CN102174737A - Superhydrophobic fabric or superhydrophobic non-woven fabric and preparation method thereof - Google Patents
Superhydrophobic fabric or superhydrophobic non-woven fabric and preparation method thereof Download PDFInfo
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Abstract
The invention provides a preparation method of a superhydrophobic fabric or superhydrophobic non-woven fabric, which comprises the following step of: enabling a fabric containing C-H bonds or a non-woven fabric containing C-H bonds to be subjected to irradiation grafting reaction with a monomer containing long-chain alkane, thus obtaining the superhydrophobic fabric or superhydrophobic non-woven fabric, wherein the monomer containing long-chain alkane is a compound as shown in general formula (1), X is hydrogen or methyl, and n is 10-17, preferably 13-17. The invention overcomes the defects that the existing preparation process of the superhydrophobic fabric or non-woven fabric is complicated, the duration time of the modification effect is short, and the superhydrophobic fabric or non-woven fabric is intolerant of washing, is of certain toxicity, is high in cost and the like, thereby providing a washing-resistant permanent superhydrophobic fabric or non-woven fabric and a preparation method thereof. Since the used monomer is a non-fluorine monomer having the advantages of low toxicity, low cost and the like, the invention is beneficial to large-scale industrial production. The general formula (1) is shown in the specification.
Description
Technical field
The present invention relates to a kind of super-hydrophobic fabric or super-hydrophobic nonwoven fabric, the invention still further relates to the preparation method of described hydrophobic fabric or super-hydrophobic nonwoven fabric.
Background technology
The super-hydrophobic water that is meant surpasses 150 degree at the contact angle of material surface, and the wing of leaf of many plants and petal, insect, the feather of birds etc. is natural super hydrophobic material, is a kind of interesting phenomenon that nature exists.Studies show that the surface of super hydrophobic material not only has lower surface energy, and have the coarse structure of micro/nano-scale.According to this mechanism, people begin to prepare artificial super hydrophobic material, particularly super-hydrophobic textiles, and it has the characteristic of air permeable waterproof, is expected to be applied in a lot of fields.Yet, the stability, particularly washing resistance of the super-hydrophobic textiles by conventional method preparation, the actual use of distance also has a certain distance, becomes a bottleneck problem of super hydrophobic material preparation.
And the irradiation grafting method is a kind of method that macromolecular material is carried out graft modification effectively, and radiation source can be from radio isotopes such as cobalt 60, caesiums 137, or from machines such as electron accelerator, X-ray machine and UV-devices.It can be divided into two kinds of mutual radiation grafting method and pre-irradiation grafting methods again according to operating procedure.The general step of mutual radiation grafting method is placed in the closed container for treating material modified and monomer solution earlier, after logical nitrogen a period of time removes oxygen in the reaction solution in solution, in radiation source, be irradiated to the polymerization of doses initiation grafting, then the material behind the irradiation grafting is taken out, promptly get graft materials after homopolymers is cleaned.And the step of pre-irradiation grafting method is generally material modified after being irradiated to doses under air or the nitrogen atmosphere in radiation source with treating, the glass container that fills monomer solution is put in taking-up, in glass container, charge into nitrogen and remove sealed reaction system behind the oxygen, take out the material after the grafting after being heated to uniform temperature and reacting a period of time, promptly get the graft modification material after homopolymers is cleaned.
Among the preparation method of existing super hydrophobic material commonly by nano material being coated in material surface or at material surface grafted fluoropolymer monomer, but for the former, its superhydrophobic characteristic is wash resistant (promptly losing superhydrophobic characteristic after the washing for several times) not, and for the latter, because fluorochemical monomer itself has toxicity, so the scope of application has limitation, and because the price comparison costliness of fluorochemical monomer, cause production cost high, also limited its application.
Summary of the invention
Technical problem to be solved by this invention be to have overcome existing super-hydrophobic fabric or super-hydrophobic nonwoven fabric complicated process of preparation, modified effect duration short, not wash resistant, have defectives such as certain toxicity and cost height, a kind of wash resistant is provided, and fabric or nonwoven fabric with permanent super-hydrophobicity, and preparation method thereof.The present invention gives fabric or nonwoven fabric super hydrophobic surface by pre-irradiation or mutual radiation grafting method, makes the super-hydrophobic fabric or the nonwoven fabric that prepare have wash fast, lasting ultra-hydrophobicity.And because the monomer that adopts is the fluorine-free monomer, have the low and low cost and other advantages of toxicity, help large-scale industrial production.
The invention provides the preparation method of a kind of super-hydrophobic fabric or super-hydrophobic nonwoven fabric, it comprises the steps: the nonwoven fabric that will contain the fabric of c h bond or contain c h bond, with contain the long chain alkane monomer and carry out irradiation grafting reaction, super-hydrophobic fabric or super-hydrophobic nonwoven fabric; Wherein, the described long chain alkane monomer that contains is the compound shown in the general formula (1):
General formula (1)
Wherein, X is hydrogen or methyl; N is 10-17, preferably is 13-17.
In the present invention's one preferred implementation, described irradiation grafting reaction can adopt mutual radiation graft reaction method or pre-irradiation grafting reaction method to carry out:
Described mutual radiation graft reaction method comprises the steps: in the pure or pure aqueous solution, under oxygen free condition, described nonwoven fabric and the described long chain alkane monomer that contains that contains the fabric of c h bond or contain c h bond carried out irradiation, super-hydrophobic fabric or super-hydrophobic nonwoven fabric;
Described pre-irradiation grafting reaction method comprises the steps: the described nonwoven fabric that contains the fabric of c h bond or contain c h bond of irradiation, must be through the fabric that contains c h bond of pre-irradiation or through the nonwoven fabric that contains c h bond of pre-irradiation; In the alcohol or the pure aqueous solution, under oxygen free condition, heat described through pre-irradiation the fabric that contains c h bond or carry out graft reaction through the nonwoven fabric that contains c h bond and the described long chain alkane monomer that contains of pre-irradiation, must super-hydrophobic fabric or super-hydrophobic nonwoven fabric.
