CN106519124A - Preparation method of polyvinylidene fluoride membrane material - Google Patents
Preparation method of polyvinylidene fluoride membrane material Download PDFInfo
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- CN106519124A CN106519124A CN201611040494.1A CN201611040494A CN106519124A CN 106519124 A CN106519124 A CN 106519124A CN 201611040494 A CN201611040494 A CN 201611040494A CN 106519124 A CN106519124 A CN 106519124A
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- pvdf
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F259/00—Macromolecular compounds obtained by polymerising monomers on to polymers of halogen containing monomers as defined in group C08F14/00
- C08F259/08—Macromolecular compounds obtained by polymerising monomers on to polymers of halogen containing monomers as defined in group C08F14/00 on to polymers containing fluorine
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/54—Polymerisation initiated by wave energy or particle radiation by X-rays or electrons
Abstract
The invention provides a preparation method of a polyvinylidene fluoride membrane material. The method comprises the steps that irradiation is conducted on polyvinylidene fluoride, and irradiated polyvinylidene fluoride is obtained; and the irradiated polyvinylidene fluoride and ultraviolet light absorbers are subjected to a grafting reaction, and the polyvinylidene fluoride membrane material is obtained, specifically, the ultraviolet light absorbers are selected from one or more of benzophenone and benzotriazole. According to the preparation method, the polyvinylidene fluoride is pre-irradiated, radicals are generated in molecular chains, the specific ultraviolet light absorbers are further triggered to conduct the grafting reaction, the grafting ratio after the reaction is high, reaction operation is easy, and the experiment conditions are easy to control. The ultraviolet light transmittance of the polyvinylidene fluoride membrane material obtained through modification is low, and influences of the adding quantity of the ultraviolet light absorbers to mechanical performance of the PVDF are small.
Description
Technical field
The present invention relates to field of material technology, more particularly, to a kind of preparation method of PVDF membrane material.
Background technology
PVDF is a kind of semi-crystalline fluoropolymers, is widely used in automobile, the energy, aviation, electronics, chemical industry etc.
Field, with excellent processability, fatigue resistance, weatherability, chemical-resistant and excellent electrical and optical property, generally
Use as material protection layer.But the high transparent of pvdf membrane makes its transmitance in ultraviolet-visible light area very high, it is impossible to real
Referring now to the shielding and protection of ultraviolet-sensitive material, the application of its environment out of doors is limited.With UV absorbing properties
Thin film be a kind of functional polymer material with very big application market, ornament materials, packing timber can be widely used in
The fields such as material, dirigible.
Prior art is by adding UV absorbent in the material, it is to avoid macromolecular material by ultraviolet photo damage, degraded,
It is a kind of common method.But small molecule UV absorbent is added directly into material, easily migrates in storing process, ooze
Go out, affected can also loss by extraneous rainwater, light and solvent in use.Therefore it is directly that small molecule is ultraviolet
Inevitably there is migration in blending during light absorbers are added to PVDF, affects material property.
At present, by preparing polymer electrolyte UV absorbent and small molecule UV absorbent being grafted to polymer
Method on molecule is into main trend.Patent CN101096391A describes a kind of system of macromolecule ultraviolet radiation absorbent
Preparation Method, macromolecule prepared by Jing (reverse) atom transfer radical polymerization (ATRP) and equimolar 2,4- dihydroxy hexichol first
Ketone (UV-0) small molecule UV absorbent back flow reaction under conditions of catalyst is obtained the producing high-molecular of Narrow Molecular Weight Distribution
UV absorbent.But, experimental implementation complexity, the condition for preparing polymer electrolyte UV absorbent is harsh；Meanwhile, high purple
Ultraviolet absorbers addition is larger to PVDF Effect on Mechanical Properties.
The content of the invention
In view of this, the technical problem to be solved in the present invention is to provide a kind of preparation side of PVDF membrane material
Method, the PVDF membrane material UV light permeability for preparing of preparation method of the PVDF membrane material that the present invention is provided
Rate is low, and percent grafting is high, and the addition of the method UV absorbent is less to the Effect on Mechanical Properties of PVDF.
