CN106349450A - Portfolio polyether, polyurethane adhesive, raw material composition as well as preparation methods of portfolio polyether and polyurethane adhesive and application of polyurethane adhesive - Google Patents
Portfolio polyether, polyurethane adhesive, raw material composition as well as preparation methods of portfolio polyether and polyurethane adhesive and application of polyurethane adhesive Download PDFInfo
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- CN106349450A CN106349450A CN201610872659.5A CN201610872659A CN106349450A CN 106349450 A CN106349450 A CN 106349450A CN 201610872659 A CN201610872659 A CN 201610872659A CN 106349450 A CN106349450 A CN 106349450A
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- polyether
- polyether polyol
- polyurethane adhesive
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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
-
- 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
- C08G18/48—Polyethers
-
- 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
-
- 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
Abstract
The invention discloses portfolio polyether, a polyurethane adhesive, a raw material composition as well as preparation methods of the portfolio polyether and the polyurethane adhesive and application of the polyurethane adhesive. The portfolio polyether is prepared from the following components: 40 to 70 parts of polyether polyol A, 10 to 20 parts of polyether polyol B, 20 to 40 parts of castor oil, 50 to 70 parts of filling agent, 0.02 to 0.08 part of organo-metallic catalyst, 2 to 5 parts of fumed silica, 0.5 to 1 part of dehumidizer and 0.5 to 1.5 part of defoaming agent; the viscosity of the polyether polyol A and the viscosity of the polyether polyol B are smaller than or equal to 3500 and 1100 to 1500mPa.s respectively, hydroxyl values of the polyether polyol A and the polyether polyol B are 25 to 29mgKOH/g and 290 to 330mgKOH/g respectively, and the water contents of the polyether polyol A and the polyether polyol B are smaller than or equal to 0.15 percent. The raw material composition of the polyurethane adhesive is prepared from the portfolio polyether and polymetyhlene polyphenyl by a mass ratio of (4 to 3) to 1. The polyurethane adhesive prepared from the portfolio polyether, disclosed by the invention, is high in hardness and bonding strength; in addition, after curing, the surface of the polyurethane adhesive is smooth without air bubbles.
Description
Technical field
The present invention relates to polyurethane adhesive field is and in particular to a kind of combined polyether, polyurethane adhesive and raw material group
Compound, preparation method and application.
Background technology
The adhesive using earliest derives from natural materials, such as starch, dextrin, osseocolla, fish glue etc. mostly, only uses water as molten
Agent, heated preparation plastic.Because its composition is single, poor for applicability, it is difficult to meet the demand of various difference purposes.
Polyurethane adhesive is the thing by containing active hydrogen in the 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 activity and the polarity of height, with the base material containing active hydrogen, such as foam, plastics, timber, skin
The porous materials such as leather, fabric, paper, pottery, and the material of any surface finish such as metal, glass, rubber, plastics have excellent
Chemical adhesive power.
Polyurethane adhesive is a kind of medium-to-high grade adhesive, have excellent pliability, resistance to impact, chemical-resistant,
Wearability is it is most important that its lower temperature resistance.By adjusting raw material and formula, can be designed that the viscous of suitable various storeroom
Connect, various difference purposes multiclass type polyurethane adhesive.
Polyurethane adhesive common at present is solvent-borne type.The same with neoprene, there is toxicity, pollute asking of environment
Topic.Aromatic hydrocarbonfree polyurethane adhesive occurred in recent years successively, that is, adopted the mixed solvent such as ketone, esters, although toxicity reduces,
But problem is not solved at all.In order to fundamentally solve the problems, such as the harm that solvent causes, no-solvent type polyurethane is gluing
Agent is developed.Chinese patent literature cn102559125a discloses a kind of solvent-free polyurethane adhesive, and it organizes subpackage
Include isocyanates, polyester, polypropylene glycol, Oleum Ricini, diethylene glycol, glycerol and phthalic anhydride, but this no-solvent type polyurethane adhesive
Have that hardness is low, adhesion strength not, length hardening time, cured glue film surface irregularity, have the defects such as bubble.
