CN100526371C - UV-induced polymer surface modifying method - Google Patents
UV-induced polymer surface modifying method Download PDFInfo
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- CN100526371C CN100526371C CNB2006101649306A CN200610164930A CN100526371C CN 100526371 C CN100526371 C CN 100526371C CN B2006101649306 A CNB2006101649306 A CN B2006101649306A CN 200610164930 A CN200610164930 A CN 200610164930A CN 100526371 C CN100526371 C CN 100526371C
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Abstract
This invention relates a polymer's surface modification method by the UV-light induction. In the invention, the acidic water solution of trivalent cerium is used as catalyze-initiation system. Under the condition of UV-light, the superficial light coincidence reaction of saturated multifunctional group of the polymer was initiated, or the superficial light graft polymer of the unsaturated monomer was also initiated. So the superficial performance is improved. The method in this invention is fit for surface modification of many polymers, including polyolefine, aromatic polymer, homopolymer or interpolymer of latex, and other homopolymers or interpolymers. Otherwise, the method has no especial demand of the polymer's shape.
Description
Technical field
The present invention relates to a kind of method of novel UV-light auxiliary treatment polymer surfaces, to improve the surface property of polymkeric substance.
Background technology
Macromolecular material is because the too low and chemical inertness of surface of surface free energy has seriously been limited to its application in the surface and interface field.By improving the surface property of organic polymer material, as cementability organic and inorganic with other, metallic substance, interface compatibility, dyeability, static resistance and biocompatibility etc., thus greatly expand the application of polymkeric substance in extraordinary fields such as printing, dyeing, bonding, obstruct, biology and metal deposition.For example before printing, industrial packaging films such as PE, PP, PVC, PET are carried out surperficial corona treatment with the increase surface free energy usually, thereby be implemented in the purpose of these packing film surface printing patterns; Improve the surface hydrophilicity of PE film by surface modification, thereby prepare durable and can increase substantially the no droplet PE canopy film of agricultural output.
At present, the macromolecule surface modification has developed methods such as to comprise wet oxidation, dry oxidation, corona method, plasma modification, chemical etching, ultraviolet surface graft.Than other surface modifying methods, ultraviolet surface graft has the following advantages: (1) facility investment is little, running cost is low, (2) the reaction conditions gentleness, pollute little, (3) can change surface property by changing monomer and polymerization process at an easy rate, thereby have the constructivity of very strong surface property, (4) are to the performance not damage basically of material main body.Therefore, the UV-light surface modification has obtained extensive studies and concern.The ultraviolet surface graft modification comprises two big class method of modifying of polymerization and coupling process.Polymerization is meant by producing the graft polymerization reaction that free radical causes the vinyl monomer that has different functional groups at polymer surfaces, thereby realizes the purpose of surface modification.Coupling process is to connect with the covalent linkage between the functional molecular by forming polymer surfaces macromole and modification, thereby realizes the purpose of surface modification, and modification comprises the small molecules that has specific functional groups and macromole etc. with functional molecular.
At document 1:European Polymer Journal 1999,35,1557-1568 and document 2:MacromolecularRapid Communication 2004,25, adopt among the 1257-1262 with fragrant ketone, st-yrax class and other alkanoic and ketone and carry out the surface grafting polymerization reaction as light trigger, light triggers such as aromatic ketone are grafted to polymer surfaces with the multiple vinyl-based modified material that has functional group under the effect of irradiation of UV-light.For example document 1 is made light trigger with benzophenone, causes the graft polymerization of vinylformic acid at the BOPP film surface, makes the water contact angle on BOPP film surface be reduced to 78.4 °, and grafting efficiency reaches 58%.These class methods are applicable to multiple vinyl modified material, and easy and simple to handle, and cost is lower, pollute little.But have shortcoming: (1) only is only applicable to the application of vinyl-based modified material, can't be applied to the field of saturated small molecules as modified material; (2) grafting efficiency is not high, and modified effect is limited.
