CN113292930A

CN113292930A - Composition for environment-friendly composite resin, adhesive or coating and preparation method thereof

Info

Publication number: CN113292930A
Application number: CN202110536324.7A
Authority: CN
Inventors: 卢清友; 卢思竹
Original assignee: Chongqing Lierda Technology Development Co ltd
Current assignee: Chongqing Lierda Technology Development Co ltd
Priority date: 2014-03-12
Filing date: 2015-03-12
Publication date: 2021-08-24
Also published as: CN104910817A

Abstract

A composition for environment-friendly composite resin, adhesive or coating and a preparation method thereof relate to composite resin for producing and processing matrix reinforcement and flame-retardant glass fiber reinforced plastic, building plates and other composite materials, adhesive for industrial and mining enterprises and daily life and coating for protecting object surfaces, and the composition is a two-component composition containing water glass, isocyanate and prepolymer thereof, wherein the A component contains low content of organic components, and the B component at least contains isocyanate and prepolymer, thereby providing a water glass polyurethane synergistic composition which can enhance the bonding strength and/or structural strength of the composition and has better operability and stability, and the mass ratio of the two components is 1:1 or so, strong adhesive force, short curing time, smooth surface, excellent flame retardant property and corrosion inhibition effect, no halogen, safety, environmental protection, low cost and easy production.

Description

Composition for environment-friendly composite resin, adhesive or coating and preparation method thereof

The present application is a divisional application of "an environment-friendly composite resin and adhesives and coatings based on the resin" of application No. CN2015101127358 priority No. 201410090293.

Technical Field

The invention relates to a composition for bonding building materials, industrial and mining enterprises and objects in daily life, reinforcing a matrix, producing a composite material and protecting the surfaces of the objects, in particular to a cheap two-component composition containing water glass, isocyanate and a prepolymer thereof. Can be used as an adhesive between metal and nonmetal such as steel-wood, steel-brick, steel-steel, and an environment-friendly composite resin adhesive of resin liquid or paint in the door industry.

Background

The glass fiber reinforced plastic composite material is mainly prepared from unsaturated polyester resin, epoxy resin and the like such as 191, 196 and 885 which are used as adhesives, has the defects of high cost and flammability, and a large amount of volatile harmful solvents in the resin seriously pollute the environment and are harmful to health. Most of the existing quick-drying coatings are solvent-type oily coatings, are flammable and are not environment-friendly; the surface of the water-based paint is slow to dry and dry, metal corrosion is easy to cause, and the oily film-forming agent is complex in water-modifying process and high in cost. Chinese patent CN1993398B discloses a liquid resin mixture for preparing mixed resin with improved mechanical properties, which is characterized in that 100 parts of the liquid mixed resin contains 10 to 75 parts of vinyl ester and/or polyester resin, 2 to 45 parts of unsaturated monomer, 2.5 to 45 parts of water glass, 2.5 to 65 parts of polyisocyanate and/or blocked polyisocyanate, and 5 to 35 parts of organic phosphate and/or other plasticizer, the inventor has conducted intensive research and successful exploration on the improvement of the mechanical properties of the liquid mixed resin, but in order to achieve practical application value, since the amount of vinyl ester and/or polyester resin is relatively large relative to water glass, saponification reaction is easy to occur after water glass is added, gelation is generated in a short time, the liquid resin mixture is suitable for use in the field, inconvenient to use, unsaturated monomer is mainly styrene, and odor is large, is toxic and harmful suspected to be cancer; in addition, the peroxide is used as an initiator, and the phosphate is used as a cocatalyst, so that the cost is higher, the safety and the environmental protection are not good, although the phosphate has a flame retardant effect, the total amount of flame retardant components is not large, the water glass is relatively few, the organic matters are relatively more, the flame retardant effect is limited, the viscosity is high, the permeability is poor, and the operation is inconvenient. The water glass or the mixture of the water glass and the silica sol is used as an inorganic sizing material, has the characteristics of high temperature resistance, flame retardance, corrosion inhibition, low price and environmental protection, but the bonding strength and the water resistance of the sizing material or the adhesive used for manufacturing the composite material by dip coating and lamination are difficult to reach the satisfactory degree; as a cheap environment-friendly binder, sodium fluosilicate and/or metal oxide can be added into water glass for independent use, but the water glass is difficult to be used in occasions with higher requirements between metal and metal, between metal and nonmetal and between nonmetal due to the limitations of binding effect and waterproof performance. Therefore, the exploration about the modification of the water glass sizing material has not been stopped, because the water glass is a true solution, the content of nano-sized monosilicon and low-silicon polymer in the water glass component can be gradually reduced during storage, various organic substances and inorganic filling auxiliary materials in the modification have complex components and different physical and chemical properties, and are not properly selected or proportioned, not only the condensation of polysilicic acid particles in the water glass into aggregates which can not be hydrolyzed again is intensified, but also the solidification promotion effect of certain metals and oxides thereof in the unsuitable components is added, the mixed sizing material is easy to thicken and solidify in a short time, the addition of the nano-sized filling auxiliary materials in the water glass sizing material is beneficial to the homogenization of the sizing material and can improve the strength of the sizing material and the comprehensive performance and the stability of the sizing material, but the cost is higher, the mixed sizing material formed by the water glass sizing material and isocyanate or polyol prepolymer thereof has weak bonding force, and the mechanical performance of the solidified body formed after the two components are acted is also not good, it is difficult to achieve the use strength. The prior adhesive for bonding building materials, decorative materials, door cores and panels is mostly polyurethane foaming adhesive, the bonding strength of which is required to be more than 0.5MPa, and the adhesive is mainly polyurethane prepolymer which is formed by reacting polyester polyol or the polyester polyol with polyisocyanate and contains residual-NCO groups, and a proper amount of catalyst and about 50 percent of organic diluent are usually added. The industrial foaming glue diluent is usually dichloromethane, acid or acyl chloride is often added as a stabilizer to increase storage stability and prolong shelf life, and the domestic commercial foaming glue has the advantages of good toughness, high bonding strength and convenient use, and the NCO content is generally 3-6%. However, the foaming adhesive is relatively expensive, the adhesive is flammable, dense black smoke is generated during combustion to release toxic gas, a large amount of dichloromethane is released during the use of the adhesive, the adhesive is harmful to health, and acidic components or acyl chloride substances have potential corrosion risks and are poor in heat resistance and acid resistance. US patent No. 2006051595a1 and chinese patent No. CN100355852C provide a polyisocyanate-based adhesive prepared from sodium water glass (or sodium water glass plus catalyst) and polyisocyanate 1: 2-5: 1, low combustion heat, good flame retardance, low viscosity and suitability for mechanical operation, and is used for manufacturing the fireproof sandwich panel, but the technical scheme disclosed by the invention has low bonding strength, slow curing and poor bonding stability after the catalyst is added, and the adhesive has no practical value when being used as an adhesive. Although many enterprises try to replace foaming adhesive with inorganic adhesive and composite adhesive with lower cost, the technical problems of weak initial adhesion, low adhesion strength, long surface drying and drying time, large brittleness of adhesive layer and water and moisture absorption in the adhesion between metal and metal, between metal and non-metal and rigid materials are always not solved. Coatings formulated with water glass often exhibit halogen blooming and stripping due to the migration of small molecular species and the alkali aggregate effect on silicon-containing substrates. In the technical proposal of JP 2002-20698A, the concrete adhesive composition and the filler composition comprise an alkali silicic acid solution (A) and a polyisocyanate component (B) comprising a polyisocyanate (B1) having a viscosity of 400MPa.s or less (at 25 ℃) and a one-finger complex component (B2), a monocarboxylic acid and a polyoxyalkylene alkyl ether having a number average molecular weight of 500 or less, wherein A: B is 1:1, further in the examples, A1 is an aqueous sodium silicate solution (water glass) 92.6%, a catalyst DBTDL (dibutyltin dilaurate) 2.8%, PPG200 (polypropylene glycol 200)4.7%, and B component is MDI2 (diphenylmethane diisocyanate) 25.6%, PMDI2 (polyphenylmethane diisocyanate) 51.3%, MPEG-1000 (polyethylene glycol monomethyl ether) 1.5%, a diluent 21.5%, a surfactant 0.1%, and a B liquid-NCO content of 24.6%; uniformly mixing the solution A by using a stirrer to obtain a uniform system, adding the solution B into a polycondensation reactor, heating to 80 ℃, and stirring for 3 hours by using the stirrer under the protection of nitrogen to obtain the product; when in use, the components are mixed uniformly according to the ratio of A to B1 to 1. The technical problem to be solved is to provide a concrete and filler composition having good permeability, fluidity and workability, and simultaneously solving the problems of volume shrinkage, cracking, strength reduction and durability deterioration due to escape, migration and exudation of conventional diluents when conventional diluents are added (see JP-A2002-20698A paragraphs 0004 and 0005), and the essential characteristics of the technical solution are to satisfy the requirements of adapting concrete and artificial structures thereof and low viscosity of materials to 30MPa.s to 400MPa.s (see JP-A2002-20698A paragraphs 0024 and 0025), the monoester composite component (B2) and polyoxyalkylene alkyl ether and the like adopted have low viscosity per se and low content, the viscosity of a specific prepolymer generated by a small amount of active hydrogen and isocyanate is also low, and polyether glycol is used as a surfactant, the prepolymer has few crosslinking points, is difficult to further extend chain to form a dense three-dimensional interpenetrating network structure, so that larger cohesive force is difficult to generate, the water glass and the isocyanate react slowly at normal temperature, the storage stability is influenced when a catalyst is added into the water glass for normal use, and the combination of a large amount of the catalyst and the organic solvent can not make the carbon dioxide generated by the reaction reach the water glass so as to promote foaming and further reduce the adverse effect of bonding strength. (see JP 2002-20698A paragraph 0045, the original specification 0061 of the invention, comparative example 3, which is well known to those skilled in the art), is not suitable for bonding steel-wood, steel-brick, and steel-steel. Because the components of the water glass-polyurethane composite material have interaction influence and complex action mechanism, the physical and chemical properties of the material are not in positive correlation with the addition of the components, and the results of a large number of tests performed by the inventor are encouraging and unexpected.

Disclosure of Invention

Aiming at the problems, the invention provides an environment-friendly water glass synergistic composition which can enhance the bonding strength of a water glass sizing agent, reduce the VOC content of industrial foaming glue, has low cost, high bonding strength and good flame retardant property, and an adhesive, a composite resin and a coating prepared by the composition.

The purpose of the invention is realized as follows:

an environment-friendly composite resin is characterized by comprising 60-100 parts of water glass or modified water glass, 0-30 parts of an organic solvent and/or a plasticizer, 0-10 parts of polyhydric alcohol, 0-15 parts of a resin liquid and/or dispersible resin powder, 0-8 parts of a surfactant and/or sodium hexametaphosphate and/or sodium pyrophosphate and/or sodium tripolyphosphate and 0-20 parts of a filling auxiliary material; the B also contains a prepolymer generated by the prepolymerization of polyester polyol and/or polyether polyol and polyisocyanate, and the composition and the weight percentage of each component are as follows: 30-50% of isocyanate and/or blocked isocyanate, 20-30% of prepolymer, 20-50% of organic solvent and/or plasticizer and 0-0.5% of additive; the weight ratio of A to B: a and B are 1: 1.5-1.5: 1, and the water glass is sodium water glass and/or water glass; the modified water glass is prepared by adding a small amount of functional materials or additives into water glass, wherein the additives comprise silane coupling agents accounting for 0.5-5% of the total amount of the component A.

A composition for environment-friendly composite resin, adhesive or coating comprises a water glass component A, an isocyanate component B and conventional additives, and is characterized in that the A or B at least contains resin liquid or melamine resin suitable for resin, epoxy resin, silicone-acrylic resin, styrene-acrylic resin or silica gel resin, or dispersible resin powder or one or more of the modified derivatives thereof, and the composition and the parts by weight of the components are as follows: 30-100 parts of water glass, 0-10 parts of a dispersing agent, 0-550 parts of a filler, 0.3-15% of a resin liquid and/or dispersible resin powder, 0-50% of an organic solvent and/or plasticizer, 0-10% of a polyol and 0-10% of a water glass curing agent; the B also contains polyester and/or polyether polyol prepolymer, which comprises the following components in percentage by weight: 30-50% of isocyanate and/or blocked isocyanate, 20-50% of prepolymer, 20-50% of organic solvent and/or plasticizer and 0-0.3% of catalyst; when the components are mixed to form the composite sizing material, the weight ratio of A to B is 1: 1.5-1.5: 1, the filler comprises anhydrous sodium sulphate, and the polyalcohol comprises glycerol.

A composition for environment-friendly composite resin, adhesive or coating comprises a water glass component A, an isocyanate component B and conventional additives, and is characterized in that the water glass is instant solid water glass, the A at least contains a vinyl ester resin, a polyester resin, an acrylic resin, an epoxy resin, a silicone-acrylic resin, a resin liquid of a styrene-acrylic resin or a silicone resin, or a resin liquid of a dispersible resin powder or a modified derivative thereof, or a combination of more than one of the components in parts by weight: 15-50 parts of solid water glass, 1-20 parts of resin liquid or/and redispersible rubber powder dispersant, 0-40 parts of organic solvent and/or plasticizer, 0-10 parts of polyol, 0-10 parts of surfactant and/or dispersant, 0-550 parts of filling auxiliary material and 0-5 parts of curing agent, wherein water is added before the A and the B are mixed, the added water amount is 0.4-1.2 times of the weight of the solid water glass, the filling auxiliary material comprises anhydrous sodium sulphate, and the polyol comprises glycerol; the B also contains polyester and/or polyether polyol prepolymer, which comprises the following components in percentage by weight: 30-50% of isocyanate and/or blocked isocyanate, 20-50% of prepolymer, 20-50% of organic solvent and/or plasticizer and 0-0.5% of catalyst; a and B are 1-1.5: 1-1.5.

The composition for the environment-friendly composite resin, the adhesive or the coating comprises a water glass component A, a blocked isocyanate component B and a conventional additive, and is characterized in that the B at least contains one or more of vinyl ester resin, polyester resin, acrylic resin, epoxy resin, silicone-acrylic resin, styrene-acrylic resin, silicone resin liquid, melamine resin or dispersible resin powder or modified derivatives thereof, which are suitable for preparing the water glass polyurethane composite resin, wherein the weight parts of the components in the A are as follows: 30-50 parts of water glass or 15-25 parts of solid water glass, 5-7 parts of glycerol, 0.3-5 parts of surfactant, 1-5 parts of sodium tripolyphosphate, 5-8 parts of anhydrous sodium sulphate, 5-30 parts of talcum powder and/or sericite powder and/or silicon micropowder, 0-150 parts of quartz powder and/or other filling auxiliary materials suitable for being matched with the water glass, and 0-6 parts of expandable graphite; b, mixing polyurethane prepolymer, dichloromethane, solvent oil and/or dichloromethane and/or phosphate and/or propylene carbonate, resin liquid and/or redispersible rubber powder and blocked isocyanate in a ratio of 1: 0.5-0.8: 0.2-0.3: 1; the proportion of A and B is as follows: a and B are 1: 1-1.3.

