CN110760073B - Preparation method of porous micro-nano silicon sphere grafted multi-reactive organic silicon water repellent - Google Patents
Preparation method of porous micro-nano silicon sphere grafted multi-reactive organic silicon water repellent Download PDFInfo
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Abstract
The invention relates to a preparation method of a porous micro-nano silicon sphere grafted multi-reactive organosilicon water repellent agent. The method comprises the following steps: (1) preparing porous micro-nano silicon spheres; (2) preparation of a multi-reactive organosilicon water repellent intermediate: (3) preparing a porous micro-nano silicon sphere grafted multi-reactive organosilicon water repellent agent: and (3) carrying out water-adding catalytic coupling on the porous micro-nano silicon spheres and the reactive organosilicon water repellent agent intermediate by using a reactive coupling agent to prepare the multi-reactive organosilicon water repellent agent grafted by the porous micro-nano silicon spheres. The porous micro-nano silicon sphere grafted multi-reactivity organosilicon water repellent agent provided by the invention grafts micro-nano porous silicon microspheres on a polysiloxane water repellent structure, so that a low-tension surface layer with certain roughness is favorably established on the surface of smooth textile fibers, the textile fibers are endowed with excellent water repellent effect and good durability through dual physical and chemical effects, the application process is simple, and the process flow is short.
Description
Technical Field
The invention relates to a fluorine-free water-repellent antifouling finishing agent for various textile products, and particularly relates to a preparation method of a porous micro-nano silicon sphere grafted multi-reactive organosilicon water repellent agent.
Background
In the textile field, water-proof, oil-proof and dirt-proof (three-proof) finishing agents are commonly used for special function finishing of various textile products, and the most commonly adopted in three-proof finishing processing of the textile products is a side chain fluorine-containing water-repellent and oil-repellent finishing agent based on an acrylate skeleton. Although such water-and oil-repellent finishing agents have excellent three-proofing effects, the organic fluorine monomers contained therein are considered to be environmentally unfriendly and are therefore being gradually replaced by various fluorine-free water-repellent agents. At present, the fluoride-free water repellent agent which is successfully applied in the textile field mainly comprises polyurethane based on a long-chain alkyl water repellent structure, polysiloxane based on a silane chain segment water repellent structure, nano-hybrid water repellent polymer and the like. These water repellent polymers are generally prepared by introducing various chemical (or physical) water repellent structural units into the backbone or lateral position of the polymer by chemical modification methods such as block, graft, end-capping, sol-gel, etc., and emulsifying and dispersing.
The preparation method of the common fluoride-free water repellent finishing agent and the product thereof mainly comprise the following steps:
1. chemically modified cationic silicone emulsion comprising the raw materials of polymerized monomers, modifier, adjuvant and water, wherein: the polymerized monomer is organosilicon ring body; the modifier is silane coupling agent and alkyl silicate; the auxiliary agent is catalyst, emulsifier, etc.
For example, the preparation and application of polysiloxane organosilicon water repellent (14 th volume of 2018, Guangdong chemical industry) disclosed by Litianlong, Qianyou, Sun Yifeng, etc. the preparation method of modified organosilicon water repellent uses potassium hydroxide as catalyst, octamethylcyclotetrasiloxane as polymerization monomer, and mixed hydrolysate of tetraethyl orthosilicate and 3-aminopropyltriethoxysilane as modifier, and adopts starvation semi-continuous seed emulsion polymerization to prepare the compound organosilicon water repellent.
The preparation method of the cationic long-chain alkyl polysiloxane emulsion fabric waterproof agent disclosed by 'preparation and application of the cationic organosilicon emulsion waterproof agent' by picrocrystal, Anqifeng, king pigeons and the like (11 th of 2018) comprises the steps of taking octamethylcyclotetrasiloxane as a polymerization monomer, taking long-chain alkyl trimethoxy silane and methyl triethoxy silane as modifiers, and carrying out emulsion polymerization reaction under the action of a catalyst and potassium hydroxide to prepare the long-chain alkyl polysiloxane waterproof agent.
The research shows that: the contact angle of the cotton fabric treated by the water repellent agent and water can reach 105-140 degrees, and the fabric treated by the water repellent agent has soft hand feeling. However, the water repellent agent is actually an (amino) organosilicon softening agent which is subjected to certain crosslinking by a hydrolytic silane coupling agent and (or) tetraethyl orthosilicate, or is assisted by a long-chain alkyl side chain water repellent function, and the water repellent effect is limited. Meanwhile, the cationic emulsion polymerization process also causes poor emulsion stability and influences use. In addition, the water repellency principle only depends on a chemical structure with low surface tension, and the water repellency effect is not improved by constructing a rough physical surface. Finally, such water repellents lack chemical activity, are weak in binding ability with textiles, and do not last well.
2. The modified organosilicon wax emulsion based on nanometer silicon oxide pretreatment comprises the following raw materials of polymerized monomers, a modifier, an auxiliary agent and water, wherein: the polymerized monomer is active organosilicon monomer and double bond monomer; the modifier is nano silica sol; the auxiliary agent is catalyst, emulsifier, etc.