At document 3:Macromolecules 1996,29, among the 7012-7015, introduced a kind of method of carrying out surface modification by the synthetic modified material that has azidophenyl group.In the method, synthesize at first that an end is arranged is that phenylazide group, the other end are the modified material that phosphorylcholine group etc. has property functional group, under the irradiation of UV-light, realize the purpose of surface modification in the surperficial coupled reaction of polymer materials by the phenylazide group of excited state then.Playing advantage is: (1) is with strong points, can construct the surface of specific biological property by the synthetic modified material that has specific functional functional group (as phosphorylcholine, 5-nitrogen dimethylin naphthalene sulfonyl base etc.); (2) modified material exists with micromolecular form, can not exert an influence to the original surface topography of polymer materials.Its shortcoming is that the synthesis step of modification molecule is loaded down with trivial details, is unfavorable for simple operations, thereby causes production cost higher relatively.
Summary of the invention
The objective of the invention is to obtain a kind of method of the new polymer-modified material surface of UV-light, the acidic aqueous solution that promptly uses cerous salt is as the catalysis initiator, under ultraviolet light irradiation, react or cause the surface light graft polymerization of unsaturated monomer (comprising vinyl monomer or acrylic ester monomer) by causing saturated polyfunctional compound (comprising monose, macromole and water miscible molecules such as micromolecular alcohol or amine) at the optical coupling of polymer surfaces, thereby reach the purpose of improving the polymer surfaces performance.The key point of this method is to adopt the acidic solution of cerous salt as the photochemical catalysis initiator system.
Concrete method of modifying is:
A. evenly cover one deck modified solution at the surface of polymer substrates that is modified, modified solution is mainly by catalyst/initiator system, surface modification material and can the catalytic dissolution initiator system and the solvent composition of surface modification material; The surface modification material comprises saturation classes modified material and unsaturated class modified material two big classes; Wherein the mol ratio of catalyst/initiator system and saturation classes modified material is 1:20-10:1, and preferable range is 1:4-4:1; The mol ratio of catalyst/initiator system and unsaturated class modified material is 1:4000-1:20, and preferable range is 1:150-1:30;
B. the above-mentioned polymkeric substance that is coated with the thin layer modified solution is placed on and carries out irradiation under the ultraviolet source, light application time was controlled within 0-30 minute, and preferred light application time was at 3 minutes-15 minutes; Most preferably the time is in 7.5 minutes-12.5 minutes;
C. after the illumination, water is with extracting, and more violent mode washing surfaces such as agitator treating, flushing to remove remaining modified material and catalysis initiator, are removed the water on surface with the organic solvent flushing of less volatile then, and room temperature is dried; Employed organic solvent is acetone, ethanol or methyl alcohol;
The described catalyst/initiator of steps A is the mixture of cerous salt and the pairing acid of acid ion thereof, comprises Ce (NO
3)
3/ HNO
3, Ce
2(SO
4)
3/ H
2SO
4, CeCl
3/ HCl, CeBr
3/ HBr etc., preferred CeCl
3/ HCl.Wherein the concentration of cerous salt is 0.01-0.8mol/L, and preferable range is 0.2-0.6mol/L; The concentration of corresponding acid is for being 0.01-1.0mol/L; Preferable range is 0.1-1.0mol/L.
Saturation classes modification molecule described in the steps A is: (1) water miscible monose: D-fructose, L-sorbose, D-glucose, D-semi-lactosi; (2) water miscible saturated polyfunctional group small molecules: polyvalent alcohol, polyamine etc., for example glycerol, ethylene glycol, trolamine, propylene diamine; (3) functional macromolecule: any one in starch, Mierocrystalline cellulose, polyvinyl alcohol, polyethylene oxide, the polyvinylpyridine etc.Described unsaturated class modification molecule is a vinyl monomer, a kind of as in vinylformic acid, methacrylic acid, methyl methacrylate, methyl acrylate, butyl acrylate, Hydroxyethyl acrylate, vinylbenzene, vinyl acetate between to for plastic, vinyl pyridine, vinyl pyrrolidone or the acrylamide.
The described solvent of steps A is the mixed solvent that organic solvents such as deionized water or deionized water and methyl alcohol, acetone, ethanol or dimethyl sulfoxide (DMSO) are formed.In the mixed solvent of deionized water and above-mentioned organic solvent composition, the volume fraction of water is 15-30%.
