CN103304741B - Polypropylene modified functional film and preparation method thereof - Google Patents
Polypropylene modified functional film and preparation method thereof Download PDFInfo
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- CN103304741B CN103304741B CN201310217471.3A CN201310217471A CN103304741B CN 103304741 B CN103304741 B CN 103304741B CN 201310217471 A CN201310217471 A CN 201310217471A CN 103304741 B CN103304741 B CN 103304741B
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Abstract
The invention discloses a polypropylene modified functional film and a preparation method thereof. The preparation method of the polypropylene modified functional film comprises the following steps of: (1) immersing a cleaned polypropylene film in a toluene solution of benzophenone bromoisobutyrate, and airing; and putting the product into a transparent quartz vessel, introducing nitrogen and irradiating with an ultraviolet lamp; (2) extracting with dichloromethane and drying to obtain a polypropylene film with a brominated (-Br) surface; (3) putting the product into a colorimetric tube containing a reaction solvent, adding methacrylic acid or a methacrylate monomer, introducing nitrogen, and adding a visible light initiator tris(2-phenylpyridine) iridium; (4) sealing the colorimetric tube, and performing an irradiation reaction under the light of a fluorescent lamp at normal temperature; and (5) cleaning with deionized water, and washing N,N-dimethylformamide or N,N-dimethylacetamide with pure water; and taking out the product and drying to obtain the polypropylene modified functional film. The preparation method disclosed by the invention improves the hydrophilicity and dirt resistance of the film, has a simple process, and is green and environment-friendly and suitable for industrial production.
Description
Technical field
The present invention relates to a kind of method of entirely light-operated polypropylene screen surface modification and functionalization.
Background technology
In 21 century, separatory membrane can be widely used in water pollutions process, the bionics field of medicaments such as anti-protein absorption and blood compatibility.Membrane separation technique owing to having efficient, environmental protection, energy-conservation and process simple, can realize the characteristic of Automated condtrol thus make it have bright prospects in above each field.Separatory membrane is as the core of membrane technique, and its chemical property and the performance of structure to membrane sepn play decisive role.Polypropylene (PP) has excellent chemical stability, radiation resistance, thermotolerance, ageing resistance and is easy to the advantages such as film forming, therefore obtain the extensive concern of scientific research personnel, be applied to the industries such as chemical industry, electronics, weaving, food, biochemistry by a large amount of.But, because PP surface energy is very low, hydrophobicity is extremely strong, carrying out surface adsorption pollution very easily occurs in sepn process, causing separation performance to decline, cleaning and maintenance cost being strengthened, and limits the application at other field.At present, have the modification direction of PP film: 1. the wetting ability and the biocompatibility that improve film improve film stain resistance and work-ing life; 2. pair PP film carries out functionalization, the use field of expanded film.
Surface graft modification technology, because on the basis not changing material body character, is operated by simple process flow, introduces the Main Means that the advantages such as several functions group become PP membrane modifying.Conventional membrane surface modification technology comprises that chemical conversion treatment modification, film are surface recombination modified, radiation modification and the modification of film chemical grafting treated etc.PP film has good chemically-resistant character, and in chemical conversion treatment modification, reagent is difficult to its bulk reaction, and the physical strength etc. of modification caudacoria can not make bulk properties be affected; Composite modified top coat easily comes off; The matter of utmost importance of chemical grafting treated modification is exactly the controllable growth how realizing chain; Radiation modification utilizes the irradiation of energetic ray or ion not only to produce free radical and monomer polymerization in film surface reaction, and energetic ray can destroy the mechanical property of membrane body equally.In a lot of situation, people adopt high-energy radiation to carry out graft modification to film, not only compromise the physical strength of film self, and very easily self-polymeric reaction occur.Atom transfer radical polymerization (ATRP) is widely used in film grafting field in addition, but due to its reaction process requirement condition higher, have strict ratio requirement to the activity of part and catalyst levels, energy consumption is high, complicated operation.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, a kind of polypropylene modification functional membrane that can improve PP film surface hydrophilicity and improve its stain resistance is provided.
Second object of the present invention is to provide a kind of normal-temperature reaction, low power consuming, environmental protection, is applicable to the preparation method of the polypropylene modification functional membrane that following infant industry is produced.
