CN113183481B - Reusable glass-like or glass-like product and preparation method and recycling method thereof - Google Patents

Reusable glass-like or glass-like product and preparation method and recycling method thereof Download PDF

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CN113183481B
CN113183481B CN202010028275.1A CN202010028275A CN113183481B CN 113183481 B CN113183481 B CN 113183481B CN 202010028275 A CN202010028275 A CN 202010028275A CN 113183481 B CN113183481 B CN 113183481B
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glass
silane coupling
coupling agent
solvent
dispersion liquid
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CN113183481A (en
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侯仪
朱光达
赵宁
徐坚
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Institute of Chemistry CAS
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Institute of Chemistry CAS
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Priority to US17/597,077 priority patent/US20220315776A1/en
Priority to PCT/CN2020/117109 priority patent/WO2021139215A1/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C67/00—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00
    • B29C67/02—Moulding by agglomerating
    • B29C67/04—Sintering
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C67/00—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00
    • B29C67/24—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00 characterised by the choice of material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2027/00—Use of polyvinylhalogenides or derivatives thereof as moulding material
    • B29K2027/12—Use of polyvinylhalogenides or derivatives thereof as moulding material containing fluorine
    • B29K2027/18—PTFE, i.e. polytetrafluorethene, e.g. ePTFE, i.e. expanded polytetrafluorethene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2083/00—Use of polymers having silicon, with or without sulfur, nitrogen, oxygen, or carbon only, in the main chain, as moulding material

Abstract

The invention discloses a reusable glass-like or glass-like product, a preparation method and a recycling method thereof. A reusable glass-like or glass-like article composition system comprising: (A) A mixed dispersion of silane coupling agent hydrolysate and an alkali solution; (B) a low surface energy polymer solution; (C) a silane coupling agent dispersion liquid. The components are mixed to prepare a mixed system, and the mixed system is subjected to heat treatment and sintering to obtain the glass-like or glass-like product. The glass-like or glass-like product provided by the invention can be dissolved in water or a water-containing solvent under the heating condition, the recovery method is simple and convenient, and the sol dispersion liquid obtained by dissolution can be reshaped to obtain the glass-like or glass-like product.

Description

Reusable glass-like or glass-like product and preparation method and recycling method thereof
Technical Field
The invention belongs to the field of glass products, and particularly relates to reusable glass-like or glass-like products, a preparation method and a recycling method thereof.
Background
Transparent glass materials are widely used in many fields. However, glass waste generated in daily life and industrial production is large, and in order to realize sustainable utilization of resources, waste glass can be collected, so that waste materials are changed into valuable materials.
At present, the recovery process of glass is complex, impurities are removed through fine selection, namely impurities such as metal, ceramics and the like in the recovered material of a glass bottle need to be removed, because glass container manufacturers need to use high-purity raw materials; second, color sorting is required because colored glass is unusable in the manufacture of colorless flint glass, and therefore, post-consumer cullet must be color sorted manually or by machine. The cullet, if used without color selection, can only be used to produce light green glass containers. Therefore, it is necessary to find a simple method for preparing glass-like or glass-like products which are easy to reuse.
Disclosure of Invention
The present invention provides a reusable glass-like or glass-like article composition system comprising:
(A) A mixed dispersion of silane coupling agent hydrolysate and an alkali solution;
(B) A low surface energy polymer solution;
(C) A silane coupling agent dispersion liquid.
The invention also provides a directly reusable glass-like or glass-like article prepared from the composition system.
The invention also provides a preparation method of the glass-like or glass-like product, which comprises the following steps:
mixing (A) mixed dispersion of silane coupling agent hydrolysate and alkali solution, (B) low surface energy polymer solution and (C) silane coupling agent dispersion to prepare a mixed system; and carrying out heat treatment and sintering on the mixed system to obtain the glass-like or glass-like product.
According to the invention, the preparation method comprises the following steps:
1) Mixing the silane coupling agent hydrolysate with an organic alkali solution to prepare the (A) mixed dispersion liquid;
preferably, the silane coupling agent hydrolysate is prepared from siloxane monomers under the catalytic heating condition;
2) Dissolving a low surface energy polymer in a solvent a to obtain (B) a low surface energy polymer solution;
3) Dissolving a silane coupling agent in the solvent b, and stirring at normal temperature to obtain (C) silane coupling agent dispersion liquid;
4) Mixing the silane coupling agent hydrolysate and the alkali solution to obtain a mixed dispersion liquid, (B) the low-surface-energy polymer solution and (C) the silane coupling agent dispersion liquid to obtain a mixed system;
5) Carrying out heat treatment on the mixed system to obtain silicon-based glass gel;
6) And sintering the silicon-based glass gel to obtain the glass or glass-like product.
The invention also provides glass-like or glass-like products prepared by the method.
The invention also provides a recycling method of the glass-like or glass-like product, which comprises the following steps: dissolving the glass-like or glass-like product in water or an aqueous solvent, and recovering the obtained sol dispersion.
Wherein the aqueous solvent may be selected from a mixed solvent of water and an organic solvent.
