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CN112321632B - Silane copolymer for aqueous system and preparation method thereof - Google Patents

Silane copolymer for aqueous system and preparation method thereof Download PDF

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Publication number
CN112321632B
CN112321632B CN202011166393.5A CN202011166393A CN112321632B CN 112321632 B CN112321632 B CN 112321632B CN 202011166393 A CN202011166393 A CN 202011166393A CN 112321632 B CN112321632 B CN 112321632B
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silane
methyl
formula
ethyl
silane copolymer
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CN112321632A (en
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冯琼华
黄天次
李胜杰
肖俊平
姚晨
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HUBEI BLUESKY NEW MATERIALS Inc
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HUBEI BLUESKY NEW MATERIALS Inc
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • C07F7/1804—Compounds having Si-O-C linkages
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • C07F7/1804—Compounds having Si-O-C linkages
    • C07F7/1872—Preparation; Treatments not provided for in C07F7/20
    • C07F7/1892—Preparation; Treatments not provided for in C07F7/20 by reactions not provided for in C07F7/1876 - C07F7/1888

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  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Silicon Polymers (AREA)

Abstract

The invention discloses a silane copolymer and a preparation method thereof, wherein the silane copolymer comprises the following components: 1) Adding aminoalkylsilane A and one or two of aminoalkylsilane B, glycidoxyalkylsilane, methacryloxyalkylsilane, alkylsilane, orthosilicate silane, vinylsilane, acryloxypropylsilane, allylsilane, mercaptopropylsilane and ureidopropylsilane into a reactor, adding a solvent A and a catalyst, and stirring uniformly to obtain a silane reaction solution; 2) Dropwise adding a mixed solution formed by ultrapure water and another part of solvent A into a silane reaction solution at 42-60 ℃; and (3) carrying out heat preservation reaction after the dripping is finished, and obtaining the silane copolymer after the reaction is finished and post-treatment is carried out. The invention endows the silane copolymer with various excellent performances by introducing different types of silane, and has the advantages of simple and convenient industrialization of the synthesis process, low VOC, environmental friendliness, good water solubility, long-time stable existence in an aqueous system, good storage stability and the like.

Description

Silane copolymer for aqueous system and preparation method thereof
Technical Field
The invention relates to the field of water-based system silane, in particular to an environment-friendly silane copolymer for a water-based system and a preparation method thereof.
Background
The molecular structural formula of the silane coupling agent is generally Y-R-Si (OR) 3 (wherein Y is an organofunctional group and SiOR is a siloxy group). The siloxy groups are reactive with inorganic materials and the organic functional groups are reactive or compatible with organic materials. Thus, when the silane coupling agent is interposed between the inorganic and organic interfaces, a bonding layer of an organic matrix-the silane coupling agent-the inorganic matrix can be formed.
Typical reactive groups on silane coupling agents include vinyl, amino, epoxy, methacryloxy, mercapto, isocyanate, etc., with different reactive groups imparting different application scenarios to the silane. For example, mercaptosilanes have good adhesion to metals, but have poor compatibility with water; the aminosilane can exist stably in the aqueous system; long chain alkylsilanes can provide hydrophobicity, and the like. With the development of the market, a single silane coupling agent is difficult to meet the application requirements in various aspects, and the silane coupling agent and the performance improvement thereof for the field of aqueous systems are always the development trend and the difficulty of the industry. The silane copolymer contains fewer alkoxy groups and a plurality of organic functional groups in the structure, so the silane copolymer has low VOC and wide application field, and is a modified polymer material with high added value.
In industrial applications, the desired effect can be achieved with a small amount of silane, typically 0.5 to 2.0% of the mass of the substrate. Therefore, in order to improve the dispersibility of silane, other organic solvents are generally used for dissolution and dilution, but this is inconvenient in use, generates volatile gas, and has high cost. In aqueous systems, however, silanes are themselves very sensitive to water and can self-polymerize to failure in a multi-water environment. It is therefore highly desirable to find a process for preparing silane copolymers in environmentally friendly aqueous systems.
The patent name of the invention is 'aqueous silane coupling agent-polyether grafted polysiloxane polymer coating', and the patent number of the invention is CN103360021A, which describes a polyether grafted polysiloxane polymer. The long-chain polyether exists in the structure, so that the paint prepared by the long-chain polyether has the advantages of wear resistance, acid resistance, alkali resistance, good adhesion effect, stable film formation and the like, and is suitable for wall coating. However, the solvent and catalyst are not removed during the preparation of the polyether-grafted polysiloxane polymer, which may destabilize the polymer to cure upon storage and may cause environmental pollution due to toluene volatilization during use.
The invention patent with the patent name of silane copolymer and preparation method thereof and the patent number of CN1150254C describes a silane copolymer component which can be used for cosmetics such as hair, skin and the like. It is obtained by addition polycondensation of one or more hydrophilic organic substances with silane in an aqueous solution, which has the excellent properties of other organic compounds in addition to the properties of the silane itself. When it is used in cosmetics, it can improve its adsorption ability, drainage property, ultraviolet absorption ability, etc. However, in the preparation process, in an aqueous system, silane can be condensed by itself preferentially, so that the synthesis yield of the silane copolymer is low.
German patent DE69722775 describes a method for increasing the storage stability of aqueous solutions of silanes and for widening the pH stability thereof. Which uses one or more nonionic surfactants as stabilizers for the aqueous silane solution, one of which is an alkyl sugar surfactant. The preparation process of the aqueous solution of the silane is complex and needs to introduce more surfactant for treatment, which leads to the increase of the preparation cost and the application field of the silane is not improved.
In summary, the copolymer formed from silane and other organic substances or different kinds of silane can give more excellent properties. Therefore, it is not easy to find a method for preparing a general, stable, simple and environment-friendly aqueous system silane copolymer.
Disclosure of Invention
Therefore, the invention provides a preparation method of an environment-friendly and stable silane copolymer with various silane performances for an aqueous system, which is environment-friendly.