Therefore, prepare nontoxic and adhesion strength is high, hardness is high, hardening time is short, cured glue film surfacing bubble-free
Non-solvent polyurethane adhesive become the important subject of this area.
Content of the invention
The technical problem to be solved is to overcome existing solvent borne polyurethane adhesive to there is toxicity and ring
Border is polluted, and existing no-solvent type polyurethane adhesive exists that hardness is low, adhesion strength not, length hardening time, solidification
The alveolate defect of film surface out-of-flatness afterwards, there is provided 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 friendliness.The polyurethane adhesive of the present invention
Stick hardness is high, and adhesive strength is big, and smooth surface bubble-free after solidification, can be used for construction material such as pvc material 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:
The invention provides a kind of combined polyether, it includes the component of following weight portion: polyether polyol a40～70 part,
10～20 parts of polyether polyol b, 20～40 parts of Oleum Ricini, 50～70 parts of filler, organo-metallic catalyst 0.02～0.08
Part, aerosil (gas phase sio2) 2～5 parts, 0.5～1 part of dehumidizer and 0.5～1.5 part of defoamer；
Described polyether polyol a is the modified polyether polyol of acrylonitrile-styrene graft, and described polyether polyol a exists
Viscosity at 25 DEG C is≤3500mpa s, and hydroxyl value is 25～29mgkoh/g, and water content is≤0.15%, and described percentage ratio is
The quality of water accounts for the percentage ratio of described polyether polyol a gross mass；
Viscosity at 25 DEG C for described polyether polyol b is 1100～1500mpa s, and hydroxyl value is 290～330mgkoh/
G, water content is≤0.15%, and described percentage ratio is that the quality of water accounts for the percentage ratio of described polyether polyol b gross mass.
In the present invention, described combined polyether does not include various organic solvents commonly used in the art, such as ketones solvent,
Esters solvent, ether solvent etc..
In the present invention, described viscosity can be obtained using the test of this area conventional method, for example, can be measured using rotary viscosity
?.
In the present invention, described water content is art technology term, refers to that the quality of water in sample accounts for sample gross mass
Percentage ratio.It is preferred that water content≤0.05% of described polyether polyol a.
In the present invention, the modified polyether polyol of described acrylonitrile-styrene graft refers to polyether polyol as parent,
Acrylonitrile and styrene are grafted monomers, and what by acrylonitrile and styrene, graft copolymerization in polyether polyol medium obtained changes
Property polyether polyol.The modified polyether polyol of described acrylonitrile-styrene graft can be obtained using this area conventional method, relatively
Goodly, in grafted monomers, cinnamic content is 60～70%, and the content of acrylonitrile is 30～40%, and described percentage ratio is respectively to connect
Branch monomer mass accounts for the percentage ratio of grafted monomers gross mass.
In the present invention, the solid content preferably 23.0～25.0% of described polyether polyol a.Described solid content is ability
Field technique term, refers to that the solid masses after sample drying accounts for the percentage ratio of sample gross mass before drying, the hundred of solid content herein
Divide and account for, than the solid masses for polyether polyol a after drying, the percentage ratio drying polyethers prior polyhydric alcohol a gross mass.
It is preferred that described polyether polyol a is to be by the trade mark that Shandong Lanxing Dongda Chemical Co., Ltd produces
The polyether polyol of pop36/28, this pop36/28 polyether polyol is the modified polyether polyol of acrylonitrile-styrene graft,
Viscosity≤3500mpa.s, hydroxyl value is 25～29mgkoh/g, water content≤0.05%, and solid content is 23.0～25.0%, dissociates
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).
It is preferred that described polyether polyol b is the trade mark that Hebei Yadong Chemical Group company limited produces be 8310 poly-
Ethoxylated polyhydric alcohol, the viscosity of this 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, described Oleum Ricini can be Oleum Ricini commonly used in the art, its typically by ricinoleic acid (9- thiazolinyl-
12- hydroxy octadecadienoic acid) form with glycerine esterification.It is preferred that the hydroxyl value of described Oleum Ricini is 150～170mgkoh/g, water content
For≤0.5%, iodine number is≤90mg/100g, and wherein, the percentage ratio of described water content is that the quality of water accounts for the total matter of described Oleum Ricini
The percentage ratio of amount.
