CN112063363A - Environment-friendly glass cement and preparation method thereof - Google Patents
Environment-friendly glass cement and preparation method thereof Download PDFInfo
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- CN112063363A CN112063363A CN202011010713.8A CN202011010713A CN112063363A CN 112063363 A CN112063363 A CN 112063363A CN 202011010713 A CN202011010713 A CN 202011010713A CN 112063363 A CN112063363 A CN 112063363A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
- C09J183/04—Polysiloxanes
- C09J183/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Abstract
The invention discloses an environment-friendly glass cement which is characterized by comprising the following components in parts by weight: 1-3 parts of hydrogenated acrylic rosin, 20-35 parts of 4, 10-dioxatricyclo [5.2.1.0(2,6) ] dec-8-ene-3-one/2-trimethylsiloxy-1, 1,1,5,5, 5-hexafluoro-2-pentane-4-one/allyl methyl trisulfide/2-trimethylsiloxy-4-propenoxybenzophenone copolymer, 10-20 parts of silicate-modified 1-allyl-3-methyl imidazole chloride/1- [3- (triethoxysilyl) propyl ] -1H-pyrrole-2, 5-dione/3-amino-2-butene thioamide copolymer, 2-4 parts of organic nanoparticles, and a copolymer prepared by mixing the above components, 3-6 parts of emulsifier, 1-3 parts of epoxy-terminated hyperbranched poly (amine-ester), 2-4 parts of quaternized imidazole nano microspheres and 45-55 parts of deionized water. The invention also provides a preparation method of the environment-friendly glass cement. The environment-friendly glass cement disclosed by the invention is strong in adhesive force, good in comprehensive performance, flame retardance and waterproof performance, good in antibacterial and mildew-proof capacity and performance stability, safe and environment-friendly to use.
Description
Technical Field
The invention relates to the technical field of chemical materials, in particular to an environment-friendly glass cement and a preparation method thereof.
Background
The glass cement is a material for bonding and sealing various kinds of glass and other base materials, is closely related to the daily life of people, and is widely applied to butt joint sealing of glass curtain walls, interior decoration, sealing of abutted seams of glass containers, sealing and sticking of sanitary wares, toilets, cosmetic mirrors and the like. With the development of the times and the formation of modern civilization, the glass cement is developing towards the directions of functionality, diversity and individuation.
The glass cement products on the market at present are various, including acid glass cement, hollow glass cement, special cement for large glass and the like, and the quality of the glass cement is good and uneven. The glass cement has the problems of weak adhesive force, easy glue opening, unsatisfactory use effect and the like more or less, and contains benzene solvents, ethyl acetate or banana oil and the like, thereby not only polluting the environment, but also being harmful to constructors and being flammable. After the paint is used for a period of time, the paint often becomes mildewed, blackened and yellowed in a humid environment, and the appearance is affected.
The Chinese patent with application number 201210550581.7 discloses a mildew-proof and environment-friendly glass cement and a preparation method thereof, wherein the selected formula comprises the following components in percentage by weight: 70-72 parts of polyacrylate emulsion, 10 parts of marine organism degerming agent, 0.2-5 parts of coupling agent, 17 parts of silica sol and 0.1-1 part of ammonia water. The invention creatively blends the degerming agent into the glass cement, so that the glass cement has long-acting antibacterial performance, and the blackening or discoloration phenomenon caused by mildew can be avoided after the glass cement is used; the VOC emission is zero, and the requirements of green and environmental protection are met; has extremely high adhesive force and waterproof function, and can replace the traditional glass cement. However, the glass cement has the defects of poor performance stability, high film forming temperature, low film hardness, poor rebound viscosity resistance, poor water resistance, poor adhesion and the like.
Therefore, the development of the environment-friendly glass cement which has strong adhesive force, good comprehensive performance, good flame retardance and waterproof performance, good antibacterial and mildewproof capability and good performance stability, is safe and environment-friendly to use, meets the market demand, has wide market value and application prospect, and has very important significance for promoting the development of the glass cement industry.
Disclosure of Invention
In view of the above, the invention aims to provide an environment-friendly glass cement which has the advantages of strong adhesive force, good comprehensive performance, flame retardance, aging resistance and waterproof performance, good antibacterial and mildew-proof capability and performance stability, and safe and environment-friendly use. Meanwhile, the invention also provides a preparation method of the environment-friendly glass cement, and the preparation method has the advantages of low raw material price, simple production process, suitability for batch production and popularization and application.
In order to achieve the purpose, the invention adopts the technical scheme that:
the environment-friendly glass cement is characterized by comprising the following components in parts by weight: 1-3 parts of hydrogenated acrylic rosin, 20-35 parts of 4, 10-dioxatricyclo [5.2.1.0(2,6) ] dec-8-ene-3-one/2-trimethylsiloxy-1, 1,1,5,5, 5-hexafluoro-2-pentane-4-one/allyl methyl trisulfide/2-trimethylsiloxy-4-propenoxybenzophenone copolymer, 10-20 parts of silicate-modified 1-allyl-3-methyl imidazole chloride/1- [3- (triethoxysilyl) propyl ] -1H-pyrrole-2, 5-dione/3-amino-2-butene thioamide copolymer, 2-4 parts of organic nanoparticles, and a copolymer prepared by mixing the above components, 3-6 parts of emulsifier, 1-3 parts of epoxy-terminated hyperbranched poly (amine-ester), 2-4 parts of quaternized imidazole nano microspheres and 45-55 parts of deionized water.
Preferably, the preparation method of the quaternized imidazole nanosphere is as follows: chinese patent application No. 201510734546.4, example 2.
Preferably, the preparation method of the epoxy-terminated hyperbranched poly (amine-ester) is as follows: the first embodiment of the chinese patent application No. 201910615830.8.
Preferably, the emulsifier is at least one of sodium dodecyl benzene sulfonate, polyoxypropylene polyoxyethylene glycerol ether and nonylphenol polyoxyethylene ether.
Preferably, the preparation method of the organic nanoparticles is as follows: chinese patent application No. 200410008986.3, example 3.
Preferably, the preparation method of the silicate modified 1-allyl-3-methyl imidazole chloride/1- [3- (triethoxysilyl) propyl ] -1H-pyrrole-2, 5-diketone/3-amino-2-butylene thioamide copolymer comprises the following steps:
i, adding 1-allyl-3-methyl imidazole chloride, 1- [3- (triethoxysilyl) propyl ] -1H-pyrrole-2, 5-dione, 3-amino-2-butene thioamide and an initiator into a high boiling point solvent, stirring and reacting for 3-5 hours at 65-75 ℃ in the atmosphere of nitrogen or inert gas, and then removing the solvent by rotary evaporation to obtain an intermediate product;
and II, adding the intermediate product prepared in the step I into an aqueous solution of 10-20% sodium silicate by mass, stirring for 5-8 hours at 50-60 ℃, adding the obtained initial product into a dialysis bag, dialyzing for 10-20 hours in deionized water, and then removing water in the dialysis bag by rotary evaporation to obtain the silicate modified 1-allyl-3-methylimidazole chloride/1- [3- (triethoxysilyl) propyl ] -1H-pyrrole-2, 5-diketone/3-amino-2-butenethioamide copolymer.
