CN111909648B - Green quick-drying AB glue of stable performance - Google Patents

Abstract

A green quick-drying AB adhesive with stable performance relates to a modified polyurethane adhesive, in particular to a high-performance two-component adhesive capable of bonding metal such as steel and the like and hard non-metal base materials, and provides a two-component environment-friendly polyurethane adhesive which is fast in curing, good in wettability to steel, high in bonding strength, stable in performance, low in cost and easy to prepare. The alkali-resistant polyether polyol and water glass or modified water glass are compounded or combined with a proper amount of auxiliary agent, or the polyether polyol in the component A containing the water glass or the modified water glass in the technical scheme is transferred into the component containing polyisocyanate, and the corresponding proportion is adjusted at the same time. The high-strength polyurethane adhesive can be quickly cured at a lower temperature without a catalyst, realizes early strength and high strength, has good adhesion, and has good operability and storage stability.

Description

Green quick-drying AB glue of stable performance

Technical Field

The invention relates to a divisional application of 'environment-friendly steel adhesive' in a Chinese patent application with the application number of 2019104835915, the priority date of 2019-06-04, 2018-06-04.

The invention relates to the field of polyurethane adhesives, in particular to a high-performance double-component environment-friendly quick-drying AB adhesive capable of adhering metal and hard non-metal base materials such as steel.

Background

The polyurethane adhesive has carbamate group (-NHCOO-) or isocyanate group (terminal-NCO) in the molecular chain structure, and can perform chain extension, branching and crosslinking reaction with active hydrogen-containing components including water glass and a substrate interface to finally form a solidified body with certain bonding strength and mechanical strength. However, conventional solvent-free polyurethane adhesives such as PUR are expensive, require high temperature heating and use special equipment when applied; solvent type polyurethane is toxic and harmful and pollutes the environment; the waterborne polyurethane has high manufacturing cost, slow curing, poor water resistance and weak bonding force to the poor wettability of nonpolar base materials such as steel and the like. Generally, the bonding strength of a polyurethane adhesive is difficult to exceed 8Mpa due to the limitation of material properties, and the maximum strength can be reached only within three days or even seven days at normal temperature, so that the polyurethane adhesive is not suitable for being used as a steel adhesive. The water glass is a traditional inorganic sizing material, has small viscosity, good fluidity, wide sources, low cost, almost no toxicity or pollution, can accelerate the curing reaction after being mixed with a certain curing agent such as sodium fluosilicate to generate silica gel with stronger bonding property, has good affinity to concrete, can play a role in bonding, seepage prevention and reinforcement on building structures, but has brittle colloid, poor water resistance, easy generation of alkali aggregate effect, poor interface wettability on metal substrates such as steel, small bonding strength and poor stability of a bonding body. In view of these problems, the chinese patent application CN103627330a "a compound adhesive" is prepared by adding a synergist and an additive to water glass, and adding a foaming adhesive formed by a polyester polyol and/or a polyether polyol prepolymer and a proper amount of a solvent to an isocyanate component, so that these problems are also effectively solved, and the adhesive can be cured quickly without a catalyst; chinese patent application CN104910817A "an environment-friendly composite resin and an adhesive and a coating based on the resin" further improves the performance of a sizing material, improves the stability of the sizing material and reduces the production cost; in order to adapt to industrial application, the chinese patent application CN105885704a "a low viscosity high strength environment-friendly two-component glue solution and its preparation method" also improves the adhesive property of the glue material greatly by adding a proper amount of silane coupling agent and dodecyl glycol ester in the water glass component, and the glue application amount has the viscosity capable of mechanical spraying; chinese patent application CN 104910817A' an inorganic-organic high environmental protection double-component adhesive and a preparation method thereof also provide an effective solution for the problem of inhomogeneous mixing of a water glass-polyurethane system containing a filler and a solvent; chinese patent application CN107488431A "aqueous oily low-viscosity environment-friendly two-component adhesive and preparation method thereof" analyzes the cause of the hair growing phenomenon of the composite adhesive of water glass aqueous component and polyurethane oily component and provides an effective solution. Although the series of water glass polyurethane composite adhesives can replace a plurality of solvent adhesives for buildings and industries, have obvious cost performance advantages and application prospects, are very suitable for bonding base materials such as wood, stone, ceramics, cement and the like or between the base materials and steel, however, a large amount of organic solvent is often added for activating prepolymers in a water glass-polyurethane system to achieve better bonding performance, the water glass-polyurethane composite adhesives are not suitable for occasions requiring special environmental protection and safety, and when the organic solvent is not added or only slightly added, a large amount of filler is often added into the component A to influence the fluidity, and precipitates and dead sediments are easily generated. However, because of the existence of a large amount of water glass and high molecular hard segment components, the interface bonding force with metal substrates such as steel is limited, the steel-steel bonding strength, especially the shear strength, is always difficult to be stabilized over 5Mpa, and the rigidity is large and the flexibility is insufficient, the interface is usually damaged in a steel-steel opposite-pull bonding test, the steel-steel bonding strength is not suitable for bonding between steel and steel in a movable structure or an object, the steel-steel bonding strength cannot be used as a structural adhesive, and a catalyst is usually added for surface drying and primary curing within 3 minutes or 5 minutes, and tests show that the stability of the steel-steel bonding effect is often influenced when an organic amine catalyst or an organic tin catalyst is added into a water glass-polyurethane system adhesive containing a large amount of water glass, the catalyst is easy to hydrolyze and lose efficacy when added into the component A, the storage stability is also influenced when added into the component B, and attempts to improve the wettability of the steel-steel interface and improve the interface bonding force by adding a proper amount of small molecular components and adhesion promoters for compensating the performance loss caused by adding the catalyst are also slight. The inventor tries to add a small amount of polyester, polyester polyol, plasticizer and the like into the water glass component to further improve the toughness of the glue stock or to enable the glue stock to be used because the water glass component can float on the liquid surface quickly due to hydrophobicity, and adds a small amount of surfactant and dispersant or uses emulsion or aqueous components thereof, because the water glass is too far away from the density phase of the water glass component, the water glass generally gradually delaminates after days or even hours, so that the normal use and the commercial value of the two-component glue are affected, and the addition of a large amount of emulsifier also can significantly affect the bonding strength and the water resistance. The same problem exists with the addition of small amounts of polyether polyols, and it is well known that due to the poor adhesive strength and mechanical strength of polyether urethane adhesives, as a conventional means in the art, polyester polyols are usually added to obtain higher adhesive strength, but due to the special alkaline environment and the presence of ester bonds, the adhesives encounter the technical problems of hydrolysis-delamination-gelation which are difficult to solve for a long time, the storage period is generally difficult to exceed one or two months, multiple emulsification, dispersion and anti-sedimentation, and the effect of anti-hydrolysis treatment is not good, which is often considered, and the expected effect is difficult to achieve by conventional tests and conventional technical means, while the addition of polyisocyanates in the component B to improve the wettability and adhesion with the steel interface, the effect is also poor, and the reaction speed and curing time are also affected. The inventor has long explored related problems under hard conditions and has achieved unexpected effects.

Disclosure of Invention

The invention aims to provide a green quick-drying AB adhesive with stable performance and a preparation method thereof, and aims to solve the technical problems of preparing a polyurethane composite adhesive with quick curing, good wettability to steel, higher bonding strength, more stable performance and lower cost and providing a preparation method thereof. Polyester polyol and/or polyether polyol are compounded with water glass or modified water glass, and a proper amount of plasticizer is combined with a polyisocyanate component, particularly a polyisocyanate-prepolymer component to prepare the environment-friendly quick-drying AB adhesive and the foaming adhesive thereof, so that the purposes of green and environment protection, improvement of advantages and disadvantages, optimization of bonding performance, reduction of cost, quick drying and early strength can be realized.

The specific technical scheme of the invention is as follows:

the green quick-drying AB glue with stable performance comprises water glass and polyisocyanate, and is characterized in that the modified water glass in the component A: the polyether polyol is 4~8:3~4, the modified water glass is water glass: gamma-aminopropyltriethoxysilane as 100:1 to 2.5, or water glass: gamma-aminopropyltriethoxysilane: dodecanol ester is 100:1 to 2.5:0.8 to 1.6, wherein the molecular weight of the polyether polyol is 400 to 6500, and the polyether polyol with the molecular weight of 3000 to 6000 is contained; the polyester polyol and/or polyether polyol in the component B: plasticizer: the polyisocyanate is 1 to 0.5 to 1, 3.5 to 5, 0 to 10 percent of additive is additionally added into the component A or the component B, the additive comprises one or more of pigment, filler, essence, water, organic solvent, dispersant, viscosity-reducing and viscosity-stabilizing agent, flatting agent, thickening agent, toughening agent, catalyst, polymerization inhibitor, flame-retardant glue, smoke suppressor, defoaming agent, preservative, antirust agent, antioxidant, hydrolysis-resistant agent or low-temperature resistant agent, and the proportion of the component A to the component B is 1.5:1 to 1.5.

A green quick-drying AB adhesive with stable performance comprises water glass and polyisocyanate, and is characterized in that in the component A, the modified water glass comprises 3 to 9 parts of polyether polyol, 1 to 3 parts of polyether polyol; the modified water glass is prepared from the following components: gamma-aminopropyltriethoxysilane 100:0.5 to 3; or the modified water glass is water glass: gamma-aminopropyltriethoxysilane: dodecanol ester is 100:0,5 to 3:0.5 to 3, selecting polyether polyol with alkali resistance; and polyester polyol in the component B: polyether polyol: plasticizer: diphenylmethane diisocyanate and/or polymethylene polyphenyl polyisocyanate and/or isophorone diisocyanate and/or hexamethylene polyphenyl polyisocyanate is 1: 0~2:0.3 to 1:5 to 10, 0 to 100 percent of additive is added into the component A or the component B, the polyether polyol is bifunctional or polyfunctional polyether polyol, is one or a combination of polypropylene oxide polyol, polymer polyol, polytetrahydrofuran polyol or polyethylene oxide polyol, the molecular weight is 2000 to 5000, the proportion of the component A to the component B is 1.5:1 to 1.5.

The environment-friendly quick-drying AB glue is characterized in that the component A is modified water glass: the polyether polyol is 4~8:3~4, the modified water glass is water glass: gamma-aminopropyltriethoxysilane as 100:1 to 2.5, or water glass: gamma-aminopropyltriethoxysilane: the dodecanol ester is 100:1 to 2.5:0.8 to 1.6: 0 to 10 percent of additive is additionally added into the component A or the component B; and B component polyester polyol: plasticizer: the polyisocyanate is 1.

