CN106521945B - The polynary antifouling copolymer of collaboration modifies spandex fibre and preparation method - Google Patents
The polynary antifouling copolymer of collaboration modifies spandex fibre and preparation method Download PDFInfo
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- CN106521945B CN106521945B CN201610965885.8A CN201610965885A CN106521945B CN 106521945 B CN106521945 B CN 106521945B CN 201610965885 A CN201610965885 A CN 201610965885A CN 106521945 B CN106521945 B CN 106521945B
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- D06M14/00—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials
- D06M14/08—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials on to materials of synthetic origin
- D06M14/12—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials on to materials of synthetic origin of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
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- D06N7/00—Flexible sheet materials not otherwise provided for, e.g. textile threads, filaments, yarns or tow, glued on macromolecular material
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- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
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- D06N2203/04—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
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Abstract
The present invention is using spandex fibre as raw material, cause the method for atom transfer radical polymerization using surface, the copolymer with amphoteric compound structural unit and the structural unit containing capsaicin compound has been modified in fiber surface, has been prepared for that there is good antifouling and pollution release performance fiber.On the one hand the copolymer has hydrophilic amphoteric compound sulphonic acid betaine methacrylate structural units, it is possible to provide good anti-protein sticks and bactericidal property；Another aspect N- (5- methyl -3- tert-butyl -2- hydroxybenzyl) acrylamide structural unit, the performance sticked and grown with good inhibition fouling organism.Surfacing prepared by the present invention has the polynary antifouling effect of collaboration simultaneously, and anti-pollution is very superior in static briny environment and flowing Seawater environment, and has good protective action, therefore the prospect that is widely used to multiple dimensioned fouling organism；Surfacing substrate prepared by the present invention is applied widely；It is nontoxic and pollution-free, marine environment will not be impacted.
Description
Technical field
The invention belongs to Material Fields, and in particular to a kind of function antifouling surface material, more particularly to it is a kind of with good
Bionical antifouling surface material of the polynary collaboration of anti-pollution and preparation method thereof.
Background technique
Marine fouling organism is to grow the alow general designation with the animal on marine facility surface, plant and microorganism.Sea
Foreign fouling organism causes significant damage to sea transport, exploration of ocean resources and exploitation, specifically includes: 1. increasing the resistance on naval vessel
Power increases amount of fuel, reduces ship's speed, causes huge economic loss；2. causing oceanographic instrumentation distorted signals, reduced performance very
To instrument failure is caused, block the seawater pipeline on instrument facility；3. causing the Anaerobic Corrosion of metal, shortens ship and use the longevity
Life；4. influencing the security performance of ship, the development and utilization of marine resources and development seriously restrict.Prevent marine biofouling
Most effective means are brushing nonpolluting coatings, but traditional nonpolluting coating is the exudation by poisonous anti-fouling agent, to aufwuch into
To reach antifouling purpose, this method will cause environmental pollution and the mortality of marine organisms, destroy the ecological balance for row poisoning,
Just gradually forbidden by national laws regulation.Therefore, developing low toxicity, efficient anti-fouling material, oneself is extremely urgent.
The chemical composition and microstructure of material surface are to influence the principal element of material anti-pollution.In recent years, it studied
Personnel develop a series of anti-fouling material of nontoxic no releases, mainly pass through the physicochemical properties of control material surface, machine
Tool property and surface texture realize anti-fouling effect to influence the interaction of material surface and protein, microorganism etc..Currently,
Items research achieves impressive progress in marine anti-pollution field, mainly includes following research direction: 1. designing bionical
The epidermal structure or physiological phenomenon of certain marine organisms are imitated in antifouling interface, assign the special surface texture of material or
Performance makes marine organisms be not easy to adhere to or adhere to loosely, to achieve the purpose that prevent marine organisms from adhering to.For example, research people
Member is prepared for a series of people according to the surface textures of the marine organisms such as echinoderm, ocean mammal, scallop, coral is bionical
Work antifouling surface structure.2. change the chemical composition of material surface using the polymer and enzyme etc. with good anti-pollution, from
And make material surface that there is anti-pollution.For example, researcher has synthesized a series of while having had hydrophilic radical (polyvinyl alcohol)
With the ampholyte copolymer of hydrophobic grouping (highly branched fluoropolymer), pass through hydrophobicity and hydrophilic interaction, protein
Or the adhesion between glycoprotein and ampholyte copolymer functionalized surface substantially reduces.However, being stained in complicated marine environment
Biological species are various, and size is different, and the coating only formed with single surface microstructure or single component surface chemistry can only
For being stained for individual species biology, it is difficult to meet the needs of practical antifouling.
