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CN109553719A - A kind of water repellent antistatic copolymer and preparation method thereof and composition - Google Patents

A kind of water repellent antistatic copolymer and preparation method thereof and composition Download PDF

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Publication number
CN109553719A
CN109553719A CN201811472626.7A CN201811472626A CN109553719A CN 109553719 A CN109553719 A CN 109553719A CN 201811472626 A CN201811472626 A CN 201811472626A CN 109553719 A CN109553719 A CN 109553719A
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weight
parts
copolymer
formula
water
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CN109553719B (en
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郭素明
李正雄
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Shanghai Yayun Technology Co ltd
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Shanghai Ya Yun New Materials Co Ltd
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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
    • C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
    • C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
    • 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
    • D06M15/687—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing atoms other than phosphorus, silicon, sulfur, nitrogen, oxygen or carbon in the main chain
    • 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
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/10—Repellency against liquids
    • D06M2200/12—Hydrophobic properties
    • 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
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/25—Resistance to light or sun, i.e. protection of the textile itself as well as UV shielding materials or treatment compositions therefor; Anti-yellowing treatments

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Abstract

本发明公开了一种拒水抗静电共聚物及其制备方法和组合物。该共聚物包括如下共聚单元。本发明产品不仅具有拒水、抗静电、抗紫外的性能，而且稳定性好，耐水洗性好，具有优异的摩擦牢度。 The invention discloses a water-repellent and antistatic copolymer and its preparation method and composition. The copolymer includes the following copolymerized units. The product of the invention not only has the properties of water repellency, antistatic and anti-ultraviolet, but also has good stability, good washing resistance and excellent rubbing fastness.

Description

A kind of water repellent antistatic copolymer and preparation method thereof and composition
Technical field
The present invention relates to a kind of textile auxiliaries, and in particular to a kind of water repellent antistatic copolymer and preparation method thereof and combination Object.
Background technique
With the development and the improvement of people's living standards of domestic and international textile, the textile with simple function is insufficient To meet the needs of people, the product for seeking multiple performance unification becomes the trend of future development.Both at home and abroad for textile It is mostly the independent or several composite finishing of water repellent, antistatic agent and anti ultraviolet agent, finishing technique is numerous in finishing functions research While trivial and complicated for operation, water repellent, antistatic agent and anti ultraviolet agent there may be incompatible or mutual effect and Influence the final finishing effect of fabric.
Many researchers explore the preparation and application of multiple functions monomer, as disclosed in publication number CN104974527A A kind of polymer-modified foamed composite of organic siliconresin and its preparation method and application, adds polyurethane foam in the patent Foam, organic siliconresin, inorganic filler realize antistatic effect to a certain extent, but hydrophobic and crocking resistance is undesirable.Again It is formed as disclosed a kind of in publication number CN102959035A by hydrophobic polymer block and hydrophilic polymer blocks anti- Electrostatic agent by the polyolefin modified obtained antistatic agent resin of Organic fluoride, but does not have other application performance.
Hydrophilic group in surfactant-based antistatic agent molecule is arranged towards air side, forms single molecule conductive layer. This reduces surface free energy towards air side with the hydrophobic group on water repellent agent molecule and realizes hydrophobic effect and contradict.
In order to solve this difficult point, the present invention is quiet using resisting containing the polymerizable unit with metal capturing ability to cation Electric agent is modified, and making it not only has unimolecule hydrophilic layer, but also forms conductive layer.Then, fluorine-containing auxiliary agent or siliceous additive modification It realizes while function groups exist simultaneously and reach antistatic on strand but also with hydrophobic, water-fastness function.
Summary of the invention
It is an object of the invention to explore the synchronous realization of multiple functions finishing effect, a kind of stable performance, environmental protection, height are provided The water repellent antistatic copolymer of effect and preparation method thereof and composition.
One aspect of the present invention provides a kind of water repellent antistatic copolymer, it includes following copolymerization units:
R in formula1For H, CH3Or CH2CH3, R2、R3、R4And R6It is each independently H or CH3；R5And R7It is respectively independent Ground is C1-4Alkyl, such as methyl, ethyl, propyl, butyl；
n1For 0-17, preferably 1-15；n2For 0-10, preferably 1-5；n3For 0-4, preferably 1-3；
The weight ratio for the copolymerization units that formula A, formula B, formula C and formula D are indicated is 30-50:1-10:10-20:30-50, described to refuse The weight average molecular weight of water antistatic copolymer is 10000-45000.
