CN109610177A - A kind of preparation method and application of cationic polyurethane acrylate water repellent - Google Patents
A kind of preparation method and application of cationic polyurethane acrylate water repellent Download PDFInfo
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- CN109610177A CN109610177A CN201811517772.7A CN201811517772A CN109610177A CN 109610177 A CN109610177 A CN 109610177A CN 201811517772 A CN201811517772 A CN 201811517772A CN 109610177 A CN109610177 A CN 109610177A
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
- D06M15/568—Reaction products of isocyanates with polyethers
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- 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
- C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
- C08F283/008—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00 on to unsaturated polymers
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
- C08G18/4269—Lactones
- C08G18/4277—Caprolactone and/or substituted caprolactone
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4825—Polyethers containing two hydroxy groups
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
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- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
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- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
- D06M15/572—Reaction products of isocyanates with polyesters or polyesteramides
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- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/01—Stain or soil resistance
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- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/10—Repellency against liquids
- D06M2200/12—Hydrophobic properties
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Abstract
本发明公开了一种阳离子型聚氨酯丙烯酸酯类拒水剂的制备方法及其应用，属于环保型纺织品领域。本发明制备的拒水剂中聚氨酯和丙烯酸酯部分靠化学键连接，聚合物具有优良的成膜性、柔韧性、拒水性；采用聚合过程中引入可阳离子化单体的方式实现了聚合物自乳化，避免了常规丙烯酸酯类拒水剂靠外加低分子表面活性剂乳化带来的拒水效果降低及环境污染等问题；同时，阳离子型拒水剂避免了常规阴离子型产品无法和织物进行紧密吸附的问题，更有利于拒水剂在织物表面的均匀成膜；本发明制备的阳离子型聚氨酯‑丙烯酸酯类拒水剂避免了含氟拒水剂带来的环境污染和生物积累毒性的问题，应用前景广阔。
The invention discloses a preparation method and application of a cationic polyurethane acrylate water-repellent agent, and belongs to the field of environment-friendly textiles. The polyurethane and acrylate parts of the water repellent prepared by the invention are connected by chemical bonds, and the polymer has excellent film-forming property, flexibility and water repellency; the self-emulsification of the polymer is realized by introducing a cationizable monomer in the polymerization process , to avoid the problems of reduced water repellent effect and environmental pollution caused by emulsification of conventional acrylate water repellents by external low molecular surfactants; at the same time, cationic water repellents avoid the inability of conventional anionic products to be tightly adsorbed with fabrics It is more conducive to the uniform film formation of the water-repellent agent on the surface of the fabric; the cationic polyurethane-acrylate water-repellent prepared by the present invention avoids the problems of environmental pollution and bioaccumulation toxicity caused by the fluorine-containing water-repellent agent, The application prospect is broad.
Description
Technical field
The present invention relates to a kind of preparation of cation type polyurethane acrylate water repellent and application methods, belong to weaving neck
Domain.
Background technique
The development of science and technology pushes the continuous development of textile industry, and consumer gradually increases the demand of functional textile
Height, various functional textiles obtain extensive concern and development.Hydrophobic fabric is due to property such as its antifouling, automatically cleanings of excellent water repellent
It can be widely used.Fabric water repellent it is with a long history, common water repellent is mainly fluorinated compound, organic silicon and aliphatic hydrocarbon
Class compound.Fluorinated water repellent can assign fabric excellent water repellent effect, and still, fluorinated is refused in synthesis and use process
Aqua has certain bioaccumulation and toxicity, therefore there are problems that ecological pollution；Meanwhile it is expensive, causes to produce and make
Use higher cost.Organic silicon water repellent can assign the preferable water repellency of fabric and flexibility, but the disadvantage is that increase fabric table
The pilling in face and de- seam property.It is preferable can to assign fabric based on acrylic ester compound for long-chain fat hydro carbons water repellent
Hydrophobic performance.But its use when have hot sticky cold crisp, flexibility it is poor, not solvent resistant the defects of.Polyurethane is a kind of molecular backbone
On the high-molecular compound containing urethane repeating units, have many advantages, such as that low temperature resistant, flexibility is good, adhesion strength is high,
But it lacks hydrophobic performance.The complementation of the advantage and disadvantage of polyurethane and acrylic polymer is conducive to improve polyacrylate
The wearability of water repellent.Since the eighties in last century, polyurethane is used to modified acroleic acid esters product, to obtain advantage
The novel water repellent of performance complement.The method that early stage polyurethane-modified polyacrylate uses physical blending, utilizes polyurethane and third
The mode of olefin(e) acid ester Hydrogenbond, improves the intersolubility of two kinds of molecules.But since hydrogen bond intermolecular force is weaker, so that poly- ammonia
The stability of ester acrylate water repellent is poor.To improve polyurethane and acrylate compatibility, the side of chemical crosslinking can be used
Chemical bonding occurs between polyurethane and acrylate and improves its stability for formula.Chemical crosslinking mostly uses the diacetone third containing carbonyl
Alkene acyl monomer forms crosslinking through dehydration and obtains cross-linking system, but due to before crosslinking, polyurethane and acrylate shape
At relatively stable macromolecular, so that there are certain restrictions for the crosslinking between two kinds of macromolecules.Conventional acrylic esters water repellent system
It needs during standby using additional low molecule emulsifier.Additional emulsifier will affect the water repellent effect of water repellent, while it is dissolved in water,
It causes damages to environment, if emulsifier polyoxyethylene octyl phenol ether biological degradability is poor, some countries and regions have started
Limit its dosage.And additional emulsifier in the preparation of water repellent, use process and processing fabric waste liquid during taking
Discharge and dissolution and washing process, can all cause certain pollution to environment.Self-emulsifying is realized by introducing hydrophilic segment,
It is the group of anion or cation as ionizable.Self-emulsifying water repellent can effectively avoid since additional emulsifier causes product to lack
It falls into.Elecrtonegativity is presented in fabric in water, therefore anionic product can not carry out adsorbed close, and anionic water repellent with fabric
To the more demanding of water quality, limit it and widely apply.Aqueous polyurethane is mostly anionic polyurethane at present, is not had also
Cation type polyurethane-acrylic type water repellent report.In addition, there is also washing fastness for existing routine non-fluorine water repellent
The problem of difference, general washing fastness are no more than 10 average family washing of drum type washing machine.