In order to achieve the above purpose, the invention discloses a silane copolymer for an aqueous system, which has a structural formula shown in formula I:
(R 1 O)[(R 1 O) 1-x (R 2 ) x S i(A)O] a [S i(B)(R 3 ) y (OR 4 ) 1-y O] b [S i(C)(R 5 ) z (OR 6 ) 1-z O] c R 7 a formula I;
in the formula I, A is aminoalkyl, B, C is one of glycidoxyalkyl, methacryloxyalkyl, alkyl, alkoxy, vinyl, acryloxypropyl, allyl, mercaptopropyl and ureidopropyl respectively; a is more than or equal to 1, b is more than or equal to 0, and c is more than or equal to 0; r is R 1 、R 4 、R 6 、R 7 Is any one of methyl and propyl; r is R 2 、R 3 、R 5 Is methyl, x, y and z are respectively 0 or 1.
Further, in the formula I, the values of a, b and c are more than or equal to 2 and less than or equal to a+b+c and less than or equal to 10, and the number of the chain links is controlled so as to meet the reaction compatibility with the matrix resin when the silane copolymer is used as a coupling agent, and meanwhile, poor compatibility with water caused by too high crosslinking degree is avoided.
The invention adopts the molecular structure of the water-based system silane copolymer, and solves the technical problem that most silanes are unstable in the water-based system. The core advantages are that: firstly, constructing enough different kinds of active reactive groups in a molecular structure, wherein the active reactive groups are based on amino groups, so that the active reactive groups have better compatibility with water, can be effectively used in an aqueous system, and meanwhile, according to specific use occasions, corresponding groups are designed on a molecular chain, for example, alkyl groups are designed in the molecular chain to provide hydrophobicity, and mercapto groups are designed in the molecular chain to further strengthen the adhesion to metal; reactive groups such as epoxy groups, vinyl groups, methacryloxy groups and the like are designed in a molecular chain to provide compatibility and reactivity with a polymer; the silane copolymer has higher effective components in the same unit volume compared with silane monomers, and generates less hydrolytic alcohol when in action; and thirdly, the silane copolymer has better chemical stability, can exist stably for a long time and is convenient for storage and transportation.
The invention also discloses a preparation method of the silane copolymer for the aqueous system, which comprises the following steps:
1) Adding aminoalkylsilane A and one or two of aminoalkylsilane B, glycidoxyalkylsilane, methacryloxyalkylsilane, alkylsilane, orthosilicate silane, vinylsilane, acryloxypropylsilane, allylsilane, mercaptopropylsilane and ureidopropylsilane into a reactor, adding a solvent A and a supported catalyst, and stirring uniformly at room temperature to obtain a silane reaction solution;
2) Adding ultrapure water into the other part of solvent A, uniformly mixing to obtain a mixed solution, and slowly dripping the mixed solution into the silane reaction solution obtained in the step 1) at 42-60 ℃; after the dripping is finished, continuing to perform heat preservation reaction for 2-5 hours, and completely performing reaction when the moisture content in the detection system is less than 2000 ppm;
3) Distilling to remove the solvent A in the reaction liquid obtained in the step 2), and filtering to remove the solid catalyst to obtain the silane copolymer for the aqueous system.
In step 1) of the present invention, aminoalkylsilane A is reacted with one or two other silanes, which may be aminoalkylsilane B, glycidoxyalkylsilane, methacryloxyalkylsilane, alkylsilane, orthosilicate silane, vinylsilane, acryloxypropylsilane, allylsilane, mercaptopropylsilane, ureidopropylsilane. Other silanes may be selected for polymerization with aminoalkylsilane a to design the corresponding groups on the molecular chain, depending on the particular application.
The preparation method provided by the invention has the advantages that: firstly, the solvent is used to make the whole system react homogeneously, and the reaction speed and the heat release condition can be controlled to avoid excessive local polymerization; secondly, the solid catalyst and the solvent can be effectively recycled, and meanwhile, the neutralization step is omitted, so that the process cost is reduced; thirdly, the reaction degree can be definitely determined by detecting the moisture content in the system, so that the reaction process can be conveniently monitored.
Further, the molecular formulas of the amino alkyl silane A, the amino alkyl silane B, the glycidoxy alkyl silane, the methacryloxyalkyl silane, the alkyl silane, the orthosilicate silane, the vinyl silane, the acryloxypropyl silane, the allyl silane, the mercaptopropyl silane and the ureidopropyl silane are all shown in a formula I I:
Y-S i(R 8 ) n (OR 9 ) (3-n) I I
when the formula of formula I I represents aminoalkylsilane a or aminoalkylsilane B, Y is one of the following: aminopropyl, aminoethylaminopropyl; r is R 8 Is methyl; r is R 9 Methyl or ethyl; n is an integer of 0 or 1; the aminoalkylsilane A and the aminoalkylsilane B are the same or different;
when the formula of formula I I represents glycidoxyalkylsilane, Y is glycidoxypropyl or epoxycyclohexylethyl; r is R 8 Is methyl; r is R 9 Methyl or ethyl; n is an integer of 0 or 1;
when the formula of formula I I represents a methacryloxyalkylsilane, Y is methacryloxypropyl or methacryloxymethyl; r is R 8 Is methyl; r is R 9 Methyl or ethyl; n is an integer of 0 or 1;
when the formula I I represents an alkylsilane, Y is one of the following: methyl, ethyl, propyl, n-octyl, cyclohexyl, isobutyl; r is R 8 Is methyl; r is R 9 Methyl or ethyl; n is an integer of 0 or 1;
when the formula I I represents a orthosilicate silane, Y is methoxy or ethoxy, R 8 Is methyl; r is R 9 Methyl or ethyl, n is an integer of 0 or 1;
when the formula I I is vinyl silane, Y is vinyl, R 8 Is methyl; r is R 9 Methyl or ethyl, n is an integer of 0 or 1;
when the formula I I represents acryloxypropyl silane, Y is acryloxypropyl, R 8 Is methyl; r is R 9 Methyl or ethyl, n is an integer of 0 or 1;
when the formula I I represents an allylsilane, Y is allyl and R 8 Is methyl; r is R 9 Methyl or ethyl, n is an integer of 0 or 1;
when the molecular formula of formula I I represents mercaptopropyl silane, Y is mercaptopropyl, R 8 Is methyl; r is R 9 Methyl or ethyl, n is an integer of 0 or 1;
when the formula of formula I I represents a ureidopropylsilane, Y is ureidopropyl, R 8 Is methyl; r is R 9 Methyl or ethyl, n is an integer of 0 or 1.