Wherein, described alcohol can be selected to make and contain the homodisperse alcohols solvent of long chain alkane monomer according to this area general knowledge, as in methyl alcohol, ethanol and the propyl alcohol etc. one or more, preferably is methyl alcohol.The described consumption that contains the long chain alkane monomer can be selected according to this area conventional method, preferably makes the described quality that contains the long chain alkane monomer account for the 2-50% of alcoholic solution quality, more preferably is 10-40%; Described alcoholic solution refers to the aqueous solution and the described common solution of forming of long chain alkane monomer that contains of described alcohol or described alcohol.In this preferable concentration range, can realize the best monomer-grafted rate of long chain alkane that contains, thereby realize best ultra-hydrophobicity.
Wherein, the described nonwoven fabric that contains the fabric of c h bond or contain c h bond can be selected the fabric or the nonwoven fabric of various routines in this area for use, contain c h bond as long as make in the strand of described fabric or nonwoven fabric, thus can with the gamma ray effect under can carry out graft reaction and get final product with the described long chain alkane monomer that contains.Described fabric can be selected the fabric with fibre structure of various routines in this area for use, as the line of making by fiber, by these thread various braided fabrics, sewings or other fabricated products etc., the fabric that contains c h bond among the present invention preferably is the synthetic fabrics that contains c h bond, the fabric that synthetic fiber that contain the natural fabric of c h bond or contain c h bond and the natural fabric that contains c h bond are mixed.Described nonwoven fabric can be the nonwoven fabric of the various routines in this area, as have fibre structure or do not have the nonwoven fabric of fibre structure, the nonwoven fabric that contains c h bond of the present invention preferably serve as reasons synthetic fiber that contain c h bond and/or the nonwoven fabric of making by the natural fabric that contains c h bond.
The described synthetic fiber that contain c h bond comprise the hydrophobic polymer synthetic fiber that contain c h bond in the conventional all kinds of strands that use in fabric or nonwoven fabric field, and described macromolecule is one or more in following: polyethylene, polypropylene, nylon, polysulfones, polyether sulfone, polyether-ether-ketone, polyether-ketone, polyacrylonitrile, terylene, Kynoar, polyvinyl chloride, polystyrene, polyethylene terephthalate and Merlon etc.Described high molecular molecular weight is the conventional molecular weight in fabric or nonwoven fabric field, and what its weight average molecular weight was preferable is 200,000-1,000,000, more preferably is 300,000-600,000.The described natural fabric that contains c h bond comprises the various natural fabrics that contain c h bond in fabric or the nonwoven fabric field in the conventional strand that uses, and preferable is cotton fiber and/or flax fibre etc.
Wherein, the described consumption that contains the fabric of c h bond or contain the nonwoven fabric of c h bond can be selected according to this area conventional method, so that the described nonwoven fabric that contains the fabric of c h bond or contain c h bond can be advisable by the abundant submergence of described alcoholic solution, describedly contain the fabric of c h bond or contain the nonwoven fabric of c h bond and the by weight/volume of described alcoholic solution preferably is 1: 5-1: 50g/ml.Described alcoholic solution refers to the aqueous solution and the described common solution of forming of long chain alkane monomer that contains of described alcohol or described alcohol.
Wherein, the irradiation bomb that uses in the described irradiation grafting reaction can be selected irradiation bomb commonly used in the irradiation grafting field for use, preferably is
60Co cobalt source, it can reach the purpose of giving fabric or nonwoven fabric ultra-hydrophobicity within a short period of time.The irradiation dose in described cobalt source can be selected according to this area conventional method, preferably is 1kGy-50kGy, more preferably is 5-25kGy, is 5kGy-15kGy best.
Wherein, described oxygen free condition can adopt the deoxidation method of this area routine to realize, preferably is to lead to nitrogen 3-30 minute in reaction solution.
Wherein, in described pre-irradiation grafting reaction, described reaction temperature can be selected according to this area conventional method, preferably is 60-95 ℃, more preferably is 65-85 ℃.The reaction time of described pre-irradiation grafting reaction is advisable for making graft reaction be tending towards saturated, was generally 0.5-6 hour, and preferably be 1-3 hour.
Before carrying out irradiation grafting reaction, preferably the described nonwoven fabric that contains the fabric of c h bond or contain c h bond is carried out preliminary treatment, among the present invention to remove the impurity of described fabric or nonwoven surface.Described preliminary treatment can adopt the method for this area routine to carry out, the preferred following method of the present invention: with the described nonwoven fabric that contains the fabric of c h bond or contain c h bond successively in the second alcohol and water 3 minutes final vacuums of ultrasonic cleaning be dried to constant weight and get final product.
After irradiation grafting reaction of the present invention finishes, preferably carry out post processing.Described post processing preferably is: take out described super-hydrophobic fabric or super-hydrophobic nonwoven fabric, with acetone or butanone is solvent, extracting was removed homopolymers more than 72 hours in apparatus,Soxhlet's, and vacuumize (preferably being in 60 ℃ of vacuumizes) to constant weight, gets final product.
The present invention also provides a kind of super-hydrophobic fabric or super-hydrophobic nonwoven fabric that is made by said method.Super-hydrophobic fabric of the present invention or super-hydrophobic nonwoven fabric are fabric or the nonwoven fabric with super hydrophobic surface.Wherein, the percent grafting that contains the long chain alkane monomer described in described super-hydrophobic fabric or the super-hydrophobic nonwoven fabric is generally more than 10%.The contact angle of super-hydrophobic fabric of the present invention or super-hydrophobic nonwoven fabric is all greater than 150 degree, and contact angle remains unchanged substantially after repeatedly washing.
Among the present invention, above-mentioned optimum condition can make up arbitrarily on the basis that meets this area general knowledge, promptly gets each preferred embodiments of the present invention.
Raw material that the present invention is used and reagent are all commercially available to be got.
Positive progressive effect of the present invention is:
1, form closely between hydrophobic long chain alkane monomer and fabric or the nonwoven fabric in super-hydrophobic fabric of the present invention or the super-hydrophobic nonwoven fabric and combine, thereby make fabric or nonwoven fabric have the wash resistant effect, collapsible, and super-hydrophobic effect can be kept more than 2 years.After AATCC method of testing 61-2003 washing 50 times, contact angle still remains on more than 150 degree, does not change substantially.