Another aspect of the present invention provides a kind of preparation method of above-mentioned water repellent antistatic copolymer, it includes following step It is rapid: by 30-50 parts by weight Formulas I) indicate comonomer, 1-10 parts by weight Formula II) indicate comonomer, 10-20 parts by weight Formula III) indicate comonomer and 30-50 parts by weight formula IV) indicate comonomer emulsion polymerization:
R in formula1For H, CH3Or CH2CH3, R2、R3、R4And R6It is each independently H or CH3；R5And R7It is respectively independent Ground is C1-4Alkyl, for example methyl, ethyl, propyl, butyl；
n1For 0-17, preferably 1-15；n2For 0-10, preferably 1-5；n3For 0-4, preferably 1-3；
Another aspect of the present invention provides a kind of water repellent antistatic composition, it includes a) the antistatic copolymerization of above-mentioned water repellent Object and b) uvioresistant copolymer.
The antistatic property of antistatic copolymer of the invention and combinations thereof is good, while but also with hydrophobic, water-fastness function Energy.In addition, antistatic composition of the invention is also equipped with uvioresistant function, facile hydrolysis, appearance and structural stability do not mention product It is high.
Specific embodiment
In one preferred embodiment, water repellent antistatic copolymer of the invention includes following copolymerization units:
R in formula1For H, CH3Or CH2CH3, R2、R3、R4And R6Respectively H or CH3；R5And R7For C1-4Alkyl, such as first Base, ethyl, propyl, butyl；
n1For 0-17, preferably 1-15, more preferably 1-11；n2For 0-10, preferably 1-5, more preferably 2 or 3；n3 For 0-4, preferably 1-3, more preferably 2 or 3；
The weight ratio for the copolymerization units that formula A, formula B, formula C and formula D are indicated is 35-45:2-8:12-18:35-45, described to refuse The weight average molecular weight of water antistatic copolymer is 15000-35000.
In one preferred embodiment, the preparation method of water repellent antistatic copolymer of the present invention includes the following steps: By 35-45 parts by weight Formulas I) indicate comonomer, 2-8 parts by weight Formula II) indicate comonomer, 12-18 parts by weight formula III) indicate comonomer and 35-45 parts by weight formula IV) indicate comonomer emulsion polymerization:
R in formula1For H, CH3Or CH2CH3, R2、R3、R4And R6For H or CH3；R5And R7For C1-4Alkyl, as methyl, Ethyl, propyl, butyl；
n1For 0-17, preferably 1-15, more preferably 1-11；n2For 0-10, preferably 1-5, more preferably 2 or 3；n3 For 0-4, preferably 1-3, more preferably 2 or 3；
In a preferred embodiment, the comonomer of formula (I) is first by (methyl) acrylamide and carbon disulfide The comonomer containing dithiocarbamates is formed in the presence of the alkaline agent of sodium hydroxide etc, it is then anti-with the mantoquita of copper sulphate etc It should be made.The comonomer of formula (I) for example " can contain two sulphur according to paper written by He'nan University master Chen Quan on May 1st, 2003 Preparation and its performance study for Carbamate groups polymer " in the preparation of documented method.The comonomer of formula (I) is for example Including (methyl) acrylamide, crotonamide, 2- methyl -2- amylene amide or their mixture.
In a preferred embodiment, the comonomer of formula (II) is for example including (methyl) acrylic acid trifluoro second Ester, (methyl) hexafluorobutyl acrylate, (methyl) acrylic acid hexafluoro isopropyl ester, (methyl) dodecafluorhe-ptylacrylate, (methyl) Base ethyl ester, (methyl) acrylic acid are complete for perluorooctyl acrylate, (methyl) perfluoroethyl ethyl ester, (methyl) perfluoroethyl Fluorine octyl ethyl ester, (methyl) perfluoroethyl dodecyl ethyl ester or their mixture.