Preferably, the mass ratio of the 1-allyl-3-methyl imidazole chloride, the 1- [3- (triethoxysilyl) propyl ] -1H-pyrrole-2, 5-diketone, the 3-amino-2-butene thioamide, the initiator and the high boiling point solvent in the step I is 0.5:0.3:1 (0.02-0.03): 6-10); and in the step II, the mass ratio of the intermediate product to the aqueous solution of sodium silicate is 1 (5-10).
Preferably, the initiator is at least one of azobisisobutyronitrile and azobisisoheptonitrile; the high boiling point solvent is at least one of dimethyl sulfoxide, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone; the inert gas is any one of helium, neon and argon.
Preferably, the 4, 10-dioxatricyclo [5.2.1.0(2,6) ] dec-8-en-3-one/2-trimethylsiloxy-1, 1,1,5,5, 5-hexafluoro-2-pentan-4-one/allylmethyltrisulfide/2-trimethylsiloxy-4-propenyloxybenzophenone copolymer comprises the following steps: adding 4, 10-dioxatricyclo [5.2.1.0(2,6) ] dec-8-ene-3-one, 2-trimethylsiloxy-1, 1,1,5,5, 5-hexafluoro-2-pentane-4-one, allylmethyltrisulfide, 2-trimethylsiloxy-4-propenyloxybenzophenone and azobisisobutyronitrile into N-methylpyrrolidone, stirring and reacting for 3-5 hours at 70-80 ℃ in a nitrogen atmosphere, and then removing N-methylpyrrolidone by rotary evaporation to obtain 4, 10-dioxatricyclo [5.2.1.0(2,6) ] dec-8-ene-3-one/2-trimethylsiloxy-1, 1,1,5,5, 5-hexafluoro-2-pentane-4-one/allylmethyltrisulfide/2-trimethyl Siloxy-4-propenyloxybenzophenone copolymers.
Preferably, the mass ratio of the 4, 10-dioxatricyclo [5.2.1.0(2,6) ] dec-8-en-3-one, 2-trimethylsiloxy-1, 1,1,5,5, 5-hexafluoro-2-pentan-4-one, allylmethyl trisulfide, 2-trimethylsiloxy-4-propenyloxybenzophenone, azobisisobutyronitrile and N-methylpyrrolidone is 1:0.5:0.2:0.2 (0.01-0.02): 6-10.
The invention also aims to provide a preparation method of the environment-friendly glass cement, which is characterized by comprising the following steps:
s1, adding water and an emulsifier into an emulsifying kettle, wherein the adding amount of the water is 45-55% of the total amount, the adding amount of the emulsifier is 70-80% of the total amount, adding hydrogenated acrylic rosin, 4, 10-dioxatricyclo [5.2.1.0(2,6) ] dec-8-ene-3-one/2-trimethylsiloxy-1, 1,1,5,5, 5-hexafluoro-2-pentane-4-one/allyl methyl trisulfide/2-trimethylsiloxy-4-propenyloxybenzophenone copolymer and epoxy-terminated hyperbranched poly (amine-ester) while stirring, and uniformly stirring to obtain a mixture A;
s2, adding the residual amount of water and the residual amount of emulsifier into another emulsifying kettle, adding a silicate modified 1-allyl-3-methyl imidazole chloride/1- [3- (triethoxysilyl) propyl ] -1H-pyrrole-2, 5-diketone/3-amino-2-butylene thioamide copolymer, organic nanoparticles and quaternized imidazole nano-microspheres while stirring uniformly to obtain a mixture B;
and S3, mixing the mixture A prepared in the step S1 and the mixture B prepared in the step S2, and stirring uniformly to obtain the environment-friendly glass cement.
Adopt the produced beneficial effect of above-mentioned technical scheme to lie in:
(1) the preparation method of the environment-friendly glass cement provided by the invention can be prepared by uniformly mixing the components, does not need other complicated procedures or special equipment, has low price of the preparation raw materials, is environment-friendly and harmless, has a simple production process, is suitable for batch production, and can be popularized and applied.
(2) The environment-friendly glass cement provided by the invention is formed by combining a plurality of components, and through reasonable selection and synergistic effect of the components and contents, the environment-friendly glass cement can integrally and effectively overcome the defects that the glass cement on the market has weak adhesive force, is easy to crack, has undesirable use effect, contains benzene solvents, ethyl acetate or banana oil and the like, pollutes the environment, is harmful to constructors and is inflammable; after the paint is used for a period of time, the paint often becomes mildewed, blackened and yellowed under a humid environment, and the paint has the technical defects of influencing the beauty, and has the advantages of strong adhesive force, good comprehensive performance, good flame retardance and waterproof performance, good antibacterial and mildewproof capability and performance stability, and safe and environment-friendly use.
(3) The components of the environment-friendly glass cement provided by the invention are mutually associated and interacted, and carboxyl on hydrogenated acrylic rosin is easy to be connected with quaternary ammonium salt on a quaternized imidazole nano microsphere and a silicate modified 1-allyl-3-methyl imidazole chloride/1- [3- (triethoxysilyl) propyl ] -1H-pyrrole-2, 5-diketone/3-amino-2-butylene thioamide copolymer through ion exchange to realize ionic bond connection; the epoxy structures on the 4, 10-dioxatricyclo [5.2.1.0(2,6) ] dec-8-en-3-one/2-trimethylsiloxy-1, 1,1,5,5, 5-hexafluoro-2-pentan-4-one/allylmethyltrithio ether/2-trimethylsiloxy-4-propenyloxybenzophenone copolymer and the epoxy-terminated hyperbranched poly (amine-ester) are easy to carry out ring-opening reaction with the amino groups on the silicate-modified 1-allyl-3-methylchloroimidazole/1- [3- (triethoxysilyl) propyl ] -1H-pyrrole-2, 5-dione/3-amino-2-butenylthioamide copolymer, and the glass cement is cured during curing to form a three-dimensional network structure, so that the glass cement has good performance stability and high comprehensive performance on the whole.
(4) The raw materials used by the environment-friendly glass cement provided by the invention are sold in the market, have wide sources, are environment-friendly and harmless, and combine the advantages of silicate, rosin, multi-heterocyclic rings and bridging groups, so that the product has high bonding strength; the weather resistance and the mechanical property are improved by introducing a cross-linking structure and a fluorine-silicon group; the organic nano material is added into the glass cement product for the first time, so that the compatibility between the glass cement product and other components can be enhanced, the bonding performance between the glass cement product and a base material can be improved, and the performance stability can be improved through ways of adsorption, wrapping and the like.