In the present invention, described filler can be filler commonly used in the art, for strengthening finally be obtained gluing
The intensity of agent.It is preferred that described filler is Calcium Carbonate.
In the present invention, described organo-metallic catalyst can be organo-metallic catalyst commonly used in the art, for example, have
Machine bismuth metallic catalyst, replacement organic mercury metallic catalyst and Organic leadP metallic catalyst etc..It is preferred that described organic metal is urged
Agent is organo-bismuth metallic catalyst and/or Organic leadP metallic catalyst.Heretofore described organo-metallic catalyst acts primarily as
The effect of gel.It is preferred that the consumption of described organo-metallic catalyst is 0.04～0.06 part, described part is weight portion.
In the present invention, described aerosil can be aerosil commonly used in the art, conventional gas phase two
The dioxide-containing silica of silicon oxide is general >=99.5wt%, particle diameter is generally less than 100nm, such as 20～60nm.Described gas phase two
Silicon oxide can be prepared using method commonly used in the art, is typically prepared using chemical vapour deposition technique.This
In bright, described aerosil acts primarily as peptizaiton, is formed homogeneous for by fully dispersed for filler in polyether polyol
System.Described aerosil is preferably purchased from Jiangxi Ao Te fine powder company limited.
In the present invention, described dehumidizer can be dehumidizer commonly used in the art, such as calcium chloride, silica gel, calcium oxide
With montmorillonite etc..It is preferred that described dehumidizer is calcium chloride and/or calcium oxide.Heretofore described dehumidizer is mainly used in inhaling
A small amount of moisture content of residual in receipts raw material, it is to avoid during preparing polyurethane adhesive, the moisture content in raw material and isocyanates
Reaction forms small bubble, the performance of impact adhesive in surface of pressure-sensitive adhesive.
In the present invention, described defoamer can be defoamer commonly used in the art, preferably polyoxyethylene polyoxy third
One or more of alkene tetramethylolmethane ether, polyoxyethylene polyoxy propanol amidogen ether and polypropylene glycerol aether.
In the present invention, described combined polyether preferably may also include other components commonly used in the art, for example, disperse
Agent.Described dispersant can be dispersant commonly used in the art, such as fatty acid dispersant, aliphatic amide type dispersant
With esters dispersant etc., it is preferred that described dispersant is vinyl bis-stearamides and/or glycerol monostearate.Described point
The consumption of powder can select according to this area is conventional, preferably 0.6～1.5 part.
In a preferred embodiment of the present invention, described combined polyether is grouped into by the group of following weight portion: polyether polyol a
40～70 parts, 10～20 parts of polyether polyol b, 20～40 parts of Oleum Ricini, 50～70 parts of Calcium Carbonate, organo-metallic catalyst
0.02～0.08 part, 2～5 parts of aerosil, 0.5～1 part of dehumidizer and 0.5～1.5 part of defoamer；Described polyether polyols
Alcohol a is the modified polyether polyol of acrylonitrile-styrene graft, viscosity at 25 DEG C for described polyether polyol a is≤
3500mpa s, hydroxyl value is 25～29mgkoh/g, and water content is≤0.15%；Viscosity at 25 DEG C for described polyether polyol b
For 1100～1500mpa s, hydroxyl value is 290～330mgkoh/g, and water content is≤0.15%.
In another preferred embodiment of the present invention, described combined polyether is grouped into by the group of following weight portion: polyether polyols
40～70 parts of alcohol a, 10～20 parts of polyether polyol b, 20～40 parts of Oleum Ricini, 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 defoamer 0.5
～1.5 parts；Described polyether polyol a is the modified polyether polyol of acrylonitrile-styrene graft, and described polyether polyol a exists
Viscosity at 25 DEG C is≤3500mpa s, and hydroxyl value is 25～29mgkoh/g, and water content is≤0.15%；Described polyether polyols
Viscosity at 25 DEG C for the alcohol b is 1100～1500mpa s, and hydroxyl value is 290～330mgkoh/g, and water content is≤0.15%.