The preparation method of the composition for the environment-friendly composite resin, the adhesive or the coating is characterized by comprising the following steps of: group A1. mixing the resin liquid and/or dispersible resin with organic solvent and/or plasticizer, stirring, adding

The polyhydric alcohol is uniformly stirred and then is independently packaged or is uniformly mixed with the filling auxiliary materials and then is independently packaged; or continuing the following steps;

2. adding part or all of liquid water glass into the mixture added with the polyhydric alcohol, adding a surfactant and/or a sodium phosphate dispersant under stirring, and complementing all the water glass in the formula;

3. slowly adding anhydrous sodium sulphate and other filling auxiliary materials under stirring or directly adding anhydrous sodium sulphate and other filling auxiliary materials into water glass solution under stirring

Adding anhydrous sodium sulphate and/or filling auxiliary materials and additives;

4. mixing the above materials, stirring at room temperature or at a temperature suitable for the stability of the raw materials and composition

Stirring or stirring strongly, grinding until homogenizing, and sieving or directly discharging, barreling and sealing;

5. adding solid sodium silicate, directly adding anhydrous sodium sulphate after step 1, stirring, and adding other fillers

Uniformly stirring auxiliary materials and solid sodium silicate, and packaging; adding water in an amount which is 0.4-1.2 times of the total amount of the mixed materials before use

And entering step 4; the components stored separately from the water glass are mixed with the water glass containing other ingredients

Entering a step 4;

after the reaction of the isocyanate and the polyester polyol and/or the polyether polyol reaches the end point, the temperature is reduced to be lower than 50 ℃, the diluent, the isocyanate and/or the blocked isocyanate and the plasticizer are added under the protection atmosphere and stirring, the mixture is fully mixed, and the mixture is subjected to nitrogen replacement, barreling and sealing; or mixing 35-50% of polyurethane prepolymer, 25-50% of diluent and 0-10% of plasticizer and/or viscosity reducer at the temperature of lower than 40 ℃, adding 25-50% of isocyanate or black material under the protection of nitrogen, or directly mixing foamed rubber containing 30-50% of prepolymer with black material and/or closed isocyanate according to the ratio of 0.5: 1-1: 0.5, then adding 0-10% of plasticizer and/or viscosity reducer and 0-50% of organic solvent and/or plasticizer, and uniformly stirring. The environment-friendly composite resin is characterized in that the component parts by weight in the component A are as follows: 65-85 parts of liquid water glass or 30-45 parts of solid water glass, 3-10 parts of resin liquid and/or redispersible rubber powder, 3-10 parts of organic solvent and/or phosphate ester, 0-2 parts of ethylene glycol, 4-6 parts of glycerol, 0-5 parts of surfactant, 1-3 parts of sodium pyrophosphate and/or sodium tripolyphosphate, 3-16 parts of anhydrous sodium sulphate, 0-16 parts of talcum powder and/or sericite and/or silicon micropowder and 0-3 parts of anti-aging agent and/or other additives; b contains 10-20% of-NCO.

The composite board made of the environment-friendly composite resin is characterized in that wood chips and/or sawdust and/or waste fibers are used as main raw materials, resin or adhesive is used as a cementing agent, the water content of the composite board is controlled within 15%, the composite board is subjected to hot grinding defibering treatment or is directly added with a composite mixed by A: B1-1.5, the total amount of the composite is 10-50% of the total amount of the composite, and the composite board is filled into a mold or paved for molding, and then is subjected to hot pressing or cold heading or enters a continuous flat press for compression molding.

The weight parts of the components are as follows: 60-85 parts of liquid water glass or 20-45 parts of solid water glass, 1.5-15 parts of resin liquid and/or dispersible resin, 3-30 parts of organic solvent and/or plasticizer, 3-8 parts of ethylene glycol and/or glycerol, 0.5-8 parts of surfactant and/or sodium pyrophosphate and/or sodium tripolyphosphate and 0-20 parts of filling auxiliary materials; the polyurethane prepolymer, isocyanate and/or blocked isocyanate, diluent and/or viscosity reducer in the B are 1:1, the plasticizer is 1.5-10%, the catalyst is 0, and the finishing material contains anhydrous sodium sulphate.

65-85 parts of liquid water glass or 30-45 parts of solid water glass, 3-10 parts of resin liquid and/or redispersible rubber powder, 3-10 parts of organic solvent and/or phosphate ester, 0-2 parts of ethylene glycol, 4-6 parts of glycerol, 0-5 parts of surfactant, 1-3 parts of sodium pyrophosphate and/or sodium tripolyphosphate, 3-16 parts of anhydrous sodium sulphate, 0-16 parts of talcum powder and/or sericite and/or silicon micropowder and 0-3 parts of anti-aging agent and/or other additives; b contains 10-20% of-NCO.

The composition and the weight parts of each component are as follows: 75-85 parts of liquid water glass or 37-43 parts of solid water glass, 3-10 parts of unsaturated polyester resin and/or redispersible rubber powder, 3-10 parts of organic solvent and/or plasticizer, 5-7 parts of polyol, 0-5 parts of surfactant, 1-3 parts of sodium tripolyphosphate, 15-150 parts of filler and 0-10 parts of additive, wherein the filler comprises anhydrous sodium sulphate.

The resin composition at least contains one or more of vinyl ester resin, polyester resin, acrylic resin, epoxy resin, silicone-acrylic resin, styrene-acrylic resin, silicone resin liquid, melamine resin, or dispersible resin powder or modified derivatives thereof, which are suitable for preparing the water glass polyurethane composite resin, wherein the weight parts of the components in the A are as follows: 30-50 parts of water glass or 15-25 parts of solid water glass, 5-7 parts of glycerol, 0.3-5 parts of surfactant, 1-5 parts of sodium tripolyphosphate, 5-8 parts of anhydrous sodium sulphate, 5-30 parts of talcum powder and/or sericite powder and/or silicon micropowder, 0-150 parts of quartz powder and/or other filling auxiliary materials suitable for being matched with the water glass, and 0-6 parts of expandable graphite; b, mixing polyurethane prepolymer, dichloromethane, solvent oil and/or dichloromethane and/or phosphate and/or propylene carbonate, resin liquid and/or redispersible rubber powder and blocked isocyanate in a ratio of 1: 0.5-0.8: 0.2-0.3: 1; the proportion of A and B is as follows: a and B are 1: 1-1.3.

The composition for the environment-friendly composite resin, the adhesive or the coating is characterized in that the sodium silicate is one or the combination of more than one of sodium silicate, sodium silicate and lithium sodium silicate or the mixture of the sodium silicate and sodium silicate and/or lithium sodium silicate and/or silica sol and/or organic silicon; the blocked isocyanate is a water glass deblockable blocked isocyanate and/or a low-temperature blocked isocyanate which is sensitive to an alkaline environment; the dispersible resin powder is redispersible rubber powder; the organic solvent and/or plasticizer is one or more of alkyl silane, phthalate, vegetable oil, solvent oil, methylene dichloride, phosphate or phosphite ester and/or propylene carbonate.

The filler content is 2.5-10%.

30-35% of medium isocyanate and/or blocked isocyanate, 25-35% of prepolymer, 25-35% of organic solvent, 0-10% of plasticizer and 0-0.05% of catalyst; the isocyanate is one or more of diphenylmethane diisocyanate (MDI), polymethylene polyphenyl polyisocyanate (PAPI), isophorone diisocyanate (IPDI) and derivatives of the isocyanate.

The proportion of B to B is (weight ratio) = 1: 1.

the filler or pigment filler comprises one or more of mica powder, anhydrous sodium sulphate, quartz powder and talcum powder or the combination of anhydrous sodium sulphate and sericite and/or talcum powder.

A composition for environment-friendly composite resin, adhesive or coating comprises a water glass component A, an isocyanate component B and conventional additives, and is characterized in that the A or B at least contains one or more of vinyl ester resin, polyester resin, acrylic resin, epoxy resin, silicone-acrylic resin, styrene-acrylic resin or silicone resin liquid or dispersible resin powder or modified derivatives thereof, which are suitable for preparing water glass polyurethane prepolymer composite resin, and the composition comprises the following components in parts by weight: 30-100 parts of water glass, 0-10 parts of a dispersing agent and 0-550 parts of a filling auxiliary material; the B also contains polyester and/or polyether polyol prepolymer, which comprises the following components in percentage by weight: 30-50% of isocyanate and/or blocked isocyanate, 20-50% of prepolymer, 20-50% of organic solvent and/or plasticizer and 0-0.3% of catalyst; a or B or another component C also contains 0.3-15% of resin liquid and/or dispersible resin powder, 0-50% of organic solvent and/or plasticizer, 0-10% of polyol and 0-10% of water glass curing agent; when the components are mixed to form the composite sizing material, the weight ratio of the components is 1-1.5: 1-1.5.

The known dispersible resin powders and/or organic solvents and/or plasticizers and/or other auxiliary fillers which do not contain reactive groups can be added to the polyisocyanate component or the known blocked isocyanates which are relatively sensitive to water glass and are relatively stable in the normal state can be mixed with the resin and/or dispersible resin powders, organic solvents and/or plasticizers and/or other auxiliary fillers, the mixing amount and the added amount of water glass during use are determined according to the above-mentioned component ratio relationship, the stirring is carried out uniformly, the water glass with high pH value is gradually deblocked, and the required adaptation period is adjusted by simple experiments.

A composition for environment-friendly composite resin, adhesive or coating comprises a water glass component A, an isocyanate component B and conventional additives, and is characterized in that the water glass is instant solid water glass, the A at least contains a vinyl ester resin, a polyester resin, an acrylic resin, an epoxy resin, a silicone-acrylic resin, a resin liquid of a styrene-acrylic resin or a silicone resin, or a resin liquid of a dispersible resin powder or a modified derivative thereof, or a combination of more than one of the components in parts by weight: 15-50 parts of solid water glass, 1-20 parts of resin liquid and/or dispersible resin, 0-40 parts of organic solvent and/or plasticizer, 0-10 parts of polyol, 0-10 parts of dispersing agent, 0-550 parts of filling auxiliary material and 0-5 parts of curing agent; b also contains polyester and/or polyether polyol prepolymer, 30-50% of isocyanate and/or blocked isocyanate, 20-50% of prepolymer, 20-50% of organic solvent and/or plasticizer and 0-0.5% of catalyst; the mixture ratio of A to B is (weight ratio): a and B are 1-1.5: 1-1.5; and adding water into the A before mixing with the B, wherein the water adding amount is 0, 4-1.2 times of the weight of the solid water glass. The instant solid water glass is also called instant powder sodium silicate, the molecular formula of the instant solid water glass is Na2O mSiO2 nH2O, the formula weight is generally between 280 and 350, and the instant powder water glass is prepared by the processing processes of material melting, filtering, mold adjusting, spray drying and the like of sodium silicate, a sodium carbonate method and the like.

The environment-friendly composite resin is characterized in that in the component B, 30-35% of isocyanate and/or blocked isocyanate, 25-35% of prepolymer, 25-35% of organic solvent, 0-10% of plasticizer and 0-0.05% of catalyst are used; the isocyanate is one or more of diphenylmethane diisocyanate (MDI), modified MDI, polymeric MDI/black, polymethylene polyphenyl polyisocyanate (PAPI), isophorone diisocyanate (IPDI), Toluene Diisocyanate (TDI), Hexamethylene Diisocyanate Trimer (HDT), cyclopentane diisocyanate, dicyclohexylmethane diisocyanate, diphenyl diisocyanate, phenyl diisocyanate and derivatives of the isocyanate; the ratio of A to B is 1.2: 1.2 (weight ratio). The prepolymer is prepared by reacting polyether polyol and/or polyester polyol with polyisocyanate, and contains 2-20% of NCO, preferably 8-18%. The polyisocyanate can be one or more of isophorone diisocyanate (IPDI), Hexamethylene Diisocyanate (HDI), polymethylene polyphenyl polyisocyanate (PAPI), diphenylmethane diisocyanate (MDI), polymeric MDI, Toluene Diisocyanate (TDI) and cyclopentane diisocyanate, dicyclohexylmethane diisocyanate, diphenyl diisocyanate and phenyl diisocyanate; the diluent is solvent oil, acetone, benzoylacetone, diethyl phenylmalonate, dimethyl malonate, propylene carbonate, ethyl acetate, methyl acetate, dimethyl carbonate, 1 dichloroethane, trichloromethane, trichlorofluoromethane, cyclohexane, pentane, toluene, xylene and dimethyl silane; the vinyl acetate polymer is one or the combination of more than two of vinyl acetate emulsion, ethylene-vinyl acetate copolymer, vinyl acetate-acrylic acid copolymer, vinyl acetate-hydroxyethyl acrylate copolymer, redispersible rubber powder, vinyl acetate polymer and vinyl ester resin, polyester resin, epoxy resin, acrylic resin or emulsion, silicone-acrylic resin or emulsion, styrene-acrylic resin or emulsion, aldehyde ketone resin, melamine formaldehyde resin, urea formaldehyde resin, alkyd resin and other active substances containing alkenyl, hydroxyl, carboxyl and/or other active hydrogen and capable of performing crosslinking reaction with-NCO group; the resin liquid or the resin powder also comprises acrylic emulsion, silicone-acrylic emulsion, styrene-acrylic emulsion, vinyl chloride-vinylidene chloride copolymer emulsion, alkyd resin, aldehyde ketone resin and PVC paste resin; the diluent and/or plasticizer is one or the combination of more than one of alkane, cycloparaffin, aromatic hydrocarbon, solvent oil, liquid paraffin, chlorinated paraffin, styrene, acrylic ester, ethyl acetate, phthalate, triethylene glycol diacetate, diethylene glycol butyl ether acetate, methylsilane, turpentine, vegetable oil and epoxidized vegetable oil which are liquid at normal temperature and are suitable for preparing the composite resin; the polyalcohol is one or the combination of more than one of ethylene glycol, propylene glycol, butanediol, diethylene glycol, neopentyl glycol, alkanediol, cyclohexanedimethanol, glycerol, triethylene glycol, dipropylene glycol, pentaerythritol, D-mannitol, D-sorbitol, xylitol, trimethylolpropane, 1, 2, 6-hexanetriol, tetramethylolmethane and derivatives as well as low molecular weight polyester polyalcohol and/or polyether polyalcohol; the dispersing agent is one or the combination of more than one of a surfactant, sodium hexametaphosphate, sodium pyrophosphate and sodium tripolyphosphate; the filler is one or the combination of more than one of mineral powder, metal powder or metal oxide powder, reinforced fiber and expandable graphite; the auxiliary materials are one or the combination of more than one of a tackifier, a viscosity reducer, a stabilizer, a defoaming agent, a flatting agent and a pigment; the additive is one or the combination of more than one of a coupling agent, an antioxidant, an ultraviolet absorbent, a preservative, an antirust agent, a flame retardant, a polymerization inhibitor, a sealant, a water glass curing agent, an anti-skinning agent and a brightening agent; the weight of the instant solid water glass after being added with water can be equivalent to the amount of original liquid water glass before the instant solid water glass is changed into the solid water glass by spray drying, namely, the solid water glass is changed into the liquid water glass again by the water lost in the process of adding the solid water glass into the drying process.

