CN111154051A - Waterproof and moisture permeable acrylic resin, and preparation method and application thereof - Google Patents
Waterproof and moisture permeable acrylic resin, and preparation method and application thereof Download PDFInfo
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- CN111154051A CN111154051A CN202010003220.5A CN202010003220A CN111154051A CN 111154051 A CN111154051 A CN 111154051A CN 202010003220 A CN202010003220 A CN 202010003220A CN 111154051 A CN111154051 A CN 111154051A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
- C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
- C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
- C08F255/023—On to modified polymers, e.g. chlorinated polymers
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/04—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06N3/042—Acrylic polymers
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Abstract
The invention discloses a waterproof moisture-permeable acrylic resin, a preparation method and application thereof. The acrylic resin is prepared by blending functional monomers with high EO content and PE modified by a hydrophilic agent, and then carrying out emulsion polymerization on the mixed solution and other main monomers, wherein a strong hydrophilic group is introduced into a molecular main chain, and the resin has a microphase separation structure after film formation, so that the moisture conduction effect of the internal moisture of the fabric from inside to outside is achieved by utilizing the hydrophilicity of the resin and the microphase separation structure, and meanwhile, the high hydrophilicity of the resin improves the leveling property of the resin, so that the prepared waterproof moisture-permeable adhesive for the fabric has excellent leveling property on the surface of the fabric, and under the condition of blade coating construction, the formed coating has high density, and plays a role in isolating the external moisture of the fabric, thereby the whole fabric has the waterproof moisture-permeable function.
Description
Technical Field
The invention belongs to the field of water-based acrylic resin materials, and particularly relates to a waterproof and moisture-permeable acrylic resin, and a preparation method and application thereof.
Background
With the improvement of living standard of people, the requirements on outdoor sportswear are more and more, and the water resistance and moisture permeability are a great trend. At present, the traditional mainstream waterproof moisture permeable adhesive mainly takes a solvent type as a main material, a large amount of organic solvent is contained in the mainstream waterproof moisture permeable adhesive, the volatilization of the solvent causes serious harm to the environment and causes great harm to the health of people, the water-based waterproof moisture permeable adhesive is more and more popular with people along with the enhancement of environmental awareness of people, and the water-based waterproof moisture permeable adhesive takes water as a medium, is nontoxic and noncombustible and does no harm to the environment and the human body. The main body part of the waterproof moisture-permeable adhesive is resin emulsion, so that the environmental protection property of the emulsion plays a decisive role in the environmental protection property of the waterproof moisture-permeable adhesive.
At present, the water-based waterproof moisture-permeable adhesive resin mainly takes water-based polyurethane as a main material, but the cost is higher, and the use and the popularization of a downstream market are limited. In addition, waterproof moisture-permeable coatings such as PTFE films and TPU films also exist in the market, and the cost is high, and the process is complex. Therefore, how to prepare the high-cost-performance high-water-based waterproof moisture-permeable coating through a simple processing technology is the key point for promoting the oil-to-water conversion of the whole waterproof moisture-permeable market.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a waterproof moisture-permeable water-based acrylic resin, which is characterized in that a strong hydrophilic group and a hydrophilic agent modified PE are introduced into a molecular main chain, the moisture conduction effect of the internal moisture of a fabric from inside to outside is achieved by utilizing a structure that the hydrophilicity of the resin is separated from the micro-phase of the resin, and meanwhile, the resin leveling property is improved by the high hydrophilicity of the resin, so that the prepared waterproof moisture-permeable adhesive for the fabric has excellent leveling property on the surface of the fabric, and the formed coating has high density under the condition of one-time construction, plays a role in isolating the external moisture of the fabric, and further ensures that the whole fabric has the waterproof moisture-permeable function. The traditional acrylic resin is difficult to introduce a large amount of hydrophilic groups into a molecular chain due to the limitation of raw materials, and the invention adopts a novel raw material and a high-EO content functional monomer, so that a large amount of hydrophilic groups can be introduced into the molecular chain.
According to a first aspect of the present invention, there is provided a waterproof moisture-permeable water-based acrylic resin comprising or prepared by reacting the following components in parts by mass:
water: 38-68 parts, preferably 40-65 parts, more preferably 44-55 parts;
emulsifier: 0.08 to 3.5 parts, preferably 0.1 to 3 parts, more preferably 0.5 to 1.5 parts;
initiator: 0.04-0.6 part, preferably 0.05-0.5 part, more preferably 0.15-0.2 part;
soft monomer: 13-42 parts, preferably 15-40 parts, more preferably 25-30 parts;
hard monomer: 4-32 parts, preferably 5-30 parts, more preferably 10-25 parts;
functional monomer: 1.5-12 parts, preferably 2-10 parts, more preferably 5-8 parts;
modifying PE by using a hydrophilic agent: 1.5 to 10 parts, preferably 2 to 8 parts, more preferably 3 to 6 parts.
Further, deionized water is used as water. Further, the hydrophilic group in the waterproof and moisture permeable water-based acrylic resin is derived from the provision of a functional monomer, and the functional monomer is selected from one or more of methoxy polyethylene glycol acrylate with the molecular weight of 350-. Commercially available products that may be used are available from manufacturers of charm technology under the trade name mPEG-AC. The molecular weight is number average molecular weight.