2, generally speaking, the ultra-hydrophobicity of super-hydrophobic fabric or super-hydrophobic nonwoven fabric depends on the hydrophobic performance of the monomer of institute's grafting.But the present invention be surprised to find that with described contain long chain alkane monomer and fabric or nonwoven fabric grafting after, the contact angle of fabric or nonwoven fabric can obviously surpass the contact angle that contains long chain alkane monomer itself up to more than 150 degree.
3, with conventional employing toxicity height, expensive fluorochemical monomer as hydrophobic monomer, the present invention has adopted hypotoxicity, cheap long chain alkane monomer, the monomer cost can descend nearly 300 times, has better market prospects.
4, preparation method of the present invention is applicable to the production of large batch of fabric or nonwoven fabric, avoids existing hydrophobic treatments to need the defective of large tracts of land equipment etc., has great economic benefit.
The specific embodiment
Below in conjunction with embodiment technical scheme of the present invention is described further, but the present invention is not limited.The experimental technique of unreceipted actual conditions in the following example carries out according to normal condition.
The preparation of embodiment 1 super-hydrophobic PET fabric (fabric 1)
With PET (weight average molecular weight=300,000) fabric successively in the second alcohol and water ultrasonic cleaning after 3 minutes in 60 ℃ of vacuumizes to constant weight.5g PET fabric put into to fill contain long chain alkane monomer (CH
2=CHC (O) O (CH
2)
10CH
3) the glass conical flask of ethanolic solution 100mL (concentration of this monomer in containing the ethanolic solution of this monomer is 2wt%) in, after logical nitrogen 10min is airtight,
60Behind the irradiation 5kGy, extracting in apparatus,Soxhlet's to constant weight, got super-hydrophobic PET fabric (fabric 1) in 60 ℃ of vacuumizes after 72 hours as solvent with butanone with the fabric taking-up in the Co cobalt source, and wherein containing the monomer-grafted rate of long chain alkane is 11.3%.
With prepared fabric 1 according to measuring the contact angle of water before and after the washing (each sample is minimum gets its mean value after different position finding 8 times) after the AATCC method of testing 61-2003 washing 50 times at fabric face.
Measurement result shows that water is spent up to 155 at the average contact angle on fabric 1 surface.And contact angle is 151 degree after 50 washings, shows that this fabric 1 not only has very excellent ultra-hydrophobicity, and the fabric of this super-hydrophobicity can wash resistant simultaneously.The The performance test results of gained fabric 1 specifically sees Table 1.
Comparative example 1PET original fabrics (contrast 1)
Same measure water at the contact angle of the PET of not grafting fabric face in contrast, method of testing is with embodiment 1
Unmodified PET (weight average molecular weight=300,000) fabric is through contact angle determination, and water only is 73 degree at the contact angle of this fabric face, illustrates that this fabric face does not have superhydrophobic characteristic.The The performance test results of gained fabric specifically sees Table 1.
The preparation of embodiment 2 super-hydrophobic cotton fabrics (fabric 2)
With COTTON FABRIC successively in the second alcohol and water ultrasonic cleaning after 3 minutes in 60 ℃ of vacuumizes to constant weight.The 5g COTTON FABRIC put into to fill contain long chain alkane monomer (CH
2=C (CH
3) C (O) O (CH
2)
17CH
3) the glass conical flask of methanol solution 100mL (concentration of this monomer in containing the methanol solution of this monomer is 10wt%) in, after logical nitrogen 20min is airtight,
60Behind the irradiation 25kGy, extracting in apparatus,Soxhlet's to constant weight, got super-hydrophobic cotton fabric (fabric 2) in 60 ℃ of vacuumizes after 72 hours as solvent with butanone with the fabric taking-up in the Co cobalt source, and the percent grafting that wherein contains the long chain alkane monomer is 22.0%.
The contact angle of test fabric 2, method of testing is with embodiment 1.Measurement result shows that water is spent up to 168 at the average contact angle on fabric 2 surfaces.And contact angle still can remain on 161 degree after 50 washings, shows this fabric 2 and not only has very excellent ultra-hydrophobicity, and this super-hydrophobic fabric can wash resistant simultaneously.The The performance test results of gained fabric 2 specifically sees Table 1.
Comparative example's 2 cotton original fabrics (contrast 2)
Unmodified COTTON FABRIC is through contact angle determination, and method of testing is with embodiment 1.Water is 0 degree at the contact angle of this fabric face, illustrates that this fabric does not possess super-hydrophobicity, and the The performance test results of gained fabric specifically sees Table 1.
The preparation of embodiment 3 super-hydrophobic polypropylene fabrics (fabric 3)
With hydrophobic polypropylene (weight average molecular weight=400,000) fabric successively in the second alcohol and water ultrasonic cleaning after 3 minutes in 60 ℃ of vacuumizes to constant weight.The 5g polypropylene fabric put into to fill contain long chain alkane monomer (CH
2=C (CH
3) C (O) O (CH
2)
16CH
3) the glass conical flask of ethanolic solution 100mL (concentration of this monomer in containing the ethanolic solution of this monomer is 50wt%) in, after logical nitrogen 30min is airtight,
60Behind the irradiation 50kGy, extracting in apparatus,Soxhlet's got super-hydrophobic polypropylene fabric (fabric 3) in 60 ℃ of vacuumize to constant weights after 72 hours as solvent with butanone with the fabric taking-up in the Co cobalt source, and the percent grafting that wherein contains the long chain alkane monomer is 37.4%.
Test the contact angle of prepared fabric 3, method of testing is with embodiment 1.Measurement result shows that water is spent up to 169 at the average contact angle on fabric 3 surfaces.And contact angle still can remain on 168 degree after 50 washings, shows this fabric 3 and not only has very excellent ultra-hydrophobicity, and the fabric of this super-hydrophobicity can wash resistant simultaneously.The The performance test results of gained fabric 3 specifically sees Table 1.