(5) According to the environment-friendly glass cement provided by the invention, the quaternary ammonium salt, the trisulfide and the thioamide are introduced and have synergistic effects, so that the antibacterial and antifungal effects are good, and the broad-spectrum antibacterial effect is achieved; the addition of the quaternized imidazole nano-microspheres can improve flame retardance, and can improve bonding performance under the synergistic effect with ethoxysilyl, amino and hydroxyl on the branched chain of the copolymer; the addition of the epoxy-terminated hyperbranched poly (amine-ester) can improve the compatibility and the bonding property; the introduction of 2-trimethylsiloxy-1, 1,1,5,5, 5-hexafluoro-2-pentane-4-ketone and 2-trimethylsiloxy-4-propenyloxybenzophenone structural units introduces hydrophobic groups into the glass cement to improve the water resistance of the glass cement, and the introduction of benzophenone and fluorine-containing structures can improve the aging resistance, and all components and structures have synergistic effect, so that the comprehensive performance of the prepared product is better.
Detailed Description
In order to make the technical solutions of the present invention better understood and make the above features, objects, and advantages of the present invention more comprehensible, the present invention is further described with reference to the following examples. The examples are intended to illustrate the invention only and are not intended to limit the scope of the invention.
In the embodiment of the invention, the raw materials are all purchased commercially; the preparation method of the quaternized imidazole nanosphere is as follows: chinese invention patent example 2 with application number 201510734546.4; a method for preparing the epoxy-terminated hyperbranched poly (amine-ester), see: the first embodiment of the chinese patent with application number 201910615830.8; the preparation method of the organic nano-particles is as follows: chinese patent application No. 200410008986.3, example 3.
Example 1
The environment-friendly glass cement is characterized by comprising the following components in parts by weight: 1 part of hydrogenated acrylic acid rosin, 20 parts of 4, 10-dioxatricyclo [5.2.1.0(2,6) ] dec-8-en-3-one/2-trimethylsiloxy-1, 1,1,5,5, 5-hexafluoro-2-pentan-4-one/allylmethyltrisulfide/2-trimethylsiloxy-4-propenoxybenzophenone copolymer, 10 parts of silicate-modified 1-allyl-3-methylchloroimidazole/1- [3- (triethoxysilyl) propyl ] -1H-pyrrole-2, 5-dione/3-amino-2-butenylthioamide copolymer, 2 parts of organic nanoparticles, 3 parts of sodium dodecylbenzenesulfonate, 3 parts of N-tert-butylbenzenesulfonamide, N-butyllithium-carbonate, N-butyllithium, 1 part of epoxy-terminated hyperbranched poly (amine-ester), 2 parts of quaternized imidazole nano microspheres and 45 parts of deionized water.
The preparation method of the silicate modified 1-allyl-3-methyl imidazole chloride/1- [3- (triethoxysilyl) propyl ] -1H-pyrrole-2, 5-diketone/3-amino-2-butylene thioamide copolymer comprises the following steps:
adding 1-allyl-3-methyl imidazole chloride, 1- [3- (triethoxysilyl) propyl ] -1H-pyrrole-2, 5-dione, 3-amino-2-butene thioamide and an initiator into a high boiling point solvent, stirring and reacting for 3 hours at 65 ℃ in a nitrogen atmosphere, and then removing the solvent by rotary evaporation to obtain an intermediate product;
and II, adding the intermediate product prepared in the step I into an aqueous solution of 10-20% sodium silicate in percentage by mass, stirring for 5 hours at 50 ℃, adding the obtained initial product into a dialysis bag, dialyzing for 10 hours in deionized water, and then removing water in the dialysis bag by rotary evaporation to obtain the silicate modified 1-allyl-3-methylimidazole chloride/1- [3- (triethoxysilyl) propyl ] -1H-pyrrole-2, 5-diketone/3-amino-2-butene thioamide copolymer.
In the step I, the mass ratio of the 1-allyl-3-methyl imidazole chloride, the 1- [3- (triethoxysilyl) propyl ] -1H-pyrrole-2, 5-diketone, the 3-amino-2-butene thioamide, the initiator and the high-boiling-point solvent is 0.5:0.3:1:0.02: 6; in the step II, the mass ratio of the intermediate product to the aqueous solution of sodium silicate is 1: 5; the initiator is azobisisobutyronitrile; the high boiling point solvent is dimethyl sulfoxide.
The 4, 10-dioxatricyclo [5.2.1.0(2,6) ] dec-8-en-3-one/2-trimethylsiloxy-1, 1,1,5,5, 5-hexafluoro-2-pentan-4-one/allylmethyltrisulfide/2-trimethylsiloxy-4-propenyloxybenzophenone copolymer comprises the following steps: adding 4, 10-dioxatricyclo [5.2.1.0(2,6) ] dec-8-ene-3-one, 2-trimethylsiloxy-1, 1,1,5,5, 5-hexafluoro-2-pentane-4-one, allylmethyltrithio ether, 2-trimethylsiloxy-4-propenyloxybenzophenone and azobisisobutyronitrile into N-methylpyrrolidone, stirring and reacting for 3 hours at 70 ℃ in a nitrogen atmosphere, and then removing N-methylpyrrolidone by rotary evaporation to obtain 4, 10-dioxatricyclo [5.2.1.0(2,6) ] dec-8-ene-3-one/2-trimethylsiloxy-1, 1,1,5,5, 5-hexafluoro-2-pentane-4-one/allylmethyltrithio ether/2-trimethylsiloxy-4-one -a copolymer of propyleneoxybenzophenone.
The mass ratio of the 4, 10-dioxane tricyclo [5.2.1.0(2,6) ] dec-8-ene-3-one, 2-trimethylsiloxy-1, 1,1,5,5, 5-hexafluoro-2-pentane-4-one, allyl methyl trisulfide, 2-trimethylsiloxy-4-propenyloxybenzophenone, azobisisobutyronitrile and N-methylpyrrolidone is 1:0.5:0.2:0.2:0.01: 6.
