CN1266200C - Two-step method of ultraviolet light initiation graft for high molecular material surface - Google Patents
Two-step method of ultraviolet light initiation graft for high molecular material surface Download PDFInfo
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- CN1266200C CN1266200C CN 200310100364 CN200310100364A CN1266200C CN 1266200 C CN1266200 C CN 1266200C CN 200310100364 CN200310100364 CN 200310100364 CN 200310100364 A CN200310100364 A CN 200310100364A CN 1266200 C CN1266200 C CN 1266200C
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Abstract
The present invention relates to a two-step modification method for ultraviolet light initiation graft of a macromolecular material surface, in which ultraviolet light irradiates not on the macromolecular material surface but on the volatilized gas or the inert organic solution of a photosensitizer, and the macromolecular material is put in the volatilized gas of the photosensitizer or soaked in the inert organic solution of the photosensitizer for a free radical reaction to introduce a sleep base. The present invention is implemented in the modes of gas-phase batch process, liquid-phase batch process, gas-phase continuous process, liquid phase continuous process, etc., adopts a hydrogen abstraction-type initiator for the photosensitizer, and is suitable for surface modification on the macromolecular material with polymer chains containing carbon-hydrogen bonds and capable of doing light graft modification. The shapes of the macromolecular material comprise films, coating, fiber, sheets, pipes, particles, profile material or porous media. The present invention realizes the goal of surface modification on the macromolecular material in complicated shapes with a surface light graft method.
Description
Technical field the present invention relates to a kind of method to the modification of polymer surface light, particularly is reflected at polymer surface by the UV-light chemistry and introduces the method for modifying that the dormancy base of radical polymerization carries out graft polymerization.
Background technology the most frequently used macromolecule material surface modification method at present is to adopt chemical process to connect polar side chain, as thermal initiation, UV-light initiation, nuclear radiation and electron beam initiation, microwave initiation, plasma body initiation etc.The surface graft modification method that UV-light causes has following three outstanding characteristics: 1. long wave ultraviolet light is not absorbed by polymkeric substance, but can be absorbed and initiation reaction by light trigger, so can strictly being limited in the surface or the inferior surface of material, graft polymerization carries out, both can reach the purpose of surface modification, the unlikely again performance that influences material body; 2. the light source of ultraviolet radiation and equipment cost are low, are easy to continuous operation; 3. modification performance longer duration.
The surface light crosslinking technology can be divided into single stage method and two step method by technology, is described below respectively:
Single stage method is traditional UV-light initiation grafting method of modifying, the polymer base material of photosensitizers and monomer and preparation modification is together put into reaction system implement modification under the condition of ultraviolet lighting.
Two step method comprises introduces dormancy base step and hot joining branch polymerization procedure, earlier at polymer base material surface-coated photosensitizers solution, under ultraviolet light irradiation, introduce the dormancy base, " activation " dormancy base under illumination or heating condition again, and produce free radical simultaneously, thereby the graft polymerization reaction of trigger monomer carries out modification to the surface of polymer base material.People such as the Sun Yu of Beijing University of Chemical Technology phoenix are at " LDPE/NVP system surface photo-grafting polymerization studies " (Beijing University of Chemical Technology's journal, 1999, reported LDPE/NVP system surface photo-grafting polymerization process 2:17), at first getting the certain density BP/ acetone soln of 10 μ L with microsyringe is injected between two PE films, exhausted air, the control thickness of liquid film is about about 2 μ m.Then the PE film is clipped between two pieces of quartz glass, is placed on the sample table of ultraviolet polymerization reaction unit, take out behind the UV-irradiation certain hour, behind the remaining photosensitizers of acetone flush away, room temperature is dried, and obtains having the LDPE film of photosensitive group.Extracting 10 μ L monomer solutions with microsyringe then is injected between these two PE films that draw photosensitive group, be clipped between two pieces of quartz glass behind the exhausted air again, behind the UV-irradiation certain hour, take out, with 80 ℃ of hot water flush away residual monomers and homopolymer, oven dry.Through the confirmation of Fourier transform infrared spectroscopy and weighting method, N-vinyl pyrrolidone (NVP) has been received LDPE film surface really.
Beijing University of Chemical Technology poplar ten thousand Thailands are at " light-initiated and surface modification " (polymer chemistry, 2001, Chemical Industry Press) in UV-light is caused the surface graft modification technology and carried out comprehensive elaboration, point out that the grafted monomer that is suitable for UV-light initiation surface graft modification comprises all vinyl monomers that can carry out radical polymerization, for example: vinylformic acid, acrylate, acrylate, acrylamide, vinylbenzene, vinylchlorid, vinyl cyanide, vinyl-acetic ester or 4-vinylpridine etc.Be suitable for photosensitizers that UV-light causes surface graft modification and comprise benzophenone (BP) and derivative thereof, some aldehyde, aliphatic ketone, cyclic ketones, aralkyl ketone, quinone, α, beta-diketon, contain the anthrone of stiffening ring structure etc.
Up to now, utilize the surface light grafting that polymer surface is carried out modification and be used for many aspects, not only comprise the wetting ability of improving polymer surface, also have dyeability, cementability, antistatic, wear resistance, preservative property, stability and biocompatibility etc.
At present the report of relevant surface light graft modification generally all think graft reaction can only UV-light can direct irradiation the position take place.Two step method is at place one's entire reliance upon when polymer surface is introduced the dormancy base irradiation of UV-light of the first step, only just have the ability to capture hydrogen atom and combine formation dormancy base again with surface free radical from polymer surface at the position photosensitizers that is subjected to ultraviolet light irradiation, the second step graft polymerization then can only occur in the surface that has formed the dormancy base, can only UV-light can direct irradiation the surface carry out modification.Therefore, be subjected to very big restriction in actual applications.For UV-light can not direct irradiation the position, for example: the endoporus of the internal surface of tubing, the endoporus of porous medium, separatory membrane, have rough surface of complicated shape or the like, owing to can carry out modification in the surface of direct irradiation in UV-light, therefore influenced bulk modified effect.Limited surface light graft modification The Application of Technology greatly.
Summary of the invention the object of the present invention is to provide a kind of polymer surface to light can not direct irradiation the position utilize two step method to introduce the photo-grafting method of modifying of the dormancy base that can continue to cause free radical reaction by photochemical reaction.
