CN110551477A - High-environment-friendly multipurpose two-component adhesive - Google Patents
High-environment-friendly multipurpose two-component adhesive Download PDFInfo
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- CN110551477A CN110551477A CN201811497465.7A CN201811497465A CN110551477A CN 110551477 A CN110551477 A CN 110551477A CN 201811497465 A CN201811497465 A CN 201811497465A CN 110551477 A CN110551477 A CN 110551477A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/08—Polyurethanes from polyethers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
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Abstract
A high-environment-friendly multipurpose two-component adhesive relates to a water glass-polyurethane two-component environment-friendly adhesive capable of adhering multiple hard base materials, and aims to solve the technical problems of good thixotropy and adhesion performance and capability of effectively inhibiting foaming, precipitation and the like caused by adding more fillers in a water glass-polyurethane system, and is characterized in that in the component A, modified water glass is polyether polyol, the fillers are 2.6 ~: 1.7 ~.3 or 3.5 ~: 1: 2.0 ~.3, silane coupling agents are added into the water glass, or silane coupling agents and polyhydric alcohol esters or polyhydric alcohol ethers are added into the water glass, the fillers are substances suitable for being matched with the water glass, in the component B, the polyether polyol, the plasticizer is polyisocyanate, the plasticizer is 1: ~.5: 0.5: 5.5: 6312, the component B is B1: 1.2: 1.5: 5: 5.5: 6312, the component B is B1: 1.2: 1.1: 1.2: 1.5: 5: 6312, the antirust flame retardant is strong in property, the antirust agent is capable of inhibiting the early-hardening of a low carbon, the foaming, the quick-hardening, the aging, the antirust, the component B is capable of inhibiting the early-hardening, and the antirust, so that the antirust, and the.
Description
Technical Field
the invention relates to an environment-friendly polyurethane adhesive, in particular to a water glass-polyurethane two-component environment-friendly adhesive which is low in VOC and can be used for bonding multiple hard base materials.
Background
The polyurethane adhesive has carbamate (-NHCOO-) or isocyanate (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 adhesive 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 (usually heating), poor water resistance and poor adhesive force to the weak polar non-polar base materials such as steel and the like. 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 the problems, the Chinese patent application CN103627330A 'a compound sizing material' effectively solves the problems by adding a synergist and an additive into water glass and adding a foaming adhesive formed by a polyester polyol and/or a polyether polyol prepolymer and a proper amount of solvent into an isocyanate component, and simultaneously enables the sizing material to be cured quickly 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 CN104910817A 'an inorganic-organic high environmental protection double-component adhesive and a preparation method thereof' also provides 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 growth phenomenon of the water glass aqueous component and polyurethane oily component composite adhesive and provides an effective solution, although these series of water glass-polyurethane composite adhesives can replace many solvent adhesives for buildings and industries, have obvious cost performance advantages, are suitable for the bonding of wood, stone, ceramic, cement and other base materials or between them and steel, however, because the water glass-polyurethane system contains a certain amount of foaming adhesive or organic solvent, is not suitable for the occasions requiring strict environment protection and safety, and the thixotropy glue solution is insufficient and easy to flow and drip, the strength, heat resistance and weather resistance of the adhesive material are also required to be further improved, and in order to improve the thixotropy, mechanical strength, bonding strength, heat resistance, weather resistance and flame resistance, the addition of a large amount of filler in the component A influences the fluidity, and is easy to generate precipitation and form dead sediment, and the rigidity is large and the flexibility is insufficient, interface damage is often caused in a steel-steel opposite-pulling bonding test, and a catalyst is often added within 3 minutes or 5 minutes to obtain surface drying and primary curing effects, and tests show that the stability of the steel-steel bonding effect is often influenced when a certain catalyst is added into a water glass-polyurethane system adhesive containing a large amount of water glass, the catalyst is possibly hydrolyzed to lose efficacy when being added into the component A, the storage stability is also influenced when the catalyst is added into the component B, and the wetting property of a sizing material on a steel interface and the interface bonding force are improved by adding a proper amount of small molecular components and adhesion promoters to compensate the performance loss caused by the catalyst, so the effect is very slight. The inventor has tried to add a small amount of polyester, polyester polyol, plasticizer, etc. to the water glass component to further improve the toughness of the glue stock, or the water glass component can float on the liquid surface quickly due to its hydrophobicity to affect the use of the glue stock, and the addition of a small amount of surfactant and dispersant or the use of emulsion or aqueous component thereof can gradually delaminate after the addition due to the water glass being too far away from the density phase thereof, which affects the normal use and commercial value of the two-component glue, and the effects of various emulsification, dispersion and anti-settling treatments are not good enough, and the mutual influence of the performances is often lost, and the expected effects are difficult to be achieved by the conventional experiments and the conventional technical means, and the addition of a large amount of emulsifier can also significantly affect the bonding strength and the. Although a large amount of hydroxide ions in the water glass-polyisocyanate system can absorb carbon dioxide generated by reaction, so that the system is not easy to foam, the foaming with a larger multiplying power is often generated under the conditions that a large amount of fillers are added, the reaction is fast and the quality of two components is close, so that the bonding strength is greatly reduced. The inventor has long searched for related problems under hard conditions in order to effectively inhibit foaming and greatly improve the bonding strength of the adhesive to hard materials such as steel, masonry, cement, wood and the like under the condition that a large amount of water glass and filler are present and conventional raw materials are used, and has obtained unexpected effects.
Disclosure of Invention
The invention aims to provide a green and environment-friendly water glass-polyurethane adhesive and a preparation method thereof, and aims to solve the technical problems of preparing a high-environment-friendly polyurethane composite adhesive which is fast in curing, good in wettability to hard base materials such as steel and the like, high in bonding strength and low in cost and providing a preparation method thereof. The polyester polyol and/or polyether polyol and modified water glass are compounded, combined with a proper amount of plasticizer and filling auxiliary materials, and then are prepared into an environment-friendly adhesive with a polyisocyanate component, particularly a polyisocyanate-prepolymer component, so that the purposes of green environmental protection, good advantages and disadvantages, optimized bonding performance, cost reduction, quick drying and early strength are realized.