It forms polynary act synergistically by constructing surface texture and surface chemistry and the anti-pollution of material can be improved.It is many
Hydrophilic polymer is proved to have good anti-pollution；Hydrophobic polymer object surface can be lower, and having well prevents
The performance of pollution release.Patent of invention ZL 00819633.8 disclose " comprising fiber and the copolymer containing metal from polishing type sea
Fiber is added in anti-fouling paint for foreign anti-fouling paint composition ", the patent of invention, can improve the antifouling of anti-fouling paint to a certain extent
Performance, but in these formulations, the additive amount of fiber is limited, can not form highdensity soft-surface, fiber it is antifouling
It acts on limited.Equal (the Multiscale hairy surfaces for nearly perfect marine of ten thousand phenanthrene
Antibiofouling, J.Mater.Chem.B, 2013,1:3599-3606) with natural dynamic with high density softness wool fibre
Object fur devises a kind of bionical antifouling surface material as template.The antifouling and pollution release of the research, which is tested, to be proved, soft
And the high fiber of density especially in dynamic marine environment, has good antifouling effect in marine environment.This be by
In fiber is made of continuous or discontinuous filament；And soft fiber can be waved constantly in the fluid environment,
Position is unstable, is highly detrimental to the attachment and growth of marine organisms.However, natural animal fur is not only expensive, and
Not seawater corrosion resistance, preparation process poor controllability, therefore do not have the prospect of practical application.
Currently, by hydrophilic polymer and hydrophobic polymer modification in the artificial of the high density softness with good anti-pollution
Fiber surface, preparing the polynary method for cooperateing with antifouling surface material, there is not been reported.
Summary of the invention
The present invention causes the method for atom transfer radical polymerization using surface, in fiber table using spandex fibre as raw material
The copolymer with amphoteric compound structural unit and the structural unit containing capsaicin compound has been modified in face, is prepared for having good
Antifouling and pollution release performance fiber.On the one hand the copolymer has hydrophilic amphoteric compound sulphonic acid betaine methyl
Acrylate structural unit, it is possible to provide good anti-protein sticks and bactericidal property；Another aspect N- (the tertiary fourth of 5- methyl -3-
Base -2- hydroxybenzyl) acrylamide structural unit, the performance sticked and grown with good inhibition fouling organism.
Technical solution of the present invention: sulphonic acid betaine methacrylate-N- (5- methyl -3- tert-butyl -2- hydroxyl benzyl
Base) acrylamide copolymer modification spandex fibre, the structural formula of the spandex fibre are as follows:
Sulphonic acid betaine methacrylate-N- (5- methyl -3- tert-butyl -2- hydroxybenzyl) acrylamide copolymer is repaired
Spandex fibre is adornd, the preparation method used causes Transfer Radical Polymerization for surface；Including the following steps: 1. adopt
With vapour deposition process in the bromo- methylpropanoic acid butyl ester trichlorosilane of spandex fibre surface modification 1-；Existed by the method for vapor deposition
Fiber surface modifies immersion type modification silane idol of the bromo- methylpropanoic acid butyl ester trichlorosilane of 1- as initiator, with conventional solution
The method of connection agent is compared, and vapour deposition process reaction environment exclusion has completely cut off the side reaction of silane coupling agent and water, saved silicon
The dosage of alkane coupling agent；It is more evenly fine and close to the modification of material surface and since gas penetrating power is strong, it is more suitable for modification and exists
Highdensity fiber surface.2. weighing suitable sulphonic acid betaine methacrylate, N- (5- methyl -3- tert-butyl -2- hydroxyl
Benzyl) fiber that 1. obtains of acrylamide, stannous chloride, bipy 2,2' bipyridyl and step.3. by step 2. ready material
The in the mixed solvent of methanol-water is added, is stirred to react 4-12h under the conditions of atmosphere of inert gases protection, 45-55 DEG C of temperature.