Preparation and application of a nano hybrid organosilicon waterproofing agent (printing and dyeing, 2017, 8 th) disclosed in Wanglai, Anqiufeng, Panjia and the like, and the self-made nano silica sol is used as a cotton fabric modifier; the silicone oil containing hydrogen, hexadecene and allyl glycidyl ether are used as raw materials, polysiloxane containing epoxy groups is prepared under the catalysis of complex platinum, and then aminolysis ring-opening reaction and emulsification are carried out on the polysiloxane and ethylenediamine, so as to prepare the organosilicon water repellent.
The research shows that: the cotton fabric is treated by sequentially adopting the nano silica sol and the water repellent agent emulsion, and the static contact angle of water on the surface of the fabric reaches 142.5 degrees. However, in the scheme, the surface of the cotton fabric needs to be pretreated by the nano silica sol, and the process is relatively complex; in addition, the average particle size of the nano silica sol is only about 90nm, which is obviously insufficient for constructing a rough surface required for water repellency; furthermore, the water repellent lacks chemical activity, and the durability of the finishing effect cannot be ensured.
3. The raw materials of the organosilicon type waterborne polyurethane emulsion based on long-chain alkyl modification comprise a polymerized monomer, a modifier, an auxiliary agent and water, wherein: the polymerization monomer is active polysiloxane, diisocyanate, chain extender, cross linker and the like; the modifier is long-chain alkyl ester; the auxiliary agent is a catalyst or the like.
A preparation method of a lateral long-chain alkyl modified polyurethane emulsion disclosed by 'preparation and performance of stearic acid modified hyperbranched polyester fluorine-free water repellent agent' of beam column, gesha, Yao Weishang and the like (the 'report of composite materials' 2016 (volume 7) 33) comprises the steps of taking terminal hydroxypropyl silicone oil, trimethylolpropane, N-methyldiethanolamine and toluene diisocyanate as polymerization monomers, taking stearic acid terminated hyperbranched polyester as a modifier, and compounding the two to prepare the composite organic silicon type polyurethane water repellent agent.
The research shows that: the water absorption rate of the water repellent adhesive film is only 6-7%, the static water contact angle of the treated fabric is 135.3 degrees, and the water repellent effect reaches 90 minutes. However, this approach requires the use of specially made hyperbranched polyesters, which are expensive and not readily available as raw materials; in addition, the water repellency principle only depends on a chemical structure with lower surface tension, and the water repellency effect is improved by constructing a rough physical surface; finally, such water repellents lack chemical activity and are relatively weak in binding to textiles.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: provides a preparation method of a porous micro-nano silicon sphere grafted multi-reactive organosilicon water repellent agent. According to the invention, the micro-nano porous silicon microspheres are grafted on the polysiloxane water-repellent structure, so that a low-tension surface layer with appropriate roughness is favorably established on the surface of smooth textile fibers, and the textile fibers are endowed with excellent water-repellent effect and good durability through dual physical and chemical effects; after the fabric is treated by the water repellent agent and dried, the porous structure in the silicon microspheres is rich in air, so that the water repellent effect of the water repellent agent can be further enhanced.
The technical scheme adopted by the invention for solving the technical problems is as follows:
the preparation method of the porous micro-nano silicon sphere grafted multi-reactive organosilicon water repellent comprises the following steps:
(1) preparing porous micro-nano silicon spheres: taking alkyl silicate as a base material, carrying out hydrolysis reaction on the alkyl silicate and an alcohol-water solvent under an alkaline condition for a period of time, adding a cross-linking agent, and continuously reacting for a period of time under the alkaline condition to obtain porous micro-nano silicon spheres;
(2) preparation of a multi-reactive organosilicon water repellent intermediate: the first step is as follows: carrying out catalytic hydrosilylation reaction on hydrogen-containing silicone oil and allyl glycidyl ether, namely carrying out hydrosilylation reaction on double bonds on the allyl glycidyl ether and the hydrogen-containing silicone oil, and introducing epoxy groups into side chain positions of the hydrogen-containing silicone oil;
secondly, carrying out epoxy ring-opening addition reaction on the reaction product of the first step and an amino coupling agent, namely, carrying out ring opening on the lateral epoxy group in the reaction product of the first step and carrying out addition reaction on the lateral epoxy group and the amino group on the amino coupling agent, and introducing a siloxy group into the side chain position of the hydrogen-containing silicone oil to obtain a multi-reactive organosilicon water repellent agent intermediate;
(3) preparing a porous micro-nano silicon sphere grafted multi-reactive organosilicon water repellent agent: and (3) carrying out water-adding catalytic coupling on the porous micro-nano silicon spheres and the reactive organosilicon water repellent agent intermediate by using a reactive coupling agent to prepare the multi-reactive organosilicon water repellent agent grafted by the porous micro-nano silicon spheres.
