CN110317307A - Easy decontamination multifunction finishing agent of a kind of free-floride water repellent and the preparation method and application thereof - Google Patents
Easy decontamination multifunction finishing agent of a kind of free-floride water repellent and the preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses easy decontamination multifunction finishing agents of a kind of floride-free water repellent and the preparation method and application thereof.Free-floride waterproof soil-releasing finishing agent of the invention is the water-based emulsion or aqueous solution of polymer shown in Formulas I.Inventive polymers, structural formula are shown in formula I:In Formulas I, R1For long chain acrylate or long chain methacrylate structure segment；R2For the cage silsesquioxane structure segment containing mono acrylic ester base or monomethacrylates base；R3For the poly glycol monomethyl ether structure segment containing mono acrylic ester based structures or monomethacrylates based structures；R4For the structure segment of functional monomer, selected from acrylate or methacrylate monomers containing at least one of hydroxyl, epoxy group, amide groups, dimethylamino, carboxyl, ester group, alkoxy, blocked terminal isocyanate groups and halide end group, a, b, c, d indicate the degree of polymerization.The invention belongs to environment-friendly type finishing agent, easy decontamination, no biotoxicity and non-biodegradable；It prepares simple, mild condition.
Description
Technical field
The present invention relates to easy decontamination multifunction finishing agents of a kind of floride-free water repellent and the preparation method and application thereof.
Background technique
Soil-releasing finishing agent is widely used as a kind of functional form auxiliary agent in the textile industry, is classified from performance and is easily gone
Dirty finishing agent includes hydrophilic soil release finishing agent and water repellent soil-releasing finishing agent.Wherein hydrophilic soil release finishing agent is usually divided into again
Anionic hydrophilic soil release finishing agent, usually by the polyvinyls containing hydrophilic carboxylic acid and vinyl carboxylic-containing acid
Or it hydrolyzes and obtains after acrylate base monomer such as acrylic acid, methacrylic acid and maleic anhydride copolymerization；Another kind of is nonionic
Type hydrophilic soil release finishing agent, the monomer usually with polyoxyethylene groups, ether are obtained by condensation polymerization or addition polymerization.
Water repellent soil-releasing finishing agent, usually by long chain fluorine-containing acrylate monomer and with long-chain polyoxyethylene structure, long-chain polyether
The vinyl of structure or acrylate base monomer addition polymerization obtain.With the improvement of people's environmental awareness, national governments and the people
Between organization all propose the limitation requirement used for fluorinated chemicals one after another, wherein European Union put into effect within 2006 it is related entirely
The ban of fluoro-octane sulfonyl compound (PFOS) only allows PFOS or its related substances to contain low, it is specified that on EU market
Amount is lower to be used, i.e. the levels of PFOS or its related substances in manufactured goods should be lower than 0.005%, should in semi-finished product
Lower than 0.1%, the limited content of PFOS is 1 μ g/m in textile or coating2.The appearance of this ban of European Union leads to scientific research personnel
The optimal perfluoro capryl class monomer of effect (C8 monomer) must be abandoned, the substitute of C8 monomer is perfluoro hexyl class monomer at present
(C6 monomer) avoids the PFOS generated in polymeric by-products.
Green peace organization combines such as Nike, Adidas, excellent clothing library, H&M textile industry brand quotient since 2015,
Plan to be entirely limited perfluorochemical (PFCs) in the year two thousand twenty, the substitution of perfluorochemical in water repellent soil-releasing finishing agent
It is extremely urgent.Water repellent soil-releasing finishing agent needs to consider the factor of two aspects in design, and first is water repellent effect, is needed
Hydrophobic structure is introduced in segment；Second is easy clean effect, needs to control water to fibrous inside and spot and fiber interface
Diffusion velocity, the faster spot of diffusion velocity is easier to fall off from fiber, but this there are contradictions with hydrophobic structure is introduced, therefore it is flat
The relationship of the good the two of weighing apparatus is just able to achieve the easy clean effect of effective water repellent.Why the water repellent soil-releasing finishing agent of traditional classical selects
Fluorochemical monomer is selected, there is stronger polarity just because of fluorine atom, other yuan can be captured when fluorine atom and other elements combination
The electronics of element forms the rock-steady structure of 8 electronics of outermost layer, so that the substance containing fluorine element has lower surface energy,
About 10mN/m, in baking film forming procedure fluorine-containing long-chain can Autonomic Migration Framework to fiber surface formation water repellent film, fabric in air,
Hydrophobic layer can reach water repellent, antifouling effect, and fabric hydrophilic segment in washing can be turned to outside to induce fiber surface
Spot be distributed in cleaning solution and reach easy clean effect.
Therefore water repellent and decontaminable balance need material surface energy to be changed with local environment difference, and one kind has
Three-dimensional silane structure discloses in Chinese patent CN106810650B without fluoro water proofing agent, which also discloses around a kind of high
It imitates hydrophobic POSS structures alone to be studied, POSS structures alone itself has compared with low-surface-energy, while also having as side chain
There is good migration, is a kind of novel organic-inorganic hybrid monomer for being expected to substitution fluorochemical monomer, and this is without fluoro water proofing agent pair
Biological and environmentally friendly, preparation method is simply easy to industrialize, but hydrophobic side chain is only accounted for when product design, does not design hydrophilic
Segment causes in the relatively slow easily clean effect of washing Shi Shuixiang fibrous inside and spot and the diffusion velocity of fiber interface and pays no attention to
Think.
Summary of the invention
The object of the present invention is to provide easy decontamination multifunction finishing agents of a kind of floride-free water repellent and the preparation method and application thereof.