4. the fiber after 3. reacting step washs, removal is attached to the solvent of fiber surface to get the ammonia modified to copolymer
Synthetic fibre fiber.Wherein, the reaction equation of step 2. are as follows:
Wherein, step 2. in, according to parts by weight, the spandex fibre be 75~92 parts, the bromo- methylpropanoic acid butyl ester three of 1-
Chlorosilane is 0.025~0.05 part, and sulphonic acid betaine methacrylate is 5~9 parts, the N- (5- methyl -3- tert-butyl -
2- hydroxybenzyl) acrylamide be 7~8 parts, the stannous chloride be 0.025-0.045 part, described 2,2 '-bipyridyls be 0.3
~0.5 part.
Wherein, 3. the volume ratio of first alcohol and water is 0.5-5:1 to step in the Methanol+Water；Step 4. institute
The method for stating washing is to be respectively washed 3-4 times using toluene and acetone.
Sulphonic acid betaine methacrylate-N- (5- methyl -3- tert-butyl -2- hydroxybenzyl) propylene is prepared in the present invention
The reaction mechanism of amide copolymer modification spandex fibre are as follows: by the bromo- methylpropanoic acid butyl ester trichlorine silicon of spandex fibre surface modification 1-
Alkane, stannous chloride and 2,2 '-bipyridyls are catalyst, carry out the atom transition free radical polymerization reaction of surface initiation.The present invention
The thickness of spandex fibre surface modification polymer is accurately controlled using the method for well-controlled radical polymerization, so that the sample of preparation
Product fibre property is uniform, and specification is controllable.
Polynary collaboration antifouling surface material with good anti-pollution, by sulphonic acid betaine methacrylate-N- (5-
Methyl -3- tert-butyl -2- hydroxybenzyl) the obtained material of acrylamide copolymer modification spandex fibre implantation substrate surface.Institute
The technique for being implanted into and using is stated for electrostatic flocking technology, specifically includes the following steps: 1. uniformly brushing in substrate surface to be processed
Resin glue；2. using electrostatic flocking technology by sulphonic acid betaine methacrylate-N- (5- methyl -3- tert-butyl -2- hydroxyl benzyl
Base) acrylamide copolymer modification spandex fibre implantation step 2. prevent to get to good by processed substrate, naturally dry
The polynary collaboration antifouling surface material of dirty performance.A large amount of fiber is implanted into substrate by the innovative method using electrostatic spinning
Surface, can prepare the antifouling surface material with high-density fiber, and this highdensity flexible fibre has good antifouling
Performance.
Wherein, step 2. in, according to parts by weight, resin glue be 11-18 part, spandex fibre be 75-92 parts.
The resin glue is polyacrylic acid ester gum, (ethylene-vinyl acetate copolymer) glue, (acrylonitrile -1,3-butadiene -
Styrol copolymer) glue or (polyethylene terephthalate) glue.The substrate to be processed is aluminium sheet, iron plate, steel plate, pottery
Porcelain, plank, glass, plastic plate or rubber slab；The substrate surface to be processed carries out cleaning treatment in advance, degreases or becomes rusty
Erosion.
Beneficial effects of the present invention:
(1) surfacing prepared by the present invention has the polynary antifouling effect of collaboration simultaneously, in static briny environment and dynamic
Anti-pollution is very superior in briny environment, and has good protective action to multiple dimensioned fouling organism, therefore have very
Broad application prospect；
(2) surfacing substrate prepared by the present invention is applied widely；It is nontoxic and pollution-free, shadow will not be caused to marine environment
It rings,.
Figure of description
Attached drawing 1 is that microalgae in (A) soil resistant fibre surface (B) glass surface sticks form stereoscan photograph.
Specific embodiment
The present invention will be further explained with reference to the examples below.
