CN113651961A - Modified organosilicon waterproofing agent and preparation method thereof - Google Patents
Modified organosilicon waterproofing agent and preparation method thereof Download PDFInfo
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- D06M2200/25—Resistance to light or sun, i.e. protection of the textile itself as well as UV shielding materials or treatment compositions therefor; Anti-yellowing treatments
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- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/50—Modified hand or grip properties; Softening compositions
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Abstract
The invention discloses a modified organosilicon waterproofing agent and a preparation method thereof, wherein the modified organosilicon waterproofing agent is prepared from the following raw materials, by weight, 20-30 parts of amino modified organosiloxane, 20-30 parts of modified quaternary ammonium salt polysilane, 1-3 parts of a surfactant, 1-5 parts of tripropylene glycol, 1-5 parts of ethylene glycol butyl ether, 0.01-0.1 part of an initiator, and 60-80 parts of deionized water. The invention takes long-chain alkyl silicon as a main molecular framework, carries out functional design on the molecules of the organosilicon waterproofing agent, carries out amination modification and quaternary ammonium salinization modification, respectively obtains amino modified organic silicon oil and modified quaternary ammonium salt polysilane, and introduces terminal epoxy groups into the modified quaternary ammonium salt polysilane.
Description
Technical Field
The invention belongs to the technical field of waterproof agent processing, and particularly relates to a modified organic silicon waterproof agent and a preparation method thereof.
Background
The water-proofing agent can be used for water-proofing treatment of building wall surface, textile surface, leather and wood, etc. The principle can be summarized as that the waterproof agent can form a layer of continuous film on the surface of a target object, so that water is not easy to permeate the target object, and the aim of preventing water is fulfilled. Wherein, the textile waterproof agent is commonly used fluorine-containing waterproof agent. The fluorine-containing waterproof agent is expensive, the used fluorine-containing raw material has high energy consumption and heavy pollution in production, and the carried fluorine-containing substances are difficult to degrade and have bioaccumulation toxicity. Accordingly, fluorine-free water repellent agents have been the subject of research in recent years.
However, the existing fluoride-free waterproof agent troubles printing and dyeing enterprises, and is mainly characterized in that after being finished by the waterproof agent, the fabric feels hard, the fabric selectivity is strong, and the durability of the waterproof effect is poor. The hand feeling is mostly solved by using a softening agent, and the water resistance is generally reduced; the durability is that the hand feeling is further reduced by using a cross-linking agent together or increasing the using amount of a waterproof agent; the general fluorine-free waterproof agent has strong selectivity on the types of fabrics, is only suitable for partial fabrics, and printing and dyeing enterprises can only use a plurality of waterproof agents to meet the requirements of different types of fabrics. In addition, in recent years, with the improvement of living standard and the upgrade of national industry, the textile printing and dyeing industry has more and more demand for high-grade fluoride-free water-proofing agents, the function of the water-proofing agent is not required to be simple, and the water-proofing agent also has the requirements on properties such as mildew resistance, wrinkle resistance, static resistance and the like.
Therefore, the invention aims at the problems and develops a modified organosilicon waterproofing agent and a preparation method thereof so as to meet the development requirements of textile application.
Disclosure of Invention
The invention aims to provide a modified organic silicon waterproof agent and a preparation method thereof, which solve the problem that the function of the organic silicon waterproof agent applied to textiles is single at present and meet the development requirement of textile application.
The purpose of the invention can be solved by the following technical scheme:
a modified organosilicon waterproofing agent is prepared from (by weight parts) amino modified organosiloxane 20-30, modified quaternary ammonium polysilane 20-30, surfactant 1-3, tripropylene glycol 1-5, butyl cellosolve 1-5, initiator 0.01-0.1, and deionized water 60-80;
the preparation method of the modified organosilicon waterproofing agent comprises the following steps:
uniformly mixing amino modified organic silicone oil, modified quaternary ammonium salt polysilane, a surfactant, tripropylene glycol and ethylene glycol butyl, then adjusting the pH of the solution to be between 5 and 7 by formic acid, and then adding deionized water to be uniformly mixed to obtain a pre-emulsion;
and step two, adding an initiator into the pre-emulsion obtained in the step one, uniformly stirring, and reacting for 6-8 hours at 70-90 ℃ to obtain the modified organosilicon waterproofing agent.
Further, the amino modified organic silicone oil is prepared by the following steps:
step S1, adding a triethylamine solution of allyl glycidyl ether and chloroplatinic acid into a four-neck flask provided with a stirrer, a dropping funnel, a reflux condenser tube and a thermometer, slowly dropping tetramethyldihydrodisiloxane at 85-90 ℃ for 1-1.5h, continuing to react for 1-2h after dropping, then carrying out reduced pressure fractionation and purification, collecting fractions at 180 ℃ and 200 ℃ and under-0.01 MPa, and obtaining 1, 3-bis (3-glycidoxypropyl) -1,1,3, 3-tetramethyldisiloxane;
step S2, adding hexamethylene diamine and the 1, 3-di (3-glycidoxypropyl) -1,1,3, 3-tetramethyldisiloxane obtained in the step S1 into a reaction bottle, and reacting at 85-95 ℃ for 4-6h to obtain an amino-terminated organosilicon intermediate, wherein the reaction formula is shown as follows, X is-CH2CH2CH2OCH2-；
Step S3, sequentially adding the amino-terminated organosilicon intermediate obtained in the step S2 and octadecyltrimethoxysilane into a three-neck flask provided with an electric stirrer, a thermometer and a zigzag condenser, stirring at a stirring speed of 300r/min and 250-2CH2CH2OCH2-。
Further, the concentration of the triethylamine solution of chloroplatinic acid in step S1 is 0.008-0.012 mol/L.