Therefore it provides a kind of high performance cation polyurethane-esters of acrylic acid water repellent is that have the urgent market demand
's.
Summary of the invention
To solve the above-mentioned problems, the application range of polyurethane-acrylate class water repellent is widened, the present invention constructs one
Kind has the polyurethane-acrylate class water repellent of cationic structural.By introducing unsaturated monomer sealing end, cationisable's list
Body, crosslinkable monomers prepare polyurethane-acrylate class water repellent, the i.e. high fastness water-based emulsion of self-emulsifying cation.
The first purpose of the invention is to provide a kind of cation type polyurethane-esters of acrylic acid water repellent preparation sides
Method, which comprises
(1) base polyurethane prepolymer for use as is prepared using polymer polyatomic alcohol, part hydramine and diisocyanate；
(2) base polyurethane prepolymer for use as and remaining hydramine and unsaturated alcohol obtain the polyurethane molecular main chain of double bond sealing end；
(3) add water self-emulsifying, obtain waterborne cation polyurethane from lotion；
(4) polyurethane is polymerize from lotion with acrylate monomer to building graft copolymer, obtains cation type polyurethane-
Esters of acrylic acid water repellent.
In one embodiment of the present invention, isocyano (diisocyanate monomer) and hydroxyl are (poly- in the step (1)
Close object polyalcohol, hydramine, unsaturated alcohol) molar ratio be 1.2~2.2.
In one embodiment of the present invention, the polymer polyatomic alcohol accounts for hydroxyl monomer (polymer polyatomic alcohol, alcohol
Amine, unsaturated alcohol) gross mass 84-90%.
In one embodiment of the present invention, the hydramine accounts for hydroxyl monomer (polymer polyatomic alcohol, hydramine, unsaturation
Alcohol) gross mass 2-8%.
In one embodiment of the present invention, the unsaturated alcohol accounts for hydroxyl monomer (polymer polyatomic alcohol, hydramine, no
Saturated alcohols) gross mass 2-8%.
In one embodiment of the present invention, self-emulsifying is that neutralizer and water is added in the step (3), according to solid content
15%~40% stirring to obtain.
In one embodiment of the present invention, acrylic ester monomer and polyurethane contain from lotion in the step (4)
Admittedly the mass ratio measured is (1~2): 1.
In one embodiment of the present invention, the step (4) is to introduce acrylic ester monomer using pre-swollen method to be
Acrylic ester monomer is added in self-emulsifying cation type polyurethane lotion, after certain time acquisition swelling solution is sufficiently stirred
Carry out the polymerization caused by initiator.
In one embodiment of the present invention, the diisocyanate includes that isophorone diisocyanate, toluene two are different
Cyanate, methyl diphenylene diisocyanate, lysine diisocyanate, hexamethylene diisocyanate, 1,4- benzene diisocyanate
One of ester, 1,5- naphthalene diisocyanate, dicyclohexyl methyl hydride diisocyanate, hexamethylene diisocyanate are a variety of.
In one embodiment of the present invention, the polymer polyatomic alcohol includes the polyethers two that molecular weight is 200~1000
One or more mixing of first alcohol, polyester diol.
In one embodiment of the present invention, the hydramine include diethanol amine, triethanolamine, N methyldiethanol amine,
One of tertiarybutyldiethanolamine, dimethyl diethanol amine, N- ethyldiethanolamine are a variety of.
In one embodiment of the present invention, the unsaturated alcohol includes hydroxy-ethyl acrylate, hydroxyethyl methacrylate
One or both of.
In one embodiment of the present invention, the neutralizer includes glacial acetic acid, hydrochloric acid, lactic acid, dimethyl sulphoniopropionate
One of or it is a variety of.
In one embodiment of the present invention, the esters of acrylic acid alkane monomer includes methyl acrylate, acrylic acid fourth
Ester, Hexyl 2-propenoate, 2-ethyl hexyl acrylate, decyl acrylate, dodecyl acrylate, tetradecyl acrylate, Process Conditions of Cetane Acrylate, third
Olefin(e) acid octadecyl ester, methyl methacrylate, butyl methacrylate, hexyl methacrylate, 2-Propenoic acid, 2-methyl-, octyl ester, methyl-prop
Olefin(e) acid last of the ten Heavenly stems ester, lauryl methacrylate, tetradecyl methylacrylate, hexadecyl metrhacrylate, octadecyl methacrylate
One or more of.
In one embodiment of the present invention, the esters of acrylic acid function monomer includes Glycidyl Acrylate, methyl
Glycidyl Acrylate, hydroxy-ethyl acrylate, one of hydroxyethyl methacrylate or a variety of.
In one embodiment of the present invention, the initiator includes azodiisobutyronitrile, azobisisoheptonitrile, persulfuric acid
One of potassium, ammonium persulfate, dibenzoyl peroxide are a variety of.
In one embodiment of the present invention, Water-based cationic polyurethane is from the preparation side of lotion in the step (3)
Method specifically includes:
Be 1.2~2.2 according to isocyano and hydroxyl ratio, by polymer polyatomic alcohol (account for polymer polyatomic alcohol, hydramine,
The 84%~90% of unsaturated alcohol gross mass), hydramine (account for polymer polyatomic alcohol, hydramine, unsaturated alcohol gross mass 2%~
8%), unsaturated alcohol (account for polymer polyatomic alcohol, hydramine, unsaturated alcohol gross mass 2%~8%) vacuum is dry at 50-60 DEG C
Dry water removal；It takes part hydramine that polymer polyatomic alcohol is added, dibutyl tin dilaurate is added and (accounts for and participates in reaction total monomer quality
0.2%) under nitrogen protection, Yu Wendu 50-70 DEG C, diisocyanate is slowly added dropwise, using di-n-butylamine method measure reactant
In system-nco value, temperature is increased after reaching theoretical value (isocyano theoretical residual≤32%) to 60~80 DEG C, is added surplus
Remaining hydramine, in measurement reaction system-NCO content reaches theoretical value (isocyano theoretical residual≤7%) and unsaturation is added afterwards
Alcohol, until in reaction system-NCO content reaches theoretical value (isocyano theoretical residual≤0.5%), realize unsaturated double-bond
Sealing end.Reaction system reduces temperature to room temperature, be added neutralizer (degree of neutralization 100%~120%) adjust reaction pH (pH=6~
7) deionized water, is added by product quality solid content 15%~40% and high-speed stirred self-emulsifying obtains waterborne cation polyurethane
From lotion.
