CN109750506B - Organosilicon acrylate composite waterproof finishing agent emulsion - Google Patents
Organosilicon acrylate composite waterproof finishing agent emulsion Download PDFInfo
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Abstract
The invention discloses an organosilicon acrylate composite waterproof finishing agent emulsion, which is prepared by blending organosilicon emulsion and silicon-containing acrylate emulsion, wherein the organosilicon emulsion accounts for 52-68% by mass percent, and the silicon-containing acrylate emulsion accounts for 32-48% by mass percent; the organic silicon emulsion mainly comprises vinyl nano SiO2The sol, polymerizable organosilicon monomer and vinyl siloxane emulsion are polymerized; the silicon-containing acrylate emulsion is mainly prepared by emulsion polymerization of an acrylate monomer and a vinyl organosilicon monomer. The acrylate emulsion has good film forming property, adhesion, weather resistance and compatibility with polar and nonpolar polymers, is compounded with the organic silicon emulsion, and can overcome the defects of poor film forming fastness and poor washing fastness of the single-component organic silicon emulsion on the surface of a fabric. The emulsion can form an organic silicon film with low surface energy, can change the roughness of the surface and synergistically enhance the water repellency of the surface.
Description
Technical Field
The invention relates to a waterproof finishing agent, in particular to a waterproof finishing agent compounded by organic silicon and acrylic ester, and belongs to the field of textile functional finishing agents.
Background
The technological progress of the textile industry and the development of chemical auxiliaries improve the properties, especially the functionality, of textiles. Fabrics with excellent waterproof function are increasingly popular.
The waterproof principle of the textile is that the textile is finished by using the waterproof finishing agent, the porosity of the fibers of the fabric is reduced and is lower than the diameter of water molecules, so that the purpose of preventing the water molecules from penetrating through the fabric is achieved, and a good waterproof effect is formed.
Most of the early finishing agents used for textile waterproof are aluminum soap type and paraffin type finishing agents, which form a deposited film on the surface of the textile, but the durability of the textile waterproof is weak because the bonding fastness with the textile is poor. At present, the waterproof agent for textiles is mainly fluorine-series, organosilicon and other auxiliaries. Due to the non-environmental protection property of the fluorine-based auxiliary agent, the fluorine-based auxiliary agent tends to be used cautiously in textiles. The organic silicon compound generally comprises methyl silicone oil, hydroxyl silicone oil and the like, has good waterproof effect and durability, and better meets the requirements of ecological environment protection compared with fluorine compounds.
The single-component organosilicon waterproof has some defects, such as poor film forming fastness, poor washing fastness and the like on the surface of a fabric, so that the waterproof performance of the fabric can be enhanced by modifying organosilicon polymers, acrylate and other polymer emulsions.
Disclosure of Invention
The invention aims to provide an organic silicon acrylate composite waterproof finishing agent which is prepared by blending and modifying organic silicon emulsion and silicon-containing acrylate emulsion.
In order to achieve the purpose, the invention adopts the following technical scheme.