Further, the solvent A is one or a mixture of more than two of the following: methanol, ethanol, isopropanol, propanol, tetrahydrofuran, acetone, butanone. More preferably, the solvent A is methanol, ethanol or butanone. The solvent can make the whole system react homogeneously, and can control the reaction speed and heat release, so as to avoid excessive local polymerization.
Further, the mass ratio of the total mass of each silane added in the step 1 to the solvent A is 1:0.8 to 1.2.
Further, the carrier used for the supported catalyst is one or a mixture of more than two of the following: clay, styrene-type spherical exchange resins, porous silica gel, precipitated or fumed silica, porous alumina, aluminum silicate or porous ceramics. More preferably, the carrier used for the supported catalyst is styrene type spherical exchange resin or porous silica gel.
Further, the catalyst is an acidic catalyst, and the acidic catalyst is one of the following: titanate type, sulfuric acid type, phosphoric acid type or sulfonate type. More preferably, the catalyst is trimethylsilyl phosphoric acid or trifluoropropyl sulfonic acid. The catalyst can be effectively recycled, and meanwhile, the neutralization step is omitted, so that the process cost is reduced.
Further, in the step 2), the mass ratio of the ultrapure water to the other solvent A is 1:3-7.
Preferably, the aminoalkylsilane a or aminoalkylsilane B is one of the following: 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, 3-aminopropyl methyldimethoxysilane, 3-aminopropyl methyldiethoxysilane, 2-aminoethyl-3-aminopropyl trimethoxysilane, 2-aminoethyl-3-aminopropyl triethoxysilane, 2-aminoethyl-3-aminopropyl methyldimethoxysilane, 2-aminoethyl-3-aminopropyl methyldiethoxysilane.
The glycidoxy alkylsilane is one of the following: 3-glycidoxypropyl trimethoxysilane, 3-glycidoxypropyl triethoxysilane, 3-glycidoxypropyl methyldimethoxysilane, 3-glycidoxypropyl methyldiethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltriethoxysilane.
The methacryloxyalkylsilane is one of the following: methacryloxypropyl trimethoxysilane, methacryloxypropyl triethoxysilane, methacryloxypropyl methyldimethoxysilane, methacryloxypropyl methyldiethoxysilane, methacryloxymethyl trimethoxysilane, methacryloxymethyl triethoxysilane, methacryloxymethyl methyldimethoxysilane, methacryloxymethyl methyldiethoxysilane.
The alkylsilane is one of the following: methyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, propylmethyldimethoxysilane, propylmethyldiethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, n-octylmethyldimethoxysilane, n-octylmethyldiethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane, isobutyltrimethoxysilane, isobutylmethyldimethoxysilane, isobutylmethyldiethoxysilane.
The orthosilicate silane is methyl orthosilicate or ethyl orthosilicate.
The vinyl silane is vinyl trimethoxy silane or vinyl triethoxy silane.
The allyl silane is allyl trimethoxy silane or allyl triethoxy silane.
The acryloxypropyl silane is acryloxypropyl trimethoxysilane or acryloxypropyl triethoxysilane.
The mercaptopropyl silane is one of the following: mercaptopropyl trimethoxysilane, mercaptopropyl triethoxysilane, mercaptopropyl methyl dimethoxy silane, or mercaptopropyl methyl diethoxy silane.
The ureidopropylsilane is ureidopropyltrimethoxysilane or ureidopropyltriethoxysilane.
The beneficial effects of the invention are as follows:
1. the water-based system silane copolymer is designed into a molecular structure, and enough different types of active reactive groups are constructed in the molecular structure, wherein the water-based system silane copolymer is endowed with good compatibility with water based on amino groups, so that the water-based system silane copolymer can be effectively used in a water-based system;
2. the invention can carry out customized synthesis of the silane copolymer according to the use condition, and various excellent performances of the silane copolymer are endowed by introducing different types of silane. For example, designing alkyl groups in the molecular chain to provide hydrophobicity, designing mercapto groups in the molecular chain further enhances adhesion to metals; reactive groups such as epoxy groups, vinyl groups, methacryloxy groups and the like are designed in a molecular chain to provide compatibility and reactivity with a polymer;
3. the silane copolymer of the invention has higher effective components in the same unit volume and generates less hydrolytic alcohol when in action compared with silane monomers;
4. the silane copolymer disclosed by the invention has the advantages of simple synthesis process, convenience in industrialization, low VOC, environment friendliness, good water solubility, long-time stable existence in an aqueous system, good storage stability and the like.
Detailed Description
In order to describe the technical content, constructional features, achieved objects and effects of the technical solution in detail, the following description is made in detail with reference to specific embodiments.
In the invention, the prepared silane oligomer is subjected to detection of the solid content of the silane copolymer. The specific detection method comprises the following steps:
1. weighing about 10g (m) (about 0.001 g) of sample into a constant weight empty crucible, and weighing m 1 (weighing to 0.001 g), and performing two parallel tests;
2. slowly and uniformly dripping 1mL of distilled water and 1mL of concentrated sulfuric acid into a sample in sequence in a fume hood;
3. shaking uniformly, standing in air until the liquid in the crucible becomes gel;
4. placing the crucible in a muffle furnace, heating the muffle furnace to 100 ℃, heating for 1h, heating to 750 ℃ and continuing heating and ashing for 3h;
5. closing the muffle furnace to cool, taking out after 1h, putting into a dryer to cool to room temperature, and weighing m 2 。
6. Calculating the solid content X of the sample according to the formula III:
the free methanol, ethanol or other solvent content was determined by GC.