The two of technical scheme:
Present invention also offers the preparation method of combinations thereof polyethers.Described preparation method can be according to this area conventional method
Carry out, by each component mixing of described combined polyether, you can.It is preferred that described preparation method is carried out in accordance with the following steps: first will
Described aerosil and described filler mixing, obtain solid mixture, then again by described solid mixture with described
Polyether polyol a, described polyether polyol b, described Oleum Ricini, described organo-metallic catalyst, described dehumidizer and described disappear
Infusion mixes.When described combined polyether includes dispersant, described dispersant is preferably after obtaining solid mixture, solid with described
Body compound, described polyether polyol a, described polyether polyol b, described Oleum Ricini, described organo-metallic catalyst, described remove
Humectant and the mixing of described defoamer.
Wherein, described mixing can be carried out according to this area routine operation, typically puddle in kettle in rustless steel and carry out.This area
Technical staff all know described in be mixed into mix uniform to each component.Generally 2～5 hours time of described mixing.
The three of technical scheme:
Present invention also offers a kind of feedstock composition of polyurethane adhesive, described feedstock composition is included as the following group
Point: described combined polyether and polymethine polyphenyl polyisocyanate (abbreviation papi)；Described combined polyether and described multiple first
The mass ratio of Quito polyphenyl polyisocyanate is (4～3): 1.
Wherein, described polymethine polyphenyl polyisocyanate can be many for the many phenyl of polymethine commonly used in the art
Isocyanates, preferably one or more of pm-200,44v20, mr-200 and m20s.Described pm-200 is preferably by peaceful
Bo Wanhua polyurethane company limited provides, and described 44v20 is preferably provided by Baeyer polyurethane company limited, and described mr-200 is relatively
There is provided by Nippon Polyurethane Industry Co., Ltd., described m20s is preferably carried by Shanghai Basf Polyurethane Co., Ltd. goodly
For.
In the present invention, the feedstock composition of described 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 described polyurethane adhesive is grouped into by following group: institute
State combined polyether and polymethine polyphenyl polyisocyanate；Described combined polyether and described polymethine many phenyl polyisocyanic acid
The mass ratio of ester is (4～3): 1.
The four of technical scheme:
Present invention also offers a kind of preparation method of polyurethane adhesive, described preparation method comprise the steps: by
Described combined polyether and the mixing of described polymethine polyphenyl polyisocyanate, are reacted, are obtained final product.
Wherein, described mixing can be carried out according to this area routine operation.Those skilled in the art are mixed into described in all knowing
Mix uniform to each component.
Wherein, the condition of described reaction can be carried out according to the normal condition of this area.
The five of technical scheme:
Present invention also offers the polyurethane adhesive being obtained by above-mentioned preparation method.
The six of technical scheme:
Present invention also offers above-mentioned polyurethane adhesive produces and building water-proof paint in construction material bonding, filled board
In application.
Wherein, when described polyurethane adhesive is applied in construction material bonding, filled board production and building water-proof paint,
According to general knowledge, those skilled in the art all know how this uses, the raw material components combined polyether of typically described polyurethane adhesive
Separately deposit before use with polymethine polyphenyl polyisocyanate, do not mixed, again by described combined polyether during use
Reacted with the mixing of polymethine polyphenyl polyisocyanate.
On the basis of meeting common sense in the field, above-mentioned each optimum condition, can combination in any, obtain final product each preferable reality of the present invention
Example.
Agents useful for same of the present invention and raw material are all commercially available.
The positive effect of the present invention is:
(1) combined polyether of the present invention does not contain the solvent of any toxic and volatile, both will not during preparation and use
Human body is damaged and very environmental protection does not result in pollution.
(2) polyurethane adhesive that the combined polyether of the present invention is obtained after being acted on polymethine polyphenyl polyisocyanate
There is good adhesive strength and hardness, and the smooth bubble-free of surface of pressure-sensitive adhesive.
Specific embodiment
Further illustrate the present invention below by the mode of embodiment, but therefore do not limit the present invention to described reality
Apply among a scope.The experimental technique of unreceipted actual conditions in the following example, conventionally and condition, or according to business
Product description selects.