The organic silicon acrylate composite waterproof finishing agent emulsion is formed by blending 52-68% of organic silicon emulsion and 32-48% of silicon-containing acrylate emulsion in percentage by mass;
the organic silicon emulsion mainly comprises vinyl nano SiO2The sol, polymerizable organosilicon monomer (shown as formula 1) and vinyl siloxane emulsion are polymerized, and the preparation method comprises the following steps:
1) adding 80 parts of vinyl siloxane emulsion, 40 parts of water, 2 parts of AEO-9 and 1 part of AEO-7 into an emulsifier, slowly adding 24 parts of polymerizable organic silicon monomer while stirring, and continuously stirring and emulsifying for 0.5h to obtain pre-emulsion;
2) 50 parts of vinyl siloxane emulsion and 14 parts of vinyl nano SiO2Adding sol, 50 parts of water and 20% of pre-emulsion (volume ratio) into a reaction kettle, stirring and dispersing uniformly, and heating in a water bath; 1.7 parts of initiator is dissolved with 20 parts of water to form an initiator aqueous solution;
3) continuously stirring, adding 30% of initiator aqueous solution (volume ratio) when the temperature in the reaction kettle rises to 75-78 ℃, and carrying out heat preservation reaction for 0.5 h;
4) dropwise adding the rest pre-emulsion and the initiator aqueous solution for 2h, and then carrying out heat preservation reaction for 1 h;
5) heating to 82-85 ℃ to continue reacting for 0.5h, then cooling and filtering to obtain an organic silicon emulsion;
the silicon-containing acrylate emulsion is mainly prepared by emulsion polymerization of an acrylate monomer and a vinyl organosilicon monomer (shown as a formula 2), wherein the acrylate monomer comprises methyl methacrylate, ethyl acrylate and butyl acrylate, and the preparation method of the emulsion comprises the following steps:
a) adding 48-60 parts of acrylate monomer, 18 parts of vinyl organosilicon monomer, 6 parts of sodium dodecyl sulfate, 4 parts of AEO-9, 2 parts of glycerol, 1 part of PEG-200 and 240 parts of water into a reactor, stirring and emulsifying for 0.5h to obtain emulsion;
b) heating in water bath, adding a solution of 0.2 part of initiator and 4 parts of water when the temperature of the reactor rises to 68-70 ℃, and reacting for 0.5 hour under heat preservation;
c) dripping 0.4 part of initiator and 10 parts of water solution and 54 parts of acrylate monomer within 2 hours; continuously preserving the heat and reacting for 2 hours;
d) heating to 80 ℃, reacting for 0.5h under the condition of heat preservation, then cooling and filtering to obtain silicon-containing acrylate emulsion;
(H3C)3Si—O-CH2CH2NH-CH2CH＝CH2formula 2
The vinyl nano SiO2The sol is prepared from a vinyl silane coupling agent, a catalyst, water and an emulsifier, and the method comprises the following steps: adding 4 parts of vinyl trimethoxy silane, 1.2 parts of sodium dodecyl benzene sulfonate, 1.7 parts of AEO-9 and 0.6 part of PEG-400 into 100 parts of water, stirring and dispersing, adding 2.3 parts of ammonia water under stirring, and continuously stirring for reacting for 4 hours to form vinyl nano SiO2Sol;
the vinyl siloxane emulsion is prepared from D4(Octamethylcyclotetrasiloxane) D4 ViThe catalyst is prepared by the reaction of (tetramethyl tetravinylcyclotetrasiloxane), an emulsifier, a catalyst and water, and comprises the following specific steps: 80 parts of D410 parts of D4 ViAdding 4 parts of sodium dodecyl benzene sulfonate, 3 parts of OP-10 and 4 parts of dodecyl benzene sulfonic acid into a reactor, stirring and emulsifying for 1h, heating to 83-85 ℃ in a water bath, keeping the temperature for continuous reaction for 5h, cooling and filtering to obtain the vinyl siloxane emulsion.
The mass ratio of the acrylate monomer, methyl methacrylate, ethyl acrylate and butyl acrylate is 1:1: 2.
The initiator is one of sodium persulfate, potassium persulfate and ammonium persulfate.
The organosilicon has a unique chemical structure, and oxygen atoms and silicon atoms in a silicon-oxygen chain structure are alternately arranged and form a spiral straight-chain structure in a winding way. Two groups (typically methyl) attached to each silicon atom rotate around the Si — O. The methyl and silicon atoms in the molecular chain have weak hydrophilicity, and the only oxygen atom with better affinity with water is wrapped by the methyl, so the polysiloxane has good hydrophobicity.
Waterproofing of surfaces is usually achieved by modifying the surface with low surface energy substances or by altering the roughness and surface microtopography of the surface.
The organic silicon emulsion of the invention uses vinyl siloxane emulsion and vinyl nano SiO2The emulsion can form an organic silicon film with low surface energy, can change the roughness of the surface and synergistically enhance the water repellency of the surface. Nano SiO2The sol is combined with organic siloxane through C ═ C bond, so that nano SiO is overcome2Difficult to be stably and uniformly dispersed.