First purpose of the invention is to provide a kind of polymer, and structural formula is shown in formula I:
In Formulas I,
R1For long chain acrylate or long chain methacrylate structure segment, a indicates the degree of polymerization, R1Structure such as Formula II
It is shown；
In Formula II, * indicates reactive group R1The reflecting point of polymerization, R0For hydrogen or methyl, n is the natural number between 15~21；
R2For the cage silsesquioxane structure segment containing mono acrylic ester base or monomethacrylates base, b is indicated
The degree of polymerization, R2Structure as shown in formula III；
In formula III, * indicates reactive group R2The reflecting point of polymerization, R0For hydrogen or methyl, R is ethyl, isobutyl group or different pungent
Base, n are the natural number between 1~3；
R3For the poly glycol monomethyl ether structural chain containing mono acrylic ester based structures or monomethacrylates based structures
Section, c indicate the degree of polymerization, R3Structure such as formula IV (with mono acrylic ester base poly glycol monomethyl ether) shown in；
In formula IV, * indicates reactive group R3The reflecting point of polymerization, R0For hydrogen or methyl, n is the natural number between 3~21；
R4For the structure segment of functional monomer, it is selected from and contains hydroxyl, epoxy group, amide groups, dimethylamino, carboxyl, ester
The acrylate or methacrylate monomers of at least one of base, alkoxy, blocked terminal isocyanate groups and halide end group, d table
Show the degree of polymerization；
A is the natural number between 1~150, and b is the natural number between 1~50, and c is the natural number between 1~100, d 1
Natural number between~100.
In above-mentioned polymer, R4Structure segment selected from following functional monomer: hydroxy-ethyl acrylate, N- methylol third
One of acrylamide, glycidyl methacrylate and the chloro- 2 hydroxyl-propyl methacrylate of 3- or multiple combinations；
A is the natural number between 60~130, and b is the natural number between 10~40, and c is the natural number between 20~80, d
For the natural number between 30~70.
In above-mentioned polymer, polymer shown in Formulas I is any of following formula I-I, Formulas I-II, Formulas I-III, Formulas I-IV
Kind:
In Formulas I-I, a is the natural number between 100~120, and b is the natural number between 10~30, and c is between 60~80
Natural number, d are the natural number between 30~50；
In Formulas I-II, a is the natural number between 60~80, and b is the natural number between 10~30, and c is between 30~50
Natural number, d1+d2For the natural number between 30~50；
In I-III, a is the natural number between 110~130, and b is the natural number between 10~30, and c is between 20~40
Natural number, d are the natural number between 40~60；
In Formulas I-IV, a is the natural number between 90~110, and b is the natural number between 20~40, and c is between 40~60
Natural number, d1+d2For the natural number between 50~70.
In the present invention, the polymerization for preparing polymer of the present invention is unrestricted.It can choose various polymerization sides
Method, such as emulsion polymerization, polymerisation in solution.In one or more specific embodiments of the invention, emulsifier, organic co-solvent are utilized
The pre-polymerization liquid that agent and water are formed carries out emulsion polymerization, obtains floride-free waterproof soil-releasing finishing agent.By the way that floride-free waterproof is diluted with water
Soil-releasing finishing agent obtains floride-free waterproof soil-releasing finiss working solution.
Second purpose of the invention is to provide a kind of floride-free waterproof soil-releasing finishing agent, the free-floride waterproof soil-releasing finishing agent
For the water-based emulsion or aqueous solution of polymer shown in above-mentioned Formulas I.The water-based emulsion or aqueous solution refer to aqueous Jie
Matter is the liquid of decentralized medium, and the water-based emulsion of polymer shown in the Formulas I is that polymer shown in the Formulas I is dispersed in emulsification
The water-based emulsion formed in the aqueous medium of agent, organic cosolvent and water composition；
The aqueous solution of polymer shown in the Formulas I is that polymer shown in the Formulas I is directly dispersing in organic cosolvent
With the aqueous solution formed in the aqueous medium of water composition.
Third purpose of the present invention is to provide the preparation method of above-mentioned floride-free waterproof soil-releasing finishing agent, including walks as follows
It is rapid: long chain acrylate or long chain methacrylate, cage-type silsesquioxane, mono acrylic ester base or monomethacrylates
The pre-emulsion that poly glycol monomethyl ether, functional monomer, emulsifier, organic cosolvent and the water of based structures are formed is in initiator
Through free-radical emulsion polymerization under effect, the floride-free waterproof soil-releasing finishing agent is obtained；
The long chain acrylate or long chain methacrylate be made of hydrocarbon hydrophobic grouping and double bond it is polymerizable
Monomer, hydrocarbon hydrophobic grouping are the straight chain containing 16~22 carbon atoms, and structural formula is shown as a formula V:
In Formula V, R0For hydrogen or methyl, n is the natural number between 15~21；
The structure of the cage-type silsesquioxane is as shown in Formula IV:
In Formula IV, R base is ethyl, isobutyl group or iso-octyl, R0For hydrogen or methyl, n is the natural number between 1~3；
The poly glycol monomethyl ether of the mono acrylic ester base or monomethacrylates based structures is by containing poly- second two
The polymerisable monomer that alcohol structure hydrophilic radical and double bond are constituted, polyethylene glycol structures hydrophilic radical repetitive unit are the direct-connected of 1-20
Structure, structural formula is as shown in Formula VII:
In Formula VII, R0For hydrogen or methyl, n is the natural number between 3~21；
The functional monomer is to contain hydroxyl, epoxy group, amide groups, dimethylamino, carboxyl, ester group, alkoxy, sealing end
The acrylate or methacrylate monomers of at least one of isocyanate group and halide end group.
Above-mentioned preparation method, in Formula V, n 15,17 or 21；The long chain acrylate shown in Formula V is acrylic acid 16
Ester and/or octadecyl acrylate；The long chain methacrylate shown in Formula V is octadecyl methacrylate and/or acrylic acid
20 diester；
In Formula IV, R base is isobutyl group or iso-octyl, R0For hydrogen or methyl, n is 1 or 3；The cage model sesquialter shown in Formula IV
Siloxanes concretely seven isobutyl group acryloxypropyl cage-type silsesquioxanes (seven isobutyl group propyl acrylate base cage model sesquialters
Siloxanes), seven isobutyl methyl acryloxypropyl cage-type silsesquioxanes (seven isobutyl methyl propyl acrylate base cage modles times
Half siloxanes), seven isobutyl methyl methyl acrylate base cage-type silsesquioxanes, seven iso-octyl methyl methacrylate base cage modles
Any one of silsesquioxane；
In Formula VII, n 3,6,12 or 21；Mono acrylic ester base shown in Formula VII or monomethacrylates based structures it is poly-
Glycol monoethyl ether concretely 150 methyl ether methacrylate of polyethylene glycol (MPEG-150MA), Liquid Macrogol methyl
Ether acrylate (MPEG-300A), Macrogol 600 methyl ether acrylate (MPEG-600A), cetomacrogol 1000 methyl ether
Any one of methacrylate (MPEG-1000MA).
