CN115710325B - Polyvinylidene fluoride resin for solar backboard and preparation method thereof - Google Patents
Polyvinylidene fluoride resin for solar backboard and preparation method thereof Download PDFInfo
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- CN115710325B CN115710325B CN202211427601.1A CN202211427601A CN115710325B CN 115710325 B CN115710325 B CN 115710325B CN 202211427601 A CN202211427601 A CN 202211427601A CN 115710325 B CN115710325 B CN 115710325B
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- transfer agent
- chain transfer
- polyvinylidene fluoride
- ultraviolet light
- fluoride resin
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- 239000002033 PVDF binder Substances 0.000 title claims abstract description 56
- 229920002981 polyvinylidene fluoride Polymers 0.000 title claims abstract description 55
- 229920005989 resin Polymers 0.000 title claims abstract description 50
- 239000011347 resin Substances 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000004383 yellowing Methods 0.000 claims abstract description 31
- 239000012986 chain transfer agent Substances 0.000 claims description 61
- 239000000178 monomer Substances 0.000 claims description 28
- ZQBAKBUEJOMQEX-UHFFFAOYSA-N phenyl salicylate Chemical group OC1=CC=CC=C1C(=O)OC1=CC=CC=C1 ZQBAKBUEJOMQEX-UHFFFAOYSA-N 0.000 claims description 28
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 claims description 26
- 150000001875 compounds Chemical class 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 15
- 239000002270 dispersing agent Substances 0.000 claims description 14
- 230000031700 light absorption Effects 0.000 claims description 14
- 229960000969 phenyl salicylate Drugs 0.000 claims description 14
- 239000003999 initiator Substances 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 claims description 8
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 claims description 8
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 claims description 8
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 claims description 8
- 238000006116 polymerization reaction Methods 0.000 claims description 8
- AQKYLAIZOGOPAW-UHFFFAOYSA-N 2-methylbutan-2-yl 2,2-dimethylpropaneperoxoate Chemical compound CCC(C)(C)OOC(=O)C(C)(C)C AQKYLAIZOGOPAW-UHFFFAOYSA-N 0.000 claims description 7
- 238000007599 discharging Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 238000010557 suspension polymerization reaction Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 150000002148 esters Chemical class 0.000 claims description 5
- VMVNZNXAVJHNDJ-UHFFFAOYSA-N methyl 2,2,2-trifluoroacetate Chemical compound COC(=O)C(F)(F)F VMVNZNXAVJHNDJ-UHFFFAOYSA-N 0.000 claims description 5
- BWJUFXUULUEGMA-UHFFFAOYSA-N propan-2-yl propan-2-yloxycarbonyloxy carbonate Chemical compound CC(C)OC(=O)OOC(=O)OC(C)C BWJUFXUULUEGMA-UHFFFAOYSA-N 0.000 claims description 4
- 229940057847 polyethylene glycol 600 Drugs 0.000 claims description 3
- 239000004354 Hydroxyethyl cellulose Substances 0.000 claims description 2
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 claims description 2
- STSCVKRWJPWALQ-UHFFFAOYSA-N TRIFLUOROACETIC ACID ETHYL ESTER Chemical compound CCOC(=O)C(F)(F)F STSCVKRWJPWALQ-UHFFFAOYSA-N 0.000 claims description 2
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- CWINGZLCRSDKCL-UHFFFAOYSA-N ethoxycarbonyloxy ethyl carbonate Chemical compound CCOC(=O)OOC(=O)OCC CWINGZLCRSDKCL-UHFFFAOYSA-N 0.000 claims description 2
- DBOFMRQAMAZKQY-UHFFFAOYSA-N ethyl 2,2,3,3,3-pentafluoropropanoate Chemical compound CCOC(=O)C(F)(F)C(F)(F)F DBOFMRQAMAZKQY-UHFFFAOYSA-N 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- JMKJCPUVEMZGEC-UHFFFAOYSA-N methyl 2,2,3,3,3-pentafluoropropanoate Chemical compound COC(=O)C(F)(F)C(F)(F)F JMKJCPUVEMZGEC-UHFFFAOYSA-N 0.000 claims description 2
- 229920000609 methyl cellulose Polymers 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 239000001923 methylcellulose Substances 0.000 claims description 2
- 235000010981 methylcellulose Nutrition 0.000 claims description 2
- 239000003505 polymerization initiator Substances 0.000 claims description 2