In following embodiments, polyether polyol pop36/28 used is the modified polyether polyols of acrylonitrile-styrene graft
Alcohol, is provided by Shandong Lanxing Dongda Chemical Co., Ltd, its viscosity≤3500mpa s, and hydroxyl value is 25～29mgkoh/g,
Water content≤0.05%, solid content is 23.0～25.0%, free acrylonitrile content≤10.0mg/kg, free styrene-content
≤ 50.0mg/kg, the styrene of grafting is (60～70): (30～40) with the mass ratio of the acrylonitrile of grafting.
Polyether polyol 8310 used by Hebei Yadong Chemical Group company limited provide, its viscosity be 1100～
1500mpa s, hydroxyl value is 290～330mgkoh/g, water content≤0.15%, k+Content≤50mg/kg.
The hydroxyl value of described Oleum Ricini is 150～170mgkoh/g, water content≤0.5%, iodine number≤90mg/100g.
Described aerosil is provided by Jiangxi Ao Te fine powder company limited.
Polymethine polyphenyl polyisocyanate pm-200 used is provided by Ningbo Wanhua Polyurethane Co., Ltd., 44v20
There is provided by Baeyer polyurethane company limited, mr-200 is provided by Nippon Polyurethane Industry Co., Ltd., and m20s is by Shanghai BASF
Polyurethane company limited provides.
Other raw materials and reagent are all commercially available.
Embodiment 1
I, a kind of combined polyether, its raw material components and consumption are as shown in the table:
| Component | Substance classes | Consumption |
| Polyether polyol a | Polyether polyol pop36/28 | 50 parts |
| Polyether polyol b | Polyether polyol 8310 | 15 parts |
| Oleum Ricini | Oleum Ricini | 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 |
| Defoamer | Polyoxyethylene polyoxypropylene tetramethylolmethane ether | 0.5 part |
The preparation method of this combined polyether is as follows: according to proportioning, by each component, in rustless steel puddling kettle, mix homogeneously is
Can, incorporation time is 2h.
Ii, a kind of polyurethane adhesive, its feedstock composition is by the combinations thereof polyethers for 4:1 for the mass ratio and polymethine
Polyphenyl polyisocyanate pm-200 forms.
The preparation method of this polyurethane adhesive is as follows: according to proportioning, combined polyether and pm-200 mixing is reacted, that is,
?.
Embodiment 2
I, a kind of combined polyether, its raw material components and consumption are as shown in the table:
The preparation method of this combined polyether is as follows: according to proportioning, by each component, in rustless steel puddling kettle, mix homogeneously is
Can, incorporation time is 2h.
Ii, a kind of polyurethane adhesive, its feedstock composition is by the combinations thereof polyethers for 3:1 for the mass ratio and polymethine
Polyphenyl polyisocyanate pm-200 forms.
The preparation method of this polyurethane adhesive is as follows: according to proportioning, combined polyether and pm-200 mixing is reacted, that is,
?.
Embodiment 3
I, a kind of combined polyether, its raw material components and consumption are as shown in the table:
| Component | Substance classes | Consumption |
| Polyether polyol a | Polyether polyol pop36/28 | 40 parts |
| Polyether polyol b | Polyether polyol 8310 | 20 parts |
| Oleum Ricini | Oleum Ricini | 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 |
| Defoamer | Polyoxyethylene polyoxy propanol amidogen ether | 1.5 part |
The preparation method of this combined polyether is as follows: according to proportioning, by each component, in rustless steel puddling kettle, mix homogeneously is
Can, incorporation time is 3h.
Ii, a kind of polyurethane adhesive, its feedstock composition is by the combinations thereof polyethers for 4:1 for the mass ratio and polymethine
Polyphenyl polyisocyanate pm-200 forms.
The preparation method of this polyurethane adhesive is as follows: according to proportioning, combined polyether and pm-200 mixing is reacted, that is,
?.