The composition for the environment-friendly composite resin, the adhesive or the coating is characterized in that the component A comprises the following components in parts by weight: 60-85 parts of liquid water glass or 20-45 parts of solid water glass, 1.5-15 parts of resin liquid and/or dispersible resin, 3-30 parts of organic solvent and/or plasticizer, 3-8 parts of ethylene glycol and/or glycerol, 0.5-8 parts of surfactant and/or sodium hexametaphosphate and/or sodium pyrophosphate and/or sodium tripolyphosphate and 0-20 parts of filling auxiliary materials; in the B, the ratio of the polyurethane prepolymer to isocyanate and/or blocked isocyanate to the diluent and/or the viscosity reducer is 1:1, the ratio of the plasticizer is 1.5-10%, and the ratio of the catalyst is 0.

The environment-friendly composite resin is characterized in that the component parts by weight in the component A are as follows: 65-85 parts of liquid water glass or 30-45 parts of solid water glass, 3-10 parts of resin liquid and/or redispersible rubber powder, 3-10 parts of organic solvent and/or phosphate ester, 0-2 parts of ethylene glycol, 4-6 parts of glycerol, 0-5 parts of surfactant, 1-3 parts of sodium pyrophosphate and/or sodium tripolyphosphate, 3-16 parts of anhydrous sodium sulphate, 0-16 parts of talcum powder and/or sericite and/or silicon micropowder and 0-3 parts of anti-aging agent and/or other additives; b contains 10-20% of-NCO.

The environment-friendly composite resin is characterized in that the component parts by weight in the component A are as follows: 30-45 parts of solid water glass, 3-10 parts of resin liquid and/or redispersible rubber powder, 3-10 parts of organic solvent and/or phosphate, 0-2 parts of ethylene glycol, 4-6 parts of glycerol, 0-5 parts of surfactant, 1-3 parts of sodium pyrophosphate and/or sodium tripolyphosphate, 3-16 parts of anhydrous sodium sulphate, 0-16 parts of talcum powder and/or sericite and/or silicon micropowder and 0-3 parts of anti-aging agent and/or other additives; b contains 10-20% of-NCO.

The composition for the environment-friendly composite resin, the adhesive or the coating is characterized in that the composition A comprises the following components in parts by weight: 75-85 parts of liquid water glass or 37-43 parts of solid water glass, 3-10 parts of unsaturated polyester resin and/or redispersible rubber powder, 3-10 parts of organic solvent and/or plasticizer, 5-7 parts of polyhydric alcohol, 0-5 parts of surfactant, 1-3 parts of sodium tripolyphosphate, 15-150 parts of filler and 0-10 parts of additive.

A composition for environment-friendly composite resin, adhesive or coating comprises a water glass component A, a blocked isocyanate component B and conventional additives, and is characterized in that the B at least contains one or more of vinyl ester resin, polyester resin, acrylic resin, epoxy resin, silicone-acrylic resin, styrene-acrylic resin or silicone resin liquid or dispersible resin powder or modified derivatives thereof, which are suitable for preparing water glass polyurethane composite resin, wherein the weight parts of the components in the A are as follows: 30-50 parts of water glass or 15-25 parts of solid water glass, 5-7 parts of glycerol, 0.3-5 parts of surfactant, 1-5 parts of sodium tripolyphosphate, 5-8 parts of anhydrous sodium sulphate, 5-30 parts of talcum powder and/or sericite powder and/or silicon micropowder, 0-150 parts of quartz powder and/or other filling auxiliary materials suitable for being matched with the water glass, and 0-6 parts of expandable graphite; b, mixing polyurethane prepolymer, dichloromethane, solvent oil and/or dichloromethane and/or phosphate and/or propylene carbonate, resin liquid and/or redispersible rubber powder and blocked isocyanate in a ratio of 1: 0.5-0.8: 0.2-0.3: 1; the proportion of A and B is as follows: a and B are 1: 1-1.3.

The composition for the environment-friendly composite resin, the adhesive or the coating is characterized in that the sodium silicate is one or more of sodium silicate, sodium silicate and lithium silicate or a mixture of the sodium silicate and sodium silicate and/or lithium silicate and/or silica sol and/or organic silicon; the blocked isocyanate is a water glass deblockable blocked isocyanate and/or a low-temperature blocked isocyanate which is sensitive to an alkaline environment; the dispersible resin powder is redispersible rubber powder; the organic solvent and/or plasticizer is one or more of alkyl silane, phthalate, vegetable oil, solvent oil, methylene dichloride, phosphate or phosphite ester and/or propylene carbonate.

The redispersible rubber powder is one or more of vinyl acetate and ethylene copolymer rubber powder, ethylene and vinyl chloride and vinyl metasilicate ternary copolymer rubber powder, vinyl acetate and ethylene and higher fatty acid vinyl ester ternary copolymer rubber powder, vinyl acetate and higher fatty acid vinyl ester copolymer rubber powder, acrylate and styrene copolymer rubber powder, vinyl acetate and acrylate and higher fatty acid vinyl ester ternary copolymer rubber powder, vinyl acetate homopolymerization rubber powder and styrene and butadiene copolymer rubber powder; the phthalate ester can be dioctyl phthalate, dibutyl phthalate, dinonyl phthalate, didecyl phthalate, diisoundecyl phthalate; the phosphate or phosphite ester can be trichloroethyl phosphate, tributyl phosphate, trimethyl phosphate, triethyl phosphate, tributyl phosphate (TBP), trioctyl phosphate, triphenyl phosphate (TPP), tricresyl phosphate (TTP); the vegetable oil can be tung oil, soybean oil, sunflower seed oil, and castor oil; the acrylate is methyl acrylate, ethyl acrylate, butyl acrylate and the like; the organic solvent and/or plasticizer can also be one or more of dioctyl adipate, benzoylacetone, diethyl phenylmalonate, dimethyl malonate, propylene carbonate, dichloroethane, trichloromethane, trichlorofluoromethane, cyclohexane, pentane, toluene, xylene, dimethylsilane and glycidyl ether; the solvent oil can be No. 100-200 solvent oil; the mineral powder is one or more of mica powder, calcium powder, light calcined powder, anhydrous sodium sulphate, kaolin, bentonite, perlite powder and quartz powder and talcum powder; the metal powder or metal oxide powder is one or more of copper powder, alloy powder, titanium dioxide, lime powder, aluminum oxide, zinc oxide, magnesium oxide and iron oxide. The mineral powder is preferably one or a combination of more than one of mica powder, anhydrous sodium sulphate, quartz powder and talcum powder, in particular the combination of anhydrous sodium sulphate and sericite and/or talcum powder; the dispersant is preferably a surfactant and/or sodium tripolyphosphate; the surfactant may be sodium dodecyl benzene sulfonate and/or cocamidopropyl betaine and/or OP-10 and/or TX-10.

The preparation method of the composition for the environment-friendly composite resin, the adhesive or the coating is characterized by comprising the following steps of:

a group 1. mixing resin liquid and/or dispersible resin with organic solvent and/or plasticizer, stirring, adding polyol, stirring uniformly, packaging separately or packaging separately after mixing uniformly with auxiliary materials; or continuing the following steps;

3. slowly adding anhydrous sodium sulphate and other filling auxiliary materials under stirring or directly adding anhydrous sodium sulphate and/or filling auxiliary materials and additives into the water glass solution under stirring;

4. mixing the above rubber materials, stirring or strongly stirring at normal temperature or at a temperature suitable for the stability of the formula raw materials and the composition, grinding until homogenization, and finally sieving or directly discharging, barreling and sealing;

5. adding solid water glass, directly adding anhydrous sodium sulphate after the step 1, stirring, adding other filling auxiliary materials and the solid water glass, stirring uniformly, and packaging; adding water in an amount which is 0.4-1.2 times of the total amount of the mixture before use, and entering the step 4; the separately stored components are mixed with water glass containing other ingredients, and the process proceeds to step 4.

After the reaction of the isocyanate and the polyester polyol and/or the polyether polyol reaches the end point, cooling to a temperature lower than 50 ℃, adding the diluent in a protective atmosphere under stirring, adding the isocyanate and/or the blocked isocyanate and the plasticizer under stirring at a temperature lower than 40 ℃, fully mixing, replacing with nitrogen, barreling and sealing; or mixing 25-50% of polyurethane prepolymer, 25-50 parts of diluent and 0-10% of plasticizer and/or viscosity reducer at the temperature of lower than 40 ℃, adding 30-50% of isocyanate or black material under the protection of nitrogen, or directly mixing foamed rubber containing 30-50% of prepolymer with black material and/or closed isocyanate according to the ratio of 0.5-1: 0.5-1, and then adding 0-10% of plasticizer and/or viscosity reducer; and/or adding 0.3-15% of resin liquid and/or dispersible resin powder, 0-50% of organic solvent and/or plasticizer, 0-10% of polyol and 0-10% of water glass curing agent, and uniformly stirring.

The present invention uses wood chips and/or waste fibre as main raw material, its water content is controlled within 15%, and then the wood chips and/or waste fibre are undergone the process of hot grinding defibering treatment or directly utilizes two-component spray-coating machine to uniformly add 10-50% of environment-protecting composite resin mixed according to A: B1-1.5 or adhesive of the present invention, and then the above-mentioned material is filled into mould or laid to form, and then the above-mentioned material is passed through the processes of hot pressing or cold heading or is fed into continuous flat press to make press-forming. The additive comprises 0.5-5% of the total amount of the component A of a coupling agent such as a titanate coupling agent and a silane coupling agent. The organic rubber material, particularly the redispersible rubber powder, forms uniformly dispersed organic rubber slurry after fully reacting with the organic solvent and/or the plasticizer and the polyol, and then the polyol, the water glass, the sodium tripolyphosphate, the anhydrous sodium sulphate and other fillers are added, so that the synergistic effect of the composition can be further strengthened, and tests show that the adhesive strength of a plurality of composite rubber materials can be higher. The composite sizing material is a general name of composite resin and adhesive and coating based on the resin. The formula in the invention is suitable for environment-friendly resin, adhesive and coating, and can be used universally. For the adhesive, the addition of a proper amount of solid filler, especially fine particle powder in the formula can obviously increase the bonding strength, improve the thixotropy, enhance the weather resistance and the rigidity and the hardness of colloid, but the addition is excessive, for example, more than 100 percent of composite sizing material, affects the sizing on most occasions, is inconvenient for large-area coating, and can also cause the reduction of the bonding strength and the deterioration of the mechanical property; the composite resin for preparing the glass fiber reinforced plastic composite material can be free from or less than the added filler, so that the infiltration, permeation and pasting of the composite resin liquid are facilitated. Of course, in the case of needing to reinforce the mechanical property and weather resistance of the material, 2.5-10% of solid filler of composite resin can be added. For the coating, the adhesive and the composite resin formula of the invention can be directly used according to the applicable objects and occasions, but in order to ensure better performance and effect or lower cost, a proper amount of additives such as coupling agent, anti-ultraviolet agent, antioxidant and the like, and filling auxiliary materials such as anti-settling agent, thinner, leveling agent, defoaming agent, solid powder, pigment and the like can be mixed or added according to the conventional formula, and the A: B can be adjusted to 1: 0.5-1. After liquid water glass is mixed with metal oxide filler, particularly partial resin and/or plasticizer and/or organic solvent, due to the solidification promotion effect of metal oxide and the saponification of organic ester under alkaline environment, the generated organic acid can slowly cause the dehydration, aggregation and solidification of the water glass, and resin liquid or resin powder, active solvent/plasticizer and polyhydric alcohol are added into isocyanate component, and the isocyanate component can react to gradually thicken, so that the shelf life of the formula at normal temperature is only about one to two months, even shorter. In this case, it is preferable that the isocyanate and the blocked isocyanate are used in a mixture without adding a catalyst, and the blocked isocyanate is most effective in storage. Of course, stabilizers such as sodium acrylate or inert diluents in the water glass mixed solution may have a certain effect on prolonging the storage period; solid water glass is adopted, the mixture is uniformly mixed and packaged, and water is added when the mixture is used, so that the shelf life is greatly prolonged.

The composite resin can be used for producing glass fiber reinforced plastics, especially flame-retardant glass fiber reinforced plastics products or other composite materials; the adhesive can be used for bonding of anti-theft doors, fireproof door cores and door bodies, furniture and panel production, bonding of ceramic tiles, stones, heat insulation materials and other building decoration materials, repairing, plugging and reinforcing of walls, stone carving, mines, construction sites, dangerous rocks and the like, bonding and fixing of equipment and workpieces, and bonding and maintenance of fire-fighting equipment and facilities; the coating can be used for anticorrosion and flame-retardant protection of buildings and equipment, especially for the protection of bonding surfaces.

The invention is suitable for making composite materials by using medium-alkali, especially alkali-free or alkali-resistant fibers as reinforcing materials.

The invention has the positive effects that:

1. because the proportion of the resin liquid or the resin powder is small, the proportion of the cheap water glass is large, the production process is simple, the production cost can be greatly reduced compared with the prior art, and in addition, the viscosity of the formula is easier to adjust compared with the formula with high resin content, and the film is less prone to peeling;

2. because the water glass replaces a certain part of foaming glue, the dosage of an organic solvent is obviously reduced, and in addition, halide and phosphate are not used or are used as flame retardants less, the pollution to the environment and the harm to the health are reduced;

3. according to the invention, the proportion of the water glass is increased, and the consumption of the resin and the plasticizer is reduced, the water glass is dehydrated in the process of constructing the polyurea-resin composite interpenetration structure to form a large number of silica gel particles which are uniformly distributed and embedded in the polyurea-resin composite interpenetration structure, so that the polyurea-resin composite interpenetration structure has excellent flame retardant property;

4. the invention also utilizes the functions of dispersion and emulsification and slow corrosion of water glass and the functions of alkali catalysis and deblocking assistance, can uniformly disperse isocyanate and prepolymer, can complete polyurea and interpenetration crosslinking reaction under the induction of the prepolymer of the composition at normal temperature without conventional catalysts, and is also helpful for deblocking blocked isocyanate; the adhesive strength of the composition is unexpected due to the interaction of the resin, the prepolymer and various components and the synergistic effect of a plurality of components, and the glass fiber reinforced plastic composite material prepared from the composite resin is also rigid and flexible, and has strong initial adhesion, short actual drying time, smooth surface and water resistance;

5. the technical scheme is formed step by step in the selection direction of meeting basic functions, striving for low cost and flame retardance and environmental protection on the basis of repeated tests, and has stronger economical efficiency and practicability;

6. the solid water glass scheme of the invention can greatly prolong the storage period so as to further improve the economy and practicability of the solid water glass.