Comparative example's 3 polypropylene original fabrics (contrast 3)
Unmodified polypropylene (weight average molecular weight=400,000) fabric is through contact angle determination, and method of testing is with embodiment 1.This fabric face has certain hydrophily.Water is 88 degree at its surperficial contact angle, illustrates that this fabric does not possess super-hydrophobicity, and the The performance test results of gained fabric specifically sees Table 1.
The preparation (fabric 4) of embodiment 4 super-hydrophobic polypropylene nitrile fabrics
With polyacrylonitrile (weight average molecular weight=600,000) fabric successively in the second alcohol and water ultrasonic cleaning after 3 minutes in 60 ℃ of vacuumizes to constant weight.5g polyacrylonitrile fabric put into to fill contain long chain alkane monomer (CH
2=CHC (O) O (CH
2)
15CH
3) the glass conical flask of methanol solution 100mL (concentration of this monomer in containing the methanol solution of this monomer is 25wt%) in, after logical nitrogen 30min is airtight,
60Behind the irradiation 15kGy, extracting in apparatus,Soxhlet's got super-hydrophobic polypropylene nitrile fabric (fabric 4) in 60 ℃ of vacuumize to constant weights after 72 hours as solvent with butanone with the fabric taking-up in the Co cobalt source, and the percent grafting that wherein contains the long chain alkane monomer is 37.4%.
Test the contact angle of prepared fabric 4, method of testing is with embodiment 1.Measurement result shows that water is spent up to 171 at the average contact angle on fabric 4 surfaces.And contact angle still can remain on 168 degree after 50 washings, shows this fabric 4 and not only has very excellent ultra-hydrophobicity, and this super-hydrophobicity can wash resistant simultaneously.The The performance test results of gained fabric 4 specifically sees Table 1.
Comparative example's 4 polyacrylonitrile original fabrics (contrast 4)
Unmodified polypropylene nitrile (weight average molecular weight=600,000) fabric is through contact angle determination, and method of testing is with embodiment 1.Water is 65 degree at the contact angle of this fabric face, illustrates that this fabric does not possess super-hydrophobicity, and the The performance test results of gained fabric specifically sees Table 1.
The preparation of embodiment 5 super-hydrophobic nylon fabrics (fabric 5)
With nylon (weight average molecular weight=200,000) fabric successively in the second alcohol and water ultrasonic cleaning after 3 minutes in 60 ℃ of vacuumizes to constant weight.The 20g nylon fabrics put into to fill contain long chain alkane monomer (CH
2=CHC (O) O (CH
2)
12CH
3) the glass conical flask of propanol solution 100mL (concentration of this monomer in containing the propanol solution of this monomer is 2wt%) in, after logical nitrogen 10min is airtight,
60Behind the irradiation 5kGy, extracting in apparatus,Soxhlet's to constant weight, got super-hydrophobic nylon fabrics (fabric 5) in 60 ℃ of vacuumizes after 72 hours as solvent with butanone with the fabric taking-up in the Co cobalt source, and the percent grafting that wherein contains the long chain alkane monomer is 11%.
Test the contact angle of prepared fabric 5, method of testing is with embodiment 1.The The performance test results of gained fabric 5 specifically sees Table 1.
The preparation of embodiment 6 super-hydrophobic dacrons (fabric 6)
With terylene (weight average molecular weight=550,000) fabric successively in the second alcohol and water ultrasonic cleaning after 3 minutes in 60 ℃ of vacuumizes to constant weight.The 5g dacron is put into plastic bag, in the air atmosphere
60Take out behind the irradiation 30kGy in the Co cobalt source, put into to fill and contain long chain alkane monomer (CH
2=C (CH
3) C (O) O (CH
2)
14CH
3) the glass conical flask of ethanolic solution 100mL (concentration of this monomer in containing the ethanolic solution of this monomer is 20wt%) in, after logical nitrogen 30min is airtight, after reacting 3 hours under 65 ℃, fabric is taken out with butanone as solvent extracting after 72 hours in apparatus,Soxhlet's, get super-hydrophobic dacron (fabric 6) in 60 ℃ of vacuumize to constant weights, the percent grafting that wherein contains the long chain alkane monomer is 14%.
Test the contact angle of prepared fabric 6, method of testing is with embodiment 1.The The performance test results of gained fabric 6 specifically sees Table 1.
The preparation of embodiment 7 super-hydrophobic linens (fabric 7)
With flax fibre successively in the second alcohol and water ultrasonic cleaning after 3 minutes in 60 ℃ of vacuumizes to constant weight.The 5g polyvinyl chloride put into to fill contain long chain alkane monomer (CH
2=C (CH
3) C (O) O (CH
2)
17CH
3) the glass conical flask of methanol solution 100mL (concentration of this monomer in containing the methanol solution of this monomer is 10wt%) in, after logical nitrogen 20min is airtight,
60Behind the irradiation 25kGy, extracting in apparatus,Soxhlet's to constant weight, got super-hydrophobic linen (fabric 7) in 60 ℃ of vacuumizes after 72 hours as solvent with butanone with the fabric taking-up in the Co cobalt source, and the percent grafting that wherein contains the long chain alkane monomer is 39%.
Test the contact angle of prepared fabric 7, method of testing is with embodiment 1.The The performance test results of gained fabric 7 specifically sees Table 1.
The preparation of embodiment 8 super-hydrophobic polypropylene nonwoven fabric (nonwoven fabric 1)
With polypropylene (weight average molecular weight=530,000) nonwoven fabric successively in the second alcohol and water ultrasonic cleaning after 3 minutes in 60 ℃ of vacuumizes to constant weight.The 5g polypropylene non-woven fabric is put into valve bag, charge into nitrogen and also exist the sealing back
60Take out after being irradiated to 20kGy in the Co cobalt source, put into to fill and contain long chain alkane monomer (CH
2=CHC (O) O (CH
2)
12CH
3) the glass conical flask of ethanolic solution 100mL (concentration of this monomer in containing the ethanolic solution of this monomer is 20wt%) in, after logical nitrogen 30min is airtight, after reaction 3 as a child under 65 ℃, nonwoven fabric is taken out with butanone as solvent extracting after 72 hours in apparatus,Soxhlet's, get super-hydrophobic polypropylene nonwoven fabric (nonwoven fabric 1) in 60 ℃ of vacuumize to constant weights, the percent grafting that wherein contains the long chain alkane monomer is 42.1%.