In a preferred embodiment, the comonomer of formula (III) is for example including (methyl) acryloxypropyl Trimethoxy silane, (methyl) acrylyl oxy-ethyl trimethoxy silane, (methyl) acryloxy trimethoxy silane, (first Base) acrylic acyl-oxygen octadecyl three butoxy silane or their mixture.
In a preferred embodiment, the comonomer of formula (IV) is for example including (methyl) acrylyl oxy-ethyl (trimethyl) ammonium chloride, (methyl) acryloxypropyl ammonium chloride, (methyl) acryloyl-oxy butyl ammonium chloride or their mixing Object.
In a preferred embodiment, the emulsion polymerization can carry out in the presence of a free-radical initiator.On The radical initiator stated is for example including persulfate, percarbonate or their mixture.Persulfate is for example including over cure Sour ammonium, sodium peroxydisulfate or their mixture.
In a preferred embodiment, the emulsion polymerization can be in anionic surfactant, neutral-surface It is carried out in the presence of activating agent or their mixtures.
In a more preferred embodiment, anionic surfactant is, for example, C10-18Sodium alkyl sulfate, such as ten Sodium dialkyl sulfate.The neutral surface active agent is, for example, C10-18Fatty alcohol polyoxyethylene ether, such as 13 carbon alcohol polyoxy of isomery (EO number is 6-15 to vinethene, preferably 9).
In a particularly preferred embodiment, the weight ratio of the anion emulsifier and nonionic emulsifier is 1: 2-1:5.The emulsion polymerization carries out at 40-90 DEG C.Antistatic copolymer made from above-mentioned emulsion polymerization reaction is excellent Choosing is random copolymer, block copolymer or their mixture.
In one preferred embodiment, water repellent antistatic composition of the invention include a) above-mentioned water repellent it is antistatic total Polymers and b) uvioresistant copolymer, wherein the weight ratio of the water repellent antistatic copolymer and uvioresistant copolymer is 10- 30:70-90, preferably 15-25:75-85.
In a more preferred embodiment, it is living that water repellent antistatic composition of the invention also contains anionic surface Property agent, neutral surface active agent, dispersing agent or their mixture.The anionic surfactant is C10-18Alkylsurfuric acid Sodium, the neutral surface active agent are C10-18Fatty alcohol polyoxyethylene ether.The anionic surfactant and neutral-surface Activating agent can be identical as anionic surfactant used in above-mentioned emulsion polymerization reaction and neutral surface active agent or not Together.
In a more preferred embodiment, water repellent antistatic composition of the invention also contains dispersing agent, such as It is C12-20Fatty acid amide, such as stearmide.
In a more preferred embodiment, the uvioresistant copolymer is containing benzophenone structural unit Poly- (methyl) acrylate.
In a particularly preferred embodiment, the uvioresistant copolymer is (methyl) acrylic acid C6-12Alkyl The copolymer of the polymerisable monomer of ester, (methyl) glycidyl acrylate and the unit containing benzophenone structural, preferably they Random copolymer or block copolymer.It is used to form (methyl) the acrylic acid C of the uvioresistant copolymer6-12Arrcostab, (first Base) weight ratio of polymerisable monomer of glycidyl acrylate and the unit containing benzophenone structural is 25-50:25-40:15- 30.The weight average molecular weight of the uvioresistant copolymer is 20000-50000, preferably 20000-40000.
In a particularly preferred embodiment, the uvioresistant copolymer passes through (methyl) acrylic acid C2-12Alkyl The emulsion polymerization of the polymerisable monomer of ester, (methyl) glycidyl acrylate and the unit containing benzophenone structural is made.
In a particularly preferred embodiment, (methyl) acrylic acid C1-18Arrcostab is represented by the formula:
In formula (V), R8It is H or CH3；n4For 0-17, preferably 1-11, more preferably 2-9.
In a particularly preferred embodiment, (methyl) acrylic acid C1-18Arrcostab is, for example, (methyl) acrylic acid second Ester, (methyl) propyl acrylate, (methyl) butyl acrylate, (methyl) Hexyl 2-propenoate, (methyl) decyl acrylate, (methyl) Isoamyl acrylate or their mixture.