- YPVDWEHVCUBACK-UHFFFAOYSA-N propoxycarbonyloxy propyl carbonate Chemical compound CCCOC(=O)OOC(=O)OCCC YPVDWEHVCUBACK-UHFFFAOYSA-N 0.000 claims description 2
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 2
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 238000012546 transfer Methods 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 13
- 238000002474 experimental method Methods 0.000 description 12
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 11
- 229910052731 fluorine Inorganic materials 0.000 description 11
- 239000011737 fluorine Substances 0.000 description 11
- 238000012360 testing method Methods 0.000 description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 9
- 239000001301 oxygen Substances 0.000 description 9
- 229910052760 oxygen Inorganic materials 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 9
- JVHJRIQPDBCRRE-UHFFFAOYSA-N ethyl 2,2,3,3,4,4,4-heptafluorobutanoate Chemical compound CCOC(=O)C(F)(F)C(F)(F)C(F)(F)F JVHJRIQPDBCRRE-UHFFFAOYSA-N 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 230000006750 UV protection Effects 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 229920002521 macromolecule Polymers 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 229920002620 polyvinyl fluoride Polymers 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- 239000004576 sand Substances 0.000 description 3
- 229940124543 ultraviolet light absorber Drugs 0.000 description 3
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 3
- 229920002799 BoPET Polymers 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000009434 installation Methods 0.000 description 2
- 230000004224 protection Effects 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UKCBKQLNTLMFAA-UHFFFAOYSA-N F.[F] Chemical compound F.[F] UKCBKQLNTLMFAA-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- WPPLKRDOKPISSC-UHFFFAOYSA-N pentyl 2,2-dimethylpropaneperoxoate Chemical group CCCCCOOC(=O)C(C)(C)C WPPLKRDOKPISSC-UHFFFAOYSA-N 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000008093 supporting effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses polyvinylidene fluoride resin for a solar backboard and a preparation method thereof. The ultraviolet light absorbing group and the yellowing resistant group are grafted to the end part of the polyvinylidene fluoride resin to endow the polyvinylidene fluoride resin with excellent ultraviolet light resistance and yellowing resistance.
Description
Technical Field
The invention relates to the field of polymers, in particular to a method for preparing polyvinylidene fluoride resin for a solar backboard.
Background
The solar backboard is positioned at the outermost layer of the photovoltaic module and used for protecting the crystalline silicon wafer from being corroded by water vapor and oxygen. The solar backboard is respectively from outside to inside: fluorine film (outer protective layer), adhesive, PET film, adhesive, fluorine film (inner protective layer). The fluorine film mainly protects the PET film from being corroded by ultraviolet rays and wind sand, reduces the degradation speed of PET, and determines the service life of the backboard. The photovoltaic power station is exposed in sand, ultraviolet rays, high temperature and water vapor for a long time, the protective material is easy to age and crack, and the protective capability can be lost after the protective material cracks, so that the service life of the photovoltaic is shortened. Early dupont adopts PVF to manufacture a solar backboard fluorine film, later-stage Acomat promotes PVDF (polyvinylidene fluoride) to the field of photovoltaic backboard, and PVDF fluorine content is higher than PVF (polyvinyl fluoride), so that weather resistance and chemical resistance of PVDF are stronger, compactness of PVDF is better, stronger wind and sand resistance is brought, the PVDF is more suitable for severe outdoor environment, flame retardant capability of PVDF is stronger, and probability of fire occurrence can be reduced. The fluorine film has better ultraviolet light resistance and lower yellowing degree under the condition of long-term direct solar irradiation, and is important to the solar backboard.