Test the contact angle of prepared nonwoven fabric 1, method of testing is with embodiment 1.Measurement result shows that water is spent up to 169 at the average contact angle on this nonwoven fabric 1 surface.And contact angle still can remain on 167 degree after 50 washings, shows this nonwoven fabric 1 and not only has very excellent ultra-hydrophobicity, and this super-hydrophobicity can wash resistant simultaneously.The The performance test results of gained nonwoven fabric 1 specifically sees Table 1.
Comparative example's 5 original polypropylene non-woven fabrics (contrast 5)
Polypropylene (weight average molecular weight=530,000) nonwoven fabric is through contact angle determination, and method of testing is with embodiment 1.Water is 95 degree at the contact angle of this nonwoven surface, illustrates that this nonwoven fabric does not possess super-hydrophobicity, and the The performance test results of gained nonwoven fabric specifically sees Table 1.
The preparation of embodiment 9 super-hydrophobic PET nonwoven fabric (nonwoven fabric 2)
With PET (weight average molecular weight=730,000) nonwoven fabric successively in the second alcohol and water ultrasonic cleaning after 3 minutes in 60 ℃ of vacuumizes to constant weight.5g PET nonwoven fabric is put into valve bag, charge into nitrogen and also exist the sealing back
60Take out after being irradiated to 50kGy in the Co cobalt source, put into to fill and contain long chain alkane monomer (CH
2=C (CH
3) C (O) O (CH
2)
16CH
3) the glass conical flask of methanol solution 100mL (concentration of this monomer in containing the methanol solution of this monomer is 40wt%) in, after logical nitrogen 30min is airtight, after reaction 6 as a child under 75 ℃, nonwoven fabric is taken out with butanone as solvent extracting after 72 hours in apparatus,Soxhlet's, get super-hydrophobic PET nonwoven fabric (nonwoven fabric 2) in 60 ℃ of vacuumize to constant weights, the percent grafting that wherein contains the long chain alkane monomer is 27.1%.
Test the contact angle of prepared nonwoven fabric 2, method of testing is with embodiment 1.Measurement result shows that water is spent up to 159 at the average contact angle on these nonwoven fabric 2 surfaces.And contact angle still can remain on 155 degree after 50 washings, shows this nonwoven fabric 2 and not only has very excellent ultra-hydrophobicity, and this super-hydrophobicity can wash resistant simultaneously.The The performance test results of gained nonwoven fabric 2 specifically sees Table 1.
The original nonwoven fabric of comparative example 6PET (contrast 6)
Unmodified PET (weight average molecular weight=730,000) nonwoven fabric is through contact angle determination, and method of testing is with embodiment 1.Water is 75 degree at the contact angle of this nonwoven surface, illustrates that this nonwoven fabric does not possess super-hydrophobicity, and the The performance test results of gained nonwoven fabric specifically sees Table 1.
The preparation of embodiment 10 ultra-hydrophobic polyvinylidene fluoride nonwoven fabric (nonwoven fabric 3)
With Kynoar (weight average molecular weight=340,000) nonwoven fabric successively in the second alcohol and water ultrasonic cleaning after 3 minutes in 60 ℃ of vacuumizes to constant weight.5g Kynoar nonwoven fabric is put into valve bag, charge into nitrogen and also exist the sealing back
60Take out after being irradiated to 25kGy in the Co cobalt source, put into to fill and contain long chain alkane monomer (CH
2=CHC (O) O (CH
2)
16CH
3) the glass conical flask of methanol solution 100mL (concentration of this monomer in containing the methanol solution of this monomer is 20wt%) in, after logical nitrogen 30min is airtight, after reaction 3 as a child under 65 ℃, nonwoven fabric is taken out with ethyl acetate as solvent extracting after 72 hours in apparatus,Soxhlet's, get ultra-hydrophobic polyvinylidene fluoride nonwoven fabric (nonwoven fabric 3) in 60 ℃ of vacuumize to constant weights, the percent grafting that wherein contains the long chain alkane monomer is 38.6%.
Test prepared nonwoven fabric 3 contact angles, method of testing is with embodiment 1.Measurement result shows that water is spent up to 169 at the average contact angle of 3 of this nonwoven fabric.And contact angle still can remain on 167 degree after 50 washings, shows this nonwoven fabric 3 and not only has very excellent ultra-hydrophobicity, and this super-hydrophobicity can wash resistant simultaneously.The The performance test results of gained nonwoven fabric 3 specifically sees Table 1.
Comparative example's 7 original Kynoar nonwoven fabric (contrast 7)
Original Kynoar (weight average molecular weight=340,000) nonwoven fabric is through contact angle determination, and method of testing is with embodiment 1.Water is 71 degree at the contact angle of this nonwoven surface, illustrates that this nonwoven fabric does not possess super-hydrophobicity, and the The performance test results of gained nonwoven fabric specifically sees Table 1.
The preparation of embodiment 11 super-hydrophobic polysulfones nonwoven fabric (nonwoven fabric 4)
With polysulfones (weight average molecular weight=580,000) nonwoven fabric successively in the second alcohol and water ultrasonic cleaning after 3 minutes in 60 ℃ of vacuumizes to constant weight.5g polysulfones nonwoven fabric is put into valve bag, charge in valve bag that the sealing back exists behind the nitrogen
60Take out behind the irradiation 40kGy in the Co cobalt source, put into to fill and contain long chain alkane monomer (CH
2=C (CH
3) C (O) O (CH
2)
17CH
3) the glass conical flask of methanol solution 100mL (concentration of this monomer in containing the methanol solution of this monomer is 15wt%) in, after logical nitrogen 30min is airtight, after reacting 1 hour under 65 ℃, nonwoven fabric is taken out with butanone as solvent extracting after 72 hours in apparatus,Soxhlet's, get super-hydrophobic polysulfones nonwoven fabric (nonwoven fabric 4) in 60 ℃ of vacuumize to constant weights, the percent grafting that wherein contains the long chain alkane monomer is 37%.
