CN104074052B - A kind of fluorine-silicon copolymer waterproof oil-proof finishing agent aqueous liquid dispersion - Google Patents
A kind of fluorine-silicon copolymer waterproof oil-proof finishing agent aqueous liquid dispersion Download PDFInfo
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- CN104074052B CN104074052B CN201410215875.3A CN201410215875A CN104074052B CN 104074052 B CN104074052 B CN 104074052B CN 201410215875 A CN201410215875 A CN 201410215875A CN 104074052 B CN104074052 B CN 104074052B
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Abstract
The invention discloses a kind of fluorine-silicon copolymer waterproof oil-proof finishing agent aqueous liquid dispersion, the most composed of the following components: fluorochemical monomer 13.5～25 parts, silicon-containing monomer 0.15～1.35 parts, non-fluorine-containing, silicon-containing monomer 1.65～16.35 parts, initiator 0.3～0.45 part, emulsifying agent 2.5～3 parts, disperse medium 105～120 parts, the fluorine-silicon copolymer waterproof oil-proof finishing agent aqueous liquid dispersion waterproof and oilproof performance of the present invention is excellent, and good endurance.
Description
Technical field
The present invention relates to a kind of fluorine-silicon copolymer waterproof oil-proof finishing agent aqueous liquid dispersion, belong to fabric finishing agent technology neck
Territory.
Background technology
Fluorine-contained finishing agent has good water and oil repellant antifouling property, also has significant heat stability and chemically stable
Property, therefore it is widely applied in fields such as weaving, printing and dyeing, leathers.Fluorine-contained finishing agent processes for leather can make leather table
Face forms the hydrophobic and oil repellent anti-soil film of one layer of perfluoroalkyl, makes leather surface become soft and full, high resilience, has waterproof anti-
The functions such as oil is antifouling, resistance to chemical attack.The effective ingredient being currently applied to the waterproof oil-proof finishing agent product that leather processes is main
It it is fluorine-contaninig polyacrylate.Fluorine-contaninig polyacrylate is in surface activity, Water-proof and oil-proof, antifouling, chemical stability, weatherability, resistance to
The aspect such as corrosivity, non-oxidizability has unrivaled advantage, can give the waterproof and oilproof performance that product is good, but low temperature resistant
Poor performance.
Silicon-containing polymer have relatively low glass transition temperature, excellent resistance to high/low warm nature, oxytolerant oxidative degradation,
The performances such as weatherability and excellent hydrophobicity, gloss retention, ultraviolet resistance, but solvent resistance is poor.The advantage utilizing both, complementary
Defect, synthesizes fluorine-silicon copolymer thing, is expected to obtain the waterproof oil-proof finishing agent that performance is more excellent.
People have carried out numerous studies to fluorine silicon finishing agent, such as China Patent Publication No. CN1924184A, publication date
On March 7th, 2007, denomination of invention: a kind of, fluorine silicon finishing agent of flexible, breathable arrangement grease proofing for textile water proof.This Shen
Case please disclose a kind of, fluorine silicon finishing agent of flexible, breathable arrangement grease proofing for textile water proof, this finishing agent is a kind of O/W
Type emulsion, it is mainly composed of the fluorine-containing Arrcostab of methacrylic acid or the fluorine-containing Arrcostab of acrylic acid and mixture M thereof1, Long carbon chain
Alkyl acrylate or alkyl methacrylate and mixture M thereof2The Methyl Hydrogen Polysiloxane Fluid of graft modification, prepared fluorine silicon
In finishing agent, fluorochemical monomer content is below 10%.But the water and oil-resistant of the finishing agent prepared is poor, durability is managed the most not
Think.
Summary of the invention
The technical problem to be solved in the present invention is the defect overcoming prior art, it is provided that a kind of waterproof and oilproof performance is excellent,
The fluorine-silicon copolymer waterproof oil-proof finishing agent aqueous liquid dispersion of good endurance.
