CN106637959A - Ultraviolet curing reaction-based fluoride-free and water-repellent finishing method of cotton fabric - Google Patents
Ultraviolet curing reaction-based fluoride-free and water-repellent finishing method of cotton fabric Download PDFInfo
- Publication number
- CN106637959A CN106637959A CN201611166801.0A CN201611166801A CN106637959A CN 106637959 A CN106637959 A CN 106637959A CN 201611166801 A CN201611166801 A CN 201611166801A CN 106637959 A CN106637959 A CN 106637959A
- Authority
- CN
- China
- Prior art keywords
- water
- bafta
- free
- ultraviolet light
- cotton fabric
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/50—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with organometallic compounds; with organic compounds containing boron, silicon, selenium or tellurium atoms
- D06M13/51—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond
- D06M13/513—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond with at least one carbon-silicon bond
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M10/00—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements
- D06M10/04—Physical treatment combined with treatment with chemical compounds or elements
- D06M10/08—Organic compounds
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M10/00—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements
- D06M10/04—Physical treatment combined with treatment with chemical compounds or elements
- D06M10/08—Organic compounds
- D06M10/10—Macromolecular compounds
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/02—Natural fibres, other than mineral fibres
- D06M2101/04—Vegetal fibres
- D06M2101/06—Vegetal fibres cellulosic
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/10—Repellency against liquids
- D06M2200/12—Hydrophobic properties
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
The invention discloses an ultraviolet curing reaction-based fluoride-free and water-repellent finishing method of cotton fabric. The method comprises the steps of putting the cotton fabric into 3-mercaptopropyl triethoxysilane ethyl acetate solution and carrying out mercapto modification to obtain pretreated cotton fabric; dipping the cotton fabric subjected to mercapto modification into vinyl polyhedral oligomeric silsesquioxane solution, and obtaining the fluoride-free and water-repellent cotton fabric, which has a surface with an approximate super-hydrophobic effect, under the ultraviolet curing condition. The reaction is based on the principle of click chemistry, so that a static contact angle is basically remained unchanged after soaping treatment is carried out. Furthermore, according to a test method of AATCC 22-2005 waterproof spray test, the waterproof spray test score of the cotton fabric subjected to water-repellent finishing reaches 95. The ultraviolet curing reaction-based fluoride-free and water-repellent finishing method of the cotton fabric is simple in operation and high in efficiency, obvious in water-repellent effect under the condition that a finishing agent is fluoride-free, and high in finishing washing fastness.
Description
Technical field
The invention belongs to functional finish of cotton fabric field, more particularly to a kind of bafta reacted based on ultraviolet light polymerization without
Fluorine water-repellent finishing method.
Background technology
The purpose of water repellent finish is the wetting for preventing water to fabric, using the additonal pressure of fabric capillary, prevents liquid
The transmission of water, but still maintain the breathable moisture permeability of fabric.WATER REPELLENT FANISH FABRIC is initially used for producing military uniform, protective garment,
It is now widely used for making gym suit, safari suit, traveling bag, tent etc..Perfluor finishing agent is because of its excellent heat endurance, change
Stability, high surface and hydrophobic oleophobic performance are learned, and is widely used in industrial production and personal consumption field.It is conventional at present
Fluorine surfactant be mainly based on perfluoro octyl sulfonic acid (PFOS) or perfluoro caprylic acid (PFOA) raw material.In recent years,
Increasingly deep with correlative study, people gradually recognize refractory organicses, environmental persistence and the biological accumulation of PFOA/PFOS
Property, therefore, its substitute is found, substitute technology becomes the study hotspot of relevant industries.
At present long chain fluorine-containing water and oil repellent finish alternative orientation substantially it is following some：
One is exploitation short-chain perfluoroaldyl fluorocarbons, and such finishing agent is in contrast without obvious persistence biological accumulation
Property, the short time excludes in vitro with human metabolism, and its degradation product is nontoxic.But shortcoming is such product with waterproof and goes
Based on greasy dirt function, PFOS oil-repellent finiss levels are not reached.
Two is fluorine-containing and other surfactants compound synergics.There are some researches show, as long as in hc-surfactant
Minimal amount of fluorine-containing surfactant is added, its ability for reducing water surface tension is just greatly improved, and can be substantially reduced
Oil/water circle and tension force.The special performance of fluorine-containing surfactant can be played, by fluorine-containing surfactant and hydrocarbon surface-active
Agent is compounded, it is possible to greatly reduce the consumption of fluorine-containing surfactant, reduces into wood, most importantly reduces the pollution of PFOS.
Three is exploitation oil-refusing finishing agent containing silicofluoride.There are some researches show, methyl silicone and perfluorinated octyl sulfuryl amine propylene
Critical surface tension of the acid esters on film is respectively 27mN/m and 5mN/m；On cotton be respectively 38～45mN/m and 24～
25mN/m.Proper alignment as water-refusing oil-refusing finishing agent on fiber is methyl hydrogen silicone or dimethyl silscone-CH3, fluorine
For-the CF of acrylate3With-CF2All in fiber surface outer layer, it is better that waterproof refuses oily effect.Fluorine silicon finishing agent is provided simultaneously with
The advantage of fluorine-containing and siliceous finishing agent, but have the disadvantage that building-up process is relative complex, it is relatively costly.
