI, hexa-methylene two are different
One or more in cyanate.
Beneficial effects of the present invention are as follows：The advantage of inventive formulation is as follows：(1) vegetable oil or modified vegetable oil generation are used
Compound is birdsed of the same feather flock together for Conventional petroleum products and chemical synthesis is birdsed of the same feather flock together compound, with good biocompatibility, environmental protection, saves the energy
Feature.(2) adhesive is free of VOC, such as acetone, benzene, and also without big heavy metal is endangered, environmental-protecting performance is dashed forward
Go out.(3) adhesion strength is big, and curing rate is moderate, and A, B component can need regulation ratio according to soft durometer, easy to use.(4) adopt
Isocyanates and a small amount of vegetable oil part pre-reaction in adhesive component A and B component are thickened with expandable microspheres, increases gluing
The initial cohesiveness of agent, while strengthening the first glutinous intensity and water resistance of adhesive using tackifying resin.(5) vegetable oil prepared by
Polylol degree of functionality height (functionality polyols>2), preparation adhesive solidification after journey thermosetting, can not only bear 100 DEG C with
On temperature, fine heat-resisting performance, and acid-proof alkaline is stronger.(6) vegetable oil polyol prepared by contains longer fat
Base carbochain, adhesive has stronger water resistance.(7) present invention is modified using two methods to vegetable oil, method one
The polyol viscosity of preparation is small, good fluidity；Polyester polyol molecule amount prepared by method two is big, and relative viscosity is big, prepares
Adhesive tack it is good, pliability is strong, and method of modifying can be selected as needed.(8) released in production process without pernicious gas,
Production safety environmental protection.(9) it is wide using scope, double component solvent-free vegetable oil base adhesive of the invention almost to all material all
Cementitious energy, as shown in Table 1；The double component solvent-free vegetable oil base adhesive of the present invention has good adhesion strength, such as
Shown in table two.
The double component solvent-free vegetable oil base adhesive scope of application of table one
Note：" √ " represents to paste, and "×" represents to paste.
The double component solvent-free vegetable oil base adhesive adhesion strength of table two
| Base material | Steel | Stone material | Timber | Plastics | Rubber | Polyurethane | Canvas | Leather |
| Paste intensity/MPa | ≧9 | ≧8 | ≧7 | ≧1.5 | ≧3 | ≧7 | ≧3 | ≧5 |
| Time/h is fully cured in room temperature | 48 | 48 | 48 | 48 | 48 | 48 | 48 | 48 |
Embodiment
To describe the technology contents of the present invention in detail, feature, the objects and the effects being constructed, below in conjunction with specific implementation
Mode is explained in detail.
Embodiment 1
The concrete technology method of the present embodiment is as follows：
A kind of double component solvent-free vegetable oil base adhesive, it is characterised in that the double component solvent-free vegetable oil base rubber
It is 1 that glutinous agent, which includes mass ratio,:2 two components of A and B：
Component A includes：
The modified vegetable oil of 30 parts by weight；Modified vegetable oil is selected from modified soybean oil；
The tackifying resin of 60 parts by weight；Tackifying resin is C5 resins；
The coupling agent of 1 parts by weight；Coupling agent is vinyl trichlorosilane；
The filler of 80 parts by weight；Filler is precipitated calcium carbonate；
The chain extender of 10 parts by weight；Chain extender is propane diols.
The preparation method of component A is：
The method of modifying of modified vegetable oil is：It is 1 by mol ratio:3 soybean oil and glycerine are with accounting for soybean oil quality
0.1% sulfuric acid mixing, is warming up to 240 DEG C and maintains this temperature 2 hours, reaction system is down into room under nitrogen protection
Temperature obtains modified soybean oil；
The mixture of modified vegetable oil, tackifying resin, coupling agent and chain extender is stirred at 50 DEG C to 90 DEG C to 1 to 3 small
When, room temperature is down to, filler is added, stirs and component A is made；
B component includes：
The isocyanates of 100 parts by weight；Isocyanates is methyl diphenylene diisocyanate.
The preparation method of B component is：Methyl diphenylene diisocyanate is directly used as B component.