Further, in step S1, the ratio of the allyl glycidyl ether to the triethylamine solution of chloroplatinic acid to the tetramethyldihydrodisiloxane is 2 to 3mol:1 to 3mL:1 mol.
Further, in step S2, hexamethylenediamine and 1, 3-bis (3-glycidoxypropyl) -1,1,3, 3-tetramethyldisiloxane are added in a molar mass ratio of 1.8 to 2.2: 1.
Further, the adding mass ratio of the amino-terminated organosilicon intermediate, the octadecyl trimethoxy silane and the catalyst in the step S3 is 10-20:3-8: 0.01-0.05.
Further, in step S3, the catalyst is tetramethylammonium hydroxide.
Further, the modified quaternary ammonium salt polysilane is prepared by the following steps:
step A, sequentially adding methyl hydrogen-containing silicone oil, allyl glycidyl ether and isopropanol into a three-neck flask, placing the three-neck flask into a constant-temperature oil bath, uniformly stirring, starting to add a complex platinum catalyst when the temperature rises to 75-83 ℃ of a set temperature, and reacting at the constant temperature of 70-90 ℃ for 2-4 hours to obtain end-ring oxidized organic silicone oil, wherein the reaction formula is shown as follows;
and step B, sequentially adding the end-ring oxidized organic silicon oil, dodecyl dimethyl amine and isopropanol obtained in the step A into a three-neck flask, heating and stirring, setting the reaction temperature to be 80-90 ℃, keeping the system slightly boiling, adjusting the pH value of the system by using glacial acetic acid, maintaining the pH value of the system to be 5-6, continuously reacting for 8-10 hours at a constant temperature, and removing the isopropanol and low-boiling-point substances by reduced pressure distillation after the reaction is finished to obtain the modified quaternary ammonium salt polysilane, wherein the reaction formula is shown as follows.
Further, the mass ratio of methyl hydrogen silicone oil, allyl glycidyl ether and isopropanol added in the step A is 80-160:8-20: 150-300.
Further, the mass ratio of the terminal epoxidized organic silicone oil, the dodecyl dimethyl amine and the isopropanol added in the step B is 150-200:8-20: 150-300.
Further, the surfactant is fatty alcohol polyoxyethylene ether surfactant.
Further, the initiator is hexadecyl trimethoxy silane.
A preparation method of a modified organosilicon waterproofing agent comprises the following steps:
uniformly mixing amino modified organic silicone oil, modified quaternary ammonium salt polysilane, a surfactant, tripropylene glycol and ethylene glycol butyl, then adjusting the pH of the solution to be between 5 and 7 by formic acid, and then adding deionized water to be uniformly mixed to obtain a pre-emulsion;
and step two, adding an initiator into the pre-emulsion obtained in the step one, uniformly stirring, reacting for 6-8 hours at 70-90 ℃, and cooling the reaction solution to room temperature to obtain the modified organosilicon waterproofing agent.
The invention has the beneficial effects that:
1. the invention starts from the defect that the fabric feels hard after being finished by the waterproof agent, takes long-chain alkyl silicon in long-chain alkyl silicon oil as a main molecular skeleton, carries out functional design on the molecule of the organic silicon waterproof agent, respectively carries out amination modification and quaternary ammonium salinization modification on the long-chain alkyl silicon oil, respectively obtains amino modified organic silicon oil and modified quaternary ammonium salt polysilane, and introduces end epoxy groups into the modified quaternary ammonium salt polysilane.
2. The modified quaternary ammonium salt polysilane synthesized by the invention has the dual characteristics of organic polysiloxane and inorganic quaternary ammonium salt, so that the finished fabric has excellent performances of softness, yellowing resistance, water washing resistance and the like, and the treated fabric has sterilization, mildew resistance and antistatic property because the molecules of the modified quaternary ammonium salt polysilane have cationic property.
3. The invention utilizes amino modified organic silicon oil and modified quaternary ammonium salt polysilane to generate crosslinking and emulsification under the action of a surfactant and an initiator to obtain the modified organic silicon waterproof agent emulsion. The terminal amino groups and the terminal epoxy groups can perform a crosslinking reaction with an initiator and a surfactant, so that the film forming property of the waterproof agent is enhanced, and the waterproof property is enhanced.
In conclusion, the organosilicon waterproof agent obtained by the invention has good film-forming property, long-chain alkyl silicon is used as a main framework, quaternary ammonium salt is introduced into the framework, and the fabric treated by the organosilicon waterproof agent has good smoothness, flexibility, washing resistance, sterilization and mildew resistance and antistatic property.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1:
a modified organosilicon waterproofing agent is prepared from 20 parts by weight of amino modified organosiloxane, 30 parts by weight of modified quaternary ammonium polysilane, 3 parts by weight of surfactant, 5 parts by weight of tripropylene glycol, 5 parts by weight of butyl cellosolve, 0.1 part by weight of initiator and 60 parts by weight of deionized water, wherein the surfactant is fatty alcohol polyoxyethylene ether surfactant, and the initiator is hexadecyl trimethoxy silane;
the preparation method of the modified organosilicon waterproofing agent comprises the following steps:
uniformly mixing amino modified organic silicone oil, modified quaternary ammonium salt polysilane, a surfactant, tripropylene glycol and ethylene glycol butyl, then adjusting the pH of the solution to be between 5 and 7 by formic acid, and then adding deionized water to be uniformly mixed to obtain a pre-emulsion;
and step two, adding an initiator into the pre-emulsion obtained in the step one, uniformly stirring, reacting for 6 hours at 85 ℃, and cooling the reaction solution to room temperature to obtain the modified organosilicon waterproofing agent.