The invention also provides a recycling method of the glass-like or glass-like product, which comprises the following steps: heating the recovered sol dispersion liquid to form the sol dispersion liquid, and sintering the sol dispersion liquid to obtain the glass-like or glass-like product;
wherein, the sintering treatment is the same as the preparation method.
The invention also provides a shaping method of the glass-like or glass-like product, which comprises the following steps: placing the unsintered glass-like or glass-like product on the surface of a template with a certain shape, and shaping the glass-like or glass-like product under the condition of 90-150 ℃ water vapor atmosphere. For example, the shaping method specifically includes the following steps: placing the unsintered glass-like or glass-like product on the surface of a template with a certain shape, softening the glass and coating the glass on the surface of the template under the condition of 90-150 ℃ of water vapor atmosphere, heating (for example, 60-80 ℃) to harden the coated glass, removing the template, and sintering to obtain the shaped glass-like or glass-like product.
The invention also provides the application of the composite system in preparing reusable glass-like or glass-like products.
The invention has the beneficial effects that:
1. the reusable and recyclable glass-like and glass-like product provided by the invention has simple preparation method, and can be prepared by blending the solution under mild conditions, and carrying out heat treatment and sintering on the blended solution.
2. The glass-like and the glass-like product provided by the invention can be dissolved in water or a water-containing solvent under the heating condition, and the recovery method is simple and convenient.
3. The recovered glass-like sol dispersion can be reformed into glass-like products under certain heating conditions.
4. The glass-like and the glass-like product provided by the invention have higher hardness, toughness and impact resistance.
5. The glass-like and glass-like products prepared by the invention have the characteristics of fire resistance, pollution prevention, heat preservation and ultraviolet resistance besides the function of recycling, and have wide application prospect.
6. The glass-like and glass-like products of the present invention can be processed into appliances of various shapes under mild water vapor conditions, and can be used as a substitute for glassware.
Drawings
FIG. 1 is a scanning electron micrograph of the surface of the glass-like bulk prepared in example 1, at a magnification of 20000 times.
Fig. 2 is a photograph of a real object of the glass-like block prepared in example 1.
FIG. 3 is a photograph showing the glass-like mass produced in example 1 after recovery and dissolution.
Fig. 4 is a graph showing the hardness and modulus comparison results of the glass-like bulk prepared in example 1 and the glass-like samples thereof recovered 10 times.
FIG. 5 is a variation of the cup-shaped glassware article prepared in example 1, which was subjected to a melting and reshaping process.
Fig. 6 is a graph of the transmittance of the glass-like bulk prepared in example 1 and that of ordinary glass in the ultraviolet and visible light bands.
Figure 7 is a fire resistance test for the glass-like block prepared in example 1.
Detailed Description
[ composition System for glass-like articles or glass-like articles ]
As mentioned above, the present invention provides a composition system for a glass-like or glass-like article comprising:
(A) A mixed dispersion of silane coupling agent hydrolysate and an alkali solution;
(B) A low surface energy polymer solution;
(C) A silane coupling agent dispersion liquid.
In the composition system, the mass ratio of (A) a mixed dispersion of a silane coupling agent hydrolysate and an alkali solution, (B) a low-surface-energy polymer solution, and (C) a silane coupling agent dispersion is (100-1500) to 1 (50-200), for example, to (300-1000) to 1 (70-150), and is exemplified by the following ratio of (1.
The pH of the composition system is from 8.5 to 14, preferably from 8.8 to 13, more preferably from 9 to 12.
In the composition system, the mixed dispersion liquid of the silane coupling agent hydrolysate and the alkali solution (A) comprises silane coupling agent hydrolysate, organic alkali and a solvent c. The silane coupling agent hydrolysate is prepared from silane coupling agent monomers under the catalytic heating condition.
[ component (A) in the composition System ]
And the mixed dispersion liquid of the silane coupling agent hydrolysate and the alkali solution comprises the silane coupling agent hydrolysate and the alkali solution.
Wherein, the raw materials for preparing the silane coupling agent hydrolysate comprise siloxane monomers, a catalyst and a solvent c. Wherein the siloxane monomer may be selected from at least one of siloxanes having hydrophobic end groups, such as methyltriethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, dodecyltriethoxysilane, dodecyltrimethoxysilane, gamma- (methacryloyloxy) propyltrimethoxysilane, gamma- (methacryloyloxy) propyltriethoxysilane, gamma-mercaptopropyltrimethoxysilane, gamma-mercaptopropyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, and the like; preferably at least one of propyltrimethoxysilane, dodecyltriethoxysilane, propyltriethoxysilane, phenyltriethoxysilane, ethyltriethoxysilane, and gamma-mercaptopropyltrimethoxysilane.
Wherein the catalyst is selected from hydrochloric acid or at least one of sodium hydroxide and potassium hydroxide, such as hydrochloric acid, sodium hydroxide or potassium hydroxide, exemplified by hydrochloric acid.
Wherein, the preparation raw materials of the alkali solution comprise organic alkali and a solvent c. The organic base is selected from at least one of dimethylamine, trimethylamine, ethylamine, triethylamine, benzylamine, aniline, p-toluidine, p-chloroaniline, p-nitroaniline, diphenylamine, pyridine, triethanolamine and urea; for example, at least one of dimethylamine, trimethylamine, ethylamine, triethylamine and aniline; exemplified are triethylamine and/or aniline.