Embodiment 4
I, a kind of combined polyether, its raw material components and consumption are as shown in the table:
| Component | Substance classes | Consumption |
| Polyether polyol a | Polyether polyol pop36/28 | 60 parts |
| Polyether polyol b | Polyether polyol 8310 | 15 parts |
| Oleum Ricini | Oleum Ricini | 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 |
| Defoamer | Polypropylene glycerol aether | 0.8 part |
The preparation method of this combined polyether is as follows: according to proportioning, by each component, in rustless steel puddling kettle, mix homogeneously is
Can, incorporation time is 2.5h.
Ii, a kind of polyurethane adhesive, its feedstock composition is by the combinations thereof polyethers for 3:1 for the mass ratio and polymethine
Polyphenyl polyisocyanate pm-200 forms.
The preparation method of this polyurethane adhesive is as follows: according to proportioning, combined polyether and pm-200 mixing is reacted, that is,
?.
Embodiment 5
I, a kind of combined polyether, its raw material components and consumption are as shown in the table:
The preparation method of this combined polyether is as follows: according to proportioning, by each component, in rustless steel puddling kettle, mix homogeneously is
Can, incorporation time is 2h.
Ii, a kind of polyurethane adhesive, its feedstock composition is by the combinations thereof polyethers for 3:1 for the mass ratio and polymethine
Polyphenyl polyisocyanate pm-200 forms.
The preparation method of this polyurethane adhesive is as follows: according to proportioning, combined polyether and pm-200 mixing is reacted, that is,
?.
Embodiment 6
I, a kind of combined polyether, its raw material components and consumption are as shown in the table:
| Component | Substance classes | Consumption |
| Polyether polyol a | Polyether polyol pop36/28 | 50 parts |
| Polyether polyol b | Polyether polyol 8310 | 15 parts |
| Oleum Ricini | Oleum Ricini | 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 |
| Defoamer | Polyoxyethylene polyoxypropylene tetramethylolmethane ether | 0.5 part |
The preparation method of this combined polyether is as follows: according to proportioning, by each component, in rustless steel puddling kettle, mix homogeneously is
Can, incorporation time is 2.5h.
Ii, a kind of polyurethane adhesive, its feedstock composition is by the combinations thereof polyethers for 4:1 for the mass ratio and polymethine
Polyphenyl polyisocyanate 44v20 forms.
The preparation method of this polyurethane adhesive is as follows: according to proportioning, combined polyether and 44v20 mixing is reacted, that is,
?.
Embodiment 7
I, a kind of combined polyether, its raw material components and consumption are as shown in the table:
| Component | Substance classes | Consumption |
| Polyether polyol a | Polyether polyol pop36/28 | 50 parts |
| Polyether polyol b | Polyether polyol 8310 | 15 parts |
| Oleum Ricini | Oleum Ricini | 35 parts |
| Filler | Calcium Carbonate | 65 parts |
| Organo-metallic catalyst | Organic leadP metallic catalyst | 0.04 part |
| Dispersant | Glycerol monostearate | 0.6 part |
| Aerosil | Aerosil | 3 parts |
| Dehumidizer | Calcium chloride | 0.5 part |
| Defoamer | Polyoxyethylene polyoxy propanol amidogen ether | 1 part |
The preparation method of this combined polyether is as follows: according to proportioning, by each component, in rustless steel puddling kettle, mix homogeneously is
Can, incorporation time is 2h.
Ii, a kind of polyurethane adhesive, its feedstock composition is by the combinations thereof polyethers for 4:1 for the mass ratio and polymethine
Polyphenyl polyisocyanate mr-200 forms.
The preparation method of this polyurethane adhesive is as follows: according to proportioning, combined polyether and mr-200 mixing is reacted, that is,
?.
Embodiment 8
I, a kind of combined polyether, its raw material components and consumption are as shown in the table:
The preparation method of this combined polyether is as follows: according to proportioning, by each component, in rustless steel puddling kettle, mix homogeneously is
Can, incorporation time is 2h.
Ii, a kind of polyurethane adhesive, its feedstock composition is by the combinations thereof polyethers for 4:1 for the mass ratio and polymethine
Polyphenyl polyisocyanate m20s forms.
The preparation method of this polyurethane adhesive is as follows: according to proportioning, combined polyether and m20s mixing, reaction obtains final product.