Wherein, the amino modified organic silicone oil is prepared by the following steps:
step S1, adding a triethylamine solution of allyl glycidyl ether and chloroplatinic acid into a four-neck flask provided with a stirrer, a dropping funnel, a reflux condenser tube and a thermometer, slowly dropping tetramethyldihydrodisiloxane at 850 ℃ for 1h, reacting for 1h after dropping, then carrying out reduced pressure fractionation and purification, collecting fractions under the conditions of 180 ℃ and 200 MPa to obtain 1, 3-bis (3-glycidoxypropyl) -1,1,3, 3-tetramethyldisiloxane, wherein the concentration of the triethylamine solution of chloroplatinic acid is 0.008mol/L, and the dosage ratio of the triethylamine solution of allyl glycidyl ether, chloroplatinic acid and tetramethyldihydrodisiloxane is 2-3mol:1-3mL:1 mol.
Step S2, adding hexamethylene diamine and the 1, 3-di (3-glycidoxypropyl) -1,1,3, 3-tetramethyldisiloxane obtained in the step S1 into a reaction flask, and reacting at 90 ℃ for 5 hours to obtain an amino-terminated organosilicon intermediate, wherein the addition molar mass ratio of the hexamethylene diamine to the 1, 3-di (3-glycidoxypropyl) -1,1,3, 3-tetramethyldisiloxane is 1.8: 1;
and S3, sequentially adding the amino-terminated organosilicon intermediate and octadecyltrimethoxysilane obtained in the step S2 into a three-neck flask provided with an electric stirrer, a thermometer and a zigzag condenser, stirring at 250r/min, heating to 70 ℃, adding a catalyst, continuously heating to 100 ℃, keeping the temperature for reaction for 3 hours, heating to 140 ℃ after the reaction is finished, and performing reduced pressure distillation to remove low-boiling-point substances and the catalyst to obtain the amino-modified organosilicon oil, wherein the adding mass ratio of the amino-terminated organosilicon intermediate, the octadecyltrimethoxysilane and the catalyst is 10:3:0.01, and the catalyst is tetramethylammonium hydroxide.
The modified quaternary ammonium salt polysilane is prepared by the following steps:
step A, sequentially adding methyl hydrogen-containing silicone oil, allyl glycidyl ether and isopropanol into a three-neck flask, placing the three-neck flask into a constant-temperature oil bath, uniformly stirring, starting to add a complex platinum catalyst when the temperature rises to a set temperature of 80 ℃, and reacting at a constant temperature of 85 ℃ for 3 hours to obtain end-ring oxidized organic silicone oil, wherein the adding mass ratio of the methyl hydrogen-containing silicone oil, the allyl glycidyl ether and the isopropanol is 80:8: 150;
and step B, sequentially adding the end-ring oxidized organic silicon oil, the dodecyl dimethyl amine and the isopropanol obtained in the step A into a three-neck flask, heating and stirring, setting the reaction temperature to be 80 ℃, keeping the system slightly boiling, adjusting the pH value of the system by using glacial acetic acid, maintaining the pH value of the system to be 5-6, continuously reacting for 8 hours at constant temperature, and removing the isopropanol and low-boiling-point substances by reduced pressure distillation after the reaction is finished to obtain the modified quaternary ammonium salt polysilane, wherein the mass ratio of the end-ring oxidized organic silicon oil, the dodecyl dimethyl amine and the isopropanol is 150:8: 150.
Example 2:
the modified organosilicon waterproof agent is prepared from the following raw materials, by weight, 25 parts of amino-modified organosiloxane, 25 parts of modified quaternary ammonium polysilane, 2 parts of a surfactant, 3 parts of tripropylene glycol, 3 parts of butyl cellosolve, 0.03 part of an initiator and 70 parts of deionized water, wherein the surfactant is a fatty alcohol polyoxyethylene ether surfactant, and the initiator is hexadecyl trimethoxy silane;
the preparation method of the modified organosilicon waterproofing agent comprises the following steps:
uniformly mixing amino modified organic silicone oil, modified quaternary ammonium salt polysilane, a surfactant, tripropylene glycol and ethylene glycol butyl, then adjusting the pH of the solution to be between 5 and 7 by formic acid, and then adding deionized water to be uniformly mixed to obtain a pre-emulsion;
and step two, adding an initiator into the pre-emulsion obtained in the step one, uniformly stirring, reacting for 7 hours at the temperature of 80 ℃, and cooling the reaction solution to room temperature to obtain the modified organosilicon waterproofing agent.