Embodiment 1:
Sulphonic acid betaine methacrylate-N- (5- methyl -3- tert-butyl -2- hydroxybenzyl) acrylamide copolymer is repaired
Adorn spandex fibre, the structural formula of the spandex fibre are as follows:
Sulphonic acid betaine methacrylate-N- (5- methyl -3- tert-butyl -2- hydroxybenzyl) acrylamide copolymer is repaired
Spandex fibre is adornd, the preparation method used causes Transfer Radical Polymerization for surface；Including the following steps: 1. lead to
It crosses vapour deposition process and modifies the bromo- methylpropanoic acid butyl ester trichlorosilane of 0.027 part of 1- in 78 parts of polyimide polyester fiber surfaces；With
The method of the immersion type modification silane coupling agent of conventional solution is compared, and vapour deposition process reaction environment exclusion has completely cut off silane
The dosage of silane coupling agent has been saved in the side reaction of coupling agent and water；And since gas penetrating power is strong, material surface is repaired
Decorations are more evenly fine and close, are more suitable for modification in highdensity fiber surface.2. weighing 6 parts of sulphonic acid betaine methacrylates, 7
Part-N- (5- methyl -3- tert-butyl -2- hydroxybenzyl) acrylamide, 0.025 part of stannous chloride, 0.4 part of bipy 2,2' bipyridyl, 78
1. fiber that part step is prepared, reaction step is as shown in Eq.1.3. by step, 2. the mixed of first alcohol and water is added in ready material
It closes in solution (volume ratio of first alcohol and water is 2), is stirred to react 4h under the conditions of atmosphere of inert gases protection, 45 DEG C of temperature；④
Fiber methanol and acetone after 3. reacting step are cleaned with water 3 times respectively.
(Eq.1)
Sulphonic acid betaine methacrylate-N- (5- methyl -3- tert-butyl -2- hydroxybenzyl) propylene is prepared in the present invention
The reaction mechanism of amide copolymer modification spandex fibre are as follows: by the bromo- methylpropanoic acid butyl ester trichlorine silicon of spandex fibre surface modification 1-
Alkane, stannous chloride and 2,2 '-bipyridyls are catalyst, carry out the atom transition free radical polymerization reaction of surface initiation.The present invention
The thickness of spandex fibre surface modification polymer is accurately controlled using the method for well-controlled radical polymerization, so that the sample of preparation
Product fibre property is uniform, and specification is controllable.
Polynary collaboration antifouling surface material with good anti-pollution, by sulphonic acid betaine methacrylate-N- (5-
Methyl -3- tert-butyl -2- hydroxybenzyl) the obtained material of acrylamide copolymer modification spandex fibre implantation substrate surface.Institute
The technique for being implanted into and using is stated for electrostatic flocking technology, specifically includes the following steps: 1. surface of steel plate brushing 12 after the pre-treatment
Part polyacrylic acid ester gum, 2. uses electrostatic flocking technology, by 78 parts of sulphonic acid betaine methacrylate-N- (5- methyl -3- uncle
Butyl-2-hydroxy benzyl) acrylamide copolymer modification spandex fibre implant plate surface, naturally dry is to get good to having
The polynary collaboration antifouling surface material of good anti-pollution.A large amount of fiber is implanted into using the method for electrostatic spinning by innovative
Substrate surface, can prepare the antifouling surface material with high-density fiber, and this highdensity flexible fibre has good
Anti-pollution.
Antifouling test: sample is impregnated for 24 hours in distilled water, is then transferred into the artificial seawater of blank and impregnates 1h.Again
It is about 1.2 × 10 that sample, which is respectively put into ulva spores concentration,6In the artificial seawater of a/mL.Every kind of sample is static or dynamic
After placing 1h under state environment, then immersed respectively equipped with being cleaned in brand-new artificial seawater three times, to remove the spore not sticked.It is all
Sample be all briefly exposed in air during flushing.Sticking spore data is according to three groups of parallel samples micro-
30 random fields sticks the average gained of quantity in the mirror visual field.
