CN104562684B - A kind of water and oil repellent agent and preparation method thereof - Google Patents
A kind of water and oil repellent agent and preparation method thereof Download PDFInfo
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- CN104562684B CN104562684B CN201510073917.9A CN201510073917A CN104562684B CN 104562684 B CN104562684 B CN 104562684B CN 201510073917 A CN201510073917 A CN 201510073917A CN 104562684 B CN104562684 B CN 104562684B
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- oil repellent
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 81
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 56
- 230000002940 repellent Effects 0.000 title claims abstract description 45
- 239000005871 repellent Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000000178 monomer Substances 0.000 claims abstract description 40
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 21
- -1 acrylic ester Chemical class 0.000 claims abstract description 18
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 12
- 239000001993 wax Substances 0.000 claims abstract description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000004200 microcrystalline wax Substances 0.000 claims abstract description 11
- 239000008367 deionised water Substances 0.000 claims abstract description 10
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 10
- 239000006184 cosolvent Substances 0.000 claims abstract description 9
- 229920001577 copolymer Polymers 0.000 claims abstract description 7
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 7
- 238000004132 cross linking Methods 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 7
- 125000003709 fluoroalkyl group Chemical group 0.000 claims abstract description 6
- 239000000306 component Substances 0.000 claims abstract description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 50
- 238000006243 chemical reaction Methods 0.000 claims description 28
- 239000000839 emulsion Substances 0.000 claims description 28
- SNVLJLYUUXKWOJ-UHFFFAOYSA-N methylidenecarbene Chemical compound C=[C] SNVLJLYUUXKWOJ-UHFFFAOYSA-N 0.000 claims description 23
- 229920000642 polymer Polymers 0.000 claims description 15
- 239000002245 particle Substances 0.000 claims description 12
- 125000002091 cationic group Chemical group 0.000 claims description 9
- 239000003999 initiator Substances 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 239000012875 nonionic emulsifier Substances 0.000 claims description 8
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 claims description 7
- UWNADWZGEHDQAB-UHFFFAOYSA-N i-Pr2C2H4i-Pr2 Natural products CC(C)CCC(C)C UWNADWZGEHDQAB-UHFFFAOYSA-N 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 238000010907 mechanical stirring Methods 0.000 claims description 4
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- 238000007720 emulsion polymerization reaction Methods 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 2
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical group OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 2
- POYODSZSSBWJPD-UHFFFAOYSA-N 2-methylprop-2-enoyloxy 2-methylprop-2-eneperoxoate Chemical compound CC(=C)C(=O)OOOC(=O)C(C)=C POYODSZSSBWJPD-UHFFFAOYSA-N 0.000 claims description 2
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 claims description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- 239000004593 Epoxy Substances 0.000 claims description 2
- 125000005396 acrylic acid ester group Chemical group 0.000 claims description 2
- 150000001298 alcohols Chemical class 0.000 claims description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 2
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 claims description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 2
- 238000009835 boiling Methods 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 claims description 2
- 230000008676 import Effects 0.000 claims description 2
- VLCAYQIMSMPEBW-UHFFFAOYSA-N methyl 3-hydroxy-2-methylidenebutanoate Chemical compound COC(=O)C(=C)C(C)O VLCAYQIMSMPEBW-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 150000002978 peroxides Chemical class 0.000 claims description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 2
- 235000019394 potassium persulphate Nutrition 0.000 claims description 2
- 238000010992 reflux Methods 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 239000007858 starting material Substances 0.000 claims description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 2
- PYGXUPRQBBNETH-UHFFFAOYSA-N acetic acid;2-hydroxypropyl prop-2-enoate Chemical compound CC(O)=O.CC(O)COC(=O)C=C PYGXUPRQBBNETH-UHFFFAOYSA-N 0.000 claims 1
- 125000001309 chloro group Chemical group Cl* 0.000 claims 1
- 230000009257 reactivity Effects 0.000 claims 1
- 239000012188 paraffin wax Substances 0.000 abstract description 11
- 239000004744 fabric Substances 0.000 abstract description 9
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 239000007788 liquid Substances 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 9
- 229910052731 fluorine Inorganic materials 0.000 description 9
- 239000011737 fluorine Substances 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- CCJAYIGMMRQRAO-UHFFFAOYSA-N 2-[4-[(2-hydroxyphenyl)methylideneamino]butyliminomethyl]phenol Chemical compound OC1=CC=CC=C1C=NCCCCN=CC1=CC=CC=C1O CCJAYIGMMRQRAO-UHFFFAOYSA-N 0.000 description 5
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 5