Wherein, the amino modified organic silicone oil is prepared by the following steps:
step S1, adding a triethylamine solution of allyl glycidyl ether and chloroplatinic acid into a four-neck flask provided with a stirrer, a dropping funnel, a reflux condenser tube and a thermometer, slowly dropping tetramethyldihydrodisiloxane at 85 ℃ for 1h, reacting for 1h after dropping, then carrying out reduced pressure fractionation and purification, collecting fractions under the conditions of 180 ℃ and 200 MPa to obtain 1, 3-bis (3-glycidoxypropyl) -1,1,3, 3-tetramethyldisiloxane, wherein the concentration of the triethylamine solution of chloroplatinic acid is 0.01mol/L, and the dosage ratio of the allyl glycidyl ether to the triethylamine solution of chloroplatinic acid to the tetramethyldihydrodisiloxane is 2.5mol:2mL:1 mol.
Step S2, adding hexamethylene diamine and the 1, 3-di (3-glycidoxypropyl) -1,1,3, 3-tetramethyldisiloxane obtained in the step S1 into a reaction bottle, and reacting at 85 ℃ for 5 hours to obtain an amino-terminated organosilicon intermediate, wherein the addition molar mass ratio of the hexamethylene diamine to the 1, 3-di (3-glycidoxypropyl) -1,1,3, 3-tetramethyldisiloxane is 2: 1;
and S3, sequentially adding the amino-terminated organosilicon intermediate and octadecyltrimethoxysilane obtained in the step S2 into a three-neck flask provided with an electric stirrer, a thermometer and a zigzag condenser, stirring at 250r/min, heating to 70 ℃, adding a catalyst, continuously heating to 100 ℃, keeping the temperature for reaction for 3 hours, heating to 140 ℃ after the reaction is finished, and performing reduced pressure distillation to remove low-boiling-point substances and the catalyst to obtain the amino-modified organosilicon oil, wherein the adding mass ratio of the amino-terminated organosilicon intermediate, the octadecyltrimethoxysilane and the catalyst is 15:5:0.03, and the catalyst is tetramethylammonium hydroxide.
The modified quaternary ammonium salt polysilane is prepared by the following steps:
step A, sequentially adding methyl hydrogen-containing silicone oil, allyl glycidyl ether and isopropanol into a three-neck flask, placing the three-neck flask into a constant-temperature oil bath, uniformly stirring, starting to add a complex platinum catalyst when the temperature rises to a set temperature of 80 ℃, and reacting at a constant temperature of 85 ℃ for 3 hours to obtain end-ring oxidized organic silicone oil, wherein the adding mass ratio of the methyl hydrogen-containing silicone oil, the allyl glycidyl ether and the isopropanol is 120:10: 200;
and step B, sequentially adding the end-ring oxidized organic silicon oil, dodecyl dimethyl amine and isopropanol obtained in the step A into a three-neck flask, heating and stirring, setting the reaction temperature to be 85 ℃, keeping the system slightly boiling, adjusting the pH value of the system by using glacial acetic acid, maintaining the pH value of the system to be 5-6, continuously reacting for 8 hours at constant temperature, and removing isopropanol and low-boiling-point substances by reduced pressure distillation after the reaction is finished to obtain the modified quaternary ammonium salt polysilane, wherein the mass ratio of the end-ring oxidized organic silicon oil, the dodecyl dimethyl amine and the isopropanol is 180:10: 200.
Example 3:
a modified organosilicon waterproofing agent is prepared from 30 parts by weight of amino modified organosiloxane, 20 parts by weight of modified quaternary ammonium polysilane, 3 parts by weight of surfactant, 5 parts by weight of tripropylene glycol, 5 parts by weight of butyl cellosolve, 0.1 part by weight of initiator and 80 parts by weight of deionized water, wherein the surfactant is fatty alcohol polyoxyethylene ether surfactant, and the initiator is hexadecyl trimethoxy silane;
the preparation method of the modified organosilicon waterproofing agent comprises the following steps:
uniformly mixing amino modified organic silicone oil, modified quaternary ammonium salt polysilane, a surfactant, tripropylene glycol and ethylene glycol butyl, then adjusting the pH of the solution to be between 5 and 7 by formic acid, and then adding deionized water to be uniformly mixed to obtain a pre-emulsion;
and step two, adding an initiator into the pre-emulsion obtained in the step one, uniformly stirring, reacting for 7 hours at 85 ℃, and cooling the reaction solution to room temperature to obtain the modified organosilicon waterproofing agent.
Wherein, the amino modified organic silicone oil is prepared by the following steps:
step S1, adding a triethylamine solution of allyl glycidyl ether and chloroplatinic acid into a four-neck flask provided with a stirrer, a dropping funnel, a reflux condenser tube and a thermometer, slowly dropping tetramethyldihydrodisiloxane at 85 ℃ for 1h, reacting for 1h after dropping, then carrying out reduced pressure fractionation and purification, collecting fractions under the conditions of 180 ℃ and 0.01MPa to obtain 1, 3-bis (3-glycidoxypropyl) -1,1,3, 3-tetramethyldisiloxane, wherein the concentration of the triethylamine solution of chloroplatinic acid is 0.012mol/L, and the dosage ratio of the allyl glycidyl ether to the triethylamine solution of chloroplatinic acid to the tetramethyldihydrodisiloxane is 3mol:3mL:1 mol.