Further, in the waterproof moisture-permeable water-based acrylic resin, the soft monomer is selected from one or more of monomers with the glass transition temperature of less than 0 ℃, preferably one or more of butyl acrylate, ethyl acrylate and isooctyl acrylate.
Further, in the waterproof moisture-permeable water-based acrylic resin, the hard monomer is selected from one or more of monomers with the glass transition temperature of more than 0 ℃, preferably one or two of styrene and methyl methacrylate.
Further, in the waterproof moisture-permeable water-based acrylic resin, the initiator is one or more of peroxide and persulfate initiator, preferably one or more of ammonium persulfate, potassium persulfate and tert-butyl peroxide.
Furthermore, in the waterproof moisture-permeable water-based acrylic resin, the emulsifier is selected from one or more of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, tridecanol polyoxyethylene ether sodium sulfate and the like.
Further, in the waterproof moisture-permeable water-based acrylic resin, the hydrophilic modified PE can be prepared by reacting a hydrophilic agent with PE, for example, 10 parts by mass of PE powder is added to 50 to 120 parts by mass of water under stirring, then 1 to 5 parts by mass of the hydrophilic agent is added, after stirring at room temperature (for example, 30 to 120min, preferably about 60min), the resulting mixture is dried (for example, baking in an oven at 80 ℃ for 24h) to obtain the hydrophilic modified PE. The hydrophilic agent can adopt polyether polyol hydrophilic modifier, for example, one or more of CON73 and CON73CL of Youjiu plastic Limited company, Shanghai province, can be selected, PE can be selected from one or more of TL20-40, TL30-40, TL40-60, TL50-40 and TL60-40 of Shenzhen special new material science and technology Limited company, the suitable PE size is 0.25-0.45nm, and the molecular weight is not limited.
According to a second aspect of the present invention, there is provided a method for preparing the waterproof moisture-permeable aqueous acrylic resin of the present invention, which can adopt a conventional method for preparing an aqueous acrylic resin. In a preferred embodiment, the preparation method of the waterproof moisture-permeable water-based acrylic resin comprises the following steps:
a. preparing kettle bottom liquid A: adding a first part of water (preferably deionized water) which accounts for 37-41 wt%, preferably 38-40 wt% of the total amount of water into a polymerization kettle with a stirrer, a condenser and a constant flow pump feeding device, and heating to 50-90 ℃ until the temperature in the kettle reaches;
b. preparing a functional monomer mixed solution B: mixing a functional monomer (such as methoxy polyethylene glycol methacrylate with the molecular weight of 350-;
c. preparation of pre-emulsion C: a second portion of water, which accounts for 3 to 7 weight percent of the total amount of water, preferably 4 to 6 weight percent; a first part of emulsifier, which accounts for 41 to 50 weight percent of the total weight of the emulsifier, preferably 43 to 48 weight percent; stirring and mixing all the mixed liquor B into uniform pre-emulsion, and keeping stirring for later use;
d. preparation of pre-emulsion D: mixing the soft monomer, the hard monomer, the residual emulsifier and the third part of water in 47-51 wt%, preferably 48-50 wt% of the total amount of water, stirring to obtain a uniform pre-emulsion, and keeping stirring for later use;
e. preparation of initiator solution E: stirring the initiator and the fourth part of water which account for 3-7 wt% of the total amount of water, preferably 4-7 wt% of the total amount of water until the initiator and the fourth part of water are completely dissolved for later use;
f. when the temperature in the polymerization kettle reaches 50-90 ℃, adding the whole pre-emulsion C into the kettle, wherein the weight of the pre-emulsion D is 30-70% of the total weight, the weight of the initiator solution E is 30-70% of the total weight, and keeping the temperature in the polymerization kettle at 60-90 ℃ (for 0.3-1h, preferably about 0.5 h);
g. dropwise adding the residual pre-emulsion D and the residual initiator solution E into the polymerization kettle through a constant flow pump feeding device and a constant flow dropwise adding metering device respectively;
h. after the dripping is finished, the temperature in the polymerization kettle is controlled to be 60-90 ℃, the polymerization kettle is kept for 20-60min (for example), the temperature is reduced (generally to be 30-50 ℃, for example about 40 ℃), the mixture is stirred, and the water-based acrylic resin with water resistance and moisture permeability is obtained after filtration and discharging.
The total amount of emulsifier in the two parts and the total amount of water in the four parts should be within the ranges specified above.
Further, the total dropping time of the step g is controlled to be 500 minutes in 120-;
without being bound by theory, it is believed that the moisture permeability of the waterproof moisture-permeable water-based acrylic resin is derived from the moisture-conducting effect provided by the synergistic effect of hydrophilic groups in the main chain of acrylate molecules and a microphase separation structure after the resin is formed into a film; the waterproof moisture-permeable water-based acrylic resin has the waterproof property derived from excellent leveling property brought by high hydrophilicity of the resin.