According to the scheme, the water used in the step (1) is soft water, and the soft water has the total hardness of less than 30ppm of CaO (namely 3 degrees);
according to the scheme, the components in the step (1) are as follows in parts by mass: 70-100 parts of alkyl silicate, 500-700 parts of alcohol, 70-100 parts of water and 200-300 parts of cross-linking agent;
according to the scheme, the alkyl silicate in the step (1) is ethyl orthosilicate; the alcohol is one or a mixture of ethanol and isopropanol; the crosslinking agent is boric acid.
According to the scheme, the size of the porous micro-nano silicon spheres is 0.2-3 mu m.
According to the scheme, the alkaline condition of the hydrolysis reaction in the step (1) is that the pH value of an ammonia water adjusting system is 10-12; adding a cross-linking agent to continue reacting under the alkaline condition that a pH regulator is added to adjust the pH of the reaction system to 10-12; the pH regulator is 50 +/-5% sodium hydroxide solution.
According to the scheme, the hydrogen-containing silicone oil in the step (2) is methyl hydrogen-containing silicone oil containing 3-6 mmol/g of hydrogen;
the allyl glycidyl ether is one of acrylic glycidyl ether and methacrylic glycidyl ether;
the amino coupling agent is one of 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, N-aminoethyl-3-aminopropyltrimethoxysilane and N-aminoethyl-3-aminopropyltriethoxysilane;
the catalyst for the hydrosilylation is chloroplatinic acid;
a pH regulator is added in the epoxy group ring-opening addition reaction to regulate the pH value to 6-7, and the pH regulator is acetic acid;
the alcohol is isopropanol;
according to the scheme, the preparation method comprises the following components in parts by mole: 0.15-0.20 part of hydrogen-containing silicone oil (calculated by Si-H), 0.20-0.25 part of allyl glycidyl ether, 0.30-0.40 part of silane coupling agent, 3.0-5.0 parts of alcohol and 0.20-0.30 part of water for coupling in the step (3), wherein the mole number of the allyl glycidyl ether is 1.10-1.25 times of that of Si-H, the silane coupling agent comprises an amino coupling agent and a reactive coupling agent, and the amino coupling agent accounts for 40-60 mol% of the silane coupling agent;
according to the scheme, the dosage of the chloroplatinic acid catalyst in the step (2) is 0.1-0.15 ten thousandth of the total mass of the hydrogen-containing silicone oil and the allyl glycidyl ether.
According to the scheme, the reactive coupling agent in the step (3) is a combination of two of 3- (2, 3-epoxypropoxy) propyl trimethoxy silane, 3-methacryloxypropyl trimethoxy silane and N-aminoethyl-3-aminopropylmethyldimethoxy silane; adding water into the catalytic coupling reaction in the step (3) to obtain pure water, preferably, the pure water is deionized water;
according to the scheme, the preparation steps of the porous micro-nano silicon spheres in the step (1) are as follows:
(1.1) adding 10-20% of alcohol, soft water and ammonia water into a reactor at the temperature of 20-35 ℃, wherein the ammonia water is used for adjusting the pH of the system to 10-12, and adding alkyl silicate after uniformly stirring; keeping the reaction temperature unchanged, stirring and reacting for 180-300 min;
(1.2) adding the residual alcohol into the reaction system in the step (1.1), keeping the temperature unchanged, stirring and reacting for 100-150 min;
(1.3) adding a cross-linking agent and a 50 +/-5% sodium hydroxide aqueous solution, adjusting the pH of the system to 10-12, controlling the reaction temperature to be 75-85 ℃, and maintaining stirring and reacting for 100-150 min;
and (1.4) filtering the reaction liquid in the step (1.3), fully washing filter residues, naturally airing and grinding to obtain the micro-nano porous micro-nano silicon spheres for later use.
According to the scheme, the preparation steps of the multi-reactive organosilicon water repellent intermediate in the step (2) are as follows:
(2.1) putting hydrogen-containing silicone oil, allyl glycidyl ether and a catalyst chloroplatinic acid into a reactor, stirring, controlling the reaction temperature to be 75-85 ℃, and carrying out heat preservation reaction for 350-500 min; thereafter, excess allyl glycidyl ether was distilled off under reduced pressure;
(2.2) cooling the reaction system in the step (2.1) to 30-40 ℃, adding alcohol into the reaction system, keeping the temperature unchanged, dropwise adding an amino coupling agent into the reaction system within 10-20 min while stirring, and then carrying out heat preservation reaction for 20-40 min;
and (2.3) keeping the reaction temperature at 30-40 ℃, adding a pH regulator into the reaction system in the step (2.2), regulating the pH to 6-7, and continuing to perform heat preservation reaction for 50-80 min to obtain the polyreactive organosilicon water repellent intermediate.
According to the scheme, the preparation method of the porous micro-nano silicon sphere grafted multi-reactive organosilicon water repellent agent in the step (3) comprises the following steps:
(3.1) keeping the reaction temperature at 30-40 ℃, adding metered porous micro-nano silicon spheres, a tin-containing catalyst and pure water into a reaction system of the intermediate of the multi-reactive organosilicon water repellent agent, and dropwise adding a reactive coupling agent into the reaction system within 10-20 min while stirring;
(3.2) maintaining stirring and carrying out heat preservation reaction for 350-500 min to prepare a porous micro-nano silicon sphere grafted multi-reactivity organosilicon water repellent agent;
according to the scheme, the dosage of the tin-containing catalyst in the step (3) is 4.0-6.0 ten-thousandth of the total mass of the hydrogen-containing silicone oil, the allyl glycidyl ether and the silane coupling agent; the mass of the porous micro-nano silicon spheres accounts for 3.0-5.0 per mill of the total mass of the hydrogen-containing silicone oil, the allyl glycidyl ether and the silane coupling agent.