Embodiment 2
The concrete technology method of the present embodiment is as follows：
A kind of double component solvent-free vegetable oil base adhesive, it is characterised in that the double component solvent-free vegetable oil base rubber
It is 5 that glutinous agent, which includes mass ratio,:1 two components of A and B：
Component A includes：
The modified vegetable oil of 90 parts by weight；Modified vegetable oil is selected from modified palm oil；
The tackifying resin of 10 parts by weight；Tackifying resin is copolymerized petroleum resin；
The coupling agent of 5 parts by weight；Coupling agent is VTES；
The filler of 10 parts by weight；Filler is calcite in powder；
The microcapsule expansion microballoon of 10 parts by weight；The wall shell of microcapsule expansion microballoon is sodium alginate, and microcapsule expansion is micro-
A diameter of 10 microns after ball expansion；
The preparation method of component A is：
The method of modifying of modified vegetable oil is：It is 2 by mol ratio:1 palm oil and butantriol are with accounting for palm oil quality 1%
Sulfonic acid mixing, 220 DEG C are warming up under nitrogen protection and this temperature is maintained 3 hours, reaction system is cooled to 150 DEG C
Obtain alcoholysis product；It is 3 by mol ratio:1 alcoholysis product and ethanedioic acid is mixed with accounting for the sulfuric acid of ethanedioic acid quality 1%, at 220 DEG C
Lower reaction 6 hours, treats that acid number reaches 3mgKOH/g, cools to 180 DEG C, and vacuumizing makes water content≤0.05% obtain modified palm fibre
Palmitic acid oil；
The mixture of modified vegetable oil, tackifying resin, coupling agent is stirred 1 hour at 90 DEG C, room temperature is down to, adds
Filler and microcapsule expansion microballoon, stir and component A are made；
B component includes：
The isocyanates of 70 parts by weight；Isocyanates is toluene di-isocyanate(TDI)；
The modified vegetable oil of 30 parts by weight；Modified vegetable oil is selected from modified palm oil；
The preparation method of B component is：Isocyanates is heated to 50 DEG C, modified vegetable oil is added dropwise while stirring, reaction 4 is small
When, it is down to room temperature and B component is made.
Embodiment 3
The concrete technology method of the present embodiment is as follows：
A kind of double component solvent-free vegetable oil base adhesive, it is characterised in that the double component solvent-free vegetable oil base rubber
It is 1 that glutinous agent, which includes mass ratio,:1 two components of A and B：
Component A includes：
The modified vegetable oil of 40 parts by weight；Modified vegetable oil is selected from modified peanut oil；
The tackifying resin of 50 parts by weight；Tackifying resin is m-pentadiene petro-resin；
The coupling agent of 2 parts by weight；Coupling agent is isopropyl three (dioctylphyrophosphoric acid acyloxy) titanate esters；
The filler of 70 parts by weight；Filler is mica powder；
The microcapsule expansion microballoon of 1 parts by weight；The wall shell of microcapsule expansion microballoon is chitosan, and microcapsule expansion microballoon is swollen
A diameter of 210 microns after swollen；
The chain extender of 9 parts by weight；Chain extender is 1,4- cyclohexanediols；
The preparation method of component A is：
The method of modifying of modified vegetable oil is：It is 2 by mol ratio:3 peanut oil and erythrol are with accounting for Quality of Peanut Oil
0.2% mixed in hydrochloric acid, is warming up to 225 DEG C and maintains this temperature 2.5 hours, reaction system is down under nitrogen protection
Room temperature is to obtain being modified peanut oil；
The mixture of modified vegetable oil, tackifying resin, coupling agent and chain extender is stirred 1.5 hours at 60 DEG C, is down to
Room temperature, adds filler and microcapsule expansion microballoon, stirs and component A is made；
B component includes：
The isocyanates of 90 parts by weight；Isocyanates is poly methylene poly phenyl poly isocyanate；
The modified vegetable oil of 10 parts by weight；Modified vegetable oil is selected from modified peanut oil；
The preparation method of B component is：Isocyanates is heated to 80 DEG C, modified vegetable oil, reaction 2.5 are added dropwise while stirring
Hour, it is down to room temperature and B component is made.