Technical scheme of the present invention is summarized as follows:
Polypropylene modification functional membrane controls grafting method by complete illumination to be grafted with polymethyl acrylic acid or methacrylate based polymers on the surface at polypropylene screen.
Described methacrylic polymer is selected from polymethylmethacrylate, poly-(polyoxyethylene glycol) methacrylic ester, poly (glycidyl methacrylate), poly-thetine methacrylic ester, poly-2-(dimethylamino) ethylmethyl acrylate, poly-2-(diisopropylaminoethyl) ethylmethyl acrylate, poly-2-(diethylamino) ethylmethyl acrylate, poly-HEMA, poly-3-hydroxy propyl methacrylate, poly-2-hydroxy propyl methacrylate, poly-2, 3-dihydroxypropyl methacrylic ester or polymethyl acrylic acid-2-Glucoamino ethyl ester.
A preparation method for polypropylene modification functional membrane, comprises the steps:
(1) polypropylene screen is cleaned, by the 1cm cleaned up
2-30cm
2it is 5-30min in the toluene solution of 1-200 mg/ml benzophenone base bromo acid ester that polypropylene screen is immersed in concentration, take out, dry, put into transparent quartz apparatus, transparent glass dish or transparent synthetic glass vessel, logical nitrogen 3-60min, then under the condition of logical nitrogen, be the ultraviolet lamp of 254-365nm at wavelength, irradiation distance is under the condition of 5-50cm, irradiates 5-30min;
(2) take out the film after step (1) process with dichloromethane extraction in soxhlet's extractor, take out, 30-80 DEG C of drying, obtains the polypropylene screen of surface-Br base in an oven;
(3) polypropylene screen of surface-Br base is put in the colorimetric cylinder of the reaction solvent containing 10-50mL, add 1-30mL or 1-5g methacrylic acid or methacrylate-based monomer, logical nitrogen 5-180min, add visible light initiator three (2-phenylpyridine) and close iridium 5-100mg, continue logical nitrogen 5-180min, described reaction solvent is DMF or N,N-dimethylacetamide;
(4) colorimetric cylinder is sealed, at normal temperatures, under 40-200w daylight light, irradiate reaction 2-48h;
(5) film after step (4) being processed takes out, after deionized water stirring and washing 1-5 time, and concussion pure water under 15-70 DEG C of water-bath, DMF or N, N N,N-DIMETHYLACETAMIDE washing 6-48h, take out, dry at 30-80 DEG C, namely make polypropylene modification functional membrane.
Described step (1) is preferably: cleaning polypropylene screen, by the 10cm cleaned up
2-20cm
2it is 10-20min in the toluene solution of 10-100 mg/ml benzophenone base bromo acid ester that polypropylene screen is immersed in concentration, take out, dry, put into transparent quartz apparatus, transparent glass dish or transparent synthetic glass vessel, logical nitrogen 10-30min, then under the condition of logical nitrogen, be the ultraviolet lamp of 365nm at wavelength, irradiation distance is under the condition of 10-20cm, irradiates 15min.
The step of the described cleaning polypropylene screen of step (1) is: in 15-70 DEG C of water-bath, polypropylene screen is placed on rinsing 6-48h in cleaning solvent, and every 4-6h changes a cleaning solvent, and described cleaning solvent is analytically pure methyl alcohol, acetone or alcohol.
Described step (2) is preferably: take out the film after step (1) process with dichloromethane extraction in soxhlet's extractor, take out, 50-60 DEG C of drying, obtains the polypropylene screen of surface-Br base in an oven.
Described step (3) is preferably: put in the colorimetric cylinder of the reaction solvent containing 20-30mL by the polypropylene screen of surface-Br base, add 10-20mL or 1-5g methacrylic acid or methacrylate-based monomer, logical nitrogen 10-100min, add visible light initiator three (2-phenylpyridine) and close iridium 10-50mg, continue logical nitrogen 10-100min, described reaction solvent is DMF or N,N-dimethylacetamide.
Described methacrylate-based monomer is methyl methacrylate, polyethylene glycol methacrylate-styrene polymer, glycidyl methacrylate, thetine methacrylic ester, 2-(dimethylamino) ethylmethyl acrylate, 2-(diisopropylaminoethyl) ethylmethyl acrylate, 2-(diethylamino) ethylmethyl acrylate, HEMA, 3-hydroxy propyl methacrylate, 2-hydroxy propyl methacrylate, 2,3-dihydroxypropyl methacrylic esters or methacrylic acid-2-Glucoamino ethyl ester.