The polyhydric alcohol contains a plurality of hydrophilic hydroxyl groups, is dispersed in water glass and can wrap or isolate ionized charged particles such as sodium sulfate and the like, reduces the damage of electrolyte to a colloid balance structure, and adds the solubilization effect of the polyhydric alcohol on the sodium sulfate and the like and reasons that the solubilization effect of the polyhydric alcohol on the sodium sulfate and the like is not known, and a composition formed by the action of a proper amount of low-molecular polyhydric alcohol, anhydrous sodium sulphate, the water glass and the like is objectively stable, and the thixotropy, the adhesion and the toughness of a rubber material can be obviously improved; the sodium sulfate can be dissolved in the water glass, so that the prepared glue solution also has a semitransparent effect and is easy to color. In the double-component composite sizing material, hydroxyl in the polyol serving as a soft segment can be crosslinked with an NCO end group in the other component, so that an interpenetration structure formed by the water glass mixture and the prepolymer is firmer, and the double-component composite sizing material has better mechanical property, is safe and is environment-friendly; the halogenated hydrocarbon, the plasticizer and a proper amount of organic rubber material are fully swelled to form uniformly dispersed organic rubber paste, and the uniformly dispersed organic rubber paste is added into the composition of the water glass/silica sol, the anhydrous sodium sulphate and the polyol, so that the synergistic effect generated under the interaction of the composition can be further strengthened, and the bonding strength of the composite rubber material is higher. The sizing material uses water glass as a main material and does not contain or only contains a small amount of volatile organic solvent, so that the sizing material has the advantages of low cost, flame retardance, corrosion inhibition, environmental protection and good heat and weather resistance. Because a very limited number of chemical raw materials or semi-finished products can be prepared by simple stirring, the production is easy.

Detailed Description

In the raw materials used in the embodiment of the invention, polyurethane prepolymer and foaming adhesive are produced by Chongqing Banan polyester adhesive factory and are prepared by taking polymethylene polyphenyl polyisocyanate (PAPI), polyether polyol and polyester polyol as raw materials, wherein the molecular weight of the polyether polyol is 5000, the molecular weight of the polyester polyol is 1800-2000, the weight ratio of the polyether polyol to the polyester polyol is 1-2: 1, and the content of-NCO group in the prepolymer is about 8-13%. The foaming glue is a product obtained by diluting a prepolymer with dichloromethane, wherein the dichloromethane accounts for about 40-50%, and 0.05-0.1% of an amine or tin catalyst is added. The isocyanate is black material produced by Shenzhen Kuaiyue electronic technology Limited, polymerized MDI (main components are diphenylmethane diisocyanate and isomers and oligomers thereof, NCO 28-32%), modified MDI (8221, NCO 31.7-32.7%) and isophorone diisocyanate (IPDI, NCO 37.5-37.8%) produced by Germany Bayer; the blocked isocyanate was polymeric MDI blocked with acetoacetate-ethylene glycol-methyl acrylate, see CN200580026701.1 and Hungarian patent application P0401799 and a known method for preparing samples. Water glass with the modulus of 2.6-2.9, produced by Chongqing Huadong chemical industry Co., Ltd; the solid water glass is fully called instant solid water glass which is also called instant powdery sodium silicate and is produced by Beijing Yongqing county Jing Yongqing chemical industry Co Ltd (in the embodiment, the unknown water glass is sodium water glass). The epoxy resin is E-44(6101) produced by Feicheng Delaware chemical Co. Polyamide resin (650 low molecular weight), produced in Kao Tan chemical plant in Hunan Tan City. Sodium tripolyphosphate is an industrial product, and is produced by Chongqing Chuandong chemical industry Co. Glycerol, dichloromethane, epoxidized soybean oil, castor oil and dimethyl silicone oil are used as chemical reagents. Redispersible rubber powder (copolymer rubber powder of vinyl acetate and ethylene, the specific components of which are not indicated in the embodiment), vinyl resin, 196, 885, 191 resin (Jiangyin golden ox), solvent oil, anhydrous sodium sulphate, talcum powder, phthalate, phosphate, epoxidized soybean oil, acrylic resin/emulsion, quartz powder (800 meshes 1250 meshes), expandable graphite (80-100 meshes) and other chemical raw materials are purchased from Chongqing Shichengqiao chemical markets. The screw used for testing the bonding strength is round head, the diameter is 12mm, the screw length is 87mm, the end surface of the nail head is filed by a flat file and then is vertically adhered to a pine strip (25mm 30mm) coated with the bi-component adhesive and having a smooth surface. Drying for 24-48 hours at normal temperature after gluing, testing, using a mineral water bottle filled with tap water as a weight, tying a nylon ferrule on the bottle neck, when multiple bottles are hung, penetrating a plurality of ferrule systems by using a rope to be tied on a screw rod, keeping the screw rod vertically downward, lifting the mineral water bottle off the ground, increasing progressively each time until an adhesive layer is damaged and falls, and recording the hanging weight; 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 is calculated above and below the average weight and is for reference only.

In the following comparative examples and examples, except for special reference, the material B prepared from the component A, 1 part by weight of black material and 2 parts by weight of foaming adhesive (1 part by weight of polyurethane prepolymer and 1 part by weight of dichloromethane diluent) is mixed according to the weight ratio of 1:1, and then the surface drying time is measured for 20-60 minutes, the measurement is carried out at normal temperature for 24-36 hours, and each group of samples is repeated for 3-5 times (all parts by weight). Although the peel of the batten appears on most of the test nails and the final result cannot be measured, the structural strength of the batten where the test nails are located is different due to different wood development processes and different cork degrees, the test nails are randomly distributed on the batten and have a plurality of repetitions, and the trend observation is assisted, so that the adhesive strength and performance of different colloids and formulas can be reflected from one aspect, and the adhesive strength and performance are irrelevant to the wettability, the adhesive material binding force, the colloid permeability and the colloid mechanical performance of the composite resin adhesive.

Manufacture of composite resin hand-pasted glass fiber reinforced plastic

Preparing composite resin:

group A: can be 100% sodium water glass or a mixture of sodium water glass and water glass or/and lithium water glass and/or silica sol and/or silicone. Can also be prepared from one or more of the following raw materials:

1. mixing and stirring redispersible rubber powder and/or resin with organic solvent and/or plasticizer, adding polyol, and stirring for a while

2. Adding part or all of liquid water glass into the mixture, adding surfactant and/or sodium phosphate dispersant under stirring, and supplementing all water glass in the formula

3. Slowly adding anhydrous sodium sulphate and other filling auxiliary materials under stirring or directly adding anhydrous sodium sulphate and/or filling auxiliary materials and additives into water glass solution under stirring

4. Mixing the above rubber materials, stirring and grinding at normal temperature or at a temperature suitable for the stability of the formula raw materials and the composition until homogenization, and finally sieving or directly discharging, barreling and sealing;

5. adding solid water glass, directly adding anhydrous sodium sulphate after the step 1, stirring, adding other filling auxiliary materials and the solid water glass, stirring uniformly, and packaging; before use, water is added according to 0.4-1.2 times of the total seeds of the mixture and the mixture is uniformly stirred;

after the excessive polyisocyanate and the polyester polyol and/or the polyether polyol react to reach the end point, cooling to a temperature lower than 50-60 ℃, adding a diluent in a protective atmosphere and stirring, adding isocyanate and/or closed isocyanate, a plasticizer or a catalyst in stirring, fully mixing, replacing with nitrogen, barreling and sealing; or mixing 25-50% of polyurethane prepolymer and 25-50 parts of diluent at the temperature lower than 40 ℃, adding 25-50% of isocyanate or black material under the protection of nitrogen, or directly and uniformly mixing the foaming adhesive containing 30-50% of prepolymer and the black material according to the ratio of 1: 0.5-1.

Of course, the method is not limited to the above steps, and other feeding sequences and stirring and grinding processes can be adopted to achieve the using effect, but the steps introduced in the invention have better effect on part of the formula, such as redispersible rubber powder, phthalate, methylsilane, castor oil, dichloromethane and the like. Some urethane-grade starting components, such as phthalates, which are free of hydroxyl, active hydrogen and other reactive groups, may be added to the B component, and if the isocyanate NCO in B is fully blocked and is normally stable, more components may be added, and the water content is not so severely limited. When in use, the A and the B are mixed uniformly or sprayed, rolled, scraped and brushed, and the mixture is used up in time according to the formula.

Raw materials: A. b, mixing and uniformly stirring the composite resin solution when in use; the glass fiber cloth is alkali-free glass fiber cloth with the thickness of 0.24 mm.

In the following examples, A and B are uniformly mixed according to a ratio of 1:1, then a mold is coated with a priming coat, a layer of glass fiber cloth is laid, after the composite resin is coated thoroughly, a layer of glass fiber cloth is laid, and then the composite resin is coated until 3-4 layers are formed. Most, except individually, cured within 45 minutes, and after 60 minutes was die cut and trimmed. And (3) trial burning: the test specimen is held in hand, and observed off fire after being continuously ignited for 10 seconds by a lighter under the corner of the test specimen in the transverse direction or the longitudinal direction. And (3) roughly measuring the strength: three layers of alkali-resistant glass fiber cloth are pasted one by a single-sided profiling, redundant resin is scraped when the other side is manufactured, demoulding is carried out for 2 hours, the thickness of the glass fiber cloth is about 0.9mm, the glass fiber cloth is trimmed to be 35mm in width and 50mm in length, after 24 hours, the smooth surface is downward, the surface is kept horizontally suspended, one end is clamped in order, mineral water bottles are hung at the position 10mm away from the clamping end, 580 g of each bottle is hung, the inclination angle of the surface of a sample does not exceed 45 degrees within 30 seconds, the bottle hanging quantity is relatively rigid, and the smooth surface and the opposite rough surface are folded to be relatively flexible and only serve as reference. The percentages, parts and ratios of all the following comparative examples and examples are not specified to be by weight, and the B component, which is 2 parts of the foamed rubber plus one part of the polymeric MDI and 1: 1A: B, is not listed.

Comparative example 1191 resin 50 Accelerator 1.5 curing agent 1.5

Igniting the fuel and generating a large amount of black smoke; the bottle hanging amount is less than or equal to 3 bottles and less than or equal to 3.5 bottles; the smooth surface is folded in half, obvious crease is formed, and the crease is slightly folded towards the hair surface.

Comparative example 2191 resin 50 Accelerator 1.5-3 phosphate (TCEP) 5-10 curing agent 1.5-4.5

When the addition amount of the phosphate ester flame retardant is 10 percent of the resin, the ignition is combustible; the bottle hanging amount is less than or equal to 2 bottles and less than or equal to 2.5 bottles; the smooth surface is folded in half, obvious creases are formed, and the creases are slightly formed in half towards the rough surface; when the addition amount is 20 percent of resin, the glass fiber reinforced plastic is obviously sticky and softened, the performance is seriously deteriorated, and the glass fiber reinforced plastic can still be burnt during ignition to generate unpleasant smell and dense black smoke; the bottle hanging amount is less than or equal to 1 bottle and less than 1.5 bottles.

Comparative example 3

50g of water glass and 50g of polyisocyanate

No curing is observed within 24 hours, the coating is dry and solid after 3 days, and the glass fiber is easy to delaminate, soft, lack of rigidity and almost non-combustible; the bottle hanging amount is less than or equal to 1 bottle and less than 1.5 bottles; the light facing surface is folded in half and has a heavier crease, and the hair surface is folded in half and has an obvious crease.

Comparative example 4

Water glass 40 foamed glue 40

Heat generation, curing for several minutes, and poor strength. Almost non-combustible.

COMPARATIVE EXAMPLE 5 (formulation according to CN993398B, close to example 25)

191 resin 60 benzoyl peroxide 1.2 polymeric MDI 18 water glass 16 triphenyl phosphate flame retardant 6

The reaction is fast, and the solidification lasts for about five minutes; the material is combustible; the bottle hanging amount is less than or equal to 2 bottles and less than or equal to 2.5 bottles; the light facing surface is folded in half and the hair side is folded in half, and the crease is slight.

Example 1

A: water glass 75191 resin (containing 3% accelerator) 4 Castor oil 5 Glycerol 5 sodium tripolyphosphate 1

Taking 50g B: taking 50g of catalyst-free prepolymer, dichloromethane, No. 200 solvent oil and black material as the ratio of 1: 0.5: 1

Surface drying within 30 minutes; continuously igniting longitudinally, and extinguishing within 20 seconds after the ignition; the bottle hanging amount is more than 3.5 bottles and less than or equal to 4 bottles; the light facing surface is folded in half and has a crease, and the crease is heavy and folded in half towards the hair side.

Example 2

A: 30g of sodium sulfate 0.6 of sodium dodecyl benzene sulfonate 0.6 of water glass 755 phosphate (TCEP)

B: 35g of catalyst-free prepolymer, dichloromethane, No. 200 solvent oil, 196 resin, phosphate (TCEP), blocked polyisocyanate (TCEP) 1: 0.5: 0.15: 1

Surface drying within 30 minutes; difficult to ignite, the ignition is continued longitudinally, and the flame is extinguished within 4 seconds; the bottle hanging amount is more than 7 bottles and less than or equal to 7.5 bottles; the light facing surface is folded in half and has a crease, and the crease is heavy and folded in half towards the hair side.

Example 3

A: solid water glass mixture: redispersible rubber powder 4 castor oil 4 glycerol 5 sodium dodecyl sulfate 1.5 sodium tripolyphosphate 1 anhydrous sodium sulphate 8 and solid sodium silicate 40 are stirred uniformly and sealed and packaged;

20g of the mixture is taken, 12g of water is added, and the mixture is stirred uniformly

B: 30g of catalyst-free prepolymer, dichloromethane, No. 200 solvent oil and black material are taken

Surface drying within 30 minutes; difficult to ignite, the ignition is continued longitudinally, and the flame is extinguished within 5 seconds; the bottle hanging amount is more than 5.5 bottles and less than or equal to 6 bottles; the light facing surface is folded in half and provided with a crease, and the crease is lighter when the light facing surface is folded in half.