Wherein the solvent c is at least one selected from ethanol, acetone, methyl butanone, methyl isobutyl ketone, methyl acetate, ethyl acetate, propyl acetate, methanol, isopropanol, toluene, cyclohexane, cyclohexanone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether and ethylene glycol monobutyl ether; for example, at least one selected from ethanol, methanol, and isopropanol, and ethanol is exemplified.
In the mixed dispersion of the silane coupling agent hydrolysate and the alkali solution, the mass ratio of the siloxane monomer, the catalyst, the organic base and the solvent c is (5-10000) to (100-10000), for example, the mass ratio is (100-3000) to (0.6-10) to (500-5000), and the mass ratio is (300).
[ component (B) in the composition System ]
The low surface energy polymer solution comprises a low surface energy polymer and a solvent a.
Wherein the low surface energy polymer is selected from at least one of fluorocarbon resin, organic silicon resin and fluorine-silicon resin. For example, the fluorocarbon resin includes a low surface energy polymer containing fluorine atoms in the polymer chain, preferably at least one of polytetrafluoroethylene resin (PTFE), polyvinylidene fluoride resin (PVDF), polychlorotrifluoroethylene resin (FEVE), polyvinyl fluoride resin (PVF), and the like; exemplary is polytetrafluoroethylene resin (PTFE). For example, the silicone resin includes polysiloxane having a Si — O skeleton in its main chain, preferably at least one of polymers such as methyl silicone resin, phenyl vinyl silicone resin, phenyl epoxy silicone resin, borosilicate resin, and poly-n-hexyltriphenylethynyl silane resin, and is exemplified by polymethyl silicone resin or phenyl vinyl silicone resin. For example, the fluorosilicone resin includes a low surface energy material having advantages and superior properties of each of a fluorocarbon resin and a silicone resin, and is preferably at least one of polytrifluoropropylmethylsiloxane, polymethylnonafluorohexylsiloxane, polytridecylfluorooctylmethylsiloxane and polymethylheptadecafluorodecylsiloxane, and is exemplified by polytrifluoropropylmethylsiloxane.
Wherein the weight average molecular weight of the fluorocarbon resin is 5000-100 ten thousand, such as 8000-50 ten thousand, such as 1-10 ten thousand, and an exemplary weight is 1 ten thousand.
Wherein the silicone resin has a weight average molecular weight of 1000 to 300, for example 5000 to 100, further for example 1 to 50, exemplarily 1 ten thousand.
Wherein the weight average molecular weight of the fluorosilicone resin is 3000-300 ten thousand, for example 5000-150 ten thousand, or 1-75 ten thousand, and an example is 1 ten thousand.
Wherein the solvent a is selected from ketone solvents and/or ester solvents, such as at least one selected from acetone, methyl butanone, methyl isobutyl ketone, methyl acetate, ethyl acetate, propyl acetate and the like; illustrative is ethyl acetate.
The concentration of the low surface energy polymer solution is 0.1 to 100mg/mL, such as 5 to 25mg/mL, exemplary 10mg/mL, 12.5mg/mL, 15mg/mL, 20mg/mL, 25mg/mL.
[ component (C) in the composition System ]
The silane coupling agent dispersion liquid contains a silane coupling agent and a solvent b.
Wherein the silane coupling agent is R 1 Si(R 2 )(OR) 2 (ii) a Wherein R is 1 And R 2 Are identical or different and are independently selected from the group consisting of-R a NH 2 、-R a SH、-N(R a ) 3 、-R a NR b NH 2 、
Figure BDA0002363269690000061
-OR a At least one of; wherein R is a And R b Identical or different, independently of one another, from C 1-8 Alkyl, preferably C 1-4 Alkyl, illustratively, R a And R b Identical or different, independently of one another, is methyl or ethyl; wherein R is the same or different and is independently selected from C 1-8 Alkyl, preferably C 1-4 Alkyl, illustratively, R are the same or different and are independently of each other methyl or ethyl.
Alternatively, the silane coupling agent is R 1 And R 2 Silane coupling agent (a-1) in which one OR both of them are OR and R 1 And R 2 A mixture of silane coupling agents (a-2) which are OR, the content of a-2 may be 0 but less than 100%, and the content of a-1 is greater than 0 but 100% OR less.
Preferably, the silane coupling agent may be at least one selected from the group consisting of γ -aminopropyltriethoxysilane, diethylaminomethyltriethoxysilane, 3- (2-aminoethylamino) propyltriethoxysilane, 3- (2-aminoethylamino) propyltrimethoxysilane, γ - (methacryloyloxy) propyltrimethoxysilane, γ -mercaptopropyltrimethoxysilane, and the like; illustrative are 3- (2-aminoethylamino) propyltrimethoxysilane, gamma-aminopropyltriethoxysilane, gamma-mercaptopropyltrimethoxysilane, 3- (2-aminoethylamino) propyltrimethoxysilane, gamma- (methacryloyloxy) propyltrimethoxysilane or diethylaminomethyltriethoxysilane.
