CN105155262B - A kind of preparation method of the grease proofing pure-cotton fabric of high-hygroscopicity - Google Patents
A kind of preparation method of the grease proofing pure-cotton fabric of high-hygroscopicity Download PDFInfo
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- CN105155262B CN105155262B CN201510608631.6A CN201510608631A CN105155262B CN 105155262 B CN105155262 B CN 105155262B CN 201510608631 A CN201510608631 A CN 201510608631A CN 105155262 B CN105155262 B CN 105155262B
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Abstract
The invention discloses a kind of preparation method of the grease proofing pure-cotton fabric of high-hygroscopicity, the Oilproof fabric includes precoat and anti-oil reservoir, and precoat is all cotton fibers, and anti-oil reservoir is sprayed on precoat；The preparation method of high-hygroscopicity Oilproof fabric includes arrangement step, ultraviolet initiation coating reaction process, grafting copolyreaction process, the postprocessing working procedures of oil-repellent liquid.The purified cotton cloth that the present invention is modified not only has oil preventing performance, and compensate for the consumption of hydroxyl in cellulose, so as to keep the hygroscopicity of fabric.
Description
Technical field
The invention belongs to field of textile, and in particular to a kind of to have grease proofing, high hygroscopic property cotton complex function
Fabric.
Background technology
In recent decades, the need for according to the development trend of domestic and international textile and people's life, with high content of technology is more
Functional product is increasingly valued by people.To increasing textile such as garment material, non-woven fabrics, decoration weaving
Product, carpet, fabrics for industrial use etc. carry out the Multifunctional finishing such as grease proofing, antifouling, fire-retardant and radiation proof, and do not change fabric and exist
The application of performance is more and more extensive in terms of ventilative, moisture-inhibiting, has caused the concern of people.
Before no fluorocarbons is as water and oil repellent agent, to reach water resistance is all to use organo-silicon compound,
But organosilicon only has the effect of waterproof, without grease proofing performance.This can determine by its surface, one grown up later
The finishing agent of a little rubber types, is that fabric face is coated in the form of coating, the existing waterproof of these coatings also has grease proofing effect
Really, but sealing system is characterized in, fabric is possible to lose original permeability, will had as clothes dress because airtight
Feeling of oppression and heat, substantially reduces the comfort of dress.And fluorocarbons water and oil repellent agent is not only than any waterproofing agent with more excellent
Waterproof and oilproof performance, and it is most prominent the characteristics of be treated that fabric does not lose fabric through the agent of fluorine carbon waterproof oil-proof finishing
The original gas permeability of material.Due to the peculiar property of fluorine atom, organo-fluorine polymer has hydrocarbon polymer incomparable
Chemical property, is summarized as " three high two hate ", i.e. high surface, high heat-resistant stability, high chemical stability, hydrophobic and hates oil
Property.It can overcome the weakness of other types water and oil repellent agent, not only waterproof and oilproof, and assign fabric contamination resistant and ventilative
Property.
The method that fluorinated organic compound introduces textile material has a variety of, and the invention of Publication No. 201310577164.6 is special
Profit is that fluoroalkyl copolymer and polyvinylidene blending are constituted into anti-oil reservoir, is handed under crosslinking agent effect with cellulose
Connection, so as to be fixed on fabric face.Publication number is then heavy using physical vapor for 201410568359.2 patent of invention
Nano fluoride and ceramic powders nano particle finishing agent are applied to fabric face by area method, and forming one layer on the surface has
The film of " three proofings " function.
The content of the invention
It is a primary object of the present invention to provide a kind of more effective feasible grease proofing textile material method of modifying, in cotton
Fabric face introduces organic fluorocompound, its grease proofing performance is assigned, while not influenceing the moisture absorption penetrability of fabric.