The green quick-drying AB glue with stable performance is characterized in that water glass in the component A is modified water glass, wherein 1 to 2.5wt% of gamma-aminopropyltriethoxysilane is added into the water glass, or 1 to 2.5wt% of gamma-aminopropyltriethoxysilane, 1 to 3wt% of dodecanol ester, and 1 to 1.5wt% of dodecanol ester are further preferably added into the water glass; and the plasticizer in the component B: polyester polyol: 1 to 4 parts of diphenylmethane diisocyanate or polymethylene polyphenyl polyisocyanate and/or isophorone diisocyanate and/or hexamethylene polyphenyl polyisocyanate: 8 to 15, preferably 1.5 to 3:8 to 12, more preferably 1 to 2 to 3; the component A or the component B is added with 0 to 100wt% of additive, preferably 0.1 to 10wt%; a and B are 1:1 to 1.5, preferably A: B is 1:1 to 1.2, in particular A: B is 1:1; or A and B are 1 to 1.5:1, preferably A: B is 1 to 1.4:1, further preferably, A: B is 1 to 1.3:1, more preferably 1 to 1.2:1, particularly preferably 1 to 1.1:1.

the B component may contain a small amount of polyether polyol.

And the water glass in the component A is prepared from polyether glycol 4:1.5 to 4.5 percent by weight of catalyst, and 0 to 0.5 percent by weight of catalyst.

In the component A, the ratio of water glass to polyether polyol is 4:2 to 3.5 and 0 to 0.3wt% of catalyst.

The additive in the component A or the component B of the green quick-drying AB glue with stable performance comprises one or more of pigment, filler, essence, water, organic solvent, surfactant, dispersant, viscosity reducer, viscosity stabilizer, leveling agent, thickener, toughening agent, reinforcing agent, catalyst, polymerization inhibitor, flame-retardant glue, smoke suppressor, defoaming agent, preservative, antirust agent, antioxidant, hydrolysis resistant agent or low temperature resistant agent.

The catalyst is preferably delayed catalyst or post catalyst, such as DY-20, DY-12, DY-5501, DY-8154, etc.

The additive in the component A comprises 1 to 10wt% of a surfactant or a dispersant, preferably 3 to 7wt%, and more preferably 4 to 6wt%.

The surfactant is preferably a polyether polyol which is resistant to alkali.

The additive in the component A also comprises 1 to 20wt% of organic solvent, preferably 3 to 15wt%, more preferably 5 to 10wt%.

The organic solvent is preferably an environmental-friendly solvent commonly used in the industry, and preferably can be used as a diluent, a stabilizer and a reaction regulator, and can also be used as an organic solvent or a plasticizer with a plasticizing effect directly or through a subsequent reaction, such as 1,2-propylene glycol carbonate, dimethyl carbonate, glyceryl triacetate, a mixed dibasic acid ester, one or more of ethanol, isopropanol, benzyl alcohol, ethylene glycol, propylene glycol, polyethylene glycol and polypropylene glycol, and the like.

The additive in the component A also comprises 0.5 to 10wt% of water, more preferably 0.5 to 8wt% of water, and most preferably within 3wt% or 5wt% of water. The addition of a proper amount of water is beneficial to adjusting the viscosity and the fluidity and the reaction speed.

The additive in A can also comprise one or more of ethylene glycol, polyethylene glycol, triethylene diamine, glycerol, polyether amine and tris (2-hydroxyethyl) isocyanurate.

The viscosity-reducing and viscosity-stabilizing agent in the component can be one or more of dodecanol ester, hexadecanol ester, phthalate ester and monohydric alcohol, wherein the phthalate ester is preferably dioctyl ester, the monohydric alcohol is liquid fatty alcohol and/or aromatic alcohol, and the fatty alcohol is one or more of methanol, ethanol, propanol, butanol and pentanol.

The aromatic alcohol is one or more of benzyl alcohol, phenethyl alcohol and derivatives thereof. The aromatic alcohol is benzyl alcohol.

The sodium silicate content in the water glass of the component A is 30 to 60wt%, and the modulus is 1.5 to 3.5; the modulus is preferably 2.2 to 2.6 or 3.0 to 3.4.

The polyester polyol in the component B: diphenylmethane diisocyanate or polymethylene polyphenyl polyisocyanate: the isophorone diisocyanate and/or hexamethylene polyphenyl polyisocyanate is (1).

The polyester polyol in the component B: diphenylmethane diisocyanate or polymethylene polyphenyl polyisocyanate: the isophorone diisocyanate and/or hexamethylene polyphenyl polyisocyanate is (1).

The polyester polyol in the component B: diphenylmethane diisocyanate or polymethylene polyphenyl polyisocyanate: the isophorone diisocyanate and/or hexamethylene polyphenyl polyisocyanate is 1: 4-12.

The polyester polyol in the component B: diphenylmethane diisocyanate or polymethylene polyphenyl polyisocyanate: the isophorone diisocyanate and/or hexamethylene polyphenyl polyisocyanate is 1 to 4 to 8.

The polyisocyanate is diphenylmethane diisocyanate and/or polymethylene polyphenyl polyisocyanate and isophorone diisocyanate and/or hexamethylene polyphenyl polyisocyanate.

The aliphatic or cycloaliphatic polyisocyanate is HDI or IPDI and polymers thereof, preferably IPDI.

IPDI and/or HDI or their trimer in the component B account for 1/2~1/5 of polyisocyanate.

IPDI in the component B accounts for 1/2~1/3 of polyisocyanate. IPDI in the B component accounts for 1/2~1/5 of the polyisocyanate.

0 to 100wt% of polyisocyanate is additionally added into the component B.

10-100 wt% of polyisocyanate is additionally added into the component B.

The green quick-drying AB glue with stable performance is a two-component glue, and is characterized in that the preparation method of the component A comprises the following steps:

a. for the technical proposal that the component A is water glass and/or modified water glass,

self-contained water glass; or preparing a modified water glass component: heating water glass to 40-80 ℃, adding 0-0.5 wt% of nano silicon powder into the water glass while stirring, continuing to stir for 15-30 minutes after the nano silicon powder is added, keeping the temperature at 30-50 ℃, dropwise adding 0.5-3 wt% of silane coupling agent, preferably gamma-aminopropyltriethoxysilane while stirring, continuing to stir for 15-30 minutes after the nano silicon powder is added, controlling the temperature at 25-40 ℃, adding 0.5-3 wt% of alcohol ester or alcohol ether, preferably decaglycol ester, continuing to stir for 30-90 minutes, continuing to stir before the temperature is reduced to the room temperature, directly discharging the water glass after stirring is stopped, or timely sealing the water glass by a material to prevent a film from forming; or, in order to save labor, time and electricity, the mixture can be temporarily stirred for 30 to 12 minutes after primary stirring, and then stirred for 30 to 60 minutes after layering to obtain the uniform rubber material with the viscosity of more than 3000 mpa.s.

Preparation of the component B: adding the polyester polyol, polyether polyol and plasticizer subjected to water removal treatment into a reaction tank, uniformly stirring, adding the polyester polyol, polyether polyol and plasticizer into another reaction tank containing polyisocyanate at the temperature of not higher than 40 ℃, preferably not higher than 30 ℃ or at room temperature, stirring while adding, continuously stirring for 30-60 minutes after adding, and directly discharging or filtering;

b. for the technical proposal that the component A is water glass and/or modified water glass and polyether glycol, and the water glass and/or modified water glass, polyether polyol and alkali-resistant plasticizer without ester group,

self-contained water glass; or preparing modified water glass according to the step 1; adding a water glass component or a modified water glass component into an alkali-resistant plasticizer containing polyether polyol or polyether polyol and no ester group at 30-50 ℃ or normal temperature, stirring while adding, continuing stirring after adding, adding a filler, a viscosity reducer and other auxiliaries as necessary, continuing stirring for 60-120 minutes to fully homogenize and emulsify, and then directly discharging or filtering;

the component B can be prepared according to the preparation method of the component B in the component A; the preparation method can also be as follows:

1. placing solid polyester polyol in an oven, heating to be liquid, and then adding the solid polyester polyol into a reaction kettle, or directly adding the liquid polyester polyol into the reaction kettle;

2. adding the plasticizer into the polyester polyol under stirring;

3. then adding polyether polyol;

4. vacuum dehydrating at 110-120 ℃ for 1.5-3 h, then cooling to 60-80 ℃, or directly selecting polyurethane-grade polyether polyol, polyester polyol and plasticizer at the temperature, uniformly mixing, adding the mixture into isocyanate while stirring, continuously stirring for 1~2 hours, cooling to 40-50 ℃, adding additives if necessary, uniformly stirring, and then directly discharging or filtering and discharging.

For the component A without polyether polyol addition polymerization, when the corresponding component B is prepared, polyester polyol, polyether polyol and a small amount of diluent or plasticizer which are subjected to water removal treatment are preferably uniformly mixed at normal temperature, then slowly added into polyisocyanate under stirring at the temperature of 20-30 ℃ or lower, such as 10-20 ℃, and then uniformly stirred under the protection of nitrogen when necessary, and then discharged (filtered when necessary), so that the mixed two-component adhesive can keep better wettability and interfacial adhesion after the treatment, and meanwhile, the reaction speed is not too fast, and the adaptation period can be prolonged; when in use, the component A and the component B are uniformly mixed according to the weight ratio of 1.5 to 1.5 and then are applied.

In the present invention, the polyester polyol may be polyester polyol based on adipic acid, terephthalic anhydride, phthalic anhydride-1,4 butanediol, 1,6 hexanediol, diethylene glycol or neopentyl glycol, such as PE3030, PE2811, PE2708, PE1320, PE2612, PE2512, PE9956, PE5556, etc., and one or a combination of HF8011, HF8020, HF8025, HF8031, HF8040, HF8056, HF8211, HF8356, HF8765, HF86304, HF86407, etc., hydroxyl value of 22 to 680, acid value of 0.1 to 3, molecular weight of 400 to 6000; the polyester polyol can also be prepared by condensation or ester exchange of dicarboxylic acid or anhydride or ester and polyhydric alcohol including dihydric alcohol or polymerization of lactone and polyhydric alcohol; the dicarboxylic acid may be phthalic acid or phthalic anhydride or its ester, adipic acid, halogenated phthalic acid, etc., and the polyol may be ethylene glycol, propylene glycol, diethylene glycol, trimethylolpropane, pentaerythritol, etc.