The preparation method of the porous micro-nano silicon sphere grafted multi-reactive organosilicon water repellent dispersion comprises the steps of mixing and emulsifying the porous micro-nano silicon sphere grafted multi-reactive organosilicon water repellent with soft water to prepare the porous micro-nano silicon sphere grafted multi-reactive organosilicon water repellent dispersion.
According to the scheme: the emulsification and dispersion are fully stirred and emulsified for 10-20 min at the temperature of 35-45 ℃.
According to the scheme, the consumption of the soft water is 2.5-3.5 times of the total mass of the hydrogen-containing silicone oil, the allyl glycidyl ether and the silane coupling agent.
The porous micro-nano silicon sphere grafted multi-reactive organosilicon water repellent agent prepared by the preparation method.
Compared with the prior art, the method has the following advantages and characteristics:
1. according to the porous micro-nano silicon sphere grafted multi-reactivity organosilicon water repellent agent provided by the invention, micro-nano porous silicon microspheres are grafted on a polysiloxane water repellent structure, so that a low-tension surface layer with certain roughness is favorably established on the surface of smooth textile fibers, the textile fibers are endowed with excellent water repellent effect and good durability through dual physical and chemical effects, the application process is simple, and the process flow is short.
2. The silicon microspheres have larger size which reaches 0.2-3 mu m, and are particularly suitable for constructing a water repellent surface with proper roughness, and meanwhile, as the micro-nano silicon spheres prepared by the invention have a porous structure, after the micro-nano silicon spheres are treated on a fabric and dried, the porous structure in the silicon microspheres is rich in air, so that the water repellent effect of a water repellent agent can be further enhanced.
3. The porous micro-nano silicon sphere grafted multi-reactivity organosilicon water repellent agent provided by the invention has two or more different reactive groups, has better applicability to various different fibers, and has a lasting finishing effect;
4. the porous micro-nano silicon sphere grafted multi-reactive organosilicon water repellent agent provided by the invention is a self-emulsifying product, does not contain an emulsifier, and is convenient, safe and environment-friendly to use.
Drawings
FIG. 1 is an SEM image of porous micro-nano silicon spheres. As can be seen from the figure: the size of the porous micro-nano silicon spheres is 0.2-3 mu m.
Detailed Description
Example 1 preparation method of porous micro-nano silicon sphere grafted multi-reactive organosilicon water repellent dispersion liquid
The preparation method comprises the following specific steps:
(1) the preparation method comprises the steps of preparing porous micro-nano silicon spheres, wherein the porous micro-nano silicon sphere raw materials are mixed and reacted to prepare the porous micro-nano silicon spheres; the method specifically comprises the following steps:
(1.1) adding alcohol, soft water and ammonia water accounting for 15% of the total amount into a reactor at the temperature of 25-30 ℃, uniformly stirring, and adding alkyl silicate; keeping the reaction temperature unchanged, stirring and reacting for 240 min;
(1.2) adding the residual alcohol into the reaction system in the step (1.1), keeping the temperature unchanged, stirring and reacting for 120 min;
(1.3) adding a cross-linking agent and a 50% sodium hydroxide aqueous solution, controlling the reaction temperature to be 80-85 ℃, and maintaining stirring and reacting for 130 min;
(1.4) filtering the reaction liquid in the step (1.3), fully washing filter residues, naturally airing and grinding to prepare porous micro-nano silicon spheres for later use;
(2) preparing a multi-reactive organosilicon water repellent intermediate, wherein hydrogen-containing silicone oil, allyl glycidyl ether, an amino coupling agent, chloroplatinic acid, a pH regulator and alcohol in the raw material of the multi-reactive organosilicon water repellent are mixed and reacted to prepare the multi-reactive organosilicon water repellent intermediate; the method specifically comprises the following steps:
(2.1) putting hydrogen-containing silicone oil, allyl glycidyl ether and chloroplatinic acid into a reactor, stirring, controlling the reaction temperature to be 80-85 ℃, and carrying out heat preservation reaction for 400 min; thereafter, excess allyl glycidyl ether was distilled off under reduced pressure;
(2.2) cooling the reaction system in the step (2.1) to 33-36 ℃, adding alcohol into the reaction system, keeping the temperature unchanged, dropwise adding an amino coupling agent into the reaction system within 15min while stirring, and then carrying out heat preservation reaction for 35 min;
(2.3) keeping the reaction temperature at 33-36 ℃, adding a pH regulator into the reaction system in the step (2.2), and continuing to perform heat preservation reaction for 60min to obtain a polyreactive organosilicon water repellent intermediate;
(3) the preparation method comprises the following steps of (1) preparing a multi-reactive organosilicon water repellent agent grafted by porous micro-nano silicon spheres, wherein the porous micro-nano silicon spheres, a reactive organosilicon water repellent agent intermediate and a reactive coupling agent, a tin-containing catalyst and pure water in the raw materials of the multi-reactive organosilicon water repellent agent are mixed and reacted to prepare the multi-reactive organosilicon water repellent agent grafted by the porous micro-nano silicon spheres; the method specifically comprises the following steps:
(3.1) keeping the reaction temperature at 33-36 ℃, adding metered porous micro-nano silicon spheres, a tin-containing catalyst and pure water into the reaction system in (2.3), and dropwise adding a reactive coupling agent into the reaction system within 15min while stirring;