Example 1:
a magnetic rotor was placed in a 1L three-necked flask, and a thermometer, a condenser tube, a constant pressure dropping funnel and a magnetic stirring and heating device were attached. 221g (1 mol) of aminopropyl triethoxysilane, 177g of ethanol and the porous silica gel supported tetra-trimethylsilicon titanate catalyst are sequentially added into a three-neck flask and uniformly mixed; then, 13.5g (0.75 mol) of ultrapure water and 72g of ethanol are taken and mixed and added into a constant pressure dropping funnel to start the dropping reaction, the reaction temperature is controlled between 42 ℃ and 47 ℃, the dropping time is 1.5h, and the heat preservation and stirring are continued for 5h after the dropping is finished. Then detecting 358ppm of water in the kettle liquid, filtering out the solid catalyst, and distilling under reduced pressure to remove ethanol to obtain the silane oligomer with the polymerization degree of four. The solid content of the silane copolymer is detected: 36.30%, residual ethanol: 1.2%.
Example 2:
a magnetic rotor was placed in a 1L three-necked flask, and a thermometer, a condenser tube, a constant pressure dropping funnel and a magnetic stirring and heating device were attached. 165.75g (0.75 mol) of aminopropyl triethoxysilane, 62g (0.25 mol) of methacryloxypropyl trimethoxysilane, 230g of ethanol and a silica gel supported tetra-trimethylsilicon titanate catalyst are sequentially added into a three-neck flask and uniformly mixed; then, 13.5g (0.75 mol) of ultrapure water and 72g of ethanol are taken and mixed and added into a constant pressure dropping funnel to start the dropping reaction, the reaction temperature is controlled between 55 ℃ and 60 ℃, the dropping time is 1.5h, and the heat preservation and stirring are continued for 2h after the dropping is finished. Then detecting 522ppm of water in the kettle liquid, filtering out the solid catalyst, and distilling under reduced pressure to remove methanol and ethanol to obtain the silane copolymer with the polymerization degree of four. The solid content of the silane copolymer is detected: 32.88%, residual methanol: 0.4%, residual ethanol: 1.5%.
Example 3:
a magnetic rotor was placed in a 1L three-necked flask, and a thermometer, a condenser tube, a constant pressure dropping funnel and a magnetic stirring and heating device were attached. 110.5g (0.5 mol) of aminopropyl triethoxysilane, 139g (0.5 mol) of 3-glycidoxypropyl triethoxysilane, 230g of ethanol and a silica gel supported tetra-trimethylsilicon titanate catalyst are sequentially added into a three-neck flask and uniformly mixed; then, 13.5g (0.75 mol) of ultrapure water and 72g of ethanol are taken and mixed and added into a constant pressure dropping funnel to start the dropping reaction, the reaction temperature is controlled between 50 ℃ and 55 ℃, the dropping time is 1.5h, and the heat preservation and stirring are continued for 3.5h after the dropping is finished. Then detecting that the water content of the kettle liquid is 367ppm, filtering out the solid catalyst, and distilling under reduced pressure to remove ethanol to obtain the silane copolymer with the polymerization degree of four. The solid content of the silane copolymer is detected: 31.94%, residual ethanol: 1.0%.
Example 4:
a magnetic rotor was placed in a 1L three-necked flask, and a thermometer, a condenser tube, a constant pressure dropping funnel and a magnetic stirring and heating device were attached. 88.4g (0.4 mol) of aminopropyl triethoxysilane, 94.4g (0.4 mol) of 3-glycidoxypropyl triethoxysilane, 49.6g (0.2 mol) of methacryloxypropyl trimethoxysilane, 230g of ethanol and a silica gel supported tetra-trimethyl silicon titanate catalyst are sequentially added into a three-neck flask and uniformly mixed; then, 13.5g (0.75 mol) of ultrapure water and 72g of ethanol are taken and mixed and added into a constant pressure dropping funnel to start the dropping reaction, the reaction temperature is controlled between 42 ℃ and 46 ℃, the dropping time is 1.5h, and the heat preservation and stirring are continued for 5h after the dropping is finished. Then detecting that the water content of the kettle liquid is 428ppm, filtering out the solid catalyst, and distilling under reduced pressure to remove methanol and ethanol to obtain the silane copolymer with the polymerization degree of four. The solid content of the silane copolymer is detected: 32.25%, residual methanol: 0.5%, residual ethanol: 0.6%.
Example 5:
a magnetic rotor was placed in a 1L three-necked flask, and a thermometer, a condenser tube, a constant pressure dropping funnel and a magnetic stirring and heating device were attached. 76.4g (0.4 mol) of aminopropyl methyl diethoxy silane, 94.4g (0.4 mol) of 3-glycidoxypropyl triethoxy silane, 32.8g (0.2 mol) of propyl trimethoxy silane, 244g of ethanol and a silica gel supported dodecylbenzenesulfonic acid catalyst are sequentially added into a three-neck flask and uniformly mixed; then, 13.5g (0.75 mol) of ultrapure water and 72g of ethanol are taken and mixed and added into a constant pressure dropping funnel to start the dropping reaction, the reaction temperature is controlled between 55 ℃ and 60 ℃, the dropping time is 1.5h, and the heat preservation and stirring are continued for 2h after the dropping is finished. Then detecting that the water content of the kettle liquid is 395ppm, filtering out the solid catalyst, and distilling under reduced pressure to remove methanol and ethanol to obtain the silane copolymer with the polymerization degree of four. The solid content of the silane copolymer is detected: 35.40%, residual methanol: 0.3%, residual ethanol: 0.8%.