Usually with the method for modifying of two step method, comprise following two operation stepss, the first step: under UV-irradiation, on polymer surface, introduce free radical reaction dormancy base by photosensitizers to polymer surface UV-light initiation grafting; Second step: carry out graft polymerization reaction with the inert organic solvent of radical polymerization grafted monomer body, grafted monomer or the aqueous solution of grafted monomer again, promptly obtain the macromolecular material of surface light graft modification, the present invention is in the first step, direct irradiation is not on the polymer surface but be radiated on the volatilization gas of photosensitizers or on the photosensitizers inert organic solvent for UV-light, and macromolecular material places the volatilization gas of photosensitizers or is immersed in the photosensitizers inert organic solvent and carries out free radical reaction and introduce the dormancy base.
The present invention can adopt the gas phase interrupter method that macromolecular material and photosensitizers are put into airtight reaction unit respectively, be provided with baffle plate and photosensitizers groove in the reaction unit, reaction unit is under UV-irradiation, macromolecular material is blocked UV-irradiation by baffle plate, the reaction unit temperature is controlled under the photosensitizers volatilization temperature, the volatilization gas of UV-irradiation photosensitizers is introduced free radical reaction dormancy base at polymer surface.
The present invention can adopt the liquid phase interrupter method that macromolecular material and photosensitizers inert organic solvent are put into airtight reaction unit, be provided with baffle plate in the reaction unit, macromolecular material is immersed in the photosensitizers inert organic solvent, reaction unit is under UV-irradiation, macromolecular material is blocked UV-irradiation by baffle plate, UV-irradiation photosensitizers inert organic solvent is introduced free radical reaction dormancy base at polymer surface.
The present invention can adopt gas phase continuous processing or liquid phase continuous processing, macromolecular material is put into the circulating system device that connects into by UV-light light-transmission tube and silicone tube, in the circulating system device, inject mobile by the photosensitizers volatilization gas of nitrogen gas stream drive or the inert organic solvent of photosensitizers, UV-irradiation is introduced free radical reaction dormancy base at polymer surface on the outer wall of UV-light light-transmission tube.
The UV-light light-transmission tube that the present invention adopts is quartz glass tube, polypropylene tube, polyethylene tube, silicone tube or fluorine plastic tube.
The macromolecular material that is applicable to modification of the present invention is the macromolecular material that can carry out the photo-grafting modification that polymer chain contains C-H.For example: new LDPE (film grade), high density polyethylene(HDPE), cast polypropylene, Biaxially oriented polypropylene film (BOPP), polyethylene terephthalate, polybutylene terephthalate, polymeric amide, polyvinyl chloride, polymethylmethacrylate, polymaleic anhydride, poly-carbon ester or polycaprolactone.The shape of macromolecular material comprises film, coating, fiber, sheet material, tubing, grain material, profiled material or porous medium.
The used photosensitizers of the present invention is the hydrogen-abstraction initiator, for example: benzophenone, 2-isopropyl thioxanthone, xanthone, anthraquinone, dimethyl diketone, benzil or 9-Fluorenone.
The present invention is the novel method that the shaded surface of macromolecular material ultraviolet lighting is handled, the macromolecular material of having introduced free radical reaction dormancy base can add the grafted monomer body or solution carries out the second step graft reaction (also can realize the reaction of second step with the condition of ultraviolet lighting) under heating condition, realize the multifunction of polymer surface, reach and utilize the purpose of surface light grafted method complex-shaped macromolecule material surface modification.The present invention has corrected and has thought that in the past the surface light grafting method only is applicable to the prejudice of the direct irradiation area modification of UV-light, has expanded the range of application of surface light grafting method greatly.And, when carrying out modification with conventional UV-light initiation grafting method since UV-light to the direct irradiation of base material, thereby the excessive crosslinked accelerated material that can cause macromolecular material wears out, and influences the overall performance of material.Adopt the inventive method can overcome above shortcoming, make macromolecular material use properties and work-ing life unaffected, and macromolecular material various piece performance change homogeneous more, help the use of material.
Utilize method of the present invention carrying out the first step when introducing free radical on polymer surface, the macromolecular material that is adopted is that macromolecular material, the photosensitizers that can carry out the photo-grafting modification that polymer chain contains C-H is that hydrogen-abstraction initiator, grafted monomer, ultraviolet source etc. all are technique known.Used photosensitizers is benzophenone, 2-isopropyl thioxanthone, xanthone, anthraquinone, dimethyl diketone, benzil or 9-Fluorenone etc. among the present invention, and other hydrogen-abstraction initiator in addition all can be used as photosensitizers of the present invention and uses.The used ultraviolet source of the present invention is low pressure mercury lamp, medium pressure mercury lamp, high voltage mercury lamp.Gas phase interrupter method, liquid phase interrupter method, gas phase continuous processing or the liquid phase continuous processing that when the first step reaction dormancy base, can adopt the present invention to propose, identical at thereafter the second step graft polymerization and existing known technology.
Description of drawings
Fig. 1 is a gas phase rhythmic reaction schematic representation of apparatus of the present invention;
Fig. 2 is a liquid phase rhythmic reaction schematic representation of apparatus of the present invention;
Fig. 3 is the synoptic diagram of gas phase continuous reaction apparatus of the present invention;
Fig. 4 is the synoptic diagram of liquid phase continuous reaction apparatus of the present invention;
Piece number in above figure is represented: ultraviolet lamp 1, and baffle plate 2, sample rack 3, photosensitizers groove 4, macromolecular material 5, reactive tank 6, UV-light can manage 7 thoroughly, pump 8, ultraviolet lamp box 9, silicone tube 10.
Can implement with gas phase batch process, liquid phase batch process, gas phase continuity method, four kinds of modes of liquid phase continuity method the method that the present invention proposes, these four kinds of modes are described below respectively:
One, gas phase batch process
Gas phase intermittent reaction device as shown in Figure 1, whole device places uviol lamp 1 time. This reaction unit can be made by quartz glass entirely or lower floor is quartz glass plate or other ultraviolet light permeable membrane (such as polypropylene screen) above the simple glass, position on the upper side, middle part at reaction unit arranges a baffle plate 2, baffle plate 2 is that the material that the energy block ultraviolet sees through is made, such as aluminium sheet, simulate the state (such as the inwall of tubing, the inner surface of porous material etc.) that in actual conditions, can not directly be subjected to UV-irradiation owing to the restriction of material shape with baffle plate 2, a sample rack 3 is installed below baffle plate 2, be used for placing the sample of macromolecular material 5, place a sensitising agent groove 4 in the bottom of reaction unit.