The specific technical scheme of the invention is as follows:
a high-environment-friendly multi-purpose two-component adhesive comprises water glass and polyisocyanate, and is characterized in that in the component A, the modified water glass comprises a plasticizer, the polyol comprises a filler 19 ~ 29.5.5: 1.8 ~ 4.6.6: 1: 12.7 ~ 32.5.5, the modified water glass is prepared by adding a silane coupling agent into the water glass or adding the silane coupling agent and polyol ester or polyol ether into the water glass, and in the component B, the polyester polyol comprises polyether polyol and the polyisocyanate is 1:1 ~ 1.5.5: 5.5: ~ 12
A:B 1~1.2： 1~1.2。
a high-environment-friendly multi-purpose two-component adhesive comprises water glass and polyisocyanate, and is characterized in that in the component A, the water glass comprises a plasticizer, a polyol and a filler, wherein the filler is 15.93: 22 ~ 25: 2 ~ 4: 1: 14 ~ 28, the modified water glass is prepared by adding a silane coupling agent into the water glass or adding the silane coupling agent and polyol ester or polyol ether into the water glass, and in the component B, the polyester polyol comprises the polyether polyol and the polyisocyanate is 1:1 ~ 1.5.5: 6.5: ~ 10
A:B 1~1.5： 1~1.5。
in the component A, water glass, a plasticizer, polyol and a filler are 24 ~ 25: 2.28 ~ 3.86.86: 1: 15.93 ~ 27.04.04, the silane coupling agent is gamma-aminopropyltriethoxysilane, the polyol ester is decaglycol ester, and in the component B, the polyester polyol, the polyether polyol and a polyisocyanate are 1:1.1 ~ 1.4.4: 6.5 ~ 8
The water glass in the component A is a combination of 2.1 ~ 2.5.5 moulds (2.1 moulds for short) and 2.6 ~ 2.8.8 moulds (2.6 moulds for short), wherein the mass ratio of 2.6 moulds to 2.1 moulds is 4.43 ~ 4.52.52: 1.
the polyol in the component A is one or a combination of more than one of glycerol, polyester polyol and polyether polyol.
The polyol in the component A is glycerol.
The polyol in the component A is glycerin and/or polyester polyol and/or polyether polyol.
The polyol in the component A is glycerin and/or polyether polyol.
The polyol in the component A is polyether polyol.
the polyether polyol in the component A is 201N and/or 220N and/or 330N.
The polyether polyol in the component A is 330N.
the vegetable oil in the component A is one or more of soybean oil, epoxidized soybean oil, rapeseed oil, peanut oil, corn oil, sunflower seed oil, castor oil, sesame oil, linseed oil, tung oil, coconut oil, palm oil and chlorinated palm oil.
The phthalate is one or more of 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) and diisodecyl phthalate (DIDP).
The filler is the combination of talcum powder and silica powder or the combination of talcum powder, silica powder and anhydrous sodium sulphate, wherein the talcum powder accounts for 67.83 ~ 83.56.56% of the total weight of the filler, and the amount of the anhydrous sodium sulphate is equivalent to that of the glycerol.
In the component A, 2.6 model modified water glass, 2.1 model modified water glass, epoxidized soybean oil, dioctyl phthalate, glycerol 1, talcum powder and silicon powder are used, in the component B, polyester polyol 1, polyether polyol 1.18, polyisocyanate 6.89 and component A, B1, 1.5 ~ 1.5, 1.5 and 1 are used.
The high-environment-friendly multipurpose two-component adhesive 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,
Heating water glass to 40 ~ ℃, adding 0 ~.5 wt% of nano silicon powder while stirring, continuously stirring for 15 ~ minutes after adding, adding 0.5 ~ ℃, dropwise adding 0.5 ~ wt% of silane coupling agent, preferably gamma-aminopropyltriethoxysilane, continuously stirring for 15 ~ minutes after adding, controlling the temperature to 25 ~ ℃, adding 0.5 ~ wt% of alcohol ester or alcohol ether, preferably dodecanediol ester, continuously stirring for 30 ~ minutes, continuously stirring before cooling to room temperature, directly discharging after stopping stirring or sealing a film by filtering in time for preventing film, or, for labor and time saving and electricity saving, stirring uniformly, pausing for 30 minutes to 12 hours after stirring, and stirring 30 ~ minutes after layering to obtain a uniform sizing material with the viscosity of more than 3000 mpa.s;
The preparation of the component B comprises the steps of adding polyester polyol, polyether polyol and plasticizer which are subjected to water removal treatment into a reaction tank, uniformly stirring, adding the mixture into another reaction tank containing polyisocyanate at the temperature of not higher than 40 ℃, preferably not higher than 30 ℃ or 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,
Adding the water glass component or the modified water glass component into the alkali-resistant plasticizer containing polyether glycol or polyether polyol and not containing ester group at the temperature of 30 ~ 50 ℃ or normal temperature, stirring while adding, continuing to stir after adding, adding auxiliary agents such as filler and viscosity reducer if necessary, continuing to stir for 60 ~ 120 minutes to fully homogenize and emulsify, and then directly discharging or filtering out the materials;
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. Vacuum dehydrating at 110 ~ 120 deg.C for 1.5 ~ 3h, cooling to 60 ~ 80 deg.C, or directly selecting polyurethane-grade polyether polyol, polyester polyol and plasticizer at the temperature, mixing, adding into isocyanate under stirring, stirring for 1 ~ 2 hr, cooling to 40 ~ 50 deg.C, adding additive if necessary, stirring, and directly discharging or filtering.