Described step (4) is preferably: sealed by colorimetric cylinder, at normal temperatures, irradiates reaction 10-24h under 55-80w daylight light.
Described step (5) is preferably: the film after step (4) being processed takes out, after deionized water stirring and washing 2-3 time, concussion pure water under 25-50 DEG C of water-bath, N, N-dimethylformamide or N, N N,N-DIMETHYLACETAMIDE washing 12-36h, dries at taking out 50-60 DEG C, namely makes polypropylene modification functional membrane.
Advantage of the present invention is on the advantage basis keeping original PP film, improves wetting ability and the stain resistance of film.By the grafting density on light application time controlling diaphragm surface, technique is simple, and environmental protection, is suitable for suitability for industrialized production, by methacrylic acid different in grafting or methacrylate-based monomer and corresponding grafting density.
Accompanying drawing explanation
Fig. 1 is the former film of PP and polypropylene modification functional membrane ATR-IR infared spectrum, wherein:
A is PP former film ATR-IR infared spectrum;
B is polypropylene modification functional membrane ATR-IR infared spectrum prepared by embodiment 16;
C is polypropylene modification functional membrane ATR-IR infared spectrum prepared by embodiment 13;
D is polypropylene modification functional membrane ATR-IR infared spectrum prepared by embodiment 18;
E is polypropylene modification functional membrane ATR-IR infared spectrum prepared by embodiment 20.
Fig. 2 is the full spectrum scintigram of the former film of PP and polypropylene modification functional membrane, wherein:
A is that the former film of PP composes scintigram entirely;
B is the full spectrum scintigram of polypropylene modification functional membrane prepared by embodiment 16;
C is that polypropylene modification functional membrane prepared by embodiment 13 composes scintigram entirely;
D is the full spectrum scintigram of polypropylene modification functional membrane prepared by embodiment 18;
E is the full spectrum scintigram of polypropylene modification functional membrane prepared by embodiment 20.
Fig. 3 is that the former film of PP and polypropylene modification functional membrane C1s compose scintigram, wherein:
A is that the former film C1s of PP composes scintigram;
B is that polypropylene modification functional membrane C1s prepared by embodiment 16 composes scintigram;
C is that polypropylene modification functional membrane C1s prepared by embodiment 13 composes scintigram;
D is that polypropylene modification functional membrane C1s prepared by embodiment 18 composes scintigram;
E is that polypropylene modification functional membrane C1s prepared by embodiment 20 composes scintigram.
Embodiment
The percentage of grafting GY(μ g/cm of film
2) adopt weighting method, shown in the following formula of its calculation formula (1):
Wherein W
0and W (mg)
1(mg) quality before and after membrane modifying is respectively, A (cm
2) be the area of film.
Water contact angle is commonly used to the relative hydropathy judging film surface.The method of tested static water contact angle is adopted to characterize the hydrophilicity with different grafted monomer modifications herein.Contact angle tester model: JYSP-180, originates in the prosperous detecting instrument company limited of Beijing Jin Sheng.
With the resistance to crocking of the method evaluation film of static protein adsorption, working method is as follows:
1, BSA/PBS solution (1L) is prepared
Take NaCl(137mmol, 8.00g), KCl(2.7mmol, 0.20g), Na
2hPO
4(10.0mmol, 1.44g), KH
2pO
4(1.76mmol, 0.24g), BSA (1.00g) dissolves and is settled to 1L, and be mixed with the BSA/PBS solution of 1g/L, the about 7.4(of PH can not preserve for a long time).
2, Staticadsorption experiment step
Polypropylene modification functional membrane prepared by former for PP film and the present invention is cut into 3 × 3cm size, first in PBS solution, infiltrates 30min, put into 100mL Erlenmeyer flask, add in 10mL BSA/PBS, after sealing 30 DEG C of vibration 3h, film is taken out.Test stoste and the rear solution absorbance change of absorption, or weigh after taking-up caudacoria PBS solution wash-out, the weightening finish of the contrast former film of PP and polypropylene modification functional membrane.