According to a third aspect of the present invention, there is provided the use of the waterproof moisture-permeable aqueous acrylic resin of the present invention for the coating of a waterproof moisture-permeable fabric, which may be selected from sportswear, outdoor clothing, fireman uniform, military uniform, casual wind clothing, breathable poncho, military tent, sleeping bag, postal parcel, protective goods, or medical goods.
The invention has the following beneficial effects:
1) the invention adopts novel raw materials and a polymerization process, functional monomers with high EO content are introduced into a molecular main chain, a strong hydrophilic group is introduced into a PE modified by a hydrophilic agent, a microphase separation structure can be established during resin film forming, the moisture-conducting effect of the internal moisture of the fabric from inside to outside is achieved by utilizing the structure of the resin hydrophilicity separated from the resin microphase, meanwhile, the resin high hydrophilicity improves the resin leveling property, so that the prepared waterproof moisture-permeable adhesive for the fabric has excellent leveling property on the surface of the fabric, the formed coating has high density under the condition of one-time construction, and plays a role in isolating the external moisture of the fabric, thereby the whole fabric has the waterproof moisture-permeable function.
2) The hydrostatic pressure resistance of the fabric coated with the resin is more than 5000mmH2O, moisture permeability > 6000g/m224h, after washing for five times, the water pressure resistance and the moisture permeability are reduced by no more than 17 percent and 5 percent;
3) the invention has simple production process, convenient operation, safety and no toxicity.
Detailed Description
The invention is described below by means of specific embodiments. Unless otherwise specified, the technical means used in the present invention are well known to those skilled in the art. In addition, the embodiments should be considered illustrative, and not restrictive, of the scope of the invention, which is defined solely by the claims. It will be apparent to those skilled in the art that various changes or modifications in the components and amounts of the materials used in these embodiments can be made without departing from the spirit and scope of the invention.
In the examples, the "%" indicates the mass percent and parts are parts by mass, the percentage of the solution indicates the number of grams of solute contained in 100mL, and the percentage between liquids indicates the volume ratio of the solution at 25 ℃.
The test method in the invention is as follows:
moisture permeability: according to ASTM-E96-05, the test conditions are 50 ℃, 23% RH, 5-10h,2.5m/s wind speed, the unit is g/m2/24h。
Hydrostatic pressure: according to GB/T4744-1997, the unit is mmH2O。
Washing with water for 5 times: and (3) washing for five times by a washing machine according to GB/T8629-2001 at 40 ℃ for 45min for 5 times, and determining that the water pressure and the moisture permeability are reduced by less than 80 percent.
Softness: grading is carried out according to 1-5, 5 represents the best, 1 represents the worst, and the judgment is carried out by touching.
Surface dryness: grading is carried out according to 1-5, 5 represents the best, 1 represents the worst, and the judgment is carried out by touching.
Rebound resilience: grading is carried out according to 1-5, 5 represents the best, 1 represents the worst, and the judgment is carried out by touching.
The construction process for preparing the fabric coating by using the resin comprises the following steps:
coating slurry on semi-matte polyester fabric with a circular knife, drying at 160 deg.C for 1min, and constructing once, wherein the slurry amount is 30-40g/m2. The samples were tested after curing in an oven at 50 ℃ for 24 h.
The construction formula of the fabric coating is as follows:
| components | Addition amount (wt%) | Function of |
| Water-based acrylic resin | 98 | Resin composition |
| cymel 325 | 2 | Curing agent |
In the examples, methoxypolyethylene glycol acrylate with a molecular weight of 350, methoxypolyethylene glycol acrylate with a molecular weight of 1000, methoxypolyethylene glycol acrylate with a molecular weight of 20000, and methoxypolyethylene glycol acrylate with a molecular weight of 10000 were purchased from charm technology of manufacturers, and were all under the trade name mPEG-AC, and different molecular weights were provided according to m values.
The preparation of the hydrophilic modified PE is carried out,
adding 10 parts of PE powder (TL 20-40 of Shenzhen special force new material science and technology Limited) into 87 parts of water under the stirring condition, then adding 3 parts of hydrophilic agent (CON 73 of Baoyamei plastics Limited, Dongguan), stirring at room temperature for 60min, and baking the obtained mixed solution in an oven at 80 ℃ for 24h to obtain the hydrophilic modified PE.
