Environment-friendly quick-drying AB glue and preparation method thereof

文档序号：965900 发布日期：2020-11-03 浏览：9次中文

阅读说明：本技术 一种环保快干ab胶及其制备方法 (Environment-friendly quick-drying AB glue and preparation method thereof ) 是由卢清友卢思竹黄义邱顺于 2019-06-04 设计创作，主要内容包括：一种环保快干AB胶及其制备方法,涉及一种改性聚氨酯胶粘剂尤其是一种能粘接钢铁等金属及硬质非金属基材的复合双组份胶,提供了一种固化快、对钢铁润湿性好、粘结强度较高、性能较稳定、成本较低、易于制备的高性能环保水玻璃聚氨酯复合胶粘剂。它是将耐碱性聚醚多元醇与水玻璃或改性水玻璃复配结合适量增塑剂或添加剂,同时在聚氨酯组分中调整异氰酸酯成分和/或预聚体及环保增塑剂比例。不仅可以在没有催化剂和较低温度下较快固化,实现早强高强,而且粘接性好,具有良好的综合性能和贮存稳定性,易于制备。(An environment-friendly quick-drying AB adhesive and a preparation method thereof relate to a modified polyurethane adhesive, in particular to a composite two-component adhesive capable of bonding metal such as steel and hard non-metal base materials, and provide a high-performance environment-friendly water glass polyurethane composite adhesive which has the advantages of fast curing, good wettability to steel, higher bonding strength, more stable performance, lower cost and easy preparation. Alkali-resistant polyether polyol and water glass or modified water glass are compounded and combined with a proper amount of plasticizer or additive, and meanwhile, the proportion of isocyanate component and/or prepolymer and environment-friendly plasticizer is adjusted in polyurethane component. 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, good comprehensive performance and storage stability, and is easy to prepare.)

1. The environment-friendly quick-drying AB glue comprises water glass and polyisocyanate, and is characterized in that the component A is modified with the following components: the polyether polyol is 2.8-8: 2.5-4.5, the modified water glass is water glass: gamma-aminopropyltriethoxysilane as 100: 0.5-3, or the modified water glass is water glass: gamma-aminopropyltriethoxysilane: the dodecanol ester is 100: 0.5-3: 0.5-3, and the component B comprises polyester polyol: plasticizer: the polyisocyanate is 1: 0.3-1.5: 3-6, and polyester polyol with the water content of not more than 0.03% and a plasticizer are selected and prepared at normal temperature; and B component polyester polyol: plasticizer: the polyisocyanate is 1: 0.5-1: 3.5-5, and 0-10% of the component A or the component B is added; the proportion of the component A to the component B is 1.5: 1-1: 1.5.

2. The environment-friendly quick-drying AB glue as claimed in claim 1, wherein the polyether polyol [0041] is one or a combination of polyether polyols which are suitable for being matched with water glass, have molecular weight of 2000-5000, and have surface activity and/or alkali resistance, such as polyoxypropylene polyol, polymer polyol, polytetrahydrofuran polyol or polyoxyethylene polyol series.

3. The environmentally friendly, quick-drying AB glue of claim 2, wherein the polyether polyol is one or a combination of more than one of 220N, 210N, N204, N403, 330N, WANOL-F3135.

4. The environmentally friendly, quick drying AB glue of claim 1, wherein the polyester polyol is a polyester polyol based on adipic acid, terephthalic anhydride, phthalic anhydride-1, 4 butanediol, 1,6 hexanediol, diethylene glycol, or neopentyl glycol.

5. The environment-friendly quick-drying AB glue according to claim 4, characterized in that the component A is modified water glass: the polyether polyol is 4: 3-4, the modified water glass is water glass: gamma-aminopropyltriethoxysilane as 100: 1-2.5, or water glass: gamma-aminopropyltriethoxysilane: the dodecanol ester is 100: 1-2.5: 0.8 to 1.6.

6. The environment-friendly quick-drying AB glue according to any one of claims 1 to 5, wherein the component B comprises the following components in percentage by weight: diphenylmethane diisocyanate or polymethylene polyphenyl polyisocyanate: the isophorone diisocyanate and/or hexamethylene polyphenyl polyisocyanate is 1: 4-12.

7. The environment-friendly quick-drying AB glue of claim 6, wherein IPDI in the component B is 1/2-1/5 in the polyisocyanate.