Four is that nanometer technology is applied into water and oil repellent finish.After nano material is arranged, fabric face forms such as lotus
The rough surface of leaf, reaches the effect that waterproof refuses oil.Although the miniaturization of nanometer finishing agent particle size makes fabric have surface
Effect, small-size effect and macro quanta tunnel effect, will be a kind of preferable fabric finishing agents, but in application process,
Nano material finishing agent is susceptible to reunite, and so as to lose nano-meter characteristic, and there is a problem of arranging poor durability.
Compared to fluorine-containing water repellent, silicone fabric waterproofing agent, relative low price, the fabric of arrangement has durability
Waterproof effect, is particularly well-suited to synthetic fibers and its blend fabric, anti-particularly on filament yarn fabric in synthetic fabrics
Water effect, resistance to water and dry-cleaning property are very good, but on cotton fiber and viscose fiber fabric, washability is just more slightly worse, and this may
It is that cellulose fibre is swelling in water, caused by rupturing the organosilicon membrane of imparting fabric waterproof.Waterproofing agent of organosilicon is general
It is made up of two kinds of components, i.e., hydrogen-containing siloxane polymer (being commonly called as containing hydrogen silicone oil), dimethyl silicone polymer (are commonly called as dimethyl-silicon
Oil) or polydimethylhydroxysiloxane (being commonly called as dihydroxy silicone oil).Individually make waterproofing agent with dimethyl silicone polymer, it is necessary to
First being heated a few hours can just align into waterproofing membrane.But, the chemism of containing hydrogen silicone oil is higher, must be at 150 DEG C
Under conditions of, could process and aggregate into waterproofing membrane, and the fabric feeling after processing is not good enough.
Composite organic-inorganic material combines organic material and the respective advantage of inorganic material, with significant superiority
Can, become the focus of research.In recent years, caged silsesquioxane (POSS) is this has regular stereochemical structure to have simultaneously singly to receive
The organic-inorganic hybrid molecule of metrical scale makes it have good Research Significance.The chemical structural formula of POSS is (RSiO3/2) n, n
=6～12, R are organic group, and wherein one or more are reactive functional groups.What is carried after POSS functionalization is different organic
Group determines POSS hybrid forms different in the polymer.For example, the POSS of single reaction functional group by copolymerization or
Reactively blending is grafted on main polymer chain, and the POSS of two functional groups can be embedded into high polymer main chain, with three
The POSS of above reactive functional groups can serve as the polymer that crosslinking agent introduces build.The introducing of POSS often makes polymer
One or more performance is improved, such as thermodynamic property, crystal property, and the improvement in this performance depends on POSS poly-
Accumulation shape in compound matrix.Additionally, there are some researches show, when POSS is chemically bonded on polymer, POSS-POSS,
Interaction between POSS- polymer except producing heat endurance and the enhanced POSS modified polies beyond the region of objective existence of molecular level, most
Prominent is that POSS based polyalcohols can form the nanoscale features being made up of Major particle, the micron order being made up of aggregation spy
The level form levied, and the multiple dimensioned roughness in surface and produce super hydrophobic surface.
Therefore, as attempted by water repellent finishing agent in combination with POSS, to prepare the finishing agent of more premium properties, at present, this
The research of aspect has been reported.For example, there are some researches show, ultraviolet hardening POSS fluorinated block copolymers have relatively low
Surface energy and limited surface mobility, can occur Partial Reconstruction on surface, coating present higher water contact angle (113～
116.5 °), higher receding contact angle (100～113 °), the low angle of lag (8～11 °) of contact and relatively low surface energy (11.1
～11.6 millijoules/square metre).Additionally, in coating scratch resistance and water repellent research, by 8F-POSS (octafluoro alkyl POSS) and
8M-POSS (prestox acryloxy POSS) mixes under the conditions of ultraviolet light polymerization and arranges in coating surface, increased its table
While surface roughness, compare 8M-POSS and individually apply, both act synergistically and cause water repellent effect raising 60%, mar-proof hard
Degree increases by 400%.
Studies have found that, 80 DEG C of heating stirrings 2 under AIBN catalyst actions by vinyl POSS and 17 fluorine decyl mercaptans
My god, generate fluoroPOSS-PMMA (fluorination POSS- polymethyl methacrylates) the surface static contact angle that product process is formed
Lifted to 114 ° to 124 ° from original 71 °.But the method reaction time is long, and effect is general.
Disclose UV curing method additionally, having been reported that, will vinyl POSS and perfluoro decyl mercaptan in dichloromethane
Irradiation generates F-POSS under uviol lamp in alkane solvents, and bafta is sufficiently impregnated with the F-POSS ethanol solutions of synthesis.Arrange
To cotton fabric waterproofing effect static contact angle and roll angle it is reachable～153 ° and～6 °.But the method has the disadvantage finishing agent fastness
Difference, it is not water-fastness, and fluorine-containing mercaptan is expensive.
