CN106349450B - Combined polyether, polyurethane adhesive and feedstock composition, preparation method and application - Google Patents
Combined polyether, polyurethane adhesive and feedstock composition, preparation method and application Download PDFInfo
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- CN106349450B CN106349450B CN201610872659.5A CN201610872659A CN106349450B CN 106349450 B CN106349450 B CN 106349450B CN 201610872659 A CN201610872659 A CN 201610872659A CN 106349450 B CN106349450 B CN 106349450B
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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
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/6696—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/36 or hydroxylated esters of higher fatty acids of C08G18/38
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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
- C08G18/30—Low-molecular-weight compounds
- C08G18/36—Hydroxylated esters of higher fatty acids
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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
- C08G18/63—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers
- C08G18/632—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers onto polyethers
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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
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/08—Polyurethanes from polyethers
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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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Abstract
The invention discloses combined polyether, polyurethane adhesive and feedstock composition, preparation method and application.Combined polyether includes component：10~20 parts of 40~70 parts of polyether polyol A, polyether polyol B, 0.5~1.5 part of 20~40 parts of castor oil, 50~70 parts of filler, 0.02~0.08 part of organo-metallic catalyst, 2~5 parts of aerosil, 0.5~1 part of dehumidizer and antifoaming agent；The viscosity of polyether polyol A, B is respectively≤3500 and 1100~1500mPas, and hydroxyl value is respectively 25~29 and 290~330mgKOH/g, and water content is ≤0.15%.The feedstock composition of polyurethane adhesive includes that mass ratio is (4~3):1 combined polyether and polymethine polyphenyl polyisocyanate.The polyurethane adhesive hardness made from combined polyether of the present invention is high, and adhesive strength is big, and cures the smooth bubble-free of rear surface.
Description
Technical field
The present invention relates to polyurethane adhesive fields, and in particular to a kind of combined polyether, polyurethane adhesive and raw material group
Close object, preparation method and application.
Background technology
The adhesive used earliest is only made with water molten greatly mostly from natural materials, such as starch, dextrin, gelatine, fish glue
Agent, heated preparation plastic.It is poor for applicability because its ingredient is single, it is difficult to meet the needs of various different purposes.
Polyurethane adhesive is by the object containing active hydrogen in isocyanate groups in system and system or outside system
Matter reacts, and generates polyurethanyl group or polyureas, so that system intensity greatly improves, and then realizes the mesh of bonding
's.Polyurethane adhesive shows the activity and polarity of height, and the base material containing active hydrogen, such as foam, plastics, timber, skin
The material of any surface finish such as the porous materials such as leather, fabric, paper, ceramics and metal, glass, rubber, plastics has excellent
Chemical adhesive power.
Polyurethane adhesive is a kind of medium-to-high grade adhesive, have excellent flexibility, impact resistance, chemical-resistant,
Wearability, it is most important that its lower temperature resistance.By adjusting raw material and formula, can be designed that viscous between suitable a variety of materials
It connects, the multiclass type polyurethane adhesive of various different purposes.
Polyurethane adhesive common at present is solvent type.It is the same with neoprene, there is toxicity, pollute asking for environment
Topic.Occur aromatic hydrocarbonfree polyurethane adhesive successively in recent years, that is, use mixed solvents, the toxicity such as ketone, esters although to reduce,
But problem is not solved at all.In order to fundamentally solve the problems, such as to be endangered caused by solvent, no-solvent type polyurethane gluing
Agent is developed.Chinese patent literature CN102559125A discloses a kind of solvent-free polyurethane adhesive, group subpackage
Include isocyanates, polyester, polypropylene glycol, castor oil, diethylene glycol (DEG), glycerine and phthalic anhydride, but the no-solvent type polyurethane adhesive
That there are hardness is low, adhesion strength is inadequate, hardening time is long, the out-of-flatness of cured glue film surface, has the defects of bubble.
Therefore, prepare that nontoxic and adhesion strength is high, hardness is high, hardening time is short, the smooth bubble-free of cured glue film surface
Non-solvent polyurethane adhesive at this field important subject.