Example 6:
a magnetic rotor was placed in a 1L three-necked flask, and a thermometer, a condenser tube, a constant pressure dropping funnel and a magnetic stirring and heating device were attached. 76.4g (0.4 mol) of aminopropyl methyl diethoxy silane, 94.4g (0.4 mol) of 3-glycidoxypropyl triethoxy silane, 56.8g (0.2 mol) of octyl trimethoxy silane, 230g of acetone and a fumed silica supported tetra-trimethyl silicon titanate catalyst are sequentially added into a three-neck flask and uniformly mixed; then, 13.5g (0.75 mol) of ultrapure water and 72g of acetone are taken and mixed and added into a constant pressure dropping funnel to start the dropping reaction, the reaction temperature is controlled between 55 ℃ and 60 ℃, the dropping time is 1.5h, and the heat preservation and stirring are continued for 2h after the dropping is finished. Then detecting that the water content of the kettle liquid is 524ppm, filtering out the solid catalyst, and distilling under reduced pressure to remove methanol, ethanol and acetone to obtain the silane copolymer with the polymerization degree of four. The solid content of the silane copolymer is detected: 32.12%, residual methanol: 0.2%, residual ethanol: 0.4%, residual acetone: 0.3%.
Example 7:
a magnetic rotor was placed in a 1L three-necked flask, and a thermometer, a condenser tube, a constant pressure dropping funnel and a magnetic stirring and heating device were attached. 76.4g (0.4 mol) of aminopropyl methyl diethoxy silane, 88g (0.4 mol) of 3-glycidoxypropyl methyl dimethoxy silane, 30.4g (0.2 mol) of methyl orthosilicate, 226g of tetrahydrofuran and a porous ceramic supported trimethylsilyl phosphate catalyst are sequentially added into a three-necked flask and uniformly mixed; then, 13.5g (0.75 mol) of ultrapure water and 72g of tetrahydrofuran are taken and mixed, and then added into a constant pressure dropping funnel to start the dropping reaction, the reaction temperature is controlled between 55 ℃ and 60 ℃, the dropping time is 1.5h, and the heat preservation and stirring are continued for 2h after the dropping is finished. Then detecting that the water content of the kettle liquid is 304ppm, filtering out the solid catalyst, and distilling under reduced pressure to remove methanol, ethanol and tetrahydrofuran to obtain the silane copolymer with the polymerization degree of four. The solid content of the silane copolymer is detected: 36.14%, residual methanol: 0.3%, residual ethanol: 0.3%, residual tetrahydrofuran: 0.4%.
Example 8:
a magnetic rotor was placed in a 1L three-necked flask, and a thermometer, a condenser tube, a constant pressure dropping funnel and a magnetic stirring and heating device were attached. 88.8g (0.4 mol) of 2-aminoethyl-3-aminopropyl trimethoxysilane, 88g (0.4 mol) of 3-glycidoxypropyl methyl dimethoxy silane, 30.4g (0.2 mol) of methyl orthosilicate, 230g of methanol and a fumed silica supported tetra-trimethyl silicon titanate catalyst are sequentially added into a three-neck flask and uniformly mixed; then, 13.5g (0.75 mol) of ultrapure water and 72g of methanol are taken and mixed and added into a constant pressure dropping funnel to start the dropping reaction, the reaction temperature is controlled between 55 ℃ and 60 ℃, the dropping time is 1.5h, and the heat preservation and stirring are continued for 2h after the dropping is finished. Then the water content of the kettle liquid is 284ppm, the solid catalyst is filtered off, and the methanol is removed by reduced pressure distillation, so as to obtain the silane copolymer with the polymerization degree of four. The solid content of the silane copolymer is detected: 33.95%, residual methanol: 0.9%.
Example 9:
a magnetic rotor was placed in a 1L three-necked flask, and a thermometer, a condenser tube, a constant pressure dropping funnel and a magnetic stirring and heating device were attached. 158.4g (0.6 mol) of 2-aminoethyl-3-aminopropyl triethoxysilane, 49.6g (0.2 mol) of methacryloxypropyl trimethoxysilane, 32.8g (0.2 mol) of propyl trimethoxysilane, 230g of ethanol and a clay supported tetra-trimethylsilyl titanate catalyst are sequentially added into a three-neck flask and uniformly mixed; then, 13.5g (0.75 mol) of ultrapure water and 72g of ethanol are taken and mixed and added into a constant pressure dropping funnel to start the dropping reaction, the reaction temperature is controlled between 55 ℃ and 60 ℃, the dropping time is 1.5h, and the heat preservation and stirring are continued for 2h after the dropping is finished. Then detecting that the water content of the kettle liquid is 524ppm, filtering out the solid catalyst, and distilling under reduced pressure to remove the methanol and the ethanol to obtain the silane copolymer with the polymerization degree of four. The solid content of the silane copolymer is detected: 33.54%, residual methanol: 0.5%, residual ethanol: 0.6%.
Example 10:
a magnetic rotor was placed in a 1L three-necked flask, and a thermometer, a condenser tube, a constant pressure dropping funnel and a magnetic stirring and heating device were attached. 158.4g (0.6 mol) of 2-aminoethyl-3-aminopropyl triethoxysilane, 44.2g (0.2 mol) of vinyl triethoxysilane, 46.8g (0.2 mol) of octyl trimethoxysilane, 240g of ethanol and a styrene type spherical exchange resin supported tetra-trimethyl silicon titanate catalyst are sequentially added into a three-neck flask and uniformly mixed; then, 13.5g (0.75 mol) of ultrapure water and 72g of ethanol are taken and mixed and added into a constant pressure dropping funnel to start the dropping reaction, the reaction temperature is controlled between 42 ℃ and 60 ℃, the dropping time is 1.5h, and the heat preservation and stirring are continued for 2h after the dropping is finished. Then detecting that the water content of the kettle liquid is 585ppm, filtering out the solid catalyst, and distilling under reduced pressure to remove methanol and ethanol to obtain the silane copolymer with the polymerization degree of four. The solid content of the silane copolymer is detected: 31.26%, residual methanol: 0.2%, residual ethanol: 0.7%.