Embodiment 4
The concrete technology method of the present embodiment is as follows：
A kind of double component solvent-free vegetable oil base adhesive, it is characterised in that the double component solvent-free vegetable oil base rubber
It is 9 that glutinous agent, which includes mass ratio,:2 two components of A and B：
Component A includes：
The modified vegetable oil of 80 parts by weight；Modified vegetable oil is selected from modified linseed oil；
The tackifying resin of 20 parts by weight；Tackifying resin is rosin；
The coupling agent of 4 parts by weight；Coupling agent is monoalkoxy type titanate coupling agent；
The filler of 20 parts by weight；Filler is kaolin；
The microcapsule expansion microballoon of 9 parts by weight；The wall shell of microcapsule expansion microballoon is carboxymethyl cellulose, microcapsule expansion
A diameter of 35 microns after microsphere expansion；
The chain extender of 1 parts by weight；Chain extender is hydrogenated bisphenol A；
The preparation method of component A is：
The method of modifying of modified vegetable oil is：It is 4 by mol ratio:3 linseed oil and pentaerythrite are with accounting for flax oil quality
0.9% copper chloride mixing, is warming up to 235 DEG C and maintains this temperature 3 hours under nitrogen protection；Reaction system is cooled
Alcoholysis product is obtained to 180 DEG C；It is 1 by mol ratio:2 alcoholysis product and malonic acid are mixed with accounting for the sulfonic acid of malonic acid quality 0.1%
Close, reacted 2 hours at 230 DEG C, treat that acid number reaches 20mgKOH/g, cool to 150 DEG C, vacuumizing makes water content≤0.05%
Obtain being modified linseed oil；
The mixture of modified vegetable oil, tackifying resin, coupling agent and chain extender is stirred 2.5 hours at 80 DEG C, is down to
Room temperature, adds filler and microcapsule expansion microballoon, stirs and component A is made；
B component includes：
The isocyanates of 80 parts by weight；Isocyanates is IPDI；
The modified vegetable oil of 20 parts by weight；Modified vegetable oil is selected from modified linseed oil；
The preparation method of B component is：Isocyanates is heated to 60 DEG C, modified vegetable oil, reaction 3.5 are added dropwise while stirring
Hour, it is down to room temperature and B component is made.
Embodiment 5
The concrete technology method of the present embodiment is as follows：
A kind of double component solvent-free vegetable oil base adhesive, it is characterised in that the double component solvent-free vegetable oil base rubber
It is 3 that glutinous agent, which includes mass ratio,:2 two components of A and B：
Component A includes：
The modified vegetable oil of 50 parts by weight；Modified vegetable oil is selected from modified colza；
The tackifying resin of 40 parts by weight；Tackifying resin is rosin modified phenolic resin；
The coupling agent of 3 parts by weight；Coupling agent is tetra isopropyl two (dioctyl phosphito acyloxy) titanate esters；
The filler of 60 parts by weight；Filler is calcium oxide；
The microcapsule expansion microballoon of 2 parts by weight；The wall shell of microcapsule expansion microballoon is methylcellulose, and microcapsule expansion is micro-
A diameter of 185 microns after ball expansion；
The chain extender of 8 parts by weight；Chain extender is dimethylenebenzene glycol；
The preparation method of component A is：
The method of modifying of modified vegetable oil is：It is 1 by mol ratio:1 vegetable oil and pentitol are with accounting for vegetable seed oil quality
0.3% zinc chloride mixing, is warming up to 230 DEG C and maintains this temperature 2 hours, reaction system is down under nitrogen protection
Room temperature is to obtain modified colza；
The mixture of modified vegetable oil, tackifying resin, coupling agent and chain extender is stirred 2 hours at 70 DEG C, room is down to
Temperature, adds filler and microcapsule expansion microballoon, stirs and component A is made；
B component includes：
The isocyanates of 95 parts by weight；Isocyanates is hexamethylene diisocyanate；
The modified vegetable oil of 15 parts by weight；Modified vegetable oil is selected from modified colza；
The preparation method of B component is：Isocyanates is heated to 55 DEG C, modified vegetable oil is added dropwise while stirring, reaction 3 is small
When, it is down to room temperature and B component is made.