The invention provides a kind of preparation method of PVDF membrane material, including：
Irradiation is carried out to Kynoar, the Kynoar after irradiation is obtained；
Kynoar after irradiation and UV absorbent are carried out into graft reaction, PVDF membrane material is obtained；
The UV absorbent is selected from one or more of benzophenone and benzotriazole apoplexy due to endogenous wind.
Preferably, the irradiation is employing60Co- gamma-rays or electron accelerator carry out irradiation.
Preferably, the irradiation dose is 10～30kGy.
Preferably, the Kynoar after the irradiation is (4～10) with the weight ratio of UV absorbent：1.It is preferred that
, the temperature of the graft reaction is 180～240 DEG C.
Preferably, the time of the graft reaction is 2～8min.
Preferably, the graft reaction is specially：After Kynoar just after irradiation is mixed with UV absorbent,
It is placed in graft reaction in banbury or double screw extruder.
Preferably, the benzophenone includes 2- hydroxyls -4 (3- methacryloxy -2- hydroxy propyloxy groups) benzene first
Ketone, 2- acrylic acid -2- (4- benzoyl -3- hydroxyphenoxies) ethyl esters and 2- hydroxyl -4- acryl-oyloxyethoxy benzophenone
In one or more；The benzotriazole include [2- (2- hydroxy-4-methyl acryloxy phenyl) benzotriazole],
RUVA-93 and [2- (2- hydroxyl -4- acryloxy phenyl) benzotriazole], 2- [2- hydroxyl -5- [2- (methacryloxypropyl)
Ethyl] phenyl] -2H- benzotriazole and 2 (2- hydroxy-4-methyl acryloyl group phenyl) the chloro- 2H- benzotriazole of 5- or 2 (2- hydroxyls
Base -4- allyl phenyls) one or more in the chloro- 2H- benzotriazole of 5-.
Compared with prior art, the invention provides a kind of preparation method of PVDF membrane material, including：To poly- inclined
Fluorothene carries out irradiation, obtains the Kynoar after irradiation；Kynoar after irradiation is carried out with UV absorbent
Graft reaction, obtains PVDF membrane material；The UV absorbent is selected from benzophenone and benzotriazole apoplexy due to endogenous wind
One or more.Kynoar is carried out pre-irradiation by the present invention so that is produced free radical in strand, is further caused specific
Ultraviolet absorber carry out graft reaction, there is after reaction higher percent grafting, operation is simple, and experiment condition is easily controlled
System.The modified PVDF membrane material uv transmittance for obtaining of the present invention is low, and the method UV absorbent adds
Dosage is less to the Effect on Mechanical Properties of PVDF.
Description of the drawings
Fig. 1 is the PVDF-g-BPMA film hydrogen nuclear magnetic resonance spectrograms that the embodiment of the present invention 4 is prepared；
Fig. 2 is the PVDF-g-RUVA-93 film hydrogen nuclear magnetic resonance spectrograms that the embodiment of the present invention 8 is prepared；
Gather inclined before polyvinylidene fluoride film and grafting after the reaction that Fig. 3 is prepared for the embodiment of the present invention 4 and embodiment 8
The measure figure of fluorothene；
After the reaction that Fig. 4 is prepared for embodiment 4 and embodiment 8, the UV-vis of polyvinylidene fluoride film passes through spectrogram；
Fig. 5 is UV light permeability before and after PVDF/BPMA composite membranes in comparative example of the present invention 1 and the extracting of PVDF-g-BPMA films
Comparison diagram；
Fig. 6 is the mechanics performance determining result figure of P (MMA-co-BPMA)/PVDF and PVDF-g-BPMA films in comparative example 2,
Wherein, (a) for Different adding amount P (MMA-co-BPMA) and PVDF composite membrane, (b) be different percent graftings PVDF-g-
BPMA films.
Specific embodiment
The invention provides a kind of preparation method of PVDF membrane material, including：
Irradiation is carried out to Kynoar, the Kynoar after irradiation is obtained；
Kynoar after irradiation and UV absorbent are carried out into graft reaction, PVDF membrane material is obtained；
The UV absorbent is selected from one or more of benzophenone and benzotriazole apoplexy due to endogenous wind.
PVDF is a kind of semi-crystalline fluoropolymers, is widely used in automobile, the energy, aviation, electronics, chemical industry etc.
Field, with excellent processability, fatigue resistance, weatherability, chemical-resistant and excellent electrical and optical property, generally
Use as material protection layer.
