CN107142006A - A kind of bonding silane coupling agent of raising metal surface polyurethane elastomer coat adhesive force and preparation method thereof - Google Patents
A kind of bonding silane coupling agent of raising metal surface polyurethane elastomer coat adhesive force and preparation method thereof Download PDFInfo
- Publication number
- CN107142006A CN107142006A CN201710430924.9A CN201710430924A CN107142006A CN 107142006 A CN107142006 A CN 107142006A CN 201710430924 A CN201710430924 A CN 201710430924A CN 107142006 A CN107142006 A CN 107142006A
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- silane coupling
- coupling agent
- polyurethane elastomer
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- metal surface
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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
- C09D175/14—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
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- 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
- C08G18/08—Processes
- C08G18/16—Catalysts
- C08G18/22—Catalysts containing metal compounds
- C08G18/222—Catalysts containing metal compounds metal compounds not provided for in groups C08G18/225 - C08G18/26
-
- 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
- C08G18/08—Processes
- C08G18/16—Catalysts
- C08G18/22—Catalysts containing metal compounds
- C08G18/227—Catalysts containing metal compounds of antimony, bismuth or arsenic
-
- 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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Abstract
A kind of bonding silane coupling agent of raising metal surface polyurethane elastomer coat adhesive force of the present invention belongs to paint field, the present invention is made up of silane coupling agent base-material and the component of accelerator two, the silane coupling agent base-material, it is made up of damp solidifying polyurethane resin, adhesion promoter, defoamer and organic solvent, the damp solidifying polyurethane resin is the reaction product of diisocyanate and alcoholysis castor oil, the silane coupling agent accelerator, is made up of the mixed catalyst and organic solvent of organic zinc and organo-bismuth；Silane coupling agent base-material is well mixed with accelerator by proportioning, using modes such as spraying, brushing and roller coating, it is applied over substrate surface, after surface drying, no-solvent polyurethane elastomer coating is applied in the silane coupling agent surface of surface drying, after dry solidification 7 days, no-solvent polyurethane elastomer coating has excellent adhesive strength in metal surface.
Description
Technical field
A kind of bonding silane coupling agent of raising metal surface polyurethane elastomer coat adhesive force of the present invention and preparation method thereof
Belong to paint field, and in particular to modified polyurethane paint.
Background technology
No-solvent polyurethane elastomer coating have excellent wear-resisting, shock resistance, anti-cavitation corrosion, water-fast, insulation, it is corrosion-resistant and
The combination properties such as damping, and VOC free pollution, are a kind of environment-friendly metal protective coatings of permanent protective property energy, are widely used in water
The various fields such as electricity, ship, petrochemical industry, mining machinery, bridge, hydraulic.
With metal base have reliable adhesive strength be no-solvent polyurethane elastomer coating play its protective effect and
Functional premise.But the rate of drying of no-solvent polyurethane elastomer coating is fast, when directly applying to metal surface, wetability
Can be poor, adhesive strength is low, under the conditions of such as cavitating, wash away and impact in many operating modes, easy to fall off and lose safeguard function, limitation
Its application under related working condition, using routine and the higher epoxy primer of metal base adhesive strength, there is also poly-
Urethane elastomer coating is not enough with epoxy coating interfacial bonding strength, the problem of intermediate peeling occur in use.
For the surface of identical roughness, the molecular force for depending primarily on coating of the bonding force size of coating.Apply
The generation of layer bonding force mainly has two stages.First stage is liquid polymers molecule by means of Brownian movement to matrix surface
Diffusion, makes polar group or chain link that both are all close to each other；Two kinds of intermolecular distances of second stage progressively shorten, and produce
Mutual suction-operated, reaches stabilization.
No-solvent polyurethane elastomer coating is because of curing reaction speed, and polymer molecule is to base diffusion into the surface and shape
Difficulty into stronger adhesion is larger, therefore prepare has good bonding strong with metal base and polyurethane elastomer coat simultaneously
The transition silane coupling agent of degree, can further improve the reliability of no-solvent polyurethane elastomer coating, to polyurethane elastomer coat
Application have great importance.