The acrylate emulsion has good film forming property, adhesion, weather resistance and compatibility with polar and nonpolar polymers, and can overcome the defects of poor film forming fastness and poor washing fastness of the single-component organosilicon emulsion on the surface of a fabric by compounding with the organosilicon emulsion, so that the waterproof performance can be enhanced by modifying the organosilicon emulsion and the silicon-containing acrylate emulsion. The acrylic ester is modified by the vinyl organic silicon monomer, so that the surface tension of the acrylic ester emulsion is reduced, the composite compatibility and stability of the acrylic ester emulsion and the organic silicon emulsion are improved, and the defect of unstable reaction caused by hydrolysis, condensation and the like of the conventional organic silicon modified monomer is overcome.
The silicone monomer used in the existing silicone acrylate emulsion and silicone polyurethane emulsion is usually vinyl silicone oil, hydroxy silicone oil, octamethylcyclotetrasiloxane, tetravinyl octamethylcyclotetrasiloxane and a silane coupling agent containing C ═ C bond as a silicone modifier. The viscosity of vinyl silicone oil and hydroxyl silicone oil is highDifficult to emulsify, D4Silane coupling agents and the like containing hydrolyzable groups Si-O-CH3In the emulsion polymerization process, hydrolysis and condensation occur to a certain extent, so that excessive crosslinking among polymer molecules causes unstable reaction, and a stable organosilicon modified emulsion with high silicon content is difficult to obtain. The invention prepares organosilicon monomer which is difficult to hydrolyze, and Si-OCH in methoxysilane3Replacement of the radical by a more sterically hindered Si (CH)3)3The stable emulsion prepared by emulsifying and copolymerizing the acrylic ester monomer not only solves the problem of containing Si-OCH3The hydrolysis problem of the monomers of the group in the emulsion polymerization process improves the water repellency of the emulsion.
The siloxane bond has a large bond angle and can rotate freely, so that the organic silicon molecule has good lubricity and flexibility, and the interaction force between the siloxane chains is small, the molar volume is large, and the organic silicon molecule has good high air permeability.
Detailed Description
The preparation method of the polymerizable organosilicon monomer and the vinyl organosilicon monomer is as follows.
The polymerizable organosilicon monomer is prepared by reacting 2- (trimethylsiloxy) ethanolamine with ethyl methacrylate, and the method comprises the following steps:
adding dehydrated 2- (trimethylsiloxy) ethanolamine, ethyl methacrylate and dibutyltin dilaurate into a reactor provided with a stirrer, a thermometer and a condenser, and stirring at 100 ℃ for 5 hours to react to obtain a functional organic silicon monomer containing C ═ C bonds; the molar ratio of the 2- (trimethylsiloxy) ethanolamine to the isocyanate ethyl methacrylate is 1:1, and the mass of the dibutyltin dilaurate accounts for 0.4 percent of the total mass of the reaction monomers. The involved reaction process is shown as (1).
The vinyl organosilicon monomer is prepared by the reaction of 2- (trimethylsiloxy) ethanolamine and allyl chloride, and the preparation method comprises the following steps:
in a 250mL three-necked flask, 1mol of 2- (trimethylsiloxy) ethanolamine, 1.5mol of triethylamine and 100mL of methylene chloride were added in this order. Placing the three-necked bottle in an ice-water bath, slowly dropwise adding 1.2mol of allyl chloride at the temperature, heating the reaction system to room temperature after dropwise adding, continuously reacting for 1.5 hours at the temperature, stopping the reaction, filtering to remove triethylamine chlorate, distilling under reduced pressure to remove dichloromethane and excessive triethylamine, and collecting fractions to obtain the vinyl organosilicon monomer, namely N-2 (trimethylsiloxy) ethyl enamine. The involved reaction process is shown as (2).