Put into respectively on the sample rack 3 macromolecular material 5 and a certain amount of sensitising agent for the treatment of modification and sensitising agent groove 4, the reaction unit temperature is controlled under the sensitising agent volatilization temperature, under ultraviolet lighting, react, reaction certain hour (the too short modification purpose that do not reach of time, time oversize then can be excessively crosslinked, affect the material main body performance) after take out to clean and to dry for subsequent usely, so just finished the step at polymer surface introducing radical reaction dormancy base.
Two, liquid phase batch process
Liquid phase intermittent reaction device as shown in Figure 2, whole device places uviol lamp 1 time. This reaction unit is made by quartz glass or lower floor is quartz glass plate or other ultraviolet light permeable membrane (such as polypropylene screen) above the simple glass, one baffle plate 2 is set in the position on reaction unit top, baffle plate 2 is that the material that the energy block ultraviolet sees through is made, such as aluminium sheet, a sample rack 3 is installed below baffle plate 2 is used for placing macromolecular material 5.
The macromolecular material 5 for the treatment of modification is put on the sample rack 3, the sensitising agent inert organic solvent that reinjects is immersed in wherein macromolecular material fully, inert organic solvents is used acetone, methyl alcohol, absolute ethyl alcohol etc. usually, the reaction unit temperature is controlled at room temperature to the scope of the boiling temperature of organic solvent, under ultraviolet lighting, react, reaction certain hour (the too short modified effect that do not reach of time, time is oversize then cause excessively crosslinked influential to the material main body performance) after take out to clean and dry for subsequent usely, so just finished the step at polymer surface introducing radical reaction dormancy base.
Three, gas phase continuity method
The gas phase continuous reaction apparatus as shown in Figure 3, this reaction unit by silicone tube 10, ultraviolet light can thoroughly manage 7, pump 8, sensitising agent groove 4 and reactive tank 6 connect and consist of the circulatory system, ultraviolet light can manage 7 thoroughly can use quartz glass tube, PA tube or polyethylene pipe etc. Uviol lamp 1 and ultraviolet light can be managed the 7 ultraviolet lamp boxes 9 that place the UV absorption material to make thoroughly, and sensitising agent is heated volatilization and is transported in the circulatory system by pump 8 in sensitising agent groove 4, can thoroughly manage 7 outer wall during reaction with uviol lamp 1 irradiating ultraviolet light.
The macromolecular material 5 for the treatment of modification is put into respectively reactive tank 6 and sensitising agent groove 4 with a certain amount of sensitising agent, system temperature is controlled at the sensitising agent volatilization temperature, can thoroughly manage sensitising agent volatilization gas in 7 with the UV-irradiation ultraviolet light, take out to clean behind the reaction certain hour and dry for subsequent usely, so just finished the step at polymer surface introducing radical reaction dormancy base.
Four, liquid phase continuous processing
The liquid phase continuous reaction apparatus as shown in Figure 4, this reaction unit by silicone tube 10, UV-light can manage 7 thoroughly, pump 8, reactive tank 6 connect and constitute the recycle system, UV-light can manage 7 thoroughly can use quartz glass tube, polypropylene tube or polyethylene tube etc.Ultraviolet lamp 1 and UV-light can be managed the 7 ultraviolet lamp boxes 9 that place the uv-absorbing material to make thoroughly, and photosensitizers is heated volatilization and is transported in the recycle system by pump 8 in photosensitizers groove 4, can manage 7 outer wall during reaction thoroughly with ultraviolet lamp 1 irradiating ultraviolet light.
The macromolecular material 5 for the treatment of modification is put into reactive tank 6, in circulating system, inject the inert organic solvent of photosensitizers again with pump 8, system temperature is controlled at room temperature to the boiling temperature scope of organic solvent, can manage photosensitizers solution system in 7 thoroughly with the UV-irradiation UV-light, take out to clean behind the reaction certain hour and dry standbyly, so just finished step at polymer surface introducing free radical reaction dormancy base.
The sample that above-mentioned four kinds of methods are introduced the macromolecular material 5 of dormancy base is put into the reactive tank 6 that fills grafted monomer body, monomeric organic solution or the monomeric aqueous solution, (the dormancy base of substrate surface can not disconnect when being lower than 80 ℃ in the temperature that is higher than 80 ℃, can not continue to realize the purpose of modification with monomer reaction) reaction down, (reaction times, the oversize material main body performance of then can destroying also may cause a large amount of homopolymerizations of monomer to the reaction certain hour, influence modified effect) the back taking-up, water and acetone clean and water extracting 24h then, dry under the room temperature.So just obtained through surface modification macromolecular material.
Introducing dormancy base and two steps of hot joining branch polymerization can repeatedly repeat in the method for the present invention, thereby also can select for use different grafted monomer to obtain the improvement of many-sided performance around the time to same macromolecular material processing.
Macromolecular material after handling through the inventive method shows that by its dormancy base coupling rate and percentage of grafting graft reaction successfully carries out, and water contact angle obviously reduces before and after the surface modification in addition, show the polymer surface wetting ability be improved significantly.The polymeric particles material is obviously reduced through porosity after the modification, shows that also grafted monomer has been grafted to polymeric particles material internal surface.Select suitable monomer then can meet the demands according to the many-sided needs in the practical application, such as improving water proof oxygen barrier, dyeability, biocompatibility or the like.
Embodiment
In following examples, embodiment 1～13 is the gas phase interrupter method, and embodiment 14～24 is the liquid phase interrupter method, and embodiment 25～33 is the gas phase continuous processing, and embodiment 34～48 is the liquid phase continuous processing.