In a particularly preferred embodiment, (methyl) glycidyl acrylate is represented by the formula:
In formula (VI), R9It is H or CH3。
In a particularly preferred embodiment, (methyl) glycidyl acrylate is, for example, the contracting of (methyl) acrylic acid Water glyceride, glycidyl acrylate or their mixture.
In a particularly preferred embodiment, following general formula is can be used in the polymerisable monomer of the unit containing benzophenone structural It indicates:
In formula, R10For H or CH3；R11And R12It is each independently the substituent groups such as H or F, OH.
In a particularly preferred embodiment, the polymerisable monomer of the unit containing benzophenone structural is can ethylene linkage polymerization Monomer, e.g. 2- hydroxy-4-methyl propylene acyloxy benzophenone, 2- hydroxyl -4- propylene acyloxy benzophenone, Fluorine-containing polymerizable Benzophenone-type light initiator or their mixture.
Contain antistatic, uvioresistant, acrylic monomer in raw material of the present invention, copolymer is controlled by ratio between adjusting raw material Performance indicator, facile hydrolysis, appearance and structural stability do not improve product.
Embodiment
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention Rather than it limits the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, those skilled in the art Member can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited Range.
The performance of the multi-functional copolymer of the antistatic uvioresistant of water repellent obtained passes through following tests in various embodiments of the present invention Verifying.
The multi-functional performance of copolymer test of the antistatic uvioresistant of water repellent
1. fabric: terylene woven fabric
2. technique
Pad (second dipping and rolling, finishing agent 80-140g/L, finishing fluid pH4-8, pick-up 60-80%) → preliminary drying (70-90 DEG C, 2-3min) → bake (150-190 DEG C, 1-3min)
3. performance test
3.1 stability
Product is placed in closed sample bottle, is placed 6 months at 25 DEG C, whether observation product be layered, precipitate Substance.
3.2 crock fastness
Resistance to dry, wet fastness to rubbing: being pressed GB/T 3920-2008, tested using crock fastness tester, graded higher, resistance to It is dry, wet friction is better.
3.3 UPF
Referring to AATCC 183-2004 " transmission or barrier properties that ultraviolet radioactive passes through fabric ", penetrated in antiultraviolet And tested on preventing coating protection tester, UPF value is bigger, and UVResistant effect is better.
The test of 3.4 sheet resistances
The fabric of 2 square metres of sizes is cut, isolation mesa is arrived in tiling, with ZC36 type megger instrument test fabric surface electricity It resistance rate 4 times, is averaged, sheet resistance value is smaller, and antistatic effect is better.
3.5 waterproof performance
Referring to AATCC 22-2005 " water repellency test: spray process ", get wet test and and standard specimen on instrument in dacron Control grading, score value is higher, and hydrophobic effect is better.
3.6 wash durability
The washing test of fabric family is carried out in standard file referring to AATCC 135-2004.
The measurement of 3.7 weight average molecular weight: it is surveyed using HLC-8320GPC type gel permeation chromatograph (Japanese TOSOH Co., Ltd) Fixed, mobile phase is DMF at 25 DEG C, using polymethyl methacrylate (PMMA) as reference.
Embodiment 1:
1) ethyl alcohol of 1.86 parts by weight Methacrylamides, 2.98 parts by weight of sodium hydroxide, 3.35 parts by weight carbon disulfide Solution 10 DEG C or less reactions in deionized water solvent after adsorbing 0.93 parts sulfuric acid copper, filter, water, acetone washing, 50- 80 DEG C of vacuum drying drying, are made 6 parts by weight faint yellow solids.Fusing point is 84-87.5 DEG C.
2) product made from 6 parts by weight steps 1), 1 weight parts of methacrylic acid, ten difluoro heptyl ester, 2 parts by weight metering systems 0.20 parts by weight 12 are added in monomethacryloxypropyl trimethoxy silane, 6 parts by weight methylacryoyloxyethyl (trimethyl) ammonium chlorides Sodium alkyl sulfate, 0.60 parts by weight isomery, 13 carbon alcohol polyoxyethylene ether (EO number is 9), 35.1 parts by weight of deionized water are at room temperature Emulsification is uniformly mixed, and is warming up to 40-55 DEG C of 0.53 parts by weight lauryl sodium sulfate of addition, 1.07 parts by weight isomery, 13 carbon alcohol Polyoxyethylene ether (EO number is 9), is added dropwise the ammonium persulfate aqueous solution that 0.15 parts by weight concentration is 10 weight %, stirring reacts 3 Hour, cooling, discharging latex A.After measured, the weight average molecular weight of copolymer is 20000 in latex A.