The preparation method of the 2- (trimethylsiloxy) ethanolamine comprises the following steps: adding ethanolamine into a reactor with a mechanical stirrer and a thermometer, stirring and dropwise adding hexamethyldisilazane, reacting at 5-50 ℃ for 0.5-2 h, and obtaining 2- (trimethylsiloxy) ethanolamine through decompression and filtration after the reaction is finished. The molar ratio of ethanolamine to hexamethyldisilazane was 2: 1.
Example 1:
the organic silicon acrylate composite waterproof finishing agent emulsion is formed by blending an organic silicon emulsion and a silicon-containing acrylate emulsion, wherein the organic silicon emulsion accounts for 68 percent and the silicon-containing acrylate emulsion accounts for 32 percent by mass; slowly adding the organic silicon emulsion into the silicon-containing acrylate emulsion under stirring, and uniformly mixing to obtain the silicon-containing acrylate emulsion;
the organic silicon emulsion mainly comprises vinyl nano SiO2The sol, polymerizable organosilicon monomer (shown as formula 1) and vinyl siloxane emulsion are polymerized, and the preparation method comprises the following steps:
1) adding 80 parts of vinyl siloxane emulsion, 40 parts of water, 2 parts of AEO-9 and 1 part of AEO-7 into an emulsifier, slowly adding 24 parts of polymerizable organic silicon monomer while stirring, and continuously stirring and emulsifying for 0.5h to obtain pre-emulsion;
2) 50 parts of vinyl siloxane emulsion and 14 parts of vinyl nano SiO2Adding sol, 50 parts of water and 20% of pre-emulsion (volume ratio) into a reaction kettle,stirring and dispersing uniformly, and heating in a water bath; 1.7 parts of initiator sodium persulfate is dissolved in 20 parts of water to form an initiator aqueous solution;
3) continuously stirring, adding 30% of initiator sodium persulfate aqueous solution (volume ratio) when the temperature in the reaction kettle rises to 75-78 ℃, and reacting for 0.5h under the condition of heat preservation;
4) dropwise adding the rest pre-emulsion and an initiator sodium persulfate aqueous solution for 2h, and then carrying out heat preservation reaction for 1 h;
5) heating to 82-85 ℃ to continue reacting for 0.5h, then cooling and filtering to obtain an organic silicon emulsion;
the silicon-containing acrylate emulsion is mainly prepared by polymerizing an acrylate monomer and a vinyl organic silicon monomer (shown as the formula 2) through emulsion, wherein the acrylate monomer comprises methyl methacrylate, ethyl acrylate and butyl acrylate, and the preparation method of the emulsion comprises the following steps:
a) adding 48 parts of acrylate monomer, 18 parts of vinyl organosilicon monomer, 6 parts of sodium dodecyl sulfate, 4 parts of AEO-9, 2 parts of glycerol, 1 part of PEG-200 and 240 parts of water into a reactor, stirring and emulsifying for 0.5h to obtain emulsion;
b) heating in water bath, adding a solution of 0.2 part of initiator sodium persulfate and 4 parts of water when the temperature of the reactor rises to 68-70 ℃, and reacting for 0.5h under heat preservation;
c) dropwise adding a solution of 0.4 part of initiator sodium persulfate and 10 parts of water and 54 parts of acrylate monomer within 2 h; continuously preserving the heat and reacting for 2 hours;
d) heating to 80 ℃, reacting for 0.5h under the condition of heat preservation, then cooling and filtering to obtain silicon-containing acrylate emulsion;
(H3C)3Si-O-CH2CH2NH-CH2CH＝CH2formula 2
The vinyl nano SiO2The sol is prepared from a vinyl silane coupling agent, a catalyst, water and an emulsifier, and the method comprises the following steps: 4 parts of vinyl trimethoxy silane and 1.2 parts of sodium dodecyl benzene sulfonate1.7 parts of AEO-9 and 0.6 part of PEG-400 are added into 100 parts of water, stirred and dispersed, then 2.3 parts of ammonia water is added under stirring, and the mixture is continuously stirred and reacts for 4 hours to form vinyl nano SiO2Sol;
the vinyl siloxane emulsion is prepared from D4(Octamethylcyclotetrasiloxane) D4 ViThe catalyst is prepared by the reaction of (tetramethyl tetravinylcyclotetrasiloxane), an emulsifier, a catalyst and water, and comprises the following specific steps: 80 parts of D410 parts of D4 ViAdding 4 parts of sodium dodecyl benzene sulfonate, 3 parts of OP-10 and 4 parts of dodecyl benzene sulfonic acid into a reactor, stirring and emulsifying for 1h, heating to 83-85 ℃ in a water bath, keeping the temperature for continuous reaction for 5h, cooling and filtering to obtain the vinyl siloxane emulsion.