In one embodiment of the present invention, cation type polyurethane-esters of acrylic acid water repellent in the step (4)
Preparation method specifically includes:
Self-emulsifying cation type polyurethane lotion is added dropwise to acrylic ester monomer (acrylate at 40~50 DEG C
The mass ratio of monomer gross mass and the polyurethane solid content from lotion is (1~2): in 1), and with 3000~5000r/min revolving speed
After stirring 15~20min, with 500~1000r/min revolving speed stirring 12 hours, the acrylate list of cation type polyurethane is obtained
Body pre-swollen liquid.A certain amount of initiator (initiator amount is the 0.1%~1% of acrylate monomer dosage) is added, in nitrogen
Atmosphere is enclosed under protection, and 2~3h is kept the temperature under the conditions of 70~80 DEG C.30~40 DEG C of heat preservation dischargings are naturally cooled to, cationic is obtained
Polyurethane-acrylate water repellent.
A second object of the present invention is to provide a kind of cation type polyurethane-esters of acrylic acid water repellent, the water repellents
Agent is prepared using the above method.
Third object of the present invention is to provide a kind of cation type polyurethane-esters of acrylic acid water repellent, it is described sun from
The structure of subtype polyurethane-acrylate class water repellent includes structure shown in formula (I):
Aa-Bb-C-Dd-E-Dm-C-Bn-Ai
Formula (1)
Wherein a, b, d, m, n, i are the natural number of 1-100, and the general formula of the chemical structure of A is (2), and the general formula of the chemical structure of B is
(3), C is the moieties of unsaturated alcohol, and the general formula of the chemical structure of D is (4), and the general formula of the chemical structure of E is (5)；B, C, D, E
Arrangement position is unfixed；
Wherein R1For the carbochain of carbon atom number 1-18；R2For H or-CH3；R3For H or-CH3；R4For polyglycidyl or hydroxyl second
Ester；Wherein R5For the anisomeric cyanate radical group of diisocyanate monomer；R6For the non-hydroxyl group of polyalcohol organic compound；Its
Middle R7, R8, R9For alkane group.
Fourth object of the present invention is to provide a kind of method of fabric hydrophobic treatment, the method be by fabric dipping with
It is handled in treatment fluid, then rolls and bake to obtain the final product；It include above-mentioned cation type polyurethane-esters of acrylic acid in the processing
Water repellent
Fifth object of the present invention is to provide a kind of hydrophobic fabric, the fabric is comprising above-mentioned cationic poly ammonia
Ester-esters of acrylic acid water repellent, or be prepared using above-mentioned dewatering process method.
The invention has the following advantages:
1, the method for the present invention prepares water repellent using the cation type polyurethane and acrylic ester copolymer of unsaturated double-bond sealing end
Agent.Polyurethane and acrylate improve the compatibility of polymer molecule segment by chemistry key connection, in use process, polymerization
Object will not occur mutually to separate, and film-formation result is more preferable.
2, the method for the present invention introduces hydrophilic group hydramine in pre-polymerization, and competition polymerization occurs, and diisocyanate is first anti-with hydramine
It answers, then is reacted with polymer diatomic alcohol, keep the chain length between two hydrophilic groups shorter, cationic hydrophilic base phase is to being evenly distributed on
In performed polymer.
3, the method for the present invention implements polymer certainly by the way of introducing cationisable's monomer during polyurethane polymerization
Emulsification, avoid Conventional acrylic esters water repellent by additional low-molecular-weight surfactant emulsification bring water repellent effect reduce and
The problems such as environmental pollution.Cationic water repellent avoids conventional anion type product and can not carry out tightly with fabric (aobvious elecrtonegativity)
The problem of close absorption, is more advantageous to water repellent in the homogeneous film formation of fabric surface.
4, the polymer polyol alcohol monomer energy in cation type polyurethane-acrylate water repellent of the method for the present invention preparation
Product flexibility is enough provided, diisocyanate unit is capable of providing intensity, and hydramine is capable of providing product self-emulsifying hydrophily, polyurethane
Soft or hard molecule segment in backbone structure can assign the good lower temperature resistance of fabric, flexibility, adhesion strength.Acrylate
Class alkane monomer can effectively reduce surface energy, play the role of water repellent.Third of the functional group containing crosslinking in water repellent molecular structure
The introducing of olefin(e) acid ester monomer can establish the crosslinking between polymer molecule and the chemical bond between fabric, and it is higher to assign product
Fastness.Overcome that conventional water repellent product fastness is poor, and the deficiency of crosslinking agent need to be added in fabric finishing liquor to improve fastness.
5, cation type polyurethane prepared by the present invention-acrylate water repellent is avoided using fluorine-containing water repellent bring
The problem of environmental pollution and biological accumulation toxicity, while acrylic ester monomer hot sticky cold crisp, soft is improved to a certain extent
Poor toughness, not solvent resistant the shortcomings that.Polyurethane and acrylate structural have complementary advantages, the physical mechanical property of fabric after arrangement,
It all makes moderate progress in terms of resistance to water soluble characteristic and thermodynamic property.
6, water repellent of the present invention is easy to operate to the water repellent finish of fabric, more energy saving.The water repellent prepared is in close
Property, the fabric damage after arrangement is small, and product has good uniformity, can form one layer of water repellent film in fabric surface, mentions significantly
High fabric water repellent ability.And the addition of polyurethane, soft fabric can be assigned and plentiful feel.In addition, its VOC emission amount
It is extremely low, it is applicable in environmental requirement.Generally speaking, fabric has good water repellent, softness, ventilative, soil resistant, water-fastness after arrangement
Characteristic.