The preparation method of the environment-friendly glass cement is characterized by comprising the following steps:
s1, adding water and sodium dodecyl benzene sulfonate into an emulsifying kettle, wherein the adding amount of the water is 45% of the total amount, the adding amount of the sodium dodecyl benzene sulfonate is 70% of the total amount, adding hydrogenated acrylic rosin, 4, 10-dioxatricyclo [5.2.1.0(2,6) ] dec-8-ene-3-one/2-trimethylsiloxy-1, 1,1,5,5, 5-hexafluoro-2-pentane-4-one/allyl methyl trisulfide/2-trimethylsiloxy-4-propenyloxybenzophenone copolymer and epoxy-terminated hyperbranched poly (amine-ester) while stirring, and uniformly stirring to obtain a mixture A;
s2, adding the residual amount of water and the residual amount of sodium dodecyl benzene sulfonate into another emulsifying kettle, adding a silicate modified 1-allyl-3-methyl imidazole chloride/1- [3- (triethoxysilyl) propyl ] -1H-pyrrole-2, 5-diketone/3-amino-2-butylene thioamide copolymer, organic nanoparticles and quaternized imidazole nano-microspheres while stirring, and obtaining a mixture B;
and S3, mixing the mixture A prepared in the step S1 and the mixture B prepared in the step S2, and stirring uniformly to obtain the environment-friendly glass cement.
Example 2
The environment-friendly glass cement is characterized by comprising the following components in parts by weight: 1.5 parts of hydrogenated acrylic acid rosin, 25 parts of 4, 10-dioxatricyclo [5.2.1.0(2,6) ] dec-8-ene-3-one/2-trimethylsiloxy-1, 1,1,5,5, 5-hexafluoro-2-pentane-4-one/allyl methyl trisulfide/2-trimethylsiloxy-4-propenoxybenzophenone copolymer, 12 parts of silicate-modified 1-allyl-3-methylchloroimidazole/1- [3- (triethoxysilyl) propyl ] -1H-pyrrole-2, 5-dione/3-amino-2-butenylthioamide copolymer, 2.5 parts of organic nanoparticles, 4 parts of polyoxypropylene polyoxyethylene glycerol ether, 4 parts of poly (oxypropylene-co-oxyethylene) glycidyl ether, 1.5 parts of epoxy-terminated hyperbranched poly (amine-ester), 2.5 parts of quaternized imidazole nano microspheres and 48 parts of deionized water.
The preparation method of the silicate modified 1-allyl-3-methyl imidazole chloride/1- [3- (triethoxysilyl) propyl ] -1H-pyrrole-2, 5-diketone/3-amino-2-butylene thioamide copolymer comprises the following steps:
i, adding 1-allyl-3-methyl imidazole chloride, 1- [3- (triethoxysilyl) propyl ] -1H-pyrrole-2, 5-dione, 3-amino-2-butene thioamide and an initiator into a high boiling point solvent, stirring and reacting for 3.5 hours at 68 ℃ under the atmosphere of helium, and then removing the solvent by rotary evaporation to obtain an intermediate product;
II, adding the intermediate product prepared in the step I into an aqueous solution of sodium silicate with the mass fraction of 13%, stirring for 6 hours at 53 ℃, adding the obtained initial product into a dialysis bag, dialyzing for 13 hours in deionized water, and then removing water in the dialysis bag by rotary evaporation to obtain the silicate modified 1-allyl-3-methylimidazole chloride/1- [3- (triethoxysilyl) propyl ] -1H-pyrrole-2, 5-diketone/3-amino-2-butylene thioamide copolymer.
In the step I, the mass ratio of the 1-allyl-3-methyl imidazole chloride, the 1- [3- (triethoxysilyl) propyl ] -1H-pyrrole-2, 5-diketone, the 3-amino-2-butene thioamide, the initiator and the high-boiling-point solvent is 0.5:0.3:1:0.023: 7; in the step II, the mass ratio of the intermediate product to the aqueous solution of sodium silicate is 1: 6; the initiator is azobisisoheptonitrile; the high boiling point solvent is N, N-dimethylformamide.
The 4, 10-dioxatricyclo [5.2.1.0(2,6) ] dec-8-en-3-one/2-trimethylsiloxy-1, 1,1,5,5, 5-hexafluoro-2-pentan-4-one/allylmethyltrisulfide/2-trimethylsiloxy-4-propenyloxybenzophenone copolymer comprises the following steps: adding 4, 10-dioxatricyclo [5.2.1.0(2,6) ] dec-8-ene-3-one, 2-trimethylsiloxy-1, 1,1,5,5, 5-hexafluoro-2-pentane-4-one, allylmethyltrisulfide, 2-trimethylsiloxy-4-propenyloxybenzophenone and azobisisobutyronitrile into N-methylpyrrolidone, stirring and reacting for 3.5 hours at 73 ℃, and then removing N-methylpyrrolidone by rotary evaporation to obtain 4, 10-dioxatricyclo [5.2.1.0(2,6) ] dec-8-ene-3-one/2-trimethylsiloxy-1, 1,1,5,5, 5-hexafluoro-2-pentane-4-one/allylmethyltrisulfide/2-trimethylsiloxy-4-one -a copolymer of propyleneoxybenzophenone.
The mass ratio of the 4, 10-dioxane tricyclo [5.2.1.0(2,6) ] dec-8-ene-3-one, 2-trimethylsiloxy-1, 1,1,5,5, 5-hexafluoro-2-pentane-4-one, allyl methyl trisulfide, 2-trimethylsiloxy-4-propenyloxybenzophenone, azobisisobutyronitrile and N-methylpyrrolidone is 1:0.5:0.2:0.2:0.013: 7.
The preparation method of the environment-friendly glass cement is characterized by comprising the following steps:
s1, adding water and polyoxypropylene polyoxyethylene glycerol ether into an emulsifying kettle, wherein the addition amount of the water is 48% of the total amount, the addition amount of the polyoxypropylene polyoxyethylene glycerol ether is 73% of the total amount, adding hydrogenated acrylic rosin, 4, 10-dioxatricyclo [5.2.1.0(2,6) ] deca-8-ene-3-one/2-trimethylsiloxy-1, 1,1,5,5, 5-hexafluoro-2-pentane-4-one/allyl methyl trisulfide/2-trimethylsiloxy-4-propyleneoxybenzophenone copolymer and epoxy-terminated hyperbranched poly (amine-ester) while stirring, and uniformly stirring to obtain a mixture A;
s2, adding the residual amount of water and the residual amount of polyoxypropylene polyoxyethylene glycerol ether into another emulsifying kettle, adding a silicate modified 1-allyl-3-methyl chlorinated imidazole/1- [3- (triethoxysilyl) propyl ] -1H-pyrrole-2, 5-diketone/3-amino-2-butylene thioamide copolymer, organic nanoparticles and quaternized imidazole nano-microspheres while stirring uniformly to obtain a mixture B;
and S3, mixing the mixture A prepared in the step S1 and the mixture B prepared in the step S2, and stirring uniformly to obtain the environment-friendly glass cement.