The content of the invention
It is an object of the invention to provide a kind of bonding primary coat of raising metal surface polyurethane elastomer coat adhesive force
Agent, overcomes existing no-solvent polyurethane elastomer coating in the problem of metallic substrate surface poor adhesive force, makes no-solvent polyurethane
Elastomer obtains high bond strength in metal surface, effectively solves polyurethane elastomer coat and the bar such as is cavitating, washes away and impacting
The problem that comes off under part.
The purpose of the present invention is achieved through the following technical solutions：
First, the bonding silane coupling agent of a kind of raising metal surface polyurethane elastomer coat adhesive force of the invention, by silane coupling agent base-material
With the component of accelerator two composition, by mass, its silane coupling agent base-material is 100 parts, and accelerator is 10~50 parts, the silane coupling agent base
Material, its component formula by mass is as follows：
Damp solidifying polyurethane resin：
60~80 parts of the reaction product of diisocyanate and alcoholysis castor oil；
Adhesion promoter：
0.4~0.8 part of epoxy silane coupling；
Defoamer：
0.3~0.8 part of modified polyorganosiloxane, polyethers or higher alcohols defoamer；
Levelling agent：
0.5~1 part of acrylate copolymer, organosilicon or fluorocarbons class；
Organic solvent：
15~25 parts of the mixture of butyl acetate and dimethylbenzene.
The damp solidifying polyurethane resin, by mass, the reaction product of its diisocyanate and alcoholysis castor oil it
The ratio of diisocyanate and alcoholysis castor oil is 40~50 ︰ 20~30, and wherein diisocyanate is diphenylmethane diisocyanate
One or both of ester, IPDI and toluene di-isocyanate(TDI).
The organic solvent, by mass, the ratio of butyl acetate and dimethylbenzene is 30 ︰ 40~70.
The accelerator, its component formula by mass is as follows：
Mixed catalyst：
0.02~0.08 part of the mixture of organic zinc and organo-bismuth；
Organic solvent：
15~25 parts of dimethylbenzene.
The mixed catalyst, by mass, the ratio of organic zinc and organo-bismuth for the ︰ of You Ji Xin ︰ organo-bismuths=80 10~
20。
2nd, a kind of preparation method of the bonding silane coupling agent of raising metal surface polyurethane elastomer coat adhesive force of the invention is：
（1）Damp solidifying polyurethane resin, adhesion promoter, defoamer, levelling agent and organic solvent are added to by proportioning
In dispersion tank, high-speed stirred is uniformly dispersed, and obtains silane coupling agent base-material；
（2）By mass, according to step（1）The total amount of the silane coupling agent base-material of preparation, is 100 ︰ 10 by silane coupling agent Ji Liao ︰ accelerator
~50 parts of ratio, prepares accelerator；
（3）Mixed catalyst and organic solvent are added in dispersion tank by proportioning, high-speed stirred is uniform, is promoted agent.
Described damp solidifying polyurethane resin making step is：
A certain amount of diisocyanate is taken into reactor, Er Yi Qing Suan Zhi ︰ alcoholysis castor oil ratio is 40~50 ︰ 20 by mass
~30 ratio, is gradually added alcoholysis castor oil, stirs, and is heated to 75 DEG C, is incubated 2~4h, is cooled to normal temperature, obtains institute
State damp solidifying polyurethane resin.
3rd, the application method of the bonding silane coupling agent of a kind of raising metal surface polyurethane elastomer coat adhesive force of the invention
It is：
Matched according to quality meter, silane coupling agent base-material is well mixed with accelerator, using modes such as spraying, brushing and roller coating, applied
It is applied to after substrate surface, surface drying, by the construction method of no-solvent polyurethane elastomer coating, no-solvent polyurethane elastomer is applied
Layer is applied in the silane coupling agent surface of surface drying, and dry solidification is after 7 days, and no-solvent polyurethane elastomer coating is to have in metal surface
Excellent adhesive strength.