The additive in the component A or the component B of the high-environment-friendly multipurpose double-component adhesive comprises one or more of pigment, filler, essence, water, an organic solvent, a surfactant, a dispersing agent, a viscosity reducer, a flatting agent, a thickening agent, a toughening agent, a reinforcing agent, a catalyst, a polymerization inhibitor, a flame retardant adhesive, a smoke suppressor, a defoaming agent, a preservative, an antirust agent, an antioxidant, an anti-hydrolysis agent or a 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 component a comprises 1 ~ 10%, preferably 3 ~ 7%, more preferably 4 ~ 6% of a surfactant or dispersant.
The surfactant is preferably a polyether polyol which is resistant to alkali.
The additive in the component A also comprises 1 ~ 20% of organic solvent, preferably 3 ~ 15%, more preferably 5 ~ 10%.
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 ~ 10% of water, further preferably 0.5 ~ 8% of water, and most preferably less than 3% or 5% of water.
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 content of sodium silicate in the component A water glass is 30 ~ 60%, the modulus is 1.5 ~ 3.5.5, and the modulus is preferably 2.2 ~ 2.6.6 or 3.0 ~ 3.4.4.
In the component B, polyester polyol, namely diphenylmethane diisocyanate or polymethylene polyphenyl polyisocyanate, namely isophorone diisocyanate and/or hexamethylene polyphenyl polyisocyanate is 1:4 ~ 12:0.1 ~ 13.
In the component B, polyester polyol, namely diphenylmethane diisocyanate or polymethylene polyphenyl polyisocyanate, namely isophorone diisocyanate and/or hexamethylene polyphenyl polyisocyanate is 1:4 ~ 12:1 ~ 12.5.5.
In the component B, polyester polyol, namely diphenylmethane diisocyanate or polymethylene polyphenyl polyisocyanate, namely isophorone diisocyanate and/or hexamethylene polyphenyl polyisocyanate is 1:4 ~ 12:4 ~ 12.
In the component B, polyester polyol is diphenylmethane diisocyanate or polymethylene polyphenyl polyisocyanate, and isophorone diisocyanate and/or hexamethylene polyphenyl polyisocyanate is 1:4 ~ 8:4 ~ 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 highly environmentally friendly, multipurpose two-component adhesive of claim 1 ~ 3 in which IPDI and/or HDI or their trimer in the B component is 1/2 ~ 1/5 of polyisocyanate.
The high environmental protection multi-purpose two-component adhesive as claimed in claim 1 ~ 3, wherein IPDI in component B is 1/2 ~ 1/3 of polyisocyanate.
the IPDI in the B component accounts for 1/2 ~ 1/5 of the polyisocyanate.
0 ~ 100% of polyisocyanate is additionally added into the component B.
10 percent ~ 100 percent of polyisocyanate 100 percent is additionally added into the component B.
The environment-friendly steel adhesive is two components 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,
1 preparing water glass or preparing a modified water glass component, namely heating the water glass to 40 ~ 80 ℃, adding 0 ~ 0.5.5 wt% of nano silicon powder while stirring, continuously stirring for 15 ~ 30 minutes after adding, keeping the temperature at 30 ~ 50 ℃, dropwise adding 0.5 ~ 3wt% of silane coupling agent, preferably gamma-aminopropyltriethoxysilane, while stirring, continuously stirring for 15 ~ 30 minutes after adding, controlling the temperature at 25 ~ 40 ℃, adding 0.5 ~ 3wt% of alcohol ester or alcohol ether, preferably dodecanol ester, continuously stirring for 30 ~ 90 minutes before cooling to room temperature, continuously stirring, directly discharging after stopping stirring or timely sealing a cover by filtering to prevent a film;
2 heating or keeping the temperature at 25 ~ 60 ℃, adding the filler under stirring, adding other auxiliary materials and auxiliary agents, and continuously stirring until the mixture is uniform.
Or, in order to save labor, time and electricity, the mixture can be temporarily kept for 30 minutes to 12 hours after the mixture is primarily stirred, and then stirred for 30 ~ 60 minutes after layering, so that the uniform rubber material with the viscosity of more than 3000mpa.s can be obtained.
The preparation of the component B comprises the steps of adding polyester polyol, polyether polyol and plasticizer which are subjected to water removal treatment into a reaction tank, uniformly stirring, adding the mixture into another reaction tank containing polyisocyanate at the temperature of not higher than 40 ℃, preferably not higher than 30 ℃ or 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,
Adding the water glass component or the modified water glass component into the alkali-resistant plasticizer containing polyether glycol or polyether polyol and not containing ester group at the temperature of 30 ~ 50 ℃ or normal temperature, stirring while adding, continuing to stir after adding, adding auxiliary agents such as filler and viscosity reducer if necessary, continuing to stir for 60 ~ 120 minutes to fully homogenize and emulsify, and then directly discharging or filtering out the materials;
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. vacuum dehydrating at 110 ~ 120 deg.C for 1.5 ~ 3h, cooling to 60 ~ 80 deg.C, or directly selecting polyurethane-grade polyether polyol, polyester polyol and plasticizer at the temperature, mixing, adding into isocyanate under stirring, stirring for 1 ~ 2 hr, cooling to 40 ~ 50 deg.C, adding additive if necessary, stirring, and directly discharging or filtering.
For the component A without polyether polyol addition polymerization, the corresponding component B is prepared by uniformly mixing polyester polyol, polyether polyol and a small amount of diluent or plasticizer which are subjected to water removal treatment at normal temperature, slowly adding the mixture into polyisocyanate under stirring at 20 ~ 30 ℃ or lower temperature such as 10 ~ 20 ℃, stirring uniformly, and discharging (filtering if necessary) under nitrogen protection, wherein the mixed two-component adhesive can keep better wettability and interface adhesion after being uniformly stirred, and does not generate too fast reaction speed, so that the adaptation period can be prolonged, and the component A and the component B are uniformly mixed according to the weight ratio of 1.5:1 ~ 1:1.5 and then applied when in use.