To achieve the above objectives, the technical solution adopted by the present invention is：
A kind of preparation method of high-hygroscopicity Oilproof fabric, the Oilproof fabric includes precoat and anti-oil reservoir, precoat
For all cotton fibers, anti-oil reservoir is sprayed on precoat；The preparation method of high-hygroscopicity Oilproof fabric comprises the following steps：
1) arrangement step of oil-repellent liquid：Weigh the molfraction of perfluorohexyl ethylene 15~25；The propylene of polyethylene glycol two
The molfraction of acid esters 6~10；The molfraction of hydroxyethyl methacrylate 8~15；The molfraction of light trigger 0.5~1；Grafting is altogether
The poly- molfraction of initiator 0.2~0.8；The molfraction of reaction medium 58~70, each component is added in flask simultaneously, fully stirred
Mixing is mixed, mixing speed is 100~1000 revs/min, and whipping temp is 10~70 DEG C, obtains oil-repellent liquid；
2) ultraviolet initiation coating reaction process：A certain amount of cotton fabric is added into a sealable container, so
Add afterwards after oil-repellent liquid, nitrogen purging 30min, with power be the 200~300W ultra violet lamp closed container 5~
30min, to trigger radical polymerization between each monomer to carry out radical reaction；
3) grafting copolyreaction process：Grafting copolyreaction occurs in cellulose and polyethylene glycol diacrylate
Between ester, with step 2) in ultraviolet initiation coating reaction carry out simultaneously, stop ultraviolet radioactive after, it is necessary to continue keep identical
Temperature and nitrogen guard mode 3h, to allow graft reaction fully to carry out；
4) postprocessing working procedures：The cotton fiber first cleaned with 100 DEG C of hot water stirs after being modified, be then with Main Components
The detergent of 8~15wt% carboxylic acid group's glycine betaines and the concentration of configuration are cleaned for 6~16wt% aqueous sodium carbonate, then with steaming
Distilled water is cleaned three times, is placed under hot blast environment and is dried, and obtains the all-cotton fabric with preferably grease proofing and moisture pick-up properties.
Step 1) in mixing speed be optimized for 200~600 revs/min, whipping temp is optimized for 25~55 DEG C.
Step 2) described in the charging mass ratio of cotton fabric and oil-repellent liquid be 100: 150~450.
Described polyethyleneglycol diacrylate molecular weight is 400~1000.
Described light trigger is any one in benzophenone, Dialkoxy acetophenones, alpha-hydroxyalkyl benzophenone.
Described graft copolymerization evocating agent is ammonium ceric nitrate or potassium peroxydisulfate.
Described reaction medium is acetone or tetrahydrofuran or benzene.
The advantage of patent of the present invention is：Relative to the surface that the anti-oil reservoir of macromolecule is directly sprayed on to fabric, by low point
Perfluorohexyl ethylene, polyethylene glycol methacrylate-styrene polymer, the hydroxyethyl methacrylate monomer of son amount are configured to low anti-of viscosity
Oil coating, it is easier to inside infiltration to cellulose.Under the initiation of light trigger, occur certainly between each monomer containing alkylene
By base polymerisation, block copolymer is become from small molecule monomer, the near surface of cellulose is deposited on.This block copolymer both contained
Have the fluorine-containing groupses of " double to hate " performance, again containing can be with fiber-reactive diacrylate.In initiator ammonium ceric nitrate or mistake
Under the initiation of potassium sulfate, grafting occurs for the unsaturated double-bond and cellulose skeleton of polyethyleneglycol diacrylate one end
Copolyreaction, the monomer that the double bond of the other end contains alkenyl with other carries out polymerisation, and the heat that ultraviolet irradiation is produced is then
The graft copolymerization provides required temperature.By such one-step method, one layer of oil-repellent is covered on cotton fiber surface, together
When the Covalent bonding together coating and fibrous face bed of material.In addition, in conventional cellulose graft or cross-linking reaction, the hydroxyl on cellulose
Gene is consumed and reduced, and reduces the hygroscopicity of fabric.And there is provided substantial amounts of after hydroxyethyl methacrylate polymerization in the present invention
Hydroxyl, compensate for the consumption of hydroxyl in cellulose, so as to keep the hygroscopicity of fabric.
Brief description of the drawings
Fig. 1 is the hydrophily of cotton fiber prepared by embodiment 1；
Fig. 2 is the oleophobic property of cotton fiber prepared by embodiment 1；
Fig. 3 is the hydrophily of cotton fiber prepared by embodiment 2；
Fig. 4 is the oleophobic property of cotton fiber prepared by embodiment 2；
Fig. 5 is the hydrophily of cotton fiber prepared by embodiment 3；
Fig. 6 is the oleophobic property of cotton fiber prepared by embodiment 3；
Embodiment
Describe to be used to disclose the present invention below so that those skilled in the art can realize the present invention.It is excellent in describing below
Embodiment is selected to be only used as citing, it may occur to persons skilled in the art that other obvious modifications.