Example 2:
the organic silicon acrylate composite waterproof finishing agent emulsion is formed by blending an organic silicon emulsion and a silicon-containing acrylate emulsion, wherein the organic silicon emulsion accounts for 59 percent and the silicon-containing acrylate emulsion accounts for 41 percent by mass; slowly adding the organic silicon emulsion into the silicon-containing acrylate emulsion under stirring, and uniformly mixing to obtain the silicon-containing acrylate emulsion;
the organic silicon emulsion mainly comprises vinyl nano SiO2The sol, polymerizable organosilicon monomer (shown as formula 1) and vinyl siloxane emulsion are polymerized, and the preparation method comprises the following steps:
1) adding 80 parts of vinyl siloxane emulsion, 40 parts of water, 2 parts of AEO-9 and 1 part of AEO-7 into an emulsifier, slowly adding 24 parts of polymerizable organic silicon monomer while stirring, and continuously stirring and emulsifying for 0.5h to obtain pre-emulsion;
2) 50 parts of vinyl siloxane emulsion and 14 parts of vinyl nano SiO2Adding sol, 50 parts of water and 20% of pre-emulsion (volume ratio) into a reaction kettle, stirring and dispersing uniformly, and heating in a water bath; 1.7 parts of initiator potassium persulfate is dissolved with 20 parts of water to form an initiator aqueous solution;
3) continuously stirring, adding 30% of initiator water potassium persulfate solution (volume ratio) when the temperature in the reaction kettle rises to 75-78 ℃, and reacting for 0.5h under heat preservation;
4) dropwise adding the rest pre-emulsion and an initiator potassium persulfate aqueous solution for 2h, and then carrying out heat preservation reaction for 1 h;
5) heating to 82-85 ℃ to continue reacting for 0.5h, then cooling and filtering to obtain an organic silicon emulsion;
the silicon-containing acrylate emulsion is mainly prepared by polymerizing an acrylate monomer and a vinyl organic silicon monomer (shown as the formula 2) through emulsion, wherein the acrylate monomer comprises methyl methacrylate, ethyl acrylate and butyl acrylate, and the preparation method of the emulsion comprises the following steps:
a) adding 54 parts of acrylate monomer, 18 parts of vinyl organosilicon monomer, 6 parts of sodium dodecyl sulfate, 4 parts of AEO-9, 2 parts of glycerol, 1 part of PEG-200 and 240 parts of water into a reactor, stirring and emulsifying for 0.5h to obtain emulsion;
b) heating in water bath, adding a solution of 0.2 part of initiator potassium persulfate and 4 parts of water when the temperature of the reactor rises to 68-70 ℃, and reacting for 0.5h under heat preservation;
c) dropwise adding a solution of 0.4 part of initiator potassium persulfate and 10 parts of water and 54 parts of acrylate monomer within 2 h; continuously preserving the heat and reacting for 2 hours;
d) heating to 80 ℃, reacting for 0.5h under the condition of heat preservation, then cooling and filtering to obtain silicon-containing acrylate emulsion;
(H3C)3Si-O-CH2CH2NH-CH2CH＝CH2formula 2
The vinyl nano SiO2The sol is prepared from a vinyl silane coupling agent, a catalyst, water and an emulsifier, and the method comprises the following steps: adding 4 parts of vinyl trimethoxy silane, 1.2 parts of sodium dodecyl benzene sulfonate, 1.7 parts of AEO-9 and 0.6 part of PEG-400 into 100 parts of water, stirring and dispersing, adding 2.3 parts of ammonia water under stirring, and continuously stirring for reacting for 4 hours to form vinyl nano SiO2Sol;
the vinyl siloxane emulsion is prepared from D4(Octamethylcyclotetrasiloxane) D4 Vi(tetramethyltetravinylcyclotetrasiloxane), emulsifier,The catalyst is prepared by the reaction of a catalyst and water, and the specific steps are as follows: 80 parts of D410 parts of D4 ViAdding 4 parts of sodium dodecyl benzene sulfonate, 3 parts of OP-10 and 4 parts of dodecyl benzene sulfonic acid into a reactor, stirring and emulsifying for 1h, heating to 83-85 ℃ in a water bath, keeping the temperature for continuous reaction for 5h, cooling and filtering to obtain the vinyl siloxane emulsion.