Example 1
The waterproof moisture-permeable water-based acrylic resin comprises the following raw materials in parts by mass: 60 parts of deionized water, an emulsifier (CM30, Solvay, tridecanol polyoxyethylene ether sodium sulfate): 3 parts of a mixture; ammonium persulfate initiator: 0.05 part; soft monomers of BA: 30 parts of (1); st hard monomer: 10 parts of (A); methoxy polyethylene glycol acrylate: 10 parts of (A); modifying PE by using a hydrophilic agent: 8 parts of a mixture;
the preparation method of the waterproof moisture-permeable water-based acrylic resin comprises the following steps:
a. preparing kettle bottom liquid A: adding 40 percent of the total amount of deionized water into a polymerization kettle with a stirrer, a condenser and a constant flow pump feeding device, and heating until the temperature in the kettle reaches 50 ℃;
b. preparing a functional monomer mixed solution B: adding methoxy polyethylene glycol acrylate with molecular weight of 10000 to a beaker: 10 parts of (A); modifying 8 parts of PE by using a hydrophilic agent, and carrying out ultrasonic treatment on the mixed solution beaker in an ultrasonic instrument for 30min for later use;
c. preparation of pre-emulsion C: adding 7% of the total amount of deionized water into a pre-emulsification tank with a monomer metering tank and a stirrer; 41% of the total amount of emulsifier; and (3) mixing liquid B: 18 parts of a mixture; stirring and mixing the mixture into uniform pre-emulsion, and keeping stirring for later use;
d. preparation of pre-emulsion D: adding soft monomers into a pre-emulsification tank with a monomer metering tank and a stirrer: 30 parts of (1); hard monomer: 10 parts of (A); the rest of the emulsifier; 50% of the total amount of deionized water; stirring and mixing the mixture into uniform pre-emulsion, and keeping stirring for later use;
e. preparation of initiator solution E: adding 0.05 part by mass of an initiator into an initiator tank with a stirrer and a constant-current dropwise adding device; 3% of the total amount of the deionized water, and stirring until the deionized water is completely dissolved for later use;
f. when the temperature in the polymerization kettle reaches 50 ℃, adding all the pre-emulsion C into the kettle, wherein the pre-emulsion C accounts for 30% of the total amount of the pre-emulsion D and 30% of the total amount of the initiator solution E, and controlling the temperature in the polymerization kettle to be 60 ℃ for reaction for 1.0 h.
g. Dropwise adding the residual pre-emulsion D and the residual initiator solution E into the polymerization kettle through a constant flow pump feeding device and a constant flow dropwise adding metering device;
h. and (3) after the dropwise addition, controlling the temperature in the polymerization kettle at 60 ℃, keeping the temperature for 20min, cooling to 40 ℃, stirring, filtering and discharging to obtain the acrylic resin with waterproof and moisture-permeable performances.
Wherein the total dropping time of the step g is controlled to be 120 minutes.
Example 2
The waterproof and moisture permeable acrylic resin comprises the following raw materials in parts by mass: 40 parts of deionized water, an emulsifier (CM30, Solvay, tridecanol polyoxyethylene ether sodium sulfate): 0.1 part; potassium persulfate initiator: 0.5 part; EA Soft monomer: 40 parts of a mixture; st hard monomer: 5 parts of a mixture; methoxy polyethylene glycol acrylate: 5 parts of a mixture; modifying PE by using a hydrophilic agent: 3 parts of a mixture;
the preparation method of the acrylic resin for water resistance and moisture permeability comprises the following steps:
a. preparing kettle bottom liquid A: adding 41 percent of the total amount of deionized water into a polymerization kettle with a stirrer, a condenser and a constant flow pump feeding device, and heating until the temperature in the kettle reaches 90 ℃;
b. preparing a functional monomer mixed solution B: to a beaker was added methoxypolyethylene glycol acrylate with a molecular weight of 1000: 5 parts of a mixture; 3 parts of PE modified by a hydrophilic agent, and placing the beaker filled with the mixed solution in an ultrasonic instrument for 30min ultrasonic treatment for later use;
c. preparation of pre-emulsion C: 3% of the total amount of deionized water is added into a pre-emulsification tank with a monomer metering tank and a stirrer; 50% of the total amount of emulsifier; and (3) mixing liquid B: 8 parts of a mixture; stirring and mixing the mixture into uniform pre-emulsion, and keeping stirring for later use;
d. preparation of pre-emulsion D: adding soft monomers into a pre-emulsification tank with a monomer metering tank and a stirrer: 40 parts of a mixture; hard monomer: 5 parts of a mixture; the rest of the emulsifier; 50% of the total amount of deionized water; stirring and mixing the mixture into uniform pre-emulsion, and keeping stirring for later use;
e. preparation of initiator solution E: adding 0.5 part by mass of an initiator into an initiator tank with a stirrer and a constant-current dropwise adding device; 6 percent of the total amount of the deionized water is stirred until the deionized water is completely dissolved for standby;
f. when the temperature in the polymerization kettle reaches 90 ℃, adding all the pre-emulsion C into the kettle, wherein the pre-emulsion C accounts for 70% of the total amount of the pre-emulsion D and 70% of the total amount of the initiator solution E, and controlling the temperature in the polymerization kettle to be at 90 ℃ for reaction for 0.3 h.
g. Dropwise adding the residual pre-emulsion D and the residual initiator solution E into the polymerization kettle through a constant flow pump feeding device and a constant flow dropwise adding metering device;
h. and (3) after the dropwise addition, controlling the temperature in the polymerization kettle at 70 ℃, keeping the temperature for 40min, cooling, stirring, filtering and discharging to obtain the acrylic resin with waterproof and moisture-permeable performances.
Wherein the total dropping time of the step g is controlled to be 180 minutes.