3, absorbance measurement
Coomassie brilliant G-250 staining reagent is prepared: taking 100mg Coomassie brilliant G-250, to be dissolved in 50mL volumetric concentration be in the aqueous ethanolic solution of 95%, then add the phosphate aqueous solution that 120mL mass concentration is 85%, is settled to 1L, stand-by (approximately preserving 15d).
Under photometer being placed in 595nm wavelength, zeroing.Get respectively in 0.1mL PBS, liquid to be measured, BSA solution instillation tubule, respectively add 5mL Xylene Brilliant Cyanine G supernatant, vibration shakes up.Do blank solution with PBS liquid, test other sample absorbance values.Contrast standard curve, characterizes the static protein adsorption amount (mg/cm of modified membrane
2).
Below in conjunction with specific embodiment, the present invention is further illustrated.
Embodiment 1
Polypropylene modification functional membrane, this film is grafted with poly-(polyoxyethylene glycol) methacrylic ester by complete illumination control method on the surface at polypropylene screen.
Embodiment 2
Polypropylene modification functional membrane, this film is grafted with polymethylmethacrylate by complete illumination control method on the surface at polypropylene screen.
Embodiment 3
Polypropylene modification functional membrane, this film is grafted with poly (glycidyl methacrylate) by complete illumination control method on the surface at polypropylene screen.
Embodiment 4
Polypropylene modification functional membrane, this film is grafted with poly-thetine methacrylic ester by complete illumination control method on the surface at polypropylene screen.
Embodiment 5
Polypropylene modification functional membrane, this film is grafted with poly-2-(dimethylamino by complete illumination control method on the surface at polypropylene screen) ethylmethyl acrylate.
Embodiment 6
Polypropylene modification functional membrane, this film is grafted with poly-2-(diisopropylaminoethyl by complete illumination control method on the surface at polypropylene screen) ethylmethyl acrylate.
Embodiment 7
Polypropylene alkene modified function film, this film is grafted with poly-2-(diethylamino by complete illumination control method on the surface at polypropylene screen) ethylmethyl acrylate.
Embodiment 8
Polypropylene modification functional membrane, this film is grafted with poly-HEMA by complete illumination control method on the surface at polypropylene screen.
Embodiment 9
Polypropylene modification functional membrane, this film is grafted with poly-3-hydroxy propyl methacrylate by complete illumination control method on the surface at polypropylene screen.
Embodiment 10
Polypropylene modification functional membrane, this film is grafted with poly-2-hydroxy propyl methacrylate by complete illumination control method on the surface at polypropylene screen.
Embodiment 11
Polypropylene modification functional membrane, this film is grafted with poly-2,3-dihydroxypropyl methacrylic esters by complete illumination control method on the surface at polypropylene screen.
Embodiment 12
Polypropylene modification functional membrane, this film is grafted with polymethyl acrylic acid-2-Glucoamino ethyl ester by complete illumination control method on the surface at polypropylene screen.
Embodiment 13
A preparation method for polypropylene modification functional membrane, comprises the steps:
(1) in 25 DEG C of water-baths, polypropylene screen is placed on rinsing 12h in appropriate analytically pure methyl alcohol, every 6h changes once analytically pure methyl alcohol, is 1cm by the area cleaned up
2polypropylene screen to be immersed in concentration be 5min in the toluene solution of 1 mg/ml benzophenone base bromo acid ester, take out, after drying, put into vitreous silica vessel, logical nitrogen 3min, then under the condition of logical nitrogen, 5min is irradiated, irradiation distance 5cm under 312nm ultraviolet lamp;
(2) take out the film after step (1) process with dichloromethane extraction in soxhlet's extractor, take out, 30 DEG C of dryings, obtain the polypropylene screen of surface-Br base in an oven;
(3) polypropylene screen of surface-Br base is put into the N containing 15mL, in dinethylformamide colorimetric cylinder, add polyethylene glycol methacrylate-styrene polymer 7mL, logical nitrogen 5min, then add visible light initiator three (2-phenylpyridine) and close iridium 10mg, continue logical nitrogen 5min;
(4) colorimetric cylinder is sealed, under normal temperature, under 40w daylight light, irradiate reaction 10h;
(5) film step (4) processed takes out, and after deionized water stirring and washing 2 times, under 15 DEG C of water-baths, with pure water concussion washing 12h, dries, namely make polypropylene modification functional membrane at taking out 30 DEG C.