Step S2, adding hexamethylene diamine and the 1, 3-di (3-glycidoxypropyl) -1,1,3, 3-tetramethyldisiloxane obtained in the step S1 into a reaction bottle, and reacting at 95 ℃ for 4h to obtain an amino-terminated organosilicon intermediate, wherein the addition molar mass ratio of the hexamethylene diamine to the 1, 3-di (3-glycidoxypropyl) -1,1,3, 3-tetramethyldisiloxane is 2.2: 1;
and S3, sequentially adding the amino-terminated organosilicon intermediate and octadecyltrimethoxysilane obtained in the step S2 into a three-neck flask provided with an electric stirrer, a thermometer and a zigzag condenser, stirring at 250r/min, heating to 70 ℃, adding a catalyst, continuously heating to 100 ℃, keeping the temperature for reaction for 3 hours, heating to 145 ℃ after the reaction is finished, and performing reduced pressure distillation to remove low-boiling-point substances and the catalyst to obtain the amino-modified organosilicon oil, wherein the adding mass ratio of the amino-terminated organosilicon intermediate, the octadecyltrimethoxysilane and the catalyst is 20:8:0.05, and the catalyst is tetramethylammonium hydroxide.
The modified quaternary ammonium salt polysilane is prepared by the following steps:
step A, sequentially adding methyl hydrogen-containing silicone oil, allyl glycidyl ether and isopropanol into a three-neck flask, placing the three-neck flask into a constant-temperature oil bath, uniformly stirring, starting to add a platinum complex catalyst when the temperature rises to 80 ℃, and reacting at the constant temperature of 85 ℃ for 3 hours to obtain end-terminated oxidized organic silicone oil, wherein the adding mass ratio of the methyl hydrogen-containing silicone oil, the allyl glycidyl ether and the isopropanol is 160:20: 300;
and step B, sequentially adding the end-ring oxidized organic silicon oil, the dodecyl dimethyl amine and the isopropanol obtained in the step A into a three-neck flask, heating and stirring, setting the reaction temperature to be 85 ℃, keeping the system slightly boiling, adjusting the pH value of the system by using glacial acetic acid, maintaining the pH value of the system to be 5-6, continuously reacting for 8 hours at a constant temperature, and removing the isopropanol and low-boiling-point substances by reduced pressure distillation after the reaction is finished to obtain the modified quaternary ammonium salt polysilane, wherein the mass ratio of the end-ring oxidized organic silicon oil, the dodecyl dimethyl amine and the isopropanol is 200:20: 300.
Comparative example 1:
a modified organosilicon waterproofing agent is prepared from 50 parts by weight of amino modified organosiloxane, 3 parts by weight of surfactant, 5 parts by weight of tripropylene glycol, 5 parts by weight of butyl cellosolve and 60 parts by weight of deionized water, wherein the surfactant is fatty alcohol polyoxyethylene ether surfactant;
the preparation method of the modified organosilicon waterproofing agent comprises the following steps:
uniformly mixing amino modified organic silicon oil, a surfactant, tripropylene glycol and ethylene glycol butyl, adjusting the pH of the solution to 5-7 by formic acid, adding deionized water, and uniformly mixing to obtain the modified organic silicon waterproof agent.
Wherein, the amino modified organic silicone oil is prepared by the following steps:
step S1, adding a triethylamine solution of allyl glycidyl ether and chloroplatinic acid into a four-neck flask provided with a stirrer, a dropping funnel, a reflux condenser tube and a thermometer, slowly dropping tetramethyldihydrodisiloxane at 850 ℃ for 1h, reacting for 1h after dropping, then carrying out reduced pressure fractionation and purification, collecting fractions under the conditions of 180 ℃ and 200 MPa to obtain 1, 3-bis (3-glycidoxypropyl) -1,1,3, 3-tetramethyldisiloxane, wherein the concentration of the triethylamine solution of chloroplatinic acid is 0.008mol/L, and the dosage ratio of the triethylamine solution of allyl glycidyl ether, chloroplatinic acid and tetramethyldihydrodisiloxane is 2-3mol:1-3mL:1 mol.
Step S2, adding hexamethylene diamine and the 1, 3-di (3-glycidoxypropyl) -1,1,3, 3-tetramethyldisiloxane obtained in the step S1 into a reaction flask, and reacting at 90 ℃ for 5 hours to obtain an amino-terminated organosilicon intermediate, wherein the addition molar mass ratio of the hexamethylene diamine to the 1, 3-di (3-glycidoxypropyl) -1,1,3, 3-tetramethyldisiloxane is 1.8: 1;
and S3, sequentially adding the amino-terminated organosilicon intermediate and octadecyltrimethoxysilane obtained in the step S2 into a three-neck flask provided with an electric stirrer, a thermometer and a zigzag condenser, stirring at 250r/min, heating to 70 ℃, adding a catalyst, continuously heating to 100 ℃, keeping the temperature for reaction for 3 hours, heating to 140 ℃ after the reaction is finished, and performing reduced pressure distillation to remove low-boiling-point substances and the catalyst to obtain the amino-modified organosilicon oil, wherein the adding mass ratio of the amino-terminated organosilicon intermediate, the octadecyltrimethoxysilane and the catalyst is 10:3:0.01, and the catalyst is tetramethylammonium hydroxide.