The polymeric substrate that is modified is a polyolefine material, the homopolymerization of rubber, copolymerization or blend, aromatic(based)polymer and with the blend and the multipolymer of other polymkeric substance; Material commonly used is high density polyethylene, low density polyethylene (LDPE), cast polypropylene, Biaxially oriented polypropylene film (BOPP), isoprene-isobutylene rubber, styrene-butadiene rubber(SBR), NR/SBR, chlorohydrin rubber, polystyrene; Engineering plastics such as fluoroplastics, polyimide etc.
The shape need of polymer materials is modified: the material surface solution that can be modified evenly covers and can make UV-light shine polymer surfaces with certain intensity, as sheet material, film, these base materials can be the intermingling material of solid polymkeric substance single-material, polymkeric substance, superimposed material or the organic coating on nonmetal or metal species base layer by layer.
The method that makes the surface of polymer substrates that is modified evenly cover one deck modified solution can adopt: " sandwich " structure cladding process (seeing Fig. 1-2), pickling process, spin-coating method, spread coating etc.;
The described ultraviolet source of step B is that low pressure, middle pressure, high voltage mercury lamp or other can be launched the equipment of UV-light wave band, preferably uses high voltage mercury lamp.The ultraviolet light wavelength is in the scope of 200-400nm, and irradiation intensity is at 4000-12000 μ w/cm
2In the scope (is that λ=254nm irradiation intensity is a reference standard with the wavelength).
Key point of the present invention is the trivalent cerium ion used and the photochemical catalysis initiator system of respective acids.The surface modification principle of saturation classes modification molecule is: (1) is oxidized to the quaternary cerium ion thereby the trivalent cerium ion of aqueous phase transits to excited state by hydrogen ion under the irradiation of UV-light; (2) C-H on quadrivalent cerium ion selective oxidation polymeric substrate and the modification molecule generates surface free radical and saturated molecule free radical simultaneously; Between (3) two kinds of free radicals coupling taking place, the modification molecule is fixed to polymer surfaces, thereby reaches the purpose of surface modification.For unsaturated ethylene base class modified material surface modification principle be: the trivalent cerium ion of (1) aqueous phase transits to excited state and is oxidized to the quaternary cerium ion by hydrogen ion under the irradiation of UV-light; (2) C-H of quadrivalent cerium ionic oxide formation surface of polymer substrates generates surface free radical; (3) surface free radical directly causes the polyreaction of vinyl-based modified material, and the modification molecule is fixed to polymer surfaces.
In above-mentioned two kinds of mechanism of modifications, quaternary cerium ion oxidation C-H generates after the free radical, and self all is reduced into tervalent cerium ion, and generates hydrogen ion simultaneously; Can reaction repeated between these two, play the effect that circulation causes.
Unusual effect of the present invention is: with respect to the saturation classes modified material, the surface hydrophilicity of the polymeric substrate after the modification significantly improves.Wherein, the BOPP film of D-fructose modification also has biocompatibility, can adsorb canavaline (ConA).With respect to unsaturated class modified material, the surface hydrophilicity of the polymeric substrate after the modification significantly improves, and the grafting efficiency of system also can reach very high degree.
Range of application of the present invention comprises the following aspects:
One. improve the surface hydrophilicity of polymer materials, specifically be used for: 1. the novel nothing of preparation is dripped type PE canopy film; 2. improve the dyeability of fiber; 3. be used for preparing anti-static fabric; 4. be used to improve the dyeability of collision bumper.
Two. improve the resistance oxygen water preventing ability of polymer surfaces, as be used for preparing novel wrapping material;
Three. improve the cohesiveness of polymer surfaces, as be used for the stacked wrapping material that close of prepared layer, also can be used to improve the viscosifying power between polymer materials and other metal or the non-metallic material;
Four. improve the biocompatibility of polymer surfaces, as be used for preparing the application of the biomaterial of expanding polymer-based carbon at aspects such as bioseparation, bio-carrier, bio-medical materials.