Example 3:
the organic silicon acrylate composite waterproof finishing agent emulsion is formed by blending an organic silicon emulsion and a silicon-containing acrylate emulsion, wherein the organic silicon emulsion accounts for 52 percent and the silicon-containing acrylate emulsion accounts for 48 percent by mass; slowly adding the organic silicon emulsion into the silicon-containing acrylate emulsion under stirring, and uniformly mixing to obtain the silicon-containing acrylate emulsion;
the organic silicon emulsion mainly comprises vinyl nano SiO2The sol, polymerizable organosilicon monomer (shown as formula 1) and vinyl siloxane emulsion are polymerized, and the preparation method comprises the following steps:
1) adding 80 parts of vinyl siloxane emulsion, 40 parts of water, 2 parts of AEO-9 and 1 part of AEO-7 into an emulsifier, slowly adding 24 parts of polymerizable organic silicon monomer while stirring, and continuously stirring and emulsifying for 0.5h to obtain pre-emulsion;
2) 50 parts of vinyl siloxane emulsion and 14 parts of vinyl nano SiO2Adding sol, 50 parts of water and 20% of pre-emulsion (volume ratio) into a reaction kettle, stirring and dispersing uniformly, and heating in a water bath; 1.7 parts of initiator ammonium persulfate and 20 parts of water are dissolved to form an initiator aqueous solution;
3) continuously stirring, adding 30% of initiator ammonium persulfate aqueous solution (volume ratio) when the temperature in the reaction kettle rises to 75-78 ℃, and carrying out heat preservation reaction for 0.5 h;
4) dropwise adding the rest pre-emulsion and an initiator ammonium persulfate aqueous solution for 2h, and then carrying out heat preservation reaction for 1 h;
5) heating to 82-85 ℃ to continue reacting for 0.5h, then cooling and filtering to obtain an organic silicon emulsion;
the silicon-containing acrylate emulsion is mainly prepared by polymerizing an acrylate monomer and a vinyl organic silicon monomer (shown as the formula 2) through emulsion, wherein the acrylate monomer comprises methyl methacrylate, ethyl acrylate and butyl acrylate, and the preparation method of the emulsion comprises the following steps:
a) adding 60 parts of acrylate monomer, 18 parts of vinyl organosilicon monomer, 6 parts of sodium dodecyl sulfate, 4 parts of AEO-9, 2 parts of glycerol, 1 part of PEG-200 and 240 parts of water into a reactor, stirring and emulsifying for 0.5h to obtain emulsion;
b) heating in water bath, adding a solution of 0.2 part of initiator ammonium persulfate and 4 parts of water when the temperature of the reactor rises to 68-70 ℃, and reacting for 0.5h under heat preservation;
c) dropwise adding a solution of 0.4 part of initiator ammonium persulfate and 10 parts of water and 54 parts of acrylate monomer within 2 h; continuously preserving the heat and reacting for 2 hours;
d) heating to 80 ℃, reacting for 0.5h under the condition of heat preservation, then cooling and filtering to obtain silicon-containing acrylate emulsion;
(H3C)3Si-O-CH2CH2NH-CH2CH＝CH2formula 2
The vinyl nano SiO2The sol is prepared from a vinyl silane coupling agent, a catalyst, water and an emulsifier, and the method comprises the following steps: adding 4 parts of vinyl trimethoxy silane, 1.2 parts of sodium dodecyl benzene sulfonate, 1.7 parts of AEO-9 and 0.6 part of PEG-400 into 100 parts of water, stirring and dispersing, adding 2.3 parts of ammonia water under stirring, and continuously stirring for reacting for 4 hours to form vinyl nano SiO2Sol;
the vinyl siloxane emulsion is prepared from D4(Octamethylcyclotetrasiloxane) D4 ViThe catalyst is prepared by the reaction of (tetramethyl tetravinylcyclotetrasiloxane), an emulsifier, a catalyst and water, and comprises the following specific steps: 80 parts of D410 parts of D4 ViAdding 4 parts of sodium dodecyl benzene sulfonate, 3 parts of OP-10 and 4 parts of dodecyl benzene sulfonic acid into a reactor, stirring and emulsifying for 1h, heating to 83-85 ℃ in a water bath, keeping the temperature for continuous reaction for 5h, cooling and filtering to obtain the vinyl siloxane emulsion.