After testing: the polypropylene modification functional membrane film surface water contact angle 68 degree that the present embodiment is made, percentage of grafting is 368 μ g/cm
2, BSA static adsorbance 0.15mg/cm
2.
Embodiment 14
A preparation method for polypropylene modification functional membrane, comprises the steps:
(1) in 15 DEG C of water-baths, polypropylene screen is placed on rinsing 24h in appropriate analytically pure acetone, every 6h changes once analytically pure acetone, is 10cm by the area cleaned up
2polypropylene screen to be immersed in concentration be 15min in the toluene solution of 100 mg/ml benzophenone base bromo acid esters, take out, after drying, put into transparent glass vessels, logical nitrogen 30min, then under the condition of logical nitrogen, 15min is irradiated, irradiation distance 20cm under 312nm ultraviolet lamp;
(2) take out the film after step (1) process with dichloromethane extraction in soxhlet's extractor, take out, 80 DEG C of dryings, obtain the polypropylene screen of surface-Br base in an oven;
(3) polypropylene screen of surface-Br base is put into the N containing 20mL, in the colorimetric cylinder of dinethylformamide, add polyethylene glycol methacrylate-styrene polymer 1mL, logical nitrogen 30min, then add visible light initiator three (2-phenylpyridine) and close iridium 5mg, continue logical nitrogen 100min;
(4) colorimetric cylinder is sealed, under normal temperature, under 80w daylight light, irradiate reaction 24h;
(5) film step (4) processed takes out, and after deionized water stirring and washing 4 times, under 25 DEG C of water-baths, with pure water concussion washing 48h, dries, namely make polypropylene modification functional membrane at taking out 80 DEG C.
After testing: the film film surface water contact angle 54 degree that the present embodiment is made, percentage of grafting is 445 μ g/cm
2, BSA static adsorbance 0.04mg/cm
2.
Embodiment 15
A preparation method for polypropylene modification functional membrane, comprises the steps:
(1) in 70 DEG C of water-baths, polypropylene screen is placed on rinsing 48h in appropriate analytically pure ethanol, every 6h changes once analytically pure ethanol, is 30cm by the area cleaned up
2polypropylene screen to be immersed in concentration be 10min in the toluene solution of 200 mg/ml benzophenone base bromo acid esters, take out, after drying, put into transparent organic glass vessel, logical nitrogen 60min, again under the condition of logical nitrogen, under 254nm ultraviolet lamp, irradiate 30min, irradiation distance 50cm;
(2) take out the film after step (1) process with dichloromethane extraction in soxhlet's extractor, take out, 60 DEG C of dryings, obtain the polypropylene screen of surface-Br base in an oven;
(3) polypropylene screen of surface-Br base is put into the N containing 30mL, in the colorimetric cylinder of N-N,N-DIMETHYLACETAMIDE, add polyethylene glycol methacrylate-styrene polymer 30mL, logical nitrogen 180min, then add visible light initiator three (2-phenylpyridine) and close iridium 75mg, continue logical nitrogen 180min;
(4) colorimetric cylinder is sealed, under normal temperature, under 200w daylight light, irradiate reaction 24h;
(5) film step (4) processed takes out, and after deionized water stirring and washing 5 times, under 50 DEG C of water-baths, with N,N-dimethylacetamide concussion washing 6h, dries, namely make polypropylene modification functional membrane at taking out 60 DEG C.
After testing: the film film surface water contact angle 62 degree that the present embodiment is made, percentage of grafting is 322 μ g/cm
2.