Detailed description of the invention
Fig. 1: the Static water contact angles figure of processed fabric.
Specific embodiment
The present invention is further described below with reference to specific example, the given examples are served only to explain the present invention, not
For limiting the scope of the invention.
Embodiment 1:
Cation type polyurethane-acrylate water repellent and finish fabric is prepared according to the following steps:
Preparation of the cation type polyurethane from lotion:
It is 1.2:1 according to isocyano and hydroxyl ratio, polytetrahydrofuran (Mn=850) (is accounted for into polytetrahydrofuran (Mn=
850), N methyldiethanol amine, hydroxy-ethyl acrylate gross mass 90%), N methyldiethanol amine (account for polytetrahydrofuran (Mn
=850), N methyldiethanol amine, hydroxy-ethyl acrylate gross mass 2%), hydroxy-ethyl acrylate (account for polytetrahydrofuran (Mn=
850), N methyldiethanol amine, hydroxy-ethyl acrylate gross mass 8%) at 50 DEG C be dried in vacuo water removal；
It takes 1/3N- methyl diethanolamine that polytetrahydrofuran is added, dibutyl tin dilaurate is added and (it is total single to account for participation reaction
The 0.2% of weight) under nitrogen protection, in temperature 50 C, isophorone diisocyanate is slowly added dropwise, using di-n-butylamine
Method measurement-NCO content, when measure reaction system in-nco value reach theoretical value (isocyano theoretical residual≤32%) after rise
Remaining N methyldiethanol amine is added to 60 DEG C in high-temperature, in measurement reaction system-NCO content reaches theoretical value (isocyano
Theoretical residual≤7%) hydroxy-ethyl acrylate is added afterwards, until in reaction system-NCO content reaches theoretical value (isocyano
Theoretical residual≤0.5%), realize unsaturated double-bond sealing end.Reaction system reduces temperature to room temperature, and neutralizer acetic acid is added
(degree of neutralization 100%) adjusts reaction pH (pH=6~7), and deionized water and high-speed stirred is added by product quality solid content 15%
(1000r/min) self-emulsifying obtains waterborne cation polyurethane from lotion.
Acrylic ester monomer, which is reacted with aqueous polyurethane from lotion, prepares water repellent:
Self-emulsifying cation type polyurethane lotion is added dropwise to acrylic ester monomer (acrylic acid 18 at 40 DEG C
Ester: the mass ratio of Glycidyl Acrylate is 95:5, the matter of acrylate monomer gross mass and the polyurethane solid content from lotion
Amount than be 1:1) in, and with 3000r/min revolving speed stir 15min after, with 500r/min revolving speed stirring 12 hours, obtain cation
The acrylate monomer pre-swollen liquid of type polyurethane.Initiator ammonium persulfate is added, and (initiator amount is acrylate monomer use
The 0.1% of amount), under nitrogen atmosphere protection, 3h is kept the temperature under the conditions of 70 DEG C.Naturally cool to 30 DEG C of heat preservations discharging, obtain sun from
Subtype polyurethane-acrylate water repellent.
Cation type polyurethane-esters of acrylic acid water repellent handles fabric:
Above-mentioned cation polyurethane-esters of acrylic acid water repellent agent content be 100g/L, fabric dipping after with pick-up 100%
Mangle bakes 3min in 140 DEG C after 100 DEG C of preliminary drying 2min.Fabric relevant parameter is shown in Table 1 after processing.
Embodiment 2:
Waterborne cation polyurethane is obtained from lotion referring to the condition of embodiment 1, by acrylate monomer gross mass and is gathered
The mass ratio of urethane solid content from lotion replaces with 2:1,1.5:1 by 1:1 respectively, and other conditions are constant, be prepared sun from
Subtype polyurethane-acrylate water repellent.
Referring to 1 fabric treating condition of embodiment, using resulting cation type polyurethane-acrylate water repellent to fabric
It is handled, treated, and fabric relevant parameter is shown in Table 1.
The relevant parameter of fabric after the processing of table 1
Note: fabric CIE whiteness value is 75.8 before handling, pliability 66.19, and through being 720N to breaking strength, broadwise is disconnected
Resistance to spalling is 480N, and water-fastness test tests mark according to the 2A in AATCC Test Method 61-2010 " color fastness to washing "
Standard carries out soaping for AATCC 2A standard of and is equivalent to the washing of 5 average family washing machines.
Product hydrophobic effect: as shown in Table 1, different acrylate monomer gross mass and the polyurethane solid content from lotion
Fabric water repellent effect after the cation type polyurethane prepared under mass ratio-acrylate water repellent arranges is preferable, resistance to quiet
Hydraulic pressure is high, and pilling resistance is excellent, and fabric whiteness is preferable, and breaking strength is high.
Product washing fastness: as shown in Table 1, different acrylate monomer gross mass and the polyurethane solid content from lotion
Mass ratio under cation type polyurethane-acrylate water repellent for preparing arrange after fabric by being equivalent to 25 families
After the washing of front yard washing machine, fabric Static water contact angles (hydrophobicity) are above 125 °, and hydrophobicity with higher illustrates to utilize this
After the water repellent finish fabric for inventing preparation, fabric washing fastness with higher.
Product hydrophobic effect repeatability: according to the cation type polyurethane-that under different proportion prepared by acrylate monomer
Acrylate water repellent arranges in batches through 10 times, and the coverage error of the Static water contact angles of each finish fabric is ± 2 °, by
Contact angular data is it is found that processing fabric hydrophobic effect is reproducible.
Embodiment 3:
Cation type polyurethane-acrylate water repellent is prepared referring to the condition of embodiment 1, by fabric finishing process
Middle water repellent agent content replaces with 80g/L, 60g/L, 40g/L, 20g/L by 100g/L, and other conditions are constant, carries out respectively to fabric
Processing.Treated, and fabric relevant parameter is shown in Table 2.