In order to solve above-mentioned technical problem, the present invention is achieved by the following technical solutions: a kind of fluorine-silicon copolymer is waterproof
Anti oil agent aqueous liquid dispersion, the most composed of the following components:
Further:
Described fluorochemical monomer is preferably containing Polyfluoroalkyl or the vinyl monomer of perfluorinated alkenyl.
The described vinyl monomer containing Polyfluoroalkyl or perfluorinated alkenyl is CH2=CHCOO(CH2)2(CF2)7CF3、
CH2=C(CH3)COO(CH2)2(CF2)7CF3、CH2=C(CH3)COO(CH2)2(CF2)8H、CH2=C(CH3)(CH2)2OCO(CF2)7CF3、CH2=CHCH2OC6H4CH2OC9F17In one.
Described silicon-containing monomer is preferably containing vinyl and the organosilicone compounds of siloxane group.
The described organosilicone compounds containing vinyl and siloxane group is CH2=CHSi (OCH3)3、CH2=
CHSi(OC2H5)3、CH2=CHCOO(CH2)3Si(OC2H5)3In one.
Described non-fluorine-containing, silicon-containing monomer are preferably octadecyl acrylate, lauryl methacrylate, benzene second
One or both mixture in alkene, hydroxyethyl methylacrylate.
Described initiator is preferred sodium peroxydisulfate.
Described emulsifying agent be preferably sodium lauryl sulphate, dodecylbenzene sodium sulfonate, alkylphenol-polyethenoxy base ether,
Two or more mixture in sorbitan fatty acid ester polyoxyethylene ether.
Described disperse medium is the mixture of deionized water and organic solvent, and it is total that described organic solvent accounts for disperse medium
The 5%～10% of quality.
Described organic solvent is preferably the one in acetone, isopropanol, DPE.
Fluorine-silicon copolymer waterproof oil-proof finishing agent aqueous liquid dispersion, wherein fluorine-silicon copolymer are prepared in the employing emulsion copolymerization of the present invention
Fluorochemical monomer chain link in thing imparts the excellent hydro-oleophobicity of copolymer, chemical stability etc.；Silicon-containing monomer chain link anti-
Active should can strengthen the bond strength of copolymer and treated object, keep the persistency of waterproof oil-proof result；Other monomer chain
Joint plays regulatory role, and improves waterproof and oilproof performance further, and reduces cost.
Described fluorochemical monomer is the vinyl monomer containing Polyfluoroalkyl or perfluorinated alkenyl, and available following formula formula represents:
CH2=CR—Q—Rf
In formula, R represents H or CH3；Q represents divalent organic group, such as COO (CH2)n、COO(CH2)nN(R1)SO2(R1For hydrogen or first
Base), COO (CH2)nArO、(CH2)nOCO、(CH2)nO、(CH2)nOC6H4CH2O etc.；N is 1～4；RfRepresent C1～C16Many halothane
Base or perfluorinated alkenyl.
The object lesson of fluorochemical monomer includes following compounds, and in formula, R represents H or CH3。
CH2=CRCOO(CH2)2(CF2)7CF3
CH2=CRCOO(CH2)2(CF2)4H
CH2=CRCOO(CH2)2(CF2)8H
CH2=CRCOO(CH2)2(CF2)16H
CH2=CRCOO(CH2)2(CF2)4CF(CF3)2
CH2=CRCOO(CH2)2N(CH3)SO2(CF2)7CF3
CH2=CRCOO(CH2)2OC6F11
CH2=CRCOO(CH2)2OC9F17
CH2=CR(CH2)2OCO(CF2)7CF3
CH2=CRCH2OC6F11
CH2=CRCH2OC6H4CH2OC9F17
Fluorine-silicon copolymer thing of the present invention can comprise only the polymerized unit of a kind of fluorochemical monomer, it is also possible to containing two
Plant and above polymerized unit.Comprise two kinds and above time, be preferably based on different RfThe polymerized unit of fluorochemical monomer.Described
The vinyl monomer containing Polyfluoroalkyl or perfluorinated alkenyl be preferably CH2=CHCOO(CH2)2(CF2)7CF3、CH2=C(CH3)
COO(CH2)2(CF2)7CF3、CH2=C(CH3)COO(CH2)2(CF2)8H、CH2=C(CH3)(CH2)2OCO(CF2)7CF3、CH2=
CHCH2OC6H4CH2OC9F17In one.