Comparative example 1
I, a kind of combined polyether, its raw material components and consumption are as shown in the table:
The preparation method of this combined polyether is as follows: according to proportioning, by each component, in rustless steel puddling kettle, mix homogeneously is
Can, incorporation time is 2.5h.
Ii, a kind of polyurethane adhesive, its feedstock composition is by the combinations thereof polyethers for 4:1 for the mass ratio and polymethine
Polyphenyl polyisocyanate pm-200 forms.
The preparation method of this polyurethane adhesive is as follows: according to proportioning, combined polyether and pm-200 mixing is reacted, that is,
?.
Comparative example 2
I, a kind of combined polyether, its raw material components and consumption are as shown in the table:
| Component | Substance classes | Consumption |
| Polyether polyol a | Polyether polyol pop36/28 | 65 parts |
| Polyether polyol b | Polyether polyol 310 | 10 parts |
| Oleum Ricini | Oleum Ricini | 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 |
| Defoamer | Polypropylene glycerol aether | 1.5 part |
Wherein, polyether polyol 310 used is provided by Jurong Ningwu New Materials Development Co., Ltd., and its viscosity is 200-
300mpa.s, hydroxyl value is 163-173mgkoh/g, water content≤0.15%, k+Content≤5mg/kg.
The preparation method of this combined polyether is as follows: according to proportioning, by each component, in rustless steel puddling kettle, mix homogeneously is
Can, incorporation time is 2.5h.
Ii, a kind of polyurethane adhesive, its feedstock composition is by the combinations thereof polyethers for 4:1 for the mass ratio and polymethine
Polyphenyl polyisocyanate pm-200 forms.
The preparation method of this polyurethane adhesive is as follows: according to proportioning, combined polyether and pm-200 mixing is reacted, that is,
?.
Effect example 1
The response time of testing example 1～5 polyurethane adhesive, hardening time, adhesive strength, hardness and outward appearance, with
The bi-component no-solvent type polyurethane binder of model pu88 that Shi Xuanyong Shanghai Shou Xing Industrial Co., Ltd. provides is as right
According to group.Wherein, the response time refer to polyurethane adhesive combination viscosity change from small to big to compositionss substantially flowable when
Between；Refer to the time that surface of pressure-sensitive adhesive is hardening, through pressing no deformation hardening time；Adhesive strength is pressed gb/t2791-1995 standard and is surveyed
Examination, hardness presses gb/t531-1999 standard testing, and outward appearance is using range estimation.Concrete test result is as shown in the table.
As seen from the above table, the polyurethane adhesive smooth surface depletion of QI being obtained with the non-solvent combined polyether of the present invention
Bubble, your the d hardness that continues is high, is significantly improved compared to existing no-solvent type polyurethane binder, and hardening time is shorter, glue
Knotting strength is larger, and combination property is good.The effect of embodiment 6～8 is close with embodiment 1～5.
In comparative example 1, the consumption of aerosil is 1 part, and the consumption of dispersant is 0.5 part, because filler fails
Fully dispersed in system, have impact on the hardness of final binding agent.The viscosity of polyether polyol b and hydroxyl value used in comparative example 2
The lower limit limiting less than the present invention, there are a little minute bubbles on result gained polyurethane adhesive surface, and hardness is significantly lower than this
Inventive embodiments.
Claims (10)
1. a kind of combined polyether is it is characterised in that described combined polyether includes the component of following weight portion: polyether polyol a 40
～70 parts, 10～20 parts of polyether polyol b, 20～40 parts of Oleum Ricini, 50～70 parts of filler, organo-metallic catalyst 0.02
～0.08 part, 2～5 parts of aerosil, 0.5～1 part of dehumidizer and 0.5～1.5 part of defoamer；
Described polyether polyol a is the modified polyether polyol of acrylonitrile-styrene graft, and described polyether polyol a is at 25 DEG C
Under viscosity be≤3500mpa s, hydroxyl value is 25～29mgkoh/g, and water content is≤0.15%, and described percentage ratio is water
Quality accounts for the percentage ratio of described polyether polyol a gross mass；
Viscosity at 25 DEG C for described polyether polyol b is 1100～1500mpa s, and hydroxyl value is 290～330mgkoh/g, contains
The water yield is≤0.15%, and described percentage ratio is that the quality of water accounts for the percentage ratio of described polyether polyol b gross mass.