The polyester polyol in the components is PE8815T and/or PE7762 with low temperature resistance of side groups and the like with molecular weight of less than 2500, particularly less than 2000, and the like and the polyester polyol PE2612 and/or PE2512 with high crystallinity of molecular weight of 3000 to 8000, and the like, and the design can obtain good storage stability, low-temperature fluidity and excellent wetting, attaching and bonding effects on metals such as steel and the like.

The polyester polyol prepared by alcoholysis recovery bottle material can also be selected, and the average molecular weight is 3000 to 30000, so that the molecular weight is larger.

Smaller molecular weights help to achieve better flow, wetting and storage stability, while larger molecular weights allow the compound to achieve greater strength, better thickening, emulsifying and thixotropic properties, and more stable viscosity.

The polyether polyol used in the invention is difunctional, trifunctional or multifunctional suitable for being matched with water glass, has a molecular weight of 40-6500, can be one or a combination of polyoxypropylene polyol, polymer polyol, polytetrahydrofuran polyol or polyoxyethylene polyol, preferably soft foam, especially high resilience series, has a molecular weight of 2000-5000, and preferably has certain surface activity and/or alkali resistance.

The polyether polyol preferably has alkali resistance and a combination of a molecular weight of 400 to 1000 and a molecular weight of 3000 to 6000, so that the polyether polyol has good emulsibility and a structural basis for obtaining sufficient strength.

Polyether polyols with alkali resistance and suitable for preparing the water glass mixed glue solution are selected, such as 330N, 220N, 210N and the like, and 330N is preferred. The polyether polyol can be, but is not limited to, one or a combination of more than one of 220N, 210N, N, N403, 330N, WANOL-F3135.

The polyether polyol may comprise polyoxyethylene, polyoxypropylene block polymers.

The plasticizer in the component A of the invention is a plasticizer which is common in the industry, in particular an environment-friendly plasticizer, and can be citric acid esters, such as tributyl citrate (TBC), trioctyl citrate (TOC), acetyl tributyl citrate (ATBC), acetyl trioctyl citrate (ATOC); vegetable oils, such as tung oil, sunflower seed oil, rapeseed oil, hemp seed oil, sesame oil, corn oil, peanut oil, soybean oil, etc.; synthetic vegetable esters, such as epoxidized soybean oil, epoxy acetyl methyl linoleate, epoxy butyl furoate, epoxy butyl pupate oleate, epoxy octyl soybean oleate, 9, 10-epoxy octyl stearate, etc.; animal and plant blend oil: phthalic acid esters, such as dimethyl phthalate (DMP), diethyl phthalate (DEP), dibutyl phthalate (DBP), diisobutyl phthalate (DIBP), diethylhexyl phthalate, diisooctyl phthalate, dioctyl phthalate (DOP), diisooctyl phthalate (DIOP), diisononyl N-phthalate (DINP), diisodecyl phthalate (DIDP); phosphate esters, phosphite esters; further, dioctyl terephthalate (DOTP), epoxy fatty acid methyl ester, epoxy fatty acid butyl ester, chloromethoxy fatty acid methyl ester, organosilicon modified acrylic resin, modified polyester acrylate-3212, trans-9,10-epoxyoctadecanoic acid methyl ester, CCP CIZER D-810 plasticizer, dioctyl adipate (DOA), phenyl alkylsulfonate, triethylene glycol diisooctanoate, cardanol, palm oil based plasticizer (PBPO), liquid paraffin, chlorinated paraffin or other petroleum plasticizers can be used, and kitchen waste oil and fat can also be used; preferably, the chlorinated paraffin is one or more of a combination of long-chain chlorinated paraffin, palm oil, chlorinated palm oil, butyl methacrylate, butyl acrylate, phosphate ester, epoxidized soybean oil, polyurethane plasticizer, kitchen waste grease, ester-free plasticizer and the like. The polyurethane plasticizer is a monofunctional alcohol or monofunctional isocyanate synthesized plasticizer containing urethane groups, and can also be formed by the corresponding components in the two components during the mixing reaction; the plasticizer of the present invention may also be one or a combination of more than one of the above plasticizers, and a combination of one or more of them with their derivatives.

The isocyanate in the invention can be polyisocyanate, and can be one or more of common polyisocyanate and polyisocyanurate such as diphenylmethane diisocyanate, polymethylene polyphenyl isocyanate, dicyclohexylmethane diisocyanate, cyclohexyl diisocyanate, naphthalene diisocyanate, methylcyclohexyl diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate and the like; the isocyanate prepolymer is any one or a mixture of any two or more of the following substances: the molecular weight of the prepolymer of the diphenylmethane diisocyanate is 1000-2000; the molecular weight of the prepolymer of the cyclohexyl diisocyanate is 500-1500; a prepolymer of polymethylene polyphenyl isocyanate having a molecular weight of 1500 to 4000; the prepolymer of naphthalene diisocyanate has a molecular weight of 1200 to 4000; the prepolymer of methyl cyclohexyl diisocyanate has molecular weight of 900-3000; the molecular weight of the prepolymer of dicyclohexyl methane diisocyanate is 1500-3000; the molecular weight of the prepolymer of hexamethylene diisocyanate is 900-2000; the prepolymer of isophorone diisocyanate has a molecular weight of 1200-4000.

The invention realizes the aim of the invention by utilizing the complex interaction influence among the components and through the design of the interpenetrating network structure of the macromolecule and the optimization of the formula process. Because a large amount of polyester and/or polyether glycol is added into the water glass component, a good emulsifying effect is unexpectedly generated, the early strength and high strength technical performance is also unexpectedly obtained, the rubber material can be rapidly cured at normal temperature, the strength of the structural adhesive can be approached to or even surpassed in more than 24 hours of the composition, the cured body is rigid and flexible, and the adhesive force to metal such as steel is strong; as the water glass is used as the sizing material active dispersant instead of an organic solvent, most of the compositions have almost no smell, are safe and environment-friendly, have low manufacturing cost and have certain flame retardant and corrosion-retarding effects. In addition, the inertia (no reactive group) of the monofunctional polyurethane plasticizer and the proper molecular weight for keeping the liquid state can endow the adhesive with better operability, performance stability, weather resistance and environmental protection. In tests, the component A has been found to have unexpected excellent adhesion force on metal interfaces, especially steel interfaces, when being matched with the component B added with proper amount of aliphatic/alicyclic isocyanate, especially IPDI, and the adaptation period is obviously prolonged.

The addition of silane coupling agent, especially gamma-aminopropyl triethoxy silane A component, especially gamma-aminopropyl triethoxy silane and dodecyl ester A component, B component is the technical scheme of adding proper quantity of polyester polyol, polyether polyol and plasticizer to polyisocyanate, A component not only has high stability (storage period is more than one year, the sample can still be used for two years), but also can be matched with B component containing limited quantity of polyester polyol, polyether polyol, plasticizer and polyisocyanate according to the invention in the defined A and B proportioning relation, especially when the polyester polyol, polyether polyol, plasticizer and polyisocyanate, especially IPDI/HDI-added polyisocyanate are used for preparing B component at lower temperature and/or part of polyester molecular weight is small, the unexpected early strength, high strength and excellent toughness steel-steel bonding effect can be achieved.

The component A of the invention is probably because a large amount of the existing flexible polyether polyol with hydroxyl and ether groups is added into proper water glass, especially modified water glass, and a proper amount of micromolecule plasticizer is freely inserted and flexibly matched, and hydrogen bonds and complex interaction among molecules and double electric layer protection are assisted, so that unexpected stable emulsion is formed under mechanical stirring, and a highly adaptive and highly optimized composite interpenetrating network structure can be formed in the mixing reaction of the component A and a proper amount of reasonable polyisocyanate, polyester polyol and/or polyether polyol, so that unexpected toughness and toughness are achieved, the early strength and the high strength are achieved, and the bonding force to metal substrates such as steel and the like and other rigid substrates is excellent.

The component is water glass or modified water glass polyether polyol, especially alkali-resistant polyether polyol, the component B is polyisocyanate, especially polyisocyanate containing IPDI/HDI, and a proper amount of polyester polyol and plasticizer, because the component A does not contain ester bonds, the phenomenon that ester is hydrolyzed at a higher temperature and for a longer time to cause water glass gel can be avoided, and because the component B reduces the amount of the polyether polyol which is added in an amount larger than that of the polyester polyol and simultaneously adds the inert plasticizer, the component A and the component B have better storage stability; tests show that when the added polyether glycol in the component A exceeds the conventional addition amount, the polyether glycol can be matched with water glass to generate good self-emulsifying performance, and simultaneously obtain homogeneous glue solution with fluidity, the component A is added with an additive if necessary, the density of the component A is close to or equal to that of the component B, the volume or mass ratio of the component AB is close to or equal to 1:1 so as to facilitate machine tool operation and application, and the two components also have excellent toughness and are economic in rigidity and toughness, so that the adhesive has unexpected early-strength and high-strength steel-steel bonding effects.

In addition, the component B can effectively improve the fluidity due to the dispersion, dilution and protection of the plasticizer, has obvious synergistic interaction on the adhesive property and ensures that the cured surface is smoother and finer; and a proper amount of IPDI and/or HDI is added into the component B, so that the fluidity and the storage stability are improved, the adaptation period and the surface drying time of a water glass-polyurethane system are greatly prolonged, and the adhesive force and the adhesive strength of the adhesive to a metal interface, particularly a steel interface, are remarkably improved.

According to specific needs, the polyester polyol in the component A and/or the component B can be partially or completely replaced by polyether polyol, and a small amount or no plasticizer can be added in the component A and/or the component B. The polyether polyol can accelerate the reaction speed, increase the toughness of a solidified body, and also have the effect of improving the steel-steel shear strength by properly adding the polyether polyol within a certain range. The adhesive can meet the harsh environment-friendly requirements of certain occasions by adding less or no plasticizer, and the aim of the invention can be achieved by adding less or no plasticizer when enough polyether polyol is available.

The product of the invention can be used for bonding steel-steel (including stainless steel, alloy steel and iron), steel-aluminum, steel-copper and other intermetallics, steel-wood, steel-stone, part steel-plastic and steel and rigid foam or a plurality of hard materials.

Compared with the prior art, the invention also has the following advantages:

1. quick drying and early strength, and can be quickly cured at lower temperature without catalyst, thereby realizing early strength and high strength.

2. Good adhesion, good wettability to metal interfaces such as steel and the like and high adhesion.

3. A large amount of water glass slurry is used as the component A, so that the cost of raw materials is greatly reduced, and simultaneously, due to the synergistic activation of high molecular components, the hydroxylation of nano silicon and the grafting, crosslinking and embedding of hydroxyl silicon, the antirust flame-retardant adhesive has good mechanical strength and bonding stability, is rigid and tough, has a certain antirust flame-retardant effect, and is low in manufacturing cost.