The content of the invention
The technical problem to be solved is to provide a kind of bafta free-floride water repellent reacted based on ultraviolet light polymerization
Method for sorting, by POSS in combination with floride-free water repellent finish is by click chemistry, both fusions excellent specific properties, so as to refuse in enhancing
Water effect, reduces finishing time, while raising efficiency, improves washing fastness, improves cotton fabric waterproofing performance durability degree.
In order to solve the above problems, the invention provides a kind of bafta free-floride water repellent based on ultraviolet light polymerization reaction is whole
Reason method, comprises the following steps：
Step 1)：Bafta is roughened first, is subsequently placed in the 3- mercaptopropyltriethoxysilanes of 1～5wt%
(KH-580) sulfhydryl modified, concussion, fully cleaning are carried out in ethyl acetate solution, vacuum drying obtains pre-treatment bafta；
Step 2)：Prepare containing ethenyl cage model sesquialter siloxane (vinyl-POSS), hydrosulphonyl silane or alkyl hydrosulfide
Organic solvent solution, sulfhydryl modified bafta is impregnated wherein, is processed based on click chemistry principle under the conditions of ultraviolet light polymerization
There is the floride-free water repellent bafta Jie Jin super-hydrophobic effect to surface.
Preferably, the bafta is pure continuous yarn fabric or cotton fiber blended fabric.
Preferably, the step 1) described in roughening be specially：With the NaOH of 10～20g/L and putting down for 5～10g/L
Flat plus O, is roughened at a temperature of 60～80 DEG C.
Preferably, the step 1) in sulfhydryl modified temperature be 15～35 DEG C, the time is 2～3h.
Preferably, the step 1) in 3- mercaptopropyltriethoxysilanes ethyl acetate solution in also have including other
The silane coupler of one or more mercapto groups.
Preferably, the step 2) in organic solvent be dichloromethane and ethyl acetate at least one.
Preferably, the step 2) in hydrosulphonyl silane be the silane structure compound with one or more mercapto groups
Or mixture；Alkyl hydrosulfide is long-chain fat race alkane compound or mixture with one or more mercapto groups.
Preferably, ultraviolet light polymerization condition is specially in the step 2：Using light trigger, the light trigger includes
At least one in 2,2- dimethoxy -2- phenyl acetophenones and 2,2- dihydromethyl propionic acid.Ultraviolet light polymerization reaction principle base
In sulfydryl-ethylenic click chemistry principle, ethenyl cage model sesquialter siloxane, the step single bath process of hydrosulphonyl silane (or alkyl hydrosulfide)
It is bonded directly to sulfhydryl modified cotton-textile fibres.
Bafta and 3- mercaptopropyltriethoxysilanes are carried out condensation reaction by the present invention first, obtain Modification of Cotton Fabric
Sulfydryl (- SH).3- mercaptopropyltriethoxysilanes belong to silane coupler, are by silicochloroform (HSiCl3) and with reactive base
Group unsaturated olefin platinum propylhomoserin catalysis under addition, then Jing alcoholysis and obtain.Silane coupler be substantially a class have it is organic
The silane of functional group, having simultaneously in the molecule thereof can be with inorganic material (such as glass, silica sand, metal) chemically combined reaction
Group and with organic material (synthetic resin etc.) chemically combined reactive group.The ethyoxyl of its one end can be utilized by condensation
The hydroxyl reaction of reaction and fiber surface makes fiber be modified so as to form grafting, becomes the fiber with sulfydryl.Secondly,
Cotton fiber containing sulfhydryl reactive group and the same silane with sulfydryl or alkyl hydrosulfide under the conditions of ultraviolet light polymerization with second
Thiazolinyl POSS carries out click chemistry reaction, so as to form firm chemical bond.Methyl on silicon oxygen bond (or the length of alkyl hydrosulfide
Alkyl group) itself rotate counterclockwise, the outside sweep of the hydrogen atom in alkyl is made, it is as umbrella that silica chain is completely obscured
In the surfaces of revolution of alkyl, and POSS based polyalcohols can be formed be made up of Major particle nanoscale features, by aggregation
The level form of the micrometer-class of composition, and the multiple dimensioned roughness in surface and produce hydrophobic surface, both make synergy
Obtain bafta and possess significant water repellency.Furthermore because defining stable chemical bond with fiber, water repellency is persistently, water-fast
Wash excellent performance.
The present invention is first modified process to bafta using 3- mercaptopropyltriethoxysilanes, is had cotton fiber
The sulfydryl of greater activity；Then reacted by click chemistry, make hydrosulphonyl silane (or alkyl hydrosulfide) and the second with ethylene linkage structure
Thiazolinyl POSS, with the bafta through modification ultraviolet light polymerization reaction is carried out, and is attached to both by chemical bonding
On cotton fiber molecule, product after treatment has waterproofing function.Simple to operate, efficiency high of the invention, it is floride-free in finishing agent
Under the conditions of, substantially, washing fastness is high, improves cotton fabric waterproofing performance durability degree for water repellent effect.