Emulsion stability:
(1) stability of emulsion against acid
3 parts of organic silicon acrylate composite waterproof finishing agent emulsion is added with 97 parts of acetic acid solution with the pH value of 2-3, the mixture is evenly mixed and placed for 24 hours, and the stable condition of the emulsion is observed.
(2) Alkali resistance stability of emulsion
3 parts of organic silicon acrylate composite waterproof finishing agent emulsion is added with a sodium hydroxide solution with the pH value of 12-13, the mixture is evenly mixed and placed for 24 hours, and the emulsion stability is observed.
(3) Emulsion dielectric stability
3 parts of organic silicon acrylate composite waterproof finishing agent emulsion, and 97 parts of MgCl with the mass fraction of 2%2The solution is evenly mixed and then is placed for 24 hours, and the stable condition of the emulsion is observed.
The results of the emulsion stability test are shown in table 1.
TABLE 1 emulsion stability
| Test specimen | Stability of emulsion against acid | Alkali resistance stability of emulsion | Emulsion dielectric stability |
| Example 1 | Stabilization | Stabilization | Stabilization |
| Example 2 | Stabilization | Stabilization | Stabilization |
| Example 3 | Stabilization | Stabilization | Stabilization |
The organic silicon acrylate composite waterproof finishing agent emulsion has better acid and alkali resistance and dielectric stability, which shows that the organic silicon emulsion and the silicon-containing acrylate emulsion have better compatibility.
The organic silicon acrylate composite waterproof finishing agent emulsion of the embodiment is respectively used for waterproof finishing of polyester fabrics, and the process flow is as follows: padding (one padding and one rolling with a retention rate of 80%) → drying (100 ℃) → baking (170 ℃, 90s), and testing the waterproof performance of the finished polyester fabric. Polyester fabric: 50D, 200g/m2。
Water resistance:
waterproof performance: tested according to the method described in AATCC-22-2017. Spraying method: the water temperature is 27 ℃; washing procedure: and (3) washing at 27 ℃, performing conventional washing, hanging and airing, and washing with water for 20 times. The water-repellent properties are shown in table 2.
TABLE 2 waterproof performance of waterproof finish polyester fabric sample
After the polyester fabric is finished by the emulsion of the embodiment, the original waterproof performance reaches 100 minutes, and after 20 times of washing, the original waterproof performance is still maintained for more than 80 minutes, so that the composite waterproof finishing agent emulsion of the embodiment of the invention has excellent waterproof performance.