(3.2) stirring is maintained, and the heat preservation reaction is carried out for 400min to prepare the porous micro-nano silicon sphere grafted multi-reactivity organosilicon water repellent agent;
(4) and (3) emulsifying and dispersing the product, namely mixing and emulsifying the multi-reactivity organosilicon water repellent agent grafted by the porous micro-nano silicon spheres and soft water in the raw material of the multi-reactivity organosilicon water repellent agent to prepare the porous micro-nano silicon sphere grafted multi-reactivity organosilicon water repellent agent dispersion liquid. The method specifically comprises the following steps:
(4.1) distilling under reduced pressure to remove (3.2) the alcohol in the reaction system;
and (4.2) adding soft water into the system (4.1), fully stirring and emulsifying at the temperature of 35-40 ℃ for 15min to prepare the porous micro-nano silicon ball grafted multi-reactive organosilicon water repellent dispersion liquid.
The application method of the product prepared by the method comprises the following steps: the water repellent antifouling finishing agent is used for water repellent antifouling finishing processing of various textile products, and has good applicability to various different fibers; the water repellency and antifouling performance of the textile can be remarkably improved, and the water contact angle of the finished textile can reach more than 150 degrees; the hand feeling style of the textile is not affected. Has good market prospect, safety, environmental protection and convenient use.
The product prepared by the method of the invention is stored: the finished product should be stored in a shady, cool and dry place in a sealed way.
Example 2 preparation method of porous micro-nano silicon sphere grafted multi-reactive organosilicon water repellent dispersion liquid
The preparation method comprises the following specific steps:
(1) the preparation method comprises the steps of preparing porous micro-nano silicon spheres, wherein the porous micro-nano silicon sphere raw materials are mixed and reacted to prepare the porous micro-nano silicon spheres; the method specifically comprises the following steps:
(1.1) adding 17% of alcohol, soft water and ammonia water into a reactor at the temperature of 30-33 ℃, uniformly stirring, and adding alkyl silicate; keeping the reaction temperature unchanged, stirring and reacting for 200 min;
(1.2) adding the residual alcohol into the reaction system in the step (1.1), keeping the temperature unchanged, stirring and reacting for 100 min;
(1.3) adding a cross-linking agent and a 50% sodium hydroxide aqueous solution, controlling the reaction temperature to be 78-83 ℃, and maintaining stirring and reacting for 150 min;
(1.4) filtering the reaction liquid in the step (1.3), fully washing filter residues, naturally airing and grinding to prepare porous micro-nano silicon spheres for later use;
(2) preparing a multi-reactive organosilicon water repellent intermediate, wherein hydrogen-containing silicone oil, allyl glycidyl ether, an amino coupling agent, chloroplatinic acid, a pH regulator and alcohol in the raw material of the multi-reactive organosilicon water repellent are mixed and reacted to prepare the multi-reactive organosilicon water repellent intermediate; the method specifically comprises the following steps:
(2.1) putting hydrogen-containing silicone oil, allyl glycidyl ether and chloroplatinic acid into a reactor, stirring, controlling the reaction temperature to be 77-80 ℃, and carrying out heat preservation reaction for 450 min; thereafter, excess allyl glycidyl ether was distilled off under reduced pressure;
(2.2) cooling the reaction system in the step (2.1) to 35-40 ℃, adding alcohol into the reaction system, keeping the temperature unchanged, dropwise adding an amino coupling agent into the reaction system within 20min while stirring, and then carrying out heat preservation reaction for 40 min;
(2.3) keeping the reaction temperature at 35-40 ℃, adding a pH regulator into the reaction system in the step (2.2), and continuing to perform heat preservation reaction for 70-80 min to obtain a polyreactive organosilicon water repellent intermediate;
(3) the preparation method comprises the following steps of (1) preparing a multi-reactive organosilicon water repellent agent grafted by porous micro-nano silicon spheres, wherein the porous micro-nano silicon spheres, a reactive organosilicon water repellent agent intermediate and a reactive coupling agent, a tin-containing catalyst and pure water in the raw materials of the multi-reactive organosilicon water repellent agent are mixed and reacted to prepare the multi-reactive organosilicon water repellent agent grafted by the porous micro-nano silicon spheres; the method specifically comprises the following steps:
(3.1) keeping the reaction temperature at 35-40 ℃, adding metered porous micro-nano silicon spheres, a tin-containing catalyst and pure water into the reaction system in (2.3), and dropwise adding a reactive coupling agent into the reaction system within 20min while stirring;
(3.2) stirring is maintained, and heat preservation reaction is carried out for 450min to prepare the porous micro-nano silicon sphere grafted multi-reactivity organosilicon water repellent agent;
(4) and (3) emulsifying and dispersing the product, namely mixing and emulsifying the multi-reactivity organosilicon water repellent agent grafted by the porous micro-nano silicon spheres and soft water in the raw material of the multi-reactivity organosilicon water repellent agent to prepare the multi-reactivity organosilicon water repellent agent dispersion liquid grafted by the porous micro-nano silicon spheres. The method specifically comprises the following steps:
(4.1) distilling under reduced pressure to remove (3.2) the alcohol in the reaction system;
and (4.2) adding soft water into the system (4.1), fully stirring and emulsifying at the temperature of 35-40 ℃ for 15min to prepare the porous micro-nano silicon sphere grafted multi-reactive organosilicon water repellent dispersion liquid.