The invention has the advantages that: (1) can obtain good modified effect, and is simple to operate, quick, with low cost, environment is not almost had any pollution; (2) can there be the residue of initiator at the modification substrate surface, do not have adverse influence using the surface property that surface modification produced that small molecules carries out; (3) beginning of modified-reaction and termination have excellent controllability, are applied to the patterned surface field, size and shape that can the regulated at will pattern; (4) compare with the method for other surperficial coupling modification, employed saturated modification molecule simple in structure extensively exists, and do not need to carry out special complicated building-up process.
Description of drawings
Fig. 1-1. be the reaction unit synoptic diagram, Fig. 1-2 is the enlarged view of " sandwich " coating structure
1. ultraviolet source: 2. go up quartz plate, 3. go up film (base material), 4. modified solution 5. descends film (base material), 6. descends quartz plate, 7. lifting table
Fig. 2. the canavaline among the embodiment 8 (ConA) adsorption test
A.BOPP blank film (unmodified processing); B.BOPP absorption ConA film; C.CPP blank film (unmodified processing); D.CPP absorption ConA film;
Embodiment
Below in conjunction with specific embodiment the present invention is described in detail.
Embodiment 1:
With CeCl
3/ HCl is as catalyst/initiator system, and D-fruit grape sugar is modified material, is solvent preparation modified solution with the deionized water.Wherein the concentration of D-fructose is 0.2mol/L, and concentration of hydrochloric acid is 1.0mol/L, CeCl
3Concentration is respectively 0.2mol/L, 0.4mol/L and 0.6mol/L.
With the BOPP film is film up and down, is made into the reactor of " sandwich " structure shown in Fig. 1-2 respectively with the modified solution of above-mentioned three kinds of different concns.In normal temperature environment, use the device shown in Fig. 1-1 to carry out surface modification treatment, be 1000w with power, the light intensity at λ=254nm place is 12000 μ w/cm
2High voltage mercury lamp, light application time are 12.5 minutes.BOPP film after handling with big water gaging flushing, is dipped into then in the deionized water and washed 3 times each 20 minutes under stirring condition earlier, again with acetone rinsing to remove the moisture of surface attachment, be placed on to leave standstill in the air more than 8 minutes acetone volatilized fully.
BOPP film to three kinds of modified solution modifications carries out air/water contact angle (CA) mensuration respectively, and these data are used for the wetting ability on characterize polymers surface, and the more little wetting ability of numerical value is good more.Concrete grammar is: use the OCA20 type contact angle measurement of German Dataphysics instruments company at normal temperatures, get the reading that 1 μ l deionized water writes down the air/water contact angle after vertically dropping on the surface to be measured at once at every turn.Each sample is surveyed 6 points (down together) at least.The results are shown in Table 1.
The wetting ability of three kinds of modified solution modifications of table 1. BOPP film surface changes
Embodiment 2:
With CeCl
3/ HCl is as catalyst/initiator system, and D-fruit grape sugar is modified material, is solvent preparation modified solution with the deionized water.Wherein the concentration of D-fructose is 0.2mol/L, CeCl
3Concentration is 0.4mol/L, and concentration of hydrochloric acid is respectively 0.1mol/L, 1.0mol/L.
Additive method is with embodiment 1.
The air/water contact angle determination of the BOPP film after the modification the results are shown in Table 2.
The hydrophilic variation of modification BOPP film surface under the different concentration of hydrochloric acid conditions of table 2
| Concentration of hydrochloric acid (mol/L) | 0.1 | 1.0 | Water contact angle before the modification |
| Water contact angle after the modification | 64.2° | 43.6° | 107.8° |
Embodiment 3:
Use monose (D-fructose, L-sorbose, D-glucose or D-semi-lactosi) as modified material, with CeCl respectively
3/ HCl is solvent preparation modified solution as catalyst/initiator system with the deionized water.Wherein the concentration of monose is 0.2mol/L, and CeCl3 concentration is 0.4mol/L, and concentration of hydrochloric acid is 1.0mol/L.
Additive method is with embodiment 1.
The air/water contact angle determination of the BOPP film after the modification the results are shown in Table 3.