The functional monomer can be hydroxy-ethyl acrylate, N hydroxymethyl acrylamide, glycidyl methacrylate
With one of the chloro- 2 hydroxyl-propyl methacrylate of 3- or multiple combinations, the combination such as mass ratio can be 1: 1 propylene
Sour hydroxyl ethyl ester and N hydroxymethyl acrylamide, the glycidyl methacrylate of mass ratio 1: 1 and chloro- 2 hydroxyl-propyl of 3-
Methacrylate；
The emulsifier is the cationic emulsifier of mass ratio 0.5~2: 1 and the mixture of nonionic emulsifier, specifically may be used
For the combination of cationic emulsifier and nonionic emulsifier that mass ratio is 2: 1,1.5: 1,1: 1 or 1: 1.5；
The cationic emulsifier is specially the quaternary emulsifier containing chain alkyl, and the cationic emulsifier is more
Specially in dodecyl trimethyl ammonium chloride, cetyl trimethylammonium bromide and Cetyltrimethylammonium bromide at least
It is a kind of；
The nonionic emulsifier is specially polyoxyethylene-type emulsifier or polyol type emulsifier；The non-ionic emulsifier
Agent is more specifically polyoxyethylene sorbitan monoglyceride, dodecanol polyoxyethylene (10) ether (wherein 10 indicates 10
Polyoxyethylene repetitive unit)；
The organic cosolvent is at least one of acetone, methyl ethyl ketone, dipropylene glycol and tripropylene glycol；
The initiator be water-soluble azo class initiator, peroxide initiator and redox type initiator in extremely
Few one kind；The initiator is specially azo-bis-isobutyrate hydrochloride, hydrogen peroxide, potassium peroxydisulfate.
Above-mentioned preparation method, in the pre-emulsion, the long chain acrylate or long chain methacrylate account for described
The mass percentage of pre-emulsion is 13~22%, concretely 13.6%, 14.5%, 18.2%, 21.8%；
The mass percentage that the cage-type silsesquioxane accounts for the pre-emulsion is 2~8%, concretely 2.2%,
4.4%, 5.5%, 7.3%；
The poly glycol monomethyl ether of the mono acrylic ester base or monomethacrylates based structures accounts for the pre-emulsion
Mass percentage is 7~12%, concretely 7.8%, 9.1%, 10.2%, 12%；
The mass percentage that the functional monomer accounts for the pre-emulsion is 1~5%, concretely 1.8%, 2.5%,
2.7%, 4.5%；
The emulsifier, the organic cosolvent, the quality of the initiator and monomer gross mass ratio can be 4~8: 24
~37: 0.1~0.5: 100；Wherein, the monomer gross mass is the long chain acrylate or long chain methacrylate, institute
State cage-type silsesquioxane, the poly glycol monomethyl ether of the mono acrylic ester base or monomethacrylates based structures and described
The quality sum of functional monomer；Concretely 5.3: 26.3: 0.2: 100,5.9: 36.8: 0.2:100,7.4: 24.2: 0.2:
100,4.2: 27.4: 0.2: 100 or 4.2~7.4: 24.2~36.8: 0.1~0.4: 100；
Surplus is water.
In the present invention, the emulsifier accounts for the long chain acrylate or long chain methacrylate, the cage model sesquialter
The poly glycol monomethyl ether and the functional monomer of siloxanes, the mono acrylic ester base or monomethacrylates based structures
Gross mass mass percent concretely 4.2%, 5.2%, 5.8%, 7.4%；
The organic cosolvent accounts for the long chain acrylate or long chain methacrylate, the cage model sesquialter silicon oxygen
Alkane, the poly glycol monomethyl ether of the mono acrylic ester base or monomethacrylates based structures and the functional monomer it is total
The mass percent of quality concretely 24.2%, 26.3%, 27.4%, 36.8%.
The initiator accounts for the long chain acrylate or long chain methacrylate, the cage-type silsesquioxane, institute
State the poly glycol monomethyl ether of mono acrylic ester base or monomethacrylates based structures and the gross mass of the functional monomer
Mass percent concretely 0.2%.
In above-mentioned preparation method, the method specifically comprises the following steps: (1) by the long chain acrylate or long-chain
The poly- second of methacrylate, the cage-type silsesquioxane, the mono acrylic ester base or monomethacrylates based structures
It is sheared after glycol monomethyl ether, the functional monomer, the emulsifier, the organic cosolvent and water mixing, obtains institute
State pre-emulsion；
(2) under nitrogen protection, the pre-emulsion is put into attemperator to and is added dropwise the initiator, through the freedom
Emulsion polymerization obtains the floride-free waterproof soil-releasing finishing agent.
Above-mentioned preparation method, in step (1), the revolving speed of the shearing can be 2000~8000 revs/min, concretely
3000 revs/min, 2000~3000 revs/min, 3000~8000 revs/min or 2000~5000 revs/min, the time can be 2~10 points
Clock, concretely 5 minutes, 2~5 minutes, 5~10 minutes or 3~7 minutes；
In step (2), the free-radical emulsion polymerization carries out under conditions of revolving speed can be 150~300 revs/min, has
Body can be 200 revs/min, 150~200 revs/min, 200~300 revs/min or 150~250 revs/min；
In step (2), the attemperator is constant control temperature from -100 DEG C of room temperature of equipment, concretely thermostatted water
Bath, the temperature of the free-radical emulsion polymerization can be 60~90 DEG C, concretely 84 DEG C, 60~84 DEG C, 84~90 DEG C 70~
85℃；Time can be 6~10 hours, concretely 6 hours or 6~8 hours；
The free-radical emulsion polymerization equipment further includes condensation cycle equipment；The condensation cycle equipment can be air setting
It manages, water condensing tube, concretely spherical water condensing tube.
The method also includes filtering system after reaction and collect filtrate.The strainer that the filtering uses
Mesh number be 250~400 mesh, concretely 300 mesh, 250~300 mesh, 300~400 mesh or 250~350 mesh.