The application method of the product prepared by the method comprises the following steps: the water repellent antifouling finishing agent is used for water repellent antifouling finishing processing of various textile products, and has good applicability to various different fibers; the water repellency and antifouling performance of the textile can be remarkably improved, and the water contact angle of the finished textile can reach more than 150 degrees; the hand feeling style of the textile is not affected. Has good market prospect, safety, environmental protection and convenient use. The product prepared by the method of the invention is stored: the finished product should be stored in a shady, cool and dry place in a sealed way.
Example 3 preparation method of porous micro-nano silicon sphere grafted multi-reactive organosilicon water repellent dispersion liquid
The preparation method comprises the following specific steps:
(1) the preparation method comprises the steps of preparing porous micro-nano silicon spheres, wherein the porous micro-nano silicon sphere raw materials are mixed and reacted to prepare the porous micro-nano silicon spheres; the method specifically comprises the following steps:
(1.1) adding alcohol, soft water and ammonia water accounting for 20% of the total amount into a reactor at the temperature of 25-30 ℃, uniformly stirring, and adding alkyl silicate; keeping the reaction temperature unchanged, stirring and reacting for 270 min;
(1.2) adding the residual alcohol into the reaction system in the step (1.1), keeping the temperature unchanged, stirring and reacting for 140 min;
(1.3) adding a cross-linking agent and a 50% sodium hydroxide aqueous solution, controlling the reaction temperature to be 80-85 ℃, maintaining stirring and reacting for 140 min;
(1.4) filtering the reaction liquid in the step (1.3), fully washing filter residues, naturally airing and grinding to prepare porous micro-nano silicon spheres for later use;
(2) preparing a multi-reactive organosilicon water repellent intermediate, wherein hydrogen-containing silicone oil, allyl glycidyl ether, an amino coupling agent, chloroplatinic acid, a pH regulator and alcohol in the raw material of the multi-reactive organosilicon water repellent are mixed and reacted to prepare the multi-reactive organosilicon water repellent intermediate; the method specifically comprises the following steps:
(2.1) putting hydrogen-containing silicone oil, allyl glycidyl ether and chloroplatinic acid into a reactor, stirring, controlling the reaction temperature to be 77-80 ℃, and carrying out heat preservation reaction for 480 min; thereafter, excess allyl glycidyl ether was distilled off under reduced pressure;
(2.2) cooling the reaction system in the step (2.1) to 30-35 ℃, adding alcohol into the reaction system, keeping the temperature unchanged, dropwise adding an amino coupling agent into the reaction system within 20min while stirring, and then carrying out heat preservation reaction for 40 min;
(2.3) keeping the reaction temperature at 30-35 ℃, adding a pH regulator into the reaction system in the step (2.2), and continuing to perform heat preservation reaction for 80min to obtain a polyreactive organosilicon water repellent intermediate;
(3) the preparation method comprises the following steps of (1) preparing a multi-reactive organosilicon water repellent agent grafted by porous micro-nano silicon spheres, wherein the porous micro-nano silicon spheres, a reactive organosilicon water repellent agent intermediate and a reactive coupling agent, a tin-containing catalyst and pure water in the raw materials of the multi-reactive organosilicon water repellent agent are mixed and reacted to prepare the multi-reactive organosilicon water repellent agent grafted by the porous micro-nano silicon spheres; the method specifically comprises the following steps:
(3.1) keeping the reaction temperature at 33-35 ℃, adding metered porous micro-nano silicon spheres, a tin-containing catalyst and pure water into the reaction system in (2.3), and dropwise adding a reactive coupling agent into the reaction system within 20min while stirring;
(3.2) maintaining stirring and carrying out heat preservation reaction for 480min to prepare a porous micro-nano silicon sphere grafted multi-reactive organosilicon water repellent agent;
(4) and (3) emulsifying and dispersing the product, namely mixing and emulsifying the multi-reactivity organosilicon water repellent agent grafted by the porous micro-nano silicon spheres and soft water in the raw material of the multi-reactivity organosilicon water repellent agent to prepare the porous micro-nano silicon sphere grafted multi-reactivity organosilicon water repellent agent dispersion liquid. The method specifically comprises the following steps:
(4.1) distilling under reduced pressure to remove (3.2) the alcohol in the reaction system;
and (4.2) adding soft water into the system (4.1), fully stirring and emulsifying at the temperature of 35-40 ℃ for 20min to prepare the porous micro-nano silicon ball grafted multi-reactive organosilicon water repellent dispersion liquid.