Embodiment 16
A preparation method for polypropylene modification functional membrane, comprises the steps:
(1) in 25 DEG C of water-baths, polypropylene screen is placed on rinsing 6h in appropriate analytically pure methyl alcohol, every 4h changes once analytically pure methyl alcohol, by the 20cm cleaned up
2polypropylene screen to be immersed in concentration be 25min in the toluene solution of 50 mg/ml benzophenone base bromo acid esters, take out, after drying, put into transparent quartz apparatus, logical nitrogen 3min, then under the condition of logical nitrogen, under 365nm ultraviolet lamp, irradiate 5min; Irradiation distance 10cm;
(2) take out the film after step (1) process with dichloromethane extraction in soxhlet's extractor, take out, 50 DEG C of dryings, obtain the polypropylene screen of surface-Br base in an oven;
(3) polypropylene screen of surface-Br base is put into the N containing 50mL, in the colorimetric cylinder of dinethylformamide solution, add methyl methacrylate 7mL, logical nitrogen 10min, then add visible light initiator three (2-phenylpyridine) and close iridium 100mg, continue logical nitrogen 10min;
(4) colorimetric cylinder is sealed, under normal temperature, under 55w daylight light, irradiate reaction 2h;
(5) film step (4) processed takes out, and after deionized water stirring and washing 1 time, under 25 DEG C of water-baths, with DMF concussion washing 12h, dries, namely make polypropylene modification modified function film at taking out 50 DEG C.
After testing: the film surface water contact angle 72 degree that the present embodiment is made, percentage of grafting is 288 μ g/cm
2.
Embodiment 17
A preparation method for polypropylene modification functional membrane, comprises the steps:
(1) in 25 DEG C of water-baths, polypropylene screen is placed on rinsing 12h in appropriate analytically pure methyl alcohol, every 6h changes once analytically pure methyl alcohol, by the 17.34cm cleaned up
2polypropylene screen to be immersed in concentration be 30min in the toluene solution of 50 mg/ml benzophenone base bromo acid esters, take out, after drying, put into vitreous silica vessel, logical nitrogen 3min, then under the condition of logical nitrogen, under 365nm ultraviolet lamp, irradiate 5min, irradiation distance is 5cm;
(2) with embodiment 16 step (2);
(3) polypropylene screen of surface-Br base is put into the N containing 10mL, in the colorimetric cylinder of dinethylformamide, add methacrylic acid-2-Glucoamino ethyl ester 1g, logical nitrogen 10min, then add visible light initiator three (2-phenylpyridine) and close iridium 100mg, continue logical nitrogen 10min;
(4) colorimetric cylinder is sealed, under normal temperature, under 55w daylight light, irradiate reaction 48h;
(5) film step (4) processed takes out, and after deionized water stirring and washing 1 time, under 70 DEG C of water-baths, with DMF concussion washing 36h, dries, namely make polypropylene modification modified function film at taking out 30 DEG C.
After testing: the film surface water contact angle 66 degree that the present embodiment is made, percentage of grafting is 342 μ g/cm
2.
Embodiment 18
A preparation method for polypropylene modification functional membrane, comprises the steps:
(1) in 25 DEG C of water-baths, polypropylene screen is placed on rinsing 12h in appropriate analytically pure methyl alcohol, every 6h changes once analytically pure methyl alcohol, by the 17.34cm cleaned up
2polypropylene screen to be immersed in containing concentration be 15min in the toluene solution of 50 mg/ml benzophenone base bromo acid esters, take out, after drying, put into transparent quartz apparatus, logical nitrogen 3min, again under the condition of logical nitrogen, under 365nm ultraviolet lamp, irradiate 5min, irradiation distance is 5cm;
(2) with embodiment 16 step (2);
(3) polypropylene screen of surface-Br base is put into the N containing 10mL, in the colorimetric cylinder of dinethylformamide solution, add HEMA 20mL, logical nitrogen 10min, then add visible light initiator three (2-phenylpyridine) and close iridium 75mg, continue logical nitrogen 10min;
(4), (5) are with embodiment 16(4), (5).
After testing: the film surface contact angle 58 degree that the present embodiment is made, percentage of grafting is 392 μ g/cm
2, BSA static adsorbance 0.22mg/cm
2.