The present invention is not defined for the source of the Kynoar, commercially available.
The present invention carries out irradiation to Kynoar first, obtains the Kynoar after irradiation.The irradiation is specially：
Kynoar is loaded in bag, pre-irradiation is carried out to which.
In the present invention, the irradiation is preferably adopted60Co- gamma-rays or electron accelerator carry out irradiation；More preferably adopt
With60Co- gamma-rays carry out irradiation.
In the present invention, the irradiation dose is preferably 10～30kGy；More preferably 10～25kGy；Most preferably 10～
15kGy。
The present invention carries out irradiation to Kynoar, obtains the PVDF containing free radical.
Kynoar is carried out after pre-irradiation, the Kynoar after irradiation and UV absorbent are carried out being grafted instead
Should, obtain PVDF membrane material.
It is preferred that after specially mixed the Kynoar after irradiation with UV absorbent, being placed in banbury or twin screw
Graft reaction in extruder, obtains PVDF membrane material.
The temperature of the mixing is preferably 20～40 DEG C, more preferably 25～35 DEG C.The mixing is preferably mechanical agitation
Mixing, the present invention are not defined for the mechanical agitation, alr mode well known to those skilled in the art.The present invention
It is for the concrete model and specification of the banbury or double screw extruder are not defined, well known to those skilled in the art close
Mill or double screw extruder.
In the present invention, the Kynoar after the irradiation is preferably (4～10) with the weight ratio of UV absorbent：
1；More preferably (4～8)：1；Most preferably (4～6)：1；4 are preferably the most：1
In the present invention, the temperature of the graft reaction is preferably 180～240 DEG C；More preferably 180～220 DEG C；It is optimum
Elect 180～200 DEG C as；180～190 DEG C are preferably the most.The time of the graft reaction is preferably 2～8min；More preferably 4
～6min.
In the present invention, the UV absorbent is selected from one or more of benzophenone and benzotriazole apoplexy due to endogenous wind.
The benzophenone includes but is not limited to 2- hydroxyls 4. (3. methacryloxy -2- hydroxy propyloxy groups) benzene first
Ketone (BPMA), 2- acrylic acid 2- (4- benzoyl -3- hydroxyphenoxies) ethyl esters (UV-416) and with 2- hydroxyl -4- acryloyl-oxies
One or more in oxethyl-diphenyl-ketone；The benzotriazole includes but is not limited to [2- (2- hydroxy-4-methyl propylene
Phenyl) benzotriazole] (BDHM), RUVA-93 and [2- (2 '-hydroxyl -4 '-acryloxy phenyl) benzotriazole]
(BDHA), 2- [2- hydroxyl -5- [2- (methacryloxypropyl) ethyl] phenyl] -2H- benzotriazole and 2 (2- hydroxy-4-methyls third
Enoyl- phenyl) one kind in the chloro- 2H- benzotriazole of 5- or 2 (2- hydroxyl -4- allyl phenyls) chloro- 2H- benzotriazole of 5- or
It is various.
After obtaining PVDF membrane material, above-mentioned membrane material is prepared into polyvinylidene fluoride film preferably.The present invention is right
It is not defined in the film-forming process, film-forming process well known to those skilled in the art can preferably be：By blowing
Film forming, casting film-forming or solution film forming technique are prepared.
Film thickness obtained in of the invention is 40 μm or so.
The above-mentioned ultraviolet absorber of the present invention is preferably commercially available, it is furthermore preferred that BPMA is prepared in accordance with the following methods：
By UV-0 (8.56g, 40mmol) and GMA (6.24g, 44mmol) while being put in 250ml three neck round bottom flask, lead to
Nitrogen is protected, and after magneton stirs under room temperature, adds NaOH (0.124g, 3.1mmol) to make catalyst, and 80 DEG C of temperature setting is opened
Begin to heat, stop after leading to condensed water stirring reaction 7h, obtain yellow viscous liquid.Temperature adds toluene dissolving after being down to room temperature,
Washed away after NaOH with 1% dilute sulfuric acid dip of configuration plus MgSO4Stirring 20h, sucking filtration remove MgSO4, filtrate is rotated, obtains sticky
Liquid, using silica gel post separation target product.Eluent is ethyl acetate and petroleum ether, and volume ratio is 1:3.By what is isolated
Yellow crystals are placed in 50 DEG C of vacuum drying ovens and are dried 48h and obtain pure BPMA 8.45g, and yield is 59%.