A kind of bonding silane coupling agent of raising metal surface polyurethane elastomer coat adhesive force of the present invention uses moisture-curable
Polyurethane resin be main body film forming matter, it can individually solidify in atmosphere；Use organic zinc and organo-bismuth environment-friendly type catalyst
As accelerator, the rate of drying of damp solidifying polyurethane resin can be accelerated, by adjusting damp solidifying polyurethane resin and rush
The surface drying time that the ratio for entering agent can adjust silane coupling agent is conducive to solvent-free poly- ammonia by any time of half an hour to 12 small times
The arrangement of ester elastomer coating construction period, it is to avoid because construction period is unreasonable, causes no-solvent polyurethane elastomer coating to exist
Bonding bottom is unseasoned or crosses application in the state of solidification, and influences the adhesive force of elastomer coating.The polyurethane of moisture-curable
Resin is prepared by diisocyanate and alcoholysis castor oil, and it has excellent matching with no-solvent polyurethane elastomer, wherein
Chain extender diamine or diol reaction in substantial amounts of reactive isocyanate groups, with no-solvent polyurethane elastomer, make nothing
Solvent polyurethane elastomer is chemically bonded with silane coupling agent formation, it is ensured that its interfacial bonding strength；Alcoholysis castor oil contains multiple hydroxyls
In base, the polyurethane resin prepared with di-isocyanate reaction, polar group content is higher, and the silane coupling agent after solidification can be with metal
Surface forms higher adhesive strength, reacts the silane coupling agent degree of cross linking after solidification greatly with moisture, cohesive strength is high.In addition, this hair
It is bright that a small amount of silane coupler is added in formulation for coating material, further improve the adhesive strength of silane coupling agent and metal base.
After cohesive silane coupling agent of the present invention being used in metal surfaces such as carbon steel, stainless steel, aluminium alloy and copper alloys, then
No-solvent polyurethane elastomer coating is applied, attachment of the no-solvent polyurethane elastomer coating in metal surface can be effectively improved
Power, the MPa of its bond strength >=12, it is ensured that coated polyurethane elastomer coating is not fallen off under cavitation erosion, Scouring Condition.
Embodiment
The present invention is further illustrated by the following examples.
Embodiment 1：
First, damp solidifying polyurethane resin-made is standby：
By mass, diisocyanate is taken（Methyl diphenylene diisocyanate）80 parts, into reactor, are gradually added in batches
40 parts of alcoholysis castor oil, stirs, and is heated to 75 DEG C, is incubated 2~4h, is cooled to normal temperature, obtains damp solidifying polyurethane tree
Fat.
2nd, the preparation of silane coupling agent is bonded：
Match 60 parts of damp solidifying polyurethane resin, adhesion promoter by mass（KH560）0.4 part, defoamer（It is modified
Polysiloxanes Defom 5500）0.3 part, levelling agent (acrylate copolymer Levelol 495）0.5 part and organic solvent（Second
The ︰ 40 of sour Ding Zhi ︰ dimethylbenzene=30）15 parts, it is added in dispersion tank, high-speed stirred is uniformly dispersed, obtains silane coupling agent base-material；
By mass, organic zinc is taken（KRZN1）80 parts and organo-bismuth（KRBi-1）10 parts are mixed evenly, and obtain mixed catalytic
Agent；
By mass, by 0.02 part of mixed catalyst and organic solvent（Dimethylbenzene）15 parts are mixed evenly, and are promoted agent
Component.
10 parts of accelerator are added in 100 parts of silane coupling agent base-materials in use, constituting by mass, after being well mixed, can be used
The mode applications such as spraying, brushing and roller coating.Paint film surface drying time 12 hours or so.
Embodiment 2：
First, damp solidifying polyurethane resin-made is standby：
By mass, diisocyanate is taken（Toluene di-isocyanate(TDI) TDI）100 parts, into reactor, are gradually added alcohol in batches
60 parts of castor oil is solved, is stirred, 75 DEG C are heated to, 2~4h is incubated, is cooled to normal temperature, obtains damp solidifying polyurethane resin.