Description of the drawings
Fig. 1 is the modified cotton fiber reaction mechanism schematic diagram of 3- mercaptopropyltriethoxysilanes；
Fig. 2 is sulfhydryl modified cotton fiber, hydrosulphonyl silane (or alkyl hydrosulfide) and vinyl POSS ultraviolet light polymerization clickizations
Reaction schematic diagram is learned, wherein R-SH is hydrosulphonyl silane or alkyl hydrosulfide；
Fig. 3 is embodiment 1-3 water repellent bafta static contact angle side view, and a is the static contact angle of embodiment 1
(149.2 °), b is the static contact angle of embodiment 2 (146.3 °), and c is the static contact angle of embodiment 3 (132.8 °), and d is embodiment 1
Soap process after static contact angle (147.3 °)；
Fig. 4 is standard water drenching experiment effect figure；
Fig. 5 a are the ESEM side view on raw cotton fiber surface；
Fig. 5 b are the ESEM side view on cotton fiber surface after the arrangement of embodiment 1；
Fig. 5 c are the ESEM side view on cotton fiber surface after the arrangement of embodiment 2.
Specific embodiment
To become apparent the present invention, hereby with preferred embodiment, and accompanying drawing is coordinated to be described in detail below.
The use of grammes per square metre is 90g/m in embodiment 1-32Plain weave bafta, polyester cotton grammes per square metre be 130g/m2, mix
Spin than being 35/65 for T/C.Vinyl POSS is purchased from MACKLIN companies, and lauryl mercaptan is purchased from Sigma-Aldrich companies, 3- mercaptos
Propyl-triethoxysilicane, 2,2- dimethoxy -2- phenyl acetophenones are purchased from Adamas companies, and other reagents are analyses
It is pure, in use without the need for further purifying.
Embodiment 1
Process is modified to bafta using 3- mercaptopropyltriethoxysilanes, and with vinyl POSS, hydrosulphonyl silane
Reaction, makes cotton have good water repellency, and it is concretely comprised the following steps：
(1) pretreatment stage：
1. 15g/L NaOH and 7g/L paregal O solution are prepared, 70 DEG C of temperature carry out roughening 20min to bafta；
2. 5wt%3- mercaptopropyltriethoxysilane ethyl acetate solutions are prepared, by the bafta input solution after roughening
In, beaker mouth diaphragm seal, in being placed in temperature constant magnetic stirring water-bath, 25 DEG C of concussions are processed 2 hours；
3. bafta is taken out, is fully cleaned in distilled water, 60 DEG C of vacuum dryings；
(2) the Final finishing stage：
1. the vinyl POSS and 3- mercaptopropyltriethoxysilane dichloromethane solution for preparing mass concentration respectively for 1%,
Fully ultrasonic vibration, is subsequently added 2,2- dimethoxy -2- phenyl acetophenone light triggers, ultrasonic vibration；
2. it is laid on bafta is smooth in culture dish, topples over the above-mentioned dressing liquid of certain volume, bafta is crossed in slightly submergence
Surface, covers one layer of quartz plate at culture dish mouth；
3. bafta is placed in into power under 500W ultraviolet light cold light sources, lamp away from 13cm, illumination 30min, turn-over, light again
According to 30min；n；
4. bafta is taken out, deionized water is fully washed, 60 DEG C of drying.
Embodiment 2
Process is modified to bafta using 3- mercaptopropyltriethoxysilanes, and with vinyl POSS, alkyl hydrosulfide
Reaction, makes cotton have good water repellency, and it is concretely comprised the following steps：
(1) pretreatment stage：
1. 15g/L NaOH and 7g/L paregal O solution are prepared, 70 DEG C of temperature carry out roughening 20min to bafta；
2. 5wt%3- mercaptopropyltriethoxysilane ethyl acetate solutions are prepared, by the bafta input solution after roughening
In, beaker mouth diaphragm seal, in being placed in temperature constant magnetic stirring water-bath, 25 DEG C of concussions are processed 2 hours；
3. bafta is taken out, is fully cleaned in distilled water, 60 DEG C of vacuum dryings；
(2) the Final finishing stage：
1. it is respectively 1% vinyl POSS and the dichloromethane solution of lauryl mercaptan to prepare mass concentration, and fully ultrasound is shaken
Swing, be subsequently added 2,2- dimethoxy -2- phenyl acetophenone light triggers, ultrasonic vibration；
2. it is laid on bafta is smooth in culture dish, topples over the above-mentioned dressing liquid of certain volume, bafta is crossed in slightly submergence
Surface, covers one layer of quartz plate at culture dish mouth；
3. bafta is placed in into power under 500W ultraviolet light cold light sources, lamp away from 13cm, illumination 30min, turn-over, light again
According to 30min；
4. bafta is taken out, deionized water is fully washed, 60 DEG C of drying.