Weight ratio, specific of the present invention using above-mentioned specific irradiation dose, Kynoar and UV absorbent
The parameters such as reaction temperature, time, the PVDF membrane material percent grafting for finally preparing is high, uv transmittance is low, and
And the addition of the method UV absorbent is less to the Effect on Mechanical Properties of PVDF.Meanwhile, if reaching identical ultraviolet
Assimilation effect, the method have lower addition compared with polymeric UV absorber.Proved by extracting Experimental comparison, this
Method successfully solves the problems, such as the external migration of small molecule UV absorbent.
By controlling reaction condition, realize affects the whole of more serious ultraviolet light to absorb to the present invention on material aging.Keep away
Exempted from solution grafting presence needs expend a large amount of solvents, it is serious for environmental pollution, be difficult to realize that large-scale production etc. is asked
Topic, while avoiding small molecule UV absorbent is added directly into material, the migration that occurs, oozes out in storing process, with
And the problem that loss occurs during use, is affected by extraneous rainwater, light and solvent, effectively solve small molecule ultraviolet
The external migration problem of light absorbers；In addition present invention process is simple, easily operated.
PVDF membrane material of the present invention in the following way to preparing carries out performance measurement：
By chromatography of ions (IC) instrument (ICS-1000 types, Dionex companies of the U.S.) to fluorine element content in PVDF after grafting
Tested, under different condition, reactive grafting rate is calculated.
Computing formula is：
DOG=(19-32WF)/32WF, W in formulaFFor the weight/mass percentage composition of fluorine element.
By ultraviolet-uisible spectrophotometer (3600 types of UV, Japanese Shimadzu Corporation) for obtained pvdf membrane after grafting
Carry out UV-vis transmission measurements.
The invention provides a kind of preparation method of PVDF membrane material, including：Irradiation is carried out to Kynoar,
Obtain the Kynoar after irradiation；Kynoar after irradiation and UV absorbent are carried out into graft reaction, is gathered
Vinylidene membrane material；The UV absorbent is selected from one or more of benzophenone and benzotriazole apoplexy due to endogenous wind.This
It is bright that Kynoar is carried out into pre-irradiation so as to produce free radical in strand, further cause specific ultraviolet absorber to enter
Row graft reaction, has higher percent grafting after reaction, operation is simple, easily-controlled experimental conditions.The present invention is modified
The PVDF membrane material uv transmittance for arriving is low, and mechanics of the addition of the method UV absorbent to PVDF
Performance impact is less.
In order to further illustrate the present invention, with reference to embodiments the PVDF membrane material that the present invention is provided is carried out
Describe in detail.
Embodiment 1
Using60Co- gamma-rays carry out pre-irradiation process to PVDF, and the dosage of irradiation is 10kGy.By PVDF after irradiation and
BPMA, UV-416 are placed in banbury after being sufficiently mixed, and are reacted under the conditions of 220 DEG C, obtain with ultra-violet absorption function
PVDF resins, by blown film process prepare reaction after pvdf membrane.Wherein, UV absorbent BPMA, UV-416 and PVDF
Mass ratio is 2:3:25, the material reaction time is 4min.
Embodiment 2
Using60Co- gamma-rays carry out pre-irradiation process to PVDF, and the dosage of irradiation is 20kGy.By irradiated PVDF and
It is placed in double screw extruder after benzophenone ultraviolet absorbent UV-416 mixing and is reacted.Then, by solution into
Embrane method prepares pvdf membrane after reaction.Wherein, UV-416 is 1 with PVDF mass ratioes:7,180 DEG C of reaction temperature, response time 4min.
Embodiment 3
The high-power electron beam produced using electron accelerator carries out pre-irradiation process to PVDF, and the dosage of irradiation is 15kGy.
It is placed in double screw extruder to enter under the conditions of 200 DEG C after BPMA, UV-416 of irradiated PVDF and synthesis are sufficiently mixed
Row reaction.Then, the pvdf membrane after casting filming therapy prepares reaction.Wherein, BPMA, UV-416 and PVDF mass ratio is 1:1:
20, response time 2min.