Example 11:
a magnetic rotor was placed in a 1L three-necked flask, and a thermometer, a condenser tube, a constant pressure dropping funnel and a magnetic stirring and heating device were attached. 158.4g (0.6 mol) of 2-aminoethyl-3-aminopropyl triethoxysilane, 46.8g (0.2 mol) of acryloxypropyl trimethoxysilane, 39.2g (0.2 mol) of mercaptopropyl trimethoxysilane, 240g of ethanol and the fumed silica supported tetra-trimethylsilyl titanate catalyst are sequentially added into a three-neck flask and uniformly mixed; then, 13.5g (0.75 mol) of ultrapure water and 72g of ethanol are taken and mixed and added into a constant pressure dropping funnel to start the dropping reaction, the reaction temperature is controlled between 45 ℃ and 50 ℃, the dropping time is 1.5h, and the heat preservation and stirring are continued for 4.5h after the dropping is finished. Then detecting that the water content of the kettle liquid is 526ppm, filtering out the solid catalyst, and distilling under reduced pressure to remove methanol and ethanol to obtain the silane copolymer with the polymerization degree of four. The solid content of the silane copolymer is detected: 32.31%, residual methanol: 0.3%, residual ethanol: 0.4%.
Example 12:
a magnetic rotor was placed in a 1L three-necked flask, and a thermometer, a condenser tube, a constant pressure dropping funnel and a magnetic stirring and heating device were attached. 123.6g (0.6 mol) of 2-aminoethyl-3-aminopropyl methyl dimethoxy silane, 46.4g (0.2 mol) of methacryloxypropyl methyl dimethoxy silane, 44.4g (0.2 mol) of urea propyl trimethoxy silane, 240g of methanol and a silica gel supported trifluoro propyl sulfonic acid catalyst are sequentially added into a three-neck flask and uniformly mixed; then, 13.5g (0.75 mol) of ultrapure water and 72g of methanol are taken and mixed and added into a constant pressure dropping funnel to start the dropping reaction, the reaction temperature is controlled between 42 ℃ and 46 ℃, the dropping time is 1.5h, and the heat preservation and stirring are continued for 5h after the dropping is finished. Then detecting that the water content of the kettle liquid is 592ppm, filtering out the solid catalyst, and distilling under reduced pressure to remove methanol to obtain the silane copolymer with the polymerization degree of four. The solid content of the silane copolymer is detected: 32.15%, residual methanol: 0.8%.
Example 13:
a magnetic rotor was placed in a 1L three-necked flask, and a thermometer, a condenser tube, a constant pressure dropping funnel and a magnetic stirring and heating device were attached. 158.4g (0.6 mol) of 2-aminoethyl-3-aminopropyl triethoxysilane, 39.6g (0.2 mol) of allyl triethoxysilane, 46.8g (0.2 mol) of octyl trimethoxysilane, 240g of ethanol and a silica gel supported dodecylbenzenesulfonic acid catalyst are sequentially added into a three-neck flask and uniformly mixed; then, 13.5g (0.75 mol) of ultrapure water and 72g of ethanol are taken and mixed and added into a constant pressure dropping funnel to start the dropping reaction, the reaction temperature is controlled between 42 ℃ and 46 ℃, the dropping time is 1.5h, and the heat preservation and stirring are continued for 5h after the dropping is finished. Then detecting that the water content of the kettle liquid is 425ppm, filtering out the solid catalyst, and distilling under reduced pressure to remove methanol and ethanol to obtain the silane copolymer with the polymerization degree of four. The solid content of the silane copolymer is detected: 31.84%, residual methanol: 0.3%, residual ethanol: 0.9%.
Example 14:
a magnetic rotor was placed in a 1L three-necked flask, and a thermometer, a condenser tube, a constant pressure dropping funnel and a magnetic stirring and heating device were attached. 158.4g (0.6 mol) of 2-aminoethyl-3-aminopropyl triethoxysilane, 47.2g (0.2 mol) of glycidoxypropyl trimethoxysilane, 39.2g (0.2 mol) of mercaptopropyl trimethoxysilane, 240g of ethanol and the porous ceramic supported trimethylsilyl phosphate catalyst are sequentially added into a three-neck flask and uniformly mixed; then, 13.5g (0.75 mol) of ultrapure water and 94.5g of ethanol are taken and mixed, and then added into a constant pressure dropping funnel to start the dropping reaction, the reaction temperature is controlled between 55 ℃ and 60 ℃, the dropping time is 1.5h, and the heat preservation and stirring are continued for 2h after the dropping is finished. Then detecting that the water content of the kettle liquid is 374ppm, filtering out the solid catalyst, and distilling under reduced pressure to remove methanol and ethanol to obtain the silane copolymer with the polymerization degree of four. The solid content of the silane copolymer is detected: 32.12%, residual methanol: 0.2%, residual ethanol: 0.5%.
Example 15:
a magnetic rotor was placed in a 1L three-necked flask, and a thermometer, a condenser tube, a constant pressure dropping funnel and a magnetic stirring and heating device were attached. 123.6g (0.6 mol) of 2-aminoethyl-3-aminopropyl methyl dimethoxy silane, 47.2g (0.2 mol) of glycidoxypropyl trimethoxy silane, 44.4g (0.2 mol) of urea propyl trimethoxy silane, 240g of methanol and the porous ceramic supported trimethylsilyl phosphoric acid catalyst are sequentially added into a three-neck flask and uniformly mixed; then, 13.5g (0.75 mol) of ultrapure water and 40.5g of methanol are taken and mixed, and then added into a constant pressure dropping funnel to start the dropping reaction, the reaction temperature is controlled between 55 ℃ and 60 ℃, the dropping time is 1.5h, and the stirring is continued for 2h after the dropping is finished. Then detecting that the water content of the kettle liquid is 428ppm, filtering out the solid catalyst, and distilling under reduced pressure to remove methanol to obtain the silane copolymer with the polymerization degree of four. The solid content of the silane copolymer is detected: 32.05%, residual methanol: 0.9%.