2nd, the preparation of silane coupling agent is bonded：
Match 80 parts of damp solidifying polyurethane resin, adhesion promoter by mass（KH560）0.8 part, defoamer（It is modified
Polysiloxanes Defom 5500）0.8 part, levelling agent (acrylate copolymer Levelol 495）1 part and organic solvent（Acetic acid
The ︰ 70 of Ding Zhi ︰ dimethylbenzene=30）25 parts, it is added in dispersion tank, high-speed stirred is uniformly dispersed, obtains silane coupling agent base-material；
By mass, organic zinc is taken（KRZN1）80 parts and organo-bismuth（KRBi-1）20 parts are mixed evenly, and obtain mixed catalytic
Agent；
By mass, by 0.08 part of mixed catalyst and organic solvent（Dimethylbenzene）25 parts are mixed evenly, and are promoted agent
Component.
50 parts of accelerator are added in 100 parts of silane coupling agent base-materials in use, constituting by mass, after being well mixed, can be used
The mode applications such as spraying, brushing and roller coating.Paint film surface drying time 0.5 hour or so.
Embodiment 3：
First, damp solidifying polyurethane resin-made is standby：
By mass, diisocyanate is taken（70 parts of methyl diphenylene diisocyanate, 20 parts of IPDI）Extremely
In reactor, 50 parts of alcoholysis castor oil is gradually added in batches, is stirred, be heated to 75 DEG C, be incubated 2~4h, be cooled to often
Temperature, obtains damp solidifying polyurethane resin.
2nd, the preparation of silane coupling agent is bonded：
Match 70 parts of damp solidifying polyurethane resin, adhesion promoter by mass（KH560）0.6 part, defoamer（It is modified
Polysiloxanes Defom 5500）0.5 part, levelling agent (acrylate copolymer Levelol 495）0.8 part and organic solvent（Second
The ︰ 60 of sour Ding Zhi ︰ dimethylbenzene=30）20 parts, it is added in dispersion tank, high-speed stirred is uniformly dispersed, obtains silane coupling agent base-material；
By mass, organic zinc is taken（KRZN1）80 parts and organo-bismuth（KRBi-1）15 parts are mixed evenly, and obtain mixed catalytic
Agent；
By mass, by 0.08 part of mixed catalyst and organic solvent（Dimethylbenzene）25 parts are mixed evenly, and are promoted agent
Component.
30 parts of accelerator are added in 100 parts of silane coupling agent base-materials in use, constituting by mass, after being well mixed, can be used
The mode applications such as spraying, brushing and roller coating.Paint film surface drying time 6 hours or so.
Claims (5)
1. a kind of bonding silane coupling agent of raising metal surface polyurethane elastomer coat adhesive force, by silane coupling agent base-material and accelerator
Two components are constituted, by mass, and its silane coupling agent base-material is 100 parts, and accelerator is 10~50 parts, the silane coupling agent base-material, and it is pressed
Quality meter component formula is as follows：
Damp solidifying polyurethane resin：
60~80 parts of the reaction product of diisocyanate and alcoholysis castor oil；
Adhesion promoter：
0.4~0.8 part of epoxy silane coupling；
Defoamer：
0.3~0.8 part of modified polyorganosiloxane, polyethers or higher alcohols defoamer；
Levelling agent：
0.5~1 part of acrylate copolymer, organosilicon or fluorocarbons class；
Organic solvent：
15~25 parts of the mixture of butyl acetate and dimethylbenzene；
The accelerator, its component formula by mass is as follows：
Mixed catalyst：
0.02~0.08 part of the mixture of organic zinc and organo-bismuth；
Organic solvent：
15~25 parts of dimethylbenzene.
2. a kind of bonding silane coupling agent of raising metal surface polyurethane elastomer coat adhesive force according to claim 1,
Characterized in that, damp solidifying polyurethane resin, by mass, its diisocyanate and the two of the reaction product of alcoholysis castor oil
The ratio of isocyanates and alcoholysis castor oil be 40~50 ︰ 20~30, wherein diisocyanate be methyl diphenylene diisocyanate,
One or both of IPDI and toluene di-isocyanate(TDI).