Embodiment 4
Using60Co- gamma-rays carry out pre-irradiation process to PVDF, and the dosage of irradiation is 15kGy.By irradiated PVDF and
The BPMA of synthesis is placed in banbury after being sufficiently mixed and is reacted.Then, the pvdf membrane after solution film formation prepares reaction.
Wherein, BPMA is 1 with PVDF mass ratioes:4,190 DEG C of reaction temperature, response time 6min.
The PVDF-g-BPMA films for preparing are measured using nuclear magnetic resonance, NMR, as a result as shown in figure 1, Fig. 1 is this
The PVDF-g-BPMA film hydrogen nuclear magnetic resonance spectrograms that bright embodiment 4 is prepared, as seen from the figure, are defined as PVDF-g-
BPMA。
PVDF and the PVDF-g-BPMA films for preparing are measured using infrared spectrum, as a result as shown in figure 3,
Fig. 3 is the measure figure of PVDF before pvdf membrane and grafting after the reaction for preparing of the embodiment of the present invention 4 and embodiment 8, by scheming
As can be seen that response type ultra-violet absorber is successfully grafted to PVDF strands, graft polymers are prepared.
UV-vis is carried out to the PVDF-g-BPMA films that embodiment 4 is prepared and passes through spectroscopic assay, as a result as shown in figure 4,
After the reaction that Fig. 4 is prepared for embodiment 4 and embodiment 8, the UV-vis of pvdf membrane passes through spectrogram, as seen from Figure 4,
After grafting, obtained pvdf membrane has very high ultra-violet absorption function, can realize protecting for the light of subsurface material.
Benzophenone ultraviolet absorbent connecing on PVDF strands under different condition prepared by embodiment 1～4
After branch rate and reaction, as shown in table 1, table 1 is benzophenone ultraviolet under different condition to transmitance of the pvdf membrane at 300nm
Percent grafting and transmitance of the absorbent on PVDF strands.
Percent grafting and transmitance of the benzophenone ultraviolet absorbent on PVDF strands under 1 different condition of table
Embodiment 5
Using60Co- gamma-rays carry out pre-irradiation process to PVDF.By irradiation dose for 10kGy PVDF and benzotriazole
Class UV absorbent BDHM, RUVA-93 and BDHA are placed in after being sufficiently mixed in double screw extruder and carry out under the conditions of 180 DEG C
Reaction, obtains the PVDF resins with UV absorbing properties.Then, the pvdf membrane after solution film formation prepares reaction.Its
In, UV absorbent BDHM, RUVA-93 and BDHA and PVDF mass ratioes are 1:1:1:20, the material reaction time is 4min.
Embodiment 6
Using60Co- gamma-rays carry out pre-irradiation process to PVDF, and the dosage of irradiation is 20kGy.By irradiated PVDF and
BDHM, RUVA-93 are placed in double screw extruder after being sufficiently mixed and are reacted, the PVDF after casting filming therapy prepares reaction
Film.Wherein, UV absorbent BDHM, RUVA-93 and PVDF mass ratioes are 1:1:15,220 DEG C of reaction temperature, the response time
4min。
Embodiment 7
The high-power electron beam produced using electron accelerator carries out pre-irradiation process to PVDF.It is 15kGy by irradiation dose
PVDF and RUVA-93, BDHA be sufficiently mixed after be placed in banbury and reacted under the conditions of 200 DEG C, be grafted to PVDF point
In subchain, the PVDF resins with UV absorbing properties are obtained.Then, the pvdf membrane after blown film process is reacted.
Wherein, UV absorbent RUVA-93, BDHA and PVDF mass ratioes are 2:1:25, the material reaction time is 2min.
Embodiment 8
Using60Co- gamma-rays carry out pre-irradiation process to PVDF, and the dosage of irradiation is 15kGy.By irradiated PVDF and
RUVA-93 is placed in banbury after being sufficiently mixed and is reacted, the pvdf membrane after casting filming therapy prepares reaction.Wherein,
RUVA-93 is 1 with PVDF mass ratioes:4,200 DEG C of reaction temperature, response time 6min.