Example 3
The waterproof and moisture permeable acrylic resin comprises the following raw materials in parts by mass: 65 parts of deionized water, and an emulsifier (CM30, Solvay, tridecanol polyoxyethylene ether sodium sulfate): 0.5 part; ammonium persulfate initiator: 0.15 part; EHA soft monomer: 15 parts of (1); MMA hard monomer: 30 parts of (1); methoxy polyethylene glycol acrylate: 8 parts of a mixture; modifying PE by using a hydrophilic agent: 6 parts of (1);
the preparation method of the acrylic resin for water resistance and moisture permeability comprises the following steps:
a. preparing kettle bottom liquid A: adding 37 percent of the total amount of deionized water into a polymerization kettle with a stirrer, a condenser and a constant flow pump feeding device, and heating until the temperature in the kettle reaches 60 ℃;
b. preparing a functional monomer mixed solution B: adding methoxypolyethylene glycol acrylate with molecular weight of 20000 into a beaker: 8 parts of a mixture; 6 parts of PE modified by a hydrophilic agent, and placing the beaker filled with the mixed solution in an ultrasonic instrument for 30min ultrasonic treatment for later use;
c. preparation of pre-emulsion C: 6 percent of the total amount of deionized water is added into a pre-emulsification tank with a monomer metering tank and a stirrer; 48% of the total amount of emulsifier; and (3) mixing liquid B: 14 parts of (1); stirring and mixing the mixture into uniform pre-emulsion, and keeping stirring for later use;
d. preparation of pre-emulsion D: adding soft monomers into a pre-emulsification tank with a monomer metering tank and a stirrer: 15 parts of (1); hard monomer: 30 parts of (1); the rest of the emulsifier; 51% of the total amount of deionized water; stirring and mixing the mixture into uniform pre-emulsion, and keeping stirring for later use;
e. preparation of initiator solution E: adding 0.15 part by mass of an initiator into an initiator tank with a stirrer and a constant-current dropwise adding device; 6 percent of the total amount of the deionized water is stirred until the deionized water is completely dissolved for standby;
f. when the temperature in the polymerization kettle reaches 85 ℃, adding all the pre-emulsion C into the kettle, wherein the pre-emulsion C accounts for 50 percent of the total amount of the pre-emulsion D and the initiator solution E accounts for 50 percent of the total amount of the initiator solution E, and controlling the temperature in the polymerization kettle to be 85 ℃ for reaction for 0.5 h.
g. Dropwise adding the residual pre-emulsion D and the residual initiator solution E into the polymerization kettle through a constant flow pump feeding device and a constant flow dropwise adding metering device;
h. and (3) after dropwise adding, controlling the temperature in the polymerization kettle at 70 ℃, keeping the temperature for 60min, cooling, stirring, filtering and discharging to obtain the acrylic resin with waterproof and moisture-permeable performances.
Wherein the total dropping time of the step g is controlled to be 300 minutes.
Example 4
The waterproof and moisture permeable acrylic resin comprises the following raw materials in parts by mass: 45 parts of deionized water, and an emulsifier (CM30, Solvay, tridecanol polyoxyethylene ether sodium sulfate): 1.5 parts; t-butyl peroxide initiator: 0.2 part; EHA soft monomer: 25 parts of (1); st hard monomer: 25 parts of (1); methoxy polyethylene glycol acrylate: 2 parts of (1); modifying PE by using a hydrophilic agent: 2 parts of (1);
the preparation method of the acrylic resin for water resistance and moisture permeability comprises the following steps:
a. preparing kettle bottom liquid A: adding 40 percent of the total amount of deionized water into a polymerization kettle with a stirrer, a condenser and a constant flow pump feeding device, and heating until the temperature in the kettle reaches 75 ℃;
b. preparing a functional monomer mixed solution B: to a beaker was added methoxypolyethylene glycol acrylate with a molecular weight of 350: 2 parts of (1); 2 parts of PE modified by a hydrophilic agent, and placing the beaker filled with the mixed solution in an ultrasonic instrument for 30min ultrasonic treatment for later use;
c. preparation of pre-emulsion C: adding 7% of the total amount of deionized water into a pre-emulsification tank with a monomer metering tank and a stirrer; 43% of the total amount of emulsifier; and (3) mixing liquid B: 4 parts of a mixture; stirring and mixing the mixture into uniform pre-emulsion, and keeping stirring for later use;
d. preparation of pre-emulsion D: adding soft monomers into a pre-emulsification tank with a monomer metering tank and a stirrer: 25 parts of (1); hard monomer: 25 parts of (1); the rest of the emulsifier; 47% of the total amount of deionized water; stirring and mixing the mixture into uniform pre-emulsion, and keeping stirring for later use;
e. preparation of initiator solution E: adding 0.2 part by mass of an initiator into an initiator tank with a stirrer and a constant-current dropwise adding device; 6 percent of the total amount of the deionized water is stirred until the deionized water is completely dissolved for standby;
f. when the temperature in the polymerization kettle reaches 75 ℃, adding all the pre-emulsion C into the kettle, wherein the pre-emulsion C accounts for 40% of the total amount of the pre-emulsion D and the initiator solution E accounts for 40%, and controlling the temperature in the polymerization kettle to be 75 ℃ for reaction for 0.5 h.
g. Dropwise adding the residual pre-emulsion D and the residual initiator solution E into the polymerization kettle through a constant flow pump feeding device and a constant flow dropwise adding metering device;
h. and (3) after the dropwise addition, controlling the temperature in the polymerization kettle at 70 ℃, keeping the temperature for 50min, cooling, stirring, filtering and discharging to obtain the acrylic resin with waterproof and moisture-permeable performances.