Embodiment 1
Macromolecular material is new LDPE (film grade) (LDPE) film, and reaction unit as shown in Figure 1.Macromolecular material is used acetone (extracting and washing soln) extracting 48 hours, and room temperature is dried the (Wt that weighs
1).Macromolecular material is put into the reaction unit that 1g benzophenone (BP) powder is housed, macromolecular material is in the ultraviolet lighting shadow positions (shown in Fig. 1, distance D that can irradiation area apart from UV-light is 20cm), logical nitrogen deoxygenation confined reaction device after 1 hour, the reaction unit temperature is controlled under 70 ℃, (power 1000w, the light intensity at λ=254nm place is 4660 μ w/cm with ultraviolet lamp
2) irradiation reaction is after 1 hour, cleans twice with introducing the macromolecular material that can continue to cause radical polymerization dormancy base with acetone, soaks 30 minutes in acetone again, carries out so repeatedly three times, at room temperature dries (the Wt that weighs
2).The macromolecular material of above-mentioned processing is put into acrylic acid aqueous solution (concentration is 10v/v.%) (hot joining branch solution), at N
2Reacted 60 minutes in 90 ℃ under the condition of protection.With reacted macromolecular material water (homopolymer extracted solution) extracting 24 hours, dry with being placed in the air ambient behind the acetone rinsing again, acetone is volatilized fully, (Wt weighs
3), measure the polymer surface water contact angle.Modification the results are shown in table 1, and photosensitizers coupling rate and graft polymerization rate are defined as follows in the table 1:
Dormancy base coupling rate: (Wt
2-Wt
1)/Wt
1* 100%
Graft polymerization rate: (Wt
3-Wt
2)/Wt
1* 100%
Embodiment 2
Reaction unit and operation steps are with embodiment 1.Its difference is: change macromolecular material into polyethylene terephthalate (PET) film.The remaining reaction condition is all with embodiment 1.Modification the results are shown in Table 1.
Embodiment 3
Reaction unit and operation steps are with embodiment 1.Its difference is: change macromolecular material into Biaxially oriented polypropylene film (BOPP) (BOPP) film.The remaining reaction condition is all with embodiment 1.Modification the results are shown in Table 1.
Embodiment 4
Reaction unit and operation steps are with embodiment 1.Its difference is: change macromolecular material into polypropylene non-woven fabric.The remaining reaction condition is all with embodiment 1.Modification the results are shown in Table 1.
Reaction unit and operation steps are with embodiment 1.Its difference is: a. changes macromolecular material into the LDPE film; B. photosensitizers BP is changed to 2-isopropyl thioxanthone (ITX).The remaining reaction condition is all with embodiment 1.Modification the results are shown in Table 1.
Embodiment 6
Reaction unit and operation steps are with embodiment 1.Its difference is: a. changes macromolecular material into high density polyethylene(HDPE) (HDPE) film; B. photosensitizers BP is changed to ITX.The remaining reaction condition is all with embodiment 1.Modification the results are shown in Table 1.
Reaction unit and operation steps are with embodiment 1.Its difference is: a. changes macromolecular material into the BOPP film; B. the second step hot joining branch solution changes acrylamide (AM) aqueous solution (5.0wt%) into.The remaining reaction condition is all with embodiment 1.Modification the results are shown in Table 1.
Reaction unit and operation steps are with embodiment 1.Its difference is: a. changes macromolecular material into the PET film; B. the second step hot joining branch solution changes acrylamide solution (5.0wt%) into.The remaining reaction condition is all with embodiment 1.Modification the results are shown in Table 1.
Embodiment 9
Reaction unit and operation steps are with embodiment 1.Its difference is: a. changes macromolecular material into polypropylene non-woven fabric; B. the second step hot joining branch solution changes acrylamide solution (5.0wt%) into.The remaining reaction condition is all with embodiment 1.Modification the results are shown in Table 1.
Reaction unit and operation steps are with embodiment 1.Its difference is: a. changes macromolecular material into the LDPE film; B. the second step hot joining branch solution changes acrylamide solution (5.0wt%) into.The remaining reaction condition is all with embodiment 1.Modification the results are shown in Table 1.
Embodiment 11
Reaction unit and operation steps are with embodiment 1.Its difference is: a. changes macromolecular material into the BOPP film; B. photosensitizers BP is changed to ITX; C. the second step hot joining branch solution changes pure styrene (ST) into; D. the homopolymer extract changes hexanaphthene into by water behind the second step hot joining branch.The remaining reaction condition is all with embodiment 1.Modification the results are shown in Table 1.
Embodiment 12
Reaction unit and operation steps are with embodiment 1.Its difference is: a. changes macromolecular material into polypropylene non-woven fabric; B. photosensitizers BP is changed to ITX; C. the second step hot joining branch solution changes pure styrene into; D. the homopolymer extract changes hexanaphthene into by water behind the second step hot joining branch.The remaining reaction condition is all with embodiment 1.Modification the results are shown in Table 1.
Embodiment 13
Reaction unit and operation steps are with embodiment 1.Its difference is: a. changes macromolecular material into the HDPE film; B. photosensitizers BP is changed to ITX; C. the second step hot joining branch solution changes pure styrene into; D. the homopolymer extract changes hexanaphthene into by water behind the second step hot joining branch.The remaining reaction condition is all with embodiment 1.Modification the results are shown in Table 1.
Embodiment 14
Macromolecular material is cast polypropylene (CPP) film, and reaction unit as shown in Figure 2.Macromolecular material is used dehydrated alcohol extracting 48 hours, and room temperature is dried the (Wt that weighs
1).Put it in the reaction unit that fills BP ethanol solution (concentration is 2.5wt%), reaction unit is made with silica glass, macromolecular material is in the ultraviolet lighting shadow positions (as shown in Figure 2 when reaction, distance D that can irradiation area apart from UV-light is 20cm), the confined reaction device, (power 1000w, the light intensity at λ=254nm place is 4660 μ w/cm at room temperature to use ultraviolet lamp
2) irradiation reaction will introduce the macromolecular material that can continue to cause radical polymerization dormancy base and clean twice with dehydrated alcohol after 10 minutes, soaked 30 minutes in dehydrated alcohol again, so operation is carried out three times repeatedly, dries (the Wt that weighs under the room temperature
2).The macromolecular material of above-mentioned processing is put into acrylic acid aqueous solution (concentration is 10v/v.%), at N
2Reacted 30 minutes in 90 ℃ under the condition of protection.With reacted macromolecular material water extracting 24 hours, dry with after the dehydrated alcohol flushing macromolecular material being placed in the air ambient again, dehydrated alcohol is volatilized fully, (Wt weighs
3), measure the polymer surface water contact angle.Modification the results are shown in table 2.
Embodiment 15
Reaction unit and operation steps are with embodiment 14.Its difference is: change macromolecular material into the BOPP film.The remaining reaction condition is all with embodiment 14.Modification the results are shown in Table 2.
Embodiment 16
Reaction unit and operation steps are with embodiment 14.Its difference is: change macromolecular material into the PET film.The remaining reaction condition is all with embodiment 14.Modification the results are shown in Table 2.