3) by 30 weight parts of methacrylic acid butyl esters, 25 weight parts of methacrylic acid ethylene oxidic esters, 16 parts by weight 2- hydroxyls Base -4- propylene acyloxy benzophenone, 0.3 parts by weight lauryl sodium sulfate, 0.6 parts by weight isomery, 13 carbon alcohol polyoxy second Alkene ether (EO number is 9), 155.1 parts by weight of deionized water stirring and emulsifyings are uniformly mixed, and obtain pre-emulsion B.
4) by 76.2 parts by weight pre-emulsion B, 0.30 parts by weight concentration be 10 weight % ammonium persulfate aqueous solution, be warming up to 70-80 DEG C there is blue close to lotion within reaction 10 minutes after keep the temperature 30 minutes, be slowly added into 152.3 parts by weight pre-emulsion B of residue, 1.2 parts by weight concentration are the ammonium persulfate aqueous solution of 10 weight %, are continuously heating to after 75-80 DEG C, reaction 2-3 hours and keep the temperature 30 minutes, cooling down and 0.3 pbw of glacial acetic acid is added adjusted pH value to 3~7, and discharge lotion B.After measured, copolymer in lotion B Weight average molecular weight be 30000.
5) under stirring action, 15 parts by weight copolymer emulsion A, 1 parts by weight stearmide are added drop-wise to the copolymerization of 75 parts by weight In object lotion B, 1 hour is added dropwise to get the multi-functional copolymer compositions 1 of the antistatic uvioresistant of water repellent.
Embodiment 2:
1) ethanol solution of 2.80 parts by weight crotonamides, 3.22 parts by weight of sodium hydroxide, 43.99 parts by weight carbon disulfide 10 DEG C or less the reactions in deionized water solvent after adsorbing 1.31 parts sulfuric acid copper, filter, water, acetone washing, 50-80 DEG C Vacuum drying drying, is made 8 parts by weight faint yellow solids.Fusing point is 84-87.5 DEG C.
2) product made from 8 parts by weight steps 1), by 1 weight parts of methacrylic acid, ten difluoro heptyl ester, 3 parts by weight methyl-props Alkene monomethacryloxypropyl trimethoxy silane takes 8 parts by weight methylacryoyloxyethyl (trimethyl) ammonium chlorides, and 0.35 parts by weight are added Lauryl sodium sulfate, 0.71 parts by weight isomery, 13 carbon alcohol polyoxyethylene ether (EO number is 9), 46.8 parts by weight of deionized water rooms Temperature is emulsified to be uniformly mixed, and 50 DEG C of additions 0.71 parts by weight lauryl sodium sulfate, 1.43 parts by weight isomery, 13 carbon are warming up to Alcohol polyoxyethylene ether (EO number is 9), is added dropwise the ammonium persulfate aqueous solution that 0.2 parts by weight concentration is 10 weight %, stirring, reaction 3 A hour, cooling, discharging latex A.After measured, the weight average molecular weight of copolymer is 30000 in latex A.
2) by 25 weight parts of methacrylic acid last of the ten Heavenly stems esters, 30 weight parts of methacrylic acid ethylene oxidic esters, 18 parts by weight 2- hydroxyls Base -4- propylene acyloxy benzophenone, 0.2 parts by weight lauryl sodium sulfate, 0.8 parts by weight isomery, 13 carbon alcohol polyoxy second Alkene ether (EO number is 9), 150.2 parts by weight of deionized water stirring and emulsifyings are uniformly mixed, and obtain pre-emulsion B；
3) by 75.3 parts by weight pre-emulsion B, 0.54 parts by weight concentration be 10 weight % ammonium persulfate aqueous solution, be warming up to 70-80 DEG C there is blue close to lotion within reaction 10 minutes after keep the temperature 30 minutes, be slowly added into 150.7 parts by weight pre-emulsion B of residue, 1.26 parts by weight concentration are the ammonium persulfate aqueous solution of 10 weight %, are continuously heating to after 75-80 DEG C, reaction 2-3 hours and protect Temperature 30 minutes, cooling down and 0.31 pbw of glacial acetic acid is added adjusts pH value to 5~7, and discharge lotion B.After measured, in lotion B altogether The weight average molecular weight of polymers is 30000.