The application method of the product prepared by the method comprises the following steps: the water repellent antifouling finishing agent is used for water repellent antifouling finishing processing of various textile products, and has good applicability to various different fibers; the water repellency and antifouling performance of the textile can be remarkably improved, and the water contact angle of the finished textile can reach more than 150 degrees; the hand feeling style of the textile is not affected. Has good market prospect, safety, environmental protection and convenient use. The product prepared by the method of the invention is stored: the finished product should be stored in a shady, cool and dry place in a sealed way.
The above description is only a preferred example of the present invention, and actually, the specific raw materials listed in the present invention, the upper and lower limits and interval values of each raw material, and the upper and lower limits and interval values of the process parameters (such as temperature, time, etc.) can all implement the present invention, and the examples are not listed here.
Therefore, the above embodiments are not intended to limit the present invention, and general changes and substitutions by those skilled in the art within the technical scope of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The preparation method of the porous micro-nano silicon sphere grafted multi-reactive organosilicon water repellent agent is characterized by comprising the following steps: the method comprises the following steps:
(1) preparing porous micro-nano silicon spheres: taking alkyl silicate as a base material, carrying out hydrolysis reaction on the base material by using alcohol and a water solvent under an alkaline condition for a period of time, adding a cross-linking agent, and continuously reacting for a period of time under the alkaline condition to obtain porous micro-nano silicon spheres, wherein the size of the porous micro-nano silicon spheres is 0.2-3 mu m; the cross-linking agent is boric acid;
(2) preparation of a multi-reactive organosilicon water repellent intermediate:
the first step is as follows: hydrogen-containing silicone oil and glycidyl ether are subjected to catalytic hydrosilylation reaction, wherein the glycidyl ether is one of allyl glycidyl ether, acrylic glycidyl ether and methacrylic glycidyl ether; the double bond on the glycidyl ether is added with the silicon hydride of the hydrogen-containing silicone oil, and the epoxy group is introduced into the side chain position of the hydrogen-containing silicone oil;
secondly, carrying out epoxy ring-opening addition reaction on the reaction product of the first step and an amino coupling agent, namely, carrying out ring opening on the lateral epoxy group in the reaction product of the first step and carrying out addition reaction on the lateral epoxy group and the amino group on the amino coupling agent, and introducing a siloxy group into the side chain position of the hydrogen-containing silicone oil to obtain a multi-reactive organosilicon water repellent agent intermediate; the amino coupling agent is one of 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, N-aminoethyl-3-aminopropyltrimethoxysilane and N-aminoethyl-3-aminopropyltriethoxysilane;
(3) preparing a porous micro-nano silicon sphere grafted multi-reactive organosilicon water repellent agent: adding water into a reactive coupling agent for catalytic coupling of the porous micro-nano silicon spheres and the reactive organosilicon water repellent agent intermediate to prepare a multi-reactive organosilicon water repellent agent grafted by the porous micro-nano silicon spheres; the reactive coupling agent is a combination of two of 3- (2, 3-epoxypropoxy) propyl trimethoxy silane, 3-methacryloxypropyl trimethoxy silane and N-aminoethyl-3-aminopropylmethyldimethoxy silane;
the above-mentioned amino coupling agent and reactive coupling agent are collectively referred to as a silane coupling agent.
2. The preparation method of the porous micro-nano silicon sphere grafted multi-reactive organosilicon water repellent agent according to claim 1, characterized by comprising the following steps: the components in the step (1) are as follows in parts by weight: 70-100 alkyl silicate, 500-700 alcohol, 70-100 water, 200-300 cross-linking agent.
3. The preparation method of the porous micro-nano silicon sphere grafted multi-reactive organosilicon water repellent agent according to claim 1, characterized by comprising the following steps: the alkaline condition of the hydrolysis reaction in the step (1) is that the pH value of an ammonia water adjusting system is 10-12; adding a cross-linking agent to continue reacting under the alkaline condition that a pH regulator is added to adjust the pH of the reaction system to 10-12; the pH regulator is 50 +/-5% sodium hydroxide solution.
4. The preparation method of the porous micro-nano silicon sphere grafted multi-reactive organosilicon water repellent agent according to claim 1, characterized by comprising the following steps:
the alkyl silicate in the step (1) is ethyl orthosilicate; the alcohol is one or a mixture of ethanol and isopropanol;
the hydrogen-containing silicone oil in the step (2) is methyl hydrogen-containing silicone oil containing 3-6 mmol/g of hydrogen;
the catalyst for the hydrosilylation is chloroplatinic acid;
and a pH regulator is added in the epoxy group ring-opening addition reaction to regulate the pH to be 6-7, and the pH regulator is acetic acid.