2. combined polyether as claimed in claim 1 is it is characterised in that styrene in the grafted monomers of described polyether polyol a
Content be 60～70%, the content of acrylonitrile is 30～40%, and described percentage ratio accounts for grafted monomers for each grafted monomers quality
The percentage ratio of gross mass；
And/or, water content≤0.05% of described polyether polyol a；
And/or, the solid content of described polyether polyol a is 23.0～25.0%, and described percentage ratio is polyether polyol a after drying
Solid masses account for dry polyethers prior polyhydric alcohol a gross mass percentage ratio.
3. combined polyether as claimed in claim 1 or 2 is it is characterised in that described polyether polyol a is polyether polyol
pop36/28；
And/or, described polyether polyol b is polyether polyol 8310.
4. combined polyether as claimed in claim 1 it is characterised in that described Oleum Ricini hydroxyl value be 150～170mgkoh/g,
Water content is≤0.5%, and iodine number is≤90mg/100g, and described percentage ratio is that the quality of water accounts for the hundred of described Oleum Ricini gross mass
Divide ratio；
And/or, described filler is Calcium Carbonate；
And/or, described organo-metallic catalyst is organo-bismuth metallic catalyst and/or Organic leadP metallic catalyst；
And/or, described dehumidizer is calcium chloride and/or calcium oxide；
And/or, described defoamer is polyoxyethylene polyoxypropylene tetramethylolmethane ether, polyoxyethylene polyoxy propanol amidogen ether and polyoxy third
One or more of alkene glycerin ether；
And/or, described combined polyether also includes dispersant, and the consumption of described dispersant is 0.6～1.5 part, and described part is attached most importance to
Amount part；
And/or, described combined polyether does not include organic solvent, and described organic solvent is that ketones solvent, esters solvent and ethers are molten
One or more of agent.
5. combined polyether as claimed in claim 4 it is characterised in that described organo-metallic catalyst consumption be 0.04～
0.06 part；
And/or, described dispersant is vinyl bis-stearamides and/or glycerol monostearate.
6. a kind of preparation method of combined polyether as described in any one as Claims 1 to 5 is it is characterised in that described preparation method
It is by each component mixing of described combined polyether, you can；
It is preferred that described preparation method is carried out in accordance with the following steps: first described aerosil and described filler are mixed,
Obtain solid mixture, then again by described solid mixture and described polyether polyol a, described polyether polyol b, described castor
Oleum Sesami, described organo-metallic catalyst, described dehumidizer and the mixing of described defoamer.
7. a kind of feedstock composition of polyurethane adhesive is it is characterised in that described feedstock composition includes following component: combination
Polyethers and polymethine polyphenyl polyisocyanate；Described combined polyether is that the combination as described in any one of Claims 1 to 5 gathers
Ether；The mass ratio of described combined polyether and described polymethine polyphenyl polyisocyanate is (4～3): 1；
It is preferred that described polymethine polyphenyl polyisocyanate be polymethine polyphenyl polyisocyanate pm-200, repeatedly
Methyl polyphenyl polyisocyanate 44v20, polymethine polyphenyl polyisocyanate mr-200 and polymethine many phenyl polyisocyanate
One or more of cyanate m20s；
It is preferred that described feedstock composition does not include organic solvent, described organic solvent is ketones solvent, esters solvent and ethers
One or more of solvent.
8. a kind of preparation method of polyurethane adhesive is it is characterised in that described preparation method comprises the steps: to want right
Ask the combined polyether described in 7 and the mixing of described polymethine polyphenyl polyisocyanate, reacted, obtain final product.
9. the polyurethane adhesive that a kind of preparation method as claimed in claim 8 is obtained.
10. a kind of polyurethane adhesive as claimed in claim 9 produces and building water-proof paint in construction material bonding, filled board
In application.
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