Embodiment 2:
Unlike the first embodiment, sulphonic acid betaine methacrylate-N- (5- methyl -3- tert-butyl -2- hydroxyl benzyl
Base) acrylamide copolymer modification spandex fibre, it is prepared by the following method: 1. by vapour deposition process in 92 parts of spandexs
Fiber surface modifies the bromo- methylpropanoic acid butyl ester trichlorosilane of 0.025 part of 1-；2. weigh 9 parts of sulphonic acid betaine methacrylates,
Cuprous, 0.45 part of bipy 2,2' bipyridyl, 92 parts are changed in 8 parts of-N- (5- methyl -3- tert-butyl -2- hydroxybenzyl) acrylamides, 0.04
1. fiber that step is prepared, reaction step is as shown in Eq.1；3. by step, 2. the mixing of first alcohol and water is added in ready material
In solution (volume ratio of first alcohol and water is 0.5), 8h is stirred to react under the conditions of atmosphere of inert gases protection, 50 DEG C of temperature；④
Fiber methanol and acetone after 3. reacting step carry out cleaning 4 times respectively.
Polynary collaboration antifouling surface material be by 18 parts of ceramic surface brushing (ethylene-vinyl acetate copolymer) glue,
Using electrostatic flocking technology, by step 4. in the method for 92 parts of fibers implantation ceramic surface handled well be prepared.
Embodiment 3:
Unlike the first embodiment, sulphonic acid betaine methacrylate-N- (5- methyl -3- tert-butyl -2- hydroxyl benzyl
Base) acrylamide copolymer modification spandex fibre, it is prepared by the following method: 1. by vapour deposition process in 80 parts of spandexs
Fiber surface modifies the bromo- methylpropanoic acid butyl ester trichlorosilane of 0.035 part of 1-；2. weigh 5 parts of sulphonic acid betaine methacrylates,
7 parts of-N- (5- methyl -3- tert-butyl -2- hydroxybenzyl) acrylamides, 0.025 part of stannous chloride, 0.3 part of bipy 2,2' bipyridyl,
1. fiber that 80 parts of steps are prepared, reaction step is as shown in Eq.1；3. by step, 2. first alcohol and water is added in ready material
In mixed solution (volume ratio of first alcohol and water is 3), 4h is stirred to react under the conditions of atmosphere of inert gases protection, 55 DEG C of temperature；
4. the fiber toluene and acetone after 3. reacting step carry out cleaning 3 times respectively.
Polynary collaboration antifouling surface material is by 12 parts of printing on surface of rubber plate brushing (acrylonitrile -1,3- butadiene-benzene second
Alkene copolymer) glue, using electrostatic flocking technology, by step 4. in the method system of 80 parts of fibers implantation printing on surface of rubber plate handled well
It is standby to form.
Embodiment 4:
Unlike the first embodiment, sulphonic acid betaine methacrylate-N- (5- methyl -3- tert-butyl -2- hydroxyl benzyl
Base) acrylamide copolymer modification spandex fibre, it is prepared by the following method: 1. by vapour deposition process in 75 parts of spandexs
Fiber surface modifies the bromo- methylpropanoic acid butyl ester trichlorosilane of 0.03 part of 1-；2. weighing 7 parts of sulphonic acid betaine methacrylates, 8
Part-N- (5- methyl -3- tert-butyl -2- hydroxybenzyl) acrylamide, 0.04 part of stannous chloride, 0.3 part of bipy 2,2' bipyridyl, 75
1. fiber that part step is prepared, reaction step is as shown in Eq.1；3. by step, 2. the mixed of first alcohol and water is added in ready material
(volume ratio of first alcohol and water is 0.6, is stirred to react 9h under the conditions of atmosphere of inert gases protection, 52 DEG C of temperature in conjunction solution；④
Fiber methanol and acetone after 3. reacting step carry out cleaning 4 times respectively.
Polynary collaboration antifouling surface material be by 16 parts of board surface brushing (polyethylene terephthalate) glue,
Using electrostatic flocking technology, by step 4. in the method for 75 parts of fibers implantation board surface handled well be prepared.