Comparative example 2:
the modified organosilicon waterproof agent is prepared from the following raw materials, by weight, 50 parts of modified quaternary ammonium salt polysilane, 2 parts of a surfactant, 3 parts of tripropylene glycol, 3 parts of ethylene glycol butyl ether and 70 parts of deionized water, wherein the surfactant is a fatty alcohol polyoxyethylene ether surfactant;
the preparation method of the modified organosilicon waterproofing agent comprises the following steps:
the modified quaternary ammonium salt polysilane, the surfactant, the tripropylene glycol and the ethylene glycol butyl are uniformly mixed, then formic acid is used for adjusting the pH value of the solution to be between 5 and 7, and deionized water is added for uniform mixing to obtain the modified organic silicon waterproof agent.
The modified quaternary ammonium salt polysilane is prepared by the following steps:
step A, sequentially adding methyl hydrogen-containing silicone oil, allyl glycidyl ether and isopropanol into a three-neck flask, placing the three-neck flask into a constant-temperature oil bath, uniformly stirring, starting to add a complex platinum catalyst when the temperature rises to a set temperature of 80 ℃, and reacting at a constant temperature of 85 ℃ for 3 hours to obtain end-ring oxidized organic silicone oil, wherein the adding mass ratio of the methyl hydrogen-containing silicone oil, the allyl glycidyl ether and the isopropanol is 120:10: 200;
and step B, sequentially adding the end-ring oxidized organic silicon oil, dodecyl dimethyl amine and isopropanol obtained in the step A into a three-neck flask, heating and stirring, setting the reaction temperature to be 85 ℃, keeping the system slightly boiling, adjusting the pH value of the system by using glacial acetic acid, maintaining the pH value of the system to be 5-6, continuously reacting for 8 hours at constant temperature, and removing isopropanol and low-boiling-point substances by reduced pressure distillation after the reaction is finished to obtain the modified quaternary ammonium salt polysilane, wherein the mass ratio of the end-ring oxidized organic silicon oil, the dodecyl dimethyl amine and the isopropanol is 180:10: 200.
Comparative example 3:
a modified organosilicon waterproofing agent is prepared from the following raw materials, by weight, 30 parts of methyl hydrogen-containing silicone oil, 20 parts of modified quaternary ammonium salt polysilane, 3 parts of a surfactant, 5 parts of tripropylene glycol, 5 parts of ethylene glycol butyl ether, 0.1 part of an initiator and 80 parts of deionized water, wherein the surfactant is a fatty alcohol polyoxyethylene ether surfactant, and the initiator is hexadecyl trimethoxy silane;
the preparation method of the modified organosilicon waterproofing agent comprises the following steps:
uniformly mixing methyl hydrogen-containing silicone oil, modified quaternary ammonium salt polysilane, a surfactant, tripropylene glycol and ethylene glycol butyl, adjusting the pH of the solution to be between 5 and 7 by using formic acid, adding deionized water, and uniformly mixing to obtain a pre-emulsion;
and step two, adding an initiator into the pre-emulsion obtained in the step one, uniformly stirring, reacting for 7 hours at 85 ℃, and cooling the reaction solution to room temperature to obtain the modified organosilicon waterproofing agent.
The modified quaternary ammonium salt polysilane is prepared by the following steps:
step A, sequentially adding methyl hydrogen-containing silicone oil, allyl glycidyl ether and isopropanol into a three-neck flask, placing the three-neck flask into a constant-temperature oil bath, uniformly stirring, starting to add a platinum complex catalyst when the temperature rises to 80 ℃, and reacting at the constant temperature of 85 ℃ for 3 hours to obtain end-terminated oxidized organic silicone oil, wherein the adding mass ratio of the methyl hydrogen-containing silicone oil, the allyl glycidyl ether and the isopropanol is 160:20: 300;
and step B, sequentially adding the end-ring oxidized organic silicon oil, the dodecyl dimethyl amine and the isopropanol obtained in the step A into a three-neck flask, heating and stirring, setting the reaction temperature to be 85 ℃, keeping the system slightly boiling, adjusting the pH value of the system by using glacial acetic acid, maintaining the pH value of the system to be 5-6, continuously reacting for 8 hours at a constant temperature, and removing the isopropanol and low-boiling-point substances by reduced pressure distillation after the reaction is finished to obtain the modified quaternary ammonium salt polysilane, wherein the mass ratio of the end-ring oxidized organic silicon oil, the dodecyl dimethyl amine and the isopropanol is 200:20: 300.
Comparative example 4:
a modified organosilicon waterproofing agent is prepared from 30 parts by weight of amino modified organosiloxane, 20 parts by weight of methyl hydrogen-containing silicone oil, 3 parts by weight of surfactant, 5 parts by weight of tripropylene glycol, 5 parts by weight of butyl cellosolve, 0.1 part by weight of initiator and 80 parts by weight of deionized water, wherein the surfactant is fatty alcohol polyoxyethylene ether surfactant, and the initiator is hexadecyl trimethoxy silane;
the preparation method of the modified organosilicon waterproofing agent comprises the following steps:
uniformly mixing amino modified organic silicone oil, methyl hydrogen-containing silicone oil, a surfactant, tripropylene glycol and ethylene glycol butyl, adjusting the pH of the solution to be between 5 and 7 by using formic acid, adding deionized water, and uniformly mixing to obtain a pre-emulsion;
and step two, adding an initiator into the pre-emulsion obtained in the step one, uniformly stirring, reacting for 7 hours at 85 ℃, and cooling the reaction solution to room temperature to obtain the modified organosilicon waterproofing agent.