The relevant parameter of fabric after the different water repellent agent content impregnations of table 2
Note: fabric CIE whiteness value is 75.8 before handling, pliability 66.19, and through being 720N to breaking strength, broadwise is disconnected
Resistance to spalling is 480N, and water-fastness test tests mark according to the 2A in AATCC Test Method 61-2010 " color fastness to washing "
Standard carries out soaping for AATCC 2A standard of and is equivalent to the washing of 5 average family washing machines.
Product hydrophobic effect: as shown in Table 2, the cation type polyurethane that the same terms are prepared-acrylate water repellent
Agent uses different water repellent dosages in finish fabric, and gained fabric water repellent effect is preferable, and resistance to hydrostatic pressure is high, anti-fluffing and anti-pilling
Property it is excellent, fabric whiteness is preferable, and breaking strength is high.
Product washing fastness: as shown in Table 2, cation type polyurethane-acrylate that the same terms are prepared is refused
Aqua uses different water repellent dosages in finish fabric, and gained fabric is knitted after being equivalent to 25 home washing machine washings
Object Static water contact angles (hydrophobicity) are above 125 °, and hydrophobicity with higher illustrates prepared by the method water repellent
After finish fabric, fabric washing fastness with higher.
Product hydrophobic effect repeatability: according to the polyurethane-acrylate that under different proportion prepared by acrylate monomer
Water repellent arranges in batches through 10 times, and the coverage error of the Static water contact angles of each finish fabric is ± 2 °, by contact angle number
According to it is found that processing fabric hydrophobic effect is reproducible.
Embodiment 4:
Preparation of the cation type polyurethane from lotion:
It is 2.2:1 according to isocyano and hydroxyl ratio, polyester-diol (Mn=1000) (is accounted for into polyester-diol (Mn=
1000), triethanolamine, hydroxyethyl methacrylate gross mass 84%), triethanolamine (account for polyester-diol (Mn=1000), three
The 8% of ethanol amine, hydroxyethyl methacrylate gross mass), hydroxyethyl methacrylate (account for polyester-diol (Mn=1000), three
The 8% of ethanol amine, hydroxyethyl methacrylate gross mass) water removal is dried in vacuo at 60 DEG C；
It takes 1/3 triethanolamine that polyester-diol is added, dibutyl tin dilaurate is added and (accounts for and participates in reaction total monomer quality
0.2%) under nitrogen protection, in temperature 70 C, toluene di-isocyanate(TDI) is slowly added dropwise, contained using di-n-butylamine method measurement-NCO
Amount, when measure in reaction system-nco value reach theoretical value (isocyano theoretical residual≤32%) after increase temperature to 80
DEG C, it is added remaining triethanolamine, in measurement reaction system-NCO content reaches theoretical value (isocyano theoretical residual≤7%)
After hydroxyethyl methacrylate is added, until in reaction system-NCO content reach theoretical value (isocyano theoretical residual≤
0.5%) unsaturated double-bond sealing end, is realized.Reaction system reduces temperature to room temperature, is added neutralizer hydrochloric acid (degree of neutralization 120%)
Reaction pH (pH=6~7) is adjusted, deionized water and high-speed stirred (1000r/min) is added certainly by product quality solid content 40%
Emulsification obtains waterborne cation polyurethane from lotion.
Acrylic ester monomer, which is reacted with aqueous polyurethane from lotion, prepares water repellent:
Self-emulsifying cation type polyurethane lotion is added dropwise to acrylic ester monomer (acrylic acid 16 at 50 DEG C
Ester: methyl methacrylate: the mass ratio of hydroxy-ethyl acrylate is 100:120:10, acrylate monomer gross mass and polyurethane
From in lotion the mass ratio of solid content be 2:1) in, and with 5000r/min revolving speed stir 20min after, stirred with 1000r/min revolving speed
It mixes 12 hours, obtains the acrylate monomer pre-swollen liquid of cation type polyurethane.Initiator potassium persulfate is added, and (initiator is used
Amount is the 1% of acrylate monomer dosage), under nitrogen atmosphere protection, 2h is kept the temperature under the conditions of 80 DEG C.Naturally cool to 40 DEG C of guarantors
Temperature discharging, obtains cation type polyurethane-acrylate water repellent.
Cation type polyurethane-esters of acrylic acid water repellent handles fabric:
Above-mentioned cation polyurethane-esters of acrylic acid water repellent agent content is 40g/L, is rolled after fabric dipping with pick-up 80%
Liquid bakes 2min in 150 DEG C after 105 DEG C of preliminary drying 2min.Fabric relevant parameter is shown in Table 3 after processing.
Embodiment 5:
Preparation of the cation type polyurethane from lotion:
It is 1.4:1 according to isocyano and hydroxyl ratio, Polyoxyethylene glycol (Mn=400) (is accounted for into polyethylene glycol oxide
Glycol (Mn=400), diethyl diethanolamine, hydroxy-ethyl acrylate gross mass 88%), diethyl diethanolamine (account for polyoxy
Change ethylene glycol (Mn=400), diethyl diethanolamine, hydroxy-ethyl acrylate gross mass 6%), hydroxy-ethyl acrylate (accounts for poly-
Ethylene oxide glycol (Mn=400), diethyl diethanolamine, hydroxy-ethyl acrylate gross mass 6%) be dried in vacuo at 60 DEG C
Water removal；
It takes 1/3 diethyl diethanolamine that Polyoxyethylene glycol is added, dibutyl tin dilaurate is added and (accounts for participation reaction
The 0.2% of total monomer quality) under nitrogen protection, in temperature 70 C, it is slowly added dropwise 1, hexamethylene-diisocyanate, using two positive fourths
Amine method measurement-NCO content, when measure reaction system in-nco value reach theoretical value (isocyano theoretical residual≤32%) after
Temperature is increased to 80 DEG C, is added remaining diethyl diethanolamine, in measurement reaction system-NCO content reaches theoretical value (isocyanic acid
Radical theory surplus≤7%) hydroxy-ethyl acrylate is added afterwards, until in reaction system-NCO content reaches theoretical value (isocyanic acid
Radical theory surplus≤0.5%), realize unsaturated double-bond sealing end.Reaction system reduces temperature to room temperature, and neutralizer lactic acid is added
(degree of neutralization 110%) adjusts reaction pH (pH=6~7), and deionized water and high-speed stirred is added by product quality solid content 30%
(1000r/min) self-emulsifying obtains waterborne cation polyurethane from lotion.