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, PT2612, PT2512, PE9956, PE5556, etc., and one or a combination of HF8011, HF8020, HF8025, HF8031, HF8040, HF8056, HF8211, HF8356, HF8765, HF86304, HF86407, etc., hydroxyl value 22 ~, acid value 0.1 ~, molecular weight 400 ~, and the polyester polyol may be one or a combination of other dicarboxylic acid or anhydride or ester condensed or transesterified with polyhydric alcohol including dihydric alcohol or polymerized from lactone and polyhydric alcohol, the dibasic acid may be phthalic acid or phthalic anhydride or ester thereof, adipic acid, halogenated phthalic acid, etc., and the polyhydric alcohol may be ethylene glycol, propylene glycol, diethylene glycol, trimethylolpropane, pentaerythritol, etc.
the polyester polyol in the component is PE8815T and/or PE7762 with side base low temperature resistance and molecular weight less than 2500, especially less than 2000, and the corresponding component B is the polyester polyol PT2612 and/or PT2512 with molecular weight 3000 ~ 8000 and high crystallinity, and 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 from alcoholysis recovered bottle material, namely old bottle material resin, can also be selected, and has the average molecular weight of 6000 ~ 10000, the hydroxyl value of 60 ~ 80 and the acid value of 1 ~ 1.5.5.
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 can be propylene glycol polyether with molecular weight of 400-2000 or trimethylolpropane polyether with molecular weight of 400-4000 and polytetrahydrofuran with terminal hydroxyl, and preferably has surface activity and stronger alkali resistance: the polyether polyol can be polyoxypropylene triol with the molecular weight of 3000-5000, and can also be polytetrahydrofuran diol.
The polyether polyol is preferably alkali resistant in combination with a molecular weight of 400 ~ 1000 and 3000 ~ 6000 to provide both good emulsifiability and a structural basis for adequate 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 may comprise polyoxyethylene, polyoxypropylene block polymers such as seafenadine 2020, 2040 and the like.
The polyether polyol may also be N204, N403.
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 oils, such as fish oil, chicken oil, duck oil, goose oil, lard, mutton fat, horse oil, beef tallow, etc.; 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, silicone 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 waste oil 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, illegal cooking oil and plasticizer containing no ester group. 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 component A also contains 1 ~ 5% of viscosity reducer and 1 ~ 5% of viscosity stabilizer, wherein the viscosity reducer is a mono-alcohol, preferably an aromatic alcohol, such as benzyl alcohol, the viscosity stabilizer is an aromatic alcohol, preferably benzyl alcohol, and the content of the benzyl alcohol in the component A is 2 ~ 5%, preferably 2 ~ 3%.
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, particularly, a good emulsifying effect is unexpectedly generated under the condition that a proper amount of plasticizer is added, and 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 rubber can be approached to or even surpassed in more than 24 hours, 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 that polyisocyanate is added with a proper amount of polyester polyol, polyether polyol and plasticizer, the component A not only has high stability (the storage period is more than one year and can still be normally used), 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 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 be convenient for machine tool operation and application, and the two components also have excellent toughness and are economic in rigidity and toughness, and have unexpected early-strength and high-strength steel-steel, steel-brick, steel-stone, steel-concrete, steel-wood and other 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.
The polyether glycol added into the component A, particularly 330N added into the component A, can also react with water glass and a filler to generate emulsification, dispersion and thickening effects similar to those of glycerol, can also enable the composition to generate better fluidity, can also strengthen the emulsification, dispersion and thickening effects of the glycerol, a plasticizer and the water glass component, and can prolong the storage period. Increasing the amount of polyether polyol added can shorten the curing time and increasing the amount of polyether polyol within a certain range while the system maintains a moderate excess of polyisocyanate can increase the adhesive strength.
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 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 adhesive stability, and has a certain antirust flame-retardant effect while being rigid and tough, and the manufacturing cost is low.
4. Because the environment-friendly floor mat does not contain or only contains a small amount of volatile organic solvent and can utilize illegal cooking oil, the curing is not heated, and the environment-friendly floor mat is green, environment-friendly, low-carbon and energy-saving.
5. the viscosity can be controlled according to the components and the proportion, and the viscosity can be adjusted according to the viscosity reducing and stabilizing agent and the suitable addition amount of the viscosity reducing and stabilizing agent in the invention when necessary, so that the viscosity reducing and stabilizing agent has good viscosity reducing and stabilizing effects, does not reduce the bonding effect, and has a synergistic effect.
Detailed Description
Among the raw materials used in the embodiments of the invention, 2.2 ~.5 model (density at 20 ℃ 1.526 ~.599 g/cm3), 2.6 ~ 2.9 model (density at 20 ℃ 1.436 ~ g/cm3), 3.1 ~.4 model (density at 20 ℃ 1.368 ~.394 g/cm3) series water glass is provided by Chongqing Yongsheng water glass factory, gamma-aminopropyl triethoxysilane is produced by Nanjing Allisifier industries Limited company, 2, 4-trimethyl-1, 3 pentanediol monoisobutyrate is produced by Jiangsu Ruitai chemical Limited company, old bottle resin is produced by Chongqing Nannan colorful concrete binder plant, polyethylene terephthalate bottle material recovered by conventional alcoholysis is used as polyester polyol injection comparative example, wherein polyether polyol molecular weight 2000 ~, polyether polyol 3000, isocyanate ~ 10000, polymeric MDI (NCO is used as NCO 48% (NCO 48%), PM 28 ~% and PM 32% is used in the invention, polystyrene glycol equivalent, polystyrene equivalent polyester polyol is recovered by conventional alcoholysis, polystyrene equivalent.
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:
At 30 ~ 80 deg.C, preferably 40 ~ 60 deg.C, gamma-aminopropyl triethoxysilane is dropped into water glass while stirring, and then, after mixing uniformly, the dodecyl ester is added until uniform.