Example 16:
the corresponding styrene-acrylic emulsion was prepared from the silane copolymer synthesized in example 1 according to the following formulation of table 1 and the following preparation method, and then subjected to the relevant performance test.
The synthesis method of the styrene-acrylic emulsion comprises the following steps:
step 1, adding a kettle bottom material: sequentially adding deionized water, an emulsifier SR-10 and sodium bicarbonate serving as the raw materials of the kettle bottom material into a four-necked flask, heating to 80 ℃, and stirring and mixing uniformly.
Step 2, pre-emulsification: 120g of deionized water is firstly added into a pre-emulsifying kettle, an emulsifier SR-10 is added under the stirring of 1000rpm, after 10 min of dispersion, monomers of methyl methacrylate, acrylic acid, butyl acrylate, styrene and isooctyl acrylate are sequentially added, and the pre-emulsifying liquid is obtained after 15 min of dispersion.
Step 3, dropwise adding a pre-emulsion: and (3) dripping the pre-emulsified liquid obtained in the step (2) into the reaction kettle in the step (1) at 83-85 ℃, and adding the silane copolymer prepared in the example (1) into the reaction kettle when 50% of the pre-emulsified liquid is dripped, wherein the total dripping time is about 3 hours.
And 4, post-treatment: an initiator (t-butyl hydroperoxide) was added to complete the reaction of the unpolymerized monomer. Then cooling to 70 ℃, preserving heat for 2 hours, cooling to about 40 ℃, dropwise adding ammonia water, and regulating the pH to 7 to obtain the styrene-acrylic emulsion.
Mixing paint and preparing film from the prepared emulsion: and (3) adding a film forming auxiliary agent (dodecyl ester) (the mass of the added film forming auxiliary agent is 2% of the mass of the emulsion) into the emulsion obtained in the step (4) for paint mixing and film forming.
Examples 17 to 30
The corresponding styrene-acrylic emulsion and paint film were prepared by the preparation method of the formulation of Table 1 and the preparation method of example 16 in sequence using the silane copolymer synthesized in examples 2-15, the styrene-acrylic emulsion of example 17 was prepared by the silane copolymer of example 2, and so on.
The raw material dosage of each step is shown in the following table 1.
TABLE 1 raw material dosage for each step of emulsion Synthesis
The styrene-acrylic emulsions prepared in examples 16 to 30 were subjected to the following examination, and the examination data are shown in Table 2.
Thermal storage stability: aging a certain amount of styrene-acrylic emulsion at 50 ℃, and observing whether demulsification and hardening precipitation exist or not;
solid content: solid content detection was performed according to GB/T1725-2007, a clean evaporation dish was taken and weighed to m 1 The method comprises the steps of carrying out a first treatment on the surface of the Adding a certain amount of styrene-acrylic emulsion, weighing to m 2 The method comprises the steps of carrying out a first treatment on the surface of the Baking in oven at 120deg.C for more than 4 hr to constant weight, weighing to m 3 The method comprises the steps of carrying out a first treatment on the surface of the Calculating the solid content of the emulsion according to a formula IV;
solid content/% = [ (m) 3 -m 1 )/(m 2 -m 1 )]×100％Ⅳ
And (3) paint film preparation: and (3) taking a clean glass sheet, dripping a certain amount of styrene-acrylic emulsion into the center of the pretreated glass sheet, and rapidly and uniformly brushing the glass sheet along the same direction by using a special film-making rod to form a uniform paint film without allowing blank or overflow phenomenon. Placing the painted sample in a dust-free cabinet for natural drying, and sticking a label for preservation for later use;
resistance to organic solvents: placing a glass sheet coated with a paint film into a small beaker with ethyl acetate at normal temperature for soaking, and taking out the glass sheet after 24 hours to observe the change condition of the paint film;
water resistance: according to GB/T1733-1993, carrying out paint film water resistance test, taking a glass sheet coated with a paint film, placing the glass sheet in a small beaker with distilled water at 25 ℃ for soaking, taking out the glass sheet after 24 hours, and observing whether the paint film has phenomena of color change, bubbling, falling and the like;
adhesion force: paint film adhesion test is carried out according to GB/T9286-1998, and a hundred lattices are drawn by using a cutter from a glass sheet coated with a paint film; and then bonding and tearing off by using an adhesive tape, and observing the falling-off condition of a paint film.
Table 2: detection data in the styrene-acrylic emulsions prepared in examples 16 to 30
TABLE 3 styrene-acrylic emulsion and paint film detection Performance criteria
As is clear from Table 2, after the silane copolymer for an aqueous system was added in the course of producing a styrene-acrylic emulsion, the storage stability, the solid content, the solvent resistance, the water resistance, the adhesion and the like of the paint film were excellent.
As can be seen by combining the styrene-acrylic emulsion and the film detection performance standards in tables 2 and 3, the appearance, the thermal storage stability and the nonvolatile matter content of the styrene-acrylic emulsion prepared by the invention all meet the national standard requirements, and the styrene-acrylic emulsion is a qualified product; meanwhile, the appearance, water resistance, adhesive force and drying time of the prepared paint film meet the national standard, and the paint film is a qualified product.
It is noted that relational terms such as first and second, and the like are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Moreover, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or terminal that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or terminal. Without further limitation, an element defined by the statement "comprising … …" or "comprising … …" does not exclude the presence of additional elements in a process, method, article or terminal device comprising the element. Further, herein, "greater than," "less than," "exceeding," and the like are understood to not include the present number; "above", "below", "within" and the like are understood to include this number.
It should be noted that, although the foregoing embodiments have been described herein, the scope of the present invention is not limited thereby. Therefore, changes and modifications made to the embodiments described herein, or equivalent structures or equivalent flow transformations by employing the principles of the present invention, based on the innovative concepts of the present invention, will be apparent to those skilled in the art and may be practiced, directly or indirectly, in other relevant fields.