Invention content
Technical problem to be solved by the present invention lies in existing solvent borne polyurethane adhesive is overcome, there are toxicity and ring
Border pollute and existing no-solvent type polyurethane adhesive that there are hardness is low, adhesion strength is inadequate, hardening time is long, solidification
The bladdery defect of film surface out-of-flatness afterwards provides a kind of combined polyether, polyurethane adhesive and feedstock composition, preparation
Methods and applications.The combined polyether of the present invention is non-solvent combined polyether, nontoxic, environmental-friendly.The polyurethane adhesive of the present invention
Stick hardness is high, and adhesive strength is big, and cures the smooth bubble-free of rear surface, can be used for construction material PVC material for example for building
Bonding, filled board production and building water-proof paint etc..
The present invention solves above-mentioned technical problem by the following technical programs.
One of technical scheme of the present invention：
The present invention provides a kind of combined polyethers comprising the component of following parts by weight：Polyether polyol A40~70 part,
10~20 parts of polyether polyol B, 20~40 parts of castor oil, 50~70 parts of filler, organo-metallic catalyst 0.02~0.08
Part, aerosil (gas phase SiO2) 2~5 parts, 0.5~1.5 part of 0.5~1 part of dehumidizer and antifoaming agent；
The polyether polyol A is the polyether polyol that acrylonitrile-styrene graft is modified, and the polyether polyol A exists
Viscosity at 25 DEG C is≤3500mPas, and hydroxyl value is 25~29mgKOH/g, and water content is≤0.15%, and the percentage is
The quality of water accounts for the percentage of the polyether polyol A gross masses；
Viscosity of the polyether polyol B at 25 DEG C is 1100~1500mPas, and hydroxyl value is 290~330mgKOH/
G, water content are≤0.15%, and the percentage is that the quality of water accounts for the percentage of the polyether polyol B gross masses.
In the present invention, the combined polyether include various organic solvents commonly used in the art, such as ketones solvent,
Esters solvent, ether solvent etc..
In the present invention, the viscosity can be used this field conventional method and test to obtain, such as rotary viscosity measurement can be used
.
In the present invention, the water content is art technology term, refers to that the quality of water in sample accounts for sample gross mass
Percentage.Preferably, water content≤0.05% of the polyether polyol A.
In the present invention, polyether polyol that the acrylonitrile-styrene graft is modified refer to using polyether polyol as parent,
Acrylonitrile and styrene are grafted monomers, by acrylonitrile and styrene in polyether polyol medium changing of obtaining of graft copolymerization
Property polyether polyol.The polyether polyol that the acrylonitrile-styrene graft is modified can be used this field conventional method and obtain, compared with
Goodly, the content of styrene is 60~70% in grafted monomers, and the content of acrylonitrile is 30~40%, and the percentage is respectively to connect
Branch monomer mass accounts for the percentage of grafted monomers gross mass.
In the present invention, the solid content of the polyether polyol A is preferably 23.0~25.0%.The solid content is ability
Field technique term refers to that the solid masses after sample drying accounts for the percentage for drying preceding sample gross mass, herein the hundred of solid content
Divide the percentage than accounting for drying polyethers prior polyalcohol A gross masses for the solid masses of polyether polyol A after drying.
Preferably, the polyether polyol A is the trade mark produced by Shandong Lanxing Dongda Chemical Co., Ltd is
The polyether polyol of POP36/28, the POP36/28 polyether polyol are the polyether polyol that acrylonitrile-styrene graft is modified,
Viscosity≤3500mPa.s, hydroxyl value are 25~29mgKOH/g, and water content≤0.05%, solid content is 23.0~25.0%, is dissociated
Acrylonitrile content≤10.0mg/Kg, free styrene-content≤50.0mg/Kg, the styrene of grafting and the acrylonitrile of grafting
Mass ratio is (60~70):(30~40).
Preferably, the trade mark that the polyether polyol B is the production of Hebei Yadong Chemical Group Co., Ltd be 8310 it is poly-
The viscosity of ethoxylated polyhydric alcohol, 8310 polyether polyol is 1100~1500mPa.s, and hydroxyl value is 290~330mgKOH/g, water content
≤ 0.15%, K+Content≤50mg/Kg.
In the present invention, the castor oil can be castor oil commonly used in the art, generally by ricinoleic acid (9- alkenyls-
12- hydroxy octadecadienoic acids) it is formed with glycerine esterification.Preferably, the hydroxyl value of the castor oil is 150~170mgKOH/g, water content
It is≤0.5%, iodine number is≤90mg/100g, wherein the percentage of the water content is that the quality of water accounts for the total matter of the castor oil
The percentage of amount.
In the present invention, the filler can be filler commonly used in the art, for enhancing final gluing obtained
The intensity of agent.Preferably, the filler is calcium carbonate.