Embodiment 6
The concrete technology method of the present embodiment is as follows：
A kind of double component solvent-free vegetable oil base adhesive, it is characterised in that the double component solvent-free vegetable oil base rubber
It is 4 that glutinous agent, which includes mass ratio,:1 two components of A and B：
Component A includes：
The modified vegetable oil of 70 parts by weight；Modified vegetable oil is selected from modified cottonseed oil；
The tackifying resin of 30 parts by weight；Tackifying resin is terpene resin；
The coupling agent of 1.5 parts by weight；Coupling agent is distearyl acyl-oxygen isopropyl Aluminate；
The filler of 30 parts by weight；Filler is titanium dioxide；
The microcapsule expansion microballoon of 8 parts by weight；The wall shell of microcapsule expansion microballoon is ethyl cellulose, and microcapsule expansion is micro-
A diameter of 70 microns after ball expansion；
The chain extender of 2 parts by weight；Chain extender is resorcinol hydroxy ether；
The preparation method of component A is：
The method of modifying of modified vegetable oil is：It is 5 by mol ratio:6 cottonseed oil and glycerine are with accounting for cottonseed oil quality
0.8% sodium hydroxide mixing, is warming up to 240 DEG C and maintains this temperature 2.5 hours, by reaction system under nitrogen protection
Cool to 160 DEG C and obtain alcoholysis product；It is 2 by mol ratio:1 alcoholysis product and 1,4- succinic acid are with accounting for 1,4- succinic acid quality
0.3% acidic catalyst mixing, reacts 5 hours at 225 DEG C, treats that acid number reaches 6mgKOH/g, cool to 170 DEG C, takes out true
Sky makes water content≤0.05% obtain being modified cottonseed oil；
The mixture of modified vegetable oil, tackifying resin, coupling agent and chain extender is stirred 3 hours at 55 DEG C, room is down to
Temperature, adds filler and microcapsule expansion microballoon, stirs and component A is made；
B component includes：
The isocyanates of 75 parts by weight；Isocyanates is that mass ratio is 1:1 methyl diphenylene diisocyanate and toluene
Diisocyanate；
The modified vegetable oil of 5 parts by weight；Modified vegetable oil is selected from modified cottonseed oil；
The preparation method of B component is：Isocyanates is heated to 70 DEG C, modified vegetable oil is added dropwise while stirring, reaction 2 is small
When, it is down to room temperature and B component is made.
Embodiment 7
The concrete technology method of the present embodiment is as follows：
A kind of double component solvent-free vegetable oil base adhesive, it is characterised in that the double component solvent-free vegetable oil base rubber
It is 2 that glutinous agent, which includes mass ratio,:1 two components of A and B：
Component A includes：
The modified vegetable oil of 60 parts by weight；Modified vegetable oil is selected from modified castor oil；
The tackifying resin of 15 parts by weight；Tackifying resin is terpenes-styrene resin；
The coupling agent of 4.5 parts by weight；Coupling agent is vinyl trichlorosilane；
The filler of 50 parts by weight；Filler is ultra-fine barium sulfate；
The microcapsule expansion microballoon of 3 parts by weight；The wall shell of microcapsule expansion microballoon is polyethylene glycol, microcapsule expansion microballoon
A diameter of 155 microns after expansion.
The chain extender of 7 parts by weight；Chain extender is triethanolamine；
The preparation method of component A is：
The method of modifying of modified vegetable oil is：It is 8 by mol ratio:7 castor oil and butantriol are with accounting for castor-oil plant oil quality
0.4% base catalyst potassium hydroxide mixing, is warming up to 220 DEG C and maintains this temperature 2.5 hours under nitrogen protection,
Reaction system is down to room temperature and obtains modified castor oil；
The mixture of modified vegetable oil, tackifying resin, coupling agent and chain extender is stirred 1 hour at 85 DEG C, room is down to
Temperature, adds filler and microcapsule expansion microballoon, stirs and component A is made；
B component includes：
The isocyanates of 85 parts by weight；Isocyanates is that mass ratio is 2:1 poly methylene poly phenyl poly isocyanate and
IPDI；
The modified vegetable oil of 25 parts by weight；Modified vegetable oil is selected from modified castor oil；
The preparation method of B component is：Isocyanates is heated to 65 DEG C, modified vegetable oil is added dropwise while stirring, reaction 4 is small
When, it is down to room temperature and B component is made.