Embodiment 1：
The present invention relates to a kind of method of the grease proofing modification of all-cotton fabric, following steps are specifically included：(1) oil-repellent liquid
Configuration；(2) ultraviolet initiation coating reaction；(3) the grafting copolyreaction of cellulose is carried out；(4) post-process.
The each component and its molfraction of oil-repellent are in described step (1)：15 parts of perfluorohexyl ethylene, molecule
10 parts of the polyethyleneglycol diacrylate for 400 is measured, 15 parts of hydroxyethyl methacrylate, 0.5 part of light trigger benzophenone connects
Above-mentioned each component is added and is sufficiently stirred for mixing in flask by 0.2 part of branch polymerization initiator ammonium ceric nitrate, 60 parts of anhydrous benzene simultaneously,
Mixing speed is 200 revs/min, and whipping temp is 25 DEG C, obtains oil-repellent mixed liquor；
In described step (2), 200 grams of cotton fabric is added into a sealable container, step is then added
Suddenly after 300 grams of the oil-repellent mixed liquor configured in (1), nitrogen 30min, with the 200W ultra violet lamp closed container
5min, to trigger the progress of radical polymerization between each monomer；
Grafting copolyreaction in step (3) occurs between cellulose and polyethyleneglycol diacrylate, with step
Suddenly the reaction in (2) is carried out simultaneously, but is off after ultraviolet radioactive, it is necessary to continue to keep identical temperature and nitrogen guard mode
3h, to allow graft reaction fully to carry out；
The flow of post processing is in step (4)：The cotton fiber first cleaned with 100 DEG C of hot water stirs after being modified, then
Cleaned with 8wt% carboxylic acid group's beet alkalis and the 6wt% configured aqueous sodium carbonate, then three are cleaned with distilled water
Time, it is placed under hot blast environment and dries, obtains the all-cotton fabric with preferably grease proofing and moisture pick-up properties.
As shown in Figure 1 and Figure 2, the modified cotton fiber that prepared by the embodiment, the wellability to water is, dynamic Contact in 120s
Angle shows the water penetration improved to be reduced to 40 ° from 70 °；Wellability to soybean oil is that contact angle is all tieed up within 300s
Hold at 124 ° or so, show strong oleophobic property.
Embodiment 2：
The present invention relates to a kind of method of the grease proofing modification of all-cotton fabric, following steps are specifically included：(1) oil-repellent liquid
Configuration；(2) ultraviolet initiation coating reaction；(3) the grafting copolyreaction of cellulose is carried out；(4) post-process.
The each component and its molfraction of oil-repellent are in described step (1)：20 parts of perfluorohexyl ethylene, molecule
8 parts of the polyethyleneglycol diacrylate for 700 is measured, 12 parts of hydroxyethyl methacrylate, 0.8 part of light trigger benzophenone connects
Above-mentioned each component is added and is sufficiently stirred for mixing in flask by 0.5 part of branch polymerization initiator ammonium ceric nitrate, 39 parts of anhydrous benzene simultaneously,
Mixing speed is 300 revs/min, and whipping temp is 35 DEG C, obtains oil-repellent mixed liquor；
In described step (2), 300 grams of cotton fabric is added into a sealable container, step is then added
Suddenly after 450 grams of the oil-repellent mixed liquor configured in (1), nitrogen 30min, with the 250W ultra violet lamp closed container
7min, to trigger the progress of radical polymerization between each monomer；
Grafting copolyreaction in step (3) occurs between cellulose and polyethyleneglycol diacrylate, with step
Suddenly the reaction in (2) is carried out simultaneously, but is off after ultraviolet radioactive, it is necessary to continue to keep identical temperature and nitrogen guard mode
3h, to allow graft reaction fully to carry out；
The flow of post processing is in step (4)：The cotton fiber first cleaned with 100 DEG C of hot water stirs after being modified, then
Cleaned with 10wt% carboxylic acid group's beet alkalis and the 11wt% configured aqueous sodium carbonate, then three are cleaned with distilled water
Time, it is placed under hot blast environment and dries, obtains the all-cotton fabric with preferably grease proofing and moisture pick-up properties.