Wherein, the solvent b is at least one selected from acetone, methyl butanone, methyl isobutyl ketone, methyl acetate, ethyl acetate, propyl acetate, methanol, ethanol, isopropanol, toluene, cyclohexane, cyclohexanone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether and ethylene glycol monobutyl ether; for example, at least one of methanol, ethanol, and isopropanol; exemplary is ethanol. Preferably, solvent b is the same as solvent c.
In the silane coupling agent dispersion liquid, the mass ratio of the silane coupling agent to the solvent c is 1 (10-5000), for example 1 (100-2000), and the following ratios are 1.
(reusable glass-like or glass-like article)
The present invention provides reusable glass-like or glass-like articles prepared from the above-described composition systems.
Wherein the glass-like or glass-like product is transparent glass-like or glass-like product.
[ method for producing reusable glass-like or glass-like product ]
The invention also provides a preparation method of the glass-like or glass-like product, which comprises the following steps:
mixing (A) mixed dispersion of silane coupling agent hydrolysate and alkali solution, (B) low surface energy polymer solution and (C) silane coupling agent dispersion to prepare a mixed system; and carrying out heat treatment and sintering on the mixed system to obtain the glass-like or glass-like product.
According to an embodiment of the present invention, the preparation method comprises the steps of:
1) Mixing silane coupling agent hydrolysate with organic alkali solution to prepare the mixed dispersion liquid (A);
preferably, the silane coupling agent hydrolysate is prepared from siloxane monomers under the catalytic heating condition;
2) Dissolving a low surface energy polymer in a solvent a to obtain (B) a low surface energy polymer solution;
3) Dissolving a silane coupling agent in the solvent b, and stirring at normal temperature to obtain (C) silane coupling agent dispersion liquid;
4) Mixing the silane coupling agent hydrolysate and the alkali solution to obtain a mixed dispersion liquid, (B) the low-surface-energy polymer solution and (C) the silane coupling agent dispersion liquid to obtain a mixed system;
5) Carrying out heat treatment on the mixed system to obtain silicon-based glass gel;
6) And sintering the silicon-based glass gel to obtain the glass or glass-like product.
In the present invention, the mixed dispersion of (a) the silane coupling agent hydrolysate and the alkali solution, (B) the low surface energy polymer solution, (C) the silane coupling agent dispersion, the siloxane monomer, the organic base, the low surface energy polymer, the silane coupling agent, the solvent a, and the solvent B have the meanings as described above.
In the step 1), the mass ratio of the silane coupling agent hydrolysate to the organic alkali solution is (5-10000): 1, such as (10-1000): 1, and as another example, (10-500): 1, illustratively 30.
Wherein, the concentration of the silane coupling agent hydrolysate is 50-1000mg/mL, for example 250-500mg/mL, and further for example 300-4000mg/mL.
In the organic alkali solution, the mass ratio of the organic alkali to the solvent c is 1 (10-5000), for example 1 (10-1000), and the following ratios are as follows, for example, 1.
In the step 1), the preparation raw materials of the silane coupling agent hydrolysate comprise siloxane monomers, a catalyst and a solvent c. Wherein, the siloxane monomer, the catalyst, the solvent c and the mixture ratio thereof have the meanings as described above.
In the step 1), the mass ratio of the catalyst to the solvent c is 1 (100-10000), such as 1 (200-1000), and is also 1 (300-600).
In step 1), the catalytic heating conditions include: the temperature is 50-100 deg.C, such as 70-90 deg.C, illustratively 60 deg.C, 70 deg.C, 80 deg.C, 90 deg.C. Further, the reaction time of the catalytic heating is 1 to 10h, such as 2 to 8h, exemplary 5h, 7h, 8h, 10h.
In step 1), the catalytic heating is carried out under stirring conditions, for example at a stirring speed of 200 to 5000rpm, for example at a speed of 500 to 1500rpm, illustratively 1000rpm, 2000rpm.
In step 2), the low surface energy polymer, solvent a and (B) the low surface energy polymer solution all have the meaning as described above.
In the step 2), the dissolving is stirring dissolving. For example, the agitation speed may be 200 to 5000rpm, such as 500 to 3000rpm, illustratively 2000rpm, 3000rpm. Further, the stirring time is 1 to 10 days, such as 2 to 8 days, illustratively 3 days, 5 days, 8 days, 10 days.
In step 3), the silane coupling agent, the solvent b and (C) the silane coupling agent dispersion liquid all have the meanings as described above.
In the step 4), the mass ratio of the mixed dispersion of the silane coupling agent hydrolysate and the alkali solution (A) to the silane coupling agent dispersion (C) is (10-500): 1, for example, (20-300): 1, and exemplarily 30.
In step 5), the temperature of the heat treatment is 80 to 200 ℃, such as 100 to 160 ℃, and is exemplary 100 ℃. Further, the heat treatment time is 1 to 5 hours, such as 2 to 4 hours, illustratively 3 hours, 5 hours.
In step 6), the sintering is performed under the protection of an inert atmosphere, for example, the inert atmosphere is at least one of nitrogen, argon, and the like, and preferably nitrogen.