Embodiment 8
The concrete technology method of the present embodiment is as follows：
A kind of double component solvent-free vegetable oil base adhesive, it is characterised in that the double component solvent-free vegetable oil base rubber
It is 7 that glutinous agent, which includes mass ratio,:2 two components of A and B：
Component A includes：
The modified vegetable oil of 45 parts by weight；Modified vegetable oil is selected from modified tung oil；
The tackifying resin of 55 parts by weight；Tackifying resin is phenolic resin；
The coupling agent of 2.5 parts by weight；Coupling agent is VTES；
The filler of 40 parts by weight；Filler is land plaster；
The microcapsule expansion microballoon of 7 parts by weight；The wall shell of microcapsule expansion microballoon is polyvinyl alcohol, microcapsule expansion microballoon
A diameter of 90 microns after expansion.
The chain extender of 4 parts by weight；Chain extender is methyl diethanolamine；
The preparation method of component A is：
The method of modifying of modified vegetable oil is：It is 2 by mol ratio:3 tung oil and erythrol are with accounting for tung oil quality 0.7%
Kocide SD is mixed, and 225 DEG C are warming up under nitrogen protection and this temperature is maintained 2 hours, reaction system is cooled into 170
DEG C alcoholysis product；It is 1 by mol ratio:1 alcoholysis product adipic acid is mixed with accounting for the acidic catalyst of adipic acid quality 0.7%
Close, reacted 3 hours at 230 DEG C, treat that acid number reaches 9mgKOH/g, cool to 160 DEG C, vacuumizing makes water content≤0.05% i.e.
Obtain modified tung oil；
The mixture of modified vegetable oil, tackifying resin, coupling agent and chain extender is stirred 1.5 hours at 65 DEG C, is down to
Room temperature, adds filler and microcapsule expansion microballoon, stirs and component A is made；
B component includes：
The isocyanates of 80 parts by weight；Isocyanates is that mass ratio is 1:2 toluene di-isocyanate(TDI) and hexa-methylene two
Isocyanates；
The modified vegetable oil of 15 parts by weight；Modified vegetable oil is selected from modified modified tung oil；
The preparation method of B component is：Isocyanates is heated to 85 DEG C, modified vegetable oil, reaction 2.5 are added dropwise while stirring
Hour, it is down to room temperature and B component is made.
Embodiment 9
The concrete technology method of the present embodiment is as follows：
A kind of double component solvent-free vegetable oil base adhesive, it is characterised in that the double component solvent-free vegetable oil base rubber
It is 5 that glutinous agent, which includes mass ratio,:2 two components of A and B：
Component A includes：
The modified vegetable oil of 55 parts by weight；It is 1 that modified vegetable oil, which is selected from mass ratio,:1 modification cottonseed oil and modified tung oil；
The tackifying resin of 25 parts by weight；Tackifying resin is rosin modified phenolic resin；
The coupling agent of 3.5 parts by weight；Coupling agent is isopropyl three (dioctylphyrophosphoric acid acyloxy) titanate esters；
The filler of 55 parts by weight；Filler is sierozem power；
The microcapsule expansion microballoon of 4 parts by weight；The wall shell of microcapsule expansion microballoon is polyamide, and microcapsule expansion microballoon is swollen
A diameter of 135 microns after swollen.
The chain extender of 6 parts by weight；Chain extender is diethyl toluene diamine；
The preparation method of component A is：
The method of modifying of modified vegetable oil is：It is 5 by mol ratio:(mass ratio of cottonseed oil and tung oil is 1 to 3 vegetable oil:
1) and pentaerythrite and account for vegetable oil (mass ratio of cottonseed oil and tung oil be 1:1) the sodium methoxide mixing of quality 0.5%, in nitrogen
235 DEG C are warming up under protection and this temperature is maintained 3 hours, reaction system is down into room temperature obtains being modified cottonseed oil and changing
The mixture of property tung oil；
The mixture of modified vegetable oil, tackifying resin, coupling agent and chain extender is stirred 2.5 hours at 75 DEG C, is down to
Room temperature, adds filler and microcapsule expansion microballoon, stirs and component A is made；
B component includes：
The isocyanates of 90 parts by weight；Isocyanates is that mass ratio is 1:1:1 methyl diphenylene diisocyanate, toluene
The mixture of diisocyanate and poly methylene poly phenyl poly isocyanate；
The modified vegetable oil of 25 parts by weight；It is 1 that modified vegetable oil, which is selected from mass ratio,:1 modification cottonseed oil and modified tung oil；
The preparation method of B component is：Isocyanates is heated to 75 DEG C, modified vegetable oil, reaction 3.5 are added dropwise while stirring
Hour, it is down to room temperature and B component is made.