As shown in Figure 3, Figure 4, the modified cotton fiber that prepared by the embodiment, the wellability to water is, dynamic Contact in 120s
Angle shows the water penetration improved to be reduced to 20 ° from 71 °；Wellability to soybean oil is that contact angle is all tieed up within 120s
Hold at 126 °, show strong oleophobic property.
Embodiment 3：
The present invention relates to a kind of method of the grease proofing modification of all-cotton fabric, following steps are specifically included：(1) oil-repellent liquid
Configuration；(2) ultraviolet initiation coating reaction；(3) the grafting copolyreaction of cellulose is carried out；(4) post-process.
The each component and its molfraction of oil-repellent are in described step (1)：25 parts of perfluorohexyl ethylene, molecule
Measure 6 parts of the polyethyleneglycol diacrylate for 1000,8 parts of hydroxyethyl methacrylate, 1 part of light trigger benzophenone, grafting
Above-mentioned each component is added and is sufficiently stirred for mixing in flask, stirred by 0.8 part of polymerization initiator ammonium ceric nitrate, 60 parts of anhydrous benzene simultaneously
It is 600 revs/min to mix speed, and whipping temp is 45 DEG C, obtains oil-repellent mixed liquor；
In described step (2), 100 grams of cotton fabric is added into a sealable container, step is then added
Suddenly after 450 grams of the oil-repellent mixed liquor configured in (1), nitrogen 30min, with the 300W ultra violet lamp closed container
9min, to trigger the progress of radical polymerization between each monomer；
Grafting copolyreaction in step (3) occurs between cellulose and polyethyleneglycol diacrylate, with step
Suddenly the reaction in (2) is carried out simultaneously, but is off after ultraviolet radioactive, it is necessary to continue to keep identical temperature and nitrogen guard mode
3h, to allow graft reaction fully to carry out；
The flow of post processing is in step (4)：The cotton fiber first cleaned with 100 DEG C of hot water stirs after being modified, then
Cleaned with 15wt% carboxylic acid group's beet alkalis and the 16wt% configured aqueous sodium carbonate, then three are cleaned with distilled water
Time, it is placed under hot blast environment and dries, obtains the all-cotton fabric with preferably grease proofing and moisture pick-up properties.
As shown in Figure 5, Figure 6, the modified cotton fiber that prepared by the embodiment, the wellability to water is, dynamic contact angle in 60s
To be reduced to 10 ° from 70 °, the water penetration improved is shown；Wellability to soybean oil is that contact angle is all maintained within 120s
At 138 °, strong oleophobic property is shown.
General principle, principal character and the advantages of the present invention of the present invention has been shown and described above.The technology of the industry
Personnel are it should be appreciated that the present invention is not limited to the above embodiments, and that described in above-described embodiment and specification is the present invention
Principle, various changes and modifications of the present invention are possible without departing from the spirit and scope of the present invention, these change and
Improvement is both fallen within the range of claimed invention.The protection domain of application claims by appended claims and its
Equivalent is defined.
Claims (6)
1. a kind of preparation method of the grease proofing pure-cotton fabric of high-hygroscopicity, the grease proofing pure-cotton fabric includes precoat and anti-oil reservoir,
Precoat is all cotton fibers, and anti-oil reservoir is sprayed on precoat；The preparation method of the grease proofing pure-cotton fabric of high-hygroscopicity includes following
Step：
1) arrangement step of oil-repellent liquid：Weigh the molfraction of perfluorohexyl ethylene 15~25；Polyethyleneglycol diacrylate 6
~10 molfractions；The molfraction of hydroxyethyl methacrylate 8~15；The molfraction of light trigger 0.5~1；Graft copolymerization is drawn
Send out the molfraction of agent 0.2~0.8；The molfraction of reaction medium 58~70, each component is added in flask simultaneously, is sufficiently stirred for mixing
Even, mixing speed is 100~1000 revs/min, and whipping temp is 10~70 DEG C, obtains oil-repellent liquid；
2) ultraviolet initiation coating reaction process：A certain amount of cotton fabric, Ran Houjia are added into a sealable container
Enter after oil-repellent liquid, nitrogen purging 30min, be 200~300W ultra violet lamp, 5~30min of the closed container with power,
To trigger radical polymerization between each monomer to carry out radical reaction, described cotton fabric and the charging quality of oil-repellent liquid
Than for 100: 150~450；
3) grafting copolyreaction process：Grafting copolyreaction occur cellulose and polyethyleneglycol diacrylate it
Between, with step 2) in ultraviolet initiation coating reaction carry out simultaneously, stop ultraviolet radioactive after, it is necessary to continue keep identical temperature
With nitrogen guard mode 3h, to allow graft reaction fully to carry out；
4) postprocessing working procedures：First with 100 DEG C of hot water stirs clean it is modified after cotton fiber, then with Main Components be 8~
The detergent of 15wt% carboxylic acid group's glycine betaines and the concentration of configuration are cleaned for 6~16wt% aqueous sodium carbonate, then with distilling
Water is cleaned three times, is placed under hot blast environment and is dried, and obtains the all-cotton fabric with preferably grease proofing and moisture pick-up properties.