Silicon-containing monomer of the present invention is the organosilicone compounds containing vinyl and siloxane group, available following
Formula represents:
R in formula1Represent CH3Or C2H5；R2Represent H or C1～C4Alkyl；A is 0～2；Y is CH2=CH、CH2=CHCOO
(CH2)mOr CH2=CH(CH3)COO(CH2)m, m is 1～4.
The object lesson of silicon-containing monomer of the present invention includes following compounds: CH2=CHSi(OCH3)3、CH2=CHSi
(OC2H5)3、CH2=CHSiCH3(OCH3)2、CH2=CHSiCH3(OC2H5)2、CH2=CHSi(CH3)2OCH3、CH2=CHCOO(CH2)3Si(OCH3)3、CH2=CHCOO(CH2)3Si(OC2H5)3、CH2=CH(CH3)COO(CH2)3Si(OCH3)3、CH2=CH(CH3)COO
(CH2)3Si(OC2H5)3、CH2=CHCOO(CH2)3SiCH3(OCH3)2Deng.Silicon-containing monomer can be one of which, it is also possible to be two
Kind and more than.The described organosilicone compounds containing vinyl and siloxane group is preferably CH2=CHSi (OCH3)3、
CH2=CHSi(OC2H5)3、CH2=CHCOO(CH2)3Si(OC2H5)3In one.
Other non-object lesson fluorine-containing, silicon-containing monomer of the present invention has (methyl) alkyl acrylate, (methyl) third
The esters monomers such as olefin(e) acid hydroxy alkyl ester, the alkene such as second is dilute, propylene, isobutene., the halogen alkene such as vinyl chloride, vinylidene chloride, acetic acid
Ethyl ester, styrene, α-methylstyrene, alkyl vinyl ether etc..Preferably (methyl) alkyl acrylate, (methyl) propylene
Acid hydroxy alkyl ester, styrene etc..Non-fluorine-containing, silicon-containing monomer can be one of which, it is also possible to be two kinds and more than, preferably third
In olefin(e) acid stearyl, lauryl methacrylate, styrene, hydroxyethyl methylacrylate one or both
Mixture.
Water soluble starter initiation reaction is selected in emulsion copolymerization, and available water soluble starter has sodium peroxydisulfate, over cure
Acid potassium, Ammonium persulfate., hydrogen peroxide etc., preferably sodium peroxydisulfate.
Described emulsifying agent is anionic or nonionic, or both compounds.The emulsifying agent of anionic is such as
Sodium lauryl sulphate, dodecyl sodium sulfate, dodecylbenzene sodium sulfonate etc.；The emulsifying agent of nonionic such as alkyl phenol polyoxy
Vinyl ethers (OP-10, OP-20, TX-9, TX-10 etc.), the polyoxyethylene ether of fatty alcohol, the polyoxyethylene ether of fatty acid,
Sorbitan fatty acid ester, sorbitan fatty acid ester polyoxyethylene ether (Tween-60, Tween-80 etc.) etc..Described
Emulsifying agent be preferably sodium lauryl sulphate, dodecylbenzene sodium sulfonate, alkylphenol-polyethenoxy base ether, Sorbitan alcohol ester
Two or more mixture in fat acid esters polyoxyethylene ether.
Described disperse medium is containing the organic solvent accounting for disperse medium gross mass 5%～10%, and surplus is deionized water.