In step 6), the sintering temperature is 200-600 ℃, such as 300-500 ℃, and exemplary is 400 ℃. Further, the time of the heat treatment is 0.5 to 5 hours, such as 1 to 4 hours, exemplary 1 hour, 2 hours, 3 hours.
[ method for recovering reusable glass-like articles ]
The invention also provides a method for recycling the glass-like or glass-like product, which comprises the following steps: dissolving the glass-like or glass-like product in water or an aqueous solvent, and recovering the obtained sol dispersion.
Wherein the aqueous solvent may be selected from a mixed solvent of water and an organic solvent. Preferably, the organic solvent is a water-miscible organic solvent, such as ethanol.
[ method of reusing reusable glass-like article or glass-like product ]
The invention also provides a recycling method of the glass-like or glass-like product, which comprises the following steps: heating the recovered sol dispersion liquid to form the sol dispersion liquid, and sintering the sol dispersion liquid to obtain the glass-like or glass-like product;
wherein the heating is to a temperature of 60-80 deg.C, such as 60-70 deg.C, and exemplary 60 deg.C. The purpose of the heating is to remove water or aqueous solvent from the sol dispersion.
Wherein, the sintering treatment is the same as the preparation method.
[ method of Molding reusable glass-like articles or glass-like articles ]
The invention also provides a method for shaping the glass-like or glass-like product, which comprises the following steps: the glass-like or glass-like article can be shaped by placing the glass-like or glass-like article in a mold under a steam atmosphere at 90-150 deg.C (e.g., 100-120 deg.C, illustratively 100 deg.C).
For example, the shaping method specifically includes the following steps: placing the unsintered glass-like or glass-like product on the surface of a template with a certain shape, softening the glass and coating the glass on the surface of the template under the condition of 90-150 ℃ of water vapor atmosphere, heating (for example, 60-80 ℃) to harden the coated glass, removing the template, and sintering to obtain the shaped glass-like or glass-like product.
[ application ]
The invention also provides the application of the composite system in preparing reusable glass-like or glass-like products.
The technical solution of the present invention will be further described in detail with reference to specific embodiments. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the techniques realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
Unless otherwise indicated, the raw materials and reagents used in the following examples are all commercially available products or can be prepared by known methods.
Example 1
1) Under the catalytic action of hydrochloric acid, dissolving propyl trimethoxy silane in ethanol, heating the mixture at 80 ℃, stirring at 2000rpm for 10h to prepare a hydrolysis dispersion liquid of propyl trimethoxy silane, namely a hydrolysis liquid a; wherein the mass ratio of the hydrochloric acid to the propyl trimethoxy silane to the ethanol is 1;
2) Dissolving triethanolamine serving as an organic alkali in ethanol, wherein the mass ratio of the triethanolamine to the ethanol is 1;
3) Dissolving 2.5g of low surface energy polymer polytetrafluoroethylene resin with the weight average molecular weight of 1 ten thousand in 200mL of ethyl acetate, and magnetically stirring for 3 days at normal temperature at the rotating speed of 1000rpm to obtain a polytetrafluoroethylene solution, namely solution c;
4) Adding 3- (2-aminoethylamino) propyl trimethoxy silane into ethanol, wherein the mass ratio of the 3- (2-aminoethylamino) propyl trimethoxy silane to the ethanol is 1;
5) Blending the hydrolysate a prepared in the step 1) and the solution b prepared in the step 2) according to the mass ratio of 300;
6) Blending the dispersion e prepared in the step 5), the solution c prepared in the step 3) and the dispersion d prepared in the step 4) in a mass ratio of 500; the pH of the dispersion f was 9.0;
7) And (3) placing the dispersion liquid f obtained in the step 6) into any mould, and carrying out heat treatment at 100 ℃ for 5 hours to obtain the silicon-based glass gel block.
8) And sintering the glass gel block at 400 ℃ for 2 hours under the protection of nitrogen to obtain the silicon-based glass block capable of being repeatedly used.
The scanning electron microscope image of the surface of the silicon-based glass prepared in this example is shown in fig. 1, and it can be seen that: the surface of the silicon-based glass is smooth and compact. A physical photograph of the prepared silica-based glass block is shown in fig. 2.
The glass-like mass prepared in this example was dissolved in water at 50 ℃ to give a clear and transparent sol dispersion (as shown in FIG. 3). And then the sol dispersion is dehydrated and formed at 60 ℃, and the silicon-based glass block can be obtained again after the formed sample is subjected to the same sintering treatment. Realizes the one-time circulation process of the glass-like block. This cycle can be repeated at least 10 times.
The initial hardness and modulus of the glass-like block and the hardness and modulus test results of the glass-like block obtained after 10 cycles are shown in fig. 4. As can be seen from fig. 4, the hardness and modulus of the glass-like bulk bodies before and after recycling were almost unchanged, with the hardness kept at about 1.3GPa and the modulus kept at about 13 GPa.