5th purpose of the invention is to provide polymer shown in above-mentioned Formulas I or above-mentioned floride-free waterproof soil-releasing finishing agent
Application in fabric water repellent soil-releasing finiss；
The fabric specifically includes pure cotton, terylene or nylon.
Sixth object of the present invention is to provide restore the easy decontamination effect of water repellent after a kind of washing of water repellent soil-releasing finiss fabric
The method of fruit.
It is extensive after the easy decontamination fabric washing of the water repellent that method provided by the invention using above-mentioned water repellent soil-releasing finiss obtains
The multiple decontaminable method of water repellent, include the following steps: it is water washed after using clear water sufficiently rinse fabric, then dried, dried
It is dry, that is, it realizes and restores the easy clean effect of water repellent to after the washing of the water repellent easy decontamination fabric；
The clear water can be filtered middle water, ordinary tap water, softened water, distilled water.
The drying can be 2-6 minutes for 500-1000 revs/min of dryer drying, time, and concretely household dries
It 1000 revs/min of machine, dries 5 minutes.
The drying can be 40-80 DEG C of roller drying, and the time is 40-60 minutes, concretely household roller drying machine
40 DEG C of general procedure run 60 minutes.It can also be to be dried using 60-250 DEG C of ironing of electric iron, concretely household electric iron exists
100 DEG C of ironing drying.
In above-mentioned furnace drying method, it can also include hang airing before the drying, tile and dry.
The invention has the following advantages that
1, the present invention utilizes long chain acrylic ester monomer, cage-type silsesquioxane monomer, single (methyl) acrylate base junction
The poly glycol monomethyl ether monomer of structure introduces hydrophobic long-chain third in acrylate polymer side chain by free radical polymerization simultaneously
Olefin(e) acid ester, hydrophobic cage-type silsesquioxane and the hydrophilic polyethylene glycol with certain length, lotion in air high temperature form a film when
Long chain acrylate and cage-type silsesquioxane move to fabric fibre surface and form the hydrophobic structure with low-surface-energy, arrange
The polyethylene glycol long chain hydrophilic on side chain in the water containing washing powder, liquid detergent of fabric afterwards moves to fabric fibre surface shape
Diffusion velocity of the water to fibrous inside and spot and fiber interface is improved at higher surface energy structure, while side chain is moved to water termination
It moves, promotes the removing of spot and fiber, reach easy clean effect, the effect of hydrophobe conversion is realized by side chain migration.
2, the present invention compared with traditional soil-releasing finishing agent the difference is that: traditional soil-releasing finishing agent introduces in main chain
Polyethylene glycol or similar hydrophilic segment, and the present invention is the poly glycol monomethyl ether by using single functionality acrylate structural
Monomer introduces polyethylene glycol long chain in polymer lateral chain.The advantage is that: hydrophilic radical introducing pair can be reduced to greatest extent
The influence of water repellent effect；The speed and degree that side chain migrates in washing process are much higher than main chain, and easy clean effect is faster and better.
3, the present invention compared with conventional waterproof soil-releasing finishing agent the difference is that: traditional water repellent soil-releasing finishing agent is general
Select long fluorocarbon chain acrylate monomer as hydrophobic structure, and the present invention is by using hydrophobic long chain acrylate, hydrophobic
Cage-type silsesquioxane is collectively as hydrophobic structure.The advantage is that: reducing the discharge of perfluorochemical PFCs to global water quality
Influence, while cage-type silsesquioxane there are water repellent effects to be substantially improved.
4, comprising at least one in the function monomer selected when floride-free waterproof soil-releasing finishing agent polymerization prepared by the present invention
The easy decontamination fabric of water repellent planted self-crosslinking structure, therefore pass through floride-free waterproof soil-releasing finiss passes through appropriate after completed washings
Drying condition can make fabric restore the easy clean effect of water repellent.The easy decontamination fabric of water repellent after washing is in drying condition appropriate
Under, the hydrophobic structure in fiber surface polymer film can move to fiber surface again and form low surface energy structures, so that face
Material restores the easy clean effect of water repellent.
5, the floride-free waterproof soil-releasing finishing agent prepared by the present invention belongs to environment-friendly type finishing agent, no biotoxicity and can not
Degradability, it is non-hazardous to biology and environment.
6, the polymerization that the present invention uses belongs to more mature emulsion polymerisation process, simple production process, reaction
Mild condition.
Detailed description of the invention
The floride-free waterproof soil-releasing finishing agent of Fig. 1 present invention and traditional soil-releasing finishing agent structure comparison of design schematic diagram.
The floride-free waterproof soil-releasing finiss pure cotton fabric water contact angle of Fig. 2 present invention tests photo.
The floride-free waterproof SOIL RELEASE FINISH FABRIC fiber surface of Fig. 3 present invention can change schematic diagram in surface in different environments.
Specific embodiment
Experimental method used in following embodiments is conventional method unless otherwise specified.
The materials, reagents and the like used in the following examples is commercially available unless otherwise specified.
Cage-type silsesquioxane as used in the following examples is all from Hybrid Plastics company, the U.S., wherein
Seven isobutyl group acryloxypropyl cage-type silsesquioxanes (seven isobutyl group propyl acrylate base cage-type silsesquioxanes)
The commercial grades of (AcryloIsobutyl POSS) are MA0701, seven isobutyl methyl acryloxypropyl cage model sesquialter silicon oxygen
The commercial grades of alkane (seven isobutyl methyl propyl acrylate base cage-type silsesquioxanes) (MethacrylIsobutyl POSS)
It is MA0702, seven isobutyl methyl methyl acrylate base cage-type silsesquioxanes (Methacrylate Isobutyl POSS)
Commercial grades are MA0706, seven iso-octyl methyl methacrylate base cage-type silsesquioxane (MethacrylIsooctyl
POSS commercial grades) are M0719.
Embodiment 1 prepares floride-free waterproof soil-releasing finishing agent
(1) by Process Conditions of Cetane Acrylate 50g, seven isobutyl group acryloxypropyl cage-type silsesquioxane (seven isobutyl group propylene
Propyl propionate base cage-type silsesquioxane) 15g, 150 methyl ether methacrylate of polyethylene glycol (MPEG-150MA) 25g, propylene
Sour hydroxyl ethyl ester 5g, cetyl trimethylammonium bromide 2g, polyoxyethylene sorbitan monoglyceride 2g, acetone 26g are added to
In 150g deionized water, after five minutes using 3000 revs/min of high-speed shearing machine mixing, the pre- cream of stable oil-in-water type is obtained
Liquid.