2. Heating or keeping the temperature to 30 ~ 60 ℃, preferably 40 ~ 50 ℃, adding the filler and the auxiliary material into the water glass or the modified water glass under stirring, stirring for 15 ~ 30 minutes, or adding the water glass or the modified water glass into the polyether polyol or adding the polyether polyol into the water glass or the modified water glass, stirring while adding, stirring for 10 ~ 45 minutes, preferably 15 ~ 30 minutes, after adding, adding the filler and the auxiliary material under stirring, continuously stirring for 15 ~ 30 minutes, adding the plasticizer under stirring, continuously stirring for 30 ~ 120 minutes after adding, or stirring for 15 ~ 30 minutes first, standing for 30 minutes to 12 hours, and then continuously stirring for 1 ~ 2 times (15 ~ 30 minutes each time) to obtain uniform emulsion, or adding the filler and the auxiliary material into the water glass or the modified water glass according to the method, stirring uniformly, and then adding the polyether polyol 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 ~ 3h 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 hours, adding a catalyst if necessary for continuing to react for 0.5 ~ 1 hours, 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 polyol or 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 state or a non-prepolymer state and has more and smaller molecular structures, the mixed two components keep better wettability and interface adhesion, and meanwhile, an excessive reaction speed is not generated, the component A and the component B are uniformly mixed according to the weight ratio of 1.5:1 ~ 1:1.5 and then applied when in use, in the following embodiment, the component A, B is prepared by referring to the method, and the component B is prepared by the heating method without special description.
Comparative example 1
(see CN1788064A A polyisocyanate-based adhesive example 1)
28.0% solids content, 28.0 ~ 29.5.5%, density 1.49g/ml, viscosity 380 ~ 420mpa.s, 2.0% water glass 35, NCO6.8% based on prepolymer 35 of MDI mixture with polyether polyol having weight-average molecular weight 6000, catalyst DMDEE 0.5, water 1%
the bonding strength of the aluminum-wood is 0.442 Mpa; bonding strength steel-wood <10kg/0.86Mpa (quick release)
Comparative example 2 (see JP-A200220698A sizing composition for use in concrete example 4)
The component A comprises: 100kg of sodium water glass, 3kg of catalyst DBTDL and PPG 2005 kg
And B component: MDI 2333 kg, PMDI 2667 kg, MPEG 100020 kg, diluent B280 kg, surfactant 1kg
The sample preparation test was carried out for 24 hours (air temperature 15 ~ 20 ℃ C.) with reference to the above-mentioned formulation disclosed
Bonding strength nail-nail <10kg/0.86Mpa steel-wood <10kg/0.86Mpa (releasing when lifting)
COMPARATIVE EXAMPLE 3 (REFERENCE TO CN103627330A COMPOSITE RUBBER EXAMPLE 28)
The component A comprises: 100 g of water glass, 20 g of epoxy resin, 20 g of acrylic resin, 20 g of quartz powder, 40 g of sodium tripolyphosphate, 1 g of zinc oxide, 1 g of sodium dodecyl benzene sulfonate, 1 g of AES 3g
And B component: black material 55 g of foaming rubber 100 g of expandable graphite 35 g
Steel-wood bonding strength (MPa) 1.33
Comparative example 4 (see CN104910817A an environmental friendly composite resin and adhesives and coatings based on the resin paragraph [00341] ~ [00345]
The component A comprises water glass 80 redispersible rubber powder 1.5 dioctyl phthalate 4 sodium tripolyphosphate 1.5 glycerol 6 anhydrous sodium sulfate 8 talcum powder 80
and B component: catalyst-free prepolymer 1 dichloromethane 0.5 solvent oil 0.5 black material 1A: B =1:1
Steel-wood bonding strength (MPa) 2.27 (nail head with wood) ceramic tile-screw 1.97 (nail head with glue)
Screw-bolt 2.68 (nail head with glue)
Comparative example 5 (refer to CN105885704A A Low viscosity high strength environmental protection two-component glue solution and preparation method thereof example 14)
Component A, 2.6 ~ 2.9.9 model water glass 100 gamma-aminopropyl triethoxy silane 1.8 film forming agent 1.5
The component B is the used polychrome bottle material resin, 330N =1:5, is mixed evenly, is heated to 105 ~ 110 ℃, is dewatered for 30 ~ 120 minutes, is cooled to 60 ~ 80 ℃, is added with excessive PAPI to react for 30 ~ 120 minutes under the protective atmosphere, is cooled to below 60 ℃, is added with mixed solvent (containing NCO15 percent and all solvents accounting for 14 percent)
a: B =1:1 bond strength steel-wood 1.81 (nearly full wood)
Comparative example 6 (refer to CN107488367A an inorganic-organic high environmental protection two-component adhesive and its preparation method example 2)
Component A, 2.6 ~ 2.9.9 modulus of water glass 40 silica powder 32
Component B, Huafeng HF8056, 220N and 330N are 1:1:2, MDI and PAPI half NCO are 20%
A:B = 1:1
The mixture is uniform, the sizing material is fine and smooth, the coating and spreading performance is good, the operation is easy, and the coating is uniform; the bonding strength is 2.85 Mpa (full adhesive tape wood), and the foaming amount is more than or equal to 2.5 times
Comparative example 7 (refer to CN107488431A A waterborne-oily low-viscosity environmental protection two-component adhesive and preparation method thereof example 1)
Component A, a water glass 100 silane coupling agent 1.4 with the modulus of 3.1 ~ 3.4.4 and a film forming agent 0.6
Component B, Huafeng PT2612:330N =1:1.5 plus excess PAPI NCO21.2% plus solvent 14%
A:B =1:1
the mixture is uniform, the sizing material is fine and smooth, the coating and spreading performance is good, the operation is easy, and the coating is uniform; adhesive strength 2.32 Mpa (full wood)
Example 1
A, preparing (2.6 model water glass 100, gamma-aminopropyl triethoxysilane 1.5, decaglycol ester 1) 443, (2.1 model water glass 100, gamma-aminopropyl triethoxysilane 1.5, decaglycol ester 1) 100,330N 142, talcum powder 258 and silicon micropowder 100; the preparation method of the component A comprises the following steps:
1. preparing a modified water glass component:
dropping gamma-aminopropyl triethoxysilane into 2.6-mold and 2.1-mold water glass at 40 deg.c while stirring, and adding glycol myristate while stirring; the two kinds of modified water glass are mixed evenly according to the formula amount.