Claims (9)

1. A silane copolymer for use in an aqueous system, characterized by: the structural formula is shown as formula I: (R) 1 O)[(R 1 O) 1-x (R 2 ) x Si(A)O] a [Si(B)(R 3 ) y (OR 4 ) 1-y O] b [Si(C)(R 5 ) z (OR 6 ) 1-z O] c R 7 A formula I;
in the formula I, A is aminoalkyl, B, C is one of glycidoxyalkyl, methacryloxyalkyl, alkyl, alkoxy, vinyl, acryloxypropyl, allyl, mercaptopropyl and ureidopropyl respectively; b and C are different groups; a is more than or equal to 1, b is more than 0, and c is more than 0; r is R 1 、R 4 、R 6 、R 7 Respectively any one of methyl and propyl; r is R 2 、R 3 、R 5 Methyl, x, y, z are 0 or 1 respectively; the aminoalkyl is aminopropyl or aminoethylaminopropyl; the glycidoxyalkyl is glycidoxypropyl or epoxycyclohexylethyl; the methacryloxyalkyl is methacryloxypropyl or methacryloxymethyl; the alkyl is one of methyl, ethyl, propyl, n-octyl, cyclohexyl and isobutyl; the alkoxy is methoxy or ethoxy;
in the formula I, the values of a, b and c are more than or equal to 2 and less than or equal to 10.
2. The method for producing a silane copolymer for aqueous system according to claim 1, wherein: which comprises the following steps:
1) Adding two of aminoalkylsilane A, aminoalkylsilane B, glycidoxyalkylsilane, methacryloxyalkylsilane, alkylsilane, orthosilicate silane, vinylsilane, acryloxypropylsilane, allylsilane, mercaptopropylsilane and ureidopropylsilane into a reactor, adding a solvent A and a supported catalyst, and stirring uniformly at room temperature to obtain a silane reaction solution;
2) Adding ultrapure water into the other part of solvent A, uniformly mixing to obtain a mixed solution, and slowly dripping the mixed solution into the silane reaction solution obtained in the step 1) at 42-60 ℃; after the dripping is finished, continuing to perform heat preservation reaction for 2-5 hours, and completely performing reaction when the moisture content in the detection system is less than 2000 ppm;
3) Distilling to remove the solvent A in the reaction liquid obtained in the step 2), and filtering to remove the solid catalyst to obtain the silane copolymer for the aqueous system.
3. The method for producing a silane copolymer for aqueous system according to claim 2, characterized in that: the molecular formulas of the aminoalkylsilane A, the aminoalkylsilane B, the glycidoxyalkylsilane, the methacryloxyalkylsilane, the alkylsilane, the orthosilicate silane, the vinylsilane, the acryloxypropylsilane, the allylsilane, the mercaptopropylsilane and the ureidopropylsilane are shown in the formula II:
Y-Si(R 8 ) n (OR 9 ) (3-n) I I
when the formula of formula II represents aminoalkylsilane a or aminoalkylsilane B, Y is one of the following: aminopropyl, aminoethylaminopropyl; r is R 8 Is methyl; r is R 9 Methyl or ethyl; n is an integer of 0 or 1; the aminoalkylsilane A and the aminoalkylsilane B are the same or different;
when formula II represents glycidoxyalkylsilane, Y is glycidoxypropyl or epoxycyclohexylethyl; r is R 8 Is methyl; r is R 9 Methyl or ethyl; n is an integer of 0 or 1;
when formula II represents methacryloxyalkylsilane, Y is methacryloxypropyl or methacryloxymethyl; r is R 8 Is methyl; r is R 9 Methyl or ethyl; n is an integer of 0 or 1;
when formula II represents an alkylsilane, Y is one of the following: methyl, ethyl, propyl, n-octyl, cyclohexyl, isobutyl; r is R 8 Is methyl; r is R 9 Methyl or ethyl; n is an integer of 0 or 1;
when formula II represents an orthosilicate based silane, Y is methoxy or ethoxy, R 8 Is methyl; r is R 9 Methyl or ethyl, n is an integer of 0 or 1;
when formula II represents a vinylsilane, Y is vinyl, R 8 Is methyl; r is R 9 Methyl or ethyl, n is an integer of 0 or 1;
when formula II represents acryloxypropyl silane, Y is acryloxypropyl, R 8 Is methyl; r is R 9 Methyl or ethyl, n is an integer of 0 or 1;
when the formula II represents allylsilane, Y is allyl, R 8 Is methyl; r is R 9 Methyl or ethyl, n is an integer of 0 or 1;
when formula II represents mercaptopropyl silane, Y is mercaptopropyl, R 8 Is methyl; r is R 9 Methyl or ethyl, n is an integer of 0 or 1;
when formula II represents a ureidopropyl silane, Y is ureidopropyl, R 8 Is methyl; r is R 9 Methyl or ethyl, n is an integer of 0 or 1.
4. The method for producing a silane copolymer for aqueous system according to claim 2, characterized in that: the solvent A is one or a mixture of more than two of the following: methanol, ethanol, propanol, tetrahydrofuran, acetone, butanone.
5. The process for preparing a silane copolymer for aqueous systems according to claim 4, wherein: the solvent A is isopropanol.
6. The method for producing a silane copolymer for aqueous system according to claim 2, characterized in that: the mass ratio of the total mass of each silane added in the step 1 to the solvent A is 1:0.8 to 1.2.
7. The method for producing a silane copolymer for aqueous system according to claim 2, characterized in that: the carrier used for the supported catalyst is one or a mixture of more than two of the following: clay, styrene-type spherical exchange resins, porous silica gel, precipitated or fumed silica, porous alumina, aluminum silicate or porous ceramics.
8. The method for producing a silane copolymer for aqueous system according to claim 2, characterized in that: the catalyst is an acidic catalyst, and the acidic catalyst is one of the following components: titanate type, sulfuric acid type, phosphoric acid type or sulfonate type.
9. The method for producing a silane copolymer for aqueous system according to claim 2, characterized in that: in the step 2), the mass ratio of the ultrapure water to the other part of solvent A is 1:3-7.
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