Embodiment 3
Process is modified to polyester-cotton fabric (65/35) using 3- mercaptopropyltriethoxysilanes, and with vinyl POSS,
Alkyl hydrosulfide reacts, and makes polyester-cotton blend have good water repellency, and it is concretely comprised the following steps：
(1) pretreatment stage：
1. 15g/L NaOH and 7g/L paregal O solution are prepared, 70 DEG C of temperature carry out roughening 20min to polyester-cotton fabric；
2. 5wt%3- mercaptopropyltriethoxysilane ethyl acetate solutions are prepared, the polyester-cotton fabric input after roughening is molten
In liquid, beaker mouth diaphragm seal, in being placed in temperature constant magnetic stirring water-bath, 25 DEG C of concussions are processed 2 hours；
3. polyester-cotton fabric is taken out, is fully cleaned in distilled water, 60 DEG C of vacuum dryings；
(2) the Final finishing stage：
1. it is respectively 1% vinyl POSS and the dichloromethane solution of lauryl mercaptan to prepare mass concentration, and fully ultrasound is shaken
Swing, be subsequently added 2,2- dimethoxy -2- phenyl acetophenone light triggers, ultrasonic vibration；
2. it is laid on polyester-cotton fabric is smooth in culture dish, topples over the above-mentioned dressing liquid of certain volume, polyester-cotton blend is crossed in slightly submergence
Fabric face, covers one layer of quartz plate at culture dish mouth；
3. polyester-cotton fabric is placed in into power under 500W ultraviolet light cold light sources, lamp away from 13cm, illumination 30min, turn-over, again
Illumination 30min；
4. polyester-cotton fabric is taken out, deionized water is fully washed, 60 DEG C of drying.
Bafta and 3- mercaptopropyltriethoxysilanes are carried out condensation reaction by the present invention first, obtain Modification of Cotton Fabric
Sulfydryl (- SH).3- mercaptopropyltriethoxysilanes belong to silane coupler, are by silicochloroform (HSiCl3) and with reactive base
Group unsaturated olefin platinum propylhomoserin catalysis under addition, then Jing alcoholysis and obtain.Silane coupler be substantially a class have it is organic
The silane of functional group, having simultaneously in the molecule thereof can be with inorganic material (such as glass, silica sand, metal) chemically combined reaction
Group and with organic material (synthetic resin etc.) chemically combined reactive group.The ethyoxyl of its one end can be utilized by condensation
The hydroxyl reaction of reaction and fiber surface makes fiber be modified so as to form grafting, becomes fiber (the reaction machine with sulfydryl
Reason is as shown in Figure 1).Secondly, the cotton fiber containing sulfhydryl reactive group and the same silane with sulfydryl or alkyl hydrosulfide are in purple
Click chemistry reaction is carried out with vinyl POSS under outer photo curing condition, so as to form firm chemical bond (reaction mechanism such as Fig. 2
It is shown).
Bafta is carried out after water repellent finish, by showing to its static contact angle test result such as Fig. 3：Fiber surface
Through being grafted the contact angle of embodiment 1 of hydrosulphonyl silane up to 149.2 °, the contact angle of grafting alkyl hydrosulfide embodiment 2 is 146.3 °,
Contact angle compares pure cotton fabric after the process of polyester-cotton fabric alkyl hydrosulfide slightly reduces, and is 132.84 °.Knowable to analysis result, for
The method for sorting of the present invention, silane structure compares Long carbon chain alkane structure, and contact angle slightly increases, and water repellent effect more preferably, connects
Nearly super-hydrophobic effect.Polyester cotton compares pure cotton fabric, and water repellent effect has weakened, and reason may be compared for polyester fiber
In pure cotton fabric and follow-up ultraviolet light polymerization stage can reactive group quantity it is relatively fewer, it is total and cause finishing agent treatment effect to become
It is weak.
After through 3 times at 70 DEG C, fully circulation is soaped, the water repellent fabric static contact angle of embodiment 1 remains 147.3 °.Knot
Fruit shows that the water repellent bafta that method for sorting of the present invention is obtained has excellent washing fastness.It is hereby understood that finishing agent and cotton
Fiber is compared common method for sorting durability and is greatly increased by firm chemical bonds.
According to《AATCC 22--2005 waterproof spray tests》Method of testing bafta after the water repellent finish of embodiment 2 is entered
Row test, as shown in figure 4, reference standard figure, with reference to standards of grading, because the fabric face after spray speckles with the globule, but without profit
Wet situation, evaluation fraction should be 95 points.
By bafta as former state, embodiment 1, the bafta after arranging in embodiment 2 is scanned electron microscopic observation, Fig. 5 a Central Plains
Cotton fiber surface is in natural distorted shape, and the surface of cotton fabric (such as Fig. 5 b, Fig. 5 c) after processing covers one layer of hackly thing
Matter, the groove of natural distortion is covered, and hydrophilic radical is covered under coarse hydrophobic layer on cotton fiber.And by with micro-nano
The POSS of size is even more with hackly structure that reactant is cross-linked to form and increases hydrophobic effect.
Claims (8)
1. it is a kind of based on ultraviolet light polymerization react bafta free-floride water-repellent finishing method, it is characterised in that comprise the following steps：
Step 1)：Bafta is roughened first, is subsequently placed in the acetic acid of the 3- mercaptopropyltriethoxysilanes of 1～5wt%
Sulfhydryl modified, concussion, fully cleaning are carried out in ethyl ester solution, vacuum drying obtains pre-treatment bafta；
Step 2)：The organic solvent solution containing ethenyl cage model sesquialter siloxane, hydrosulphonyl silane or alkyl hydrosulfide is prepared, by mercapto
Base modified cotton fabric impregnates wherein, is processed based on click chemistry principle under the conditions of ultraviolet light polymerization and obtains surface with close super thin
The floride-free water repellent bafta of water effect.