Embodiment 10
The concrete technology method of the present embodiment is as follows：
A kind of double component solvent-free vegetable oil base adhesive, it is characterised in that the double component solvent-free vegetable oil base rubber
It is 3 that glutinous agent, which includes mass ratio,:1 two components of A and B：
Component A includes：
The modified vegetable oil of 75 parts by weight；It is 1 that modified vegetable oil, which is selected from mass ratio,:1:1 modified soybean oil, modified peanut
Oil and modified colza；
The tackifying resin of 35 parts by weight；Tackifying resin is coumarone indene resin；
The coupling agent of 3.5 parts by weight；Coupling agent is distearyl acyl-oxygen isopropyl Aluminate；
The filler of 35 parts by weight；Filler is aluminium powder；
The microcapsule expansion microballoon of 6 parts by weight；The wall shell of microcapsule expansion microballoon is polyurethane, and microcapsule expansion microballoon is swollen
A diameter of 110 microns after swollen；
The chain extender of 5 parts by weight；Chain extender is 3,5- dimethythiotoluene diamines；
The preparation method of component A is：
The method of modifying of modified vegetable oil is：It is 1 by mol ratio:(mass ratio is 1 to 1 vegetable oil:1:1 soybean oil, flower
The mixture of oil generation and rapeseed oil) and pentitol and account for vegetable oil (mass ratio is 1:1:1 soybean oil, peanut oil and rapeseed oil
Mixture) quality 0.6% butyl lithium mixing, 230 DEG C are warming up under nitrogen protection and maintains this temperature 2.5 small
When, reaction system is cooled to 165 DEG C and obtains alcoholysis product；It is 3 by mol ratio:2 alcoholysis product and malonic acid are with accounting for malonic acid
The acidic catalyst mixing of quality 0.5%, reacts 4 hours at 220 DEG C, treats that acid number reaches 12mgKOH/g, cool to 165 DEG C,
Vacuumize the mixture for making water content≤0.05% obtain modified soybean oil, modified peanut oil and modified colza；
The mixture of modified vegetable oil, tackifying resin, coupling agent and chain extender is stirred 3 hours at 65 DEG C, room is down to
Temperature, adds filler and microcapsule expansion microballoon, stirs and component A is made；
B component includes：
The isocyanates of 85 parts by weight；Isocyanates is that mass ratio is 1:2:1 toluene di-isocyanate(TDI), isophorone two
Isocyanates and hexamethylene diisocyanate mixture；
The modified vegetable oil of 20 parts by weight；It is 1 that modified vegetable oil, which is selected from mass ratio,:1:1 modified soybean oil, modified peanut
Oil and modified colza；
The preparation method of B component is：Isocyanates is heated to 65 DEG C, modified vegetable oil is added dropwise while stirring, reaction 3 is small
When, it is down to room temperature and B component is made.
Adhesive component A 3g, B component 1g in Example 10 bond timber, in ambient temperature curing, and experimental result is such as
Under：
| Just stick intensity/MPa | 1 |
| Tensile shear strength/MPa | 6.5 |
| Time/h is fully cured in normal temperature | 48 |
| Ageing-resistant (168)/MPa at 100 DEG C | 4 |
| Acid resistance (168)/MPa | 5.5 |
Embodiments of the invention are the foregoing is only, are not intended to limit the scope of the invention, it is every to utilize this hair
Equivalent structure or equivalent flow conversion that bright description is made, or directly or indirectly it is used in other related technology necks
Domain, is included within the scope of the present invention.