3. a kind of bonding silane coupling agent of raising metal surface polyurethane elastomer coat adhesive force according to claim 1,
Characterized in that, mixed catalyst, by mass, the ratio of organic zinc and organo-bismuth is the ︰ 10~20 of You Ji Xin ︰ organo-bismuths=80.
4. a kind of bonding silane coupling agent of raising metal surface polyurethane elastomer coat adhesive force according to claim 1,
Characterized in that, preparation process is as follows：
（1）Damp solidifying polyurethane resin, adhesion promoter, defoamer, levelling agent and organic solvent are added to by proportioning
In dispersion tank, high-speed stirred is uniformly dispersed, and obtains silane coupling agent base-material；
（2）By mass, according to step（1）The total amount of the silane coupling agent base-material of preparation, is 100 ︰ 10 by silane coupling agent Ji Liao ︰ accelerator
~50 parts of ratio, prepares accelerator；
（3）Mixed catalyst and organic solvent are added in dispersion tank by proportioning, high-speed stirred is uniform, is promoted agent.
5. a kind of bonding silane coupling agent of raising metal surface polyurethane elastomer coat adhesive force according to claim 1,
Characterized in that, damp solidifying polyurethane resin making step is：
A certain amount of diisocyanate is taken into reactor, Er Yi Qing Suan Zhi ︰ alcoholysis castor oil ratio is 40~50 ︰ 20 by mass
~30 ratio, is gradually added alcoholysis castor oil, stirs, and is heated to 75 DEG C, is incubated 2~4h, is cooled to normal temperature, obtains institute
State damp solidifying polyurethane resin.
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| CN201710430924.9A CN107142006A (en) | 2017-06-09 | 2017-06-09 | A kind of bonding silane coupling agent of raising metal surface polyurethane elastomer coat adhesive force and preparation method thereof |
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Cited By (6)
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| CN109736096A (en) * | 2019-02-19 | 2019-05-10 | 东莞市喜宝体育用品科技有限公司 | A kind of bamboo charcoal fiber flies to knit vamp |
| CN109836939A (en) * | 2019-03-29 | 2019-06-04 | 顾巍 | A kind of anti-cement adhesion coating of metal form and preparation method thereof |
| CN110183610A (en) * | 2019-05-21 | 2019-08-30 | 哈尔滨工程大学 | A kind of anti-cavitation corrosion elastic polyurethane layer and preparation method thereof |
| CN110452621A (en) * | 2019-09-03 | 2019-11-15 | 宁波捷傲创益新材料有限公司 | A kind of bonding silane coupling agent and preparation method thereof for solid tire reflective strip |
| CN113522689A (en) * | 2021-07-27 | 2021-10-22 | 哈尔滨工业大学 | Metal surface pretreatment device |
| CN113717633A (en) * | 2021-05-08 | 2021-11-30 | 杭州师范大学 | Primer for bonding silicon resin thermal protection coating and preparation method and application thereof |
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| CN109736096A (en) * | 2019-02-19 | 2019-05-10 | 东莞市喜宝体育用品科技有限公司 | A kind of bamboo charcoal fiber flies to knit vamp |
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| CN109836939B (en) * | 2019-03-29 | 2023-10-24 | 顾巍 | Cement adhesion preventing coating for metal template and preparation method thereof |
| CN110183610A (en) * | 2019-05-21 | 2019-08-30 | 哈尔滨工程大学 | A kind of anti-cavitation corrosion elastic polyurethane layer and preparation method thereof |
| CN110452621A (en) * | 2019-09-03 | 2019-11-15 | 宁波捷傲创益新材料有限公司 | A kind of bonding silane coupling agent and preparation method thereof for solid tire reflective strip |
| CN113717633A (en) * | 2021-05-08 | 2021-11-30 | 杭州师范大学 | Primer for bonding silicon resin thermal protection coating and preparation method and application thereof |
| CN113522689A (en) * | 2021-07-27 | 2021-10-22 | 哈尔滨工业大学 | Metal surface pretreatment device |
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Application publication date: 20170908 |