The PVDF-g-RUVA-93 for preparing is measured using nuclear magnetic resonance, NMR, as a result as shown in Fig. 2 Fig. 2 is this
The PVDF-g-RUVA-93 hydrogen nuclear magnetic resonance spectrograms that inventive embodiments 8 are prepared, as seen from the figure, are defined as PVDF-g-
RUVA-93。
PVDF and the PVDF-g-RUVA-93 for preparing are measured using infrared spectrum, as a result as shown in figure 3,
Fig. 3 is polyvinylidene fluoride film and the front Kynoar of grafting after the reaction that the embodiment of the present invention 4 and embodiment 8 are prepared
Measurement result, as seen from the figure, response type ultra-violet absorber is successfully grafted to PVDF strands, prepares glycerol polymerization
Thing.
UV-vis is carried out to the PVDF-g-RUVA-93 films that embodiment 8 is prepared and passes through spectroscopic assay, as a result such as Fig. 4 institutes
Show, after the reaction that Fig. 4 is prepared for embodiment 4 and embodiment 8, the UV-vis of polyvinylidene fluoride film passes through spectrogram, by Fig. 4
As can be seen that pvdf membrane processed has very high ultra-violet absorption function after grafting, can realize the light of subsurface material is protected.
Under different condition prepared by embodiment 5～8, response type benzotriazole UV absorbers are on PVDF strands
Percent grafting and reaction after transmitance of the pvdf membrane 300nm at as shown in table 2, table 2 is response type benzo three under different condition
Percent grafting and transmitance of the azoles UV absorbent on PVDF strands.
Percent grafting and transmitance of the response type benzotriazole UV absorbers on PVDF strands under 2 different condition of table
Embodiment 9～12
Using60Co- gamma-rays carry out pre-irradiation process to PVDF, and the dosage of irradiation is 15kGy.By irradiated PVDF and
Hybrid reaction type UV absorbent BPMA, RUVA-93 is sufficiently mixed according to different proportion, and being placed in banbury is carried out instead
Should, obtain the PVDF resins with UV absorbing properties.Then, the pvdf membrane after blown film process is reacted.Wherein,
UVA+UVB absorbent is 1 with PVDF mass ratioes:6, reaction temperature 180-220 DEG C, response time 2-8min.
Two kinds of response type ultra-violet absorbers under the conditions of differential responses are after the percent grafting on PVDF strands and reaction
As shown in table 3, two under different condition kind response type ultra-violet absorber is in PVDF molecules for transmitance of the pvdf membrane at 300nm
Percent grafting and transmitance on chain.
Percent grafting and transmitance of the two kinds of response type ultra-violet absorbers under 3 different condition of table on PVDF strands
Comparative example 1
The external migration experiment of UV absorbent：With DMAc as solvent, PVDF/BPMA composite membranes are prepared using the tape casting
(BPMA contents 7.04wt%).PVDF-g-BPMA prepared by the PVDF/BPMA composite membranes of preparation and the embodiment of the present invention 4
Film, extracts 48h respectively by solvent of ethanol.Film before and after extracting is carried out into ultraviolet-visible light transmission measurement.As a result such as Fig. 5
Shown, Fig. 5 is UV light permeability contrast before and after PVDF/BPMA composite membranes in comparative example of the present invention 1 and the extracting of PVDF-g-BPMA films
Figure.Wherein, 1 is spectrogram before the extracting of PVDF-g-BPMA films；2 is spectrogram after the extracting of PVDF-g-BPMA films；3 is PVDF/
Spectrogram before the extracting of BPMA composite membranes, 4 is the spectrogram after the extracting of PVDF/BPMA composite membranes.
As seen from the figure, before and after ethanol extraction, PVDF-g-BPMA films do not have significant change in the transmitance of ultraviolet region,
And BPMA is directly added into the composite membrane prepared in PVDF ultra-violet absorption function after extracting to be reduced, absorption region reduces,
The transmitance of film substantially increases, it is impossible to realize whole absorptions of ultraviolet light.As a result prove, with preparation PVDF/BPMA composite membrane phases
PVDF-g-BPMA films than being prepared by the method for irradiation grafting more can effectively prevent the migration of BPMA.
Comparative example 2
Effect on Mechanical Properties is tested：Macromolecule ultraviolet radiation absorbent P (MMA-co- are prepared by the method for ATRP
BPMA) (PDI=1.11, Mn=19443), prepares the different P (MMA-co- of ultra-violet absorption agent content using solution blended process
BPMA)/PVDF composite membranes, and carry out uv transmittance, extension test.The PVDF-g-BPMA of different percent graftings is made into film
Carry out extension test.