Embodiment 17
Reaction unit and operation steps are with embodiment 14.Its difference is: change macromolecular material into the LDPE film.The remaining reaction condition is all with embodiment 14.Modification the results are shown in Table 2.
Embodiment 18
Reaction unit and operation steps are with embodiment 14.Its difference is: a. changes macromolecular material into the LDPE film; B. change pretreated extracting of macromolecular material and washings dehydrated alcohol into acetone; C. the BP ethanol solution in the first step reaction is changed into the acetone of BP and the aqueous solution (120ml acetone+80ml water+5gBP); D. the hot joining branch solution with second step changes pure methyl methacrylate (MMA) into; E. the homopolymer extract changes acetone into by water behind the second step hot joining branch.The remaining reaction condition is all with embodiment 14.Modification the results are shown in Table 2.
Embodiment 19
Reaction unit and operation steps are with embodiment 14.Its difference is: a. changes macromolecular material into the PET film; B. change pretreated extracting of macromolecular material and washings dehydrated alcohol into acetone; C. the BP ethanol solution in the first step reaction is changed into the acetone of BP and the aqueous solution (120ml acetone+80ml water+5gBP); D. the hot joining branch solution with second step changes pure methyl methacrylate into; E. the homopolymer extract changes acetone into by water behind the second step hot joining branch.The remaining reaction condition is all with embodiment 14.Modification the results are shown in Table 2.
Embodiment 20
Reaction unit and operation steps are with embodiment 14.Its difference is: a. changes macromolecular material into the HDPE film; B. change pretreated extracting of macromolecular material and washings dehydrated alcohol into acetone; C. the BP ethanol solution in the first step reaction is changed into the acetone of BP and the aqueous solution (120ml acetone+80ml water+5gBP); D. the hot joining branch solution with second step changes pure methyl methacrylate into; E. the homopolymer extract changes acetone into by water behind the second step hot joining branch.The remaining reaction condition is all with embodiment 14.Modification the results are shown in Table 2.
Embodiment 21
Reaction unit and operation steps are with embodiment 14.Its difference is: a. changes macromolecular material into the LDPE film; B. photosensitizers BP is changed to ITX; C. the BP ethanol solution in the first step reaction is changed into the ethanol solution (3.0wt%) of ITX; D. the hot joining branch solution with second step changes pure styrene into; E. the homopolymer extract changes hexanaphthene into by water behind the second step hot joining branch.The remaining reaction condition is all with embodiment 14.Modification the results are shown in Table 2.
Embodiment 22
Reaction unit and operation steps are with embodiment 14.Its difference is: a. changes macromolecular material into the PET film; B. photosensitizers BP is changed to ITX; C. the BP ethanol solution in the first step reaction is changed into the ethanol solution (3.0wt%) of ITX; D. the hot joining branch solution with second step changes pure styrene into; E. the homopolymer extract changes hexanaphthene into by water behind the second step hot joining branch.The remaining reaction condition is all with embodiment 14.Modification the results are shown in Table 2.
Embodiment 23
Reaction unit and operation steps are with embodiment 14.Its difference is: a. changes macromolecular material into the HDPE film; B. photosensitizers BP is changed to ITX; C. the BP ethanol solution in the first step reaction is changed into the ethanol solution (3.0wt%) of ITX; D. the hot joining branch solution with second step changes pure styrene into; E. the homopolymer extract changes hexanaphthene into by water behind the second step hot joining branch.The remaining reaction condition is all with embodiment 14.Modification the results are shown in Table 2.
Embodiment 24
Reaction unit and operation steps are with embodiment 14.Its difference is: change macromolecular material into the PP particle.The remaining reaction condition is all with embodiment 14.Modification the results are shown in Table 2.
Embodiment 25
Macromolecular material is the LDPE film, reaction unit as shown in Figure 3, circulate system by UV-light can manage thoroughly 7 and silicone tube 10 be formed by connecting, UV-light can be managed 7 thoroughly and be used quartz glass tube, pump is that peristaltic pump is the circulation power source.For macromolecular material is used acetone extracting 48 hours, room temperature is dried the (Wt that weighs
1).Put it into the circulating in the reaction unit of 5gBP powder is housed, the logical nitrogen deoxygenation of reaction unit 1 hour, closed cycle system, the reaction unit temperature is controlled under 70 ℃, and (power 8w, the light intensity at λ=254nm place is 4250 μ w/cm with the low pressure ultraviolet lamp
2) one section UV-light in the irradiation cycle reaction unit and the about 100cm of the silicone tube length L place between reactive tank can manage 1 hour thoroughly, to introduce the macromolecular material that can continue to cause radical polymerization dormancy base then cleans twice with acetone, in acetone, soaked 30 minutes again, three times so repeatedly, dry (the Wt that weighs under the room temperature
2).The macromolecular material of above-mentioned processing is put into acrylic acid aqueous solution (concentration is 50v/v.%), at N
2Reacted 60 minutes in 90 ℃ under the condition of protection.The extracting of reacted macromolecular material water was used acetone rinsing after 24 hours, dry in air ambient, acetone is volatilized fully, (Wt weighs
3), measure the polymer surface water contact angle.Modification the results are shown in table 3.
Embodiment 26
Reaction unit and operation steps are with embodiment 25.Its difference is: change macromolecular material into the PET film.The remaining reaction condition is all with embodiment 25.Modification the results are shown in Table 3.
Embodiment 27
Reaction unit and operation steps are with embodiment 25.Its difference is: change macromolecular material into the CPP film.The remaining reaction condition is all with embodiment 25.Modification the results are shown in Table 3.
Embodiment 28
Reaction unit and operation steps are with embodiment 25.Its difference is: change macromolecular material into the BOPP film.The remaining reaction condition is all with embodiment 25.Modification the results are shown in Table 3.
Embodiment 29
Reaction unit and operation steps are with embodiment 25.Its difference is: a. changes macromolecular material into the PP non-woven fabrics; B. the second step hot joining branch solution changes pure styrene into; C. the homopolymer extract changes hexanaphthene into by water behind the second step hot joining branch.The remaining reaction condition is all with embodiment 25.The modification result is referring to table 3.
Embodiment 30
Reaction unit and operation steps are with embodiment 25.Its difference is: a. changes macromolecular material into the HDPE film; B. change photosensitizers BP into ITX; C. the second step hot joining branch solution changes acrylamide solution (5.0wt%) into.The remaining reaction condition is all with embodiment 25.Modification the results are shown in Table 3.