The glass-like block prepared in this example was placed in a water vapor atmosphere at 100 ℃ and simultaneously placed on a mold surface having a certain shape as a mold-covering template, thereby obtaining a glass-like device having a template shape. The glassware is dissolved in water under the heating condition, then is molded at 60 ℃, and is placed on the surface of a mold with another shape as a covering template, so that glassware with different shapes (as shown in figure 5) is obtained, and the recycling of glass is realized.
As shown in fig. 6, the transmittance of the bulk glass prepared in this example was measured on a LAMBDA 950 UV-visible spectrophotometer at a wavelength of 300-800nm, and the glass has a transmittance of about 85% in the visible region and a transmittance of about 10% in the ultraviolet region, and has a certain ultraviolet resistance.
Through the test of a heat conductivity meter, the glass-like block prepared by the embodiment has a heat conductivity coefficient lower than that of common glass, and is suitable for transparent insulating glass of buildings.
The glass-like block prepared in the embodiment is placed on the flame of an alcohol lamp to be burned for 6min, and no open fire or even smoke is generated on the surface of the glass, which shows that the glass has better fire resistance and flame retardance (as shown in figure 7).
Example 2
1) Under the catalytic action of hydrochloric acid, dissolving dodecyl triethoxysilane in ethanol, heating the mixture at 70 deg.C, stirring at 1000rpm for 8h to obtain hydrolysis dispersion of dodecyl triethoxysilane, i.e. hydrolysate a; wherein the mass ratio of the hydrochloric acid to the dodecyl triethoxysilane to the ethanol is 1;
2) Dissolving organic base triethylamine in ethanol, wherein the mass ratio of the triethylamine to the ethanol is 1;
3) Dissolving 2.5g of low surface energy polymer methyl silicone resin with the weight average molecular weight of 1 ten thousand in 200mL of acetone, and magnetically stirring for 5 days at normal temperature at the rotating speed of 3000rpm to obtain a methyl silicone resin solution, namely solution c;
4) Adding gamma-aminopropyltriethoxysilane into a solvent ethanol, wherein the mass ratio of the gamma-aminopropyltriethoxysilane to the ethanol is 1;
5) Blending the hydrolysate a prepared in the step 1) and the solution b prepared in the step 2) according to the mass ratio of 100;
6) Blending the mixed dispersion e prepared in the step 5), the solution c prepared in the step 3) and the dispersion d prepared in the step 4) according to a mass ratio of 1000; the pH of the dispersion f was 10.0;
7) And (3) placing the dispersion liquid f into any mould, and carrying out heat treatment at 100 ℃ for 3 hours to obtain the silicon-based glass gel block.
8) And sintering the glass-like gel block for 1 hour at 400 ℃ under the protection of nitrogen to obtain the reusable silicon-based glass block.
Example 3
1) Under the catalytic action of hydrochloric acid, dissolving propyl triethoxysilane in ethanol, heating the mixture at 60 deg.C, stirring at 800rpm for 7h to obtain a hydrolysate of propyl triethoxysilane, i.e. hydrolysate a; wherein the mass ratio of the hydrochloric acid to the propyltriethoxysilane to the ethanol is 3;
2) Dissolving organic base triethylamine in ethanol, wherein the mass ratio of the triethylamine to the ethanol is 1;
3) Dissolving 5g of low surface energy polymer phenyl vinyl silicone resin with the weight average molecular weight of 1 ten thousand in 500mL of methyl butanone, and magnetically stirring at normal temperature for 6 days at the rotating speed of 2000rpm to obtain phenyl vinyl silicone resin solution, namely solution c;
4) Adding gamma-mercaptopropyl-trimethoxysilane into a solvent ethanol, wherein the mass ratio of the gamma-mercaptopropyl-trimethoxysilane to the ethanol is 1;
5) Blending the hydrolysate a prepared in the step 1) and the dispersion liquid b prepared in the step 2) according to a mass ratio of 30;
6) Blending the mixed dispersion liquid e prepared in the step 5), the solution c prepared in the step 3) and the dispersion liquid d prepared in the step 4) in a mass ratio of 1000; the pH of the dispersion f was 9.5;
7) And (3) placing the dispersion liquid f into any mould, and carrying out heat treatment at 100 ℃ for 5 hours to obtain the silicon-based glass gel block.
8) And sintering the glass-like gel block at 400 ℃ for 3 hours under the protection of nitrogen to obtain the reusable silicon-based glass block.
Example 4
1) Under the catalytic action of hydrochloric acid, dissolving phenyltriethoxysilane in ethanol, heating the mixture at 80 deg.C, stirring at 1000rpm for 7h to obtain hydrolysate of phenyltriethoxysilane, i.e. hydrolysate a; wherein the mass ratio of the hydrochloric acid to the phenyltriethoxysilane to the ethanol is 1;
2) Dissolving organic alkali diphenylamine in ethanol, wherein the mass ratio of diphenylamine to ethanol is 1;
3) Dissolving 10g of low surface energy polymer poly (trifluoropropylmethylsiloxane) with the weight-average molecular weight of 1 ten thousand in 500mL of methyl acetate, and magnetically stirring for 8 days at normal temperature at the rotating speed of 2000rpm to obtain poly (trifluoropropylmethylsiloxane) solution, namely solution c;
4) Adding 3- (2-aminoethylamino) propyl trimethoxy silane into ethanol serving as a solvent, wherein the mass ratio of the 3- (2-aminoethylamino) propyl trimethoxy silane to the ethanol is 1;
5) Blending the hydrolysate a prepared in the step 1) and the solution b prepared in the step 2) according to a mass ratio of 50;
6) Blending the mixed dispersion liquid e prepared in the step 5), the solution c prepared in the step 3) and the solution d prepared in the step 4) in a mass ratio of 800; the pH of the dispersion f was 8.5;
7) And (3) placing the dispersion liquid f into any mould, and carrying out heat treatment at 100 ℃ for 3 hours to obtain the silicon-based glass gel block.