As a result as shown in fig. 6, Fig. 6 is the mechanics of P (MMA-co-BPMA)/PVDF and PVDF-g-BPMA films in comparative example 2
Performance measurement result figure, wherein, is (a) composite membrane of the P (MMA-co-BPMA) and PVDF of Different adding amount, (b) connects for difference
The PVDF-g-BPMA films of branch rate.By test, only the addition as P (MMA-co-BPMA) in PVDF is increased to
Transmitance just near less than 1% of the composite membrane prepared when 30% (wt%) in 200-360nm, and now disconnected as seen from the figure
Split percentage elongation near original 49.3%.And the PVDF-g-BPMA films elongation at break change of different percent graftings is little.Therefore,
The method for understanding the irradiation grafting UV absorbent of the present invention by contrast is less for material Effect on Mechanical Properties itself.
The above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (8)
1. a kind of preparation method of PVDF membrane material, including：
Irradiation is carried out to Kynoar, the Kynoar after irradiation is obtained；
Kynoar after irradiation and UV absorbent are carried out into graft reaction, PVDF membrane material is obtained；It is described
UV absorbent is selected from one or more of benzophenone and benzotriazole apoplexy due to endogenous wind.
2. preparation method according to claim 1, it is characterised in that the irradiation is employing60Co- gamma-rays or electronics add
Fast device carries out irradiation.
3. preparation method according to claim 2, it is characterised in that the irradiation dose is 10～30kGy.
4. preparation method according to claim 1, it is characterised in that the Kynoar after the irradiation is inhaled with ultraviolet
The weight ratio for receiving agent is (4～10)：1.
5. preparation method according to claim 1, it is characterised in that the temperature of the graft reaction is 180～240 DEG C.
6. preparation method according to claim 1, it is characterised in that the time of the graft reaction is 2～8min.
7. preparation method according to claim 1, it is characterised in that the graft reaction is specially：Just after irradiation
After Kynoar is mixed with UV absorbent, graft reaction in banbury or double screw extruder is placed in.
8. preparation method according to claim 1, it is characterised in that the benzophenone includes -4 (3- first of 2- hydroxyls
Base acryloxy -2- hydroxy propyloxy groups) benzophenone, 2- acrylic acid -2- (4- benzoyl -3- hydroxyphenoxies) ethyl esters and 2-
One or more in hydroxyl -4- acryl-oyloxyethoxy benzophenone；The benzotriazole includes [2- (2- hydroxyl -4- first
Base acryloxy phenyl) benzotriazole], RUVA-93 and [2- (2- hydroxyl -4- acryloxy phenyl) benzotriazole], 2-
[2- hydroxyl -5- [2- (methacryloxypropyl) ethyl] phenyl] -2H- benzotriazole and 2 (2- hydroxy-4-methyl acryloyl group benzene
Base) one or more in the chloro- 2H- benzotriazole of 5- or 2 (2- hydroxyl -4- allyl phenyls) chloro- 2H- benzotriazole of 5-.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611040494.1A CN106519124B (en) | 2016-11-23 | 2016-11-23 | The preparation method of PVDF membrane material |
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| CN108047383A (en) * | 2018-01-23 | 2018-05-18 | 中国科学院长春应用化学研究所 | The preparation method of polyvinylidene fluoride copolymer |
| CN109351213A (en) * | 2018-08-30 | 2019-02-19 | 中国科学院长春应用化学研究所 | A kind of poly-vinylidene-fluoride composite film and preparation method thereof containing modified poly-dopamine nanoparticle |
| CN111253655A (en) * | 2019-12-23 | 2020-06-09 | 浙江瑞堂塑料科技股份有限公司 | High-weather-resistance polyethylene composite material and preparation method thereof |
| CN114058142A (en) * | 2020-08-04 | 2022-02-18 | 浙江省化工研究院有限公司 | Transparent fluorine-containing polymer film |
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| CN114058142A (en) * | 2020-08-04 | 2022-02-18 | 浙江省化工研究院有限公司 | Transparent fluorine-containing polymer film |
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