Example 3
The environment-friendly glass cement is characterized by comprising the following components in parts by weight: 2 parts of hydrogenated acrylic acid rosin, 28 parts of 4, 10-dioxatricyclo [5.2.1.0(2,6) ] dec-8-ene-3-one/2-trimethylsiloxy-1, 1,1,5,5, 5-hexafluoro-2-pentane-4-one/allyl methyl trisulfide/2-trimethylsiloxy-4-propenyloxybenzophenone copolymer, 15 parts of silicate-modified 1-allyl-3-methyl imidazole chloride/1- [3- (triethoxysilyl) propyl ] -1H-pyrrole-2, 5-dione/3-amino-2-butenylthioamide copolymer, 3 parts of organic nanoparticles, 4.5 parts of emulsifier, 1-3 parts of terminal epoxy hyperbranched poly (amine-ester), 3 parts of quaternized imidazole nano microspheres and 50 parts of deionized water; the emulsifier is nonylphenol polyoxyethylene ether.
The preparation method of the silicate modified 1-allyl-3-methyl imidazole chloride/1- [3- (triethoxysilyl) propyl ] -1H-pyrrole-2, 5-diketone/3-amino-2-butylene thioamide copolymer comprises the following steps:
i, adding 1-allyl-3-methylimidazole chloride, 1- [3- (triethoxysilyl) propyl ] -1H-pyrrole-2, 5-dione, 3-amino-2-butene thioamide and an initiator into a high-boiling-point solvent, stirring and reacting for 4 hours at 70 ℃ in a neon atmosphere, and then removing the solvent by rotary evaporation to obtain an intermediate product;
II, adding the intermediate product prepared in the step I into an aqueous solution of sodium silicate with the mass fraction of 15%, stirring for 6.5 hours at 55 ℃, adding the obtained initial product into a dialysis bag, dialyzing for 15 hours in deionized water, and then performing rotary evaporation to remove water in the dialysis bag to obtain the silicate modified 1-allyl-3-methylimidazole chloride/1- [3- (triethoxysilyl) propyl ] -1H-pyrrole-2, 5-diketone/3-amino-2-butene thioamide copolymer.
In the step I, the mass ratio of the 1-allyl-3-methyl imidazole chloride, the 1- [3- (triethoxysilyl) propyl ] -1H-pyrrole-2, 5-diketone, the 3-amino-2-butene thioamide, the initiator and the high boiling point solvent is 0.5:0.3:1:0.025: 8; in the step II, the mass ratio of the intermediate product to the aqueous solution of sodium silicate is 1: 8; the initiator is azobisisobutyronitrile; the high boiling point solvent is N, N-dimethylacetamide.
The 4, 10-dioxatricyclo [5.2.1.0(2,6) ] dec-8-en-3-one/2-trimethylsiloxy-1, 1,1,5,5, 5-hexafluoro-2-pentan-4-one/allylmethyltrisulfide/2-trimethylsiloxy-4-propenyloxybenzophenone copolymer comprises the following steps: adding 4, 10-dioxatricyclo [5.2.1.0(2,6) ] dec-8-ene-3-one, 2-trimethylsiloxy-1, 1,1,5,5, 5-hexafluoro-2-pentane-4-one, allylmethyltrithio ether, 2-trimethylsiloxy-4-propenyloxybenzophenone and azobisisobutyronitrile into N-methylpyrrolidone, stirring and reacting for 4 hours at 75 ℃ in a nitrogen atmosphere, and then removing N-methylpyrrolidone by rotary evaporation to obtain 4, 10-dioxatricyclo [5.2.1.0(2,6) ] dec-8-ene-3-one/2-trimethylsiloxy-1, 1,1,5,5, 5-hexafluoro-2-pentane-4-one/allylmethyltrithio ether/2-trimethylsiloxy-4-one -a copolymer of propyleneoxybenzophenone.
The mass ratio of the 4, 10-dioxane tricyclo [5.2.1.0(2,6) ] dec-8-ene-3-one, 2-trimethylsiloxy-1, 1,1,5,5, 5-hexafluoro-2-pentane-4-one, allyl methyl trisulfide, 2-trimethylsiloxy-4-propenyloxybenzophenone, azobisisobutyronitrile and N-methylpyrrolidone is 1:0.5:0.2: 0.015: 8.
The preparation method of the environment-friendly glass cement is characterized by comprising the following steps:
s1, adding water and an emulsifier into an emulsifying kettle, wherein the adding amount of the water is 50% of the total amount, the adding amount of the emulsifier is 75% of the total amount, adding hydrogenated acrylic rosin, 4, 10-dioxatricyclo [5.2.1.0(2,6) ] dec-8-ene-3-one/2-trimethylsiloxy-1, 1,1,5,5, 5-hexafluoro-2-pentane-4-one/allyl methyl trisulfide/2-trimethylsiloxy-4-propenyloxybenzophenone copolymer and epoxy-terminated hyperbranched poly (amine-ester) while stirring, and obtaining a mixture A after uniformly stirring;
s2, adding the residual amount of water and the residual amount of emulsifier into another emulsifying kettle, adding a silicate modified 1-allyl-3-methyl imidazole chloride/1- [3- (triethoxysilyl) propyl ] -1H-pyrrole-2, 5-diketone/3-amino-2-butylene thioamide copolymer, organic nanoparticles and quaternized imidazole nano-microspheres while stirring uniformly to obtain a mixture B;
and S3, mixing the mixture A prepared in the step S1 and the mixture B prepared in the step S2, and stirring uniformly to obtain the environment-friendly glass cement.
Example 4
The environment-friendly glass cement is characterized by comprising the following components in parts by weight: 2.5 parts of hydrogenated acrylic rosin, 33 parts of 4, 10-dioxatricyclo [5.2.1.0(2,6) ] dec-8-ene-3-one/2-trimethylsiloxy-1, 1,1,5,5, 5-hexafluoro-2-pentane-4-one/allyl methyl trisulfide/2-trimethylsiloxy-4-acryloxybenzophenone copolymer, 18 parts of silicate-modified 1-allyl-3-methyl imidazole chloride/1- [3- (triethoxysilyl) propyl ] -1H-pyrrole-2, 5-dione/3-amino-2-butene thioamide copolymer, 3.5 parts of organic nanoparticles, 5.5 parts of emulsifier, 2.5 parts of epoxy-terminated hyperbranched poly (amine-ester), 3.5 parts of quaternized imidazole nano microspheres and 53 parts of deionized water; the emulsifier is formed by mixing sodium dodecyl benzene sulfonate, polyoxypropylene polyoxyethylene glycerol ether and nonylphenol polyoxyethylene ether according to the mass ratio of 1:3: 2.