4) under stirring action, 20 parts by weight copolymer emulsion A, 1 parts by weight stearmide are added drop-wise to the copolymerization of 80 parts by weight In object lotion B, 1 hour is added dropwise to get the multi-functional copolymer compositions 2 of the antistatic uvioresistant of water repellent.
Embodiment 3:
1) 1.94 parts by weight 4- methyl -2- amylene amides, 3.10 parts by weight of sodium hydroxide, 3.49 parts by weight carbon disulfide Ethanol solution 10 DEG C or less reactions in deionized water solvent after adsorbing 0.97 parts by weight copper nitrate, filter, water, acetone washing, 50-80 DEG C of vacuum drying drying, is made 6.2 parts by weight faint yellow solids.Fusing point is 84-87.5 DEG C.
2) product made from 6 parts by weight steps 1), 1 weight parts of methacrylic acid trifluoro ethyl ester, 3 parts by weight methacryls 0.21 parts by weight dodecyl is added in oxy-ethyl-trimethyl silane, 6 parts by weight methylacryoyloxyethyl (trimethyl) ammonium chlorides Sodium sulphate, 0.64 parts by weight isomery, 13 carbon alcohol polyoxyethylene ether (EO number is 9), 38 parts by weight of deionized water room temperatures are emulsified mixed It closes uniformly, is warming up to 45 DEG C of 0.43 parts by weight lauryl sodium sulfate of addition, 1.28 parts by weight isomery, 13 carbon alcohol polyoxyethylene Ether (EO number is 9), is added dropwise the ammonium persulfate aqueous solution that 0.3 parts by weight concentration is 10 weight %, and stirring is reacted 3 hours, is dropped Temperature, discharge to obtain copolymer emulsion A.After measured, the weight average molecular weight of copolymer is 20000 in latex A.
3) 10 parts by weight propylene propyl propionates, 20 weight parts of methacrylic acid isodecyl esters, 30 weight parts of methacrylic acid are contracted The fluorine-containing polymerizable Benzophenone-type light initiator (FBPAc) of water glyceride, 18 parts by weight, 0.3 parts by weight lauryl sodium sulfate, 0.9 parts by weight isomery, 13 carbon alcohol polyoxyethylene ether (EO number is 9), 166.9 parts by weight of deionized water stirring and emulsifyings are uniformly mixed, Obtain pre-emulsion B.
4) by 82.6 parts by weight pre-emulsion B, 0.54 parts by weight concentration be 10 weight % ammonium persulfate aqueous solution, be warming up to After 70-80 DEG C blue close occurs to lotion in reaction 10 minutes and keep the temperature 30 minutes, be slowly added into 165.3 parts by weight pre-emulsion B of residue, 1.26 parts by weight concentration are the ammonium persulfate aqueous solution of 10 weight %, are continuously heating to after 75-80 DEG C, reaction 2-3 hours and protect Temperature 30 minutes, cooling down and 0.33 pbw of glacial acetic acid is added adjusts pH value to 5~7, and discharge lotion B.After measured, in lotion B altogether The weight average molecular weight of polymers is 30000.
5) under stirring action, 18 parts by weight copolymer emulsion A, 1 parts by weight ammonium stearate are added drop-wise to the copolymerization of 85 parts by weight In object lotion B, 1.5 hours are added dropwise to get the multi-functional copolymer compositions 3 of the antistatic uvioresistant of water repellent.
Embodiment 4:
1) 3.04 parts by weight 2- methyl -2- amylene amides, 3.27 parts by weight of sodium hydroxide, 4.69 parts by weight carbon disulfide Ethanol solution 10 DEG C or less reactions in deionized water solvent after adsorbing 1.52 parts by weight copper nitrates, filter, water, acetone washing, 50-80 DEG C of vacuum drying drying, is made 9.1 parts by weight faint yellow solids.Fusing point is 84-87.5 DEG C.