Example 4

A: 10g of water glass 50 low-sodium silica sol 50

B: 10g of catalyst-free prepolymer, dichloromethane, No. 200 solvent oil and black material are taken

Surface drying within 30 minutes; continuously igniting longitudinally, and extinguishing within 13 seconds after the ignition; the bottle hanging amount is more than 4.5 bottles and less than or equal to 5 bottles; the smooth surface is folded in half with a slight crease, and the hair surface is folded in half with a slight crease.

Example 5

A: water glass 75191 resin 5 resin 28.2g B: prepolymer 10 methylene dichloride 10 polymeric MDI 10 triethyl phosphate 1.8 weight 31.8 grams

Surface drying within 30 minutes; difficult to ignite, the ignition is continued longitudinally, and the flame is extinguished within 8 seconds; the bottle hanging amount is more than 3 bottles and less than or equal to 3.5 bottles; the smooth surface is folded in half, obvious creases are formed, and the hair surface is folded in half, creases are formed.

Example 6

A: water glass 30g B: foaming glue 2 Black 130 g (adhesive strength 0.8Mpa nail head belt part glue)

Surface drying within 30 minutes; difficult to ignite, the ignition is continued longitudinally, and the flame is extinguished within 1 second; the quantity of the hanging bottle is more than 2.5 bottles and less than or equal to 3.5 bottles, the bottle is folded towards the smooth surface and has heavier creases, and the bottle is folded towards the rough surface and has obvious creases.

Example 7

A: taking 30g B parts of water glass: prepolymer 1 methylene dichloride 1 polymeric MDI 1 closed isocyanate 1 rubber powder 0.1 g

Surface drying within 30 minutes; difficult to ignite, the ignition is continued longitudinally, and the flame is extinguished within 1 second; the bottle hanging amount is more than 4 bottles and less than or equal to 4.5 bottles; the smooth surface is folded in half, obvious creases are formed, the hair surface is folded in half, and the creases are light.

Example 8

A: water glass 90 redispersible rubber powder 2.5 castor oil 3 sodium tripolyphosphate 2 glycerol 5 anhydrous sodium sulphate 8 30g B: prepolymer 1 methylene dichloride 1 polymeric MDI 1 30g

Surface drying within 30 minutes; difficult to ignite, the ignition is continued longitudinally, and the flame is extinguished within 3 seconds; the bottle hanging amount is more than 5 bottles and less than or equal to 6 bottles; the smooth surface is folded in half, obvious creases are formed, the hair surface is folded in half, and the creases are light.

Example 9

A: water glass 90 redispersible rubber powder 1.5 castor oil 3 sodium tripolyphosphate 3 30g B: prepolymer 1 methylene dichloride 1 polymeric MDI 1 30g

Surface drying within 30 minutes; difficult to ignite, the ignition is continued longitudinally, and the flame is extinguished within 2 seconds; the bottle hanging amount is more than 3.5 bottles and less than or equal to 4 bottles; the smooth surface is folded in half, obvious creases are formed, the hair surface is folded in half, and the creases are light.

Example 10

A: water glass 90 redispersible rubber powder 1 castor oil 3 sodium tripolyphosphate 3 glycerol 6 30g B: prepolymer 1 methylene dichloride 1 polymeric MDI 1 30g

Surface drying within 30 minutes; difficult to ignite, the ignition is continued longitudinally, and the flame is extinguished within 1 second; the bottle hanging amount is more than 3 bottles and less than or equal to 3.5 bottles; the smooth surface is folded in half, obvious creases are formed, the hair surface is folded in half, and the creases are light.

Example 11

A: 0.530 g B parts of water glass 90 redispersible rubber powder: prepolymer 1 methylene dichloride 1 polymeric MDI 1 30g

Surface drying within 30 minutes; difficult to ignite, the ignition is continued longitudinally, and the flame is extinguished within 3 seconds; the bottle hanging amount is more than 4 bottles and less than or equal to 4.5 bottles; the smooth surface is folded in half, obvious creases are formed, the hair surface is folded in half, and the creases are light.

The following embodiments of the environment-friendly composite resin of the present invention can also solve the technical problems described above, and achieve the intended technical effects.

A: water glass (modulus 2.5-2.9), 99% silane coupling agent 1% B: catalyst-free prepolymer 5 black material 25A: B is 1:1

Surface drying for 15 minutes; difficult to ignite, the ignition is continued longitudinally, and the flame is extinguished within 3 seconds; the bottle hanging amount is more than 3 bottles and less than or equal to 4 bottles; the smooth surface is folded in half, obvious creases are formed, the hair surface is folded in half, and the creases are light.

A: water glass (modulus 2.5-2.9) B: catalyst-free prepolymer 0.75 black material 25A: B1:1

A: water glass (modulus 2.5-2.9) B: catalyst-free prepolymer 0.3 black material 100A: B1:1

Surface drying for 15 minutes; difficult to ignite, the ignition is continuously carried out longitudinally, and the ignition is extinguished within 3 seconds after the ignition is finished, so that the ignition is firm and soft.

A: water glass (modulus 3.0-3.4) melamine resin 10

B: catalyst-free prepolymer 1 black material 1 dimethyl carbonate 0.6 methyl acetate 0.05 phosphate 0.02A: B1:1

Surface drying for 65 minutes; difficult to ignite, the ignition is continuously carried out longitudinally, and the ignition is extinguished within 3 seconds after the ignition is finished, so that the ignition is firm and soft.

A; water glass (modulus 3.0-3.4) 80 styrene-acrylic emulsion 8 melamine resin 5

Surface drying for 18 minutes; difficult to ignite, the ignition is continuously carried out longitudinally, and the ignition is extinguished within 3 seconds after the ignition is finished, so that the ignition is firm and soft.

A: sodium silicate (modulus 3.0-3.4) 80 styrene-acrylic emulsion 4 sodium tripolyphosphate 1.5 anhydrous sodium sulphate 4

Surface drying for 80 minutes; difficult to ignite, the ignition is continuously carried out longitudinally, and the ignition is extinguished within 3 seconds after the ignition is finished, so that the ignition is firm and soft.

A: a proper amount of water glass (modulus 3.0-3.4) 80 fluorocarbon emulsion 6 melamine resin 20 emulsifier

Surface drying for 18 minutes; difficult to ignite, the ignition is continuously carried out longitudinally, the ignition is extinguished after the ignition is separated, and the hardness and softness are mutually matched.

A: water glass (modulus 3.0-3.4) 80 acrylic resin 6 titanium dioxide 5

Surface drying for 25 minutes; difficult to ignite, the ignition is continuously carried out longitudinally, and the ignition is extinguished within 5 seconds from the fire, and the hardness and softness are mutually matched.

A: 1.5 of water glass 90 redispersible rubber powder, 4 of epoxidized soybean oil, 4 of sodium tripolyphosphate, 2 of glycerol, 5 of anhydrous sodium sulphate, and 30g of B: catalyst-free prepolymer 25 dimethyl carbonate 10 solvent oil 10 phosphate 2 methyl acetate 3 polymeric MDI 25g

Surface drying within 30 minutes; difficult to ignite, the ignition is continued longitudinally, and the flame is extinguished within 10 seconds; hardness and softness are combined.

A: sodium silicate 80 (3.0-3.4 model) redispersible rubber powder 1.5 dioctyl phthalate 4 sodium tripolyphosphate 1.5 glycerol 5 anhydrous sodium sulphate 4 30g B: catalyst-free prepolymer 25 dimethyl carbonate 10 solvent oil 10 phosphate 2 methyl acetate 3 polymeric MDI 25g

A: water glass (modulus 2.5-2.9) B: catalyst-free prepolymer 1 black material 1 dimethyl carbonate 1A: B is 1:1

Surface drying for 15 minutes; difficult to ignite, the ignition is continued longitudinally, and the flame is extinguished within 10 seconds; hardness and softness are combined. Brushing and pasting 0.4-0.6 kg/M3 after single-layer priming by 04 glass fiber cloth; brushing and pasting layer by layer to three layers of 2.2-2.9 kg/M3

A: sodium silicate 80 redispersible gelatine powder 1 dioctyl phthalate 4 glycerol 6 sodium polyphosphate 1.5 anhydrous sodium sulphate 8 talcum powder 854 g B: catalyst-free prepolymer 25 black material 25 dimethyl carbonate 8.3 dichloromethane 4.2 solvent oil 8.3 phosphate 2.5 ethyl acetate 358 g

Surface drying for 50 minutes; difficult to ignite, the ignition is continued longitudinally, and the flame is extinguished within 5 seconds; hardness and softness are combined. Hand paste plate making, 04 fiberglass cloth, 170mm 160mm, 5 layers just finished.

A: sodium silicate 80 redispersible gelatine powder 1 dioctyl phthalate 4 glycerol 6 sodium polyphosphate 1.5 anhydrous sodium sulphate 8 talcum powder 854 g B: catalyst-free prepolymer 25 black material 25 dimethyl carbonate 8.3 dichloromethane 4.2 solvent oil 8.3 phosphate 2 methyl acetate 358 g

Surface drying for 25 minutes; difficult to ignite, the ignition is continued longitudinally, and the flame is extinguished within 10 seconds; mutual reinforcement of hardness and softness

A: water glass 80 redispersible rubber powder 1 dioctyl phthalate 4 glycerol 6 sodium polyphosphate 1.5 anhydrous sodium sulphate 8B: catalyst-free prepolymer 25 black material 25 dimethyl carbonate 8.3 dichloromethane 4.2 solvent oil 8.3 phosphate 2 methyl acetate 3

A∶B＝1∶1.5

Surface drying for 26 minutes; difficult to ignite, the ignition is continued longitudinally, and the flame is extinguished within 3 seconds; mutual reinforcement of hardness and softness

A: water glass 80 redispersible rubber powder 1 dioctyl phthalate 4 glycerol 6 sodium polyphosphate 1.2 anhydrous sodium sulphate 8B: catalyst-free prepolymer 25 black material 25 dimethyl carbonate 8.3 dichloromethane 4.2 solvent oil 8.3 phosphate 2 methyl acetate 3

A∶B＝1.5∶1

The wood chips and/or the waste fibers are used as main raw materials, the water content is controlled within 15 percent, the wood chips and/or the waste fibers are subjected to hot grinding defibering treatment or are directly and uniformly added with 10 to 50 percent of the total amount of materials by a two-component spraying machine, the environment-friendly composite resin mixed by A: B1-1.5 or the adhesive of the invention is filled into a die or paved for molding, and then the mixture is subjected to hot pressing or cold heading or is pressed and molded by a continuous flat press. The formaldehyde release amount is not detected according to the test of GB18580-2001, Formaldehyde release limit in artificial boards and products thereof for interior decoration and finishing materials; the composite material is pressed on an iron plate to prepare a composite board, and is forcedly stripped after being cured for 24 hours, so that the wood in the composite material is damaged, and the composite material has good flame-retardant and moisture-proof functions and low cost.

In the embodiment of the composite resin, the component A is uniformly stirred by a glass rod and then is lifted, and the component A is in a free dripping state at a height of 5-25cm from the liquid level, and the viscosity is 250-1000 Mpa.s; the viscosity of the component B is mostly 200-800 Mpa.s, the pH value is more than 12, the adaptation period is 5-20 minutes, the density is 1.25-1.5 g/cm3, in example 8, 250g of A, B bi-component composite resin is additionally taken, a 4-layer hand pasting plate of the 03# glass fiber cloth is 30-40 mm2, a 150mm square sample block is cut, two sides of the sample block are fixed by two 100mm wood strips to suspend the rest part of the sample block, the sample block is impacted by 1150 g of cobblestones at 2500mm high position, no damage is caused, after the single-layer 03# glass fiber cloth is coated with the paste composite resin and cured for 72 hours, the 150mm sample block is bent 180 degrees (the folding ridge is arc-shaped, the distance between the two sides of the base part is 5mm-10mm, most of the sample block is closed and not broken), and the sample block is ignited by a lighter vertically for 30 seconds. Through the testing of the quality testing center of construction engineering of Chongqing university (refer to 'impregnated paper laminated wood floor' GB/T245908-2007 'safety performance testing Specification for glass fiber reinforced plastic products used in coal mines' GB16413-2009), the bending strength of the environment-friendly composite resin glass fiber reinforced plastic is as follows: 37.5Mpa, impact resistance: 1Kg of steel ball is not damaged after falling to 1.02M height, and the flame retardant property is as follows: flame combustion was not observed.

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

5. adding solid water glass, directly adding anhydrous sodium sulphate after the step 1, stirring, adding other filling auxiliary materials and the solid water glass, stirring uniformly, and packaging; before use, water is added according to 0.4-1.2 times of the total seeds of the mixture and the mixture is uniformly stirred; if necessary, a quantity of water glass curing agent lower than the conventional quantity, such as sodium fluosilicate, condensed aluminum phosphate, metal oxide and the like, can be added into the solid water glass formula, so that the mechanical property of the interpenetrating structure is strengthened to a certain extent, but the solid water glass can be used up as soon as possible after water is added.

B component

After the excessive polyisocyanate and the polyester polyol and/or the polyether polyol react to reach the end point, cooling to the temperature of below 50-60 ℃, preferably adding a diluent at the temperature of below 50 ℃ in a protective atmosphere and under stirring, adding isocyanate and/or closed isocyanate, a plasticizer or a cocatalyst while stirring, fully mixing, replacing with nitrogen, barreling and sealing; or mixing 25-50% of polyurethane prepolymer and 25-50 parts of diluent at the temperature lower than 40 ℃, adding 25-50% of isocyanate or black material under the protection of nitrogen, or directly and uniformly mixing the foaming adhesive containing 30-50% of prepolymer and the black material according to the ratio of 0.5-1: 0.5-1. Of course, the method is not limited to the above steps, and other reasonable feeding sequences and stirring and grinding processes are adopted without tasting, so that the using effect can be achieved. The procedure described in the present invention works better with this pre-treatment for many formulations, such as redispersible powders and phthalates, methylsilane, castor oil, methylene chloride, etc. Certain polyurethane grade raw material components which do not contain hydroxyl groups, active hydrogen and other active groups, such as phthalate esters and the like, can be added to the B component, and more other components can be added if B is a mixed isocyanate containing more than half of blocked isocyanate, especially blocked isocyanate.

When in use, the A and the B are mixed uniformly or sprayed, rolled, scraped and brushed, and the mixture is used up in time according to the formula.