Embodiment 5:
Unlike the first embodiment, sulphonic acid betaine methacrylate-N- (5- methyl -3- tert-butyl -2- hydroxyl benzyl
Base) acrylamide copolymer modification spandex fibre, it is prepared by the following method: 1. by vapour deposition process in 70 parts of polyamides
The bromo- methylpropanoic acid butyl ester trichlorosilane of 0.04 part of 1- of imine fiber surface modification；2. weighing 6 parts of sulphonic acid betaine methacrylic acids
Ester, 8 parts of-N- (5- methyl -3- tert-butyl -2- hydroxybenzyl) acrylamides, 0.045 part of stannous chloride, 0.5 part of 2,2 '-connection pyrrole
1. fiber that pyridine, 87 parts of steps are prepared, reaction step is as shown in Eq.1；3. by step, 2. first alcohol and water is added in ready material
Mixed solution in (volume ratio of first alcohol and water be 1.5), be stirred to react under the conditions of atmosphere of inert gases protection, 53 DEG C of temperature
10h；4. the fiber methanol and acetone after 3. reacting step carry out cleaning 3 times respectively.
Polynary collaboration antifouling surface material is by 14 parts of polyacrylic acid ester gums of surface of steel plate brushing, using electrostatic spinning
Technique, by step 4. in handle well 70 parts of fibers implantation plastic sheet surface method be prepared.
Embodiment 6:
Unlike the first embodiment, sulphonic acid betaine methacrylate-N- (5- methyl -3- tert-butyl -2- hydroxyl benzyl
Base) acrylamide copolymer modification spandex fibre, it is prepared by the following method: 1. by vapour deposition process in 80 parts of polyamides
The bromo- methylpropanoic acid butyl ester trichlorosilane of 0.05 part of 1- of imine fiber surface modification；2. weighing 8 parts of sulphonic acid betaine methacrylic acids
Ester, 7 parts of-N- (5- methyl -3- tert-butyl -2- hydroxybenzyl) acrylamides, 0.035 part of stannous chloride, 0.3 part of 2,2 '-connection pyrrole
1. fiber that pyridine, 55 parts of steps are prepared, reaction step is as shown in Eq.1；3. by step, 2. first alcohol and water is added in ready material
Mixed solution in (volume ratio of first alcohol and water is 5, is stirred to react under the conditions of atmosphere of inert gases protection, 47 DEG C of temperature
12h；4. the fiber methanol and acetone after 3. reacting step carry out cleaning 3 times respectively.
Polynary collaboration antifouling surface material is by 11 parts of polyacrylic acid ester gums of iron plate external coating, using electrostatic spinning
Technique, by step 4. in handle well 80 parts of fibers implantation glass surface method be prepared.
The antifouling test result of the antifouling surface material of 1. embodiment 1-6 of table preparation
According to above-mentioned test result it is found that the antifouling copolymer modification spandex fibre of polynary collaboration is in dynamic and static seawater
The attachment and growth of ulva spores can be effectively inhibited in environment, and there is good anti-pollution.
Claims (9)
1. sulphonic acid betaine methacrylate-N- (5- methyl -3- tert-butyl -2- hydroxybenzyl) acrylamide copolymer is modified
Spandex fibre, it is characterised in that: the structural formula of the spandex fibre are as follows:
2. sulphonic acid betaine methacrylate-N- (5- methyl -3- tert-butyl -2- hydroxyl benzyl according to claim 1
Base) acrylamide copolymer modification spandex fibre, it is characterised in that: the preparation method used causes atom transfer freedom for surface
Base polymerization.
3. sulphonic acid betaine methacrylate-N- (5- methyl -3- tert-butyl -2- hydroxyl benzyl according to claim 2
Base) acrylamide copolymer modification spandex fibre, it is characterised in that: the preparation method including the following steps: 1. use
Vapour deposition process is in the bromo- methylpropanoic acid butyl ester trichlorosilane of spandex fibre surface modification 1-；2. weighing suitable sulphonic acid betaine
Methacrylate, N- (5- methyl -3- tert-butyl -2- hydroxybenzyl) acrylamide, stannous chloride, bipy 2,2' bipyridyl and
1. fiber that step obtains；3. by step, 2. ready material is added in Methanol+Water, is protected in atmosphere of inert gases
4-12h is stirred to react under the conditions of shield, 45-55 DEG C of temperature；4. the fiber after 3. reacting step washs, removal is attached to
The solvent of fiber surface is to get the spandex fibre modified to copolymer；The reaction equation of the step 2. are as follows:
4. sulphonic acid betaine methacrylate-N- (5- methyl -3- tert-butyl -2- hydroxyl benzyl according to claim 3
Base) acrylamide copolymer modify spandex fibre, it is characterised in that: step 2. in, according to parts by weight, the spandex fibre is
75~92 parts, the bromo- methylpropanoic acid butyl ester trichlorosilane of 1- be 0.025~0.05 part, sulphonic acid betaine methacrylate be 5~
9 parts, N- (5- methyl -3- tert-butyl -2- hydroxybenzyl) acrylamide is 7~8 parts, and the stannous chloride is 0.025-
0.045 part, described 2,2 '-bipyridyls are 0.3~0.5 part.