Organic solvent can be selected for water solublity or hydrophilic organic solvent, available water solublity or hydrophilic organic solvent have ketone (as
Acetone, butanone), alcohols (such as methanol, ethanol, isopropanol, ethylene glycol, propylene glycol, diethylene glycol, tripropylene glycol etc.), ethers (as
Ethylene glycol monoethyl ether, dihydroxypropane single-ether, DPE, dipropylene glycol monomethyl ether etc.).Be preferably acetone, isopropanol,
One in DPE.
The fluorine silicon waterproof and oilproof copolymer, aqueous dispersion of the present invention be applicable to paper, timber, plastic sheeting, fiber,
The anti-oil processing of surface waterproofing of the goods such as leather, glass, pottery, is particularly suitable for the surface waterproofing of the form fibre such as silk, cloth
Anti-oil processing.By the fluorine silicon waterproof and oilproof copolymer of the present invention is attached on treated object, at treated object
Reason.Processing method generally select coating, impregnate, spray, pad dyeing, roller coat or combinations thereof method etc..Usually, first will be by
Processed material is impregnated in the aqueous liquid dispersion of water and oil repellent of finite concentration (weight solid content is 1～10%) and processes, then
Utilizing roll to remove unnecessary liquid, the kind finally according to processed material is dried solidification (generally at 100～200 DEG C
At a temperature of process less than 2h), complete waterproof and oilproof and process.
Compared with prior art, the invention have the advantages that
1, product waterproof and oilproof performance is excellent, and the cotton polyester blend fabric classification of waterproof after process is 5 grades, grease proofing grade
More than 7 grades；
2, durability of product is good: the cotton polyester blend fabric after process through repeatedly washing after, classification of waterproof still 4 grades with
On, grease proofing grade is still more than 6 grades.
Detailed description of the invention
It is further elucidated with the present invention below in conjunction with specific embodiment, but these embodiments are only used for explaining the present invention, and not
It is for limiting the scope of the present invention.
The synthesizing formula of the fluorine-silicon copolymer waterproof oil-proof finishing agent aqueous liquid dispersion of embodiment 1～20 refers to table 3 and table 4.
The fluorine-silicon copolymer waterproof oil-proof finishing concrete preparation technology of agent aqueous liquid dispersion of embodiment 1～20 is as follows: using as
The deionized water of disperse medium and the mixture of organic solvent, emulsifying agent, initiator and all monomers are at room temperature equipped with
In the container of high-speed shearing emulsion machine, under the rotating speed of 1500r/min, pre-emulsification 30min, obtain pre-emulsion.Gained pre-emulsion
70% addition Dropping funnel in, letting nitrogen in and deoxidizing is stand-by.The pre-emulsion of remaining 30% is equipped with agitator, condenser, thermometer
And in the four-hole boiling flask of Dropping funnel, open stirring, and letting nitrogen in and deoxidizing, mixing control is at 200r/min～225r/min.By perseverance
Four-hole boiling flask is heated to 80 ± 2 DEG C by warm water bath, after reaction 30min, starts dropping residue pre-emulsion by Dropping funnel, about
2.5h dropping is complete.After dropping, continue insulation about 1.5h；It is warming up to 85 ± 2 DEG C again, is incubated about 1h.React complete
After, naturally cool to room temperature, discharging, obtain fluorine-silicon copolymer waterproof oil-proof finishing agent aqueous liquid dispersion.
The preparation technology of the aqueous liquid dispersion of water and oil repellent of comparative example 1～3 is identical with embodiment 1～20, synthesizing formula
Refer to table 5.
Water and oil-resistant is evaluated:
With fluorine-silicon copolymer waterproof oil-proof finishing agent aqueous liquid dispersion and the waterproof and oilproof of comparative example 1～3 of embodiment 1～20
Agent aqueous liquid dispersion carries out impregnation process to cotton polyester blend fabric, is then passed through roll, is finally dried solidification.To dry
Processed material after dry solidification carries out waterproof and oilproof performance evaluation, the results detailed in Table 6.