The hydrophilic variation of the different monose modification of table 3 BOPP film surface
Embodiment 4:
Use glycerol, the saturated small molecules of trolamine as modified material, with CeCl respectively
3/ HCl is solvent preparation modified solution as catalyst/initiator system with the deionized water, and wherein the concentration of glycerol or trolamine is 0.2mol/L, CeCl
3Concentration is 0.4mol/L; Concentration of hydrochloric acid is 1.0mol/L.
The method of ultraviolet light irradiation modification is with embodiment 1.BOPP film after the modification washes with big water gaging earlier, and then carries out extracting with three grades of water and handle; Modification BOPP film after the extracting is all used acetone rinsing, removes the moisture of surface attachment, base material is placed on leaves standstill in the air more than 8 minutes subsequently, and acetone is volatilized fully.
The air/water contact angle determination of the BOPP film after the modification the results are shown in Table 4.
Table 4 glycerol, the hydrophilic variation of trolamine modification BOPP film surface
Use W-Gum, polyvinyl alcohol (1788) as modified material, with CeCl respectively
3/ HCl is solvent preparation modified solution as catalyst/initiator system with the deionized water,
For W-Gum-CeCl
3The modified solution that/HCl forms, W-Gum concentration is 0.5% (m/V), and CeCl3 concentration is 0.2mol/L, and concentration of hydrochloric acid is 1.0mol/L;
For polyvinyl alcohol-CeCl
3The modified solution that/HCl forms, the concentration of polyvinyl alcohol (1788) is 1.0% (m/V), CeCl
3Concentration is 0.2mol/L; Concentration of hydrochloric acid is 1.0mol/L.
Additive method is with embodiment 1.
The air/water contact angle determination of the BOPP film after the modification the results are shown in Table 5.
The variation of the surface hydrophilicity of the BOPP film of table 5 W-Gum, polyvinyl alcohol modification
Embodiment 6
With CeCl
3/ HCl is as catalyst/initiator system, and D-fruit grape sugar is modified material, is solvent preparation modified solution with the deionized water, and wherein the concentration of D-fructose is 0.2mol/L, CeCl
3Concentration is 0.4mol/L, and concentration of hydrochloric acid is 1.0mol/L.
With the BOPP film is last film, base material under with base materials that is modified such as cast polypropylene (CPP), Biaxially oriented polypropylene film (BOPP) (BOPP), low density polyethylene (LDPE) (LDPE) film and high density polyethylene (HDPE) sheet materials being is respectively made " sandwich " structural response device shown in Fig. 1-2.
Method with embodiment 1 is carried out ultraviolet light irradiation modification and aftertreatment.
The measurement result of substrate surface water contact angle of being modified sees Table 6.
The hydrophilic variation of table 6. different substrate materials modification front and rear surfaces
| CPP | BOPP | LDPE | HDPE | |
| Water contact angle before the modification | 105.0° | 107.8° | 104.0° | 99.5° |
| Water contact angle after the modification | 41.7° | 43.6° | 38.4° | 54.3° |
Modified solution is with embodiment 6.
With film on the BOPP film, respectively with hexafluoropropylene (HFP)/tetrafluoroethylene (TFE) copolymerization film (F46) and isoprene-isobutylene rubber (IIR), styrene-butadiene rubber(SBR) (SBR), NR/SBR, chlorohydrin rubber (CHR), polystyrene (PS) sheet material etc. is modified base material for following base material, makes " sandwich " structural response device shown in Fig. 1-2.
Additive method is with embodiment 6.
The measurement result of substrate surface water contact angle of being modified sees Table 6.
The hydrophilic variation of table 7. different substrate materials modification front and rear surfaces
| F46 | PS | IIR | SBR | CHR | NR/SBR | |
| Water contact angle before the modification | 114.2° | 93.4° | 108.5° | 109.7° | 88.1° | 116.8° |
| Water contact angle after the modification | 42.5° | 75.6° | 60.3° | 31.9° | 52.3° | 49.7° |
Embodiment 8
In this embodiment, investigated the surface property degenerate case on modification post polymerization thing surface.Working method is put into 40 ℃ of thermostat containers, the surface contact angle after the mensuration different number of days for the BOPP film after D-fructose among the embodiment 3 is handled.These result of experiment are listed in the table 8.