In the present invention, the organo-metallic catalyst can be organo-metallic catalyst commonly used in the art, such as have
Machine bismuth metallic catalyst substitutes organic mercury metallic catalyst and Organic leadP metallic catalyst etc..Preferably, the organic metal is urged
Agent is organo-bismuth metallic catalyst and/or Organic leadP metallic catalyst.Heretofore described organo-metallic catalyst mainly rises
The effect of gel.Preferably, the dosage of the organo-metallic catalyst is 0.04~0.06 part, described part is parts by weight.
In the present invention, the aerosil can be aerosil commonly used in the art, conventional gas phase two
The dioxide-containing silica of silica is general >=99.5wt%, grain size is generally less than 100nm, such as 20~60nm.The gas phase two
Silica can be used method commonly used in the art and be prepared, and is generally prepared using chemical vapour deposition technique.This hair
In bright, the aerosil mainly plays peptizaiton, for filler is fully dispersed in polyether polyol, is formed uniform
System.The aerosil is preferably purchased from Jiangxi Ao Te fine powders Co., Ltd.
In the present invention, the dehumidizer can be dehumidizer commonly used in the art, such as calcium chloride, silica gel, calcium oxide
With montmorillonite etc..Preferably, the dehumidizer is calcium chloride and/or calcium oxide.Heretofore described dehumidizer is mainly used for inhaling
Remaining a small amount of moisture content in raw material is received, is avoided during preparing polyurethane adhesive, the moisture content in raw material and isocyanates
Reaction forms small bubble in surface of pressure-sensitive adhesive, influences the performance of adhesive.
In the present invention, the antifoaming agent can be antifoaming agent commonly used in the art, preferably polyoxyethylene polyoxy third
It is one or more in alkene pentaerythrite ether, polyoxyethylene polyoxy propyl alcohol amidogen ether and polypropylene glycerol aether.
In the present invention, the combined polyether preferably may also include other components commonly used in the art, such as disperse
Agent.The dispersant can be dispersant commonly used in the art, such as fatty acid dispersant, aliphatic amide type dispersant
With esters dispersant etc., preferably, the dispersant is vinyl bis-stearamides and/or glyceryl monostearate.Described point
The dosage of powder can be according to this field conventional selection, preferably 0.6~1.5 part.
In a preferred embodiment of the present invention, the combined polyether is grouped as by the group of following parts by weight：Polyether polyol A
40~70 parts, 10~20 parts of polyether polyol B, 20~40 parts of castor oil, 50~70 parts of calcium carbonate, organo-metallic catalyst
0.5~1.5 part of 0.02~0.08 part, 2~5 parts of aerosil, 0.5~1 part of dehumidizer and antifoaming agent；The polyether polyols
Alcohol A be acrylonitrile-styrene graft be modified polyether polyol, viscosity of the polyether polyol A at 25 DEG C be≤
3500mPas, hydroxyl value are 25~29mgKOH/g, and water content is≤0.15%；Viscosity of the polyether polyol B at 25 DEG C
For 1100~1500mPas, hydroxyl value is 290~330mgKOH/g, and water content is≤0.15%.
In another preferred embodiment of the present invention, the combined polyether is grouped as by the group of following parts by weight：Polyether polyols
10~20 parts of 40~70 parts of alcohol A, polyether polyol B, 20~40 parts of castor oil, 50~70 parts of calcium carbonate, metal organic catalysis
0.02~0.08 part of agent, 0.6~1.5 part of dispersant, 2~5 parts of aerosil, 0.5~1 part of dehumidizer and antifoaming agent 0.5
~1.5 parts；The polyether polyol A is the polyether polyol that acrylonitrile-styrene graft is modified, and the polyether polyol A exists
Viscosity at 25 DEG C is≤3500mPas, and hydroxyl value is 25~29mgKOH/g, and water content is≤0.15%；The polyether polyols
Viscosity of the alcohol B at 25 DEG C is 1100~1500mPas, and hydroxyl value is 290~330mgKOH/g, and water content is≤0.15%.
The two of technical scheme of the present invention：
The present invention also provides the preparation methods of said combination polyethers.The preparation method can be according to this field conventional method
It carries out, each component of the combined polyether is mixed, you can.Preferably, the preparation method carries out in accordance with the following steps：First will
The aerosil and the filler mixing, obtain solid mixture, then again by the solid mixture with it is described
Polyether polyol A, the polyether polyol B, the castor oil, the organo-metallic catalyst, the dehumidizer and described disappear
Infusion mixes.When the combined polyether includes dispersant, the dispersant is and described solid preferably after obtaining solid mixture
Body mixture, the polyether polyol B, the castor oil, the organo-metallic catalyst, described removes the polyether polyol A
Humectant and antifoaming agent mixing.