The preparation method of the silicate modified 1-allyl-3-methyl imidazole chloride/1- [3- (triethoxysilyl) propyl ] -1H-pyrrole-2, 5-diketone/3-amino-2-butylene thioamide copolymer comprises the following steps:
adding 1-allyl-3-methyl imidazole chloride, 1- [3- (triethoxysilyl) propyl ] -1H-pyrrole-2, 5-dione, 3-amino-2-butene thioamide and an initiator into a high boiling point solvent, stirring and reacting for 4.5 hours at 73 ℃ under the atmosphere of argon, and then removing the solvent by rotary evaporation to obtain an intermediate product;
II, adding the intermediate product prepared in the step I into an aqueous solution of sodium silicate with the mass fraction of 18%, stirring for 7.5 hours at 58 ℃, adding the obtained initial product into a dialysis bag, dialyzing for 18 hours in deionized water, and then performing rotary evaporation to remove water in the dialysis bag to obtain the silicate modified 1-allyl-3-methylimidazole chloride/1- [3- (triethoxysilyl) propyl ] -1H-pyrrole-2, 5-diketone/3-amino-2-butene thioamide copolymer.
In the step I, the mass ratio of the 1-allyl-3-methyl imidazole chloride, the 1- [3- (triethoxysilyl) propyl ] -1H-pyrrole-2, 5-diketone, the 3-amino-2-butene thioamide, the initiator and the high boiling point solvent is 0.5:0.3:1:0.028: 9; in the step II, the mass ratio of the intermediate product to the aqueous solution of sodium silicate is 1: 9; the initiator is formed by mixing azodiisobutyronitrile and azodiisoheptonitrile according to the mass ratio of 3: 4; the high boiling point solvent is formed by mixing dimethyl sulfoxide, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone according to a mass ratio of 1:2:2: 3.
The 4, 10-dioxatricyclo [5.2.1.0(2,6) ] dec-8-en-3-one/2-trimethylsiloxy-1, 1,1,5,5, 5-hexafluoro-2-pentan-4-one/allylmethyltrisulfide/2-trimethylsiloxy-4-propenyloxybenzophenone copolymer comprises the following steps: adding 4, 10-dioxatricyclo [5.2.1.0(2,6) ] dec-8-ene-3-one, 2-trimethylsiloxy-1, 1,1,5,5, 5-hexafluoro-2-pentane-4-one, allylmethyltrisulfide, 2-trimethylsiloxy-4-propenyloxybenzophenone and azobisisobutyronitrile into N-methylpyrrolidone, stirring and reacting for 4.5 hours at 78 ℃ in a nitrogen atmosphere, and then removing N-methylpyrrolidone by rotary evaporation to obtain 4, 10-dioxatricyclo [5.2.1.0(2,6) ] dec-8-ene-3-one/2-trimethylsiloxy-1, 1,1,5,5, 5-hexafluoro-2-pentane-4-one/allylmethyltrisulfide/2-trimethylsiloxy-4-one -a copolymer of propyleneoxybenzophenone.
The mass ratio of the 4, 10-dioxane tricyclo [5.2.1.0(2,6) ] dec-8-ene-3-one, 2-trimethylsiloxy-1, 1,1,5,5, 5-hexafluoro-2-pentane-4-one, allyl methyl trisulfide, 2-trimethylsiloxy-4-propenyloxybenzophenone, azobisisobutyronitrile and N-methylpyrrolidone is 1:0.5:0.2:0.2:0.018: 9.5.
The preparation method of the environment-friendly glass cement is characterized by comprising the following steps:
s1, adding water and an emulsifier into an emulsifying kettle, wherein the adding amount of the water is 53 percent of the total amount, the adding amount of the emulsifier is 78 percent of the total amount, adding hydrogenated acrylic rosin, 4, 10-dioxatricyclo [5.2.1.0(2,6) ] dec-8-ene-3-one/2-trimethylsiloxy-1, 1,1,5,5, 5-hexafluoro-2-pentane-4-one/allyl methyl trisulfide/2-trimethylsiloxy-4-propenyloxybenzophenone copolymer and epoxy-terminated hyperbranched poly (amine-ester) while stirring, and obtaining a mixture A after uniformly stirring;
s2, adding the residual amount of water and the residual amount of emulsifier into another emulsifying kettle, adding a silicate modified 1-allyl-3-methyl imidazole chloride/1- [3- (triethoxysilyl) propyl ] -1H-pyrrole-2, 5-diketone/3-amino-2-butylene thioamide copolymer, organic nanoparticles and quaternized imidazole nano-microspheres while stirring uniformly to obtain a mixture B;
and S3, mixing the mixture A prepared in the step S1 and the mixture B prepared in the step S2, and stirring uniformly to obtain the environment-friendly glass cement.
Example 5
The environment-friendly glass cement is characterized by comprising the following components in parts by weight: 3 parts of hydrogenated acrylic acid rosin, 35 parts of 4, 10-dioxatricyclo [5.2.1.0(2,6) ] dec-8-ene-3-one/2-trimethylsiloxy-1, 1,1,5,5, 5-hexafluoro-2-pentane-4-one/allyl methyl trisulfide/2-trimethylsiloxy-4-propenyloxybenzophenone copolymer, 20 parts of silicate-modified 1-allyl-3-methyl imidazole chloride/1- [3- (triethoxysilyl) propyl ] -1H-pyrrole-2, 5-dione/3-amino-2-butenylthioamide copolymer, 4 parts of organic nanoparticles, 6 parts of emulsifier, 3 parts of epoxy-terminated hyperbranched poly (amine-ester), 4 parts of quaternized imidazole nano microspheres and 55 parts of deionized water; the emulsifier is sodium dodecyl benzene sulfonate.
The preparation method of the silicate modified 1-allyl-3-methyl imidazole chloride/1- [3- (triethoxysilyl) propyl ] -1H-pyrrole-2, 5-diketone/3-amino-2-butylene thioamide copolymer comprises the following steps:
i, adding 1-allyl-3-methyl imidazole chloride, 1- [3- (triethoxysilyl) propyl ] -1H-pyrrole-2, 5-dione, 3-amino-2-butene thioamide and an initiator into a high boiling point solvent, stirring and reacting for 5 hours at 75 ℃ under the atmosphere of argon, and then removing the solvent by rotary evaporation to obtain an intermediate product;
II, adding the intermediate product prepared in the step I into an aqueous solution of sodium silicate with the mass fraction of 20%, stirring for 8 hours at 60 ℃, adding the obtained initial product into a dialysis bag, dialyzing for 20 hours in deionized water, and then removing water in the dialysis bag by rotary evaporation to obtain the silicate modified 1-allyl-3-methylimidazole chloride/1- [3- (triethoxysilyl) propyl ] -1H-pyrrole-2, 5-diketone/3-amino-2-butylene thioamide copolymer.
In the step I, the mass ratio of the 1-allyl-3-methyl imidazole chloride, the 1- [3- (triethoxysilyl) propyl ] -1H-pyrrole-2, 5-diketone, the 3-amino-2-butene thioamide, the initiator and the high-boiling-point solvent is 0.5:0.3:1:0.03: 10; in the step II, the mass ratio of the intermediate product to the aqueous solution of sodium silicate is 1: 10; the initiator is azobisisoheptonitrile; the high boiling point solvent is N-methyl pyrrolidone.