- 230000001804 emulsifying effect Effects 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000004033 plastic Substances 0.000 description 5
- 210000000481 breast Anatomy 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- 239000004753 textile Substances 0.000 description 3
- 239000008187 granular material Substances 0.000 description 2
- FSAJWMJJORKPKS-UHFFFAOYSA-N octadecyl prop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C=C FSAJWMJJORKPKS-UHFFFAOYSA-N 0.000 description 2
- 239000002939 oilproofing Substances 0.000 description 2
- 238000004078 waterproofing Methods 0.000 description 2
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 239000004908 Emulsion polymer Substances 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229920004933 Terylene® Polymers 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 231100000693 bioaccumulation Toxicity 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052756 noble gas Inorganic materials 0.000 description 1
- 150000002835 noble gases Chemical class 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000002464 physical blending Methods 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Landscapes
- Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
The present invention relates to a kind of water and oil repellent agent and preparation method thereof, it is 1 that this water and oil repellent agent includes quality proportioning：0.1~0.4：0.05~0.15：0.1~0.3：2 ~ 4 fluorinated copolymer component, wax component, emulsifying agent, cosolvent and deionized water, described fluorinated copolymer component is by fluorochemical monomer, acrylic ester monomer and the reactive monomer in mass ratio 20 ~ 40 with crosslinking feature：45~75：5 ~ 15 copolymerization form；Wax group is divided into paraffin between 50 DEG C ~ 70 DEG C for the fusing point or microwax or the mixture of the two.Water and oil repellent agent of the present invention can greatly improve the waterproof and oilproof performance of fabric, when especially fluorochemical monomer selects the short chain fluoroalkyl group monomer that carbon number is 1 ~ 6, makes this water and oil repellent agent than C of the prior art8The more environmental protection of class product, cost is lower, and can also reach C simultaneously8The waterproof and oilproof performance of class product.
Description
Technical field
The invention belongs to textile auxiliary field is and in particular to a kind of water and oil repellent agent and preparation method thereof.
Background technology
It is known that the main product of the water and oil repellent agent of field of textiles is all fluorine-containing acrylic acid ester emulsion polymer,
But there is following defect in such product：On the one hand it is expensive；On the other hand, main flow waterproof and oilproof on domestic market
Agent is still C8Type water and oil repellent agent（I.e. in segment, the carbon number of fluoroalkyl is 8）, people in the art knows C8Type waterproof and oilproof
Although agent waterproof oil-proof result is excellent, there is also that bioaccumulation is strong, the defect of difficult degradation simultaneously.European Union and the U.S. in recent years
Environmental Protection Administration all promulgates relevant law successively, prohibits the use of C8Type water and oil repellent agent.
It is the inexorable trend of coming years inner waterproofing oil-proofing agent development using short-chain fluorine-containing monomer and non-fluorine monomer.There is patent
CN103409999 reports short chain fluoroalkyl group C6Type water and oil repellent agent, but with traditional C8Type water and oil repellent agent is compared in performance
Still reach to less than C8Effect.And the fluorine-free water and oil repellent agent of the report such as patent CN103572602A, WO2010/115496,
Water resistance not only can not show a candle to C8Type water and oil repellent agent, or even connect C6The effect of type water and oil repellent agent does not all reach.And fluorine-free is prevented
Water oil-proofing agent, can only be precisely waterproofing agent, its critical defect be substantially can only waterproof, oil preventing performance almost do not have.?
Current hope gives under the more multi-functional background condition of water and oil repellent agent, and only only water-proof function significantly limit fluorine-free
The popularization of product, though fluorine-free product and fluorinated product carry out compounding although can reduces cost to a certain extent, but
It is because only simple physical blending, aspect of performance is still difficult to meet require.
In addition, there being United States Patent (USP) US2008/085612 report silica dioxide granule to be incorporated in water and oil repellent agent, to carry
The roughness of textile surface handled by height, improves the Water-proof and oil-proof performance of product.But due to silica particles energy
Ratio is larger, easily reunites in emulsion, hardly results in emulsion steady in a long-term, therefore using front generally will be to silica dioxide granule
Surface is modified, and step is also comparatively laborious, is unfavorable for the industrialization promotion of product.
Content of the invention
It is contemplated that overcoming the deficiencies in the prior art, provide that one kind more environmental protection, cost be lower, preparation technology is simpler
Stable and performance is not less than C8The water and oil repellent agent of type product.