In above-mentioned pre-emulsion, monomer I is Process Conditions of Cetane Acrylate, accounts for the 18.2% of lotion, and monomer II is seven isobutyl group propylene
Monomethacryloxypropyl cage-type silsesquioxane (seven isobutyl group propyl acrylate base cage-type silsesquioxanes), accounts for the 5.5% of lotion, monomer
III is 150 methyl ether methacrylate of polyethylene glycol (MPEG-150MA), accounts for the 9.1% of lotion, and monomer IV is acrylic acid hydroxyl
Ethyl ester accounts for the 1.8% of lotion.Emulsifier accounts for the 4.2% of whole monomer masses, and wherein cationic emulsifier is cetyl front three
Base ammonium bromide, nonionic emulsifier be polyoxyethylene sorbitan monoglyceride, cationic emulsifier: nonionic emulsifier=
1:1.Organic solvent is acetone, accounts for the 27.4% of whole monomer masses.
(2) by pre-emulsion pour into nitrogen, thermometer, blender, reflux unit four-hole boiling flask in nitrogen protection
Under, (initiator amount is monomer to the 20g aqueous solution of dropwise addition 0.19g initiator azo-bis-isobutyrate hydrochloride after being warming up to 84 DEG C
The 0.2% of gross mass) and 6 hours are kept the temperature, control revolving speed is 200 revs/min, after stopping heating, when system temperature is down to 30 DEG C
When stop stirring, use 300 mesh filter screen filtering and dischargings.Water-based emulsion-the present embodiment for obtaining polymer shown in Formulas I-I is floride-free
Waterproof soil-releasing finishing agent, wherein it be 10~30, c is natural number of 60~80, the d between 30-50 that a, which is 100~120, b,.
Embodiment 2 prepares floride-free waterproof soil-releasing finishing agent
(1) by octadecyl acrylate 40g, seven isobutyl methyl acryloxypropyl cage-type silsesquioxane (seven isobutyl groups
Propyl methacrylate base cage-type silsesquioxane) 20g, Liquid Macrogol methyl ether acrylate (MPEG-300A) 28g, third
Olefin(e) acid hydroxyl ethyl ester 3.5g, N hydroxymethyl acrylamide 3.5g, Cetyltrimethylammonium bromide 4.2g, dodecanol polyoxyethylene
(10) ether 2.8g, methyl ethyl ketone 23g are added in 150g deionized water, mix 5 using 3000 revs/min of high-speed shearing machines
After minute, stable oil-in-water pre-emulsion is obtained.
In above-mentioned pre-emulsion, monomer I is octadecyl acrylate, accounts for the 14.5% of lotion, and monomer II is seven isobutyl methyls
Acryloxypropyl cage-type silsesquioxane (seven isobutyl methyl propyl acrylate base cage-type silsesquioxanes), accounts for lotion
7.3%, monomer III are Liquid Macrogol methyl ether acrylate (MPEG-300A), account for the 10.2% of lotion, and monomer IV is third
1: 1 combination of olefin(e) acid hydroxyl ethyl ester, N hydroxymethyl acrylamide, accounts for the 2.5% of lotion.Emulsifier accounts for whole monomer masses
7.4%, wherein cationic emulsifier is Cetyltrimethylammonium bromide, and nonionic emulsifier is dodecanol polyoxyethylene
(10) ether, cationic emulsifier: nonionic emulsifier=1.5: 1.Organic solvent is methyl ethyl ketone, accounts for whole monomer masses
24.2%.
(2) by pre-emulsion pour into nitrogen, thermometer, blender, reflux unit four-hole boiling flask in nitrogen protection
Under, (initiator amount is monomer to the 20g aqueous solution of dropwise addition 0.19g initiator azo-bis-isobutyrate hydrochloride after being warming up to 84 DEG C
The 0.2% of gross mass) and 6 hours are kept the temperature, control revolving speed is 200 revs/min, is stopped after heating when system temperature is down to 30 DEG C
Stop stirring, uses 300 mesh filter screen filtering and dischargings.Water-based emulsion-the present embodiment for obtaining polymer shown in Formulas I-II is floride-free
Waterproof soil-releasing finishing agent, wherein it be 10~30, c is natural number of 30~50, the d1+d2 between 30-50 that a, which is 60~80, b,.
Embodiment 3 prepares floride-free waterproof soil-releasing finishing agent
(1) by octadecyl methacrylate 60g, seven isobutyl methyl methyl acrylate base cage-type silsesquioxane 6g, poly-
600 methyl ether acrylate of ethylene glycol (MPEG-600A21.5), N hydroxymethyl acrylamide 7.5g, octadecyl trimethyl bromine
Change ammonium 2g, polyoxyethylene sorbitan monoglyceride 3g, dipropylene glycol 25g to be added in 150g deionized water, use
3000 revs/min of high-speed shearing machine mixing after five minutes, obtains stable oil-in-water pre-emulsion.
In above-mentioned pre-emulsion, monomer I is octadecyl methacrylate, accounts for the 21.8% of lotion, and monomer II is seven isobutyl groups
Methyl methacrylate base cage-type silsesquioxane, accounts for the 2.2% of lotion, and monomer III is Macrogol 600 methyl ether acrylic acid
Ester (MPEG-600A) accounts for the 7.8% of lotion, and monomer IV is N hydroxymethyl acrylamide, accounts for the 2.7% of lotion.Emulsifier accounts for
The 5.3% of whole monomer masses, wherein cationic emulsifier is Cetyltrimethylammonium bromide, and nonionic emulsifier is polyoxy
Ethylene anhydrous sorbitol monoglyceride, cationic emulsifier: nonionic emulsifier=1:1.5.Organic solvent is a contracting dipropyl two
Alcohol accounts for the 26.3% of whole monomer masses.