4. Because no or only a small amount of organic solvent which is easy to generate is contained, and the kitchen waste grease can be utilized, the kitchen waste grease is solidified without heating, and the environment-friendly, low-carbon and energy-saving effects are achieved.

5. The viscosity can be adjusted according to the components and the proportion, and the operability is good.

The synthesized crude polyether glycol containing a certain amount of water, potassium hydroxide or sodium hydroxide is directly used for preparing the component A, so that the production process can be simplified, the energy consumption is reduced, the effect is improved, the production cost is greatly reduced, particularly, the product storage period can be prolonged by the technical scheme of transferring the component B polyether glycol to the component A, in addition, the component B can effectively improve the fluidity and improve the storage stability due to the dispersion, dilution and protection of the plasticizer, and meanwhile, the plasticizer also has an obvious synergistic effect on the bonding performance.

The present invention also makes it possible to obtain unexpected storage stability and bonding effects by using crude polyether polyols which have not been subjected to water removal and neutralization treatment.

Detailed Description

In the raw materials used in the embodiment of the invention, 2.2 to 2.5 model (density at 20 ℃ is 1.526 to 1.599g/cm 3), 2.6 to 2.9 model (density at 20 ℃ is 1.436 to 1.465 g/cm 3), and 3.1 to 3.4 model (density at 20 ℃ is 1.368 to 1.394 g/cm 3) series water glass are provided by Chongqing Yongsheng water glass factory; gamma-aminopropyltriethoxysilane is produced by Nanjing Bisuicides chemical Co., ltd; 2,2,4-trimethyl-1,3 pentanediol monoisobutyrate, manufactured by Jiangsu Ruita chemical Co., ltd; the old bottle material resin is produced by a Chongqing Banan polyester adhesive factory, and is polyester polyol produced by polyethylene terephthalate bottle material recovered by alcoholysis by a conventional method, wherein the molecular weight of the polyester polyol is 2000-6000, the molecular weight of the polyester polyol is 3000-10000, and the isocyanate is Wanhua produced polymeric MDI (NCO 28-32%), PM200 (NCO 28-32%) and Basff produced M20S (NCO 28-31%). Wanhua polyether polyol 330N (hydroxyl value 32 to 36). Polyester polyols PT2612, HF8056, HF7762 and the like are produced by Zhejiang Huafeng New materials GmbH. Other chemical raw materials are purchased on the Internet through the Alibara or the intelligent network or purchased in the Chongqing stone plateau bridge chemical market. The screw used for testing the positive tensile bonding strength (bonding strength for short) is round head, the diameter is 12mm, the screw length is 87mm, the end face of the nail head is polished, the nail head is bonded to the nail head after gluing and keeps coaxial, the screw is cured at the natural temperature of 8 to 35 ℃, the surface drying time is mostly 3 to 10 minutes, and the screw is tested after 24 hours. During testing, vertically and downwards hanging a heavy object by the screw rod, increasing the weight by 5kg each time until the screw falls off, and recording the hung heavy object; the shear strength is measured by bending one end of a steel strip with the width of 5mm, the thickness of 2.5mm and the length of about 100mm into a hook shape, coating glue on the other end in the length direction, overlapping for 10-15mm, polishing the surface to be bonded, bonding the surface to the opposite surface after the glue coating, keeping the same axis, curing at the natural temperature of 8-35 ℃, wherein the surface drying time is mostly 3-10 minutes, and testing after 24 hours. During testing, vertically and downwards hanging a heavy object by a screw or a steel bar, increasing by 5kg each time until the screw falls off, and recording the hanging weight and the bonding area; all 30 seconds are not dropped and then code is added. 3~5 repeats are set for each treatment, abnormal samples are removed, and the average value is obtained. The bond strength or shear strength is calculated above and below the average weight and is for reference only. It should be noted that although the test result dispersion is not large among samples of the same treatment or embodiment, the test result is larger than the test result of the standard steel-steel opposite-pulling bonding strength, and the test result of the construction engineering quality inspection and detection center in Chongqing of example 8 of the invention is 26.4Mpa according to GB 50728-2011 'engineering structure reinforcing material safety identification technical specification'. The invention and the following comparative examples and examples, unless otherwise noted, are homogeneous in parts or percentages by mass.

The invention is further illustrated by the following specific examples.

The preparation method of the component A comprises the following steps:

1. preparing water glass for later use or preparing a modified water glass component:

dropping gamma-aminopropyl triethoxy silane into water glass at 40 deg.c while stirring, and adding glycol decaester while stirring.

Adding water glass or modified water glass into polyether polyol, stirring while adding, and then continuing to stir for 30-120 minutes, or firstly stirring for 15-30 minutes, standing for 30-12 hours, and then continuing to stir for 1~2 times to obtain the uniform emulsion.

The preparation method of the component B comprises the following steps:

adding polyester polyol and a plasticizer into a reaction kettle, dehydrating for 1.5 to 3 hours at 110 to 120 ℃, then cooling to 60 ℃, or directly selecting polyurethane-grade polyether polyol and/or polyester polyol and the plasticizer, adding isocyanate under stirring to react for 1~2 hours, adding a catalyst to continue reacting for 0.5 to 1 hour if necessary, cooling to 40 to 50 ℃, adding an additive if necessary, stirring uniformly, and then filtering and discharging;

when the temperature exceeds 30 ℃, the component A does not contain polyether polyol, and the component B contains polyester polyol, a plasticizer and excessive polyisocyanate or polyester polyol, polyether polyol, a plasticizer and excessive polyisocyanate, the mixture is preferably mixed at normal temperature, so that the component B is in a non-prepolymer or incomplete prepolymer state and has more and smaller molecular structures, and the mixed two components keep better wettability and interface adhesion, and do not generate too fast reaction speed; when in use, the component A and the component B are uniformly mixed according to the weight ratio of 1.5 to 1.5 and then are applied. In the following examples A, B component is prepared by reference to the above process and component B, not specifically indicated, is prepared by this heating process.

Comparative example 1A polyester polyol (halves PE2612 and PE 7762) 42 n 21B: 2714B A

The bonding strength of the nail-nail is less than 0.5Mpa after 24 hours (the temperature is 15 to 20 ℃).

Comparative example 2A polyester polyol (halves PE2612 and PE 7762) 42 n 21 triethanolamine 9.45B: 2714B A

24 hours (the air temperature is 15 to 20 ℃), and the bonding strength nail-nail is 24kg/2.08Mpa 36kg/3.12Mpa.

Comparative example 3A polyester polyol (halves PE2612 and PE7762 each) 42 330N 21 triethanolamine 3.95 butyl methacrylate 3.00

B：2714B A:B 1 :1

The bonding strength of the nail-nail is 12kg/1.04Mpa, 20kg/1.86Mpa (not shown) after 24 hours (the temperature is 15 to 20 ℃).

Comparative example 4A Jingjiang two-component solvent-free polyurethane A: B3: 1

The bonding strength of the nail-nail 63.42kg/5.5Mpa 66.88kg/5.8Mpa (not shown) is 72 hours (the temperature is 15 to 20 ℃).

Comparative example 5 (see CN1788064A a polyisocyanate based adhesive example 2)

The bonding strength nail is less than 25kg/2.2Mpa after 24 hours (the temperature is 15 to 20 ℃).

Comparative example 6 (see JP patent publication 2002 20698A A sizing composition for concrete example 4)

The bonding strength nail is less than 10kg/0.86Mpa after 24 hours (the temperature is 15 to 20 ℃).

COMPARATIVE EXAMPLE 7 (REFERENCE CN103627330A Complex sizing example 23)

The bonding strength nail is less than 55kg/4.77Mpa after 24 hours (the temperature is 15 to 20 ℃).

Comparative example 8 (see CN104910817A an environmental friendly composite resin and adhesive and coating based on the resin, example formulation of paragraph [00400]

The adhesive strength nail is less than 55kg/4.77Mpa after 24 hours (the air temperature is 15 to 20 ℃).

Comparative example 9 (refer to CN105885704A a low viscosity high strength environmental protection two-component glue solution and preparation method example 6)

The bonding strength nail is less than 55kg/4.77Mpa after 24 hours (the temperature is 15 to 20 ℃).

Comparative example 10 (refer to CN107488367A an inorganic-organic high environmental protection two-component adhesive and preparation method example 12)

The bonding strength nail is less than 55kg/4.77Mpa after 24 hours (the temperature is 15 to 20 ℃).

Comparative example 11 (refer to CN107488431A a water-based-oil based low viscosity environmental protection two-component adhesive and preparation method example 2)

The bonding strength nail is less than 55kg/4.77Mpa after 24 hours (the temperature is 15 to 20 ℃).

Example 1

A (2.6 model water glass 100, gamma-aminopropyl triethoxy silane 1.5, dodecanol ester 1) 400, 330N292

B, polyester polyols PE2612 and PE7762 are half each) 151.8, M20S322.7 IPDI322.7 dimethyl carbonate 10.4, butyl methacrylate 100, A, B1: 1, and the adhesive strength of the nail-nail is 13.5MPa after 24 hours at normal temperature.

Example 2

A (2.6 model water glass 100 gamma-aminopropyl triethoxy silane 1.5 decaglycol ester 1) is taken as 260, (2.1 model water glass 100 gamma-aminopropyl triethoxy silane 1.5 decaglycol ester 1) is taken as 140, castor oil 70,330N 324.7

B polyester polyols PE2612 and PE7762 are half each) 258.5, M20S302.4 IPDI302.4 dimethyl carbonate 11.7, butyl methacrylate 44 phosphate 50 dioctyl phthalate 50A, B1: 1 bonding strength nail-nail is more than or equal to 9.68MPa.

Example 3

A (2.1 model water glass 100 gamma-aminopropyl triethoxy silane 1.5 decadiol ester 1) is taken as 200, (2.6 model water glass 100 gamma-aminopropyl triethoxy silane 1.5 decadiol ester 1) is taken as 200, 330N 351.8, DY-5501 0.5

B polyester polyol (half of each of PE2612 and PE 9956) 151.8, M20S322.7, IPDI322.7, dimethyl carbonate 10.5, butyl methacrylate 60, liquid paraffin 40 and hydrolysis resisting agent 0.5 percent

The A: B1: 1 bonding strength is more than or equal to 10.85Mpa.