Embodiment 19
A preparation method for polypropylene modification functional membrane, comprises the steps:
(1) disclose method by embodiment 13 to clean, by the 17.34cm cleaned up polypropylene modification functional membrane
2polypropylene screen be immersed in containing concentration to be 15min in the toluene solution of 50 mg/ml benzophenone base bromo acid esters, after drying, to put into quartz apparatus, logical nitrogen 3min, then under 365nm ultraviolet lamp, irradiate 5min, irradiation distance is 5cm;
(2) take out the film after step (1) process with dichloromethane extraction in soxhlet's extractor, take out, 40 DEG C of dryings, obtain the polypropylene screen of surface-Br base in an oven;
(3)-Br base the polypropylene screen in (2) is put into the N containing 10mL, in the colorimetric cylinder of dinethylformamide solution, add thetine methacrylic ester 5g, logical nitrogen 100min, then add visible light initiator three (2-phenylpyridine) and close iridium 100mg, continue logical nitrogen 10min;
(4), by container sealing, under normal temperature, under 55w daylight light, reaction 24h is irradiated;
(5) film is taken out, after deionized water stirring and washing 3 times, under 25 DEG C of water-baths, with DMF concussion washing 12h, dry at taking out 30 DEG C, namely make polypropylene modification modified function film.
After testing: the film surface contact angle that the present embodiment is made is 48 degree, percentage of grafting is 484 μ g/cm
2, BSA static adsorbance 0.05mg/cm
2.
Embodiment 20
A preparation method for polypropylene modification functional membrane, comprises the steps:
(1) in 25 DEG C of water-baths, polypropylene screen is placed on rinsing 12h in appropriate analytically pure methyl alcohol, every 6h changes once analytically pure methyl alcohol, by the 17.34cm cleaned up
2polypropylene screen to be immersed in containing concentration be 15min in the toluene solution of 50 mg/ml benzophenone base bromo acid esters, take out, after drying, put into vitreous silica vessel, logical nitrogen 3min, then under the condition of logical nitrogen, under 312nm ultraviolet lamp, irradiate 5min, irradiation distance is 5cm;
(2) take out the film after step (1) process with dichloromethane extraction in soxhlet's extractor, take out, 40 DEG C of dryings, obtain the polypropylene screen of surface-Br base in an oven;
(3) polypropylene screen of surface-Br base is put into the N containing 15mL, in the colorimetric cylinder of dinethylformamide solution, add glycidyl methacrylate 6.7mL, logical nitrogen 10min, then add visible light initiator three (2-phenylpyridine) and close iridium 50mg, continue logical nitrogen 10min;
(4), by container sealing, under normal temperature, under 55w daylight light, reaction 12h is irradiated;
(5) film step (4) processed takes out, and after deionized water stirring and washing 3 times, under 25 DEG C of water-baths, with pure water concussion washing 12h, dries, namely make polypropylene modification modified function film at taking out 30 DEG C.
After testing: the film surface contact angle that the present embodiment is made is 56 degree, percentage of grafting is 688 μ g/cm
2.
Through experiment, with methacrylic acid, 2-(dimethylamino) ethylmethyl acrylate, 2-(diisopropylaminoethyl) ethylmethyl acrylate, 2-(diethylamino) ethylmethyl acrylate, 3-hydroxy propyl methacrylate, 2-hydroxy propyl methacrylate or 2,3-dihydroxypropyl methacrylic ester substitutes the glycidyl methacrylate of the present embodiment, the same the present embodiment of other step, also corresponding polypropylene modification functional membrane can be prepared, after testing, its wetting ability and stain resistance all have the raising of higher degree.
Embodiment 21
A preparation method for polypropylene modification functional membrane, comprises the steps:
(1), (2), (3) are with embodiment 20(1), (2), (3).
(4) colorimetric cylinder is sealed, under normal temperature, under 55w daylight light, irradiate reaction 24h;
After testing: the film surface contact angle that the present embodiment is made is 35 degree, percentage of grafting is 1286 μ g/cm
2.
Claims (8)
1. a preparation method for polypropylene modification functional membrane, is characterized in that comprising the steps:
(1) polypropylene screen is cleaned, by the 1cm cleaned up
2-30cm
2it is 5-30min in the toluene solution of 1-200 mg/ml benzophenone base bromo acid ester that polypropylene screen is immersed in concentration, take out, dry, put into transparent quartz apparatus, transparent glass dish or transparent synthetic glass vessel, logical nitrogen 3-60min, then under the condition of logical nitrogen, be the ultraviolet lamp of 254-365nm at wavelength, irradiation distance is under the condition of 5-50cm, irradiates 5-30min;
(2) take out the film after step (1) process with dichloromethane extraction in soxhlet's extractor, take out, 30-80 DEG C of drying, obtains the polypropylene screen of surface-Br base in an oven;
(3) polypropylene screen of surface-Br base is put in the colorimetric cylinder of the reaction solvent containing 10-50mL, add 1-30mL or 1-5g methacrylic acid or methacrylate-based monomer, logical nitrogen 5-180min, add visible light initiator three (2-phenylpyridine) and close iridium 5-100mg, continue logical nitrogen 5-180min, described reaction solvent is DMF or N,N-dimethylacetamide;
(4) colorimetric cylinder is sealed, at normal temperatures, under 40-200w daylight light, irradiate reaction 2-48h;
(5) film after step (4) being processed takes out, after deionized water stirring and washing 1-5 time, concussion pure water under 15-70 DEG C of water-bath, N, N-dimethylformamide or N, N N,N-DIMETHYLACETAMIDE washing 6-48h, take out, dry at 30-80 DEG C, namely make polypropylene modification functional membrane.