Wherein, the amino modified organic silicone oil is prepared by the following steps:
step S1, adding a triethylamine solution of allyl glycidyl ether and chloroplatinic acid into a four-neck flask provided with a stirrer, a dropping funnel, a reflux condenser tube and a thermometer, slowly dropping tetramethyldihydrodisiloxane at 85 ℃ for 1h, reacting for 1h after dropping, then carrying out reduced pressure fractionation and purification, collecting fractions under the conditions of 180 ℃ and 0.01MPa to obtain 1, 3-bis (3-glycidoxypropyl) -1,1,3, 3-tetramethyldisiloxane, wherein the concentration of the triethylamine solution of chloroplatinic acid is 0.012mol/L, and the dosage ratio of the allyl glycidyl ether to the triethylamine solution of chloroplatinic acid to the tetramethyldihydrodisiloxane is 3mol:3mL:1 mol.
Step S2, adding hexamethylene diamine and the 1, 3-di (3-glycidoxypropyl) -1,1,3, 3-tetramethyldisiloxane obtained in the step S1 into a reaction bottle, and reacting at 95 ℃ for 4h to obtain an amino-terminated organosilicon intermediate, wherein the addition molar mass ratio of the hexamethylene diamine to the 1, 3-di (3-glycidoxypropyl) -1,1,3, 3-tetramethyldisiloxane is 2.2: 1;
and S3, sequentially adding the amino-terminated organosilicon intermediate and octadecyltrimethoxysilane obtained in the step S2 into a three-neck flask provided with an electric stirrer, a thermometer and a zigzag condenser, stirring at 250r/min, heating to 70 ℃, adding a catalyst, continuously heating to 100 ℃, keeping the temperature for reaction for 3 hours, heating to 145 ℃ after the reaction is finished, and performing reduced pressure distillation to remove low-boiling-point substances and the catalyst to obtain the amino-modified organosilicon oil, wherein the adding mass ratio of the amino-terminated organosilicon intermediate, the octadecyltrimethoxysilane and the catalyst is 20:8:0.05, and the catalyst is tetramethylammonium hydroxide.
Selecting 8 groups of pure white T-shirt cotton cloth with the same size and the same texture, wherein each group contains 4 pieces of pure white T-shirt cotton cloth, finishing the 7 groups of pure white T-shirt cotton cloth by using the waterproof agent obtained in the above examples 1-3 and comparative examples 1-4 respectively, the finishing conditions are the same, the group of pure white T-shirt cotton cloth is a blank group contrast test, and performing an application performance test on 8 tissue objects obtained after finishing, wherein the softness: a softness measuring instrument is adopted for measurement, the bending rigidity values of the fabric are measured for multiple times at different warp and weft positions and are weighted and averaged, and the bending rigidity/mN value is inversely proportional to the softness; hydrophilicity: the static water absorption time/s is used for expressing, the average value is calculated after multiple measurements through a suspended water dropping test method, and the static water absorption time is inversely proportional to the hydrophilicity of the fabric; water washing resistance: putting the finished cloth sample into a neutral washing powder aqueous solution, washing by using a washing color fastness tester, setting the standard washing temperature to be 25 ℃, setting the standard washing frequency to be 30 min/time, washing 20 times, dewatering, washing with clear water for multiple times to ensure that no washing powder solution remains, and drying to test the application performance; and (3) antibacterial property: and calculating the bacteriostasis rate by taking GB/T20944.3-2008 as a standard and selecting escherichia coli and staphylococcus aureus as test bacteria. The test results obtained are shown below.
TABLE 1 test data for softness, hydrophilicity and antimicrobial properties of textile sample strips
TABLE 2 test data for softness, hydrophilicity and antibacterial properties of fabric samples after 20 washes
From the data in table 1, it can be seen that the fabrics treated with the modified organic water repellent obtained in examples 1-3 have better softness and hydrophilicity and certain antibacterial property than the fabrics treated with comparative examples 1-4, and from the data in table 2, it can be seen that the fabrics treated with the modified organic water repellent obtained in examples 1-3 can maintain good softness, hydrophilicity and antibacterial property after being washed for 20 times.
In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing is merely exemplary and illustrative of the principles of the present invention and various modifications, additions and substitutions of the specific embodiments described herein may be made by those skilled in the art without departing from the principles of the present invention or exceeding the scope of the claims set forth herein.
Claims (10)
1. A modified organosilicon waterproofing agent is characterized by comprising the following raw materials, by weight, 20-30 parts of amino modified organosiloxane, 20-30 parts of modified quaternary ammonium salt polysilane, 1-3 parts of surfactant, 1-5 parts of tripropylene glycol, 1-5 parts of butyl cellosolve, 0.01-0.1 part of initiator and 60-80 parts of deionized water;
the preparation method of the modified organosilicon waterproofing agent comprises the following steps:
uniformly mixing amino modified organic silicone oil, modified quaternary ammonium salt polysilane, a surfactant, tripropylene glycol and ethylene glycol monobutyl ether, then adjusting the pH of the solution to be between 5 and 7 by formic acid, adding deionized water, and uniformly mixing to obtain a pre-emulsion;
and step two, adding an initiator into the pre-emulsion obtained in the step one, uniformly stirring, and reacting for 6-8 hours at 70-90 ℃ to obtain the modified organosilicon waterproofing agent.