The research that the polymer surfaces hydrophilicity that table 8. this law is handled is degenerated
| 0(day) | 1(day) | 3(day) | 7(day) | |
| Water contact angle | 43.6° | 43.8° | 55.7° | 57.3° |
Embodiment 9
Modified solution is with embodiment 6.
Respectively with CPP, BOPP film as base material up and down, structure " sandwich " structural response device, and, realize the purpose of patterning at circle hole shape photomask of last film adding.
The method of ultraviolet light irradiation modification is with embodiment 1.
CPP film after the modification and BOPP film be all with big water gaging flushing surface, be dipped into then under stirring condition, wash in the deionized water 3 times each 20 minutes.
Film after the modification in being the phosphate buffer soln (pH=6.86) of fluorescently-labeled canavaline (FITC-ConA) of 3.0ug/ml, concentration is soaked 1hr, and then it is each 15 minutes to be dipped in the phosphate buffer soln of identical pH value agitator treating 3 times, with three grades of water flushings, more than placing 24hr under 4 ℃ of environment, dry at last.Measure the fluorescent effect of substrate surface with the Axiovert 405M type fluorescent microscope of German Carl Zeiss company, the results are shown in accompanying drawing 2.Find out that from accompanying drawing 2 BOPP film and CPP film surface after the modification of D-fructose all can adsorb canavaline (ConA).
Embodiment 10
With CeCl
3/ HCl is as catalyst/initiator system, and vinylformic acid (AA) is modified material, and deionized water is solvent preparation modified solution, wherein CeCl
3Concentration is 0.02mol/L, and acrylic acid concentration is 10% (v/v), and concentration of hydrochloric acid is 1.0mol/L.
With the up and down film (Fig. 1-2) of BOPP film as " sandwich " structural response device.In normal temperature environment, use the device shown in Fig. 1-1 to carry out surface modification treatment, used high voltage mercury lamp power is 1000w, the light intensity at λ=254nm place is 12000 μ w/cm
2, light application time is 5 minutes.BOPP film after the modification is earlier with big water gaging flushing, dries after removing surperficial water with acetone rinsing again, carries out weighing the first time; With three grades of water the BOPP film of modification being carried out extracting then handles, again with acetone rinsing to remove the moisture of surface attachment, being placed on to leave standstill in the air more than 8 minutes volatilizees acetone fully, the air/water contact angle of the BOPP film of measuring, use acetone rinsing BOPP film again, oven dry is carried out weighing the second time, measures the grafting efficiency of grafting system.
Grafting efficiency measuring method: use the BP211D type electronic analytical balance of German Sartorius company to measure the variation of polymeric substrate quality before and after the grafting, by formula G
E=W
g/ W
pCalculate the grafting efficiency of reaction system, wherein G
EThe acute pyogenic infection of finger tip grafting efficiency, W
pBe meant the quality of the polymkeric substance that generates in the polymerization system, comprise graftomer and homopolymer, after removing monomer, record W
gBe meant the quality of graftomer, record after removing monomer and homopolymer simultaneously.
In the present embodiment, the water contact angle of the BOPP film after the AA modification drops to 27.4 °, and grafting efficiency reaches 90.4%.Compare with the method for modifying of mentioning in the document 1, this law has bigger superiority.
Embodiment 11
With CeCl
3/ HCl is as catalyst/initiator system, and vinylformic acid (AA) is solvent preparation modified solution as modified material with the deionized water.Wherein acrylic acid concentration is 10% (v/v), and concentration of hydrochloric acid is 1.0mol/L, CeCl
3Concentration be respectively 0.01mol/L, 0.02mol/L, 0.04mol/L.
Additive method is with embodiment 10.
The air/water contact angle of BOPP film and the measurement result of grafting efficiency see Table 9 after the modification.
The grafting efficiency and the surface hydrophilicity of table 9. modification BOPP film
Embodiment 12
Modified solution is with embodiment 10.
With film on the BOPP film, be following base material with base materials that is modified such as BOPP, LDPE, F46, polyimide (PI) films respectively, make " sandwich " structural response device shown in Fig. 1-2.
Additive method is with embodiment 10.