It is 2. as claimed in claim 1 to be based on the bafta free-floride water-repellent finishing method that ultraviolet light polymerization reacts, it is characterised in that
The bafta is pure continuous yarn fabric or cotton fiber blended fabric.
It is 3. as claimed in claim 1 to be based on the bafta free-floride water-repellent finishing method that ultraviolet light polymerization reacts, it is characterised in that
The step 1) described in roughening be specially：With the NaOH and the paregal O of 5～10g/L of 10～20g/L, 60～80
It is roughened at a temperature of DEG C.
It is 4. as claimed in claim 1 to be based on the bafta free-floride water-repellent finishing method that ultraviolet light polymerization reacts, it is characterised in that
The step 1) in sulfhydryl modified temperature be 15～35 DEG C, the time is 2～3h.
It is 5. as claimed in claim 1 to be based on the bafta free-floride water-repellent finishing method that ultraviolet light polymerization reacts, it is characterised in that
The step 1) in 3- mercaptopropyltriethoxysilanes ethyl acetate solution in also include other have one or more sulfydryls
The silane coupler of group.
It is 6. as claimed in claim 1 to be based on the bafta free-floride water-repellent finishing method that ultraviolet light polymerization reacts, it is characterised in that
The step 2) in organic solvent be dichloromethane and ethyl acetate at least one.
It is 7. as claimed in claim 1 to be based on the bafta free-floride water-repellent finishing method that ultraviolet light polymerization reacts, it is characterised in that
The step 2) in hydrosulphonyl silane be silane structure compound or mixture with one or more mercapto groups；Alkyl sulfide
Alcohol is long-chain fat race alkane compound or mixture with one or more mercapto groups.
It is 8. as claimed in claim 1 to be based on the bafta free-floride water-repellent finishing method that ultraviolet light polymerization reacts, it is characterised in that
Ultraviolet light polymerization condition is specially in the step 2：Using light trigger, the light trigger includes 2,2- dimethoxy -2-
At least one in phenyl acetophenone and 2,2- dihydromethyl propionic acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611166801.0A CN106637959A (en) | 2016-12-16 | 2016-12-16 | Ultraviolet curing reaction-based fluoride-free and water-repellent finishing method of cotton fabric |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611166801.0A CN106637959A (en) | 2016-12-16 | 2016-12-16 | Ultraviolet curing reaction-based fluoride-free and water-repellent finishing method of cotton fabric |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106637959A true CN106637959A (en) | 2017-05-10 |
Family
ID=58822819
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611166801.0A Pending CN106637959A (en) | 2016-12-16 | 2016-12-16 | Ultraviolet curing reaction-based fluoride-free and water-repellent finishing method of cotton fabric |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106637959A (en) |
Cited By (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107869051A (en) * | 2017-11-30 | 2018-04-03 | 东华大学 | A kind of moisture absorbable and breathable finishing method of the dacron based on click chemistry |
| CN107974836A (en) * | 2017-11-14 | 2018-05-01 | 江苏新瑞贝科技股份有限公司 | A kind of dacron free-floride water-proof finish method |
| CN108611865A (en) * | 2018-04-27 | 2018-10-02 | 江南大学 | A kind of high fastness azobenzene polyurethane hydrophobic textile product processing method and its textile |
| CN109736080A (en) * | 2019-01-04 | 2019-05-10 | 广州中科检测技术服务有限公司 | A kind of superhydrophobic fabric and the preparation method and application thereof |
| CN109914108A (en) * | 2019-03-14 | 2019-06-21 | 东华大学 | A kind of dacron free-floride water-repellent finishing method |
| CN110205821A (en) * | 2019-06-20 | 2019-09-06 | 广州百思创科技有限公司 | A kind of green free-floride water-proof aagent and its application in fibre |
| CN110552203A (en) * | 2019-08-08 | 2019-12-10 | 沈阳工业大学 | Preparation method of super-hydrophobic cotton fabric |
| CN110735325A (en) * | 2019-10-28 | 2020-01-31 | 科凯精细化工（上海）有限公司 | modified epoxy group POSS fluorine-free waterproof finishing agent and preparation method thereof |
| CN110747639A (en) * | 2019-09-09 | 2020-02-04 | 东华大学 | Preparation method of photocatalyst-loaded fabric based on covalent bond combination |
| CN110983785A (en) * | 2019-11-26 | 2020-04-10 | 广东省测试分析研究所（中国广州分析测试中心） | Preparation method of Janus type textile |
| CN111019519A (en) * | 2018-10-09 | 2020-04-17 | 上海产业技术研究院 | Crosslinkable composition, preparation method and application thereof |
| CN111188183A (en) * | 2020-02-17 | 2020-05-22 | 南通纺织丝绸产业技术研究院 | Method for preparing super-hydrophobic cotton textile by utilizing thiol-ene click chemical modification |