Wherein the total dropping time of the step g is controlled to be 500 minutes.
Comparative example 1
The common acrylic resin comprises the following raw materials in parts by weight: 60 parts of deionized water; emulsifier CM 30: 3 parts of a mixture; 0.05 part of ammonium persulfate initiator; soft monomers of BA: 30 parts of (1); st hard monomer: 10 parts of (A); acrylic acid: 10 parts.
A comparative acrylic resin was prepared by the following steps:
a. preparing kettle bottom liquid A: adding 40 percent of the total amount of deionized water into a polymerization kettle with a stirrer, a condenser and a constant flow pump feeding device, and heating until the temperature in the kettle reaches 50 ℃;
b. preparation of pre-emulsion B: soft monomers are added, for example, at ambient temperature and pressure to a pre-emulsification tank with a monomer metering tank, agitator: 30 parts of (1); hard monomer: 10 parts of (A); acrylic acid: 10 parts of (A); emulsifier: 3 parts of a mixture; 50% of the total amount of deionized water; stirring and mixing the mixture into uniform pre-emulsion, and keeping stirring for later use;
c. preparation of initiator solution C: adding 0.05 part of initiator and 10 percent of deionized water into an initiator tank with a stirrer and a constant-current dropping device at normal temperature and normal pressure, and stirring until the initiator is completely dissolved for later use;
d. when the temperature in the polymerization kettle reaches 50 ℃, adding 30 percent of the total amount of the pre-emulsion B and 30 percent of the total amount of the initiator solution C into the kettle, controlling the reaction temperature to be 60 ℃, reacting for 1.0h, and then simultaneously dripping the residual pre-emulsion B and the residual initiator solution C into the polymerization kettle through a constant flow pump feeding device and a constant flow dripping metering device;
e. and (3) after the dropwise addition, controlling the temperature in the polymerization kettle at 60 ℃, keeping the temperature for 20min, cooling to 40 ℃, stirring, filtering and discharging to obtain the common acrylic resin.
Comparative example 2
The common acrylic resin comprises the following raw materials in parts by weight: 40 parts of deionized water; emulsifier CM 30: 0.1 part; 0.5 part of ammonium persulfate initiator; EA Soft monomer: 40 parts of a mixture; st hard monomer: 5 parts of a mixture; acrylic acid: 5 parts of the raw materials.
A comparative acrylic resin was prepared by the following steps:
a. preparing kettle bottom liquid A: adding 41 percent of the total amount of deionized water into a polymerization kettle with a stirrer, a condenser and a constant flow pump feeding device, and heating until the temperature in the kettle reaches 90 ℃;
b. preparation of pre-emulsion B: soft monomers are added, for example, at ambient temperature and pressure to a pre-emulsification tank with a monomer metering tank, agitator: 40 parts of a mixture; hard monomer: 5 parts of a mixture; acrylic acid: 5 parts of a mixture; emulsifier: 0.1 part; 50% of the total amount of deionized water; stirring and mixing the mixture into uniform pre-emulsion, and keeping stirring for later use;
c. preparation of initiator solution C: adding 0.5 part of initiator and 9 percent of deionized water into an initiator tank with a stirrer and a constant-current dropping device at normal temperature and normal pressure, and stirring until the initiator is completely dissolved for later use;
d. when the temperature in the polymerization kettle reaches 90 ℃, adding 70 percent of the total amount of the pre-emulsion B and 70 percent of the total amount of the initiator solution C into the kettle, controlling the temperature in the polymerization kettle to be at 90 ℃ for reaction for 0.3h, and then simultaneously dripping the residual pre-emulsion B and the residual initiator solution C into the polymerization kettle through a constant flow pump feeding device and a constant flow dripping metering device;
e. and (3) after the dropwise addition, controlling the temperature in the polymerization kettle at 70 ℃, keeping the temperature for 60min, cooling, stirring, filtering and discharging to obtain the common acrylic resin.