The air/water contact angle after the base material modification and the measurement result of grafting efficiency of being modified sees Table 10.
The grafting efficiency of BOPP, LDPE, F46, PI and the CPP of table 10.AA modification and the variation of surface hydrophilicity
| BOPP | LDPE | F46 | PI | CPP | |
| Before the CA | 107.8° | 104.4° | 114.2° | 7.2.6° | 105° |
| Behind the CA | 27.6° | 36.6° | 73.2° | 10.3° | 25.4° |
| GE(％) | 90.4 | 75 | 40 | 87.4 | 97.4 |
Embodiment 13
With CeCl
3/ HCl is as catalyst/initiator system, respectively with vinylformic acid (AA), methacrylic acid (MAA) as modified material, be solvent preparation modified solution with the deionized water.CeCl wherein
3Concentration is 0.02mol/L, and the concentration of AA, MAA is 10% (v/v), and concentration of hydrochloric acid is 1.0mol/L.
With the CPP film is film up and down, structure " sandwich " structural response device.
Additive method is with embodiment 10.
The air/water contact angle of CPP film and the measurement result of grafting efficiency see Table 11 after the modification.
Table 11.AA and the grafting efficiency of MAA modification CPP film and the variation of surface hydrophilicity
Embodiment 14
With CeCl
3/ HCI is as catalyst/initiator system, respectively with senecioate-hydroxyl ethyl ester (HEA), butyl acrylate (BA), vinylbenzene (St) as modified material, the mixed solvent of preparing by the volume ratio of 20:80 with deionized water and methyl alcohol is solvent preparation modified solution, wherein CeCl
3Concentration is 0.02mol/L, and the concentration of HEA, BA and St is 10% (v/v), and the concentration of aqueous phase hydrochloric acid is 1.0mol/L.
With the CPP film is film up and down, structure " sandwich " structural response device.
The ultraviolet light irradiation method of modifying is with embodiment 10.
The measurement result of the grafting efficiency of CPP film sees Table 12 after the modification.
The grafting efficiency of table 12.HEA, BA and St modification CPP film
| HEA | BA | St | |
| GE(％) | 34.8 | 35.0 | 30.3 |
Embodiment 15
With CeCl
3/ HCl is modified material as catalyst/initiator system with methyl methacrylate (MMA), and the mixed solvent of volume ratio preparation of pressing 20:80 with deionized water and acetone is as solvent, MMA-CeCl
3In the modified solution that/HCl forms, CeCl
3Concentration is 0.02mol/L, and the concentration of MMA is 10% (v/v), and the concentration of aqueous phase hydrochloric acid is 1.0mol/L.
Additive method is with embodiment 14.
The grafting efficiency of CPP film is 43.8% after the modification.
Claims (7)
1. UV-induced polymer surface modifying method, concrete steps are as follows:
A. evenly cover one deck modified solution at the surface of polymer substrates that is modified, modified solution is mainly by catalyst/initiator system, surface modification material and can the catalytic dissolution initiator system and the solvent composition of surface modification material; The surface modification material comprises saturation classes modified material and unsaturated class modified material two big classes; Wherein the mol ratio of catalyst/initiator system and saturation classes modified material is 1:20-10:1, and the mol ratio of catalyst/initiator system and unsaturated class modified material is 1:4000-1:20;
Described saturation classes modified material is: a kind of in water miscible monose, glycerol, ethylene glycol, trolamine, propylene diamine, starch, Mierocrystalline cellulose, polyvinyl alcohol, polyethylene oxide, the polyvinylpyridine;
Described unsaturated class modified material is a kind of in vinylformic acid, methacrylic acid, methyl methacrylate, methyl acrylate, butyl acrylate, Hydroxyethyl acrylate, vinylbenzene, vinyl acetate between to for plastic, vinyl pyridine, vinyl pyrrolidone or the acrylamide;
Described catalyst/initiator is the mixture of cerous salt and the pairing acid of acid ion thereof, is Ce (NO
3)
3/ HNO
3, Ce
2(SO
4)
3/ H
2SO
4, CeCl
3/ HCl, CeBr
3A kind of among the/HBr, the concentration of cerous salt is 0.01-0.8mol/L in the modified solution, the concentration of corresponding acid is 0.01-1.0mol/L;
B. the above-mentioned polymkeric substance that is coated with the thin layer modified solution is placed on and carries out irradiation under the ultraviolet source, light application time was controlled within 3-30 minute;
C. after the illumination, water to remove remaining modified material and catalysis initiator, is removed the water on surface with the organic solvent flushing of less volatile with extracting, agitator treating or the more violent mode washing surface of flushing then, and room temperature is dried.