8. The environmentally friendly, quick-drying AB glue of claim 8, wherein the plasticizer of [0045] A is a plasticizer free of ester groups.

9. The environment-friendly quick-drying AB glue according to claim 8, wherein the additive in the component [0016] A further contains 1-20 wt% of an organic solvent, preferably 3-15 wt%, more preferably 5-10 wt%.

10. The environment-friendly quick-drying AB glue according to claims 1 to 9, 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 during stirring, continuing to stir for 15-30 minutes after the addition is finished, 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 addition is finished, controlling the temperature at 25-40 ℃, adding 0.5-3 wt% of alcohol ester or alcohol ether, preferably dodecanediol ester, continuing to stir for 30-90 minutes, continuing to stir before the temperature is reduced to room temperature, directly discharging the water glass after the stirring is stopped, or timely sealing the water glass by a filter material to prevent film formation; or, in order to save labor, time and electricity, the mixture can be temporarily kept for 30 to 12 minutes after being primarily stirred uniformly, and then stirred for 30 to 60 minutes after layering to obtain a 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 containing 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 out the material;

the component B can be prepared according to the preparation method of the component B in the step 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. performing vacuum dehydration at 110-120 ℃ for 1.5-3 h, then cooling to 60-80 ℃, or directly selecting and uniformly mixing polyurethane-grade polyether polyol, polyester polyol and a plasticizer at the temperature, adding the mixture into isocyanate while stirring, continuously stirring for 1-2 hours, cooling to 40-50 ℃, adding an additive if necessary, and uniformly stirring to directly discharge or filter and discharge; 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 20-30 ℃ or lower temperature such as 10-20 ℃, nitrogen protection is adopted if necessary, and discharging can be realized after uniform stirring; when in use, the component A and the component B are uniformly mixed according to the weight ratio of 1.5: 1-1: 1.5 and then are applied.

Technical Field

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 (-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" effectively solves these problems 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 solvent to an isocyanate component, and at the same time, enables the adhesive to be cured faster without a catalyst; the Chinese patent application CN104910817A 'an environment-friendly composite resin and an adhesive and a coating based on the resin' further improves the performance of the 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 a preparation method thereof," further improves the adhesive property of the glue solution greatly by adding a proper amount of silane coupling agent and dodecyl glycol ester into a water glass component, and simultaneously the glue application amount has viscosity capable of being mechanically sprayed; the 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, namely a water-based oily low-viscosity environment-friendly two-component adhesive and a preparation method thereof, analyzes the cause of the hair growing phenomenon of the composite adhesive of the water-based component of the water glass and the oily component of the polyurethane 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 and the like is limited, the steel-steel bonding strength, especially the shearing strength, is always difficult to be stabilized more than 5Mpa, and the rigidity is large and the flexibility is insufficient, the interface is usually damaged in a steel-steel opposite pulling bonding test, the steel-steel opposite pulling bonding test is not suitable for bonding between steel and the like in a movable structure or an object, the steel-steel bonding strength can not be used as a structural adhesive, and a catalyst or an organic tin catalyst is usually added for obtaining surface drying and primary curing effect within 3 minutes or 5 minutes, tests show that the stability of the steel-steel bonding effect is often influenced when the organic amine catalyst or the organic tin catalyst is added into the water glass-polyurethane system adhesive containing a large amount of water glass, the catalyst is easy to be hydrolyzed and failed when the catalyst is added into the, in order to compensate the performance loss caused by the loss, the method also tries to improve the wettability of the sizing material on the steel interface and improve the interface bonding force by adding a proper amount of small molecular components and adhesion promoters, and has little effect. 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 an environment-friendly high-performance environment-friendly quick-drying AB adhesive and a preparation method thereof, and aims to solve the technical problems of preparing a polyurethane composite adhesive which is quick to cure, good in wettability to steel, high in bonding strength, stable in performance and low in 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 environment-friendly quick-drying AB glue comprises water glass and polyisocyanate, and is characterized in that the component A is the water glass and/or modified water glass, and the modified water glass is the following components: gamma-aminopropyltriethoxysilane 100: 0.5 to 3; or the modified water glass is water glass: gamma-aminopropyltriethoxysilane: the dodecanol ester is 100: 0, 5-3: 0.5-3, and further preferably water glass: gamma-aminopropyltriethoxysilane 100: 1 to 1.8; or water glass: gamma-aminopropyltriethoxysilane: the dodecanol ester is 100: 1-1.5: 0.8' 1.2; the component B is a polyurethane component, wherein the weight ratio of polyester polyol: polyether polyol: plasticizer: 0-1 of diphenylmethane diisocyanate or polymethylene polyphenyl polyisocyanate and/or isophorone diisocyanate and/or hexamethylene polyphenyl polyisocyanate: 0.6-5: 0-1: 8-15, and 0-100% of an additive is added to the component A or the component B; a and B are 1:1.5 to 2.5.