2. Heating or keeping the temperature to 25 ~ 40 ℃ and stirring, adding silicon micropowder into the mixed modified water glass, stirring for a moment, adding talcum powder while stirring, continuing to stir for 30 minutes after the addition is finished, adding polyether polyol or adding polyether polyol into the mixed modified water glass filler mixture while stirring, continuing to stir for 90 minutes after the addition is finished, and filtering if necessary to obtain uniform emulsion.
B, polyester polyol PT 2612100, dioctyl phthalate 15, palm oil (specific gravity 1.08) 70 and M20S 827, and heating at 70 ~ 80 ℃ for 2 hours to obtain the polyester polyol PT 2612100.
a: B1: 1, surface-drying at room temperature for 3 minutes for 24 hours, and breaking the wood, the bonding strength of steel-wood 5.14 MPa
5.25 MPa steel-brick, brick failure
Example 2
A, taking 360 of (2.1 model water glass 100 gamma-aminopropyl triethoxysilane 1.5 decaglycol ester 1), taking 1596.8 of (2, 6 model water glass 100 gamma-aminopropyl triethoxysilane 1.5 decaglycol ester 1), glycerol 81, epoxy soybean oil 250.5, dioctyl phthalate 54 and talcum powder 930 silicon micropowder 360; the preparation method of the component A comprises the following steps:
1. Preparing a modified water glass component:
Dropping gamma-aminopropyl triethoxysilane into 2.6-mold and 2.1-mold water glass at 40 deg.c while stirring, and adding glycol myristate while stirring; the two kinds of modified water glass are mixed evenly according to the formula amount.
2. Heating or keeping the temperature to 20 ~ 25 ℃, adding the silicon micropowder and the talcum powder into the mixed modified water glass under stirring, continuing to stir for 30 minutes after the addition is finished, adding the glycerol, the epoxidized soybean oil and the dioctyl phthalate while stirring, and continuing to stir for 120 minutes after the addition is finished to obtain the uniform emulsion.
b polyester polyol PT 2612566.4, 330N 670, M20S3903.4
the preparation method of the component B is as described in the foregoing.
A: B1.5: 1 adhesion Strength Steel-Wood 3.85 MPa, Wood failure
4.16 MPa steel-brick, brick failure
Example 3
A comprises (2.6 model water glass 100, gamma-aminopropyl triethoxysilane 1.5, decaglycol ester 1) 540, (2.1 model water glass 100, gamma-aminopropyl triethoxysilane 1.5, decaglycol ester 1) 120, epoxidized soybean oil 43.6, dioctyl phthalate 18, glycerol 27, talcum powder 610 and silicon micropowder 120; the preparation method of the component A comprises the following steps:
1. Preparing a modified water glass component:
dropping gamma-aminopropyl triethoxysilane into 2.6-mold and 2.1-mold water glass at 40 deg.c while stirring, and adding glycol myristate while stirring; the two kinds of modified water glass are mixed evenly according to the formula amount.
2. heating or keeping the temperature to 40 ~ 60 ℃, adding the silicon micropowder and the talcum powder into the mixed modified water glass while stirring, continuing to stir for 20 minutes, then adding the glycerol, the epoxidized soybean oil and the dioctyl phthalate while stirring, continuing to stir for 30 minutes after the addition is finished, standing for 12 hours, and continuing to stir for 30 minutes to obtain the uniform emulsion.
And B, uniformly mixing polyester polyol PT 2612472, environment-friendly solvent 94.4, polyether polyol 330N 670 and M20S3903.4 (2326 and 15 percent of environment-friendly solvent), and heating at 70 ~ 80 ℃ for 2 hours.
A: B1.2: 1, surface-drying at room temperature for 3 minutes for 24 hours, bonding strength steel-wood 3.75 Mpa, wood failure
4.68 MPa steel-brick, brick failure
Example 4
a (2.6 model water glass 100, gamma-aminopropyl triethoxysilane 1.5, decaglycol ester 1) 266, (2.1 model water glass 100, gamma-aminopropyl triethoxysilane 1.5, decaglycol ester 1) 60, epoxidized soybean oil 41.8, dioctyl phthalate 9, glycerol 13.5, anhydrous sodium sulphate 13.5, talcum powder 155, silicon micropowder 60; the preparation method of the component A comprises the following steps:
Dropping gamma-aminopropyl triethoxysilane into 2.6-mold and 2.1-mold water glass at 1.40 deg.c while stirring, and adding glycol myristate while stirring; the two kinds of modified water glass are mixed evenly according to the formula amount.
2. Heating or keeping the temperature to 25 ~ 40 ℃ and stirring, adding silica powder into the mixed modified water glass, stirring for a moment, adding talcum powder while stirring, continuously stirring for 30 minutes after adding, adding the fully stirred and dissolved mixture of the anhydrous sodium glycerosulfate into the mixed modified water glass filler mixture while stirring, finally adding the epoxidized soybean oil and the dioctyl phthalate, continuously stirring for 30 ~ 120 minutes after adding, and finally filtering and discharging to obtain the uniform emulsion.
B, polyester polyol PT 2612472, environment-friendly solvent 94.4, polyether polyol 330N 670, M20S3903.4 (2326 pre +15% environment-friendly solvent) are heated for 2 hours at 70 ~ 80 ℃ after being uniformly mixed;
The specific preparation method of the component B is as described above.