Wherein, the mixing can be carried out according to this field routine operation, generally be carried out in stainless steel puddles kettle.This field
Technical staff know it is described be mixed into mix it is uniform to each component.The time of the mixing is generally 2~5 hours.
The three of technical scheme of the present invention：
The present invention also provides a kind of feedstock composition of polyurethane adhesive, the feedstock composition includes such as the following group
Point：The combined polyether and polymethine polyphenyl polyisocyanate (abbreviation PAPI)；The combined polyether and the multiple first
The mass ratio of Quito polyphenyl polyisocyanate is (4~3):1.
Wherein, the polymethine polyphenyl polyisocyanate can be that the more phenyl of polymethine commonly used in the art are more
Isocyanates, it is preferably one or more in PM-200,44V20, MR-200 and M20S.The PM-200 is preferably by peaceful
Bo Wanhua polyurethane Co., Ltd provide, the 44V20 preferably by Baeyer polyurethane Co., Ltd provide, the MR-200 compared with
It is provided goodly by Nippon Polyurethane Industry Co., Ltd., the M20S is preferably carried by Shanghai Basf Polyurethane Co., Ltd.
For.
In the present invention, the feedstock composition of the polyurethane adhesive does not include commonly used in the art various organic molten
Agent, such as ketones solvent, esters solvent, ether solvent etc..
In a preferred embodiment of the present invention, the feedstock composition of the polyurethane adhesive is grouped as by following group：Institute
State combined polyether and polymethine polyphenyl polyisocyanate；The combined polyether and the more phenyl polyisocyanic acid of the polymethine
The mass ratio of ester is (4~3):1.
The four of technical scheme of the present invention：
The present invention also provides a kind of preparation method of polyurethane adhesive, the preparation method includes the following steps：It will
The combined polyether and the polymethine polyphenyl polyisocyanate mixing, reacted to get.
Wherein, the mixing can be carried out according to this field routine operation.Those skilled in the art know described be mixed into
It mixes uniform to each component.
Wherein, the condition of the reaction can be carried out according to the normal condition of this field.
The five of technical scheme of the present invention：
The present invention also provides the polyurethane adhesives made from above-mentioned preparation method.
The six of technical scheme of the present invention：
The present invention also provides above-mentioned polyurethane adhesives in construction material bonding, filled board production and building water-proof paint
In application.
Wherein, the polyurethane adhesive construction material bonding, filled board production and building water-proof paint in application,
Those skilled in the art know how this uses according to common sense, the raw material components combined polyether of the general polyurethane adhesive
Preceding separated storage is being used with polymethine polyphenyl polyisocyanate, without mixing, again by the combined polyether when use
It is reacted with the mixing of polymethine polyphenyl polyisocyanate.
On the basis of common knowledge of the art, above-mentioned each optimum condition can be combined arbitrarily to get each preferable reality of the present invention
Example.
The reagents and materials used in the present invention are commercially available.
The positive effect of the present invention is that：
(1) combined polyether of the invention is free of the solvent of any toxic and volatile, both will not during preparation and use
Human body is damaged and very environmentally friendly will not be polluted.
(2) polyurethane adhesive that combined polyether of the invention obtains after being acted on polymethine polyphenyl polyisocyanate
With good adhesive strength and hardness, and the smooth bubble-free of surface of pressure-sensitive adhesive.
Specific implementation mode
It is further illustrated the present invention below by the mode of embodiment, but does not therefore limit the present invention to the reality
It applies among a range.In the following examples, the experimental methods for specific conditions are not specified, according to conventional methods and conditions, or according to quotient
Product specification selects.
In following embodiments, polyether polyol POP36/28 used is the polyether polyols that acrylonitrile-styrene graft is modified
Alcohol is provided by Shandong Lanxing Dongda Chemical Co., Ltd, viscosity≤3500mPas, and hydroxyl value is 25~29mgKOH/g,
Water content≤0.05%, solid content are 23.0~25.0%, and dissociate acrylonitrile content≤10.0mg/Kg, and dissociate styrene-content
The mass ratio of≤50.0mg/Kg, the styrene of grafting and the acrylonitrile of grafting is (60~70):(30~40).