Example 4

A (2.6 model water glass 100, gamma-aminopropyl triethoxy silane 1.5, dodecanol ester 1) 400, 330N308.4, 140 is taken and gamma-aminopropyl triethoxy silane 1.3 decaglycol ester 1.4 is added

Polyester polyol (half of each of PE2512 and PE 7762) 151.8, 330N108.4, M20S311.4 IPDI314.4 dimethyl carbonate 10.4 palm oil (specific gravity 1.18) 100

A: B1, surface drying is carried out for 1: 7 minutes, and the bonding strength of the nail-nail is 12.48Mpa after 24 hours at normal temperature.

Example 5

A (2.6 model water glass 100 gamma-aminopropyl triethoxy silane 1.5) 400, 330N291.8 are taken

B polyester polyol (half of each of PE2612 and PE 7762) 151.8, M20S322.7, IPDI322.7, dimethyl carbonate 10.5, butyl acrylate 100

B1: 1 at normal temperature for 24 hours, the bonding strength is more than or equal to 7.38 Mpa, 20.00 days, and the highest 29.45 Mpa.

Example 6

A (2.6 model water glass 100, gamma-aminopropyltriethoxysilane 1.5, dodecanol ester 1) 800, 330N 359B polyester polyol (half each of PE2512 and PE 7762) 195, M20S985 dimethyl carbonate 18 trichloroethyl phosphate 67 butyl methacrylate 33A, B1.1: 1, room temperature 24 hours bonding strength nail-nail ≥ 9.85MPa.

Example 7

A (2.6 model water glass 100, gamma-aminopropyl triethoxy silane 1.5, dodecanol ester 2) 400, 330N362

B polyester polyols (PE 2612: PE3320: PE7762:2

A and B1, bonding strength nail-nail of more than or equal to 9.05Mpa and foaming of 0.2 to 0.5 times at normal temperature for 24 hours.

Example 8

A (2.6 model water glass 100, gamma-aminopropyl triethoxy silane 2.5, dodecanol ester 2.5) 400, 330N300

B polyester polyols PE2612 and PE7762 are half each) 151.8, M20S430 IPDI215 dimethyl carbonate 10.4, butyl methacrylate 50 trichloroethyl phosphate 50

A: B1: 1, and the bonding strength of the nail-nail is 14.16Mpa after 24 hours at normal temperature.

Example 9

A (2.6 model water glass 100, gamma-aminopropyl triethoxy silane 1.5, dodecanol ester 1) 400, 330N308.4, 3000 mesh silicon micropowder 240

B polyester polyol (half each of PE2612 and PE 7762) 151.8, M20S330 IPDI315 dimethyl carbonate 10.4 butyl methacrylate 100

A: B1, surface drying for 1 minute, and bonding strength nail-nail of 10.85MPa at normal temperature for 24 hours.

Example 10

A (2.6 model water glass 100, gamma-aminopropyl triethoxy silane 1.8, dodecanol ester 1.2) 400, 330N292

Polyester polyol (half of each of PE2612 and PE 7762) 155, MDI-50 160 PAPI165 IPDI335 dimethyl carbonate 8, butyl methacrylate 30 trichloroethyl phosphate 70

A: B1: 1 and bonding strength nail-nail 23.02Mpa 33 seconds at normal temperature for 24 hours.

Example 11

A (2.6 model water glass 100, gamma-aminopropyl triethoxy silane 1.5, dodecanol ester 1) 400, 330N291.8

Polyester polyol (half of each of PE2612 and PE 7762) 151.8, M20S322.7 IPDI322.7 dimethyl carbonate 10.4, butyl methacrylate 50 trichloroethyl phosphate 100

A: B1: 1.5 and the bonding strength of the nail-nail is 18.48MPa after 24 hours at normal temperature.

Example 12

A: 2.6 model water glass 400, 330N306

B, polyester polyol PE2512: 87.4, PAPI619, dimethyl carbonate 12.5, butyl acrylate 100

The ratio of A to B1 is 1, the bonding strength is higher than or equal to 8.96 Mpa after 24 hours at normal temperature.

Example 13

A (2.6 model water glass 100, gamma-aminopropyl triethoxy silane 1.5, dodecanol ester 1) 400, 330N308.4, nitrile rubber resin liquid 15

B polyester polyol (half of each of PE2612 and PE 7762) 151.8, M20S311.4 IPDI314.4 dimethyl carbonate 10.4 butyl methacrylate 100

A: B1, surface drying for 6 minutes, and bonding strength nail-nail of 18.48Mpa at normal temperature for 24 hours.

Example 14

A (2.6 model water glass 100, gamma-aminopropyl triethoxy silane 1.5, dodecanol ester 1) 400, 330N308.4

B polyester polyol (half of each of PE2612 and PE 7762) 151.8, M20S311.4 IPDI314.4 dimethyl carbonate 10.4, epoxidized soybean oil 100

A: B1, surface drying for 6 minutes, and bonding strength nail-nail of 20.64MPa at normal temperature for 24 hours.

Example 15

A (2.6 model water glass 100, gamma-aminopropyl triethoxy silane 1.5, dodecanol ester 1) 400, 330N308.4 mesh silica micropowder 120

B polyester polyol (old bottle resin: PE2612: PE7762 1

A: B1, surface drying for 1: 8 minutes, and adhering the nail-nail with the bonding strength of 11.16MPa at normal temperature for 24 hours.

Example 16

A (2.6 model water glass 100, gamma-aminopropyl triethoxy silane 1.5, dodecanol ester 1) 400, 330N308.4, 3000 mesh silicon powder 160

B polyester polyols (half of PE2612 and PE 7762) 151.8, M20S311.4 IPDI314.4 dimethyl carbonate 10.4, tributyl citrate (TBC) 100,

a: B1, surface drying for 1 minute, and bonding strength nail-nail 19.67Mpa for 24 hours at normal temperature.

Example 17

A (2.6 model water glass 100, gamma-aminopropyl triethoxy silane 2.5, dodecanol ester 1.5) 400, 330N308.4 epoxy soybean oil 100 amino formaldehyde resin (03) 120 and 3000 mesh silicon micropowder 160

B polyester polyol (half of each of PE2612 and PE 7762) 151.8, M20S311.4 IPDI314.4 dimethyl carbonate 10.4.

A: B1: 1, surface dry and nearly hard after 6 minutes, and the bonding strength of the nail-nail is 21.00MPa after 24 hours at normal temperature.

Example 18

A is a water glass 100, 330N 380,

b polyester polyols PE 2612314.4M 20S322.7, IPDI322.7, dimethyl carbonate 10.5, butyl methacrylate 30 acetyl trioctyl citrate (ATOC) 70

A: B1: 1.24 day, and the bonding strength nail is 7.51Mpa.

Example 19

A (2.6 model water glass 100 gamma-aminopropyl triethoxy silane 1.5 deca glycol ester 1) is taken out 260, (2.1 model water glass 100 gamma-aminopropyl triethoxy silane 1.5 deca glycol ester 1) is taken out 140, 330N374.7

B polyester polyol (PE 2811: PE2612: PE3320: PE7762 each 1/4) 183.5, M20S302.4 IPDI302.4 dimethyl carbonate 11.7 butyl methacrylate 44 diisodecyl phthalate (DIDP) 34A.

Examples 10, 11 and 14 above were stored hermetically for 6 months before testing, and examples 5 and 8 were stored hermetically for 12 months before testing.

The following examples still have good wettability and adhesive force on the steel base material, the steel-steel bonding strength is 5 to 15Mpa after 24 hours at normal temperature, and the surface drying time is 3 to 30 minutes, the component A is modified water glass, and the modified water glass is water glass: gamma-aminopropyltriethoxysilane 100:0.8 to 2.5; or water glass: gamma-aminopropyltriethoxysilane: the dodecanol ester is 100:0,5 to 2.5: 0.5' 2.5, more preferably water glass: gamma-aminopropyltriethoxysilane 100:1 to 1.8; or water glass: gamma-aminopropyltriethoxysilane: the dodecanol ester is 100:1 to 1.5: 0.8' 1.2;

and B component polyester polyol: polyether polyol: plasticizer: the polyisocyanate is 1.51 to 4.8:0.4 to 0.69A. The component B is prepared and stored at normal temperature of 20 ℃ by using polyester polyol, polyether polyol and plasticizer with the water content of not more than 0.03wt% or not more than 0.05 wt%.

Example 20

A component of water glass: gamma-aminopropyltriethoxysilane: the dodecanol ester is 100:1.5:1

And each of the component B PE2612 and PE7762 is half: 330N: soybean oil: IPDI and PAPI are each half 1.51: 0.61.

Example 21

A component of water glass: gamma-aminopropyltriethoxysilane: the dodecanol ester is 100:0.5:1

And each of the component B PE2612 and PE7762 is half: butyl methacrylate: IPDI and PAPI are each half 1.93: 0.69.

Example 22

A component of water glass: gamma-aminopropyltriethoxysilane: the dodecanol ester is 100:0.8

And each half of the B component PE2612 and PE7762: cardanol: IPDI and PAPI are each half 1

A:B 1:2.33。

Example 23

A component of water glass: gamma-aminopropyltriethoxysilane: the dodecanol ester is 100:1.2:1

And each of the component B PE2612 and PE7762 is half: palm oil: IPDI and PAPI are each half 1.2.05

A:B 1:3 。

Example 24A component modified waterglass: 330N is 8:3.87 The modified water glass is as follows: gamma-aminopropyltriethoxysilane: the dodecanol ester is 100:1.5:1, adding 102.5 percent of mica powder and 8 percent of water

And each of the component B PE2612 and PE7762 is half: butyl methacrylate: IPDI and PAPI are each half 1: 0.53A.

Example 25A component modified waterglass: 330N and 220N are each half 6:3.36, the modified water glass is water glass: gamma-aminopropyltriethoxysilane: the dodecanol ester is 100:1.5:1

And each of the component B PE2612 and PE7762 is half: butyl acrylate: IPDI and PAPI are each half 1.61, and 3% isopropanol is added to component B;

A:B 1:1.14。

example 26A component modified waterglass: 330N is 4:3.25, the modified water glass is as follows: gamma-aminopropyltriethoxysilane: the dodecanol ester is 100:2.5:1.5 age resisters 1

And each of the component B PE2612 and PE7762 is half: butyl methacrylate: IPDI and PAPI are each half 1: 0.63.