Acrylic ester monomer, which is reacted with aqueous polyurethane from lotion, prepares water repellent:
Self-emulsifying cation type polyurethane lotion is added dropwise to acrylic ester monomer (acrylic acid 14 at 40 DEG C
Ester: octadecyl acrylate: butyl methacrylate: the mass ratio of hydroxyethyl methacrylate is 100:100:120:2, acrylic acid
The mass ratio of ester monomer gross mass and the polyurethane solid content from lotion is 1.5:1) in, and with the stirring of 5000r/min revolving speed
After 20min, with 1000r/min revolving speed stirring 12 hours, the acrylate monomer pre-swollen liquid of cation type polyurethane is obtained.Add
Enter initiator azodiisobutyronitrile (initiator amount is the 0.5% of acrylate monomer dosage), under nitrogen atmosphere protection, 75
3h is kept the temperature under the conditions of DEG C.30 DEG C of heat preservation dischargings are naturally cooled to, cation type polyurethane-acrylate water repellent is obtained.
Cation type polyurethane-esters of acrylic acid water repellent handles fabric:
Above-mentioned cation polyurethane-esters of acrylic acid water repellent agent content be 60g/L, fabric dipping after with pick-up 150%
Mangle bakes 2min in 150 DEG C after 110 DEG C of preliminary drying 2min.Fabric relevant parameter is shown in Table 3 after processing.
Embodiment 6:
Preparation of the cation type polyurethane from lotion:
It is 1.5:1 according to isocyano and hydroxyl ratio, polypropylene glycol (Mn=400) (is accounted for into polypropylene glycol (Mn=
400), N methyldiethanol amine, hydroxyethyl methacrylate gross mass 85%), N methyldiethanol amine (account for polypropylene glycol
(Mn=400), N methyldiethanol amine, hydroxyethyl methacrylate gross mass 8%), hydroxyethyl methacrylate (Zhan Jubing
Glycol (Mn=400), N methyldiethanol amine, hydroxyethyl methacrylate gross mass 7%) be dried in vacuo and remove at 50 DEG C
Water；
It takes 1/3N- methyl diethanolamine that polypropylene glycol is added, dibutyl tin dilaurate is added and (accounts for participation reaction total monomer
The 0.2% of quality) under nitrogen protection, in temperature 70 C, isoflurane chalcone diisocyanate is slowly added dropwise, using di-n-butylamine method
Measurement-NCO content, when measure reaction system in-nco value reach theoretical value (isocyano theoretical residual≤32%) after increase
Remaining N methyldiethanol amine is added to 75 DEG C in temperature, in measurement reaction system-NCO content reaches theoretical value (isocyano reason
By surplus≤7%) hydroxyethyl methacrylate is added afterwards, until in reaction system-NCO content reaches theoretical value (isocyanic acid
Radical theory surplus≤0.5%), realize unsaturated double-bond sealing end.Reaction system reduces temperature to room temperature, and neutralizer lactic acid is added
(degree of neutralization 100%) adjusts reaction pH (pH=6~7), and deionized water and high-speed stirred is added by product quality solid content 20%
(1000r/min) self-emulsifying obtains waterborne cation polyurethane from lotion.
Acrylic ester monomer, which is reacted with aqueous polyurethane from lotion, prepares water repellent:
Self-emulsifying cation type polyurethane lotion is added dropwise to acrylic ester monomer (methacrylic acid ten at 40 DEG C
Octaester: dodecyl acrylate: glycidyl methacrylate mass ratio 100:150:10, acrylate monomer gross mass and poly- ammonia
The mass ratio of ester solid content from lotion be 1:1) in, and with 3000r/min revolving speed stir 20min after, with 500r/min revolving speed
Stirring 12 hours, obtains the acrylate monomer pre-swollen liquid of cation type polyurethane.Initiator potassium persulfate (initiator is added
Dosage is the 0.5% of acrylate monomer dosage), under nitrogen atmosphere protection, 2h is kept the temperature under the conditions of 80 DEG C.Naturally cool to 30
DEG C heat preservation discharging, obtain cation type polyurethane-acrylate water repellent.
Cation type polyurethane-esters of acrylic acid water repellent handles fabric:
Above-mentioned cation polyurethane-esters of acrylic acid water repellent agent content be 20g/L, fabric dipping after with pick-up 100%
Mangle bakes 5min in 140 DEG C after 100 DEG C of preliminary drying 2min.Fabric relevant parameter is shown in Table 3 after processing.
Embodiment 7:
Preparation of the cation type polyurethane from lotion:
It is 1.8:1 according to isocyano and hydroxyl ratio, poly- 6-caprolactone glycol (Mn=1000) (is accounted for into poly- ε-in oneself
Esterdiol (Mn=1000), tertiarybutyldiethanolamine, hydroxyethyl methacrylate gross mass 90%), tertiarybutyldiethanolamine
(account for poly- 6-caprolactone glycol (Mn=1000), tertiarybutyldiethanolamine, hydroxyethyl methacrylate gross mass 7%), methyl
Hydroxy-ethyl acrylate (accounts for poly- 6-caprolactone glycol (Mn=1000), tertiarybutyldiethanolamine, the total matter of hydroxyethyl methacrylate
The 3% of amount) water removal is dried in vacuo at 50 DEG C；
It takes 1/3 tertiarybutyldiethanolamine that poly- 6-caprolactone glycol is added, dibutyl tin dilaurate is added and (it is anti-to account for participation
Answer the 0.2% of total monomer quality) under nitrogen protection, in temperature 70 C, Isosorbide-5-Nitrae-phenylene diisocyanate is slowly added dropwise, just using two
Butylamine method measurement-NCO content, when in measurement reaction system-nco value reaches theoretical value (isocyano theoretical residual≤32%)
Temperature is increased afterwards to 75 DEG C, is added remaining N methyldiethanol amine, in measurement reaction system-NCO content reaches theoretical value (isocyanide
Acid group theoretical residual≤7%) hydroxyethyl methacrylate is added afterwards, until in reaction system-NCO content reaches theoretical value
(isocyano theoretical residual≤0.5%) realizes unsaturated double-bond sealing end.Reaction system reduces temperature to room temperature, in addition
Reaction pH (pH=6~7) is adjusted with agent dimethyl sulphoniopropionate (degree of neutralization 120%), is added by product quality solid content 30%
Deionized water and high-speed stirred (1000r/min) self-emulsifying obtain waterborne cation polyurethane from lotion.