Embodiment 31
Reaction unit and operation steps are with embodiment 25.Its difference is: a. changes macromolecular material into the BOPP film; B. change photosensitizers BP into ITX; C. the second step hot joining branch solution changes acrylamide solution (5.0wt%) into.The remaining reaction condition is all with embodiment 25.Modification the results are shown in Table 3.
Embodiment 32
Reaction unit and operation steps are with embodiment 25.Its difference is: a. changes macromolecular material into the CPP film; B. change photosensitizers BP into ITX; C. the second step hot joining branch solution changes acrylamide solution (5.0wt%) into.The remaining reaction condition is all with embodiment 25.Modification the results are shown in Table 3.
Embodiment 33
Reaction unit and operation steps are with embodiment 25.Its difference is: position that circulation device medium ultraviolet lamp can be shone and the silicone tube length L between reactive tank change 10cm, 25cm, 50cm, 100cm respectively into.The remaining reaction condition is all with embodiment 25.Modification the results are shown in Table 4.
Embodiment 34
Macromolecular material is the CPP film, reaction unit as shown in Figure 4, circulate system by UV-light can manage thoroughly 7 and silicone tube 10 be formed by connecting, UV-light can be managed 7 thoroughly and be used quartz glass tube, pump is that peristaltic pump is the circulation power source.Macromolecular material is used acetone extracting 48 hours, and room temperature is dried the (Wt that weighs
1).Put it into and circulate in the reaction unit, with the acetone of peristaltic pump suction BP in circulation device and the aqueous solution (120ml acetone+80ml water+5gBP), closed cycle system, (power 8w, the light intensity at λ=254nm place is 4250 μ w/cm at room temperature to use the low pressure ultraviolet lamp again
2) can manage thoroughly 1 hour apart from the UV-light at the about 100cm of the silicone tube length L place between reactive tank in the irradiation cycle reaction unit.Clean twice with introducing the macromolecular material that can continue to cause radical polymerization dormancy base with acetone, in acetone, soaked 30 minutes again, three times so repeatedly, dry (the Wt that weighs under the room temperature
2).The above-mentioned macromolecular material of handling is put into acrylic acid aqueous solution (concentration is 50v/v.%), at N
2Reacted 60 minutes in 90 ℃ under the condition of protection.With reacted macromolecular material water extracting 24 hours, dry with behind the acetone rinsing macromolecular material being placed in the air ambient again, acetone is volatilized fully, (Wt weighs
3), measure the polymer surface water contact angle.Modification the results are shown in table 5.
Embodiment 35
Reaction unit and operation steps are with embodiment 34.Its difference is: change macromolecular material into the LDPE film.The remaining reaction condition is all with embodiment 34.Modification the results are shown in Table 5.
Embodiment 36
Reaction unit and operation steps are with embodiment 34.Its difference is: change macromolecular material into the BOPP film.The remaining reaction condition is all with embodiment 34.Modification the results are shown in Table 5.
Embodiment 37
Reaction unit and operation steps are with embodiment 34.Its difference is: change macromolecular material into the PET film.The remaining reaction condition is all with embodiment 34.Modification the results are shown in Table 5.
Embodiment 38
Reaction unit and operation steps are with embodiment 34.Its difference is: a. changes macromolecular material into the BOPP film; B. change pretreated extracting of macromolecular material and washings acetone into methyl alcohol; C. with the acetone of BP in the first step reaction and the methanol solution that the aqueous solution changes BP into (200ml methyl alcohol+5gBP); D. the hot joining branch solution with second step changes pure styrene into; E. the homopolymer extract changes hexanaphthene into by water behind the second step hot joining branch.The remaining reaction condition is all with embodiment 34.Modification the results are shown in Table 5.
Embodiment 39
Reaction unit and operation steps are with embodiment 34.Its difference is: a. changes macromolecular material into the CPP film; B. change pretreated extracting of macromolecular material and washings acetone into methyl alcohol; C. with the acetone of BP in the first step reaction and the methanol solution that the aqueous solution changes BP into (200ml methyl alcohol+5gBP); D. the hot joining branch solution with second step changes pure styrene into; E. the homopolymer extract changes hexanaphthene into by water behind the second step hot joining branch.The remaining reaction condition is all with embodiment 34.Modification the results are shown in Table 5.
Embodiment 40
Reaction unit and operation steps are with embodiment 34.Its difference is: a. changes macromolecular material into the HDPE film; B. change pretreated extracting of macromolecular material and washings acetone into methyl alcohol; C. with the acetone of BP in the first step reaction and the methanol solution that the aqueous solution changes BP into (200ml methyl alcohol+5gBP); D. the hot joining branch solution with second step changes pure styrene into; E. the homopolymer extract changes hexanaphthene into by water behind the second step hot joining branch.The remaining reaction condition is all with embodiment 34.Modification the results are shown in Table 5.
Embodiment 41
Reaction unit and operation steps are with embodiment 34.Its difference is: a. changes macromolecular material into the PET film; B. change pretreated extracting of macromolecular material and washings acetone into methyl alcohol; C. change initiator B P into IXT; D. the methanol solution of BP in the first step reaction is changed into methanol solution (the 200ml methyl alcohol+5gITX) of ITX; E. the hot joining branch solution with second step changes pure methyl methacrylate into; F. the homopolymer extract changes acetone into by water behind the second step hot joining branch.The remaining reaction condition is all with embodiment 34.Modification the results are shown in Table 5.
Embodiment 42
Reaction unit and operation steps are with embodiment 34.Its difference is: a. changes macromolecular material into the LDPE film; B. change pretreated extracting of macromolecular material and washings acetone into methyl alcohol; C. change initiator B P into IXT; D. the methanol solution of BP in the first step reaction is changed into methanol solution (the 200ml methyl alcohol+5gITX) of ITX; E. the hot joining branch solution with second step changes pure methyl methacrylate into; F. the homopolymer extract changes acetone into by water behind the second step hot joining branch.The remaining reaction condition is all with embodiment 34.Modification the results are shown in Table 5.