| CN111705509A (en) * | 2020-07-08 | 2020-09-25 | 南京轮廓服饰科技有限公司 | Graphene-based lasting antibacterial composite garment fabric |
| CN112080938A (en) * | 2020-09-08 | 2020-12-15 | 华东师范大学 | Fluorine-free durable super-hydrophobic cotton cloth and preparation method and application thereof |
| WO2021103181A1 (en) * | 2019-11-26 | 2021-06-03 | 广东省测试分析研究所（中国广州分析测试中心） | Electrically-conductive humidity-sensitive textile having a janus structure and humidity responsiveness |
| CN113152104A (en) * | 2021-06-09 | 2021-07-23 | 苏州大学 | Short-flow fluorine-free super-hydrophobic coating based on mercapto-alkene click reaction and preparation method and application thereof |
| CN113861495A (en) * | 2021-09-24 | 2021-12-31 | 东华大学 | In-situ grafted PDMS high-elastic super-hydrophobic hybrid aerogel and preparation method thereof |
| CN114232345A (en) * | 2021-12-20 | 2022-03-25 | 河南蓝翎环科防水材料有限公司 | Ultraviolet radiation resistant waterproof protective material and production process thereof |
| CN115652637A (en) * | 2022-10-25 | 2023-01-31 | 苏州大学 | Fluorine-free oil-repellent coating fabric and preparation method thereof |
| CN116289228A (en) * | 2023-03-16 | 2023-06-23 | 山东大学 | Alkoxy-functionalized double-splint type POSS super-hydrophobic coating, and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105418969A (en) * | 2015-12-04 | 2016-03-23 | 南昌航空大学 | Click chemistry based preparation method of carbon nanotube grafted carbon fiber reinforcement |
| CN105696306A (en) * | 2015-11-11 | 2016-06-22 | 陕西科技大学 | Method for preparing super-hydrophobic textile from thiol-ene click chemistry-modified fiber |
| CN105821654A (en) * | 2016-05-05 | 2016-08-03 | 东华大学 | Durable cotton fabric antifungal finishing method based on click chemistry |
-
2016
- 2016-12-16 CN CN201611166801.0A patent/CN106637959A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105696306A (en) * | 2015-11-11 | 2016-06-22 | 陕西科技大学 | Method for preparing super-hydrophobic textile from thiol-ene click chemistry-modified fiber |
| CN105418969A (en) * | 2015-12-04 | 2016-03-23 | 南昌航空大学 | Click chemistry based preparation method of carbon nanotube grafted carbon fiber reinforcement |
| CN105821654A (en) * | 2016-05-05 | 2016-08-03 | 东华大学 | Durable cotton fabric antifungal finishing method based on click chemistry |
Non-Patent Citations (1)
| Title |
|---|
| DI SUN ET AL: "Preparation of fluorine-free water repellent finishing via thiol-ene click reaction on cotton fabrics", 《MATERIAL LETTERS》 * |
Cited By (27)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107974836A (en) * | 2017-11-14 | 2018-05-01 | 江苏新瑞贝科技股份有限公司 | A kind of dacron free-floride water-proof finish method |
| CN107869051A (en) * | 2017-11-30 | 2018-04-03 | 东华大学 | A kind of moisture absorbable and breathable finishing method of the dacron based on click chemistry |
| CN108611865A (en) * | 2018-04-27 | 2018-10-02 | 江南大学 | A kind of high fastness azobenzene polyurethane hydrophobic textile product processing method and its textile |
| CN111019519A (en) * | 2018-10-09 | 2020-04-17 | 上海产业技术研究院 | Crosslinkable composition, preparation method and application thereof |
| CN109736080A (en) * | 2019-01-04 | 2019-05-10 | 广州中科检测技术服务有限公司 | A kind of superhydrophobic fabric and the preparation method and application thereof |
| CN109736080B (en) * | 2019-01-04 | 2021-09-24 | 中科检测技术服务(广州)股份有限公司 | Super-hydrophobic fabric and preparation method and application thereof |
| CN109914108A (en) * | 2019-03-14 | 2019-06-21 | 东华大学 | A kind of dacron free-floride water-repellent finishing method |
| CN110205821B (en) * | 2019-06-20 | 2021-12-14 | 广州百思创科技有限公司 | Green fluorine-free waterproof finishing agent and application thereof in fiber products |
| CN110205821A (en) * | 2019-06-20 | 2019-09-06 | 广州百思创科技有限公司 | A kind of green free-floride water-proof aagent and its application in fibre |
| CN110552203B (en) * | 2019-08-08 | 2021-12-21 | 沈阳工业大学 | Preparation method of super-hydrophobic cotton fabric |
| CN110552203A (en) * | 2019-08-08 | 2019-12-10 | 沈阳工业大学 | Preparation method of super-hydrophobic cotton fabric |
| CN110747639A (en) * | 2019-09-09 | 2020-02-04 | 东华大学 | Preparation method of photocatalyst-loaded fabric based on covalent bond combination |
| CN110747639B (en) * | 2019-09-09 | 2021-08-31 | 东华大学 | Preparation method of photocatalyst-loaded fabric based on covalent bond combination |
| CN110735325B (en) * | 2019-10-28 | 2021-11-16 | 科凯精细化工（上海）有限公司 | Modified epoxy group POSS fluorine-free waterproof finishing agent and preparation method thereof |
| CN110735325A (en) * | 2019-10-28 | 2020-01-31 | 科凯精细化工（上海）有限公司 | modified epoxy group POSS fluorine-free waterproof finishing agent and preparation method thereof |