Polyether polyol 8310 used by Hebei Yadong Chemical Group Co., Ltd provide, viscosity be 1100~
1500mPas, hydroxyl value are 290~330mgKOH/g, water content≤0.15%, K+Content≤50mg/Kg.
The hydroxyl value of the castor oil is 150~170mgKOH/g, water content≤0.5%, iodine number≤90mg/100g.
The aerosil is provided by Jiangxi Ao Te fine powders Co., Ltd.
Polymethine polyphenyl polyisocyanate PM-200 used is provided by Ningbo Wanhua Polyurethane Co., Ltd., 44V20
It is provided by Baeyer polyurethane Co., Ltd, MR-200 is provided by Nippon Polyurethane Industry Co., Ltd., and M20S is by Shanghai BASF
Polyurethane Co., Ltd provides.
Other raw materials and reagents are all commercially available.
Embodiment 1
I, a kind of combined polyether, raw material components and dosage are as shown in the table：
| Component | Substance classes | Dosage |
| Polyether polyol A | Polyether polyol POP36/28 | 50 parts |
| Polyether polyol B | Polyether polyol 8310 | 15 parts |
| Castor oil | Castor oil | 35 parts |
| Filler | Calcium carbonate | 70 parts |
| Organo-metallic catalyst | Organo-bismuth metallic catalyst | 0.06 part |
| Aerosil | Aerosil | 2 parts |
| Dehumidizer | Calcium chloride | 0.7 part |
| Antifoaming agent | Polyoxyethylene polyoxypropylene pentaerythrite ether | 0.5 part |
The preparation method of the combined polyether is as follows：According to proportioning, each component is uniformly mixed i.e. in stainless steel puddling kettle
Can, incorporation time 2h.
II, a kind of polyurethane adhesive, feedstock composition are 4 by mass ratio:1 said combination polyethers and polymethine
Polyphenyl polyisocyanate PM-200 compositions.
The preparation method of the polyurethane adhesive is as follows：According to proportioning, combined polyether and PM-200 are mixed, reaction, i.e.,
.
Embodiment 2
I, a kind of combined polyether, raw material components and dosage are as shown in the table：
The preparation method of the combined polyether is as follows：According to proportioning, each component is uniformly mixed i.e. in stainless steel puddling kettle
Can, incorporation time 2h.
II, a kind of polyurethane adhesive, feedstock composition are 3 by mass ratio:1 said combination polyethers and polymethine
Polyphenyl polyisocyanate PM-200 compositions.
The preparation method of the polyurethane adhesive is as follows：According to proportioning, combined polyether and PM-200 are mixed, reaction, i.e.,
.
Embodiment 3
I, a kind of combined polyether, raw material components and dosage are as shown in the table：
| Component | Substance classes | Dosage |
| Polyether polyol A | Polyether polyol POP36/28 | 40 parts |
| Polyether polyol B | Polyether polyol 8310 | 20 parts |
| Castor oil | Castor oil | 40 parts |
| Filler | Calcium carbonate | 50 parts |
| Organo-metallic catalyst | Organo-bismuth metallic catalyst | 0.02 part |
| Aerosil | Aerosil | 5 parts |
| Dehumidizer | Calcium chloride | 1 part |
| Antifoaming agent | Polyoxyethylene polyoxy propyl alcohol amidogen ether | 1.5 part |
The preparation method of the combined polyether is as follows：According to proportioning, each component is uniformly mixed i.e. in stainless steel puddling kettle
Can, incorporation time 3h.
II, a kind of polyurethane adhesive, feedstock composition are 4 by mass ratio:1 said combination polyethers and polymethine
Polyphenyl polyisocyanate PM-200 compositions.
The preparation method of the polyurethane adhesive is as follows：According to proportioning, combined polyether and PM-200 are mixed, reaction, i.e.,
.
Embodiment 4
I, a kind of combined polyether, raw material components and dosage are as shown in the table：
| Component | Substance classes | Dosage |
| Polyether polyol A | Polyether polyol POP36/28 | 60 parts |
| Polyether polyol B | Polyether polyol 8310 | 15 parts |
| Castor oil | Castor oil | 25 parts |
| Filler | Calcium carbonate | 65 parts |
| Organo-metallic catalyst | Organic leadP metallic catalyst | 0.08 part |
| Aerosil | Aerosil | 2 parts |
| Dehumidizer | Calcium oxide | 0.9 part |
| Antifoaming agent | Polypropylene glycerol aether | 0.8 part |
The preparation method of the combined polyether is as follows：According to proportioning, each component is uniformly mixed i.e. in stainless steel puddling kettle
Can, incorporation time 2.5h.