The environment-friendly quick-drying AB glue is characterized in that the component A is water glass and/or modified water glass, wherein the modified water glass comprises the following components in parts by weight: gamma-aminopropyltriethoxysilane 100: 0.8 to 2.5; or the modified water glass is water glass: gamma-aminopropyltriethoxysilane: the dodecanol ester is 100: 0, 5-2.5: 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: 1-1.5: 0.8' 1.2; and B component polyester polyol: polyether polyol: plasticizer: the polyisocyanate is 1: 1.91-4.33: 0.47-0.69: 3.17-5.45; a and B1 are 1: 1-3.86.

The environment-friendly quick-drying AB glue comprises water glass and polyisocyanate, and is characterized in that the component A is modified with the following components: the polyether polyol is 2.8-8: 2.5-4.5, the modified water glass is water glass: gamma-aminopropyltriethoxysilane as 100: 0.5-3, or the modified water glass is water glass: gamma-aminopropyltriethoxysilane: the dodecanol ester is 100: 0.5-3: 0.5 to 3; and B component polyester polyol: plasticizer: the polyisocyanate is 1: 0.3-1.5: 3-6, and polyester polyol with the water content of not more than 0.03% and a plasticizer are selected and prepared at normal temperature; 0-10%, preferably 3-6% of additive is additionally added into the component A or the component B; 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: 1-2.5, or water glass: gamma-aminopropyltriethoxysilane: the dodecanol ester is 100: 1-2.5: 0.8-1.6: 0-10% of additive is additionally added into the component A or the component B; and B component polyester polyol: plasticizer: the polyisocyanate is 1: 0.5-1: 3.5-5.

The environment-friendly quick-drying AB glue is characterized in that water glass in the component A is modified water glass, wherein the modified water glass is formed by adding 1-2.5 wt% of gamma-aminopropyl triethoxysilane into the water glass, or the modified water glass is formed by adding 1-2.5 wt% of gamma-aminopropyl triethoxysilane into the water glass, 1-3 wt% of decaglycol ester, and 1-1.5 wt% of decaglycol ester is further preferred; and the plasticizer in the component B: polyester polyol: the ratio of diphenylmethane diisocyanate or polymethylene polyphenyl polyisocyanate and/or isophorone diisocyanate and/or hexamethylene polyphenyl polyisocyanate is (1: 1-4): 8-15, preferably 1: 1.5-3: 8-12, more preferably 1: 2-3: 8-10; 0-100 wt%, preferably 0.1-10 wt% of an additive is added to the component A or the component B; 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 1-1.5: 1, preferably A: B is 1-1.4: 1, and 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.

0-0.5 wt% of catalyst in the component A.

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

The additive in the component A or the component B of the environment-friendly quick-drying AB glue comprises one or more of pigment, filler, essence, water, organic solvent, surfactant, dispersant, viscosity reducer, viscosity stabilizer, flatting 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 1-10 wt%, preferably 3-7 wt%, more preferably 4-6 wt% of a surfactant or a dispersant.

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

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

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 having a plasticizing effect directly or through a subsequent reaction, such as 1, 2-propylene glycol carbonate, dimethyl carbonate, glyceryl triacetate, 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 10 weight percent of water, more preferably 0.5 to 8 weight percent of water, and most preferably less than 3 weight percent or 5 weight percent 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 component (A) can be one or more of dodecanol ester, cetyl alcohol 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 component A water glass is 30-60 wt%, and the modulus is 1.5-3.5; 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 isocyanate and/or the hexamethylene polyphenyl polyisocyanate are (1: 4) - (12: 0.1) - (13).

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: 4-8.

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.