Example 27A component modified waterglass: 330N is 4:3.08, the modified water glass is prepared from the following components in percentage by weight: gamma-aminopropyltriethoxysilane: the dodecanol ester is 100:1.5:1

And each of the component B PE2612 and PE7762 is half: palm oil: IPDI and PAPI are each half 1:0.65

A:B 1:1.15。

Example 28A component modified waterglass: 330N is 8:4.5 The modified water glass is as follows: gamma-aminopropyltriethoxysilane: the dodecanol ester is 100:1.5: 5363 adding 10% magnesium salt whisker into the 1,A component; 1 percent of water

And each of the component B PE2612 and PE7762 is half: butyl methacrylate: IPDI and PM200 are each half 1:0.6

A:B 1: 1 。

In the embodiment, the polyisocyanate is M20S, so that the cost can be greatly reduced, the steel-steel bonding strength is 5 to 15Mpa after 24 hours at normal temperature, and the surface drying time is 3 to 30 minutes.

The polyisocyanate in the following examples is M20S:

mixing water glass: gamma-aminopropyltriethoxysilane 100:0.8 to 2.5, or water glass: gamma-aminopropyltriethoxysilane: the dodecanol ester is 100:1~2:0.8 to 1.6 is the component A,

and (3) taking PE2612:330N: palm oil: polyisocyanate is 1:1.5 to 2:0.5 to 0.8:3~6 is component B

A：B 1：2~3。

Example 29A component waterglass: gamma-aminopropyltriethoxysilane: the dodecanol ester is 100:1.5:1

Component B PE2612:330N: soybean oil: polyisocyanate is 1

A:B 1: 2.33 。

Example 30A component waterglass: gamma-aminopropyltriethoxysilane: the dodecanol ester is 100:1.5:1

And each of the component B PE2612 and PE7762 is half: 330N: palm oil: polyisocyanate is 1

A:B 1: 3 。

Example 31A component waterglass: gamma-aminopropyltriethoxysilane: the dodecanol ester is 100:1.5:1

And each of the component B PE2612 and PE7762 is half: 330N: epoxidized soybean oil: polyisocyanate is 1

A:B 1: 3 。

The technical scheme is that the component A is modified water glass: the polyether polyol is 4~8:3~4, the modified water glass is water glass: gamma-aminopropyltriethoxysilane as 100:1 to 2.5, or water glass: gamma-aminopropyltriethoxysilane: the dodecanol ester is 100:1 to 2.5:0.8 to 1.6: 0 to 10 percent of additive, preferably 3~6 percent, is additionally added into the component A or the component B; and B component polyester polyol: plasticizer: the polyisocyanate is 1 to 0.5 to 1 to 3.5 to 5, and the polyester polyol with the water content of not more than 0.03 percent and the plasticizer are selected for preparation at normal temperature; a is B1: 1 to 1.3.

Example 32A component modified waterglass: 330N is 8:3.38 The modified water glass is as follows: gamma-aminopropyltriethoxysilane: the dodecanol ester is 100:1.5:1

Component B PE7762: trioctyl acetyl citrate (ATOC): IPDI and M20S are each half 1: 0.56

A:B 1:1.23 。

Example 33A component modified waterglass: 210N and 330N are each 5.71:3.26, the modified water glass is that the weight ratio of water glass: gamma-aminopropyltriethoxysilane: the dodecanol ester is 100:1.5:1.5

Component B PE7762: trichloroethyl phosphate: IPDI and PAPI are each half 1: 0.47

A:B 1:1.25。

Example 34A component modified waterglass: 330N is 6:3.46, the modified water glass is water glass: gamma-aminopropyltriethoxysilane: the dodecanol ester is 100:1.5:2

And each of the component B PE2612 and PE7762 is half: plasticizer: IPDI and PAPI are respectively 1: 0.3.

Example 35A component modified waterglass: 330N is 6:3.33, the modified water glass is that the water glass: gamma-aminopropyltriethoxysilane: the dodecanol ester is 100:1.5:1, adding 3 percent of fumed silica and 3 percent of water

And each of the component B PE2612 and PE7762 is half: palm oil: IPDI and PAPI are each half 1

A:B 1: 1.15。

Example 36A component modified waterglass: polyether polyol (330n: 3.06, the modified water glass is water glass: gamma-aminopropyltriethoxysilane: the dodecanol ester is 100:1.5:1

And each of the component B PE2612 and PE7762 is half: chlorinated paraffin: IPDI and PAPI are each half 1: 0.62.

Example 37A component modified waterglass: 330N is 8:3.59 The modified water glass is as follows: gamma-aminopropyltriethoxysilane: the dodecanol ester is 100:1.5:1

And each of the component B PE2612 and PE7762 is half: long-chain chlorinated paraffin: IPDI and PAPI are each half 1: 0.52

A:B 1: 1 。

Example 38

A (2.6 model water glass 100 gamma-aminopropyltriethoxysilane 1.5 decaglycol ester 1) 600, crude polyether triol 480, long-chain chlorinated paraffin 100, B M20S 200 isophorone diisocyanate 100 environmental protection solvent oil 50: b1, 1.5 the preparation method of the component A and the preparation method of the component B are as described above, and the bonding strength of the nail-nail is 18.5Mpa within 24 hours (the air temperature is 18-20 ℃).

Example 39A (2.6 model waterglass 100. Gamma. -aminopropyltriethoxysilane 1.5 decaglycol ester 1) 600, crude polyether triol 450, B M20S 300

100 parts of isophorone diisocyanate environment-friendly solvent oil 40, namely palm oil 60; b1:1, the preparation method of the component A refers to the example 1, after the addition is finished, the stirring is continued for 60 minutes to obtain the uniform latex with the temperature of more than 8000mpa.s, and the modified water glass component is prepared as the example 1; the preparation method of the component B is as described above: the time is 6 minutes, the clock is used for indicating that the nail is nearly hard, the bonding strength is 9.80Mpa, and the time is 5 days, and the bonding strength is 12.25Mpa for 24 hours (the temperature is 8-9 ℃).

Example 40A: (2.6 model water glass 100, gamma-aminopropyltriethoxysilane 1.5, dodecanol ester 1) 500, crude polyether triol 500, long-chain chlorinated paraffin 100: b: M20S 200 isophorone diisocyanate 200 environmental protection solvent oil 50; a: b1: 1.5; the preparation method of the component A and the preparation method of the component B are as described above: the bonding strength of the nail-nail is 16.2Mpa after 24 hours (the temperature is 18 to 20 ℃).

Example 41A: (2.6 model water glass 100, gamma-aminopropyltriethoxysilane 1.5, decaglycol ester 1) 600, crude polyether triol 450 nitrile rubber solution 120 ABS 50, B: M20S 300 isophorone diisocyanate 100 environmental protection chlorinated paraffin 50 palm oil 60; a: b1.2: 1. the preparation method of the component A is shown in example 1, and the mixture is stirred for 60 minutes after the addition is finished, so that the uniform emulsion with the viscosity of more than 8000mpa.s can be obtained; modified water glass component preparation the same as example 1: the preparation method of the component B is as described above; the surface is dry and nearly hard within 6 minutes, and the bonding strength nail-nail is 9.5Mpa, 5 days and 17.2Mpa within 24 hours (the air temperature is 8~9 ℃).

In the invention, when the component A contains enough polyether polyol and the component B contains excessive polyisocyanate, the mass of the component A can be larger than that of the component B during proportioning.

The viscosity reducer for the polyurethane adhesive comprises water glass and polyisocyanate, and is characterized in that a component A comprises water glass, polyester polyol and/or polyether polyol, or water glass, polyester polyol and/or polyether polyol and a plasticizer, and the viscosity reducer is also characterized by comprising a proper amount of viscosity reducing and stabilizing agent, wherein the viscosity reducing and stabilizing agent is one or the combination of more than one of decaglycol ester, cetyl alcohol ester, phthalate ester, polyethylene glycol, polypropylene glycol, monohydric alcohol and nitrile rubber.

The content of the viscosity-reducing and viscosity-stabilizing agent accounts for 2-8 wt%, preferably 3-5 wt% of the component A, and the monohydric alcohol is liquid aliphatic alcohol and/or aromatic alcohol: the phthalate ester is dioctyl ester. The viscosity-reducing and viscosity-stabilizing agent comprises 2-6 wt% of component A, namely monohydric aliphatic alcohol and monohydric aromatic alcohol. The viscosity-reducing and viscosity-stabilizing agent comprises one or more of methanol, ethanol, propanol, pentanol, heptanol, octanol, benzyl alcohol and phenethyl alcohol. The viscosity-reducing and viscosity-stabilizing agent comprises 2-5 wt% of benzyl alcohol in the component A.

The viscosity reduction and stabilization retarder consists of viscosity reduction and stabilization and polyethylene glycol, and the addition amount of the retarder accounts for 2 to 8wt%, preferably 3 to 6wt% of the component A.

The viscosity reduction and stabilization retarder comprises a combination of polyethylene glycol and benzyl alcohol, and the addition amount of the retarder accounts for 3-5 wt% of the component A.

Polyethylene glycol accounts for 1 to 3wt% of the component A. The component A also contains additives or assistants. The essential constituents of the A-component can be identical or similar to those of the preceding claims for at least waterglass and polyester and or polyether. Directly added with filler and auxiliary agent, the paint is used for quick-drying paint, especially quick-drying metal paint. The viscosity reducer for the polyurethane adhesive is characterized by being used for preparing composite plates among steel films, steel plates and nonmetal plates.

In the following examples, 2 to 5wt% of viscosity reducer and/or viscosity stabilizer, especially 3 to 4wt% of viscosity reducer and/or viscosity stabilizer containing benzyl alcohol are added into the component A, so that the viscosity can be obviously reduced and stabilized, the viscosity is 10000 to 18000mpa.s before the addition and 3500 to 6000mpa.s after the addition by NDJ-1 rotor viscometer test; primary cure or tack-free time 3~6 minutes: the steel-steel bonding strength is 8.52 to 16.45Mpa after 24 to 48 hours, and the invention effect can be achieved. After the viscosity-reducing and viscosity-stabilizing agent is added, the viscosity of the sample is not changed greatly after the observation for 1~3 months.

The following examples still have good wettability and adhesion to steel substrates, better viscosity and storage stability, good dimensional stability after quick-drying and quick-curing in a certain adaptation period, good adhesive strength to steel, wood, stone and the like, no bad smell, safety, environmental protection, easy production and low cost.