II, a kind of polyurethane adhesive, feedstock composition are 3 by mass ratio:1 said combination polyethers and polymethine
Polyphenyl polyisocyanate PM-200 compositions.
The preparation method of the polyurethane adhesive is as follows：According to proportioning, combined polyether and PM-200 are mixed, reaction, i.e.,
.
Embodiment 5
I, a kind of combined polyether, raw material components and dosage are as shown in the table：
The preparation method of the combined polyether is as follows：According to proportioning, each component is uniformly mixed i.e. in stainless steel puddling kettle
Can, incorporation time 2h.
II, a kind of polyurethane adhesive, feedstock composition are 3 by mass ratio:1 said combination polyethers and polymethine
Polyphenyl polyisocyanate PM-200 compositions.
The preparation method of the polyurethane adhesive is as follows：According to proportioning, combined polyether and PM-200 are mixed, reaction, i.e.,
.
Embodiment 6
I, a kind of combined polyether, raw material components and dosage are as shown in the table：
| Component | Substance classes | Dosage |
| Polyether polyol A | Polyether polyol POP36/28 | 50 parts |
| Polyether polyol B | Polyether polyol 8310 | 15 parts |
| Castor oil | Castor oil | 35 parts |
| Filler | Calcium carbonate | 65 parts |
| Organo-metallic catalyst | Organo-bismuth metallic catalyst | 0.05 part |
| Dispersant | Vinyl bis-stearamides | 1.5 part |
| Aerosil | Aerosil | 2 parts |
| Dehumidizer | Calcium oxide | 1 part |
| Antifoaming agent | Polyoxyethylene polyoxypropylene pentaerythrite ether | 0.5 part |
The preparation method of the combined polyether is as follows：According to proportioning, each component is uniformly mixed i.e. in stainless steel puddling kettle
Can, incorporation time 2.5h.
II, a kind of polyurethane adhesive, feedstock composition are 4 by mass ratio:1 said combination polyethers and polymethine
Polyphenyl polyisocyanate 44V20 compositions.
The preparation method of the polyurethane adhesive is as follows：According to proportioning, combined polyether and 44V20 are mixed, reaction, i.e.,
.
Embodiment 7
I, a kind of combined polyether, raw material components and dosage are as shown in the table：
| Component | Substance classes | Dosage |
| Polyether polyol A | Polyether polyol POP36/28 | 50 parts |
| Polyether polyol B | Polyether polyol 8310 | 15 parts |
| Castor oil | Castor oil | 35 parts |
| Filler | Calcium carbonate | 65 parts |
| Organo-metallic catalyst | Organic leadP metallic catalyst | 0.04 part |
| Dispersant | Glyceryl monostearate | 0.6 part |
| Aerosil | Aerosil | 3 parts |
| Dehumidizer | Calcium chloride | 0.5 part |
| Antifoaming agent | Polyoxyethylene polyoxy propyl alcohol amidogen ether | 1 part |
The preparation method of the combined polyether is as follows：According to proportioning, each component is uniformly mixed i.e. in stainless steel puddling kettle
Can, incorporation time 2h.
II, a kind of polyurethane adhesive, feedstock composition are 4 by mass ratio:1 said combination polyethers and polymethine
Polyphenyl polyisocyanate MR-200 compositions.
The preparation method of the polyurethane adhesive is as follows：According to proportioning, combined polyether and MR-200 are mixed, reaction, i.e.,
.
Embodiment 8
I, a kind of combined polyether, raw material components and dosage are as shown in the table：
The preparation method of the combined polyether is as follows：According to proportioning, each component is uniformly mixed i.e. in stainless steel puddling kettle
Can, incorporation time 2h.
II, a kind of polyurethane adhesive, feedstock composition are 4 by mass ratio:1 said combination polyethers and polymethine
Polyphenyl polyisocyanate M20S compositions.
The preparation method of the polyurethane adhesive is as follows：According to proportioning, combined polyether and M20S are mixed, reaction to get.
Comparative example 1
I, a kind of combined polyether, raw material components and dosage are as shown in the table：
The preparation method of the combined polyether is as follows：According to proportioning, each component is uniformly mixed i.e. in stainless steel puddling kettle
Can, incorporation time 2.5h.