Test the contact angle of prepared nonwoven fabric 4, method of testing is with embodiment 1.Measurement result shows that water is spent up to 170 at the average contact angle on these nonwoven fabric 4 surfaces.And contact angle still can remain on 168 degree after 50 washings, shows that this nonwoven fabric 4 not only has very excellent ultra-hydrophobicity, and this super-hydrophobicity can wash resistant simultaneously.The The performance test results of gained nonwoven fabric 4 specifically sees Table 1.
Comparative example's 8 original polysulfones nonwoven fabric (contrast 8)
Original polysulfones (weight average molecular weight=580,000) nonwoven fabric is through contact angle determination, and method of testing is with embodiment 1.Water is 75 degree at the contact angle of this nonwoven surface, illustrates that this nonwoven fabric does not possess super-hydrophobicity, and the The performance test results of gained nonwoven fabric specifically sees Table 1.
The preparation of embodiment 12 super-hydrophobic polyether-ketone nonwoven fabric (nonwoven fabric 5)
With polyether-ketone (weight average molecular weight=1,000,000) nonwoven fabric successively in the second alcohol and water ultrasonic cleaning after 3 minutes in 60 ℃ of vacuumizes to constant weight.2g polyether-ketone nonwoven fabric is put into plastic bag, in air atmosphere
60Take out behind the irradiation 40kGy in the Co cobalt source, put into to fill and contain long chain alkane monomer (CH
2=C (CH
3) C (O) O (CH
2)
17CH
3) the glass conical flask of propanol solution 100mL (concentration of this monomer in containing the methanol solution of this monomer is 15wt%) in, after logical nitrogen 30min is airtight, after reacting 0.5 hour under 85 ℃, fabric is taken out with butanone as solvent extracting after 72 hours in apparatus,Soxhlet's, get super-hydrophobic polyether-ketone nonwoven fabric (nonwoven fabric 5) in 60 ℃ of vacuumize to constant weights, the percent grafting that wherein contains the long chain alkane monomer is 27%.
Test the contact angle of prepared nonwoven fabric 5, method of testing is with embodiment 1.The The performance test results of gained nonwoven fabric 5 specifically sees Table 1.
The preparation of embodiment 13 super-hydrophobic polystyrene nonwoven fabric (nonwoven fabric 6)
With polystyrene (weight average molecular weight=700,000) nonwoven fabric successively in the second alcohol and water ultrasonic cleaning after 3 minutes in 60 ℃ of vacuumizes to constant weight.5g polystyrene nonwoven fabric is put into plastic bag, in the air atmosphere
60Take out behind the irradiation 30kGy in the Co cobalt source, put into to fill and contain long chain alkane monomer (CH
2=C (CH
3) C (O) O (CH
2)
17CH
3) the glass conical flask of ethanolic solution 100mL (concentration of this monomer in containing the ethanolic solution of this monomer is 15wt%) in, after logical nitrogen 30min is airtight, after reacting 3 hours under 60 ℃, nonwoven fabric is taken out with butanone as solvent extracting after 72 hours in apparatus,Soxhlet's, get super-hydrophobic polystyrene nonwoven fabric (nonwoven fabric 6) in 60 ℃ of vacuumize to constant weights, the percent grafting that wherein contains the long chain alkane monomer is 38%.
Test the contact angle of prepared nonwoven fabric 6, method of testing is with embodiment 1.The The performance test results of gained nonwoven fabric 6 specifically sees Table 1.
The preparation of embodiment 14 super-hydrophobic polycarbonate nonwovens (nonwoven fabric 7)
With Merlon (weight average molecular weight=600,000) nonwoven fabric successively in the second alcohol and water ultrasonic cleaning after 3 minutes in 60 ℃ of vacuumizes to constant weight.The 5g polycarbonate nonwoven is put into plastic bag, in the air atmosphere
60Take out behind the irradiation 30kGy in the Co cobalt source, put into to fill and contain long chain alkane monomer (CH
2=C (CH
3) C (O) O (CH
2)
17CH
3) the glass conical flask of ethanolic solution 100mL (concentration of this monomer in containing the ethanolic solution of this monomer is 15wt%) in, after logical nitrogen 30min is airtight, after reacting 3 hours under 65 ℃, nonwoven fabric is taken out with butanone as solvent extracting after 72 hours in apparatus,Soxhlet's, get super-hydrophobic polycarbonate nonwoven (nonwoven fabric 7) in 60 ℃ of vacuumize to constant weights, the percent grafting that wherein contains the long chain alkane monomer is 26%.
Test the contact angle of prepared nonwoven fabric 7, method of testing is with embodiment 1.The The performance test results of gained nonwoven fabric 7 specifically sees Table 1.
The preparation of embodiment 15 super-hydrophobic polyether-ether-ketone nonwoven fabric (nonwoven fabric 8)
With polyether-ether-ketone (weight average molecular weight=400,000) nonwoven fabric successively in the second alcohol and water ultrasonic cleaning after 3 minutes in 60 ℃ of vacuumizes to constant weight.5g polyether-ether-ketone nonwoven fabric is put into plastic bag, in the air atmosphere
60Take out behind the irradiation 30kGy in the Co cobalt source, put into to fill and contain long chain alkane monomer (CH
2=C (CH
3) C (O) O (CH
2)
17CH
3) the glass conical flask of ethanolic solution 100mL (concentration of this monomer in containing the ethanolic solution of this monomer is 20wt%) in, after logical nitrogen 30min is airtight, after reacting 3 hours under 65 ℃, nonwoven fabric is taken out with butanone as solvent extracting after 72 hours in apparatus,Soxhlet's, get super-hydrophobic polyether-ether-ketone nonwoven fabric (nonwoven fabric 8) in 60 ℃ of vacuumize to constant weights, the percent grafting that wherein contains the long chain alkane monomer is 18%.
Test the contact angle of prepared nonwoven fabric 8, method of testing is with embodiment 1.The The performance test results of gained nonwoven fabric 8 specifically sees Table 1.