2. UV-induced polymer surface modifying method according to claim 1, the mol ratio that it is characterized in that described catalyst/initiator system of steps A and saturation classes modified material is 1:4-4:1; The mol ratio of catalyst/initiator system and unsaturated class modified material is 1:150-1:30;
Described catalyst/initiator is CeCl
3/ HCl, wherein CeCl
3Concentration be 0.2-0.6mol/L, the concentration of corresponding acid is 0.1-1.0mol/L;
Described solvent is the mixed solvent of deionized water or deionized water and methyl alcohol, acetone, ethanol or dimethyl sulfoxide (DMSO) composition, and the volume fraction of water is 15-30% in the mixed solvent;
Described water miscible monose is a kind of in D-fructose, L-sorbose, D-glucose or the D-semi-lactosi.
3. UV-induced polymer surface modifying method according to claim 1, it is characterized in that the described polymeric substrate that is modified of steps A is a polyolefine material, the homopolymerization of rubber, copolymerization or blend, aromatic(based)polymer reaches blend and the multipolymer with other polymkeric substance;
The shape of polymer materials of being modified is: the surface energy solution that is modified evenly covers and can make UV-light shine the shape of polymer surfaces with certain intensity.
4. UV-induced polymer surface modifying method according to claim 1 is characterized in that the described polymeric substrate that is modified of steps A is high density polyethylene(HDPE), new LDPE (film grade), cast polypropylene, Biaxially oriented polypropylene film (BOPP), isoprene-isobutylene rubber, styrene-butadiene rubber(SBR), " natural rubber-styrene-butadiene rubber(SBR) blend ", chlorohydrin rubber, polystyrene, fluoroplastics or polyimide;
The shape of polymer materials of being modified is sheet material, film or the organic coating on nonmetal, metal species base.
5. UV-induced polymer surface modifying method according to claim 1 is characterized in that the described mode that makes the surface of polymer substrates that is modified evenly cover one deck modified solution of step B has " sandwich " structure cladding process, pickling process, spin-coating method or spread coating;
Described ultraviolet source is the equipment of low pressure, middle pressure, high voltage mercury lamp or other emission UV-light wave band, and the ultraviolet light wavelength is in the scope of 200-400nm, and irradiation intensity is at 4000-12000 μ w/cm
2In the scope, be that λ=254nm irradiation intensity is a reference standard with the wavelength; Light application time is 3 minutes-15 minutes.
6. UV-induced polymer surface modifying method according to claim 1 is characterized in that the described light application time of step B is 7.5 minutes-12.5 minutes.
7. UV-induced polymer surface modifying method according to claim 1 is characterized in that the described volatile organic solvent of step C is acetone, ethanol or methyl alcohol.
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| CN102199307A (en) * | 2011-04-11 | 2011-09-28 | 北京化工大学 | Method for promoting ultraviolet light-induced hydrophilic modification of surfaces of fluoroplastics |
| CN104611926B (en) * | 2014-12-30 | 2017-02-01 | 中国地质大学（武汉） | Method for preparing ion exchange fiber by ultraviolet grafting |
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| CN107898651A (en) * | 2017-11-09 | 2018-04-13 | 苏州宝丽洁日化有限公司 | A kind of acrylamide organosilicon bi-quaternary ammonium salt grafted nonwoven fabric wet tissue and preparation method thereof |
| CN109631957A (en) * | 2019-01-14 | 2019-04-16 | 南方科技大学 | A kind of stretchable hypersensitive electronic skin and its preparation method and application |
| CN114015106A (en) * | 2021-10-25 | 2022-02-08 | 哈尔滨理工大学 | Organic small molecule graft modified BOPP film and preparation method thereof |
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