II, a kind of polyurethane adhesive, feedstock composition are 4 by mass ratio:1 said combination polyethers and polymethine
Polyphenyl polyisocyanate PM-200 compositions.
The preparation method of the polyurethane adhesive is as follows：According to proportioning, combined polyether and PM-200 are mixed, reaction, i.e.,
.
Comparative example 2
I, a kind of combined polyether, raw material components and dosage are as shown in the table：
| Component | Substance classes | Dosage |
| Polyether polyol A | Polyether polyol POP36/28 | 65 parts |
| Polyether polyol B | Polyether polyol 310 | 10 parts |
| Castor oil | Castor oil | 25 parts |
| Filler | Calcium carbonate | 55 parts |
| Organo-metallic catalyst | Organic leadP metallic catalyst | 0.05 part |
| Aerosil | Aerosil | 3 parts |
| Dehumidizer | Calcium oxide | 1 part |
| Antifoaming agent | Polypropylene glycerol aether | 1.5 part |
Wherein, polyether polyol 310 used is provided by Jurong Ningwu New Materials Development Co., Ltd., viscosity 200-
300mPa.s, hydroxyl value 163-173mgKOH/g, water content≤0.15%, K+Content≤5mg/Kg.
The preparation method of the combined polyether is as follows：According to proportioning, each component is uniformly mixed i.e. in stainless steel puddling kettle
Can, incorporation time 2.5h.
II, a kind of polyurethane adhesive, feedstock composition are 4 by mass ratio:1 said combination polyethers and polymethine
Polyphenyl polyisocyanate PM-200 compositions.
The preparation method of the polyurethane adhesive is as follows：According to proportioning, combined polyether and PM-200 are mixed, reaction, i.e.,
.
Effect example 1
Reaction time, hardening time, adhesive strength, hardness and the appearance of 1~5 polyurethane adhesive of testing example, together
The bi-component no-solvent type polyurethane binder conduct pair for the model PU88 that the Shanghai Shi Xuanyong Shou Xing Industrial Co., Ltd.s provide
According to group.Wherein, when the reaction time refers to the viscosity of polyurethane adhesive combination and changes from small to big substantially not flowable to composition
Between；Hardening time refers to surface of pressure-sensitive adhesive and is hardened, through pressing the time without deformation；Adhesive strength is surveyed by GB/T2791-1995 standards
Examination, hardness press GB/T531-1999 standard testings, and appearance is using range estimation.It is specific that test result is as follows shown in table.
As seen from the above table, the smooth no gas in polyurethane adhesive surface made from the non-solvent combined polyether with the present invention
Bubble, your the D hardness that continues is high, is significantly improved, and hardening time is shorter, glues compared to existing no-solvent type polyurethane binder
Knotting strength is larger, and comprehensive performance is good.The effect of embodiment 6~8 is close with Examples 1 to 5.
The dosage of aerosil is 1 part in comparative example 1, and the dosage of dispersant is 0.5 part, since filler fails
It is fully dispersed in system, affect the hardness of final binder.The viscosity and hydroxyl value of the polyether polyol B used in comparative example 2
Less than the lower limiting value that the present invention limits, as a result there are a little minute bubbles on gained polyurethane adhesive surface, and hardness is significantly lower than this
Inventive embodiments.
Claims (12)
1. a kind of combined polyether, which is characterized in that the combined polyether includes the component of following parts by weight：Polyether polyol A
40-70 parts, 10-20 parts of polyether polyol B, 20-40 parts of castor oil, 50-70 parts of filler, organo-metallic catalyst 0.02-
0.5-1.5 parts of 0.08 part, 2-5 parts of aerosil, 0.5-1 parts of dehumidizer and antifoaming agent；
The polyether polyol A is the polyether polyol that acrylonitrile-styrene graft is modified, and the polyether polyol A is at 25 DEG C
Under viscosity be≤3500mPas, hydroxyl value 25-29mgKOH/g, water content be≤0.15%, the percentage be water matter
Amount accounts for the percentage of the polyether polyol A gross masses；
Viscosity of the polyether polyol B at 25 DEG C is 1100-1500mPas, hydroxyl value 290-330mgKOH/g, aqueous
Amount is≤0.15%, and the percentage is that the quality of water accounts for the percentage of the polyether polyol B gross masses；
The combined polyether does not include organic solvent, and the organic solvent is in ketones solvent, esters solvent and ether solvent
It is one or more.