5. sulphonic acid betaine methacrylate-N- (5- methyl -3- tert-butyl -2- hydroxyl benzyl according to claim 3
Base) acrylamide copolymer modifies spandex fibre, it is characterised in that: step 3. in the Methanol+Water methanol and
The volume ratio of water is 0.5-5:1；4. the method for the washing is to be respectively washed 3-4 times using toluene and acetone to step.
6. the polynary collaboration antifouling surface material with good anti-pollution, it is characterised in that: be prepared by the following method:
1. in the uniform brushing resin glue of substrate surface to be processed；2. using electrostatic flocking technology by sulphonic acid betaine metering system
2. acid esters-N- (5- methyl -3- tert-butyl -2- hydroxybenzyl) acrylamide copolymer modification spandex fibre implantation step processes
Substrate, naturally dry to get to good anti-pollution polynary collaboration antifouling surface material；The sulphonic acid betaine
Methacrylate-N- (5- methyl -3- tert-butyl -2- hydroxybenzyl) acrylamide copolymer modification spandex fibre is prepared as
Transfer Radical Polymerization is caused on surface, specifically: 1. using vapour deposition process in the bromo- first of spandex fibre surface modification 1-
Base butyl propionate trichlorosilane；2. weighing suitable sulphonic acid betaine methacrylate, N- (5- methyl -3- tert-butyl -2- hydroxyl
Base benzyl) fiber that 1. obtains of acrylamide, stannous chloride, bipy 2,2' bipyridyl and step；3. by step 2. ready object
Material is added in Methanol+Water, is stirred to react 4-12h under the conditions of atmosphere of inert gases protection, 45-55 DEG C of temperature；
4. the fiber after 3. reacting step washs, removal is attached to the solvent of fiber surface to get the ammonia modified to copolymer
Synthetic fibre fiber, structural formula are as follows:
7. the preparation method of the polynary collaboration antifouling surface material according to claim 6 with good anti-pollution,
Be characterized in that: according to parts by weight, the resin glue is 11-18 parts, and the spandex fibre is 75-92 parts.
8. the preparation method of the polynary collaboration antifouling surface material according to claim 6 with good anti-pollution,
Be characterized in that: the resin glue is polyacrylic acid ester gum, (ethylene-vinyl acetate copolymer) glue, (acrylonitrile -1,3-butadiene -
Styrol copolymer) glue or (polyethylene terephthalate) glue.
9. the preparation method of the polynary collaboration antifouling surface material according to claim 6 with good anti-pollution,
Be characterized in that: the substrate to be processed is aluminium sheet, iron plate, steel plate, ceramics, plank, glass, plastic plate or rubber slab；It is described
Substrate surface to be processed carries out cleaning treatment in advance, degreases or corrodes.
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| CN102505178A (en) * | 2011-11-10 | 2012-06-20 | 东华大学 | Preparation method for attapulgite nanometer particle polyimide composite fiber |
| CN105040120A (en) * | 2015-06-17 | 2015-11-11 | 天津工业大学 | Method for preparing two-step synthesized polyimide-based micro/nano fibers |
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| CN102505178A (en) * | 2011-11-10 | 2012-06-20 | 东华大学 | Preparation method for attapulgite nanometer particle polyimide composite fiber |
| CN105040120A (en) * | 2015-06-17 | 2015-11-11 | 天津工业大学 | Method for preparing two-step synthesized polyimide-based micro/nano fibers |
Non-Patent Citations (1)
| Title |
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| Surface-initiated Atom-transfer Radical Polymerization from Polyimide Films and Their Anti-fouling Properties;LIANG LI ETAL;《Journal of Macromolecular Science, Part A》;20081231;第829，832页，图1 |
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