The environmentally friendly fast-drying AB glue of any one of claims 1 to 3, wherein IPDI and/or HDI or a trimer thereof in the component B is 1/2 to 1/5 of polyisocyanate.

The environment-friendly quick-drying AB glue according to any one of claims 1 to 3, characterized in that IPDI in the component B is contained in 1/2 to 1/3 in the polyisocyanate.

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

0-100 wt% of polyisocyanate is additionally added in the component B.

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

The environment-friendly quick-drying AB glue is two-component 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 during stirring, continuing to stir for 15-30 minutes after the addition is finished, 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 addition is finished, controlling the temperature at 25-40 ℃, adding 0.5-3 wt% of alcohol ester or alcohol ether, preferably dodecanediol ester, continuing to stir for 30-90 minutes, continuing to stir before the temperature is reduced to room temperature, directly discharging the water glass after the stirring is stopped, or timely sealing the water glass by a filter material to prevent film formation; or, in order to save labor, time and electricity, the mixture can be temporarily kept for 30 to 12 minutes after being primarily stirred uniformly, 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;

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

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

3. then adding polyether polyol;

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 20-30 ℃ or lower temperature such as 10-20 ℃, nitrogen protection is adopted if necessary, and discharging (filtering if necessary) can be realized if uniform stirring; when in use, the component A and the component B are uniformly mixed according to the weight ratio of 1.5: 1-1: 1.5 and then are applied.

In the context of the present invention, the polyester polyols can be polyester polyols 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, PT2612(PE2612)、PT2512(PE2512)PE9956, PE5556 and the like, and one or a combination of HF8011, HF8020, HF8025, HF8031, HF8040, HF8056, HF8211, HF8356, HF8765, HF86304, HF86407 and the like, a hydroxyl value of 22-680, an acid value of 0.1-3, a molecular weight of 400-4006000; 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 polyhydric alcohol may be ethylene glycol, propylene glycol, diethylene glycol, trimethylolpropane, pentaerythritol, etc.

The polyester polyols in the components are the polyester polyols PT2612 with molecular weight less than 2500, especially less than 2000, side base low temperature resistant PE8815T and/or PE7762, etc. and high crystallinity of molecular weight 3000-8000(PE2612) And/or PT2512(PE2512)The design can obtain good storage stability, low-temperature fluidity and excellent wetting, adhering and bonding effects on metals such as steel.

The polyester polyol prepared by alcoholysis recovery bottle material can also be selected, and the average molecular weight is 3000-30000, so that the polyester polyol 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 matching 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 is preferably alkali-resistant and has a combination of molecular weight of 400-1000 and molecular weight of 3000-6000, 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, N204, N403, 330N, WANOL-F3135.

The polyether polyol may comprise polyoxyethylene, polyoxypropylene block polymers.

The plasticizer in the component A 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); phosphates, phosphites; 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-epoxy octadecanoic acid methyl ester, CCP CIZER D-810 plasticizer, dioctoic acid adipate (DOA), phenyl alkylsulfonate, triethylene glycol diisocaprylate, 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 than one 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, the molecular weight of which is 1500-4000; the molecular weight of the prepolymer of the naphthalene diisocyanate is 1200-4000; the molecular weight of the prepolymer of the methyl cyclohexyl diisocyanate is 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 molecular weight of the prepolymer of isophorone diisocyanate is 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 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.

Adding silane coupling agent, especially component A of gamma-aminopropyl triethoxy silane into water glass, particularly, the component A is added with gamma-aminopropyl triethoxysilane and dodecanol ester, the component B is a technical scheme of adding a proper amount of polyester polyol, polyether polyol and plasticizer into polyisocyanate, the component A not only has high stability (the storage period is more than one year, and a sample can still be used for two years), and when the component B containing the limited amount of polyester polyol, polyether polyol, plasticizer and polyisocyanate is used in the ratio of A to B defined in the invention, in particular when the component B is prepared at relatively low temperatures with the polyester polyols, polyether polyols, plasticizers and polyisocyanates, especially IPDI/HDI-containing polyisocyanates, after removal of the water, and/or when partial polyester has smaller molecular weight, the steel-steel bonding effect with unexpected early strength, high strength and excellent toughness 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 to the component B is close to or equal to 1:1 so as to facilitate the operation and application of machines and tools, and the two components also have excellent toughness, are economic in toughness and have 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 effect on the bonding performance, 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 adhesion force and the adhesion 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 polyaddition of polyether polyols is accelerated(assimilation)The reaction speed is increased, the toughness of the solidification body is increased, and the steel-steel shear strength is improved by adding more additives within a certain range. The adhesive can meet the harsh environmental protection requirements of some 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 hard 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 certain water content 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 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