Comparative example 6 Water glass 10g polymeric MDI 10g

The sample is baked at 85-105 ℃ for 12 hours and then placed for 36 hours (24 hours at normal temperature without curing)

Thin glue with 0.7 nail head part with bonding strength (Mpa)

Comparative example 2 foaming adhesive 10g

Thin glue with bonding strength (Mpa) 1.1 nail head part

Comparative example 7191 resin 50 Accelerator 1.5 curative 1.5

Thin glue with 0.5 nail head part with bonding strength (Mpa)

COMPARATIVE EXAMPLE 8 Special glue for laminate flooring (white latex)

Thin glue with 0.9 nail head part with bonding strength (Mpa)

Comparative example 9 Marble adhesive (glue 10 curing agent 0.3)

1.8 nail head with large adhesive and small amount of veneer

Comparative example 10 epoxy resin to Polyamide resin 1:1

Wood veneer with 1.9 nail head band part and bonding strength (Mpa)

The following examples of the invention show adhesive strengths (Mpa 1.0-3.5, most nail heads are half-or nearly half-veneers.

A: 20g of water glass 30191 resin 20 phosphate (TCEP)20 anhydrous sodium sulphate 6 talcum powder 6

B: 20g of catalyst-free prepolymer, dichloromethane, No. 200 solvent oil and black material are taken according to the ratio of 10: 5: 10: 1

A: water glass 50 silica sol 15 redispersible rubber powder 8.2 glycerol 3 dichloromethane 3 anhydrous sodium sulphate 10.5 talcum powder 8.2 taking 20g B: 20g of catalyst-free prepolymer, dichloromethane, No. 200 solvent oil and black material are taken according to the ratio of 10: 5: 10: 1

A: 20g of water glass 60 styrene-acrylic emulsion 1 redispersible rubber powder 1 sodium tripolyphosphate 1 anhydrous sodium sulphate 4 light magnesium oxide

A: sodium silicate 75 redispersible rubber powder 3 dichloromethane 10.8 glycerol 7 sodium tripolyphosphate 1 anhydrous sodium sulphate 8 talcum powder 15 is prepared from 20g B: 20g of catalyst-free prepolymer, dichloromethane, No. 200 solvent oil and black material are taken according to the ratio of 10: 5: 10

A: sodium silicate 75 redispersible rubber powder 3 glycerol 7 dichloromethane 21 sodium tripolyphosphate 1.5 anhydrous sodium sulfate 8 calcium carbonate powder 8 talc powder 8B: 20g of catalyst-free prepolymer, dichloromethane and black material are taken at a ratio of 1:1

A: 26g of sodium silicate 75 pvc paste resin 3 dichloromethane 5 sodium tripolyphosphate 1 glycerol 7 anhydrous sodium sulphate 9

B: 34g of catalyst-free prepolymer, dichloromethane and black material are taken at a ratio of 10: 14: 10

A: sodium silicate 75 pvc paste resin 3 dioctyl phthalate 1.5 methylene chloride 38 glycerol 6 sodium tripolyphosphate 1.5 sodium sulfate 8 density 1.35

A: sodium silicate 75 redispersible gelatine powder 1 dichloromethane 8 glycerol 7 sodium tripolyphosphate 1.5 anhydrous sodium sulphate 8 talcum powder 15

A: 885 resin 5 phosphate (TTP)5 sodium dodecyl benzene sulfonate 0.6 sodium sulfate 75 water glass 8g

B: taking 40g of catalyst-free prepolymer, dichloromethane, No. 200 solvent oil and black material as 10: 5: 10: 1

Taking 10g of black material and foaming adhesive as 1: 2

A: 50g of water glass 75191 resin (containing 3% of accelerator), 4 castor oil, 5 glycerol and 5 sodium tripolyphosphate

B: taking 50g of catalyst-free prepolymer, dichloromethane, No. 200 solvent oil and black material as the ratio of 1: 0.5: 1

A: water glass 75191 resin (containing 3% accelerator) 4 Castor oil 5 Glycerol 5.5 sodium tripolyphosphate 1.5

Taking 50g of anhydrous sodium sulphate 9

A: sodium silicate 75191 resin 5 phosphate (TPP)5 sodium dodecyl benzene sulfonate 0.6 anhydrous sodium sulfate 8g

B: 30g of catalyst-free prepolymer, dichloromethane, No. 200 solvent oil and black material are taken according to the ratio of 10: 5: 10: 1

Taking 10g of black material and foaming adhesive as 1: 2

A: sodium silicate 75 redispersible gelatine powder 3 dichloromethane 10.8 dimethyl silicone oil 1.8 anhydrous sodium sulphate 8 sodium pyrophosphate 1 glycerol 8 talcum powder 9.5

A: sodium silicate 75 redispersible rubber powder 3 dichloromethane 20 glycerol 7 acetone 2.5 sodium tripolyphosphate 1.5 anhydrous sodium sulphate 8 talcum powder 9.5

A: sodium silicate 75 redispersible gelatine powder 1.5 sodium tripolyphosphate 1 glycerol 5 epoxidized soybean oil 4

Anhydrous sodium sulfate 8 talcum powder 15

A: sodium silicate 75 redispersible gelatine powder 2 mould silica gel liquid 1 soybean oil 4 glycerine 5 cocamidopropyl betaine 1.5 sodium tripolyphosphate 1.5 polyimide resin powder 1 anhydrous sodium sulfate 8 talcum powder 8 30g

A: sodium silicate 75 redispersible rubber powder 1.5 sodium tripolyphosphate 1 glycerol 5 epoxidized soybean oil 4 borax 0.5 anhydrous sodium sulphate 8 talcum powder 15

A: sodium silicate 75191 resin 5 phosphate (TCEP)5 OP-100.4 nitrile rubber 0.2 sodium dodecyl benzene sulfonate 0.6 anhydrous sodium sulfate 8.6 30g B: taking 10g of black material and foaming adhesive as 1:1

30g of catalyst-free prepolymer, dichloromethane, No. 200 solvent oil and black material are taken according to the ratio of 10: 5: 10: 1

A: sodium silicate 75 redispersible gelatine powder 1.5 sodium tripolyphosphate 1 glycerol 5 epoxidized soybean oil 4 anhydrous sodium sulphate 8 talcum powder 15

30g of catalyst-free prepolymer, dichloromethane, No. 200 solvent oil, phosphate (TPP) and black material are taken

A: water glass 80 redispersible rubber powder 1.5 sunflower seed oil 4 sodium tripolyphosphate 3 glycerol 6.5 anhydrous sodium sulphate 15 g

B: taking 40g of black material and foaming adhesive as 1: 2

A: water glass 80 silicone-acrylic emulsion 1.5 epoxidized soybean oil 4 sodium tripolyphosphate 1.5 glycerol 5 anhydrous sodium sulfate 8 talcum powder 10

A: water glass 80 vinyl ester resin (Fuchem 854)1.5 Dioctyl phthalate 4 Glycerol 5 sodium tripolyphosphate 3 Yuan Ming 8 Talc powder 8

A: water glass 80 vinyl ester resin (Fuchem 820)1 redispersible rubber powder 1.5 dioctyl phthalate 4 silane coupling agent 0.3 glycerol 6 sodium tripolyphosphate 1.5 anhydrous sodium sulfate 8 talcum powder 8

A: water glass 80 redispersible rubber powder 10 dioctyl phthalate 4 glycerol 5.5 sodium tripolyphosphate 1.5 anhydrous sodium sulfate 8 talcum powder 8

A: water glass 80 redispersible rubber powder 10 dioctyl phthalate 4 glycerol 9 sodium polyphosphate 1.5 anhydrous sodium sulphate 8 talcum powder 8

A: 20g of sodium silicate 80 polybutadiene epoxy resin 1.5 glycerol 9 sodium tripolyphosphate 7.5 anhydrous sodium sulphate 8 talcum powder 8

B: 22g of catalyst-free prepolymer, dichloromethane, dioctyl phthalate and polymeric MDI (methylene diphenyl diisocyanate) are taken in a ratio of 1: 0.1: 1

A: water glass 80 redispersible rubber powder 1 sodium tripolyphosphate 3 glycerol 5 ethylene glycol 2 dioctyl phthalate 4 anhydrous sodium sulphate 8 talcum powder 8 the rubber material 200 is added with polyurethane foaming white material 3

A: solid sodium silicate 40 redispersible rubber powder 1.5 dibutyl phthalate 4 glycerol 5 ethylene glycol 2 sodium tripolyphosphate 3 anhydrous sodium sulfate 8 talcum powder 8 cement 100, uniformly mixing and sealing, and adding water 40 when in use

A: water glass 80 redispersible rubber powder 1 dioctyl phthalate 4 sodium tripolyphosphate 3 melamine resin 8 glycerol 5 ethylene glycol 2 anhydrous sodium sulfate 8 talcum powder 8 the rubber material is mixed with quartz powder 1:1 evenly

A: sodium silicate 80 redispersible rubber powder 1 dioctyl phthalate 4 sodium tripolyphosphate 3 glycerol 5 ethylene glycol 2 anhydrous sodium sulfate 8 talcum powder 8 the rubber material is mixed with quartz powder 1: 2 evenly

A: sodium silicate 80 redispersible gelatine powder 1 sodium tripolyphosphate 3 glycerol 5 ethylene glycol 2 dioctyl phthalate 4 anhydrous sodium sulphate 8 talcum powder 8 the above gelatine is mixed with talcum powder 2: 1 uniformly

A: sodium silicate 80 methylsilicate 1 redispersible powder, sodium diphosphate 2 sodium dimer 3, glycerol 5.5 talcum powder, 8200 solvent oil, 4 anhydrous sodium sulphate 8

A: sodium silicate 80 tripolyphosphate, glycerol 5 titanate coupling agent 1 liquid paraffin 4 anhydrous sodium sulphate 8 talcum powder 8 10g B: 10g of blocked polyisocyanate, redispersible rubber powder and foaming adhesive are mixed according to the ratio of 1: 0 and 05: 2

A: water glass 80 redispersible rubber powder 1.5 acrylic resin 1 castor oil 4 sodium tripolyphosphate 1.5 glycerol 5 anhydrous sodium sulphate 8 talcum powder 8

A: 28.7g of water glass 80, epoxy resin 3, sodium tripolyphosphate 3, glycerol 5.5 and anhydrous sodium sulphate 15

B: 24.3g of catalyst-free prepolymer, dichloromethane, No. 200 solvent oil, dioctyl phthalate and isophorone diisocyanate are taken as raw materials, wherein the raw materials comprise 1: 0.5: 0.17: 1

Taking 7g of black material and foaming adhesive as 1: 2

A: water glass 80 epoxy resin 2 dioctyl phthalate 3 sodium tripolyphosphate 1.5 glycerol 5 sodium sulfate 8 talcum powder 8

A: water glass 80 redispersible rubber powder 1.5 dioctyl phthalate 3 castor oil 4 sodium tripolyphosphate 1.5 glycerol 5 anhydrous sodium sulphate 8 talcum powder 8

A: water glass 80 styrene-acrylic emulsion 1.5 redispersible rubber powder 1.5 dioctyl phthalate 2200 solvent oil 2 glycerol 5.5 sodium tripolyphosphate 3 anhydrous sodium sulphate 8 talcum powder 8

B: the catalyst-free prepolymer, dichloromethane and modified MDI are 1:1, A: B is 1:1

A: Water glass 80 redispersible rubber powder (Vac/VeoVa) 1.5200 solvent oil 4 glycerol 5.5 sodium tripolyphosphate 3 anhydrous sodium sulfate 8 talcum powder 8 30g B: 20g of catalyst-free prepolymer, dichloromethane and black material are taken at a ratio of 1:1

Taking 10g of black material and foaming adhesive as 1: 2

A: water glass 80 (half of sodium water glass, water glass) redispersible rubber powder (Vac/E/VeoVa)2.5 dioctyl phthalate 2.5 dibutyl phthalate 1.5 sodium tripolyphosphate 1.5 glycerin 5.5 anhydrous sodium sulfate 8 sericite 5 talc 5 20g

B: taking 16g of black material and 4g of foaming adhesive as a mixture of catalyst-free prepolymer, dichloromethane, No. 200 solvent oil, isophorone diisocyanate I as a mixture of 1: 0.5: 1

A: sodium silicate 85 redispersible rubber powder 3 dichloromethane 20 aluminum silicate cotton 5 anhydrous sodium sulphate 8 glycerol 7 sodium tripolyphosphate 1 talcum powder 15 is prepared from 20g B: 20g of catalyst-free prepolymer, dichloromethane and black material are taken at a ratio of 1:1

A: 1.5 parts of water glass 60 redispersible rubber powder, 1.5 parts of acrylic resin, 4 parts of dioctyl phthalate, 2 parts of glycerol and 5 parts of sodium tripolyphosphate, and 30g of the mixture is taken after being uniformly stirred

B: taking 25g of catalyst-free prepolymer, dichloromethane, No. 200 solvent oil and modified MDI (diphenyl-methane-diisocyanate) in a ratio of 1: 0.5: 1

Taking 5g of black material and foaming adhesive as 1: 2

A: 1.2 g of water glass 95 redispersible rubber powder 15 melamine resin 5 silane coupling agent

A: 98.5 parts of sodium silicate redispersible rubber powder, 1.5 parts of dioctyl phthalate, 4 parts of glycerol, 5.5 parts of sodium tripolyphosphate, 8.5 parts of anhydrous sodium sulphate, 8 parts of talcum powder, 8 parts of catalyst-free prepolymer, dichloromethane, No. 200 parts of solvent oil and black material, 10 parts of the prepolymer, 10 parts of the black material and the black material

A: 98.5 portions of sodium silicate redispersible rubber powder, 1.5 portions of dioctyl phthalate, 4 portions of glycerol, 5.5 portions of sodium tripolyphosphate, 8.5 portions of anhydrous sodium sulphate, 8 portions of talcum powder, 8 portions of light magnesium oxide and 10g of light magnesium oxide

A: solid water glass mixture: redispersible rubber powder 4 castor oil 4 glycerol 5 cocamidopropyl betaine 1.5 anhydrous sodium sulphate 8 talcum powder 8, adding solid water glass 40 after stirring uniformly, sealing and packaging 20g, adding water 20g, stirring uniformly

Taking 10g of black material and foaming adhesive as 1: 2

A: solid water glass mixture: redispersible rubber powder 4 castor oil 4 glycerol 5 sodium dodecyl sulfate 1.5 sodium tripolyphosphate 1 anhydrous sodium sulphate 8 talcum powder 8 are stirred evenly, then the solid water glass 40 is added, stirred evenly and sealed and packaged; taking 20g, adding 12g of water, and uniformly stirring: 30g of catalyst-free prepolymer, dichloromethane, No. 200 solvent oil and black material are taken according to the ratio of 10: 5: 10: 1

In the embodiment of the invention, the density of the component A of the adhesive is about 1.25-2.25 g/cm3, the viscosity is 380-10000 Mpas, the pH value is more than 12, the adaptation period is 5-45 minutes, and the adhesive coating amount is 800-2000 g/m 2. One side of the tile was coated with 20 × 20mm2 of the adhesive of example 58, and then placed in tap water, 2% sodium hydroxide aqueous solution and 1% sulfuric acid solution for one month, and it was not yet abnormal and could not be pulled off by hand. The steel plate and the cement plate painted with the quick-drying paint in the embodiment have no crack, discoloration, rusting and halogen generation after 8 months. In example 51, the sample was boiled with tap water for 4 hours and a 0.5 to 1% sodium hydroxide solution for 2 hours, and no abnormality such as cracking was observed, and the surface gloss was not significantly changed.