2) product made from 9 parts by weight steps 1), 1 weight parts of methacrylic acid trifluoro ethyl ester, 3 parts by weight methacryls 0.29 parts by weight dodecyl is added in oxy-ethyl-trimethyl silane, 9 parts by weight methylacryoyloxyethyl (trimethyl) ammonium chlorides Sodium sulphate, 0.88 parts by weight isomery, 13 carbon alcohol polyoxyethylene ether (EO number is 9), 51.7 parts by weight of deionized water room temperatures are emulsified It is uniformly mixed, is warming up to 50 DEG C of 0.58 parts by weight lauryl sodium sulfate of addition, 1.77 parts by weight isomery, 13 carbon alcohol polyoxy second Alkene ether (EO number is 9), is added dropwise the ammonium persulfate aqueous solution that 0.35 parts by weight concentration is 10 weight %, and 3 hours are reacted in stirring, Cooling, discharging latex A；After measured, the weight average molecular weight of copolymer is 20000 in latex A.
3) by 15 parts by weight propylene acid butyl esters, 25 parts by weight (methyl) isoamyl acrylate, 25 weight parts of methacrylic acid The fluorine-containing polymerizable Benzophenone-type light initiator (FBPAc) of ethylene oxidic ester, 20 parts by weight, 0.4 parts by weight dodecyl sulphate Sodium, 1.2 parts by weight isomery, 13 carbon alcohol polyoxyethylene ether (EO number is 9), the mixing of 156.5 parts by weight of deionized water stirring and emulsifyings are equal It is even, obtain pre-emulsion B.
4) by 81.7 parts by weight pre-emulsion B, 0.63 parts by weight concentration be 10 weight % ammonium persulfate aqueous solution, be warming up to After 70-80 DEG C blue close occurs to lotion in reaction 10 minutes and keep the temperature 30 minutes, be slowly added into 163.5 parts by weight pre-emulsion B of residue, 1.47 parts by weight concentration are the ammonium persulfate aqueous solution of 10 weight %, are continuously heating to after 75-80 DEG C, reaction 2-3 hours and protect Temperature 30 minutes, cooling down and 0.32 pbw of glacial acetic acid is added adjusts pH value to 5~7, and discharge lotion B.After measured, in lotion B altogether The weight average molecular weight of polymers is 30000.
5) under stirring action, 25 parts by weight copolymer emulsion A, 1 parts by weight ammonium stearate are added drop-wise to the copolymerization of 75 parts by weight In object lotion B, 1.5 hours are added dropwise to get the multi-functional copolymer compositions 4 of the antistatic uvioresistant of water repellent.
The application effect of each embodiment compares, as shown in table 1.
The different antistatic uvioresistant multifunction finishing agent application effects of water repellent of table 1 compare
The application effect of the multi-functional copolymer of the antistatic uvioresistant of water repellent prepared by embodiment 1-4 can be obtained from table 1, stablized Property it is suitable, do, wet fastness of rubbing it is good, water repellent, antistatic, UVResistant effect are prominent, and wash durability is excellent.
It is any ripe although the present invention is disclosed as above with embodiment, its protection scope being not intended to limit the invention Those skilled in the art are known, in made change and retouching without departing from the spirit and scope of the invention, should belong to this hair Bright protection scope.