The preparation of embodiment 16 super-hydrophobic polyethylene nonwoven fabric (nonwoven fabric 9)
With polyethylene (weight average molecular weight=800,000) nonwoven fabric successively in the second alcohol and water ultrasonic cleaning after 3 minutes in 60 ℃ of vacuumizes to constant weight.5g polyethylene nonwoven fabric is put into plastic bag, in the air atmosphere
60Take out behind the irradiation 30kGy in the Co cobalt source, put into to fill and contain long chain alkane monomer (CH
2=C (CH
3) C (O) O (CH
2)
15CH
3) the glass conical flask of ethanolic solution 100mL (concentration of this monomer in containing the ethanolic solution of this monomer is 20wt%) in, after logical nitrogen 30min is airtight, after reacting 3 hours under 65 ℃, nonwoven fabric is taken out with butanone as solvent extracting after 72 hours in apparatus,Soxhlet's, get super-hydrophobic polyethylene nonwoven fabric (nonwoven fabric 9) in 60 ℃ of vacuumize to constant weights, the percent grafting that wherein contains the long chain alkane monomer is 42%.
Test the contact angle of prepared nonwoven fabric 9, method of testing is with embodiment 1.The The performance test results of gained nonwoven fabric 9 specifically sees Table 1.
The preparation of embodiment 17 super-hydrophobic polyether sulfone nonwoven fabric (nonwoven fabric 10)
With polyether sulfone (weight average molecular weight=800,000) nonwoven fabric successively in the second alcohol and water ultrasonic cleaning after 3 minutes in 60 ℃ of vacuumizes to constant weight.5g polyether sulfone nonwoven fabric is put into plastic bag, in the air atmosphere
60Take out behind the irradiation 30kGy in the Co cobalt source, put into to fill and contain long chain alkane monomer (CH
2=C (CH
3) C (O) O (CH
2)
14CH
3) the glass conical flask of ethanolic solution 100mL (concentration of this monomer in containing the ethanolic solution of this monomer is 20wt%) in, after logical nitrogen 30min is airtight, after reacting 3 hours under 65 ℃, nonwoven fabric is taken out with butanone as solvent extracting after 72 hours in apparatus,Soxhlet's, get super-hydrophobic polyether sulfone nonwoven fabric (nonwoven fabric 10) in 60 ℃ of vacuumize to constant weights, the percent grafting that wherein contains the long chain alkane monomer is 26%.
Test the contact angle of prepared nonwoven fabric 10, method of testing is with embodiment 1.The The performance test results of gained nonwoven fabric 10 specifically sees Table 1.
The preparation of embodiment 18 super-hydrophobic polyvinyl chloride nonwoven fabric (nonwoven fabric 11)
With polyvinyl chloride successively in the second alcohol and water ultrasonic cleaning after 3 minutes in 60 ℃ of vacuumizes to constant weight.The 5g polyvinyl chloride put into to fill contain long chain alkane monomer (CH
2=C (CH
3) C (O) O (CH
2)
17CH
3) the glass conical flask of methanol solution 100mL (concentration of this monomer in containing the methanol solution of this monomer is 10wt%) in, after logical nitrogen 20min is airtight,
60In the Co cobalt source behind the irradiation 25kGy, nonwoven fabric is taken out with butanone as solvent extracting after 72 hours in apparatus,Soxhlet's, to constant weight, get super-hydrophobic polyvinyl chloride nonwoven fabric (nonwoven fabric 11) in 60 ℃ of vacuumizes, the percent grafting that wherein contains the long chain alkane monomer is 29%.
Test the contact angle of prepared nonwoven fabric 11, method of testing is with embodiment 1.The The performance test results of gained nonwoven fabric 11 specifically sees Table 1.
Effect embodiment
Above-mentioned each fabric and nonwoven fabric are carried out the cytotoxicity test, and method of testing is carried out according to GB/T 16888.5, and test result sees Table 1.
Table 1
By table 1 as seen, super-hydrophobic fabric or super-hydrophobic nonwoven fabric that the ownership gets all have good hydrophobic performance, and water is all spent greater than 150 at its surperficial contact angle.And through super-hydrophobic fabric that the inventive method prepares or super-hydrophobic nonwoven fabric after through AATCC method of testing 61-2003 washing 50 times, water still can remain on more than 150 degree at its surperficial contact angle, show lasting wash fast super-hydrophobicity, super-hydrophobic effect can keep more than 2 years.And the cytotoxicity of super-hydrophobic fabric of the present invention or nonwoven fabric is all 0 grade, and is safe and reliable.
Claims (10)
1. the preparation method of a super-hydrophobic fabric or super-hydrophobic nonwoven fabric, it is characterized in that: it comprises the steps: the nonwoven fabric that will contain the fabric of c h bond or contain c h bond, with contain the long chain alkane monomer and carry out irradiation grafting reaction, super-hydrophobic fabric or super-hydrophobic nonwoven fabric; Wherein, the described long chain alkane monomer that contains is the compound shown in the general formula (1):
Wherein, X is hydrogen or methyl; N is 10-17, preferably is 13-17.
2. preparation method as claimed in claim 1 is characterized in that: described irradiation grafting reaction adopts mutual radiation graft reaction method or pre-irradiation grafting reaction method to carry out:
Described mutual radiation graft reaction method comprises the steps: in the pure or pure aqueous solution, under oxygen free condition, described nonwoven fabric and the described long chain alkane monomer that contains that contains the fabric of c h bond or contain c h bond carried out irradiation, super-hydrophobic fabric or super-hydrophobic nonwoven fabric;
Described pre-irradiation grafting reaction method comprises the steps: the described nonwoven fabric that contains the fabric of c h bond or contain c h bond of irradiation, must be through the fabric that contains c h bond of pre-irradiation or through the nonwoven fabric that contains c h bond of pre-irradiation; In the alcohol or the pure aqueous solution, under oxygen free condition, thereby heating described through pre-irradiation the fabric that contains c h bond or carry out graft reaction through the nonwoven fabric that contains c h bond and the described long chain alkane monomer that contains of pre-irradiation, super-hydrophobic fabric or super-hydrophobic nonwoven fabric.
3. preparation method as claimed in claim 1 or 2 is characterized in that: described alcohol is one or more in methyl alcohol, ethanol and the propyl alcohol; And/or the described quality that contains the long chain alkane monomer accounts for the 2-50% of alcoholic solution quality, preferably is 10-40%; Described alcoholic solution refers to the aqueous solution and the described common solution of forming of long chain alkane monomer that contains of described alcohol or described alcohol.