It is a further object of the present invention to provide the preparation method of above-mentioned water and oil repellent agent.
For solving above technical problem, the present invention adopts the technical scheme that：
A kind of water and oil repellent agent, is the polymer emulsion through the prepared particle diameter of emulsion polymerization in 100 ~ 300 nanometer range,
Described polymer emulsion specifically comprises following components：
Quality proportioning is 1：0.1~0.4：0.05~0.15：0.1~0.3：2 ~ 4 fluorinated copolymer component, wax component, emulsifying
Agent, cosolvent and deionized water；
Wherein, described fluorinated copolymer component is that by fluorochemical monomer, acrylic ester monomer and have the anti-of crosslinking feature
Answering property monomer in mass ratio 20 ~ 40：45~75：5 ~ 15 copolymerization form；
Described wax group is divided into paraffin between 50 DEG C ~ 70 DEG C for the fusing point or microwax or the mixture of the two.
Preferably, the structural formula of described fluorochemical monomer is as follows：
CH2=C(-X)-C(=O)-O-CH2CH2-Rf；
Wherein, X is hydrogen atom or methyl, RfFluoroalkyl for carbon number 1～6；
The structural formula of described acrylic ester monomer is as follows：
CH2=C(-X)-C(=O)-O-(CH2)n-CH3；
Wherein, X is hydrogen atom or methyl, and n takes from 11 ~ 29 any number；
The described reactive monomer with crosslinking feature refers at least there is a carbon-carbon double bond and ester group, amide groups
The compound of isoreactivity group, specifically can from 2-(Acryloyloxy)ethanol, hydroxyethyl methylacrylate, Hydroxypropyl acrylate,
Hydroxypropyl methacrylate, acrylic acid epoxy ester, epoxymethacrylate, N-[2-(2-methyl-4-oxopentyl), N- methylol acryloyl
Amine, 3- chlorine-2-hydroxyl propyl acrylate, 3- chlorine-2-hydroxyl propyl methacrylate, glycidyl acrylate and methyl
The combination of one or more of glycidyl acrylate.
Preferably, described fluorine-containing single choice is from the combination of one or more of the compound of following structure：
CH2=CH-C(=O)-O-CH2CH2-C6F13、CH2=C(CH3)-C(=O)-O-CH2CH2-C6F13、CH2=CH-C(=O)-
O-CH2CH2-C4F9、CH2=C(CH3)-C(=O)-O-CH2CH2-C4F9；
Described acrylic ester monomer is selected from the combination of one or more of the compound of following structure：
CH2=CH-C(=O)-O-(CH2)11-CH3、CH2=C(CH3)-C(=O)-O-(CH2)11-CH3、CH2=CH-C(=O)-O-
(CH2)13-CH3、CH2=C(CH3)-C(=O)-O-(CH2)13-CH3、CH2=CH-C(=O)-O-(CH2)15-CH3、CH2=C(CH3)-C
(=O)-O-(CH2)15-CH3、CH2=CH-C(=O)-O-(CH2)17-CH3、CH2=C(CH3)-C(=O)-O-(CH2)17-CH3、CH2=
CH-C(=O)-O-(CH2)19-CH3、CH2=C(CH3)-C(=O)-O-(CH2)19-CH3.
Preferably, described wax group is selected from microwax.Those skilled in the art should know, the main component of paraffin is straight
Alkane, and the main component of microwax is side chain and cyclic alkane, the preferred microwax of wax component in the present invention, is more beneficial for carrying
The waterproof and oilproof performance of high product.
Preferably, described emulsifying agent is that cationic emulsifier and nonionic emulsifier combine, wherein, described sun from
The mass percent that sub- emulsifying agent accounts for described emulsifying agent total amount is 30% ~ 70%.
Further, the structural formula of described cationic emulsifier is R (CH3)3N+X-, wherein R is 12 ~ 18 for carbon number
Chain alkyl, X be chlorine or bromine atom；The structural formula of described nonionic emulsifier is RO (CH2CH2O)nH, wherein R are carbon atom
The chain alkyl for 12 ~ 20 for the number, n is any number in 3 ~ 50.Described chain alkyl, generally refer to have in alkyl molecule chain >=
The straight chain segment of 12 carbon numbers, is not excluded for a small amount of presence compared with short-chain branch in long-chain.
Preferably, described cosolvent is high boiling point alcohols solvent.