(2) by pre-emulsion pour into nitrogen, thermometer, blender, reflux unit four-hole boiling flask in nitrogen protection
Under, (initiator amount is monomer to the 20g aqueous solution of dropwise addition 0.19g initiator azo-bis-isobutyrate hydrochloride after being warming up to 84 DEG C
The 0.2% of gross mass) and 6 hours are kept the temperature, control revolving speed is 200 revs/min, is stopped after heating when system temperature is 30 DEG C near
Stop stirring, uses 300 mesh filter screen filtering and dischargings.Water-based emulsion-the present embodiment for obtaining polymer shown in Formulas I-III is floride-free
Waterproof soil-releasing finishing agent, wherein it be 10~30, c be 20~40, d is natural number between 40~60 that a, which is 110~130, b,.
Embodiment 4 prepares floride-free waterproof soil-releasing finishing agent
(1) by Behenyl acrylate 37.5g, seven iso-octyl methyl methacrylate base cage-type silsesquioxane 12g, poly-
1000 methyl ether methacrylate of ethylene glycol (MPEG-1000MA) 33g, glycidyl methacrylate 6.25g, 3- chloro- 2
Hydroxyl-propyl methacrylate 6.25g, dodecyl trimethyl ammonium chloride 3.8g, dodecanol polyoxyethylene (10) ether
1.9g, tripropylene glycol 35g are added in 140g deionized water, are mixed 5 minutes using 3000 revs/min of high-speed shearing machines
Afterwards, stable oil-in-water pre-emulsion is obtained.
In above-mentioned pre-emulsion, monomer I is Behenyl acrylate, accounts for the 13.6% of lotion, and monomer II is seven iso-octyl first
Base methyl acrylate base cage-type silsesquioxane, accounts for the 4.4% of lotion, and monomer III is cetomacrogol 1000 methyl ether methyl-prop
Olefin(e) acid ester (MPEG-1000MA), accounts for the 12% of lotion, and monomer IV is glycidyl methacrylate, chloro- 2 hydroxyl-propyl of 3-
The 1:1 of methacrylate is combined, and accounts for the 4.5% of lotion.Emulsifier accounts for the 5.9% of whole monomer masses, wherein cationic galactomannan
Agent is dodecyl trimethyl ammonium chloride, and nonionic emulsifier is dodecanol polyoxyethylene (10) ether, cationic emulsifier:
Nonionic emulsifier=2: 1.Organic solvent is tripropylene glycol, accounts for the 36.8% of whole monomer masses.
(2) by pre-emulsion pour into nitrogen, thermometer, blender, reflux unit four-hole boiling flask in nitrogen protection
Under, (initiator amount is monomer to the 20g aqueous solution of dropwise addition 0.19g initiator azo-bis-isobutyrate hydrochloride after being warming up to 84 DEG C
The 0.2% of gross mass) and 6 hours are kept the temperature, control revolving speed is 200 revs/min, is stopped after heating when system temperature is down to 30 DEG C
Stop stirring, uses 300 mesh filter screen filtering and dischargings.Water-based emulsion-the present embodiment for obtaining polymer shown in Formulas I-IV is floride-free
Waterproof soil-releasing finishing agent, wherein it be 20~40, c be 40~60, d is natural number between 50~70 that a, which is 90~110, b,.
Comparative example 1, preparation are free of the floride-free waterproof soil-releasing finishing agent of monomer II structure
(1) by octadecyl acrylate 60g, Liquid Macrogol methyl ether acrylate (MPEG-300A) 28g, acrylic acid hydroxyl
Ethyl ester 3.5g, N hydroxymethyl acrylamide 3.5g, Cetyltrimethylammonium bromide 4.2g, dodecanol polyoxyethylene (10) ether
2.8g, methyl ethyl ketone 18g are added in 155g deionized water, are mixed 5 minutes using 3000 revs/min of high-speed shearing machines
Afterwards, stable oil-in-water pre-emulsion is obtained.
(2) by pre-emulsion pour into nitrogen, thermometer, blender, reflux unit four-hole boiling flask in nitrogen protection
Under, (initiator amount is monomer to the 20g aqueous solution of dropwise addition 0.19g initiator azo-bis-isobutyrate hydrochloride after being warming up to 84 DEG C
The 0.2% of gross mass) and 6 hours are kept the temperature, control revolving speed is 200 revs/min, is stopped after heating when system temperature is down to 30 DEG C
Stop stirring, uses 300 mesh filter screen filtering and dischargings.Water-based emulsion-the present embodiment the free-floride for obtaining polymer shown in Formulas I-V is anti-
Water soil-releasing finishing agent, wherein a is that 80~100, c is natural number of 40~60, the d1+d2 between 30-50.
Comparative example 2, preparation are free of the floride-free waterproof soil-releasing finishing agent of monomer III structure
(1) by octadecyl acrylate 68g, seven isobutyl methyl acryloxypropyl cage-type silsesquioxane (seven isobutyl groups
Propyl methacrylate base cage-type silsesquioxane) 20g, hydroxy-ethyl acrylate 3.5g, N hydroxymethyl acrylamide 3.5g, 18
Alkyl trimethyl ammonium bromide 4.2g, dodecanol polyoxyethylene (10) ether 2.8g, methyl ethyl ketone 18g are added to 155g deionization
In water, after five minutes using 3000 revs/min of high-speed shearing machine mixing, stable oil-in-water pre-emulsion is obtained.
(2) by pre-emulsion pour into nitrogen, thermometer, blender, reflux unit four-hole boiling flask in nitrogen protection
Under, (initiator amount is monomer to the 20g aqueous solution of dropwise addition 0.19g initiator azo-bis-isobutyrate hydrochloride after being warming up to 84 DEG C
The 0.2% of gross mass) and 6 hours are kept the temperature, control revolving speed is 200 revs/min, is stopped after heating when system temperature is down to 30 DEG C
Stop stirring, uses 300 mesh filter screen filtering and dischargings.Water-based emulsion-the present embodiment for obtaining polymer shown in Formulas I-VI is floride-free
Waterproof soil-releasing finishing agent, wherein a is that 80~100, b is natural number of 10~30, the d1+d2 between 30-50.
The present invention utilizes the cage-type silsesquioxane monomer containing vinyl structure and polyethylene glycol (methyl) ether methyl-prop
Olefin(e) acid ester carries out free radical polymerization and prepares the easy decontamination multifunction finishing agent of floride-free water repellent.Free-floride waterproof soil-releasing finishing agent of the invention
It is as shown in Figure 1 with traditional soil-releasing finishing agent structure design difference.