2. The modified silicone waterproofing agent according to claim 1, wherein the amino-modified silicone oil is prepared by the steps of:
step S1, mixing allyl glycidyl ether and a triethylamine solution of chloroplatinic acid uniformly, slowly dripping tetramethyl dihydrodisiloxane at 85-90 ℃ for 1-1.5h, continuing to react for 1-2h after dripping, then carrying out reduced pressure fractionation and purification, collecting the fraction at the temperature of 180 ℃ and the pressure of-0.01 MPa, and obtaining 1, 3-bis (3-glycidoxypropyl) -1,1,3, 3-tetramethyl disiloxane;
step S2, mixing hexanediamine and the 1, 3-di (3-glycidoxypropyl) -1,1,3, 3-tetramethyldisiloxane obtained in the step S1 uniformly, and reacting at 85-95 ℃ for 4-6h to obtain an amino-terminated organosilicon intermediate;
and S3, uniformly mixing the amino-terminated organosilicon intermediate obtained in the step S2 and octadecyltrimethoxysilane, stirring at a stirring speed of 300r/min of 250-.
3. The modified silicone waterproofing agent according to claim 2, wherein the concentration of the triethylamine solution of chloroplatinic acid in step S1 is 0.008 to 0.012mol/L, and the use amount ratio of allyl glycidyl ether, the triethylamine solution of chloroplatinic acid, and tetramethyldihydrodisiloxane is 2 to 3mol:1 to 3mL:1 mol.
4. The modified silicone waterproofing agent according to claim 2, wherein hexamethylenediamine and 1, 3-bis (3-glycidoxypropyl) -1,1,3, 3-tetramethyldisiloxane are added in a molar mass ratio of 1.8 to 2.2:1 in step S2.
5. The modified silicone waterproofing agent according to claim 2, wherein the amino-terminated silicone intermediate, the octadecyltrimethoxysilane, and the catalyst are added in a mass ratio of 10-20:3-8:0.01-0.05 in step S3, and the catalyst is tetramethylammonium hydroxide.
6. The modified organosilicon waterproofing agent according to claim 1, wherein the modified quaternary ammonium salt polysilane is prepared by the following steps:
step A, uniformly mixing methyl hydrogen-containing silicone oil, allyl glycidyl ether and isopropanol, heating a reaction system, starting to add a complex platinum catalyst when the temperature rises to 75-83 ℃ of a set temperature, and reacting at a constant temperature of 70-90 ℃ for 2-4 hours after the complex platinum catalyst is completely added to obtain end-ring oxidized organic silicone oil;
and step B, uniformly mixing the end-ring oxidized organic silicon oil, dodecyl dimethyl amine and isopropanol obtained in the step A, heating the reaction system to 80-90 ℃, adjusting the pH value of the reaction system by using glacial acetic acid, maintaining the pH value of the reaction system between 5 and 6, continuously reacting for 8-10 hours, and carrying out reduced pressure distillation after the reaction is finished to obtain the modified quaternary ammonium salt polysilane.
7. The modified silicone waterproofing agent according to claim 6, wherein the addition mass ratio of methyl hydrogen silicone oil, allyl glycidyl ether and isopropyl alcohol in step A is 80-160:8-20: 150-.
8. The modified organosilicon waterproofing agent according to claim 6, wherein the weight ratio of the terminal epoxidized silicone oil, the dodecyldimethylamine and the isopropanol added in step B is 150-200:8-20: 150-300.
9. The modified organosilicon waterproofing agent according to claim 1 wherein the surfactant is fatty alcohol polyoxyethylene ether surfactant and the initiator is hexadecyltrimethoxysilane.
10. A preparation method of a modified organosilicon waterproofing agent is characterized by comprising the following steps:
uniformly mixing amino modified organic silicone oil, modified quaternary ammonium salt polysilane, a surfactant, tripropylene glycol and ethylene glycol butyl, then adjusting the pH of the solution to be between 5 and 7 by formic acid, and then adding deionized water to be uniformly mixed to obtain a pre-emulsion;
and step two, adding an initiator into the pre-emulsion obtained in the step one, uniformly stirring, and reacting for 6-8 hours at 70-90 ℃ to obtain the modified organosilicon waterproofing agent.
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| CN115477738A (en) * | 2022-09-29 | 2022-12-16 | 常州市中策纺织助剂有限公司 | Preparation method of polyurethane modified fluorosilicone resin waterproof agent |
| CN116175720A (en) * | 2023-02-23 | 2023-05-30 | 江苏名天木业有限公司 | Waterproof flame-retardant wood composite floor and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115477738A (en) * | 2022-09-29 | 2022-12-16 | 常州市中策纺织助剂有限公司 | Preparation method of polyurethane modified fluorosilicone resin waterproof agent |
| CN115477738B (en) * | 2022-09-29 | 2023-11-28 | 常州市中策纺织助剂有限公司 | Preparation method of polyurethane modified fluorosilicone resin waterproof agent |
| CN116175720A (en) * | 2023-02-23 | 2023-05-30 | 江苏名天木业有限公司 | Waterproof flame-retardant wood composite floor and preparation method thereof |
| CN116175720B (en) * | 2023-02-23 | 2024-08-09 | 江苏名天木业有限公司 | Waterproof flame-retardant wood composite floor and preparation method thereof |
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