Embodiment 43
Reaction unit and operation steps are with embodiment 34.Its difference is: a. changes macromolecular material into the CPP film; B. change pretreated extracting of macromolecular material and washings acetone into methyl alcohol; C. change initiator B P into IXT; D. the methanol solution of BP in the first step reaction is changed into methanol solution (the 200ml methyl alcohol+5gITX) of ITX; E. the hot joining branch solution with second step changes pure methyl methacrylate into; F. the homopolymer extract changes acetone into by water behind the second step hot joining branch.The remaining reaction condition is all with embodiment 34.Modification the results are shown in Table 5.
Embodiment 44
Reaction unit and operation steps are with embodiment 34.Its difference is: a. changes macromolecular material into the PP non-woven fabrics; B. change initiator B P into IXT; C. with the acetone of BP in the first step reaction and acetone that the aqueous solution changes ITX into and the aqueous solution (120ml acetone+80ml water+5gITX); E. the hot joining branch solution with second step changes acrylamide solution (5.0wt%) into.The remaining reaction condition is all with embodiment 34.Modification the results are shown in Table 5.
Embodiment 45
Reaction unit and operation steps are with embodiment 34.Its difference is: a. treats that the macromolecular material of modification changes the LDPE film into; B. change initiator B P into IXT; C. with the acetone of BP in the first step reaction and acetone that the aqueous solution changes ITX into and the aqueous solution (120ml acetone+80ml water+5gITX); E. the hot joining branch solution with second step changes acrylamide solution (5.0wt%) into.The remaining reaction condition is all with embodiment 34.Modification the results are shown in Table 5.
Embodiment 46
Reaction unit and operation steps are with embodiment 34.Its difference is: a. changes macromolecular material into the HDPE film; B. change initiator B P into IXT; C. with the acetone of BP in the first step reaction and acetone that the aqueous solution changes ITX into and the aqueous solution (120ml acetone+80ml water+5gITX); E. the hot joining branch solution with second step changes acrylamide solution (5.0wt%) into.The remaining reaction condition is all with embodiment 34.Modification the results are shown in Table 5.
Embodiment 47
Reaction unit and operation steps are with embodiment 34.Its difference is: a. changes macromolecular material into the PP particle; B. change pretreated extracting of macromolecular material and washings acetone into dehydrated alcohol; C. with the acetone of BP in the first step reaction and the ethanol solution that the aqueous solution changes BP into (400ml methyl alcohol+13gBP).The remaining reaction condition is all with embodiment 34.Modification the results are shown in Table 5.
Embodiment 48
Reaction unit and operation steps are with embodiment 34.Its difference is: a. changes macromolecular material into the LDPE film; B. change the position of circulation device medium ultraviolet light irradiation and the silicone tube length L between reactive tank into 10cm, 25cm, 50cm, 100cm, 200cm respectively.The remaining reaction condition is all with embodiment 34.Modification the results are shown in Table 6.
Table 1
| Embodiment | Macromolecular material | Photosensitizers | Grafted monomer | Dormancy base coupling rate (%) | Graft polymerization rate (%) | Water contact angle before the modification (°) | Water contact angle after the modification (°) |
| 1 | The LDPE film | BP | AA | 0.48 | 9.49 | 100±5 | 35±5 |
| 2 | The PET film | BP | AA | 0.09 | 3.64 | 73±5 | 40±5 |
| 3 | The BOPP film | BP | AA | 0.35 | 1.25 | 100±5 | 68±5 |
| 4 | The PP non-woven fabrics | BP | AA | 0.42 | 7.33 | 126±5 | 86±5 |
| 5 | The LDPE film | ITX | AA | 0.18 | 3.64 | 100±5 | 44±5 |
| 6 | The HDPE film | ITX | AA | 0.11 | 1.55 | 107±5 | 39±5 |
| 7 | The BOPP film | BP | AM | 0.32 | 1.22 | 100±5 | 45±5 |
| 8 | The PET film | BP | AM | 0.24 | 2.57 | 73±5 | 36±5 |
| 9 | The PP non-woven fabrics | BP | AM | 0.24 | 5.62 | 126±5 | 71±5 |
| 10 | The LDPE film | BP | AM | 0.68 | 1.19 | 100±5 | 35±5 |
| 11 | The BOPP film | ITX | ST | 0.22 | 9.03 | / | / |
| 12 | The PP non-woven fabrics | ITX | ST | 0.10 | 29.25 | / | / |
| 13 | The HDPE film | ITX | ST | 0.38 | 24.35 | / | / |
Table 2
| Embodiment | Macromolecular material | Photosensitizers | Grafted monomer | Dormancy base coupling rate (%) | Graft polymerization rate (%) | Water contact angle before the modification (°) | Water contact angle after the modification (°) |
| 14 | The CPP film | BP | AA | 0.25 | 1.44 | 99±5 | 82±5 |
| 15 | The BOPP film | BP | AA | 0.03 | 1.63 | 100±5 | 74±5 |
| 16 | The PET film | BP | AA | 0.66 | 1.92 | 73±5 | 53±5 |
| 17 | The LDPE film | BP | AA | 0.24 | 6.87 | 100±5 | 41±5 |
| 18 | The LDPE film | BP | MMA | 0.05 | 3.31 | / | / |
| 19 | The PET film | BP | MMA | 0.84 | 2.68 | / | / |
| 20 | The HDPE film | BP | MMA | 0.03 | 1.18 | / | / |
| 21 | The LDPE film | ITX | ST | 0.11 | 11.25 | / | / |
| 22 | The PET film | ITX | ST | 0.31 | 3.71 | / | / |
| 23 | The HDPE film | ITX | ST | 0.11 | 2.40 | / | / |
| 24 | The PP pellet | BP | AA | 0.25 | 8.69 | Porosity (%) 33.44 before the modification | Porosity after the modification (%) 20.36 |
Table 3
| Embodiment | Macromolecular material | Photosensitizers | Grafted monomer | Dormancy base coupling rate (%) | Graft polymerization rate (%) | Water contact angle before the modification (°) | Water contact angle after the modification (°) |
| 25 | The LDPE film | BP | AA | 0.03 | 67.83 | 100±5 | 23±5 |
| 26 | The PET film | BP | AA | 0.26 | 4.35 | 73±5 | 25±5 |
| 27 | The CPP film | BP | AA | 0.03 | 2.901 | 99±5 | 23±5 |
| 28 | The BOPP film | BP | AA | 0.08 | 1.49 | 100±5 | 46±5 |
| 29 | The PP non-woven fabrics | BP | ST | 0.01 | 3.72 | / | / |
| 30 | The HDPE film | ITX | AM | 0.05 | 1.03 | 107±5 | 49±5 |