8) And sintering the glass-like gel block for 1 hour at 400 ℃ under the protection of nitrogen to obtain the reusable silicon-based glass block.
Example 5
1) Under the catalytic action of hydrochloric acid, dissolving ethyl triethoxysilane in ethanol, heating the mixture at 90 deg.C, stirring at 1000rpm for 8h to obtain hydrolysate a; wherein the mass ratio of the hydrochloric acid to the ethyl triethoxysilane to the ethanol is 1;
2) Dissolving organic alkali aniline in ethanol, wherein the mass ratio of aniline to ethanol is 1;
3) Dissolving 25g of low surface energy polymer polytetrafluoroethylene resin with the weight average molecular weight of 1 ten thousand in 1000mL of propyl acetate, and magnetically stirring for 5 days at normal temperature at the rotating speed of 2000rpm to obtain polytetrafluoroethylene solution, namely solution c;
4) Adding gamma- (methacryloyloxy) propyl trimethoxy silane into solvent ethanol, wherein the mass ratio of the gamma- (methacryloyloxy) propyl trimethoxy silane to the ethanol is 1;
5) Blending the hydrolysate a prepared in the step 1) and the solution b prepared in the step 2) according to a mass ratio of 50;
6) Blending the mixed dispersion e prepared in the step 5), the solution c prepared in the step 3) and the solution d prepared in the step 4) in a mass ratio of 600; the pH of the dispersion f was 9.0;
7) And (4) placing the dispersion liquid f into any mould, and carrying out heat treatment for 3 hours at 100 ℃ to obtain the silica-based glass gel block.
8) And sintering the glass-like gel block for 1 hour at 400 ℃ under the protection of nitrogen to obtain the reusable silicon-based glass block.
Example 6
1) Dissolving gamma-mercaptopropyl trimethoxysilane in ethanol under the catalysis of hydrochloric acid, heating the mixture at 90 ℃, stirring at 2000rpm for 8 hours, and preparing hydrolysate of the gamma-mercaptopropyl trimethoxysilane, namely hydrolysate a; wherein, the mass ratio of the hydrochloric acid to the gamma-mercaptopropyltrimethoxysilane to the ethanol is 6;
2) Dissolving organic alkali trimethylamine in ethanol, wherein the mass ratio of the trimethylamine to the ethanol is 1;
3) Dissolving 15g of low surface energy polymer phenyl epoxy silicone resin with the weight average molecular weight of 1 ten thousand in 1000mL of methyl isobutyl ketone, and magnetically stirring at normal temperature for 10 days at the rotating speed of 2000rpm to obtain phenyl epoxy silicone resin solution, namely solution c;
4) Adding diethylaminomethyl triethoxysilane into a solvent ethanol, wherein the mass ratio of the diethylaminomethyl triethoxysilane to the ethanol is 1;
5) Blending the hydrolysate a prepared in the step 1) and the solution b prepared in the step 2) according to a mass ratio of 50;
6) Blending the mixed dispersion liquid e prepared in the step 5), the solution c prepared in the step 3) and the dispersion liquid d prepared in the step 4) in a mass ratio of 900; the pH of the dispersion f was 8.5;
7) And (3) placing the dispersion liquid f into any mould, and carrying out heat treatment at 100 ℃ for 3 hours to obtain the silicon-based glass gel block.