A: B1: 1, surface-drying at room temperature for 3 minutes for 24 hours, bonding strength of steel-wood 4.66 Mp, wood failure
5.88 MPa of steel-brick, and broken brick
Example 5
A (2.6 model water glass 100, gamma-aminopropyl triethoxysilane 1.5, decaglycol ester 1) 1207, (2.1 model water glass 100, gamma-aminopropyl triethoxysilane 1.5, decaglycol ester 1) 960, (3.1 model water glass 100, gamma-aminopropyl triethoxysilane 1.5, decaglycol ester 1) 480, epoxidized soybean oil 344.8, dioctyl phthalate 72, glycerol 108, anhydrous sodium sulphate 108, talcum powder 1240, silicon micropowder 480 and benzyl alcohol 150; the preparation method of the component A comprises the following steps:
1. preparing a modified water glass component:
Dripping gamma-aminopropyl triethoxysilane into 3.1-mould, 2.6-mould and 2.1-mould water glass respectively according to the formula amount at 40 ℃, stirring while adding, and adding the dodecyl alcohol ester to be uniform after uniformly mixing; the three kinds of modified water glass are mixed evenly according to the formula amount.
2. heating or keeping the temperature to 20 ~ 25 ℃, adding silica powder and talcum powder into the mixed modified water glass under stirring, then adding a mixture of anhydrous sodium sulphate and glycerol which are uniformly and completely dissolved under stirring, stirring while adding, continuing to stir for 30 minutes after the addition is finished, then adding epoxidized soybean oil and dioctyl phthalate into the mixed modified water glass filler mixture, stirring while adding, finally dropwise adding benzyl alcohol, continuing to stir for 60 minutes, and filtering if necessary to obtain uniform emulsion.
b, polyester polyol PT 2612472, environment-friendly solvent 94.4, polyether polyol 330N 670, M20S3903.4 (2326 pre +15% environment-friendly solvent) are mixed evenly and heated for 2 hours at 70 ~ 80 ℃.
The specific preparation method of the component B is as described above.
A: B1: 1 Steel-Wood 4.46 Mp with 24 hours tack-free surface drying at room temperature for 3 minutes and wood failure
5.82MPa steel-brick, brick failure
Example 6
A (2.6 model water glass 100, gamma-aminopropyl triethoxysilane 1.5, decaglycol ester 1) 1207, (2.1 model water glass 100, gamma-aminopropyl triethoxysilane 1.5, decaglycol ester 1) 960, (3.1 model water glass 100, gamma-aminopropyl triethoxysilane 1.5, decaglycol ester 1) 480, epoxidized soybean oil 344.8, dioctyl phthalate 72, 330N108, anhydrous sodium sulphate 108, talcum powder 1240 and silicon micropowder 480;
The preparation method of the component A comprises the following steps:
Dripping gamma-aminopropyl triethoxysilane into 3.1-mould, 2.6-mould and 2.1-mould water glass respectively according to the formula amount at 40 ℃, stirring while adding, and adding the dodecyl alcohol ester to be uniform after uniformly mixing; the three kinds of modified water glass are mixed evenly according to the formula amount.
2. heating or keeping the temperature to 40 ~ 50 ℃, adding the mixed modified water glass into polyether polyol while stirring, continuing to stir for 15 minutes, slowly adding anhydrous sodium sulphate while stirring, adding the silica powder and the talcum powder after stirring for 15 minutes, continuing to stir for 30 minutes after the addition is finished, adding the epoxidized soybean oil and the dioctyl phthalate while stirring, continuing to stir for 120 minutes after the addition is finished, filtering and barreling to obtain the uniform emulsion.
b, polyester polyol PT 2612472, environment-friendly solvent 94.4, polyether polyol 330N 670 and MDI 3903.4(2326 pre +15% of environment-friendly solvent) are evenly mixed and heated for 2 hours at 70 ~ 80 ℃.
the specific preparation method of the component B is as described above.
a: B1: 1, surface-drying at room temperature for 3 minutes for 24 hours, bonding strength of steel-wood 4.32 Mp, wood failure
Steel-brick 5.57 Mpa, brick broken
example 7
A (2.6 model water glass 100, gamma-aminopropyl triethoxysilane 1.5, decaglycol ester 1) 1207, (2.1 model water glass 100, gamma-aminopropyl triethoxysilane 1.5, decaglycol ester 1) 960, (3.1 model water glass 100, gamma-aminopropyl triethoxysilane 1.5, decaglycol ester 1) 480, palm oil 344.8, dioctyl phthalate 72, glycerol 55330N 55, talcum powder 1300 and silicon micropowder 480;
The preparation method of the component A comprises the following steps:
Dripping gamma-aminopropyl triethoxysilane into 3.1-mould, 2.6-mould and 2.1-mould water glass respectively according to the formula amount at 40 ℃, stirring while adding, and adding the dodecyl alcohol ester to be uniform after uniformly mixing; the three kinds of modified water glass are mixed evenly according to the formula amount.
2. heating or keeping the temperature to 30 ~ 40 ℃, adding polyether glycol into the mixed modified water glass while stirring, continuing to stir for 15 minutes, then adding silica micropowder and talcum powder, continuing to stir for 30 minutes after adding, then adding glycerol, palm oil and dioctyl phthalate while stirring, continuing to stir for 20 minutes after adding, standing for 8 hours, continuing to stir for 45 minutes, and filtering if necessary to obtain uniform emulsion
B, polyester polyol PT 2612472, environment-friendly solvent 94.4, polyether polyol 330N 670 and MDI 3903.4(2326 pre +15% of environment-friendly solvent) are evenly mixed and heated for 2 hours at 70 ~ 80 ℃.
The specific preparation method of the component B is as described above.
A: B1: 1, surface-drying at room temperature for 3 minutes for 24 hours, bonding strength steel-wood 4.58 Mp, wood failure
Steel-brick 5.66 Mpa, brick broken
The protection scope of the present invention shall be subject to the scope defined by the claims. Any obvious improvement, replacement or modification made by the person skilled in the art on the basis of the present invention belongs to the protection scope of the present invention.