It has been surprisingly found in the experiments that the addition of a proper amount of aliphatic or aromatic alcohol with a smaller molecular weight, especially monohydric aliphatic and/or aromatic alcohol, such as methanol, ethanol, propanol, pentanol, benzyl alcohol, phenethyl alcohol, etc., especially monohydric aromatic alcohol such as benzyl alcohol, to some of the more viscous component A of the invention under stirring, can effectively reduce and stabilize the viscosity of the composition, and the bonding strength can still achieve the invented effect. The viscosity-reducing and viscosity-stabilizing agent comprises one or more of methanol, ethanol, propanol, pentanol, heptanol, octanol, ethylene glycol, propylene glycol, butanediol, pentanediol, glycerol, polyethylene glycol, polypropylene glycol, benzyl alcohol, phenethyl alcohol and the like, preferably benzyl alcohol. Polyethylene glycol and polypropylene glycol have the function of adjusting the surface dry time. In tests, surprisingly, when the water glass accounts for more than 1/2 of the component A, the component A is prepared by the embodiment, the component A is easy to separate after being stirred for a short time, and can be obviously thickened due to association after being stirred for one time or more, while the component A with the water glass content of less than 1/2 can be uniformly emulsified after being stirred for one time, but has the tendency of thickening after being stirred for a certain time or within a certain viscosity and thickening after being stored for a longer time, and although the component A also has good emulsifying property and fluidity, the viscosity is usually more than 8000mpa.s or even 15000mpa.s (NDJ-1 test), and does not meet the use requirements of certain enterprises. The inventor adopts various commercially available viscosity reducers to achieve the expected effect, and then accidentally finds in the test that the viscosity reduction effect can be remarkably achieved by adding the viscosity reduction and stabilization agent of the invention into the component A. The viscosity-reducing and viscosity-stabilizing agent can also be one or the combination of more than one of glycol decaester, cetyl alcohol ester, phthalate, polyethylene glycol, polypropylene glycol and monohydric alcohol. The phthalate is preferably dioctyl. The monohydric alcohol is liquid fatty alcohol and/or aromatic alcohol. The aliphatic alcohol is one or more of methanol, ethanol, propanol, butanol and pentanol. The aromatic alcohol is one or more of benzyl alcohol, phenethyl alcohol and derivatives thereof. The aromatic alcohol is benzyl alcohol. It was also found that surfactants such as tween series (tween 50, 60, 80), OP-10, TX-10, cocamidopropyl betaine, polypropylene glycol, although having a certain viscosity reducing effect, accelerate the reaction rate and cause foaming, seriously affecting the bonding strength. Tests also find that the polyethylene glycol can cause the foaming of a two-component mixture, one or the combination of the solvent oil and the polyethylene glycol can obviously prolong the reaction time, and find that the combination of one or the combination of the solvent oil and the polyethylene glycol and monohydric alcohol, especially the combination of the polyethylene glycol and the monohydric alcohol such as benzyl alcohol has good viscosity reduction and stabilization effects, and also has the effects of inhibiting the foaming and prolonging the reaction time, and the bonding strength can achieve the effect of the invention, and also has the unexpected effect of temperature-dependent viscosity. The addition amount of the viscosity stabilizing and viscosity reducing agent is 3 to 6wt%, preferably 3 to 5wt%.

Example 42A component modified waterglass: 300N is 4:3.08, the modified water glass is that the water glass: gamma-aminopropyltriethoxysilane: the dodecanol ester is 100:1.5:1, adding 3wt% of benzyl alcohol and 2wt% of dioctyl ester

And each of the component B PE2612 and PE7762 is half: palm oil: IPDI and PAPI are each half 1:0.65:4.14

A：B 1：1.1。

Example 43A: (2.6 model water glass 100, gamma-aminopropyl triethoxy silane 1.5, lauryl ester 1.5) 64, PE7762, 330N 32, palm oil (specific gravity 1.18) 140 adding gamma-aminopropyl triethoxy silane 1.3 lauryl ester 1.4, after mixing evenly, using NDJ-1 rotor viscometer No. 4 rotor to measure viscosity more than 15000mpa.s, still has certain non-Newtonian fluid property, taking 200g, adding benzyl alcohol 6g, PEG400 4g, stirring evenly, using NDJ-1 rotor viscometer No. 3 rotor to measure viscosity of 6500mpa.s,72 hours 00mpa.s,7 days 6400mpa.s after 1 hour:

b:3288B A: b1: 1: preparation of a-and B-components reference example 14: the surface is dried for 24 hours in 38 minutes (air temperature 8~9 ℃) and the bonding strength nail-nail is 10.68MPa.

Example 44A: (2.6 model water glass 100 gamma-aminopropyl triethoxysilane 1.5) 400, 330N291.8 are taken, after being mixed evenly, the viscosity is measured by NDJ-1 rotor viscometer No. 4 rotor and is more than 15000mpa.s, and a certain non-Newtonian fluid characteristic is still provided, 200g is taken, benzyl alcohol 6, PEG200, dodecanol ester 1 is added and stirred evenly, after 1 hour, the viscosity is measured by NDJ-1 rotor viscometer No. 3 rotor and is 6100mpa.s, after 72 hours 5800mpa.s,7 days 5400mpa.s: b: polyester polyols (PT 2612 and PE7762 halves) 151.8, 330N 91.8, M20S322.7, ipdi322.7, dimethyl carbonate 10.5, acetyl trioctyl citrate (ATOC) 100: a: b1: surface dry for 132 minutes, and the bonding strength is nail-nail 21.15Mpa.

Example 45A: (2.6 model water glass 100, gamma-aminopropyl triethoxysilane 1.5, dodecanol ester 1) 500, 330N308.4, after being mixed uniformly, the viscosity is greater than 15000mpa.s measured by NDJ-1 rotor viscometer No. 4 rotor, and certain non-Newtonian fluid characteristics are still provided, 200g of benzyl alcohol 6g, octanol 1g and PEG400 3g are taken and stirred uniformly, after 1 hour, the viscosity is 5300mpa.s measured by NDJ-1 rotor viscometer No. 3 rotor, 72 hours 4800mpa.s for 7 days, 4500mpa.s, B: polyester polyols PE2612 and PE7762 each half) 151.8, M20S311.4 IPDI314.4 dimethyl carbonate 10.4, epoxidized soybean oil 100; a: b1: the surface is dried for 1 minute and 30 minutes, and the bonding strength of the nail-nail is 20.38Mpa after 24 hours at normal temperature.

Example 46A: (2.6 model water glass 100, gamma-aminopropyl triethoxysilane 2.5, dodecanol ester 1.5) 400, 330N308.4 epoxy soybean oil 100 amino formaldehyde resin (03) 120 plus 3000 mesh silica powder 160: after uniformly mixing, measuring the viscosity by using a spindle No. 4 NDJ-1 spindle viscometer to be more than 15000mpa.s, and still having certain non-Newtonian fluid characteristics, taking 200g, adding 1g of alcohol and 7g of benzyl alcohol, uniformly stirring, measuring the viscosity by using a spindle No. 3 NDJ-1 spindle viscometer to be 7200mpa.s,72 h 6900mpa.s,7 days 6700mpa.s after 1 hour: b: polyester polyols (half of PE2612 and PE 7762) 151.8, M20S314.4 IPDI314.4 dimethyl carbonate 10.4: a: b1: the surface is dry and nearly hard after 1 minute and the bonding strength is 2 hours at normal temperature and 24 hours-nail 22.65Mpa.

Example 47A: (2.6 model water glass 100, gamma-aminopropyl triethoxysilane 1.5, dodecanol ester 1) 800, 330N 359, after uniformly mixing, measuring the viscosity by using NDJ-1 rotor viscometer No. 4 rotor to be more than 15000mpa.s, and having certain non-Newtonian fluid characteristics, taking 200g, adding 6g of benzyl alcohol and 200g of PEG, uniformly stirring, measuring the viscosity by using NDJ-1 rotor viscometer No. 3 rotor to be 5200mpa.s,72 h 0048mpa.s and 7 days 4400mpa.s after 1 hour; b: polyester polyols (PE 2512 and PE7762 halves) 193.6, M20S 928.5 dimethyl carbonate 18.7, trichloroethyl phosphate 67 butyl methacrylate 33; a: b1: the surface is dried for 1 minute 23 minutes, and the bonding strength nail-nail is 13.28Mpa for 24 hours at normal temperature.

Example 48A: (2.6 model water glass 100, gamma-aminopropyl triethoxysilane 2, dodecanol ester 1.5) 400, 330N 340, 5000 mesh silica micropowder 50; after mixing uniformly, measuring the viscosity to be more than 15000mpa.s by using a NDJ-1 rotor viscometer No. 4 rotor and still have certain non-Newtonian fluid characteristics, taking 200g, adding 8g of benzyl alcohol, stirring uniformly, measuring the viscosity to be 6000mpa.s,72 hours 5800mpa.S and 7 days 5600mpa.s by using an NDJ-1 rotor viscometer No. 3 rotor after 1 hour; b: polyester polyols (PE 2512 and PE7762 halves) 193.6, M20S 928.5 dimethyl carbonate 18.7, trichloroethyl phosphate 67 butyl methacrylate 33; a: b1: the surface is dried for 1 minute 10 hours, and the bonding strength of the nail-nail is 13.28Mpa for 24 hours at normal temperature.

In the above examples with IPDI and/or HDI added, most of the adhesive layers have cohesive failure, wherein IPDI accounts for 1/2 of the adhesive layer failure in the polyisocyanate, and the adhesive layer has firm adhesion at the steel interface: the IPDI in the polyisocyanate exceeds 1/2.

In the various technical schemes, 3 to 50wt%, preferably 5 to 25wt%, and particularly preferably 10 to 20wt% of foaming agent is added into the component A, and the component A can be used as an environment-friendly foaming adhesive: the foaming agent is a polyurethane foaming agent and/or a low-boiling-point organic solvent and polypropylene glycol and/or polyethylene glycol with a molecular weight of 200 to 500 and/or a surfactant.

The following examples show that viscosity can be significantly reduced and stabilized by adding 2 to 5wt% monohydric alcohol, especially 3 to 4wt% ethanol and benzyl alcohol, to component A, as measured by a NPJ-1 rotor viscometer, with viscosity 10000 to 18000mpa.s before monohydric alcohol addition and 5000 to 8000mpa.s after addition: primary cure or tack-free time 3~6 minutes; 24 to 48 hours, the steel-wood bonding strength is 3.52 to 6.45Mpa, and the wood is damaged; the steel-brick bonding strength is 4.23 to 6.38Mpa, and the effect of the invention can be achieved when the brick is damaged. After the viscosity reducing and stabilizing agent is added, the viscosity of the sample is not greatly changed after 1~3 months observation.