Claims (10)
1. a kind of double component solvent-free vegetable oil base adhesive, it is characterised in that the double component solvent-free vegetable oil base rubber is sticked
It is 1 that agent, which includes mass ratio,:2 to 5:1 two components of A and B：
Component A includes：
The modified vegetable oil of 30-90 parts by weight；
The tackifying resin of 10-60 parts by weight；
The coupling agent of 1-5 parts by weight；
The filler of 10-80 parts by weight；
The microcapsule expansion microballoon of 1-10 parts by weight；
The chain extender of 0-10 parts by weight；
The preparation method of component A is：
Prepare modified vegetable oil：It is 1 by mol ratio:3 to 2:1 vegetable oil and polyalcohol are with accounting for plant oil quality 0.1%-1%
Acidic catalyst or base catalyst mixing, 220 DEG C to 240 DEG C are warming up under nitrogen protection and this temperature is maintained
2 to 3 hours, reaction system is down to room temperature and obtains modified vegetable oil；
The mixture of modified vegetable oil, tackifying resin, coupling agent and chain extender is stirred 1 to 3 hour at 50 DEG C to 90 DEG C, dropped
To room temperature, filler and microcapsule expansion microballoon are added, stirs and component A is made；
B component includes：
The isocyanates of 70-100 parts by weight；
The modified vegetable oil of 5-30 parts by weight；The modified vegetable oil of B component is to be modified using the plant oil modified method in component A
Vegetable oil afterwards；
The preparation method of B component is：Isocyanates is heated to 50 DEG C to 90 DEG C, modified vegetable oil, reaction 2 are added dropwise while stirring
To 4 hours, it is down to room temperature and B component is made, or isocyanates is directly used as B component.
2. a kind of double component solvent-free vegetable oil base adhesive, it is characterised in that the double component solvent-free vegetable oil base rubber is sticked
It is 1 that agent, which includes mass ratio,:2 to 5:1 two components of A and B：
Component A includes：
The modified vegetable oil of 30-90 parts by weight；
The tackifying resin of 10-60 parts by weight；
The coupling agent of 1-5 parts by weight；
The filler of 10-80 parts by weight；
The microcapsule expansion microballoon of 1-10 parts by weight；
The chain extender of 0-10 parts by weight；
The preparation method of component A is：
Prepare modified vegetable oil：It is 1 by mol ratio:3 to 2:1 vegetable oil and polyalcohol are with accounting for plant oil quality 0.1%-1%
Acidic catalyst or base catalyst mixing, 220 DEG C to 240 DEG C are warming up under nitrogen protection and this temperature is maintained
2 to 3 hours, reaction system is cooled to 150 DEG C to 180 DEG C and obtains alcoholysis product；It is 3 by mol ratio:1 to 1:2 alcoholysis product
Mix, reacted 2 to 6 hours at 220 DEG C to 230 DEG C with accounting for binary acid quality 0.1%-1% acidic catalyst with binary acid,
Treat that acid number reaches 20 to 3mgKOH/g, cool to 150 DEG C to 180 DEG C, vacuumizing makes water content≤0.05% obtain being modified plant
Thing oil；
The mixture of modified vegetable oil, tackifying resin, coupling agent and chain extender is stirred 1 to 3 hour at 50 DEG C to 90 DEG C, dropped
To room temperature, filler and microcapsule expansion microballoon are added, stirs and component A is made；
B component includes：
The isocyanates of 70-100 parts by weight；
The modified vegetable oil of 5-30 parts by weight；The modified vegetable oil of B component is to be modified using the plant oil modified method in component A
Vegetable oil afterwards；
The preparation method of B component is：Isocyanates is heated to 50 DEG C to 90 DEG C, modified vegetable oil, reaction 2 are added dropwise while stirring
To 4 hours, it is down to room temperature and B component is made, or isocyanates is directly used as B component.
3. double component solvent-free vegetable oil base adhesive as claimed in claim 1 or 2, it is characterised in that improved plant grease separation
From modified soybean oil, modified palm oil, modified peanut oil, modified linseed oil, modified colza, modified cottonseed oil, modified castor
One or more in oil, modified tung oil.
4. double component solvent-free vegetable oil base adhesive as claimed in claim 1 or 2, it is characterised in that acidic catalyst is
Sulfuric acid, sulfonic acid, hydrochloric acid, copper chloride or zinc chloride；Base catalyst is sodium hydroxide, potassium hydroxide, Kocide SD, organic base.
5. double component solvent-free vegetable oil base adhesive as claimed in claim 1 or 2, it is characterised in that the tackifying resin
For aliphatic hydrocarbon resins or arene resin.
6. double component solvent-free vegetable oil base adhesive as claimed in claim 1 or 2, it is characterised in that the coupling agent is
Silane coupler, titanate coupling agent or aluminate coupling agent.
7. double component solvent-free vegetable oil base adhesive as claimed in claim 1 or 2, it is characterised in that the filler is to fill out
Material：Carbonate, silicates, oxide-based, Sulfates, hydroxide or metal simple-substance.