Claims (10)
1. A high-environment-friendly multi-purpose two-component adhesive comprises water glass and polyisocyanate, and is characterized in that in the component A, the modified water glass comprises a plasticizer, the polyol comprises a filler 19 ~ 29.5.5: 1.8 ~ 4.6.6: 1: 12.7 ~ 32.5.5, the modified water glass is prepared by adding a silane coupling agent into the water glass or adding the silane coupling agent and polyol ester or polyol ether into the water glass, and in the component B, the polyester polyol comprises polyether polyol and the polyisocyanate is 1:1 ~ 1.5.5: 5.5: ~ 12
A:B 1~1.2： 1~1.2。
2. a high-environment-friendly multi-purpose two-component adhesive comprises water glass and polyisocyanate, and is characterized in that in the component A, the water glass comprises a plasticizer, a polyol and a filler, wherein the filler is 15.93: 22 ~ 25: 2 ~ 4: 1: 14 ~ 28, the modified water glass is prepared by adding a silane coupling agent into the water glass or adding the silane coupling agent and polyol ester or polyol ether into the water glass, and in the component B, the polyester polyol comprises the polyether polyol and the polyisocyanate is 1:1 ~ 1.5.5: 6.5: ~ 10
A:B 1~1.5： 1~1.5。
3. The high environmental protection multipurpose two-component adhesive as claimed in claim 1 or 2, wherein in the component A, the water glass, the plasticizer, the polyol and the filler are 24 ~ 25: 2.28 ~ 3.86.86: 1: 15.93 ~ 27.04.04, the silane coupling agent is gamma-aminopropyltriethoxysilane, the polyol ester is decaglycol ester, and in the component B, the polyester polyol, the polyether polyol and the polyisocyanate are 1:1.1 ~ 1.4.4: 6.5 ~ 8.
4. the high environmental multipurpose two-component adhesive as set forth in claim 1 or 2, wherein the water glass in the a component is a combination of 2.1 ~ 2.5 die (2.1 die for short) and 2.6 ~ 2.8.8 die (2.6 die for short), wherein the mass ratio of 2.6 die to 2.1 die is 4.43 ~ 4.52: 1.
5. The high environmental protection multi-purpose two-component adhesive as set forth in claim 1 or 2, wherein the polyol in the a component is glycerin.
6. the high environmental protection multi-purpose two-component adhesive as claimed in claim 1 or 2, wherein the vegetable oil in the component A is one or more of soybean oil, epoxidized soybean oil, rapeseed oil, peanut oil, corn oil, sunflower seed oil, castor oil, sesame oil, linseed oil, tung oil, coconut oil, palm oil, and chlorinated palm oil.
7. The high environmental protection, multi-purpose, two-component adhesive as claimed in claim 1 or 2, wherein the phthalate ester is one or a combination of more than one of 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).
8. The high environmental protection multipurpose two-component adhesive as claimed in claim 1 or 2, characterized in that the filler is a combination of talc powder and silica powder, or a combination of talc powder, silica powder and anhydrous sodium sulphate, wherein the talc powder accounts for 67.83 ~ 83.56.56% of the total weight of the filler, and the amount of the anhydrous sodium sulphate is equivalent to that of glycerol.
9. The high-environmental-protection multipurpose two-component adhesive as claimed in claim 1, wherein the component A comprises 2.6-model modified water glass, 2.1-model modified water glass, epoxidized soybean oil, dioctyl phthalate, glycerol, talcum powder, silica powder, the ratio of the components is 19 ~ 21: 4 ~ 5: 1.61 ~ 3.19.19: 0.67: 1:
in the component B, the ratio of polyester polyol to polyether polyol to polyisocyanate is 1:1 ~ 1.3.3: 6 ~ 8, and the ratio of A to B1: 1.5 ~ 1.5.5: 1.
10. The high environmental protection multipurpose two-component adhesive as claimed in any one of claims 1 ~ 9, which is characterized by the preparation method of the component A:
a. For the technical proposal that the component A is water glass and/or modified water glass,
Heating water glass to 40 ~ 80 deg.C, adding 0. 0 ~ 0.5.5 wt% of nano silicon powder while stirring, stirring for 15 ~ 30 minutes after adding, keeping the temperature at 30 ~ 50 deg.C, adding 0.5 ~ 3wt% of silane coupling agent, preferably gamma-aminopropyl triethoxysilane, dropwise while stirring, stirring for 15 ~ 30 minutes after adding, controlling the temperature at 25 ~ 40 deg.C, adding 0.5 ~ 3wt% of alcohol ester or alcohol ether, preferably dodecanol ester, stirring for 30 ~ 90 minutes, stirring for 30 ~ minutes before cooling to room temperature, stopping stirring, directly discharging or sealing with a cover to prevent conjunctiva by filtering, or stirring for 30 min to 12 hours after primary stirring, and stirring for 30 ~ 60 minutes after layering to obtain a uniform sizing material with viscosity greater than 3000 mpa.s;
The preparation of the component B comprises the steps of adding polyester polyol, polyether polyol and plasticizer which are subjected to water removal treatment into a reaction tank, uniformly stirring, adding the mixture into another reaction tank containing polyisocyanate at the temperature of not higher than 40 ℃, preferably not higher than 30 ℃ or 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,
Adding the water glass component or the modified water glass component into the alkali-resistant plasticizer containing polyether glycol or polyether polyol and not containing ester group at the temperature of 30 ~ 50 ℃ or normal temperature, stirring while adding, continuing to stir after adding, adding auxiliary agents such as filler and viscosity reducer if necessary, continuing to stir for 60 ~ 120 minutes to fully homogenize and emulsify, and then directly discharging or filtering out the materials;
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. Vacuum dehydrating at 110 ~ 120 deg.C for 1.5 ~ 3h, cooling to 60 ~ 80 deg.C, or directly selecting polyurethane-grade polyether polyol, polyester polyol and plasticizer at the temperature, mixing, adding into isocyanate under stirring, stirring for 1 ~ 2 hr, cooling to 40 ~ 50 deg.C, adding additive if necessary, stirring, and directly discharging or filtering.
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| CN201810566116X | 2018-06-04 | ||
| CN201810566116 | 2018-06-04 |
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| CN110551477A true CN110551477A (en) | 2019-12-10 |
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| CN201811497465.7A Pending CN110551477A (en) | 2018-06-04 | 2018-12-07 | High-environment-friendly multipurpose two-component adhesive |
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