Further, described cosolvent is one of ethylene glycol, propylene glycol, dipropylene glycol and tripropylene glycol
Or several mixing.
The preparation method of above-mentioned water and oil repellent agent, comprises the steps：
（1）, by comonomer, content of wax component, emulsifying agent, cosolvent and deionized water press quality proportioning 1：0.1~0.4：
0.05~0.15：0.1~0.3：2 ~ 4 weigh after be placed in the reactor with agitating device, carry out pre-dispersed, so under mechanical stirring
Under high pressure homogenizer, homogenizing obtains the meta emulsion in below 300nm for the particle diameter afterwards；Described comonomer by fluorochemical monomer, third
Olefin(e) acid esters monomer and the reactive monomer in mass ratio 20 ~ 40 with crosslinking feature：45~75：5 ~ 15 compositions；
（2）, will be through step（1）Obtained meta emulsion is placed in mechanical stirring device, reflux condensate device
Import and export with noble gases in the reaction vessel of device, stirring heats up, when temperature of reaction system rises to 50 DEG C ~ 80 °C, plus
Enter to account for the chain-transferring agent of comonomer mass percent 0.1% ~ 0.5% and account for drawing of comonomer mass percent 0.4% ~ 2.0%
Send out agent, proceed polyreaction 3-6 hour, be then down to room temperature and obtain described water and oil repellent agent.
Preferably, described chain-transferring agent is sulfur alcohol compound, and structural formula is R-SH, and wherein R is carbon number 8 ~ 12
Alkyl；Described initiator is in water soluble starter such as azo diisobutyl amidine hydrochlorate, ammonium persulfate and potassium peroxydisulfate
One or several combination it is also possible to select the oil-soluble initiator of azo or peroxide.
Due to the enforcement of above technical scheme, the present invention compared with prior art has the advantage that：
The present invention selects paraffin between 50 DEG C ~ 70 DEG C for the fusing point or microwax, with fluorochemical monomer, acrylic monomer
Etc. carrying out emulsion polymerization, paraffin or microwax form stratum nucleare, and fluorinated copolymer forms shell on wax surface, obtain particle diameter model
It is trapped among the polymer emulsion between 100 ~ 300 nanometers, can use as water and oil repellent agent.When arranging to fabric, this
Invention water and oil repellent agent can greatly improve the waterproof and oilproof performance of fabric, and especially fluorochemical monomer selects carbon number is 1 ~ 6
Short chain fluoroalkyl group monomer when, make this water and oil repellent agent than C of the prior art8The more environmental protection of type product, cost is lower, and with
When can also reach C8The waterproof and oilproof performance of type product.
Specific embodiment
With reference to specific embodiment, the present invention will be further described in detail, but is not limited to these embodiments.
Embodiment 1
(1) add following component in the plastic bottle of 500ml：CH2=C(CH3)-C(=O)-O-CH2CH2-C6F1340g, third
Olefin(e) acid dodecyl ester 55g, N hydroxymethyl acrylamide 5g, 58#Paraffin 20g, nonionic emulsifier C12H25O(CH2CH2O)20H
6g, cationic emulsifier C18H37N+(CH3)3Cl-4g, tripropylene glycol 20g, deionized water 400g；By above-mentioned reaction system in 60 °C
After stirring in water bath heats 20 minutes, then it is placed in emulsifying 10 minutes in high pressure homogenizer, obtain oil-in-water type meta emulsion, particle diameter
For 150nm.
By step（1）Gained oil-in-water type meta emulsion is poured into and is provided with mechanical agitator, thermometer, returned cold in advance
Coagulate in the glass reactor managing and being connected with nitrogen, add initiator azo diisobutyl amidine hydrochlorate 0.5g toward in reaction system
With lauryl mercaptan 0.2g, after reaction 6 hours under conditions of 75 °C of bath temperature, obtain stable polymer emulsion, that is,
Water and oil repellent agent for the present invention.GC test is carried out by gas chromatograph, monomer conversion is more than 97%.
The polymer emulsion of the present embodiment be translucent band blue light shape, particle diameter in 100 ~ 300 nanometer range, fluorine-containing copolymerization
The weight average molecular weight of thing is between 10000 ~ 100000.
Comparative example 1
It is not added with 58 in this example#Paraffin, remaining composition and reactions steps are identical with embodiment 1.