Acrylic ester monomer, which is reacted with aqueous polyurethane from lotion, prepares water repellent:
Self-emulsifying cation type polyurethane lotion is added dropwise to acrylic ester monomer (methacrylic acid ten at 50 DEG C
Four esters: 2-Propenoic acid, 2-methyl-, octyl ester: the mass ratio 100:110:5 of hydroxyethyl methacrylate, acrylate monomer gross mass and poly-
The mass ratio of urethane solid content from lotion be 1.2:1) in, and with 3000r/min revolving speed stir 20min after, with 500r/min
Revolving speed stirs 12 hours, obtains the acrylate monomer pre-swollen liquid of cation type polyurethane.Initiator potassium persulfate is added (to draw
Send out 0.5% that agent dosage is acrylate monomer dosage), under nitrogen atmosphere protection, 2h is kept the temperature under the conditions of 80 DEG C.Natural cooling
It discharges to 30 DEG C of heat preservations, obtains cation type polyurethane-acrylate water repellent.
Cation type polyurethane-esters of acrylic acid water repellent handles fabric:
Above-mentioned cation polyurethane-esters of acrylic acid water repellent agent content be 80g/L, fabric dipping after with pick-up 100%
Mangle bakes 5min in 150 DEG C after 100 DEG C of preliminary drying 2min.Fabric relevant parameter is shown in Table 3 after processing.
Reference examples 1:
Esters of acrylic acid water repellent is prepared according to the following steps:
Emulsifier sodium lauryl sulfate (SDS) and Myrj 45 (AEO-18) is molten in deionized water
Solution prepares emulsion (SDS:AEO-18=1:4, mass ratio, dosage are the 10% of monomer gross mass).Under high velocity agitation
(5000r/min) octadecyl acrylate and methyl methacrylate (monomer weight ratio 1:1, list are added into emulsion system
Body gross mass is the 20% of emulsion quality), carry out pre-emulsification.50% pre-emulsion is added in reaction vessel, by temperature
75 DEG C are risen to, initiator potassium persulfate (initiator amount 0.6%) is added dropwise under nitrogen environment protection, after the reaction was continued 2h,
Remaining pre-emulsion is added, keeps the temperature 2h, is cooled to room temperature cooling discharging.
Prepare water repellent finish fabric method:
Water repellent agent content is 80g/L, with 100% mangle of pick-up after fabric dipping, in 140 DEG C after 105 DEG C of preliminary drying 2min
Bake 5min.Fabric relevant parameter is shown in Table 3 after processing.
Reference examples 2:
Anionic polyurethane modified acroleic acid esters water repellent is prepared according to the following steps:
Referring to embodiment 1, cationisable's hydramine (N methyldiethanol amine) is only replaced with into anionic dihydroxy
Methylbutanoic acid cooperates neutralizer triethylamine, anionic polyurethane modified acroleic acid esters water repellent is prepared.
Prepare water repellent finish fabric method:
Fabric finishing method is with embodiment 1, and fabric relevant parameter is shown in Table 3 after processing.
Reference examples 3:
Referring to embodiment 1, change N methyldiethanol amine adding manner, when pre-polymerization is added without hydramine, only expands in second step
It is added completely into when chain:
Polytetrahydrofuran, dibutyl tin dilaurate (account for participate in reaction total monomer quality 0.2%) under nitrogen protection,
In temperature 50 C, isophorone diisocyanate is slowly added dropwise, using di-n-butylamine method measurement-NCO content, when measurement reactant
In system-nco value reaches theoretical value (isocyano theoretical residual≤32%) and increases temperature afterwards to 60 DEG C, addition N- methyl diethyl
Hydramine, in measurement reaction system-NCO content reaches theoretical value (isocyano theoretical residual≤7%) and acrylic acid hydroxyl is added afterwards
Ethyl ester, until in reaction system-NCO content reaches theoretical value (isocyano theoretical residual≤0.5%), realize unsaturated double
Key sealing end.Reaction system reduces temperature to room temperature, be added neutralizer acetic acid (degree of neutralization 100%) adjust reaction pH (pH=6~
7) deionized water, is added by product quality solid content 15% and high-speed stirred (1000r/min) self-emulsifying obtains waterborne cation
Polyurethane is from lotion.
Polyurethane-acrylate water repellent is obtained referring to 1 water repellent preparation condition of embodiment, and is used at fabric
Reason, treated, and fabric relevant parameter is shown in Table 3.
Reference examples 4:
Referring to embodiment 1, only change N methyldiethanol amine adding manner, when pre-polymerization is disposably added completely into hydramine:
N methyldiethanol amine, polytetrahydrofuran, dibutyl tin dilaurate (account for and participate in reaction total monomer quality
0.2%) under nitrogen protection, in temperature 50 C, be slowly added dropwise isophorone diisocyanate, increase temperature to 60 DEG C, be added
Hydroxy-ethyl acrylate realizes unsaturated double-bond sealing end.Reaction system reduces temperature to room temperature, and neutralizer acetic acid (degree of neutralization is added
100%) reaction pH (pH=6~7) is adjusted, deionized water and high-speed stirred (1000r/ is added by product quality solid content 15%
Min) self-emulsifying obtains waterborne cation polyurethane from lotion.
Polyurethane-acrylate water repellent is obtained referring to 1 water repellent preparation condition of embodiment, and is used at fabric
Reason, treated, and fabric relevant parameter is shown in Table 3.
Fabric relevant parameter after the processing of table 3
Note: fabric CIE whiteness value is 75.8 before handling, pliability 66.19, and through being 720N to breaking strength, broadwise is disconnected
Resistance to spalling is 480N, and water-fastness test tests mark according to the 2A in AATCC Test Method 61-2010 " color fastness to washing "
Standard carries out soaping for AATCC 2A standard of and is equivalent to the washing of 5 average family washing machines.