8. double component solvent-free vegetable oil base adhesive as claimed in claim 1 or 2, it is characterised in that the microcapsules are swollen
The wall shell of swollen microballoon is natural macromolecular material, semi-synthetic high polymer material or fully synthetic high polymer material, and microcapsule expansion is micro-
A diameter of 10 to 210 microns after ball expansion.
9. double component solvent-free vegetable oil base adhesive as claimed in claim 1 or 2, it is characterised in that the chain extender is
Polyalcohols, alicyclic ring alcohols, aromatic alcohols, alcamines or Diamines.
10. double component solvent-free vegetable oil base adhesive as claimed in claim 1 or 2, it is characterised in that the isocyanates
For methyl diphenylene diisocyanate, toluene di-isocyanate(TDI), poly methylene poly phenyl poly isocyanate, the isocyanide of isophorone two
One or more in acid esters, hexamethylene diisocyanate.
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| CN107033832B (en) * | 2017-05-12 | 2020-06-26 | 山东农业大学 | Formaldehyde-free composite adhesive for artificial board and preparation method thereof |
| CN107936854A (en) * | 2017-11-29 | 2018-04-20 | 温州市环球汽车衬垫有限公司 | A kind of automobile-used glue of novel plant base |
| CN109021813A (en) * | 2018-07-10 | 2018-12-18 | 泉州海邦得生物科技有限公司 | One vegetable oil Base Metal anticorrosive paint and preparation method thereof |
| CN108727972A (en) * | 2018-07-10 | 2018-11-02 | 泉州海邦得生物科技有限公司 | One anti-adhesion coating of vegetable oil base hull bottom and preparation method thereof |
| CN110819293A (en) * | 2019-11-27 | 2020-02-21 | 谭港 | Antifouling adhesive, preparation method and application thereof |
| CN112955513A (en) * | 2020-05-25 | 2021-06-11 | 厦门双瑞船舶涂料有限公司 | Solvent-free marine antifouling paint and preparation method thereof |
| CN111500246A (en) * | 2020-05-26 | 2020-08-07 | 上海灿达建材科技有限公司 | Solvent-free polyurethane adhesive for colored pavement and preparation method thereof |
| CN112662365A (en) * | 2020-12-23 | 2021-04-16 | 苏州言信新型材料有限公司 | Preparation method of bi-component polyurethane adhesive |
| CN112961605B (en) * | 2021-02-24 | 2022-07-12 | 中国铁道科学研究院集团有限公司金属及化学研究所 | Asphalt-based material decoloration high-viscosity curing emulsion and preparation method thereof |
| CN117004272A (en) * | 2023-08-18 | 2023-11-07 | 中山市富日印刷材料有限公司 | Rosin phenolic resin for printing ink with good flexibility and preparation method thereof |
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| US8022164B1 (en) * | 2010-03-04 | 2011-09-20 | Microvast, Inc. | Two-component solvent-free polyurethane adhesives |
| CN103980460A (en) * | 2013-12-27 | 2014-08-13 | 新东方油墨有限公司 | Preparation method of low-viscosity MDI monomer solvent-free bi-component polyurethane adhesive |
| CN103820069A (en) * | 2014-03-18 | 2014-05-28 | 新东方油墨有限公司 | Double-component solvent-free polyurethane adhesive and preparation method thereof |
| CN104449538B (en) * | 2014-12-04 | 2016-09-07 | 上海康达化工新材料股份有限公司 | The double component solvent-free polyurethane structure glue of normal temperature coating and its preparation method and application method |
| CN105176475A (en) * | 2015-09-16 | 2015-12-23 | 湖州倍格曼新材料股份有限公司 | Solvent-free polyurethane adhesive with high initial viscosity and preparation method thereof |
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Effective date of registration: 20230206 Address after: 353000 Floor 2, No. 121, Dongxi Road, Yanping District, Nanping City, Fujian Province Patentee after: Fujian Nanping Xingyuanhui Biotechnology Co.,Ltd. Address before: 362000 Nanfeng plant at the entrance of Chongshan village, zhangban Town, Taiwan investment zone, Quanzhou City, Fujian Province Patentee before: QUANZHOU HAIBANG DE BIOTECHNOLOGY Co.,Ltd. |