2. a kind of preparation method of the grease proofing pure-cotton fabric of high-hygroscopicity according to claim 1, it is characterised in that：Described
Polyethyleneglycol diacrylate molecular weight is 400~1000.
3. a kind of preparation method of the grease proofing pure-cotton fabric of high-hygroscopicity according to claim 1, it is characterised in that：Described
Light trigger is any one in benzophenone, Dialkoxy acetophenones, alpha-hydroxyalkyl benzophenone.
4. a kind of preparation method of the grease proofing pure-cotton fabric of high-hygroscopicity according to claim 1, it is characterised in that：Described
Graft copolymerization evocating agent is any one in ammonium ceric nitrate or potassium peroxydisulfate.
5. a kind of preparation method of the grease proofing pure-cotton fabric of high-hygroscopicity according to claim 1, it is characterised in that：Described
Reaction medium is any one in acetone or tetrahydrofuran or benzene.
6. a kind of preparation method of the grease proofing pure-cotton fabric of high-hygroscopicity according to claim 1, it is characterised in that：Step 1)
Mixing speed is 200~600 revs/min in the arrangement step of oil-repellent liquid, and whipping temp is 25~55 DEG C.
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| CN108060585A (en) * | 2017-12-20 | 2018-05-22 | 合肥洁诺无纺布制品有限公司 | A kind of preparation method of high-strength medical coated non-woven |
| CN108797115B (en) * | 2018-06-21 | 2020-08-04 | 东华大学 | Multifunctional durable after-finishing method for fabric based on eutectic solvent |
| CN109137502A (en) * | 2018-08-07 | 2019-01-04 | 苏州市天翱特种织绣有限公司 | A kind of preparation method of moisture absorbing and sweat releasing knitting fabric |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101835816A (en) * | 2007-10-24 | 2010-09-15 | 纳幕尔杜邦公司 | Hydrophillic fluorinated soil resist copolymers |
| CN103408692A (en) * | 2013-08-08 | 2013-11-27 | 中科院广州化学有限公司 | Aqueous dispersion crosslinkable random fluoropolymer and constructed super-amphiphobic coat through aqueous dispersion crosslinkable random fluoropolymer |
| CN103641942A (en) * | 2013-10-29 | 2014-03-19 | 南京工业大学 | Method for fast preparing hydrophobic-hydrophilic function-adjustable material |
| CN104744624A (en) * | 2013-12-25 | 2015-07-01 | 浙江衢州万能达科技有限公司 | Preparation method of acrylic acid series high oil-absorbing resin |
-
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101835816A (en) * | 2007-10-24 | 2010-09-15 | 纳幕尔杜邦公司 | Hydrophillic fluorinated soil resist copolymers |
| CN103408692A (en) * | 2013-08-08 | 2013-11-27 | 中科院广州化学有限公司 | Aqueous dispersion crosslinkable random fluoropolymer and constructed super-amphiphobic coat through aqueous dispersion crosslinkable random fluoropolymer |
| CN103641942A (en) * | 2013-10-29 | 2014-03-19 | 南京工业大学 | Method for fast preparing hydrophobic-hydrophilic function-adjustable material |
| CN104744624A (en) * | 2013-12-25 | 2015-07-01 | 浙江衢州万能达科技有限公司 | Preparation method of acrylic acid series high oil-absorbing resin |
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