For the floride-free waterproof soil-releasing finishing agent of 1-4 of embodiment of the present invention preparation compared with comparative example 1,2, prepared by comparative example 1
Floride-free waterproof soil-releasing finishing agent without monomer II structure, waterproof performance is poor, and the preparation of comparative example 2 is tied without monomer III
The floride-free waterproof soil-releasing finishing agent of structure, soil release performance can be poor.The present invention realize by with stereochemical structure siloxanes and
It is introduced on the side chain of polymer with longer chain polyethylene glycols hydrophilic-structure, enables emulsion film forming rear surface can be with locating
Environment difference changes, fabric in water repellent soil-releasing finiss technique when baking with the siloxanes cube compared with low-surface-energy
Structure significantly more efficient can move to surface, so that fabric has the effect of water repellent, anti-pollution, fabric hydrophobic contact angle photo is such as
Shown in Fig. 2；When fabric washs in water there is longer chain polyethylene glycols hydrophilic-structure side chain can be improved water to fibrous inside
With the diffusion velocity of spot and fiber interface, while side chain can be migrated to water termination, promote the removing of spot and fiber, be improved easy
Clean effect can be fabric after fabric washing by way of ironing, roller drying and restore hydrophobic, anti-pollution effect.Water repellent
It is as shown in Figure 3 that web surface after soil-releasing finiss can change schematic diagram.
Embodiment 5, the water repellent soil-releasing finiss to fabric
It is provided by the present invention that there is three-dimensional silane structure and prevent in the free-floride that polymer lateral chain introduces polyethylene glycol long chain
For the easy detergent of water when carrying out water repellent finish to fabric, most significant feature is can to reduce hydrophilic group to greatest extent after arranging
Group introduces the influence to water repellent effect；And the speed and degree of the side-chain of polyelycol migration of long-chain are much higher than in washing process
Main chain, easy clean effect are faster and better.Avoid the discharge for reducing perfluorochemical PFCs using fluorochemical monomer to global water simultaneously
The influence of matter, and the presence of cage-type silsesquioxane improves water repellent effect and is substantially improved.
Floride-free waterproof soil-releasing finishing agent prepared by above-described embodiment 1~4 and comparative example 1~2 is diluted, as knitting
The working solution of object water repellent soil-releasing finiss, quality-volumetric concentration are 100g/L.
Water repellent soil-releasing finiss is carried out to pure cotton, polyester-cotton fabric with above-mentioned working solution:
Pure cotton, polyester-cotton fabric are padded in respectively in above-mentioned working solution, then in turn through preliminary drying (100 DEG C, 180 seconds) and
It bakes (160 DEG C, 90 seconds), that is, completes the water repellent soil-releasing finiss to each fabric.
It is above-mentioned to pad rear each fabric liquid carrying rate and be respectively as follows: pure cotton 80%, polyester-cotton blend 70%
The easy decontamination test of water repellent is carried out after the fabric put in order is placed 24 hours at room temperature, the results are shown in Table 1.
1 embodiment 1-4 of table and the easy decontamination of water repellent of the comparative example 1-2 in pure cotton, polyester-cotton fabric are graded
Above-mentioned water repellency test is measured referring to AATCC 193 " anti-wettability: waterproof/alcoholic solution test ", easy decontamination is surveyed
Examination is measured referring to AATCC 130 " soil release performance: grease stain removes method "；
Above-mentioned test fabric is subjected to washing fastness test, referring to AATCC135 " test of washing dimensional stability " washing 1
The easy decontamination test of water repellent is carried out after secondary, is dried within roller drying 1 hour after washing using 60 DEG C, the results are shown in Table 2.
The easy decontamination of water repellent is graded after 2 embodiment 1-4 of table and comparative example 1-2 washing in pure cotton, polyester-cotton fabric
Claims (10)
1. a kind of polymer, structural formula are shown in formula I:
In Formulas I,
R1For long chain acrylate or long chain methacrylate structure segment, a indicates the degree of polymerization, R1Structure as shown in Formula II；
In Formula II, * indicates reactive group R1The reflecting point of polymerization, R0For hydrogen or methyl, n is the natural number between 15~21；
R2For the cage silsesquioxane structure segment containing mono acrylic ester base or monomethacrylates base, b indicates polymerization
Degree, R2Structure as shown in formula III；
In formula III, * indicates reactive group R2The reflecting point of polymerization, R0For hydrogen or methyl, R is ethyl, isobutyl group or iso-octyl, n
For the natural number between 1~3；
R3For the poly glycol monomethyl ether structure segment containing mono acrylic ester based structures or monomethacrylates based structures, c table
Show the degree of polymerization, R3Structure as shown in formula IV；
In formula IV, * indicates reactive group R3The reflecting point of polymerization, R0For hydrogen or methyl, n is the natural number between 3~21；
R4For the structure segment of functional monomer, it is selected from and contains hydroxyl, epoxy group, amide groups, dimethylamino, carboxyl, ester group, alkane
The acrylate or methacrylate monomers of at least one of oxygroup, blocked terminal isocyanate groups and halide end group, d indicate polymerization
Degree；
A be 1~150 between natural number, b be 1~50 between natural number, c be 1~100 between natural number, d be 1~
Natural number between 100.
2. polymer according to claim 1, it is characterised in that: R4Structure segment selected from following functional monomer: propylene
In sour hydroxyl ethyl ester, N hydroxymethyl acrylamide, glycidyl methacrylate and the chloro- 2 hydroxyl-propyl methacrylate of 3-
One or more combinations；
A is the natural number between 60~130, and b is the natural number between 10~40, and c is the natural number between 20~80, d 30
Natural number between~70.
3. polymer according to claim 1 or 2, it is characterised in that: polymer shown in Formulas I is following formula I-I, Formulas I-
II, Formulas I-III, Formulas I-IV it is any:
In Formulas I-I, a is the natural number between 100~120, and b is the natural number between 10~30, and c is the nature between 60~80
Number, d are the natural number between 30~50；
In Formulas I-II, a is the natural number between 60~80, and b is the natural number between 10~30, and c is the nature between 30~50
Number, d1+d2For the natural number between 30~50；
In I-III, a is the natural number between 110~130, and b is the natural number between 10~30, and c is the nature between 20~40
Number, d are the natural number between 40~60；
In Formulas I-IV, a is the natural number between 90~110, and b is the natural number between 20~40, and c is the nature between 40~60
Number, d1+d2For the natural number between 50~70.