The 4, 10-dioxatricyclo [5.2.1.0(2,6) ] dec-8-en-3-one/2-trimethylsiloxy-1, 1,1,5,5, 5-hexafluoro-2-pentan-4-one/allylmethyltrisulfide/2-trimethylsiloxy-4-propenyloxybenzophenone copolymer comprises the following steps: adding 4, 10-dioxatricyclo [5.2.1.0(2,6) ] dec-8-ene-3-one, 2-trimethylsiloxy-1, 1,1,5,5, 5-hexafluoro-2-pentane-4-one, allylmethyltrithio ether, 2-trimethylsiloxy-4-propenyloxybenzophenone and azobisisobutyronitrile into N-methylpyrrolidone, stirring and reacting for 5 hours at 80 ℃ in a nitrogen atmosphere, and then removing N-methylpyrrolidone by rotary evaporation to obtain 4, 10-dioxatricyclo [5.2.1.0(2,6) ] dec-8-ene-3-one/2-trimethylsiloxy-1, 1,1,5,5, 5-hexafluoro-2-pentane-4-one/allylmethyltrithio ether/2-trimethylsiloxy-4-one -a copolymer of propyleneoxybenzophenone.
The mass ratio of the 4, 10-dioxane tricyclo [5.2.1.0(2,6) ] dec-8-ene-3-one, 2-trimethylsiloxy-1, 1,1,5,5, 5-hexafluoro-2-pentane-4-one, allyl methyl trisulfide, 2-trimethylsiloxy-4-propenyloxybenzophenone, azobisisobutyronitrile and N-methylpyrrolidone is 1:0.5:0.2: 0.02: 10.
The preparation method of the environment-friendly glass cement is characterized by comprising the following steps:
s1, adding water and an emulsifier into an emulsifying kettle, wherein the adding amount of the water is 55 percent of the total amount, the adding amount of the emulsifier is 80 percent of the total amount, adding hydrogenated acrylic rosin, 4, 10-dioxatricyclo [5.2.1.0(2,6) ] dec-8-ene-3-one/2-trimethylsiloxy-1, 1,1,5,5, 5-hexafluoro-2-pentane-4-one/allyl methyl trisulfide/2-trimethylsiloxy-4-propenyloxybenzophenone copolymer and epoxy-terminated hyperbranched poly (amine-ester) while stirring, and obtaining a mixture A after uniformly stirring;
s2, adding the residual amount of water and the residual amount of emulsifier into another emulsifying kettle, adding a silicate modified 1-allyl-3-methyl imidazole chloride/1- [3- (triethoxysilyl) propyl ] -1H-pyrrole-2, 5-diketone/3-amino-2-butylene thioamide copolymer, organic nanoparticles and quaternized imidazole nano-microspheres while stirring uniformly to obtain a mixture B;
and S3, mixing the mixture A prepared in the step S1 and the mixture B prepared in the step S2, and stirring uniformly to obtain the environment-friendly glass cement.
Comparative example 1
The present example provides an environmentally friendly glass cement, which has a formulation and a preparation method substantially the same as those of example 1, except that no organic nanoparticles are added.
Comparative example 2
This example provides an environmentally friendly glass cement having substantially the same formulation and preparation as example 1, except that the silicate-modified 1-allyl-3-methylchloroimidazole/1- [3- (triethoxysilyl) propyl ] -1H-pyrrole-2, 5-dione/3-amino-2-butenylthioamide copolymer was prepared without the addition of 3-amino-2-butenylthioamide.
Comparative example 3
This example provides an environmentally friendly glass cement of substantially the same formulation and preparation method as in example 1, except that 4, 10-dioxatricyclo [5.2.1.0(2,6) ] dec-8-en-3-one/2-trimethylsiloxy-1, 1,1,5,5, 5-hexafluoro-2-pentan-4-one/allylmethyltrisulfide/2-trimethylsiloxy-4-propenoxybenzophenone copolymer was prepared without adding 4, 10-dioxatricyclo [5.2.1.0(2,6) ] dec-8-en-3-one.
Comparative example 4
This example provides an environmentally friendly glass cement having a formulation and method of preparation substantially the same as example 1, except that no quaternized imidazole nanospheres were added.
Comparative example 5
This example provides an environmentally friendly glass cement having the same formulation and preparation as in example 1 except that 1-allyl-3-methylchloroimidazole/1- [3- (triethoxysilyl) propyl ] -1H-pyrrole-2, 5-dione/3-amino-2-butenethioamide copolymer was used in place of the silicate-modified 1-allyl-3-methylchloroimidazole/1- [3- (triethoxysilyl) propyl ] -1H-pyrrole-2, 5-dione/3-amino-2-butenethioamide copolymer.
Comparative example 6
This example provides an environmentally friendly glass cement having substantially the same formulation and preparation as example 1, except that no epoxy-terminated hyperbranched poly (amine-ester) is added.
In order to further illustrate the beneficial technical effects of the environmentally friendly glass cement involved in the embodiments of the present invention, the environmentally friendly glass cement described in the above embodiments 1 to 5 and comparative examples 1 to 6 was subjected to performance tests, and the test results and test methods are shown in table 1.
TABLE 1
| Item | T-type peel strength | Aging resistance (xenon lamp aging 600h) | Tensile strength | Shelf life |
| Unit of | N/cm | — | MPa | Sky |
| Test standard | GB/T2791-1995 | GB/T1865-2009 | GB/T6329-1996 | GB/T14074.9-2006 |
| Example 1 | 72 | Does not pulverize and fall off | 13.8 | 222 |
| Example 2 | 74 | Does not pulverize and fall off | 14.2 | 225 |
| Example 3 | 77 | Does not pulverize and fall off | 14.5 | 228 |
| Example 4 | 78 | Does not pulverize and fall off | 14.7 | 230 |
| Example 5 | 80 | Non-powderMelting and falling-proof | 15.1 | 234 |
| Comparative example 1 | 63 | Powdering and falling off | 12.5 | 204 |
| Comparative example 2 | 60 | Powdering and falling off | 12.2 | 202 |
| Comparative example 3 | 57 | Powdering and falling off | 12.0 | 200 |
| Comparative example 4 | 61 | Powdering and falling off | 12.3 | 204 |
| Comparative example 5 | 58 | Does not pulverize and fall off | 12.8 | 210 |
| Comparative example 6 | 65 | Non-powderingDoes not fall off | 12.6 | 213 |
As can be seen from table 1, the environment-friendly glass cement disclosed in the embodiment of the present invention has more excellent adhesive strength, aging resistance, mechanical properties and performance stability, which are the result of the synergistic effect of the components and the formula.