Washing resistance is tested:
Above-mentioned fabric after dry solidification processes is carried out 10 cyclic washings, then the fabric after washing is prevented
Water grease proofness is evaluated, the results detailed in Table 6.Washing procedure is: with the warm water of 30L35 DEG C and 24g detergent (development of evil in febrile disease board) washing 1Kg
Fabric.Wash 12 minutes, be dehydrated 3 minutes, rinse 6 minutes, be dehydrated 5 minutes, then drum drying.
Wherein:
Waterproofing property evaluation standard is pressed GB/T4745-1997 textile fabric surface moisture resistance and is measured dip experiment execution, refers to
Table 1；
Grease proofness evaluation criterion is pressed the test of GB/T19977-2005 textile oil repellent anti-Hydrocarbon and is performed, and refers to table
2；
Table 1 waterproofing property evaluation standard: GB/T4745-1997 textile fabric surface moisture resistance measures dip experiment.
| Classification of waterproof | State |
| 5 | Surface is without moistening |
| 4 | Surface moistens on a small quantity |
| 3 | Surface portion moistens |
| 2 | Surface wettability |
| 1 | Surface all moistens |
Table 2 grease proofness evaluation criterion: the anti-Hydrocarbon of GB/T19977-2005 textile oil repellent is tested.
| Grade numbers | Experimental liquid forms | Surface tension (N/m, 25 DEG C) |
| 8 | Normal heptane | 0.0198 |
| 7 | Normal octane | 0.0214 |
| 6 | N-decane | 0.0235 |
| 5 | N-dodecane | 0.0247 |
| 4 | N-tetradecane | 0.0264 |
| 3 | Hexadecane | 0.0273 |
| 2 | Hexadecane 35/ white mineral oil 65 mixed liquor | 0.0296 |
| 1 | White mineral oil | 0.0315 |
The formula table (unit is g) of table 3 embodiment 1～10
The formula table (unit is g) of table 4 embodiment 10～20
The formula table (unit is g) of table 5 comparative example 1～3
Table 6 embodiment 1～20 and the waterproof oil-proof finishing agent aqueous liquid dispersion performance evaluation of comparative example 1～3
Table 6 illustrates, the fluorine-silicon copolymer waterproof oil-proof finishing agent aqueous liquid dispersion of the present invention has the water and oil-resistant of excellence
Energy and durability, combination property is more excellent.
Claims (1)
1. a fluorine-silicon copolymer waterproof oil-proof finishing agent aqueous liquid dispersion, it is characterised in that count by following components I or group by weight
Part II composition:
Component I:
Component II:
Then it is prepared according to above-mentioned component: disperse medium, emulsifying agent, sodium peroxydisulfate and all monomers are at room temperature added
Equipped with in the container of high-speed shearing emulsion machine, under the rotating speed of 1500r/min, pre-emulsification 30min, obtain pre-emulsion, gained is pre-
In 70% addition Dropping funnel of emulsion, letting nitrogen in and deoxidizing is stand-by, the pre-emulsion of remaining 30% be equipped with agitator, condenser,
In the four-hole boiling flask of thermometer and Dropping funnel, opening stirring, and letting nitrogen in and deoxidizing, mixing control is at 200r/min～225r/
Min, is heated to 80 ± 2 DEG C with thermostat water bath by four-hole boiling flask, after reaction 30min, starts dropping residue by Dropping funnel
Pre-emulsion, about 2.5h dropping is complete, after dropping, continues insulation 1.5h；It is warming up to 85 ± 2 DEG C again, is incubated 1h, reacts complete
After, naturally cool to room temperature, discharging, obtain fluorine-silicon copolymer waterproof oil-proof finishing agent aqueous liquid dispersion.