| CN110983785B (en) * | 2019-11-26 | 2022-08-09 | 广东省测试分析研究所（中国广州分析测试中心） | Preparation method of Janus type textile |
| CN110983785A (en) * | 2019-11-26 | 2020-04-10 | 广东省测试分析研究所（中国广州分析测试中心） | Preparation method of Janus type textile |
| WO2021103181A1 (en) * | 2019-11-26 | 2021-06-03 | 广东省测试分析研究所（中国广州分析测试中心） | Electrically-conductive humidity-sensitive textile having a janus structure and humidity responsiveness |
| CN111188183A (en) * | 2020-02-17 | 2020-05-22 | 南通纺织丝绸产业技术研究院 | Method for preparing super-hydrophobic cotton textile by utilizing thiol-ene click chemical modification |
| CN111705509A (en) * | 2020-07-08 | 2020-09-25 | 南京轮廓服饰科技有限公司 | Graphene-based lasting antibacterial composite garment fabric |
| CN112080938A (en) * | 2020-09-08 | 2020-12-15 | 华东师范大学 | Fluorine-free durable super-hydrophobic cotton cloth and preparation method and application thereof |
| CN113152104A (en) * | 2021-06-09 | 2021-07-23 | 苏州大学 | Short-flow fluorine-free super-hydrophobic coating based on mercapto-alkene click reaction and preparation method and application thereof |
| CN113861495A (en) * | 2021-09-24 | 2021-12-31 | 东华大学 | In-situ grafted PDMS high-elastic super-hydrophobic hybrid aerogel and preparation method thereof |
| CN114232345A (en) * | 2021-12-20 | 2022-03-25 | 河南蓝翎环科防水材料有限公司 | Ultraviolet radiation resistant waterproof protective material and production process thereof |
| CN115652637A (en) * | 2022-10-25 | 2023-01-31 | 苏州大学 | Fluorine-free oil-repellent coating fabric and preparation method thereof |
| CN115652637B (en) * | 2022-10-25 | 2024-02-02 | 苏州大学 | Fluorine-free oil-repellent coated fabric and preparation method thereof |
| CN116289228A (en) * | 2023-03-16 | 2023-06-23 | 山东大学 | Alkoxy-functionalized double-splint type POSS super-hydrophobic coating, and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106637959A (en) | Ultraviolet curing reaction-based fluoride-free and water-repellent finishing method of cotton fabric | |
| CN106592222A (en) | Fluoride-free water-repellent textile fabric finishing method based on ultraviolet light curing reaction | |
| CN105778153B (en) | A kind of preparation method of cage type polysilsesquioxane grafting carbon fiber reinforcement | |
| JP5786831B2 (en) | Coating composition and laminate | |
| CN102978954B (en) | Method for preparing good-stability super-hydrophobic fabrics | |
| CN112029032B (en) | Preparation method of durable fabric waterproof finishing agent and product thereof | |
| Hao et al. | Preparation of crosslinked polysiloxane/SiO2 nanocomposite via in-situ condensation and its surface modification on cotton fabrics | |
| CN104262639B (en) | The preparation method of super-hydrophobic cross linking polysiloxane-polysilsesquioxane nanosphere hybrid material | |
| CN111593570B (en) | Waterproof cloth cover flexible composite material and preparation method thereof | |
| CN103665386B (en) | A kind of fluorine silicon resin, preparation method and application thereof | |
| CN112962311B (en) | POSS (polyhedral oligomeric silsesquioxane) -based sulfhydryl-alkene click chemistry method for preparing super-hydrophobic textile | |
| CN107974836A (en) | A kind of dacron free-floride water-proof finish method | |
| CN109137468A (en) | A kind of cotton fabric fluorinated acrylate polymer water-repellent finishing method | |
| CN114058199B (en) | UV-cured super-hydrophilic anti-fog coating and preparation method and application thereof | |
| CN107059406A (en) | The preparation method of super-hydrophobic terylene | |
| CN109295715A (en) | A kind of water repellent cotton fabric and preparation method thereof | |
| Wang et al. | Color fastness enhancement of dyed wood by Si-sol@ PDMS based superhydrophobic coating | |
| Jiang et al. | Synthesis of superhydrophobic fluoro-containing silica sol coatings for cotton textile by one-step sol–gel process | |
| Altangerel et al. | Superhydrophobic modification and characterization of cashmere fiber surfaces by wet coating techniques of silica nanoparticles | |
| CN111910439B (en) | Inorganic nano SiO 2 Hybrid organosilicon fluorine-free waterproof agent and preparation method thereof | |
| CN103601891A (en) | Cross-linkable fluorosilicon resin as well as preparation method and application thereof in super-amphiphobic material | |
| CN112194638B (en) | Aniline anhydride, preparation method thereof and polyamino acid graft chain | |
| Liu et al. | Durable moisture-wicking and fast-dry polyester fabric prepared by UV-induced click reaction | |
| Jiang et al. | Water repellent treatment of cotton fabrics by electron beam irradiation | |
| CN100338297C (en) | Finishing liquid, it preparation process and application for anti-lousiness and pilling resisting treatment of wool fibric thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20170510 |