Claims (3)
1. The organic silicon acrylate composite waterproof finishing agent emulsion is characterized in that: the emulsion is formed by blending organic silicon emulsion and silicon-containing acrylate emulsion, wherein the organic silicon emulsion accounts for 52-68% and the silicon-containing acrylate emulsion accounts for 32-48% by mass;
the organic silicon emulsion mainly comprises vinyl nano SiO2The sol, the polymerizable organosilicon monomer shown as the formula 1 and the vinyl siloxane emulsion are polymerized, and the preparation method comprises the following steps:
1) adding 80 parts of vinyl siloxane emulsion, 40 parts of water, 2 parts of AEO-9 and 1 part of AEO-7 into an emulsifier, slowly adding 24 parts of polymerizable organic silicon monomer while stirring, and continuously stirring and emulsifying for 0.5h to obtain pre-emulsion;
2) 50 parts of vinyl siloxane emulsion and 14 parts of vinyl nano SiO2Adding sol, 50 parts of water and 20% of pre-emulsion in volume ratio into a reaction kettle, stirring and dispersing uniformly, and heating in a water bath; 1.7 parts of initiator is dissolved with 20 parts of water to form an initiator aqueous solution;
3) continuously stirring, adding an initiator aqueous solution with the volume ratio of 30% when the temperature in the reaction kettle rises to 75-78 ℃, and carrying out heat preservation reaction for 0.5 h;
4) dropwise adding the rest pre-emulsion and the initiator aqueous solution for 2h, and then carrying out heat preservation reaction for 1 h;
5) heating to 82-85 ℃ to continue reacting for 0.5h, then cooling and filtering to obtain an organic silicon emulsion;
the silicon-containing acrylate emulsion is mainly prepared by polymerizing an acrylate monomer and a vinyl organic silicon monomer shown in a formula 2 through emulsion, wherein the acrylate monomer comprises methyl methacrylate, ethyl acrylate and butyl acrylate, and the preparation method of the emulsion comprises the following steps:
a) adding 48-60 parts of acrylate monomer, 18 parts of vinyl organosilicon monomer, 6 parts of sodium dodecyl sulfate, 4 parts of AEO-9, 2 parts of glycerol, 1 part of PEG-200 and 240 parts of water into a reactor, stirring and emulsifying for 0.5h to obtain emulsion;
b) heating in water bath, adding a solution of 0.2 part of initiator and 4 parts of water when the temperature of the reactor rises to 68-70 ℃, and reacting for 0.5 hour under heat preservation;
c) dripping 0.4 part of initiator and 10 parts of water solution and 54 parts of acrylate monomer within 2 hours; continuously preserving the heat and reacting for 2 hours;
d) heating to 80 ℃, reacting for 0.5h under the condition of heat preservation, then cooling and filtering to obtain silicon-containing acrylate emulsion;
(H3C)3Si-O-CH2CH2NH-CH2CH＝CH2formula 2
The vinyl nano SiO2The sol is prepared from a vinyl silane coupling agent, a catalyst, water and an emulsifier, and the method comprises the following steps: adding 4 parts of vinyl trimethoxy silane, 1.2 parts of sodium dodecyl benzene sulfonate, 1.7 parts of AEO-9 and 0.6 part of PEG-400 into 100 parts of water, stirring and dispersing, adding 2.3 parts of ammonia water under stirring, and continuously stirring for reacting for 4 hours to form vinyl nano SiO2Sol;
the vinyl siloxane emulsion is prepared from D4(Octamethylcyclotetrasiloxane) D4 ViThe catalyst is prepared by the reaction of (tetramethyl tetravinylcyclotetrasiloxane), an emulsifier, a catalyst and water, and the matrix comprises the following steps: 80 parts of D410 parts of D4 ViAdding 4 parts of sodium dodecyl benzene sulfonate, 3 parts of OP-10 and 4 parts of dodecyl benzene sulfonic acid into a reactor, stirring and emulsifying for 1h, heating to 83-85 ℃ in a water bath, keeping the temperature for continuous reaction for 5h, cooling and filtering to obtain the vinyl siloxane emulsion.
2. The silicone acrylate composite waterproof finishing agent emulsion according to claim 1, characterized in that: the mass ratio of the acrylate monomer, methyl methacrylate, ethyl acrylate and butyl acrylate is 1:1: 2.
3. The silicone acrylate composite waterproof finishing agent emulsion according to claim 1, characterized in that: the initiator is one of sodium persulfate, potassium persulfate and ammonium persulfate.
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