The foregoing shows and describes the general principles and broad features of the present invention and advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (8)
1. The environment-friendly glass cement is characterized by comprising the following components in parts by weight: 1-3 parts of hydrogenated acrylic rosin, 20-35 parts of 4, 10-dioxatricyclo [5.2.1.0(2,6) ] dec-8-ene-3-one/2-trimethylsiloxy-1, 1,1,5,5, 5-hexafluoro-2-pentane-4-one/allyl methyl trisulfide/2-trimethylsiloxy-4-propenoxybenzophenone copolymer, 10-20 parts of silicate-modified 1-allyl-3-methyl imidazole chloride/1- [3- (triethoxysilyl) propyl ] -1H-pyrrole-2, 5-dione/3-amino-2-butene thioamide copolymer, 2-4 parts of organic nanoparticles, and a copolymer prepared by mixing the above components, 3-6 parts of emulsifier, 1-3 parts of epoxy-terminated hyperbranched poly (amine-ester), 2-4 parts of quaternized imidazole nano microspheres and 45-55 parts of deionized water.
2. The environment-friendly glass cement as claimed in claim 1, wherein the emulsifier is at least one of sodium dodecyl benzene sulfonate, polyoxypropylene polyoxyethylene glycerol ether and nonylphenol polyoxyethylene ether.
3. The environment-friendly glass cement as claimed in claim 1, wherein the preparation method of the silicate-modified 1-allyl-3-methylchloroimidazole/1- [3- (triethoxysilyl) propyl ] -1H-pyrrole-2, 5-dione/3-amino-2-butenylthioamide copolymer comprises the following steps:
i, adding 1-allyl-3-methyl imidazole chloride, 1- [3- (triethoxysilyl) propyl ] -1H-pyrrole-2, 5-dione, 3-amino-2-butene thioamide and an initiator into a high boiling point solvent, stirring and reacting for 3-5 hours at 65-75 ℃ in the atmosphere of nitrogen or inert gas, and then removing the solvent by rotary evaporation to obtain an intermediate product;
and II, adding the intermediate product prepared in the step I into an aqueous solution of 10-20% sodium silicate by mass, stirring for 5-8 hours at 50-60 ℃, adding the obtained initial product into a dialysis bag, dialyzing for 10-20 hours in deionized water, and then removing water in the dialysis bag by rotary evaporation to obtain the silicate modified 1-allyl-3-methylimidazole chloride/1- [3- (triethoxysilyl) propyl ] -1H-pyrrole-2, 5-diketone/3-amino-2-butenethioamide copolymer.
4. The environment-friendly glass cement as claimed in claim 3, wherein the mass ratio of the 1-allyl-3-methylchloridazole, the 1- [3- (triethoxysilyl) propyl ] -1H-pyrrole-2, 5-dione, the 3-amino-2-butenylthioamide, the initiator and the high boiling point solvent in step I is 0.5:0.3:1 (0.02-0.03): 6-10); and in the step II, the mass ratio of the intermediate product to the aqueous solution of sodium silicate is 1 (5-10).
5. The environment-friendly glass cement as claimed in claim 3, wherein the initiator is at least one of azobisisobutyronitrile and azobisisoheptonitrile; the high boiling point solvent is at least one of dimethyl sulfoxide, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone; the inert gas is any one of helium, neon and argon.
6. An environmentally friendly glass cement according to claim 1, wherein the 4, 10-dioxatricyclo [5.2.1.0(2,6) ] dec-8-en-3-one/2-trimethylsiloxy-1, 1,1,5,5, 5-hexafluoro-2-pentan-4-one/allylmethyltrisulfide/2-trimethylsiloxy-4-propenyloxybenzophenone copolymer comprises the following steps: adding 4, 10-dioxatricyclo [5.2.1.0(2,6) ] dec-8-ene-3-one, 2-trimethylsiloxy-1, 1,1,5,5, 5-hexafluoro-2-pentane-4-one, allylmethyltrisulfide, 2-trimethylsiloxy-4-propenyloxybenzophenone and azobisisobutyronitrile into N-methylpyrrolidone, stirring and reacting for 3-5 hours at 70-80 ℃ in a nitrogen atmosphere, and then removing N-methylpyrrolidone by rotary evaporation to obtain 4, 10-dioxatricyclo [5.2.1.0(2,6) ] dec-8-ene-3-one/2-trimethylsiloxy-1, 1,1,5,5, 5-hexafluoro-2-pentane-4-one/allylmethyltrisulfide/2-trimethyl Siloxy-4-propenyloxybenzophenone copolymers.
7. The environment-friendly glass cement as claimed in claim 6, wherein the mass ratio of the 4, 10-dioxatricyclo [5.2.1.0(2,6) ] dec-8-en-3-one, 2-trimethylsiloxy-1, 1,1,5,5, 5-hexafluoro-2-pentan-4-one, allylmethyltrisulfide, 2-trimethylsiloxy-4-propenyloxybenzophenone, azobisisobutyronitrile and N-methylpyrrolidone is 1:0.5:0.2:0.2 (0.01-0.02): 6-10.
8. The environment-friendly glass cement according to any one of claims 1 to 7, wherein the preparation method of the environment-friendly glass cement comprises the following steps:
s1, adding water and an emulsifier into an emulsifying kettle, wherein the adding amount of the water is 45-55% of the total amount, the adding amount of the emulsifier is 70-80% of the total amount, adding hydrogenated acrylic rosin, 4, 10-dioxatricyclo [5.2.1.0(2,6) ] dec-8-ene-3-one/2-trimethylsiloxy-1, 1,1,5,5, 5-hexafluoro-2-pentane-4-one/allyl methyl trisulfide/2-trimethylsiloxy-4-propenyloxybenzophenone copolymer and epoxy-terminated hyperbranched poly (amine-ester) while stirring, and uniformly stirring to obtain a mixture A;
s2, adding the residual amount of water and the residual amount of emulsifier into another emulsifying kettle, adding a silicate modified 1-allyl-3-methyl imidazole chloride/1- [3- (triethoxysilyl) propyl ] -1H-pyrrole-2, 5-diketone/3-amino-2-butylene thioamide copolymer, organic nanoparticles and quaternized imidazole nano-microspheres while stirring uniformly to obtain a mixture B;
and S3, mixing the mixture A prepared in the step S1 and the mixture B prepared in the step S2, and stirring uniformly to obtain the environment-friendly glass cement.
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| CN110924174A (en) * | 2019-12-09 | 2020-03-27 | 张礼国 | Fabric softener and preparation method thereof |
| CN110835509A (en) * | 2019-12-12 | 2020-02-25 | 杨国亭 | Flame-retardant adhesive for power battery |
| CN111038056A (en) * | 2019-12-30 | 2020-04-21 | 郭涛 | Environment-friendly tent material and preparation method thereof |
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