4. as each described preparation method in the claim 1～3, it is characterized in that: the fabric that the described fabric that contains c h bond is the synthetic fabrics that contains c h bond, synthetic fiber that contain the natural fabric of c h bond or contain c h bond and the natural fabric that contains c h bond are mixed; The described nonwoven fabric that contains c h bond serve as reasons synthetic fiber that contain c h bond and/or the nonwoven fabric of making by the natural fabric that contains c h bond.
5. preparation method as claimed in claim 4, it is characterized in that: the described synthetic fiber that contain c h bond comprise the hydrophobic polymer synthetic fiber that contain c h bond, and described macromolecule is one or more in following: polyethylene, polypropylene, nylon, polysulfones, polyether sulfone, polyether-ether-ketone, polyether-ketone, polyacrylonitrile, terylene, Kynoar, polyvinyl chloride, polystyrene, polyethylene terephthalate and Merlon; Described high molecular weight average molecular weight preferably is 200,000-1,000,000, more preferably is 300,000-600,000; The described natural fabric that contains c h bond comprises cotton fiber and/or flax fibre.
6. preparation method as claimed in claim 1 or 2 is characterized in that: describedly contain the fabric of c h bond or contain the nonwoven fabric of c h bond and the by weight/volume of described alcoholic solution is 1: 5-1: 50g/ml.
7. preparation method as claimed in claim 1 or 2 is characterized in that: the irradiation bomb that uses in the described irradiation grafting reaction is
60Co cobalt source; The irradiation dose in described cobalt source preferably is 1kGy-50kGy, more preferably is 5-25kGy, is 5kGy-15kGy best.
8. preparation method as claimed in claim 2 is characterized in that: in described pre-irradiation grafting reaction, described reaction temperature is 60-95 ℃, preferably is 65-85 ℃; The reaction time of described pre-irradiation grafting reaction is 0.5-6 hour, preferably is 1-3 hour.
9. preparation method as claimed in claim 1 or 2, it is characterized in that: before carrying out the reaction of described irradiation grafting, the described nonwoven fabric that contains the fabric of c h bond or contain c h bond is carried out the preliminary treatment of following step: with the described nonwoven fabric that contains the fabric of c h bond or contain c h bond successively in the second alcohol and water 3 minutes final vacuums of ultrasonic cleaning be dried to constant weight and get final product;
After described irradiation grafting reaction finishes, carry out post processing by following step: taking out described super-hydrophobic fabric or super-hydrophobic nonwoven fabric, is solvent with acetone or butanone, and extracting was removed homopolymers more than 72 hours in apparatus,Soxhlet's, vacuumize gets final product to constant weight.
10. super-hydrophobic fabric or the super-hydrophobic nonwoven fabric that makes by each described preparation method in the claim 1～9.
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| CN103182222A (en) * | 2011-12-27 | 2013-07-03 | 中国科学院上海应用物理研究所 | Modified polymer screen mesh, preparation method and application thereof |
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| CN102505473A (en) * | 2011-10-10 | 2012-06-20 | 中国科学院上海应用物理研究所 | Anti-scald textile and preparation method thereof |
| CN102505473B (en) * | 2011-10-10 | 2014-07-16 | 中国科学院上海应用物理研究所 | Anti-scald textile and preparation method thereof |
| CN103182222A (en) * | 2011-12-27 | 2013-07-03 | 中国科学院上海应用物理研究所 | Modified polymer screen mesh, preparation method and application thereof |
| CN103614911A (en) * | 2013-11-07 | 2014-03-05 | 中国石油天然气集团公司 | Functionalized non-woven oil-absorbing material and preparation method thereof |
| CN103952786A (en) * | 2014-04-25 | 2014-07-30 | 中国科学院化学研究所 | Long carbon chain polyamide fibers with controlled hydrophobicity and super-hydrophobicity and preparation method and use of long carbon chain polyamide fibers |
| CN103952786B (en) * | 2014-04-25 | 2016-05-11 | 中国科学院化学研究所 | A kind of Long Carbon Chain Polyamide fiber with controlled hydrophobic, super-hydrophobicity and its production and use |
| CN106924996A (en) * | 2015-12-31 | 2017-07-07 | 中国科学院上海应用物理研究所 | A kind of super-hydrophobic/super-oleophilic hybrid inorganic-organic materials and its preparation method and application |
| CN106924996B (en) * | 2015-12-31 | 2020-12-25 | 中国科学院上海应用物理研究所 | Super-hydrophobic/super-oleophylic organic-inorganic hybrid material and preparation method and application thereof |
| CN107019935A (en) * | 2016-02-01 | 2017-08-08 | 中国科学院上海应用物理研究所 | Super-hydrophobic/super-oleophilic hybrid inorganic-organic materials and preparation method thereof, application |
| CN107019935B (en) * | 2016-02-01 | 2020-12-08 | 中国科学院上海应用物理研究所 | Super-hydrophobic/super-oleophylic organic-inorganic hybrid material and preparation method and application thereof |
| CN109777011A (en) * | 2019-01-30 | 2019-05-21 | 中国人民解放军国防科技大学 | Polyvinylidene fluoride-based super-hydrophobic fiber reinforced composite material and preparation method thereof |
| CN110565378A (en) * | 2019-09-16 | 2019-12-13 | 安徽大学 | Super-hydrophobic modified cotton fiber for oil-water separation and preparation method thereof |
| CN110565378B (en) * | 2019-09-16 | 2022-04-05 | 安徽大学 | Super-hydrophobic modified cotton fiber for oil-water separation and preparation method thereof |
| CN111888800A (en) * | 2020-07-15 | 2020-11-06 | 深圳大学 | Grafting modified cotton material and preparation method and application thereof |
| CN114875667A (en) * | 2022-04-14 | 2022-08-09 | 水木聚力接枝新技术(深圳)有限责任公司 | Broad-spectrum antibacterial and antiviral textile based on double-long-chain ionic liquid structural monomer graft copolymerization and preparation method thereof |
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