Embodiment 2
(1) add following component in the plastic beaker of 500ml：CH2=C(H)-C(=O)-O-CH2CH2-C6F1340g, third
Olefin(e) acid cetyl ester 55g, N hydroxymethyl acrylamide 5g, 70#Paraffin 40g, nonionic emulsifier C12H25O(CH2CH2O)20H
6g, cationic emulsifier C18H37N+(CH3)3Cl-4g, tripropylene glycol 20g, deionized water 400g；By above-mentioned reaction system in 70 °
After C stirring in water bath heats 20 minutes, then it is placed in emulsifying 10 minutes in high pressure homogenizer, obtain oil-in-water type meta emulsion, grain
Footpath is 250nm.
（2）By step（1）Gained oil-in-water type meta emulsion is poured into and is provided with mechanical agitator, thermometer in advance, returns
Stream condensing tube and be connected with the glass reactor of nitrogen, toward reaction system in addition initiator azo diisobutyl amidine hydrochlorate
0.5g and lauryl mercaptan 0.2g, after reaction 6 hours under conditions of 75 °C of bath temperature, obtains stable polymer breast
The water and oil repellent agent of liquid, the as present invention.GC test is carried out by gas chromatograph, monomer conversion is more than 97%.
The polymer emulsion of the present embodiment be translucent band blue light shape, particle diameter in 100 ~ 300 nanometer range, fluorine-containing copolymerization
The weight average molecular weight of thing is between 10000 ~ 100000.
Comparative example 2
It is not added with 70 in this example#Paraffin, remaining composition and reactions steps are identical with embodiment 2.
Embodiment 3
(1) add following component in the plastic beaker of 500ml：CH2=C(CH3)-C(=O)-O-CH2CH2-C4F940g、
Aliphatic acrylate 55g, N hydroxymethyl acrylamide 5g, microwax 20g, nonionic emulsifier C12H25O(CH2CH2O)20H
6g, cationic emulsifier C18H37N+(CH3)3Cl-4g, tripropylene glycol 20g, deionized water 400g；By above-mentioned reaction system in 60 °
After C stirring in water bath heats 20 minutes, then it is placed in emulsifying 10 minutes in high pressure homogenizer, obtain oil-in-water type meta emulsion, grain
Footpath is 250nm.
（2）By step（1）Gained oil-in-water type meta emulsion is poured into and is provided with mechanical agitator, thermometer in advance, returns
Stream condensing tube and be connected with the glass reactor of nitrogen, toward reaction system in addition initiator azo diisobutyl amidine hydrochlorate
0.5g and lauryl mercaptan 0.2g, after reaction 6 hours under conditions of 75 °C of bath temperature, obtains stable polymer breast
The water and oil repellent agent of liquid, the as present invention.Tested by gas chromatograph GC, monomer conversion is more than 97%.
The polymer emulsion of the present embodiment be translucent band blue light shape, particle diameter in 100 ~ 300 nanometer range, fluorine-containing copolymerization
The weight average molecular weight of thing is between 10000 ~ 100000.
Comparative example 3
It is not added with microwax, remaining composition and reactions steps are identical with embodiment 3 in this example.
Embodiment 4
(1) add following component in the plastic beaker of 500ml：CH2=C(CH3)-C(=O)-O-CH2CH2-C4F940g、
Octadecyl acrylate 55g, N hydroxymethyl acrylamide 5g, 58#Paraffin 20g, nonionic emulsifier C12H25O(CH2CH2O)20H 6g, cationic emulsifier C18H37N+(CH3)3Cl-4g, tripropylene glycol 20g, deionized water 400g；By above-mentioned reaction system in
After 60 °C of stirring in water bath heat 20 minutes, then it is placed in emulsifying 10 minutes in high pressure homogenizer, obtain oil-in-water type meta emulsion,
Particle diameter is 150nm.
（2）By step（1）Gained oil-in-water type meta emulsion is poured into and is provided with mechanical agitator, thermometer in advance, returns
Stream condensing tube and be connected with the glass reactor of nitrogen, toward reaction system in addition initiator azo diisobutyl amidine hydrochlorate
0.5g and lauryl mercaptan 0.2g, after reaction 6 hours under conditions of 75 °C of bath temperature, obtains stable polymer breast
The water and oil repellent agent of liquid, the as present invention.Tested by gas chromatograph GC, monomer conversion is more than 97%.
The polymer emulsion of the present embodiment be translucent band blue light shape, particle diameter in 100 ~ 300 nanometer range, fluorine-containing copolymerization
The weight average molecular weight of thing is between 10000 ~ 100000.