Comparative example 3
The common acrylic resin comprises the following raw materials in parts by weight: 65 parts of deionized water, and an emulsifier CM 30: 0.5 part; ammonium persulfate initiator: 0.15 part; EHA soft monomer: 15 parts of (1); MMA hard monomer: 30 parts of (1); acrylic acid: 8 parts of a mixture; modifying PE by using a hydrophilic agent: 6 parts of (1);
a comparative acrylic resin was prepared by the following steps:
a. preparing kettle bottom liquid A: adding 37 percent of the total amount of deionized water into a polymerization kettle with a stirrer, a condenser and a constant flow pump feeding device, and heating until the temperature in the kettle reaches 60 ℃;
b. preparing a functional monomer mixed solution B: adding acrylic acid: 8 parts of a mixture; modifying 6 parts of PE by using a hydrophilic agent, and carrying out ultrasonic treatment on the mixed solution beaker in an ultrasonic instrument for 30min for later use;
c. preparation of pre-emulsion C: 6 percent of the total amount of deionized water is added into a pre-emulsification tank with a monomer metering tank and a stirrer; 48% of the total amount of emulsifier; and (3) mixing liquid B: 14 parts of (1); stirring and mixing the mixture into uniform pre-emulsion, and keeping stirring for later use;
d. preparation of pre-emulsion D: adding soft monomers into a pre-emulsification tank with a monomer metering tank and a stirrer: 15 parts of (1); hard monomer: 30 parts of (1); the rest of the emulsifier; 51% of the total amount of deionized water; stirring and mixing the mixture into uniform pre-emulsion, and keeping stirring for later use;
e. preparation of initiator solution E: adding 0.05 part by mass of an initiator into an initiator tank with a stirrer and a constant-current dropwise adding device; 6 percent of the total amount of the deionized water is stirred until the deionized water is completely dissolved for standby;
f. when the temperature in the polymerization kettle reaches 85 ℃, adding all the pre-emulsion C into the kettle, wherein the pre-emulsion C accounts for 50 percent of the total amount of the pre-emulsion D and the initiator solution E accounts for 50 percent of the total amount of the initiator solution E, and controlling the temperature in the polymerization kettle to be 85 ℃ for reaction for 0.5 h.
g. Dropwise adding the residual pre-emulsion D and the residual initiator solution E into the polymerization kettle through a constant flow pump feeding device and a constant flow dropwise adding metering device;
h. and (3) after the dropwise addition, controlling the temperature in the polymerization kettle at 70 ℃, keeping the temperature for 60min, cooling, stirring, filtering and discharging to obtain the common acrylic resin.
Wherein the total dropping time of the step g is controlled to be 300 minutes.
Comparative example 4
The common acrylic resin comprises the following raw materials in parts by weight: 60 parts of deionized water; emulsifier CM 30: 3 parts of a mixture; 0.05 part of ammonium persulfate initiator; soft monomers of BA: 30 parts of (1); st hard monomer: 10 parts of (A); methoxy polyethylene glycol acrylate: 10 parts.
A comparative acrylic resin was prepared by the following steps:
a. preparing kettle bottom liquid A: adding 40 percent of the total amount of deionized water into a polymerization kettle with a stirrer, a condenser and a constant flow pump feeding device, and heating until the temperature in the kettle reaches 50 ℃;
b. preparation of pre-emulsion B: soft monomers are added, for example, at ambient temperature and pressure to a pre-emulsification tank with a monomer metering tank, agitator: 30 parts of (1); hard monomer: 10 parts of (A); methoxy polyethylene glycol acrylate: 10 parts of (A); emulsifier: 3 parts of a mixture; 50% of the total amount of deionized water; stirring and mixing the mixture into uniform pre-emulsion, and keeping stirring for later use;
c. preparation of initiator solution C: adding 0.05 part of initiator and 10 percent of deionized water into an initiator tank with a stirrer and a constant-current dropping device at normal temperature and normal pressure, and stirring until the initiator is completely dissolved for later use;
d. when the temperature in the polymerization kettle reaches 50 ℃, adding 30 percent of the total amount of the pre-emulsion B and 30 percent of the total amount of the initiator solution C into the kettle, controlling the reaction temperature to be 60 ℃, reacting for 1.0h, and then simultaneously dripping the residual pre-emulsion B and the residual initiator solution C into the polymerization kettle through a constant flow pump feeding device and a constant flow dripping metering device;
e. and (3) after the dropwise addition, controlling the temperature in the polymerization kettle at 60 ℃, keeping the temperature for 20min, cooling to 40 ℃, stirring, filtering and discharging to obtain the common acrylic resin.
The acrylic resins of the examples and comparative examples were used to prepare fabric coatings, and the properties of the constructed samples are shown in Table 1:
TABLE 1 Properties of acrylic resin prepared Fabric coating samples in examples and comparative examples
The above description is only a part of the embodiments of the present invention, and is not intended to limit the scope of the present invention; it is intended that the following claims be interpreted as including all such alterations, modifications, and equivalents as fall within the true spirit and scope of the invention.
Claims (8)
1. The waterproof moisture-permeable water-based acrylic resin comprises the following components in parts by mass or is prepared by reacting the following raw materials in parts by mass:
water: 38-68 parts, preferably 40-65 parts, more preferably 44-55 parts;
emulsifier: 0.08 to 3.5 parts, preferably 0.1 to 3 parts, more preferably 0.5 to 1.5 parts;
initiator: 0.04-0.6 part, preferably 0.05-0.5 part, more preferably 0.15-0.2 part;
soft monomer: 13-42 parts, preferably 15-40 parts, more preferably 25-30 parts;
hard monomer: 4-32 parts, preferably 5-30 parts, more preferably 10-25 parts;
functional monomer: 1.5-12 parts, preferably 2-10 parts, more preferably 5-8 parts;
modifying PE by using a hydrophilic agent: 1.5 to 10 parts, preferably 2 to 8 parts, more preferably 3 to 6 parts.