Preparing a coating:

a preparation process comprises the following steps: grinding and screening various powder materials in advance, sequentially adding metered resin liquid or dispersible resin powder and a plasticizer into a container, stirring, then adding glycerol, stirring, adding water glass and an inorganic filler, and uniformly stirring to obtain a slurry. Grinding the slurry by a three-roll grinder for one to two times, adding the actually required conventional emulsion and other auxiliary agents, and stirring by a stirrer at 300-800 revolutions per minute for 30 minutes to 4 hours until the slurry is uniformly mixed.

The coating of the present invention is not limited to the above-mentioned method, and can be formulated by various conventional methods.

Adding various components for forming the component A into a container with a stirring device according to the adhesive, adjusting the specific weight of filling auxiliary materials such as filler, pigment, dispersing agent, flatting agent, defoaming agent and the like according to the conventional and specific application, and forming uniform emulsion under the conditions of intense stirring and/or grinding to obtain the component A. And adding the catalyst-free prepolymer, the organic solvent, the black material and other substances which form the component B into a container with a stirring device according to the formula, and uniformly stirring to obtain the component B. And adding the prepared component A and the prepared component B according to the ratio of A to B being 0.5-1: 0.5-1, and uniformly stirring to obtain the coating. The adhesive can be directly used as paint, or filler and additive can be added into the composite resin/adhesive according to the conventional method.

In the following examples, the surface drying time of the paint is less than 2 hours, the actual drying time is less than 12 hours, the oil resistance is soaked for 7 days, the humidity resistance is soaked for 7 days, the salt resistance is soaked for 3 days, and the cold and heat resistance is cycled for 15 times, so that the coating does not wrinkle and fall off. Difficult to ignite. The density of the component A of the coating is mostly 1.25-1.5 g/cm3, the viscosity is 500-3000 Mpas, the pH value is more than 12, the adaptation period is 10-45 minutes, and the glue coating amount is 1000-2500 g/m 2. The chopstick heads are coated with about 5g of sizing material, and after being cured for 36 hours, the chopstick heads are soaked in 5% dilute hydrochloric acid solution for a week, still have luster, and the adhesion state is still firm.

A: sodium silicate 80 tripolyphosphate, 1.5 sodium dodecyl benzene sulfonate, 0.8 glycerol, 5.5 anhydrous sodium sulphate, 8 talcum powder and a little defoamer

B: catalyst-free prepolymer, dichloromethane, No. 200 solvent oil, dioctyl phthalate, redispersible rubber powder and black material in the weight ratio of 1 to 0.5 to 0.08 to 0.16 to 1

Black material to foamed rubber is 1: 2A: B is 1.1: 1

A: sodium silicate 80 tripolyphosphate 1.5 Glycerol 5 redispersible powder 1.5 Castor oil 4 Natrii sulfas 8 Talcum 8

B: catalyst-free prepolymer, dichloromethane, No. 200 solvent oil and black material are 1: 0.5: 1, A: B is 1:1

A: solid water glass mixture: redispersible rubber powder 4 castor oil 4 glycerol 5 sodium dodecyl sulfate 1.5 sodium tripolyphosphate 1 anhydrous sodium sulphate 10 talcum powder 10 bentonite 8 sericite 10 antifoaming agent is stirred uniformly, then the solid water glass 40 is added, stirred uniformly, sealed and packaged; 20g of the mixture is taken, 12g of water is added, and the mixture is stirred uniformly

B: catalyst-free prepolymer, dichloromethane, No. 200 solvent oil and black material in the weight ratio of 10 to 5 to 10 to 1, and A to B in the weight ratio of 1.5 to 1

A: sodium silicate 80 redispersible rubber powder No. 2200 solvent oil 2 dioctyl phthalate 2 glycerol 5.5 sodium tripolyphosphate 3 anhydrous sodium sulfate 8 talcum powder 8 expandable graphite 5

B: catalyst-free prepolymer, dichloromethane and black material in the ratio of 1 to 1, and A to B in the ratio of 1 to 1

A: sodium silicate 80, sodium tripolyphosphate, glycerol 5, redispersible rubber powder, dioctyl phthalate, 4 anhydrous sodium sulphate, 8 talcum powder, 20 titanium dioxide, 5 light calcium carbonate, 8 OP-101 defoamer and a small amount of leveling agent

B: catalyst-free prepolymer, dichloromethane, No. 200 solvent oil and black material are 1: 0.5: 1, A: B is 1.2: 1

A: water glass 80 redispersible rubber powder 1.0 dimethyl silicone oil 2.5 decaglycol ester 8 talcum powder 10 titanium dioxide 5 light calcium carbonate 8 OP-102 defoamer a little leveling agent in right amount

B: catalyst-free prepolymer 3 black material 4A: B is 1:1

A: water glass 100 redispersible rubber powder 1.5 dimethyl silicone oil 1.5 decaglycol ester 5 talcum powder 10 titanium dioxide 5 glycerol 2.5 ethylene glycol 2.5 sodium tripolyphosphate 1.5 OP-102 defoaming agent a little leveling agent in right amount

B: catalyst-free prepolymer 4 black material 4A: B is 1.2: 1

The combination of the glass fiber reinforced plastic resin, the adhesive and the coating can be as follows:

a: water glass 80 AES3 styrene 4 redispersible rubber powder 1.5 phosphate 3 sodium tripolyphosphate 1.5

B: catalyst-free prepolymer 1 black material 1 dimethyl carbonate 0.3 methyl acetate 0.3A: B1:1

A: water glass (modulus 2.6-2.9) B: catalyst-free prepolymer 5 black material 25A: B is 1:1

A: water glass (modulus 2.6-2.9) B: catalyst-free prepolymer 0.5 black material 25A: B is 1:1

A: water glass (modulus 2.6-2.9) B: catalyst-free prepolymer 0.75 black material 25A: B1:1

A: sodium silicate 80 redispersible rubber powder 1.5 dioctyl phthalate 2 castor oil 2 sodium tripolyphosphate 1.5 glycerol 6 anhydrous sodium sulphate 8 talc powder 8B: catalyst-free prepolymer 0.75 black material 25A: B1:1

A: water glass (modulus 2.6-2.9) B: catalyst-free prepolymer 0.3 black material 100A: B1:1

A: water glass (modulus 2.6-2.9) silane coupling agent 0.6B: catalyst-free prepolymer 1 black material 1 dimethyl carbonate 1A: B is 1:1

A: sodium silicate 75 redispersible rubber powder 1.8 dioctyl phthalate 4 glycerol 5.5 sodium tripolyphosphate 1.5 anhydrous sodium sulfate 4 talc 4B: catalyst-free prepolymer 1 black material 1A: B is 1:1

A: water glass 50 redispersible rubber powder 1.0 epoxidized soybean oil 4 glycerol 5 sodium tripolyphosphate 1.5 talc 16B: catalyst-free prepolymer 1 black material 1A: B is 3: 2.5

A: water glass 80 redispersible rubber powder 1.5 dibutyl phthalate 5 glycerin 5 sodium tripolyphosphate 2 anhydrous sodium sulfate 8 titanium dioxide 50B: catalyst-free prepolymer 1 black material 1A: B is 3: 2

A: water glass 30 redispersible rubber powder 1.0 dibutyl phthalate 4 kh 5501.2

Glycerol 5 sodium tripolyphosphate 1.5 anhydrous sodium sulphate 4 diatomaceous earth 8B: catalyst-free prepolymer 1 black material 1A: B is 1:1

A: water glass 80 redispersible rubber powder 1.5 dibutyl phthalate 4 coupling agent 1.5

Glycerol 5 sodium tripolyphosphate 1.5 anhydrous sodium sulphate 4 mica powder 48B: catalyst-free prepolymer 1 black material 1A: B is 1:1

A: water glass 80 redispersible rubber powder 1.0 dibutyl phthalate 3

Glycerol 5 sodium tripolyphosphate 1.5 anhydrous sodium sulfate 4 mica powder 4B: catalyst-free prepolymer 4 black material 4 dichloromethane 1 solvent oil 1A: B is 1:1

A: water glass 80 (3.0-3.4 mould) redispersible rubber powder 1.0 dibutyl phthalate 3

Glycerol 5 sodium tripolyphosphate 1.5 anhydrous sodium sulphate 8 mica powder 8B: catalyst-free prepolymer 4 black material 4 dichloromethane 1 solvent oil 1A: B is 3: 2

A: water glass 30 (3.0-3.4 mode) glycerol 10 anhydrous sodium sulfate 8B: catalyst-free prepolymer 1 black material 1A: B is 1:1

A: water glass 80 (2.1-2.5 model) castor oil 8 redispersible rubber powder 1 sodium tripolyphosphate 1 anhydrous sodium sulphate 4B: catalyst-free prepolymer 1 black material 1A: B is 1:1

A: sodium silicate 80 (2.1-2.5 model) castor oil 6 sodium tripolyphosphate 1.5 anhydrous sodium sulphate 5B: catalyst-free prepolymer 1 black material 1A: B is 1:1

A: soluble glass 80 (modulus 2.6-2.9), redispersible rubber powder 1 dimethicone 4.8 glycerin 2.5 ethylene glycol 2.5 sodium tripolyphosphate 1 anhydrous sodium sulfate 5 mica powder 10 styrene 8B: catalyst-free prepolymer 2 black material 2 dimethyl carbonate 0.7A: B1:1

A: water glass 80 redispersible rubber powder 1 dioctyl phthalate 4 glycerol 6 sodium polyphosphate 1.5 anhydrous sodium sulphate 8 talcum powder 8B: catalyst-free prepolymer 25 black material 25 dimethyl carbonate 8.3 dichloromethane 4.2 solvent oil 8.3 phosphate 2.5 ethyl acetate 3A: B ═ 1:1

A: water glass (modulus 3.0-3.4) 80 acrylic resin 5 anhydrous sodium sulphate 5

A: sodium silicate (modulus 3.0-3.4) 80 sodium dodecyl benzene sulfonate 2 epoxy resin 6 anhydrous sodium sulfate 5 coupling agent 2

B: catalyst-free prepolymer 1 black material 1 dimethyl carbonate 1A: B is 1:1

The performance of the invention as an environment-friendly adhesive is compared with that of various common adhesives

Normal temperature and pressure bonding strength (Mpa) reference (all 48 hours later determination)

Taitebang

Batten-screw 0.96 (nail head with wood) ceramic tile-screw 0.97 (nail head with glue) screw-screw 1.04 (nail head with glue)

Marble glue

Batten-screw 0.83 (nail head with wood) ceramic tile-screw 0.95 (nail head with glue) screw-screw 2.99 (nail head with glue)

One of the series of the present invention

A: sodium silicate 80 redispersible rubber powder 1.5 dioctyl phthalate 4 sodium tripolyphosphate 1.5 glycerol 6 anhydrous sodium sulphate 8 talc 80B: catalyst-free prepolymer 1 methylene chloride 0.5 solvent oil 0.5 black material 1A: B1:1

Bond strength (Mpa):

batten-screw 2.27 (nail head with wood) ceramic tile-screw 1.97 (nail head with glue) screw-screw 2.68 (nail head with glue)

Series two of the present invention

A: water glass 80 redispersible rubber powder 1.5 epoxidized soybean oil 4 sodium tripolyphosphate 1.5 glycerol 6 anhydrous sodium sulfate 8 sericite 8B: catalyst-free prepolymer 25 dimethyl carbonate 10 solvent oil 8 phosphate 3 methyl acetate 4 polymeric MDI 25A: B1:1

Bond strength (Mpa): batten-screw 1.85 (with glue nail head) ceramic tile-screw 1.63 (with glue nail head)

Three 437 wood strips-screw 2.51 of the invention series (nail head with glue and wood)

Ceramic tile-screw 1.91 (with glue nail head) screw-screw 2.93 (with glue nail head)

Damp-heat test

The tite bang tiles-screws were boiled at atmospheric pressure for 3 days with approximately half of the fall off in two days and all fall off in three days.

The screw-screw is not dropped off after being steamed for 7 days under normal pressure, and the bonding strength is measured at room temperature for 24 hours and is 0.48Mpa (the nail head is provided with glue)

The bonding strength of the batten-screw after 7 days and 25 times of low-temperature freeze thawing test is 1.00Mpa (nail head with glue and a small amount of veneer)

The marble adhesive tile-bolt is boiled at normal pressure for 3 days and two days and completely falls off.