4. a kind of free-floride waterproof soil-releasing finishing agent, it is characterised in that: the free-floride waterproof soil-releasing finishing agent is claim 1-3
Any one of described in Formulas I shown in polymer water-based emulsion or aqueous solution.
5. the preparation method of free-floride waterproof soil-releasing finishing agent as claimed in claim 4, includes the following steps: long chain acrylate
Or the poly- second two of long chain methacrylate, cage-type silsesquioxane, mono acrylic ester base or monomethacrylates based structures
The pre-emulsion that alcohol monomethyl ether, functional monomer, emulsifier, organic cosolvent and water are formed is under the action of initiator through free radical
Emulsion polymerization obtains the floride-free waterproof soil-releasing finishing agent；
The long chain acrylate or long chain methacrylate are the polymerisable monomers being made of hydrocarbon hydrophobic grouping and double bond,
Hydrocarbon hydrophobic grouping is the straight chain containing 16~22 carbon atoms, and structural formula is shown as a formula V:
In Formula V, R0For hydrogen or methyl, n is the natural number between 15~21；
The structure of the cage-type silsesquioxane is as shown in Formula IV:
In Formula IV, R base is ethyl, isobutyl group or iso-octyl, R0For hydrogen or methyl, n is the natural number between 1~3；
The poly glycol monomethyl ether of the mono acrylic ester base or monomethacrylates based structures is by containing polyethylene glycol knot
The polymerisable monomer that structure hydrophilic radical and double bond are constituted, polyethylene glycol structures hydrophilic radical repetitive unit are the direct-connected knot of 1-20
Structure, structural formula is as shown in Formula VII:
In Formula VII, R0For hydrogen or methyl, n is the natural number between 3~21；
The functional monomer is containing hydroxyl, epoxy group, amide groups, dimethylamino, carboxyl, ester group, alkoxy, sealing end isocyanide
The acrylate or methacrylate monomers of at least one of acidic group and halide end group.
6. preparation method according to claim 5, it is characterised in that: in Formula V, n 15,17 or 21；
In Formula IV, R base is isobutyl group or iso-octyl, R0For hydrogen or methyl, n is 1 or 3；
In Formula VII, n 3,6,12 or 21；
The functional monomer can be hydroxy-ethyl acrylate, N hydroxymethyl acrylamide, glycidyl methacrylate and 3-
One of chloro- 2 hydroxyl-propyl methacrylate or multiple combinations；
The emulsifier is the cationic emulsifier of mass ratio 0.5~2: 1 and the mixture of nonionic emulsifier；
The cationic emulsifier is specially the quaternary emulsifier containing chain alkyl, and the cationic emulsifier is more specific
For at least one in dodecyl trimethyl ammonium chloride, cetyl trimethylammonium bromide and Cetyltrimethylammonium bromide
Kind；
The nonionic emulsifier is specially polyoxyethylene-type emulsifier or polyol type emulsifier；The nonionic emulsifier is more
Specially polyoxyethylene sorbitan monoglyceride, dodecanol polyoxyethylene (10) ether；
The organic cosolvent is at least one of acetone, methyl ethyl ketone, dipropylene glycol and tripropylene glycol；
The initiator is at least one in water-soluble azo class initiator, peroxide initiator and redox type initiator
Kind；The initiator is specially azo-bis-isobutyrate hydrochloride, hydrogen peroxide, potassium peroxydisulfate.
7. preparation method according to claim 5 or 6, it is characterised in that: in the pre-emulsion, the long chain acrylate
Or it is 13~22% that long chain methacrylate, which accounts for the mass percentage of the pre-emulsion,；
The mass percentage that the cage-type silsesquioxane accounts for the pre-emulsion is 2~8%；
The poly glycol monomethyl ether of the mono acrylic ester base or monomethacrylates based structures accounts for the quality of the pre-emulsion
Percentage composition is 7~12%；
The mass percentage that the functional monomer accounts for the pre-emulsion is 1~5%；
The emulsifier, the organic cosolvent, the quality of the initiator and monomer gross mass ratio be 4~8: 24~37:
0.1~0.5: 100；Wherein, the monomer gross mass is the long chain acrylate or long chain methacrylate, the cage modle
The poly glycol monomethyl ether and the functionality of silsesquioxane, the mono acrylic ester base or monomethacrylates based structures
The quality sum of monomer；
Surplus is water.
8. the preparation method according to any one of claim 5-7, it is characterised in that: described method includes following steps:
(1) by the long chain acrylate or long chain methacrylate, the cage-type silsesquioxane, the mono acrylic ester base or
The poly glycol monomethyl ether of monomethacrylates based structures, the functional monomer, the emulsifier, the organic cosolvent
It is sheared with after water mixing, obtains the pre-emulsion；
(2) under nitrogen protection, the pre-emulsion is put into attemperator to and is added dropwise the initiator, through the free radical cream
Liquid polymerization obtains the floride-free waterproof soil-releasing finishing agent.
9. preparation method according to claim 8, it is characterised in that: in step (1), the revolving speed of the shearing is 2000~
8000 revs/min, the time can be 2~10 minutes；
In step (2), the free-radical emulsion polymerization carries out under conditions of revolving speed is 150~300 revs/min；
In step (2), the attemperator is constant control temperature from -100 DEG C of room temperature of equipment, the free-radical emulsion polymerization
Temperature be 60~90 DEG C；Time is 6~10 hours；
The free-radical emulsion polymerization equipment further includes condensation cycle equipment；
The method also includes filtering system after reaction and collect filtrate.
10. polymer shown in Formulas I of any of claims 1-3 or the easy decontamination of floride-free waterproof as claimed in claim 4
Application of the finishing agent in fabric water repellent soil-releasing finiss；
The fabric specifically includes pure cotton, terylene or nylon.
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| CN117304421A (en) * | 2023-09-27 | 2023-12-29 | 浙江联胜新材股份有限公司 | Fluorine-free water repellent and preparation method thereof |
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