8) And sintering the glass-like gel block for 1 hour at 400 ℃ under the protection of nitrogen to obtain the reusable silicon-based glass block.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (13)

1. A reusable composition system for a glass-like or glass-like article, said composition system comprising:
(A) A mixed dispersion of silane coupling agent hydrolysate and an alkali solution;
(B) A low surface energy polymer solution;
(C) A silane coupling agent dispersion liquid;
the mass ratio of the silane coupling agent dispersion liquid (C) to the silane coupling agent hydrolysate (100-1500) is (50-200);
the pH value of the composition system is 8.5-14;
the mixed dispersion liquid of the silane coupling agent hydrolysate and the alkali solution comprises silane coupling agent hydrolysate, organic alkali and a solvent c, wherein the silane coupling agent hydrolysate is prepared by heating siloxane monomers in the presence of a catalyst;
the siloxane monomer is selected from at least one of the following siloxanes with hydrophobic end groups: methyltriethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, dodecyltriethoxysilane, dodecyltrimethoxysilane, gamma- (methacryloyloxy) propyltrimethoxysilane, gamma- (methacryloyloxy) propyltriethoxysilane, gamma-mercaptopropyltrimethoxysilane, gamma-mercaptopropyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane;
the catalyst is selected from hydrochloric acid or at least one of sodium hydroxide and potassium hydroxide;
the organic base is at least one selected from dimethylamine, trimethylamine, ethylamine, triethylamine, benzylamine, aniline, p-toluidine, p-chloroaniline, p-nitroaniline, diphenylamine, pyridine, triethanolamine and urea;
the low surface energy polymer solution (B) comprises a low surface energy polymer and a solvent a; the low surface energy polymer is selected from at least one of fluorocarbon resin, organic silicon resin and fluorine silicon resin;
the silane coupling agent dispersion liquid (C) comprises a silane coupling agent and a solvent b;
wherein the silane coupling agent is R 1 Si(R 2 )(OR) 2 (ii) a Wherein R is 1 And R 2 Are identical or different and are independently selected from the group consisting of-R a NH 2 、-R a SH、-N(R a ) 3 、-R a NR b NH 2 、
Figure DEST_PATH_IMAGE001
、-OR a At least one of; wherein R is a And R b Identical or different, independently of one another, from C 1-8 An alkyl group;
alternatively, the silane coupling agent is R 1 And R 2 Silane coupling agent (a-1) in which one OR both of them are OR and R 1 And R 2 A mixture of silane coupling agents (a-2) each of which is OR, the content of a-2 being 0 OR more and less than 100%, and the content of a-1 being 0 OR more and 100% OR less.
2. The composition system according to claim 1, wherein the solvent c is at least one selected from the group consisting of ethanol, acetone, methyl butanone, methyl isobutyl ketone, methyl acetate, ethyl acetate, propyl acetate, methanol, isopropanol, toluene, cyclohexane, cyclohexanone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and ethylene glycol monobutyl ether.
3. The composition system according to claim 1, wherein the solvent a is selected from ketone solvents and/or ester solvents.
4. The composition system according to claim 1, wherein the silane coupling agent dispersion liquid contains at least one silane coupling agent selected from the group consisting of γ -aminopropyltriethoxysilane, diethylaminomethyltriethoxysilane, 3- (2-aminoethylamino) propyltriethoxysilane, 3- (2-aminoethylamino) propyltrimethoxysilane, γ - (methacryloyloxy) propyltrimethoxysilane, and γ -mercaptopropyltrimethoxysilane.
5. The composition system according to claim 1, wherein the solvent b is at least one selected from the group consisting of acetone, methyl butanone, methyl isobutyl ketone, methyl acetate, ethyl acetate, propyl acetate, methanol, ethanol, isopropanol, toluene, cyclohexane, cyclohexanone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and ethylene glycol monobutyl ether.
6. Use of a composite object according to any one of claims 1 to 5 in the manufacture of a reusable glass-like or glass-like article.
7. A directly reusable glass-like or glass-like article prepared from the composition system of any of claims 1-5.
8. A method of making a directly reusable glass-like or glass-like article according to claim 7, comprising the steps of:
mixing (A) mixed dispersion of silane coupling agent hydrolysate and alkali solution, (B) low surface energy polymer solution and (C) silane coupling agent dispersion to prepare a mixed system; and carrying out heat treatment and sintering on the mixed system to obtain the glass-like or glass-like product.
9. The method of claim 8, comprising the steps of:
1) Mixing the silane coupling agent hydrolysate with an organic alkali solution to prepare the (A) mixed dispersion liquid;
the silane coupling agent hydrolysate is prepared from siloxane monomers under the condition of catalytic heating;
2) Dissolving a low surface energy polymer in a solvent a to obtain (B) a low surface energy polymer solution;
3) Dissolving a silane coupling agent in the solvent b, and stirring at normal temperature to obtain (C) silane coupling agent dispersion liquid;
4) Mixing the silane coupling agent hydrolysate and the alkali solution to obtain a mixed dispersion liquid, (B) the low-surface-energy polymer solution and (C) the silane coupling agent dispersion liquid to obtain a mixed system;
5) Carrying out heat treatment on the mixed system to obtain silicon-based glass gel;
6) And sintering the silicon-based glass gel to obtain the glass or glass-like product.
10. The method of recycling glass-like or glass-like articles of claim 7, comprising the steps of: dissolving the glass-like or glass-like product in water or an aqueous solvent, and recovering the obtained sol dispersion.
11. The recovery method according to claim 10, wherein the aqueous solvent is selected from a mixed solvent of water and an organic solvent.
12. The method of recycling the glass-like or glass-like article of claim 7, wherein the method comprises the steps of:
dissolving the glass-like or glass-like product in water or a water-containing solvent, and recovering the obtained sol dispersion liquid;
carrying out heat treatment and sintering on the recovered sol dispersion liquid to obtain the glass-like or glass-like product;
wherein the heat treatment and sintering treatment are the same as when the composition system is used to prepare the glass-like or glass-like article.
13. The method of shaping a glass-like or glass-like article according to claim 7, wherein the method comprises the steps of: and (3) placing the glass-like or glass-like product in a template, and shaping the glass-like or glass-like product under the condition of 90-150 ℃ of water vapor atmosphere.
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