5. The preparation method of the porous micro-nano silicon sphere grafted multi-reactive organosilicon water repellent agent according to claim 1, characterized by comprising the following steps: the mol parts of the components are as follows: the hydrogen-containing silicone oil is 0.15-0.20 percent of Si-H, 0.20-0.25 percent of allyl glycidyl ether, 0.30-0.40 percent of silane coupling agent, 3.0-5.0 percent of alcohol and 0.20-0.30 percent of water for coupling in the step (3), wherein the mole number of the allyl glycidyl ether is 1.10-1.25 times of the mole number of Si-H, the silane coupling agent comprises an amino coupling agent and a reactive coupling agent, and the amino coupling agent accounts for 40-60 mol percent of the silane coupling agent.
6. The preparation method of the porous micro-nano silicon sphere grafted multi-reactive organosilicon water repellent agent according to claim 1, characterized by comprising the following steps: the water used in the step (1) is soft water, and the soft water has the total hardness of less than 30ppm of CaCaO;
in the step (2), the catalyst is chloroplatinic acid, and the dosage of the chloroplatinic acid is 0.1-0.15 ten thousandth of the total mass of the hydrogen-containing silicone oil and the allyl glycidyl ether;
in the step (3), a tin-containing catalyst is used, and the dosage of the tin-containing catalyst is 4.0-6.0 ten-thousandth of the total mass of the hydrogen-containing silicone oil, the allyl glycidyl ether and the silane coupling agent; and (4) adding water into the catalytic coupling reaction in the step (3) to obtain pure water.
7. The preparation method of the porous micro-nano silicon sphere grafted multi-reactive organosilicon water repellent agent according to claim 1, characterized by comprising the following steps: the mass of the porous micro-nano silicon spheres accounts for 3.0-5.0 per mill of the total mass of the hydrogen-containing silicone oil, the allyl glycidyl ether and the silane coupling agent.
8. The preparation method of the porous micro-nano silicon sphere grafted multi-reactive organosilicon water repellent agent according to claim 1, characterized by comprising the following steps: the method comprises the following specific steps:
step (1), preparing porous micro-nano silicon spheres:
(1.1) adding 10-20% of alcohol, soft water and ammonia water into a reactor at the temperature of 20-35 ℃, wherein the ammonia water is used for adjusting the pH of the system to 10-12, and adding alkyl silicate after uniformly stirring; keeping the reaction temperature unchanged, stirring and reacting for 180-300 min;
(1.2) adding the residual alcohol into the reaction system in the step (1.1), keeping the temperature unchanged, stirring and reacting for 100-150 min;
(1.3) adding a cross-linking agent and a 50 +/-5% sodium hydroxide aqueous solution, adjusting the pH of the system to 10-12, controlling the reaction temperature to be 75-85 ℃, and maintaining stirring and reacting for 100-150 min;
(1.4) filtering the reaction liquid in the step (1.3), fully washing filter residues, naturally airing and grinding to prepare micro-nano porous micro-nano silicon spheres for later use;
step (2), the preparation steps of the intermediate of the multi-reactive organosilicon water repellent agent are as follows:
(2.1) putting hydrogen-containing silicone oil, allyl glycidyl ether and a catalyst chloroplatinic acid into a reactor, stirring, controlling the reaction temperature to be 75-85 ℃, and carrying out heat preservation reaction for 350-500 min; thereafter, excess allyl glycidyl ether was distilled off under reduced pressure;
(2.2) cooling the reaction system in the step (2.1) to 30-40 ℃, adding alcohol into the reaction system, keeping the temperature unchanged, dropwise adding an amino coupling agent into the reaction system within 10-20 min while stirring, and then carrying out heat preservation reaction for 20-40 min;
(2.3) keeping the reaction temperature at 30-40 ℃, adding a pH regulator into the reaction system in (2.2), regulating the pH to 6-7, and continuing to perform heat preservation reaction for 50-80 min to obtain a multi-reactive organosilicon water repellent intermediate;
step (3), preparing a porous micro-nano silicon sphere grafted multi-reactive organosilicon water repellent agent:
(3.1) keeping the reaction temperature at 30-40 ℃, adding metered porous micro-nano silicon spheres, a tin-containing catalyst and pure water into a reaction system of the intermediate of the multi-reactive organosilicon water repellent agent, and dropwise adding a reactive coupling agent into the reaction system within 10-20 min while stirring;
and (3.2) maintaining stirring and carrying out heat preservation reaction for 350-500 min to obtain the porous micro-nano silicon sphere grafted multi-reactive organosilicon water repellent agent.
9. The porous micro-nano silicon sphere grafted multi-reactive organosilicon water repellent agent obtained by the preparation method of any one of claims 1 to 8.
10. The preparation method of the porous micro-nano silicon sphere grafted multi-reactive organosilicon water repellent dispersion comprises the steps of mixing and emulsifying the porous micro-nano silicon sphere grafted multi-reactive organosilicon water repellent agent disclosed in claim 1 with soft water to prepare the porous micro-nano silicon sphere grafted multi-reactive organosilicon water repellent dispersion.
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