Claims (10)

1.一种拒水抗静电共聚物，它包括如下共聚单元：1. A water-repellent antistatic copolymer comprising the following copolymerization units: 式中R1为H、CH3、或者CH2CH3，R2、R3、R4、和R6各自独立地为H或者CH3；R5和R7各自独立地为C1-4烷基；wherein R 1 is H, CH 3 , or CH 2 CH 3 , R 2 , R 3 , R 4 , and R 6 are each independently H or CH 3 ; R 5 and R 7 are each independently C 1-4 alkyl; n1为1-15；n2为1-5；n3为0-4；n 1 is 1-15; n 2 is 1-5; n 3 is 0-4; 式A、式B、式C和式D表示的共聚单元的重量比为30-50:1-10:10-20:30-50，所述拒水抗静电共聚物的重均分子量为10000-45000。The weight ratio of the copolymerized units represented by formula A, formula B, formula C and formula D is 30-50:1-10:10-20:30-50, and the weight average molecular weight of the water-repellent antistatic copolymer is 10000- 45000. 2.如权利要求1所述的拒水抗静电共聚物，其特征在于，式A、式B、式C和式D表示的共聚单元的重量比为35-45:2-8:12-18:35-45，所述拒水抗静电共聚物的重均分子量为15000-35000。2. water-repellent antistatic copolymer as claimed in claim 1, is characterized in that, the weight ratio of the copolymerization unit represented by formula A, formula B, formula C and formula D is 35-45:2-8:12-18 : 35-45, and the weight-average molecular weight of the water-repellent antistatic copolymer is 15000-35000. 3.如权利要求1或2所述拒水抗静电共聚物的制备方法，它包括如下步骤：将30-50重量份式I)表示的共聚单体、1-10重量份式II)表示的共聚单体、10-20重量份式III)表示的共聚单体和30-50重量份式IV)表示的共聚单体乳液聚合：3. the preparation method of the described water-repellent antistatic copolymer as claimed in claim 1 or 2, it comprises the steps: the comonomer represented by 30-50 parts by weight of formula I), the comonomer represented by 1-10 parts by weight of formula II) Emulsion polymerization of comonomer, 10-20 parts by weight of comonomer represented by formula III) and 30-50 parts by weight of comonomer represented by formula IV): 式中R1为H、CH3、或者CH2CH3，R2、R3、R4、和R6各自独立地为H或者CH3；R5和R7各自独立地为C1-4烷基；wherein R 1 is H, CH 3 , or CH 2 CH 3 , R 2 , R 3 , R 4 , and R 6 are each independently H or CH 3 ; R 5 and R 7 are each independently C 1-4 alkyl; n1为1-15；n2为1-5；n3为0-4。n 1 is 1-15; n 2 is 1-5; n 3 is 0-4. 4.如权利要求3所述的制备方法，其特征在于，所述的乳液聚合在自由基引发剂存在下进行。4. The preparation method according to claim 3, wherein the emulsion polymerization is carried out in the presence of a free radical initiator. 5.如权利要求3或4所述的制备方法，其特征在于，所述的乳液聚合在阴离子表面活性剂、中性表面活性剂或它们混合物的存在下进行。5. The preparation method according to claim 3 or 4, wherein the emulsion polymerization is carried out in the presence of an anionic surfactant, a neutral surfactant or a mixture thereof. 6.一种拒水抗静电组合物，它包括a)如权利要求1或2所述拒水抗静电共聚物以及b)抗紫外共聚物。6. A water-repellent antistatic composition comprising a) the water-repellent antistatic copolymer of claim 1 or 2 and b) an anti-ultraviolet copolymer. 7.如权利要求6所述的拒水抗静电组合物，其特征在于，所述拒水抗静电共聚物与抗紫外共聚物的重量比为10－30：70－90。7 . The water-repellent and antistatic composition according to claim 6 , wherein the weight ratio of the water-repellent and antistatic copolymer to the anti-ultraviolet copolymer is 10-30:70-90. 8 . 8.如权利要求6或7所述的拒水抗静电组合物，其特征在于，它含有阴离子表面活性剂、中性表面活性剂、分散剂或它们的混合物。8. The water-repellent and antistatic composition according to claim 6 or 7, characterized in that it contains an anionic surfactant, a neutral surfactant, a dispersant or a mixture thereof. 9.如权利要求8所述的拒水抗静电组合物，其特征在于，所述的阴离子表面活性剂是C10-18烷基硫酸钠，所述中性表面活性剂是C10-18脂肪醇聚氧乙烯醚，所述的分散剂是C12-20脂肪酰胺。9. The water-repellent and antistatic composition of claim 8, wherein the anionic surfactant is C 10-18 sodium alkyl sulfate, and the neutral surfactant is C 10-18 fat Alcohol polyoxyethylene ether, the dispersant is C 12-20 fatty amide. 10.如权利要求6或7所述的拒水抗静电组合物，其特征在于，所述的抗紫外共聚物是含有二苯甲酮结构单元的聚(甲基)丙烯酸酯。10. The water-repellent and antistatic composition according to claim 6 or 7, wherein the anti-ultraviolet copolymer is a poly(meth)acrylate containing a benzophenone structural unit.
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