Comparative example 4
C is selected in this example8Class fluorochemical monomer replaces short chain fluoroalkyl group monomer, is added without wax component in raw material, other reactions
Step is same as Example 4, specific as follows：
(1) add following component in the plastic beaker of 500ml：CH2=C(CH3)-C(=O)-O-CH2CH2-C8F1740g、
Octadecyl acrylate 55g, N hydroxymethyl acrylamide 5g, nonionic emulsifier C12H25O(CH2CH2O)20H 6g, cation
Emulsifying agent C18H37N+(CH3)3Cl-4g, tripropylene glycol 20g, deionized water 400g；By above-mentioned reaction system in 60 °C of stirring in water bath
After heating 20 minutes, then it is placed in emulsifying 10 minutes in high pressure homogenizer, obtains oil-in-water type meta emulsion, particle diameter is 150nm.
（2）By step（1）Gained oil-in-water type meta emulsion is poured into and is provided with mechanical agitator, thermometer in advance, returns
Stream condensing tube and be connected with the glass reactor of nitrogen, toward reaction system in addition initiator azo diisobutyl amidine hydrochlorate
0.5g and lauryl mercaptan 0.2g, after reaction 6 hours under conditions of 75 °C of bath temperature, obtains stable polymer breast
The water and oil repellent agent of liquid, the as present invention.Tested by gas chromatograph GC, monomer conversion is more than 97%.
After polymer emulsion obtained by above example and comparative example stores half a year at room temperature, there is not precipitation etc.
Phenomenon, illustrates that stability of emulsion is good.
Water repellency and oil repellency evaluation are carried out to the water and oil repellent agent obtained by embodiment 1 ~ 4 and comparative example 1 ~ 4：
A, material treatment：
Cotton, terylene and three kinds of fabrics of nylon are selected to be tested, by the way of a leaching one is pricked（Will cloth be first dipped in whole
In reason liquid, then remove surplus liquid through roll-in again）Three kinds of different clothes are processed, the mass concentration of water and oil repellent agent
For 2%, the cloth processing bakees one minute under conditions of 180 DEG C, then carries out following water and oil repellant performance evaluation.
, water repellency test：
Testing standard is with reference to AATCC-22：
Using water pouring test device, in 25 seconds, by 250ml tap water sprinkle on tested fabric, observe fabric moistening
State, evaluates water repellency, testing evaluation reference table -1：
Table -1
C, oil repellency test
Testing standard is with reference to AATCC-118：
Use the experimental liquid of lowest number in table -2 first, drip five in tested sample so that 0.05mL liquid is careful, such as
In 30 seconds, no infiltration and wetting phenomena fruit occur, then and then dripped in tested sample with the experimental liquid of higher number.Real
Test and be carried out continuously, until experimental liquid in 30 seconds the fountain solution side of dripping or around till tested sample.Tested sample refuse oil
Grade is so that, in 30 seconds, the numbering having three experimental liquids being unable to moistening tested sample represents, rating is referring to table -2.
Table -2
Three kinds of different clothes after the water and oil repellent agent that each embodiment and comparative example prepare arranges, as tested
Sample carries out above-mentioned water and oil repellant performance test, and result is referring to table -3.
Table -3
From table -3 as can be seen that the introducing of paraffin or microwax can substantially make up short-chain fluorine-containing monomer on fabric
The not enough shortcoming of water and oil-resistant, reaches C8The performance of type water and oil repellent agent.
Above the present invention is described in detail, its object is to allow the personage being familiar with this art will appreciate that this
The content of invention is simultaneously carried out, and can not be limited the scope of the invention with this, all spirit institutes according to the present invention
The equivalence changes made or modification, all should cover within the scope of the present invention.
Claims (9)
1. a kind of water and oil repellent agent it is characterised in that：Described water and oil repellent agent is the particle diameter being obtained through emulsion polymerization 100 ~ 300
Polymer emulsion in nanometer range, described polymer emulsion specifically comprises following components：
Quality proportioning is 1：0.1~0.4：0.05~0.15：0.1~0.3：2 ~ 4 fluorinated copolymer component, wax component, emulsifying agent,
Cosolvent and deionized water；
Wherein, described fluorinated copolymer component is by fluorochemical monomer, acrylic ester monomer and the reactivity with crosslinking feature
Monomer in mass ratio 20 ~ 40：45~75：5 ~ 15 copolymerization form；
Described wax group is divided into microwax between 50 DEG C ~ 70 DEG C for the fusing point.