| 31 | The BOPP film | ITX | AM | 0.04 | 3.59 | 100±5 | 56±5 |
| 32 | The CPP film | ITX | AM | 0.03 | 1.11 | 99±5 | 51±5 |
Table 4
| L(cm) | Dormancy base coupling rate (%) | Graft polymerization rate (%) | Water contact angle before handling (°) | Water contact angle after handling (°) |
| 10 | 0.13 | 178.02 | 100±5 | 14±5 |
| 25 | 0.10 | 126.77 | 100±5 | 18±5 |
| 50 | 0.05 | 87.63 | 100±5 | 22±5 |
| 100 | 0.03 | 67.83 | 100±5 | 23±5 |
Table 5
| Embodiment | Macromolecular material | Photosensitizers | Grafted monomer | Dormancy base coupling rate (%) | Graft polymerization rate (%) | Water contact angle before the modification (°) | Water contact angle after the modification (°) |
| 34 | The CPP film | BP | AA | 0.08 | 1.94 | 99±5 | 24±5 |
| 35 | The LDPE film | BP | AA | 0.02 | 74.18 | 100±5 | 18±5 |
| 36 | The BOPP film | BP | AA | 0.08 | 1.32 | 100±5 | 36±5 |
| 37 | The PET film | BP | AA | 0.20 | 3.63 | 73±5 | 43±5 |
| 38 | The BOPP film | BP | ST | 0.23 | 1.42 | / | / |
| 39 | The CPP film | BP | ST | 0.26 | 2.85 | / | / |
| 40 | The HDPE film | BP | ST | 0.73 | 2.78 | / | / |
| 41 | The PET film | ITX | MMA | 0.28 | 4.55 | / | / |
| 42 | The LDPE film | ITX | MMA | 0.17 | 3.22 | / | / |
| 43 | The CPP film | ITX | MMA | 0.47 | 3.57 | / | / |
| 44 | The PP non-woven fabrics | ITX | AM | 0.04 | 0.83 | 126±5 | 64±5 |
| 45 | The LDPE film | ITX | AM | 0.24 | 2.45 | 100±5 | 40±5 |
| 46 | The HDPE film | ITX | AM | 0.05 | 2.11 | 107±5 | 58±5 |
| 47 | The PP pellet | BP | AA | 0.10 | 6.02 | Porosity (%) 32.55 before the modification | Porosity after the modification (%) 24.49 |
Table 6:
| L(cm) | Dormancy base coupling rate (%) | Graft polymerization rate (%) | Water contact angle before handling (°) | Water contact angle after handling (°) |
| 10 | 0.18 | 136.44 | 100±5 | 18±5 |
| 25 | 0.15 | 115.58 | 100±5 | 24±5 |
| 50 | 0.09 | 88.96 | 100±5 | 25±5 |
| 100 | 0.02 | 74.18 | 100±5 | 29±5 |
| 200 | 0.01 | 53.67 | 100±5 | 37±5 |
Claims (8)
1, with the method for two step method, comprises following two operation stepss, the first step: under UV-irradiation, on polymer surface, introduce free radical reaction dormancy base by photosensitizers to polymer surface UV-light initiation grafting; Second step: carry out graft polymerization reaction with the inert organic solvent of radical polymerization grafted monomer body, grafted monomer or the aqueous solution of grafted monomer again, promptly obtain the macromolecular material of surface light graft modification, it is characterized in that: in the first step, direct irradiation is not on the polymer surface but be radiated on the volatilization gas of photosensitizers or on the photosensitizers inert organic solvent for UV-light, and macromolecular material places the volatilization gas of photosensitizers or is immersed in the photosensitizers inert organic solvent and carries out free radical reaction and introduce the dormancy base; Macromolecular material is the macromolecular material that can carry out the photo-grafting modification that polymer chain contains C-H; Photosensitizers is the hydrogen-abstraction initiator.
2, method according to claim 1, it is characterized in that: adopt the gas phase interrupter method that macromolecular material and photosensitizers are put into airtight reaction unit respectively, be provided with baffle plate and photosensitizers groove in the reaction unit, reaction unit is under UV-irradiation, macromolecular material is blocked UV-irradiation by baffle plate, the reaction unit temperature is controlled under the photosensitizers volatilization temperature, and the volatilization gas of UV-irradiation photosensitizers is introduced free radical reaction dormancy base at polymer surface.
3, method according to claim 1, it is characterized in that: adopt the liquid phase interrupter method that macromolecular material and photosensitizers inert organic solvent are put into airtight reaction unit, be provided with baffle plate in the reaction unit, macromolecular material is immersed in the photosensitizers inert organic solvent, reaction unit is under UV-irradiation, macromolecular material is blocked UV-irradiation by baffle plate, and UV-irradiation photosensitizers inert organic solvent is introduced free radical reaction dormancy base at polymer surface.
4, method according to claim 1, it is characterized in that: adopt gas phase continuous processing or liquid phase continuous processing, macromolecular material is put into the circulating system device that connects into by UV-light light-transmission tube and silicone tube, in the circulating system device, inject mobile by the photosensitizers volatilization gas of nitrogen gas stream drive or the inert organic solvent of photosensitizers, UV-irradiation is introduced free radical reaction dormancy base at polymer surface on the outer wall of UV-light light-transmission tube.
5, method according to claim 4 is characterized in that: the UV-light light-transmission tube is quartz glass tube, polypropylene tube, polyethylene tube, silicone tube or fluorine plastic tube.
6, method according to claim 1 is characterized in that: macromolecular material is new LDPE (film grade), high density polyethylene(HDPE), cast polypropylene, Biaxially oriented polypropylene film (BOPP), polyethylene terephthalate, polybutylene terephthalate, polymeric amide, polyvinyl chloride, polymethylmethacrylate, polymaleic anhydride, poly-carbon ester or polycaprolactone.
7, according to claim 1,2,3 or 4 described methods, it is characterized in that: the shape of macromolecular material comprises film, coating, fiber, sheet material, tubing, grain material, profiled material or porous medium.
8, according to claim 1,2,3 or 4 described methods, it is characterized in that: photosensitizers is the hydrogen-abstraction initiator: benzophenone, 2-isopropyl thioxanthone, xanthone, anthraquinone, dimethyl diketone, benzil or 9-Fluorenone.
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