Example 49A: (3.1 model Water glass 100 gamma-aminopropyl triethoxysilane 1.5) 600, polyester polyol 100, 330N 314.8, and benzyl alcohol 3.5wt%:

b: polyester polyols (PE 2612: PE7762: PE1320, 1/3 each) 164.8 m20s403.7 ipdi403.7 dimethyl carbonate 13, butyl acrylate 100, a: b1: 1.

example 50A: (2.6 model water glass 100, gamma-aminopropyl triethoxysilane 1.5, dodecanol ester 1) 400, 330N308.4, 140 add gamma-aminopropyl triethoxysilane 1.3 dodecanol ester 1.4 benzyl alcohol 3wt%:

b: polyester polyols (half of PE2612 and PE 7762) 151.8, 330N108.4, M20S311.4 IPDI314.4 dimethyl carbonate 10.4 palm oil (specific gravity 1.18) 100, a: b1: 1.

from the above examples and comparative examples, it can be seen that the invention has better quick-drying and early strength properties and adhesive strength for polyurethane adhesives of size under the condition of no addition of catalyst, has no unpleasant odor and toxicity of acrylic acid cyan-red AB adhesive, has certain flame retardant property and slow-release antirust property, avoids the influence of the addition of catalyst in the A component containing a large amount of water glass on the metal adhesive stability, also avoids the influence of the addition of catalyst in the B component on the storage period of the adhesive, and the influence of the addition of catalyst in the A component with high pH value on the catalyst stability, and has the manufacturing cost greatly lower than that of the conventional polyurethane and acrylic acid AB adhesive.

The present invention is not limited to the above-mentioned embodiments, and any obvious modifications, substitutions or alterations by those skilled in the art based on the present invention shall fall within the protection scope of the present invention, which shall be subject to the scope defined by the appended claims.

Claims (29)

1.A green quick-drying AB glue with stable performance comprises water glass and polyisocyanate, and is characterized in that the modified water glass in the component A: the polyether polyol is 4~8:3~4, the modified water glass is water glass: gamma-aminopropyltriethoxysilane as 100:1 to 2.5, or water glass: gamma-aminopropyltriethoxysilane: dodecanol ester is 100:1 to 2.5:0.8 to 1.6, wherein the molecular weight of the polyether polyol is 400 to 6500, and the polyether polyol with the molecular weight of 3000 to 6000 is contained; the polyester polyol and/or polyether polyol in the component B: plasticizer: the polyisocyanate is 1 to 0.5 to 1, 3.5 to 5, 0 to 10 percent of additive is additionally added into the component A or the component B, the additive comprises one or more of pigment, filler, essence, water, organic solvent, dispersant, viscosity-reducing and viscosity-stabilizing agent, flatting agent, thickening agent, toughening agent, catalyst, polymerization inhibitor, flame-retardant glue, smoke suppressor, defoaming agent, preservative, antirust agent, antioxidant, hydrolysis-resistant agent or low-temperature resistant agent, and the proportion of the component A to the component B is 1.5:1 to 1.5.

2. A green quick-drying AB adhesive with stable performance comprises water glass and polyisocyanate, and is characterized in that in the component A, the modified water glass comprises 3 to 9 parts of polyether polyol, 1 to 3 parts of polyether polyol; the modified water glass is prepared from the following components in percentage by weight: gamma-aminopropyltriethoxysilane 100:0.5 to 3; or the modified water glass is water glass: gamma-aminopropyltriethoxysilane: dodecanol ester is 100:0,5 to 3:0.5 to 3, selecting polyether polyol with alkali resistance; and the polyester polyol in the component B: polyether polyol: plasticizer: diphenylmethane diisocyanate and/or polymethylene polyphenyl polyisocyanate and/or isophorone diisocyanate and/or hexamethylene polyphenyl polyisocyanate is 1: 0~2:0.3 to 1:5 to 10, 0 to 100 percent of additive is added into the component A or the component B, the polyether polyol is bifunctional or polyfunctional polyether polyol, is one or a combination of polypropylene oxide polyol, polymer polyol, polytetrahydrofuran polyol or polyethylene oxide polyol, the molecular weight is 2000 to 5000, the proportion of the component A to the component B is 1.5:1 to 1.5.

3. The green quick-drying AB glue with stable performance as claimed in claim 1~2, wherein the sodium silicate content in the water glass of component A is 30-60%, and the modulus is 1.5-3.5.

4. The green fast-drying AB glue with stable performance of claim 2, characterized in that the additive in the component A or the component B comprises one or more of pigments, fillers, essences, water, organic solvents, dispersants, viscosity-reducing and viscosity-stabilizing agents, leveling agents, thickeners, toughening agents, catalysts, polymerization inhibitors, flame-retardant glues, smoke-eliminating agents, antifoaming agents, preservatives, rust inhibitors, antioxidants, hydrolysis-resistant agents or low-temperature resistant agents.

5. The green quick-drying AB glue with stable performance as claimed in claim 3, wherein the additive of the component A contains 0 to 0.5 percent of catalyst.

6. The stable green quick-drying AB glue of any one of claims 2 or 4, wherein in the component A, the modified water glass-polyether polyol is 4:2 to 3.5 percent of catalyst, and 0 to 0.3 percent of catalyst.

7. The green quick-drying AB glue with stable performance as claimed in claim 1, wherein the polyether polyol is a combination of alkali resistance with a molecular weight of 400-1000 and a molecular weight of 3000-6000.

8. The stable green fast dry AB glue of claim 1, wherein the polyether polyol is 220N, 210N, N, N403, 330N、WANOL-F3135 or a combination of more than one.

9. The stable green fast dry AB glue of claims 2,4 or 5 wherein the polyether polyol is 220N, 330N、WANOL-F3135 or a combination of more than one.

10. The performance stabilized green fast dry AB glue of claim 7, wherein the polyether polyol comprises one or a combination of more than one of 330N or WANOL-F3135.

11. The stable green fast dry AB glue of claim 1 wherein the polyether polyol comprises a polyoxyethylene polyoxypropylene block polymer.

12. The green fast dry AB glue with stable performance of any one of claims 1,2, 4, 5, 7, 8, 10 or 11, characterized in that the additive in the component A further comprises 1 to 20 percent of organic solvent.

13. A green fast dry AB glue with stable performance according to any one of claims 1,2, 4, 5, 7, 8, 10 or 11, characterized in that the additive in the component A contains 0.5 to 10 percent of water.

14. The stable green fast dry AB glue of claim 1,2, 4, 5, 7, 8, 10 or 11, wherein the additive in component A contains 1-10% of surfactant or dispersant, and the surfactant is alkali-resistant polyether polyol.

15. The green fast dry AB glue of claim 1,4, 5, 7, 8, 10 or 11 wherein the viscosity reducing and stabilizing agent is selected from the group consisting of lauryl alcohol ester, cetyl alcohol ester, phthalate ester, monohydric alcohol, and combinations thereof.

16. The stable green fast dry AB glue of any of claims 1,2, 4, 5, 7, 8, 10 or 11 wherein the viscosity reducing and stabilizing agent of the additive is one or a combination of mineral spirit and polyethylene glycol in combination with monohydric alcohol.

17. The stable green quick-drying AB glue of claim 15, wherein the monohydric alcohol is liquid aliphatic alcohol and/or aromatic alcohol, and the aliphatic alcohol is one or more of methanol, ethanol, propanol, butanol and pentanol; the aromatic alcohol is one or more of benzyl alcohol, phenethyl alcohol and derivatives thereof.

18. The stable green quick-drying AB glue of claim 16, wherein the monohydric alcohol is liquid aliphatic alcohol and/or aromatic alcohol, and the aliphatic alcohol is one or more of methanol, ethanol, propanol, butanol and pentanol; the aromatic alcohol is one or more of benzyl alcohol, phenethyl alcohol and derivatives thereof.

19. The stable green fast dry AB glue of any one of claims 17 or 18 wherein the aromatic alcohol is benzyl alcohol.

20. The stable green fast dry AB glue of any one of claims 1,2, 4, 5, 7, 8, 10, 11, 17 or 18 wherein IPDI in the isocyanate contained in component B is 1/5~1/2 of the polyisocyanate.

21. The stable green quick-drying AB glue of claim 19, wherein IPDI in component B accounts for 1/3~1/2 of polyisocyanate.

22. The stable green fast dry AB glue of any of claims 1,2, 4, 5, 7, 8, 10, 11, 17 or 18 wherein the polyisocyanate is M20S.

23. The stable green fast dry AB gum of any one of claims 1,2, 4, 5, 7, 8, 10, 11, 17, 18, or 21, wherein the polyester polyol is one or more polyester polyols based on adipic acid, terephthalic anhydride, phthalic anhydride, and 1,4-butanediol, 1,6-hexanediol, diethylene glycol, or neopentyl glycol.

24. The stable green fast dry AB gum of claims 1,2, 4, 5, 7, 8, 10, 11, 17, 18, or 21, wherein the polyester polyol is one or a combination of PE3030, PE2811, PE2708, PE1320, PT2612, PT2512, PE9956, PE5556, HF8011, HF8020, HF8025, HF8056, HF8211, HF 8356.

25. The stable green fast dry AB glue of claims 1,2, 4, 5, 7, 8, 10, 11, 17, 18 or 21 wherein the polyester polyol in the component is one or a combination of more than one of PE8815T, PE7762, PT2612 and PT 2512.

26. The green fast dry AB glue with stable performance as claimed in any one of claims 1,2, 4, 5, 7, 8, 10, 11, 17, 18 or 21, which is characterized in that polyester polyol prepared from alcoholysis recovered bottle material is selected, and the average molecular weight is 3000 to 30000.

27. A green, fast drying, AB glue having stable properties according to any of claims 1,2, 4, 5, 7, 8, 10, 11, 17, 18 or 21, characterized in that the polyether polyol of part A is a crude polyether polyol which has not been subjected to water removal and neutralization.

28. A green fast drying AB glue having stable properties according to any of claims 1,2, 4, 5, 7, 8, 10, 11, 17, 18 or 21 wherein component A is optionally blended with a plasticizer.

29. The preparation method of the green quick-drying AB glue with stable performance according to any one of claims 1,2, 4, 5, 7, 8, 10, 11, 17, 18 or 21, characterized in that the component A is prepared by adding modified water glass into polyether polyol, stirring while adding, and then continuing to stir for 30 to 120 minutes, or stirring first for 15 to 30 minutes, standing for 30 to 12 hours, and then continuing to stir for 1~2 times to obtain a uniform emulsion; the component B is prepared by mixing polyester polyol and/or polyether polyol, plasticizer and polyisocyanate at normal temperature to ensure that the component B is in a non-prepolymer state or an incomplete prepolymer state.