2. water and oil repellent agent according to claim 1 it is characterised in that：
The structural formula of described fluorochemical monomer is as follows：
CH2=C(-X)-C(=O)-O-CH2CH2-Rf；
Wherein, X is hydrogen atom or methyl, and Rf is the fluoroalkyl of carbon number 1～6；
The structural formula of described acrylic ester monomer is as follows：
CH2=C(-X)-C(=O)-O-(CH2)n-CH3；
Wherein, X is hydrogen atom or methyl, and n takes from 11 ~ 29 any number；
The described reactive monomer with crosslinking feature is selected from 2-(Acryloyloxy)ethanol, hydroxyethyl methylacrylate, acrylic acid hydroxypropyl
Ester, Hydroxypropyl methacrylate, acrylic acid epoxy ester, epoxymethacrylate, N-[2-(2-methyl-4-oxopentyl), N- methylol propylene
Amide, 3- chlorine-2-hydroxyl propyl acrylate, 3- chlorine-2-hydroxyl propyl methacrylate, glycidyl acrylate and first
The combination of one or more of base glycidyl acrylate.
3. water and oil repellent agent according to claim 1 it is characterised in that：
Described fluorochemical monomer is selected from the combination of one or more of the compound of following structure：
CH2=CH-C(=O)-O-CH2CH2-C6F13、CH2=C(CH3)-C(=O)-O-CH2CH2-C6F13、CH2=CH-C(=O)-O-
CH2CH2-C4F9、CH2=C(CH3)-C(=O)-O-CH2CH2-C4F9；
Described acrylic ester monomer is selected from the combination of one or more of the compound of following structure：
CH2=CH-C(=O)-O-(CH2)11-CH3、CH2=C(CH3)-C(=O)-O-(CH2)11-CH3、CH2=CH-C(=O)-O-
(CH2)13-CH3、CH2=C(CH3)-C(=O)-O-(CH2)13-CH3、CH2=CH-C(=O)-O-(CH2)15-CH3、CH2=C(CH3)-C
(=O)-O-(CH2)15-CH3、CH2=CH-C(=O)-O-(CH2)17-CH3、CH2=C(CH3)-C(=O)-O-(CH2)17-CH3、CH2=
CH-C(=O)-O-(CH2)19-CH3、CH2=C(CH3)-C(=O)-O-(CH2)19-CH3.
4. water and oil repellent agent according to claim 1 it is characterised in that:Described emulsifying agent is cationic emulsifier and non-
Ionic emulsifying agent combines, wherein, described cationic emulsifier account for described emulsifying agent total amount mass percent be 30% ~
70%.
5. water and oil repellent agent according to claim 4 it is characterised in that：The structural formula of described cationic emulsifier is R
(CH3)3N+X-, wherein R is 12 ~ 18 chain alkyl for carbon number, and X is chlorine or bromine atom；The knot of described nonionic emulsifier
Structure formula is RO (CH2CH2O)nH, wherein R are 12 ~ 20 chain alkyl for carbon number, and n is any number in 3 ~ 50.
6. water and oil repellent agent according to claim 1 it is characterised in that：Described cosolvent is high boiling point alcohols solvent.
7. water and oil repellent agent according to claim 6 it is characterised in that：Described cosolvent be ethylene glycol, propylene glycol, one contracting
The mixing of one or more of dipropylene glycol and tripropylene glycol.
8. the water and oil repellent agent described in any one of claim 1 ~ 7 claim preparation method it is characterised in that：Including such as
Lower step：
（1）, by comonomer, content of wax component, emulsifying agent, cosolvent and deionized water press quality proportioning 1：0.1~0.4：0.05~
0.15：0.1~0.3：2 ~ 4 weigh after be placed in the reactor with agitating device, carry out under mechanical stirring differential dissipate, Ran Hou
Under high pressure homogenizer, homogenizing obtains the meta emulsion in below 300nm for the particle diameter；Described comonomer is by fluorochemical monomer, acrylic acid
Esters monomer and the reactive monomer in mass ratio 20 ~ 40 with crosslinking feature：45~75：5 ~ 15 compositions；
（2）, will be through step（1）Obtained meta emulsion is placed in mechanical stirring device, reflux condensate device and lazy
Property gas import and export in the reaction vessel of device, stirring heat up, when temperature of reaction system rises to 50 DEG C ~ 80 °C, addition accounts for
The chain-transferring agent of comonomer mass percent 0.1% ~ 0.5% and the initiator accounting for comonomer mass percent 0.4% ~ 2.0%,
Proceed polyreaction 3-6 hour, be then down to room temperature and obtain described water and oil repellent agent.