The wood bar-screw is not dropped off after being steamed for 7 days under normal pressure, the bonding strength is measured to be 0.35Mpa (the nail head is adhesive-free and has black rust) after being placed for 24 hours at room temperature

The screw-screw is steamed under normal pressure for 7 days to half-fall off, and the bonding strength is measured after the screw-screw is placed for 24 hours at room temperature and is 0.30Mpa (the nail head has no glue and has brown black rust)

The bonding strength of the batten-screw after 7 days and 25 times of low-temperature freeze thawing test is 1.05Mpa (nail head with glue)

Epoxy resin (E-44 and half of polyamide resin 650)

The ceramic tile-screw is boiled under normal pressure for 3 days, most of the sample interfaces are cracked, and the sample is placed at room temperature for 24 hours to measure the bonding strength of 0.35Mpa (the nail head is glue-free, brown and black)

The wood strip-screw is not dropped off after being steamed for 7 days under normal pressure, and the bonding strength is measured by 0.40-1.30 Mpa (nail head black brown glue-free or with brown glue film) after being placed for 24 hours at room temperature

The screw-screw atmospheric pressure steaming is 7 days, cracks appear on the interface of a nearly half sample, the sample is placed at room temperature for 24 hours, and the bonding strength is 0.40-2.21 Mpa (the part of the nail head with glue has brown and black rust)

The bonding strength of the batten-screw in 7 days and 25 times of low-temperature freeze thawing test is 1.53Mpa (nail head almost has no glue)

The fourth series of the present invention

A: water glass 80 redispersible rubber powder 1.5 epoxidized soybean oil 3 dimethicone 1 sodium tripolyphosphate 1.5 glycerin 6 anhydrous sodium sulfate 8 sericite 100B: catalyst-free prepolymer 1 methylene chloride 0.5 solvent oil 0.5 black material 1A: B1:1

Bond strength (Mpa):

ceramic tile-screw is not dropped off after boiling for 3 days under normal pressure, and the bonding strength is measured at room temperature for 24 hours and is 0.63Mpa (nail head with glue)

The wood strip-screw is not peeled off after being steamed for 7 days under normal pressure, and the bonding strength is measured to be 1.22Mpa (the nail head is black brown without glue or with brown glue film) after being placed for 24 hours at room temperature

The screw-screw is not dropped off after being steamed for 7 days under normal pressure, and the bonding strength is measured by placing for 24 hours at room temperature and is 1.10Mpa (the nail head is provided with glue)

The bonding strength of the batten-screw after 7 days and 25 times of low-temperature freeze thawing test is 2.02Mpa (nail head with wood skin)

The fifth series of the present invention

A: water glass 80 redispersible rubber powder 1.5 epoxidized soybean oil 2 dioctyl phthalate 2 sodium tripolyphosphate 1.5 glycerol 6 anhydrous sodium sulphate 8 talc powder 80B: catalyst-free prepolymer 1 dimethyl carbonate 0.5 solvent oil 0.5 black material 1A: B1:1

Bond strength (Mpa):

ceramic tile-screw is not dropped off after boiling for 3 days under normal pressure, and the bonding strength is measured at room temperature for 24 hours and is 1.05Mpa (nail head with glue)

The wood bar-screw is not peeled off after being steamed for 7 days under normal pressure, and the bonding strength is measured to be 1.31Mpa (the part of the nail head is glued) after being placed for 24 hours at room temperature

The screw-screw is not dropped off after being steamed for 7 days under normal pressure, and the bonding strength is measured to be 0.98Mpa (with a small amount of glue on the nail head) after being placed for 24 hours at room temperature

Bonding strength of batten-screw 7 days 25 times low temperature freeze thawing test 1.08Mpa (nail head with glue)

Dry heat test

The Titebang ceramic tile-the screw is not peeled off after being baked for 7 days at 60-120 ℃, the iron block with the bonding strength of 1.16Mpa (nail head with glue and dark brown) is measured after being placed for 24 hours at room temperature, the screw is not peeled off after being baked for 7 days at 60-120 ℃, and the bonding strength of 0.93Mpa (nail head with glue) is measured after being placed for 24 hours at room temperature

The marble glue ceramic tile-screw is not peeled off after being baked for 7 days at the temperature of 60-120 ℃, and the iron block with the bonding strength of 1.47Mpa (with glue on the nail head or broken tiles) and the screw are baked for 7 days at the temperature of 60-120 ℃ after being placed for 24 hours at room temperature.

Epoxy resin (E-44 and half of polyamide resin 650)

The ceramic tile-the screw-the iron block with the bonding strength 1.76Mpa (the nail head with the broken tile) is baked for 7 days at the temperature of 60-120 ℃ and does not fall off, the iron block with the bonding strength 1.76Mpa (the screw head with the broken tile) is baked for 24 hours at the room temperature-the screw-the iron block with the bonding strength 2.43Mpa (the nail head with the broken tile) is baked for 7 days at the

The invention series six

A: soluble glass 80 (modulus 3.0-3.4), redispersible rubber powder 1.5 dioctyl phthalate 4 sodium tripolyphosphate 1.5 glycerol 6 anhydrous sodium sulfate 8 sericite 100B: catalyst-free prepolymer 1 black material 1A: B is 3: 2

Bond strength (Mpa):

the bonding strength of the batten-screw is 2.35Mpa (nail head tape and/or veneer) measured at normal temperature and pressure for 48 hours

Ceramic tile-screw normal temperature and pressure 48 hours adhesive strength 2.76Mpa (nail head with glue and/or ceramic tile fragment)

The ceramic tile-the screw-the iron block which is not dropped after being baked for 7 days at 60-120 ℃ and has the bonding strength of 1.35Mpa (almost no glue on the nail head) when being placed for 24 hours at room temperature-the screw-the iron block which is not dropped after being baked for 7 days at 60-120 ℃ and has the bonding strength of 0.85Mpa (almost no glue on the nail head) when being placed for 24 hours at room temperature

Seven of the series of the present invention

A: soluble glass 80 (modulus 3.0-3.4), redispersible rubber powder 1.5 dioctyl phthalate 4 sodium tripolyphosphate 1.5 glycerol 5 anhydrous sodium sulfate 8 sericite 9B: catalyst-free prepolymer 1 dimethyl carbonate 0.33 solvent oil 0.33 methyl acetate 0.33 black material 1A: B1:1

Bond strength (Mpa):

the bonding strength of the batten-screw is 1.98Mpa (nail head with glue and/or veneer) measured at normal temperature and pressure for 48 hours

Ceramic tile-screw normal pressure 48 hours measuring bonding strength 2.06Mpa (nail head belt glue and/or ceramic tile fragment)

The ceramic tile-screw is not peeled off after being baked for 7 days at 60-120 ℃, and the bonding strength is measured to be 1.46Mpa (with glue on the nail head) after being placed for 24 hours at room temperature

The iron block-screw is not peeled off after being baked for 7 days at 60-120 ℃, and the bonding strength is measured to be 2.13Mpa (nail head with glue) after being placed for 24 hours at room temperature

Although the adaptation period of the composite resin, the adhesive and the coating in the invention is related to the air temperature, the adaptation period can be controlled within the range of several minutes to several hours according to the selection of the formula and the known techniques such as the type of isocyanate, the blocking condition, the adjustment of diluents, catalysts, phosphate esters and other components.

Claims

1. An environment-friendly composite resin is characterized by comprising 60-100 parts of water glass or modified water glass, 0-30 parts of an organic solvent and/or a plasticizer, 0-10 parts of polyhydric alcohol, 0-15 parts of resin liquid and/or dispersible resin powder, 0-8 parts of a surfactant and/or sodium hexametaphosphate and/or sodium pyrophosphate and/or sodium tripolyphosphate and 0-20 parts of a filling auxiliary material; the B also contains a prepolymer generated by the prepolymerization of polyester polyol and/or polyether polyol and polyisocyanate, and the composition and the weight percentage of each component are as follows: 30-50% of isocyanate and/or blocked isocyanate, 20-30% of prepolymer, 20-50% of organic solvent and/or plasticizer and 0-0.5% of additive; the weight ratio of A to B: a and B are 1: 1.5-1.5: 1, and the water glass is sodium water glass and/or water glass; the modified water glass is prepared by adding a small amount of functional materials or additives into water glass, wherein the additives comprise silane coupling agents accounting for 0.5-5% of the total amount of the component A.

2. A composition for environment-friendly composite resin, adhesive or coating comprises a water glass component A, an isocyanate component B and conventional additives, and is characterized in that the A or B at least contains resin liquid or melamine resin suitable for resin, epoxy resin, silicone-acrylic resin, styrene-acrylic resin or silica gel resin, or dispersible resin powder or one or more of the modified derivatives thereof, and the composition and the parts by weight of the components are as follows: 30-100 parts of water glass, 0-10 parts of a dispersing agent, 0-550 parts of a filler, 0.3-15% of a resin liquid and/or dispersible resin powder, 0-50% of an organic solvent and/or plasticizer, 0-10% of a polyol and 0-10% of a water glass curing agent; the B also contains polyester and/or polyether polyol prepolymer, which comprises the following components in percentage by weight: 30-50% of isocyanate and/or blocked isocyanate, 20-50% of prepolymer, 20-50% of organic solvent and/or plasticizer and 0-0.3% of catalyst; when the components are mixed to form the composite sizing material, the weight ratio of A to B is 1: 1.5-1.5: 1, the filler comprises anhydrous sodium sulphate, and the polyalcohol comprises glycerol.

3. A composition for environment-friendly composite resin, adhesive or coating comprises a water glass component A, an isocyanate component B and conventional additives, and is characterized in that the water glass is instant solid water glass, the A at least contains a vinyl ester resin, a polyester resin, an acrylic resin, an epoxy resin, a silicone-acrylic resin, a resin liquid of a styrene-acrylic resin or a silicone resin, or a resin liquid of a dispersible resin powder or a modified derivative thereof, or a combination of more than one of the components in parts by weight: 15-50 parts of solid water glass, 1-20 parts of resin liquid or/and redispersible rubber powder dispersant, 0-40 parts of organic solvent and/or plasticizer, 0-10 parts of polyol, 0-10 parts of surfactant and/or dispersant, 0-550 parts of filling auxiliary material and 0-5 parts of curing agent, wherein water is added before the A and the B are mixed, the added water amount is 0.4-1.2 times of the weight of the solid water glass, the filling material at least comprises anhydrous sodium sulphate, and the polyol at least comprises glycerol; the B also contains polyester and/or polyether polyol prepolymer, which comprises the following components in percentage by weight: 30-50% of isocyanate and/or blocked isocyanate, 20-50% of prepolymer, 20-50% of organic solvent and/or plasticizer and 0-0.5% of catalyst; a and B are 1-1.5: 1-1.5.

4. The composition for environment-friendly composite resin, adhesive or coating according to any one of claims 2 or 3, wherein the component A comprises the following components in parts by weight: 60-85 parts of liquid water glass or 20-45 parts of solid water glass, 1.5-15 parts of resin liquid and/or dispersible resin, 3-30 parts of organic solvent and/or plasticizer, 3-8 parts of ethylene glycol and/or glycerol, 0.5-8 parts of surfactant and/or sodium pyrophosphate and/or sodium tripolyphosphate and 0-20 parts of filling auxiliary materials; the polyurethane prepolymer, isocyanate and/or blocked isocyanate, diluent and/or viscosity reducer in the B are 1:1, the plasticizer is 1.5-10%, the catalyst is 0, and the finishing material contains anhydrous sodium sulphate.

5. The environment-friendly composite resin as claimed in claim 1, wherein the component A comprises the following components in parts by weight: 65-85 parts of liquid water glass or 30-45 parts of solid water glass, 3-10 parts of resin liquid and/or redispersible rubber powder, 3-10 parts of organic solvent and/or phosphate ester, 0-2 parts of ethylene glycol, 4-6 parts of glycerol, 0-5 parts of surfactant, 1-3 parts of sodium pyrophosphate and/or sodium tripolyphosphate, 3-16 parts of anhydrous sodium sulphate, 0-16 parts of talcum powder and/or sericite and/or silicon micropowder and 0-3 parts of anti-aging agent and/or other additives; b contains 10-20% of-NCO.

6. The composition for environment-friendly composite resin, adhesive or coating as claimed in claim 5, wherein the composition A comprises the following components in parts by weight: 75-85 parts of liquid water glass or 37-43 parts of solid water glass, 3-10 parts of unsaturated polyester resin and/or redispersible rubber powder, 3-10 parts of organic solvent and/or plasticizer, 5-7 parts of polyol, 0-5 parts of surfactant, 1-3 parts of sodium tripolyphosphate, 15-150 parts of filler and 0-10 parts of additive, wherein the filler comprises anhydrous sodium sulphate.

7. The composition for the environment-friendly composite resin, the adhesive or the coating comprises a water glass component A, a blocked isocyanate component B and a conventional additive, and is characterized in that the B at least contains one or more of vinyl ester resin, polyester resin, acrylic resin, epoxy resin, silicone-acrylic resin, styrene-acrylic resin, silicone resin liquid, melamine resin or dispersible resin powder or modified derivatives thereof, which are suitable for preparing the water glass polyurethane composite resin, wherein the weight parts of the components in the A are as follows: 30-50 parts of water glass or 15-25 parts of solid water glass, 5-7 parts of glycerol, 0.3-5 parts of surfactant, 1-5 parts of sodium tripolyphosphate, 5-8 parts of anhydrous sodium sulphate, 5-30 parts of talcum powder and/or sericite powder and/or silicon micropowder, 0-150 parts of quartz powder and/or other filling auxiliary materials suitable for being matched with the water glass, and 0-6 parts of expandable graphite; b, mixing polyurethane prepolymer, dichloromethane, solvent oil and/or dichloromethane and/or phosphate and/or propylene carbonate, resin liquid and/or redispersible rubber powder and blocked isocyanate in a ratio of 1: 0.5-0.8: 0.2-0.3: 1; the proportion of A and B is as follows: a and B are 1: 1-1.3.

8. The environment-friendly composite resin as claimed in any one of claims 3 or 6, wherein the isocyanate and/or blocked isocyanate in B is 30-35%, the prepolymer is 25-35%, the organic solvent is 25-35%, the plasticizer is 0-10%, and the catalyst is 0-0.05%; the isocyanate is one or more of diphenylmethane diisocyanate (MDI), polymethylene polyphenyl polyisocyanate (PAPI), isophorone diisocyanate (IPDI) and derivatives of the isocyanate.

9. The method for preparing the composition for environment-friendly composite resin, adhesive or coating according to any one of claims 1 to 12, which is characterized by comprising the following steps:

group A

1. Mixing the resin liquid and/or dispersible resin with organic solvent and/or plasticizer, stirring, and adding

The polyhydric alcohol is uniformly stirred and then is independently packaged or is uniformly mixed with the filling auxiliary materials and then is independently packaged; or continue to be

A step of;

2. adding part or all of liquid water glass into the mixture added with the polyalcohol, and adding the mixture under stirring

Surfactant and/or sodium phosphate dispersant to make up all water glass in the formulation;

Entering a step 4;

group B

After the reaction of isocyanate and polyester polyol and/or polyether polyol reaches the end point, cooling to a temperature lower than 50 ℃, adding a diluent, isocyanate and/or blocked isocyanate and a plasticizer under the conditions of protecting atmosphere and stirring, fully mixing, replacing with nitrogen, barreling and sealing; or mixing 35-50% of polyurethane prepolymer, 25-50% of diluent and 0-10% of plasticizer and/or viscosity reducer at the temperature of lower than 40 ℃, adding 25-50% of isocyanate or black material under the protection of nitrogen, or directly mixing foamed rubber containing 30-50% of prepolymer with black material and/or closed isocyanate according to the ratio of 0.5: 1-1: 0.5, then adding 0-10% of plasticizer and/or viscosity reducer and 0-50% of organic solvent and/or plasticizer, and uniformly stirring.

10. A composite board is made of the environment-friendly composite resin as claimed in any one of claims 1, 5 or 9, wherein wood chips and/or sawdust and/or waste fibers are used as main raw materials, resin or adhesive is used as a cementing agent, the water content of the composite board is controlled within 15%, and the composite board is characterized in that the composite board is subjected to hot grinding defibering treatment or is directly uniformly added with a composite mixed by A: B1-1.5 in an amount of 10-50% of the total amount of materials by a two-component spraying machine, is filled into a mold or is paved and molded, and is subjected to hot pressing or cold heading or is pressed and molded by a continuous flat press.