2. The waterproof moisture-permeable water-based acrylic resin as claimed in claim 1, wherein the hydrophilic group is derived from the provision of a functional monomer selected from one or more of methoxypolyethylene glycol acrylates having a molecular weight of 350-.
3. The water-resistant moisture-permeable acrylic resin for water use according to claim 1 or 2, wherein the soft monomer is selected from one or more of monomers having a glass transition temperature of less than 0 ℃, preferably one or more of butyl acrylate, ethyl acrylate and isooctyl acrylate; and/or
The hard monomer is selected from one or more of monomers with the glass transition temperature of more than 0 ℃, preferably one or two of styrene and methyl methacrylate.
4. The waterproof moisture-permeable aqueous acrylic resin according to any one of claims 1 to 3, wherein the initiator is one or more of a peroxide and a persulfate initiator, preferably one or more of ammonium persulfate, potassium persulfate and tert-butyl peroxide; and/or
The emulsifier is one or more selected from sodium dodecyl sulfate, sodium dodecyl benzene sulfonate and tridecanol polyoxyethylene ether sodium sulfate.
5. The waterproof moisture-permeable aqueous acrylic resin according to any one of claims 1 to 4, wherein the hydrophilic-modified PE is prepared using a reaction of a hydrophilic agent and PE,
preferably, the hydrophilically modified PE is prepared by the following steps: adding 10 parts by mass of PE powder into 50-120 parts by mass of water under the condition of stirring, then adding 1-5 parts by mass of hydrophilic agent, stirring at room temperature, and drying the obtained mixed solution to obtain the hydrophilic modified PE.
6. A process for preparing the water-resistant moisture-permeable acrylic resin for water use according to any one of claims 1 to 5, which comprises the steps of:
a. preparing kettle bottom liquid A: adding a first part of water which accounts for 37-41 wt%, preferably 38-40 wt% of the total amount of water into a polymerization kettle, and heating until the temperature in the kettle reaches 50-90 ℃;
b. preparing a functional monomer mixed solution B: mixing a functional monomer (such as methoxy polyethylene glycol methacrylate with the molecular weight of 350-;
c. preparation of pre-emulsion C: a second portion of water, which accounts for 3 to 7 weight percent of the total amount of water, preferably 4 to 6 weight percent; first part of emulsifier: 41 to 50 wt%, preferably 43 to 48 wt% of the total amount of emulsifier; stirring and mixing all the mixed liquor B into uniform pre-emulsion, and keeping stirring for later use;
d. preparation of pre-emulsion D: stirring and mixing the soft monomer, the hard monomer, the residual emulsifier and the third part of water, wherein the soft monomer, the hard monomer, the residual emulsifier and the third part of water account for 47-51 percent of the total amount of water, preferably 48-50 percent of the total amount of water, and keeping stirring for later use;
e. preparation of initiator solution E: stirring the initiator and the fourth part of water to completely dissolve for later use, wherein the initiator and the fourth part of water account for 3-7 wt% of the total amount of water, and preferably 4-7 wt%;
f. when the temperature in the polymerization kettle reaches 50-90 ℃, adding the whole pre-emulsion C into the kettle, wherein the weight of the pre-emulsion D is 30-70% of the total weight, the weight of the initiator solution E is 30-70% of the total weight, and keeping the temperature in the polymerization kettle at 60-90 ℃ (for 0.3-1h, preferably about 0.5 h);
g. respectively dripping the residual pre-emulsion D and the residual initiator solution E into the polymerization kettle;
h. after the dripping is finished, the temperature in the polymerization kettle is controlled to be 60-90 ℃, the polymerization kettle is kept for 20-60min (for example), the temperature is reduced (generally to be 30-50 ℃, for example about 40 ℃), the mixture is stirred, and the water-based acrylic resin with water resistance and moisture permeability is obtained after filtration and discharging.
7. The preparation method according to claim 6, wherein the total dropping time of step g is controlled to be 120-500 minutes, more preferably 180-300 minutes.
8. Use of the waterproof moisture-permeable aqueous acrylic resin described in any one of claims 1 to 5 or obtained by the production process of claim 6 or 7 for coating waterproof moisture-permeable fabrics selected from sportswear, outdoor clothing, firefighter uniform, military uniform, casual wind clothing, breathable poncho, military tents, sleeping bags, postal bags, protective articles, or medical care articles.
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| CN105907343A (en) * | 2016-05-17 | 2016-08-31 | 湖南省和祥润新材料有限公司 | Water-borne acrylic compound adhesive and preparing method thereof |
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| CN105907343A (en) * | 2016-05-17 | 2016-08-31 | 湖南省和祥润新材料有限公司 | Water-borne acrylic compound adhesive and preparing method thereof |
| CN106520055A (en) * | 2016-11-07 | 2017-03-22 | 南京诺邦新材料有限公司 | Dual-curing display screen shading adhesive for ink-jet printing and preparation method of dual-curing shading adhesive |
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