2. combined polyether as described in claim 1, which is characterized in that styrene in the grafted monomers of the polyether polyol A
Content be 60-70%, the content of acrylonitrile is 30-40%, and it is total that the percentage is that each grafted monomers quality accounts for grafted monomers
The percentage of quality；
And/or water content≤0.05% of the polyether polyol A；
And/or the solid content of the polyether polyol A is 23.0-25.0%, the percentage is polyether polyol A after drying
Solid masses account for drying polyethers prior polyalcohol A gross masses percentage.
3. combined polyether as claimed in claim 1 or 2, which is characterized in that the polyether polyol A is polyether polyol
POP36/28；
And/or the polyether polyol B is polyether polyol 8310.
4. combined polyether as described in claim 1, which is characterized in that the hydroxyl value of the castor oil is 150-170mgKOH/g,
Water content is≤0.5%, and iodine number is≤90mg/100g, and the percentage is that the quality of water accounts for the hundred of the castor oil gross mass
Divide ratio；
And/or the filler is calcium carbonate；
And/or the organo-metallic catalyst is organo-bismuth metallic catalyst and/or Organic leadP metallic catalyst；
And/or the dehumidizer is calcium chloride and/or calcium oxide；
And/or the antifoaming agent is polyoxyethylene polyoxypropylene pentaerythrite ether, polyoxyethylene polyoxy propyl alcohol amidogen ether and polyoxy third
It is one or more in alkene glycerin ether；
And/or the combined polyether further includes dispersant, the dosage of the dispersant is 0.6-1.5 parts, and described part is weight
Part.
5. combined polyether as claimed in claim 4, which is characterized in that the dosage of the organo-metallic catalyst is 0.04-
0.06 part；
And/or the dispersant is vinyl bis-stearamides and/or glyceryl monostearate.
6. a kind of preparation method of the combined polyether as described in claim any one of 1-5, which is characterized in that the preparation method is that
The each component of the combined polyether is mixed, you can.
7. preparation method as claimed in claim 6, which is characterized in that the preparation method carries out in accordance with the following steps：First will
The aerosil and the filler mixing, obtain solid mixture, then again by the solid mixture with it is described
Polyether polyol A, the polyether polyol B, the castor oil, the organo-metallic catalyst, the dehumidizer and described disappear
Infusion mixes.
8. a kind of feedstock composition of polyurethane adhesive, which is characterized in that the feedstock composition includes following component：Combination
Polyethers and polymethine polyphenyl polyisocyanate；The combined polyether is that combination as described in any one in claim 1-5 is poly-
Ether；The mass ratio of the combined polyether and the polymethine polyphenyl polyisocyanate is (4-3)：1.
9. the feedstock composition of polyurethane adhesive as claimed in claim 8, which is characterized in that the more phenyl of polymethine
Polyisocyanates be polymethine polyphenyl polyisocyanate PM-200, polymethine polyphenyl polyisocyanate 44V20, repeatedly
It is one or more in methyl polyphenyl polyisocyanate MR-200 and polymethine polyphenyl polyisocyanate M20S.
10. a kind of preparation method of polyurethane adhesive, which is characterized in that the preparation method includes the following steps：By right
It is required that combined polyether described in 8 and polymethine polyphenyl polyisocyanate mixing, reacted to get.
11. polyurethane adhesive made from a kind of preparation method as claimed in claim 10.
12. a kind of application of polyurethane adhesive as claimed in claim 11 in construction material bonding and building water-proof paint.
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| CN110028884A (en) * | 2019-04-23 | 2019-07-19 | 成都新柯力化工科技有限公司 | A kind of compactness polyureas building water-proof paint and preparation method |
| CN110437787A (en) * | 2019-06-24 | 2019-11-12 | 萍乡高恒材料科技有限公司 | A kind of exhaust no-solvent polyurethane pressure sensitive adhesive composition certainly |
| CN112143443B (en) * | 2020-09-30 | 2022-04-29 | 有行鲨鱼（上海）科技股份有限公司 | Polyurethane composite adhesive and preparation method thereof |
| CN112175499A (en) * | 2020-10-10 | 2021-01-05 | 安顺市乾辰谷材科技有限公司 | Insulating paint resistant to humid environment and used for FIW completely-insulated wire |
| CN114989776B (en) * | 2022-06-16 | 2024-04-16 | 北京高盟新材料股份有限公司 | Single-component polyurethane adhesive for high-humidity wood and preparation method thereof |
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