Product hydrophobic effect: water repellent processing after fabric hydrophobic performance data as shown in table 1-3, comparative example 1-7
With reference examples 1-4 it is found that the present invention design cation type polyurethane modified acroleic acid esters water repellent processing fabric ratio only
Containing the modified acrylate water repellent of esters of acrylic acid water repellent and anionic polyurethane there is better water repellent effect (to connect
Feeler is all larger than 140 °) and preferable ultimate strength (strength loss be lower than 10%), meanwhile, relative to being added at one time hydramine
Water repellent prepared by hydramine is added portionwise with better water repellent effect in technique.
Product hydrophobic effect repeatability: the fabric arranged by embodiment 1 arranges, each finish fabric in batches through 10 times
Static water contact angles range be 146 ± 3 °, by contact angular data it is found that processing fabric hydrophobic effect it is reproducible.
Water-wash resistance: referring to AATCC 61-2010 " washing color fastness " standard, to after the arrangement of water repellent agent emulsion
Fabric carries out washing fastness test.After washing, the Static water contact angles of fabric are measured.The fabric that embodiment 1-7 is arranged
After being equivalent to the washing of 25 home washing machines, although static contact angle is declined compared with before soap, cloth specimen contact angle
130 ° are all larger than, fabric still has higher hydrophobic performance, illustrates that the water repellent has preferable wash durability.
Ultimate strength: referring to 3923-2013 " measurement strip of fabric tension performance ultimate strength and elongation at break of GB/T
Sample method ", the fabric for arranging front and back to water repellent carries out ultimate strength test.It can be seen from the data in Table 3 that by cationic
The ultimate strength loss for the fabric that polyurethane-acrylate water repellent arranges is smaller.
The above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114409853A (en) * | 2022-02-07 | 2022-04-29 | 湖南隆森化工有限公司 | Fluorine-free waterproof agent and preparation method thereof |
| CN115181218A (en) * | 2022-07-15 | 2022-10-14 | 青岛大学 | A kind of preparation method and application of cationic polyurethane-acrylate water repellent |
| CN116516696A (en) * | 2023-03-21 | 2023-08-01 | 青岛大学 | Preparation and application of a polyurethane-acrylate fluorine-free water repellent disperse dye integrated product |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1721460A (en) * | 2004-07-14 | 2006-01-18 | 拜尔材料科学有限公司 | Polyisocyanates with improved compatibility with high hydroxyl content polyols |
| EP1699841B1 (en) * | 2003-12-05 | 2012-11-21 | 3M Innovative Properties Company | Coating compositions with perfluoropolyetherisocyanate derived silane and alkoxysilanes |
| CN104004142A (en) * | 2014-05-22 | 2014-08-27 | 浙江传化股份有限公司 | Cationic-nonionic water-based polyurethane-polyacrylate composite emulsion and preparation method thereof |
| CN104610869A (en) * | 2015-02-05 | 2015-05-13 | 林爱娜 | Waterproof anti-fouling waterborne polyurethane coating and preparation method thereof |
| CN105332287A (en) * | 2015-10-14 | 2016-02-17 | 安徽中恩化工有限公司 | Coating resin used for high temperature resistant high adhesive force wet hand wearable PVC gloves, and preparation method thereof |
| US20160160437A1 (en) * | 2011-08-04 | 2016-06-09 | Soon Kie JUNG | Textile fabric sheet having stain and liquid resistance and the preparation method thereof |
| CN108978226A (en) * | 2018-07-17 | 2018-12-11 | 江南大学 | A kind of preparation of polyurethane-modified polyacrylate class water repellent and application method |
-
2018
- 2018-12-12 CN CN201811517772.7A patent/CN109610177B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1699841B1 (en) * | 2003-12-05 | 2012-11-21 | 3M Innovative Properties Company | Coating compositions with perfluoropolyetherisocyanate derived silane and alkoxysilanes |
| CN1721460A (en) * | 2004-07-14 | 2006-01-18 | 拜尔材料科学有限公司 | Polyisocyanates with improved compatibility with high hydroxyl content polyols |
| US20160160437A1 (en) * | 2011-08-04 | 2016-06-09 | Soon Kie JUNG | Textile fabric sheet having stain and liquid resistance and the preparation method thereof |
| CN104004142A (en) * | 2014-05-22 | 2014-08-27 | 浙江传化股份有限公司 | Cationic-nonionic water-based polyurethane-polyacrylate composite emulsion and preparation method thereof |
| CN104610869A (en) * | 2015-02-05 | 2015-05-13 | 林爱娜 | Waterproof anti-fouling waterborne polyurethane coating and preparation method thereof |
| CN105332287A (en) * | 2015-10-14 | 2016-02-17 | 安徽中恩化工有限公司 | Coating resin used for high temperature resistant high adhesive force wet hand wearable PVC gloves, and preparation method thereof |
| CN108978226A (en) * | 2018-07-17 | 2018-12-11 | 江南大学 | A kind of preparation of polyurethane-modified polyacrylate class water repellent and application method |
Non-Patent Citations (1)
| Title |
|---|
| 周华龙: "《皮革化工材料》", 31 July 2000 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114409853A (en) * | 2022-02-07 | 2022-04-29 | 湖南隆森化工有限公司 | Fluorine-free waterproof agent and preparation method thereof |
| CN114409853B (en) * | 2022-02-07 | 2024-03-26 | 湖南隆森化工有限公司 | Fluorine-free waterproof agent and preparation method thereof |
| CN115181218A (en) * | 2022-07-15 | 2022-10-14 | 青岛大学 | A kind of preparation method and application of cationic polyurethane-acrylate water repellent |
| CN115181218B (en) * | 2022-07-15 | 2024-05-28 | 青岛大学 | Preparation method and application of cationic polyurethane-acrylate water repellent |
| CN116516696A (en) * | 2023-03-21 | 2023-08-01 | 青岛大学 | Preparation and application of a polyurethane-acrylate fluorine-free water repellent disperse dye integrated product |
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