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Families Citing this family (7)
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|---|---|---|---|---|
| CN105037732A (en) * | 2015-08-04 | 2015-11-11 | 杭州富纳新材料科技有限公司 | Method for preparing fluorine-containing organic silicone polymer micro-nano emulsion |
| CN105969031B (en) * | 2016-05-26 | 2018-05-15 | 清远市美佳乐环保新材股份有限公司 | A kind of leather environmental protection flame retardant waterproofing agent and preparation method thereof |
| CN106119443B (en) * | 2016-06-15 | 2018-08-21 | 崔晓雪 | The grease proofing antifouling care agent of aerosol type surface waterproofing |
| CN110219174A (en) * | 2019-07-15 | 2019-09-10 | 广东湛丰精细化工有限公司 | A kind of no soap water-dispersion type water-refusing oil-refusing finishing agent and preparation method thereof |
| CN110835385A (en) * | 2019-10-31 | 2020-02-25 | 桐乡市钜成涂装科技有限公司 | Water-proof and oil-proof agent copolymer emulsion containing fluorine silicon for fabric and preparation method thereof |
| CN110894267B (en) * | 2019-11-27 | 2022-03-04 | 东莞东阳光科研发有限公司 | Fluorine-silicon graft copolymer, surface treating agent and application |
| CN111909436A (en) * | 2020-08-28 | 2020-11-10 | 新乡亿博环保科技有限公司 | Environment-friendly garbage collection barrel and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1924184A (en) * | 2006-09-20 | 2007-03-07 | 广州市白云化工实业有限公司 | Fluorine and silicon containing finishing agent for resisting water and oil and mild ventilating finishing textile and synthesis method thereof |
| CN101981248A (en) * | 2008-03-31 | 2011-02-23 | 大金工业株式会社 | Dispersion of fluorosilicones and fluorine- and silicon-containing surface treatment agent |
| CN102060956A (en) * | 2010-11-16 | 2011-05-18 | 巨化集团公司 | Method for preparing water-oil repellent fluorine-containing textile finishing agent |
| CN102094329A (en) * | 2009-12-09 | 2011-06-15 | 北京服装学院 | Fluorine and silicon containing water and oil repellent finishing agent, preparation and application thereof |
| CN102493193A (en) * | 2011-12-14 | 2012-06-13 | 太仓中化环保化工有限公司 | Fluorine-containing water and oil repellant agent and preparing method thereof |
| CN103194904A (en) * | 2013-04-27 | 2013-07-10 | 苏州大学 | Water-repellent and oil-repellent fabric finishing agent, as well as preparation method and applications thereof |
-
2014
- 2014-05-21 CN CN201410215875.3A patent/CN104074052B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1924184A (en) * | 2006-09-20 | 2007-03-07 | 广州市白云化工实业有限公司 | Fluorine and silicon containing finishing agent for resisting water and oil and mild ventilating finishing textile and synthesis method thereof |
| CN101981248A (en) * | 2008-03-31 | 2011-02-23 | 大金工业株式会社 | Dispersion of fluorosilicones and fluorine- and silicon-containing surface treatment agent |
| CN102094329A (en) * | 2009-12-09 | 2011-06-15 | 北京服装学院 | Fluorine and silicon containing water and oil repellent finishing agent, preparation and application thereof |
| CN102060956A (en) * | 2010-11-16 | 2011-05-18 | 巨化集团公司 | Method for preparing water-oil repellent fluorine-containing textile finishing agent |
| CN102493193A (en) * | 2011-12-14 | 2012-06-13 | 太仓中化环保化工有限公司 | Fluorine-containing water and oil repellant agent and preparing method thereof |
| CN103194904A (en) * | 2013-04-27 | 2013-07-10 | 苏州大学 | Water-repellent and oil-repellent fabric finishing agent, as well as preparation method and applications thereof |
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Effective date of registration: 20180920 Address after: 324004 Zhejiang Quzhou Juhua Group Co., Ltd. Patentee after: Juhua Group Co., Ltd. Address before: 324004 Zhejiang Quzhou City Kecheng District Juhua Group Technology Center Patentee before: Technology Center of Juhua Group |