Among the raw materials used in the embodiment of the invention, 2.2-2.5 model (density at 20 ℃ is 1.526-1.599 g/cm3), 2.6-2.9 model (density at 20 ℃ is 1.436-1.465 g/cm3) and 3.1-3.4 model (density at 20 ℃ is 1.368-1.394 g/cm3) 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 is manufactured by Jiangsu Ruitai chemical Co., Ltd; the old bottle material resin is produced by a Chongqing Banan colorful adhesive factory and is produced by the conventional methodThe polyester polyol prepared from the polyethylene terephthalate bottle material recycled by alcoholysis by the method has the advantages that the molecular weight of the polyether polyol is 2000-6000, the molecular weight of the polyester polyol is 3000-10000, the isocyanate is polymeric MDI (NCO 28-32%) produced by Wanhua, PM200(NCO 28-32%) and M20S (NCO 28-31%) produced by Basff. Wanhua polyether polyol 330N (hydroxyl value is 32-36). Polyester polyol PT2612 produced by Zhejiang Huafeng New Material Co., Ltd（1612）HF8056, HF7762, and the like. Other chemical raw materials are purchased on the Internet or in the Chongqing Shijiqiao chemical market through the Alibaba or the Huiyou. 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 glue is cured at the natural temperature of 8-35 ℃, the surface drying time is mostly 3-10 minutes, and the test is carried out 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 hanging heavy object; the shear strength is measured by bending one end of a steel bar with the width of 5mm and the thickness of 2.5mm and the length of about 100mm into a hook shape, gluing and laminating the other end of the steel bar in the length direction for 10-15 mm, polishing the surface to be bonded, bonding the glued surface and the glued surface in opposite directions, 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, gradually 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. And 3-5 repeated treatment is carried out, 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 among samples of the same treatment or embodiment is not large, the test result is larger than that of the standard steel-steel opposite-pulling bonding strength, and the test result of the construction engineering quality inspection and detection center in Chongqing city in the embodiment 8 of the invention is 27.3Mpa according to GB 50728-. 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. the water glass is reserved, or the modified water glass component is prepared by the following steps:

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 stirring for 15-30 minutes first, standing for 30-12 hours, and then continuing to stir for 1-2 times to obtain 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 1.5-3 h at 110-120 ℃ in vacuum, then cooling to 60 ℃, or directly selecting polyurethane-grade polyether polyol and/or polyester polyol and the plasticizer, adding isocyanate under stirring for reacting for 1-2 h, adding a catalyst if necessary for continuously reacting for 0.5-1 h, cooling to 40-50 ℃, adding an additive if necessary, stirring uniformly, and then filtering and discharging;

when the temperature is over 30 ℃, the component A does not contain polyether polyol, and the component B contains polyester polyol, plasticizer and excessive polyisocyanate or polyester polyol, polyether polyol, 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 cannot 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: 1-1: 1.5 and then are applied. In the following examples, the A, B component was prepared by reference to the above-described method, and the B component, not specifically indicated, was prepared by the present heating method.

Comparative example 1A polyester polyol (PT 2612)(PE2612)And PE7762 halves) 42330N 21B: 2714B A: B1: 1

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

Comparative example 2A polyester polyol (PT 2612)(PE2612)And PE7762 halves) 42330N 21 triethanolamine 9.45B: 2714B A: B1: 1

24 hours (the temperature is 15-20 ℃) and the bonding strength is 24kg/2.08MPa and 36kg/3.12 MPa.

Comparative example 3A polyester polyol (PT 2612)(PE2612)And half of PE 7762) 42330N 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 15-20 ℃).

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 15-20 ℃).

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 15-20 ℃).

Comparative example 6 (see JP patent publication 200220698A sizing composition for use in concrete example 4)

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

COMPARATIVE EXAMPLE 7 (REFERENCE TO CN103627330A COMPOSITE RUBBER EXAMPLE 23)