2. the preparation method of a kind of polypropylene modification functional membrane according to claim 1, is characterized in that described step (1) is: cleaning polypropylene screen, by the 10cm cleaned up
2-20cm
2it is 10-20min in the toluene solution of 10-100 mg/ml benzophenone base bromo acid ester that polypropylene screen is immersed in concentration, take out, dry, put into transparent quartz apparatus, transparent glass dish or transparent synthetic glass vessel, logical nitrogen 10-30min, then under the condition of logical nitrogen, be the ultraviolet lamp of 365nm at wavelength, irradiation distance is under the condition of 10-20cm, irradiates 15min.
3. the preparation method of polypropylene modification functional membrane according to claim 1 and 2, it is characterized in that the step of the described cleaning polypropylene screen of step (1) is: in 15-70 DEG C of water-bath, polypropylene screen is placed on rinsing 6-48h in cleaning solvent, every 4-6h changes a cleaning solvent, and described cleaning solvent is analytically pure methyl alcohol, acetone or alcohol.
4. the preparation method of a kind of polypropylene modification functional membrane according to claim 1, it is characterized in that described step (2) is: take out the film after step (1) process in soxhlet's extractor with dichloromethane extraction, take out, 50-60 DEG C of drying, obtains the polypropylene screen of surface-Br base in an oven.
5. the preparation method of a kind of polypropylene modification functional membrane according to claim 1, it is characterized in that described step (3) is: put in the colorimetric cylinder of the reaction solvent containing 20-30mL by the polypropylene screen of surface-Br base, add 10-20mL or 1-5g methacrylic acid or methacrylate-based monomer, logical nitrogen 10-100min, add visible light initiator three (2-phenylpyridine) and close iridium 10-50mg, continue logical nitrogen 10-100min, described reaction solvent is N, dinethylformamide or N,N-dimethylacetamide.
6. the preparation method of polypropylene modification functional membrane according to claim 1 or 5, it is characterized in that described methacrylate-based monomer is methyl methacrylate, polyethylene glycol methacrylate-styrene polymer, glycidyl methacrylate, thetine methacrylic ester, 2-(dimethylamino) ethylmethyl acrylate, 2-(diisopropylaminoethyl) ethylmethyl acrylate, 2-(diethylamino) ethylmethyl acrylate, HEMA, 3-hydroxy propyl methacrylate, 2-hydroxy propyl methacrylate, 2, 3-dihydroxypropyl methacrylic ester or methacrylic acid-2-Glucoamino ethyl ester.
7. the preparation method of polypropylene modification functional membrane according to claim 1, is characterized in that described step (4) is: sealed by colorimetric cylinder, at normal temperatures, irradiates reaction 10-24h under 55-80w daylight light.
8. the preparation method of polypropylene modification functional membrane according to claim 1, it is characterized in that described step (5) is: the film after step (4) being processed takes out, after deionized water stirring and washing 2-3 time, concussion pure water under 25-50 DEG C of water-bath, DMF or N, N N,N-DIMETHYLACETAMIDE washing 12-36h, dry at taking out 50-60 DEG C, namely make polypropylene modification functional membrane.
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| CN101307122A (en) * | 2008-06-27 | 2008-11-19 | 北京化工大学 | Light polymerization process for preparing block or graft polymer |
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| CN101307122A (en) * | 2008-06-27 | 2008-11-19 | 北京化工大学 | Light polymerization process for preparing block or graft polymer |
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