9. water and oil repellent agent according to claim 8 preparation method it is characterised in that：The structure of described chain-transferring agent
Formula is R-SH, and wherein R is the alkyl of carbon number 8 ~ 12；Described initiator is water soluble starter azo diisobutyl amidine salt
One of hydrochlorate, ammonium persulfate and potassium peroxydisulfate or several combinations, or draw for the oil-soluble of azo or peroxide
Send out agent.
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| CN108705647A (en) * | 2017-07-15 | 2018-10-26 | 芜湖乾凯材料科技有限公司 | Environment protection pressed-fibre board based on modified liquid paraffin and its processing method |
| CN107326674A (en) * | 2017-07-21 | 2017-11-07 | 安徽华锦柏亚纤纺科技有限公司 | A kind of waterproof oil-proof finishing method of polyester-cotton blend woven |
| CN108193496B (en) * | 2017-12-07 | 2021-04-30 | 上海市纺织科学研究院有限公司 | Fluorocarbon waterproofing agent for anti-sticking roller and preparation method thereof |
| CN108250350B (en) * | 2018-02-08 | 2020-02-07 | 江南大学 | Preparation and application of short-chain fluorine-containing copolymer water-repellent and oil-repellent finishing agent |
| CN109400802B (en) * | 2018-10-25 | 2020-12-25 | 中国科学技术大学 | Hydrophobic and oleophobic modifier and preparation method thereof, and preparation method of modified powder |
| CN109867744A (en) * | 2019-02-21 | 2019-06-11 | 上海普信高分子材料有限公司 | A kind of preparation method of the stable fluorinated polymer surface treating agent of pair of anion |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102016151A (en) * | 2008-02-26 | 2011-04-13 | 霍尼韦尔国际公司 | Low weight and high durability soft body armor composite using topical wax coatings |
| CN202519938U (en) * | 2012-04-13 | 2012-11-07 | 滁州市汇丰木业装饰工程有限公司 | Waterproof floor |
| CN104169490A (en) * | 2012-01-31 | 2014-11-26 | 英威达技术有限公司 | Liquid and soil repellent compositions for fibers |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL266708A (en) * | 1960-07-05 | 1900-01-01 | ||
| JP4206767B2 (en) * | 2003-02-07 | 2009-01-14 | 旭硝子株式会社 | Water / oil repellent aqueous composition |
| JP2005146490A (en) * | 2003-11-13 | 2005-06-09 | Aoki Yushi Kogyo Kk | Water-resistant oil-resistant agent for paper and water-resistant oil-resistant paper made by using the agent |
| CN100383336C (en) * | 2006-04-25 | 2008-04-23 | 辽宁氟材料研究院有限公司 | Emulsion type fluorine-containing textile finishing agent and preparation method thereof |
| CN101922118B (en) * | 2009-06-10 | 2013-05-22 | 东丽纤维研究所（中国）有限公司 | Environmentally-friendly durable water repellent fabric and processing method thereof |
| CN102493193B (en) * | 2011-12-14 | 2014-01-29 | 太仓中化环保化工有限公司 | Fluorine-containing water and oil repellant agent and preparing method thereof |
| JP6063135B2 (en) * | 2012-03-19 | 2017-01-18 | 東洋紡Ｓｔｃ株式会社 | Method for producing fiber structure having water and oil repellency |
| CN102660871B (en) * | 2012-04-13 | 2014-09-03 | 无锡市恒创嘉业纳米材料科技有限公司 | Fluorine containing water repellent oil repellent composition and its preparation method |
| CN103726321A (en) * | 2012-10-16 | 2014-04-16 | 东丽纤维研究所（中国）有限公司 | Textile subjected to water repellency treatment and production method for textile |
-
2015
- 2015-02-12 CN CN201510073917.9A patent/CN104562684B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102016151A (en) * | 2008-02-26 | 2011-04-13 | 霍尼韦尔国际公司 | Low weight and high durability soft body armor composite using topical wax coatings |
| CN104169490A (en) * | 2012-01-31 | 2014-11-26 | 英威达技术有限公司 | Liquid and soil repellent compositions for fibers |
| CN202519938U (en) * | 2012-04-13 | 2012-11-07 | 滁州市汇丰木业装饰工程有限公司 | Waterproof floor |
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