Under the background of carbon neutralization, the national energy agency proposes to realize the aim of more than 12 hundred million kilowatts of wind-electricity photovoltaic devices by 2030, and the aim is predicted by China photovoltaic industry association: the new installation capacity of the photovoltaic in China is expected to reach 355-440GW in 2021-2025, and the increase of the installation capacity of the photovoltaic is expected to greatly drive the increase of PVDF requirements. In the background of rapid increase of demand, how to improve the ultraviolet resistance and yellowing resistance of polyvinylidene fluoride resin for solar back plates is the current research focus.
The PVDF resin is a high polymer material with semi-crystalline thermoplasticity and particularly stable chemical structure, has the characteristics of fluororesin and general resin, has excellent chemical corrosion resistance, weather resistance and combustion supporting property, has excellent mechanical properties, and is widely applied to the fields of solar back plates, water treatment films, lithium electric adhesives, fluorocarbon coatings and the like. The ultraviolet light resistance and the yellowing resistance of the polyvinylidene fluoride resin are particularly required in the solar back plate direction due to the special use environment, and the ultraviolet light resistance and the yellowing resistance of the polyvinylidene fluoride resin are required to be improved by optimizing and adjusting the original structure.
Most researchers in industry adopt to add ultraviolet light absorber into polyvinylidene fluoride resin for physical mixing so as to improve ultraviolet light resistance of polyvinylidene fluoride, and the problem is that the ultraviolet light absorber is in free state and volatilized or decomposed under direct sun irradiation for a long time and cannot play a role. In addition, the preparation process of the polyvinylidene fluoride resin is to control the molecular weight and the distribution of the polyvinylidene fluoride resin, a chain transfer agent is required to be added, the active hydrogen in the chain transfer agent is extracted from a polymer chain to terminate the reaction in the free radical polymerization process, meanwhile, the chain transfer agent residue is continuously used as an active point to continuously initiate the reaction, so that a chain transfer agent group is introduced into the end part of the polymer chain, esters or alcohols and ketones are generally selected as the chain transfer agent in the industry, such as ethyl acetate, diethyl carbonate, acetone and the like, the introduction of the groups into the end part of the polymer chain by the chain transfer agent is not stable enough, and the heat resistance, the chemical resistance and the weather resistance are not enough to meet the use environment requirements of a solar backboard, and the chain transfer agent is easy to yellow and decompose.
The new material (CN 109337260) is prepared by using polyvinylidene fluoride resin and other vinyl resins as matrix resins and adding additives such as an antioxidant, an ultraviolet light absorber and the like.
The invention relates to polyvinylidene fluoride resin for a solar backboard, which is prepared from China Shenzhou boat (CN 103755850), wherein an initiator for polymerization is organic peroxyesters with low reaction activation energy, a regulator is low molecular weight esters, the ultraviolet resistance critical to the solar backboard is not improved, and the yellowing resistance is improved only to a limited extent.
Therefore, how to improve the ultraviolet light resistance and yellowing resistance of the polyvinylidene fluoride resin from the essential structure is very important for meeting the full life cycle and efficient operation of the photovoltaic backboard. According to the invention, the ultraviolet light absorption group and the yellowing resistance group are introduced into the polymer end group of the polyvinylidene fluoride resin by adopting the compound chain transfer agent, so that the polyvinylidene fluoride resin is endowed with excellent ultraviolet light resistance and yellowing resistance, and the prepared polyvinylidene fluoride resin has excellent and long-acting protection effect when being used for a solar backboard.
Disclosure of Invention
The invention aims to provide polyvinylidene fluoride resin for solar back plates and a preparation method thereof.
The inventor discovers that phenyl salicylate has excellent ultraviolet light absorption capability and can be used as a chain transfer agent in free radical polymerization, so that the ultraviolet light absorption group is introduced into the end part of a macromolecule to improve the ultraviolet light resistance of polyvinylidene fluoride resin, the phenyl salicylate is connected with PVDF macromolecule in a chemical bond mode and is wrapped by fluorine-containing macromolecule chains, the state stability and the resistance are far higher than those of a physical mixing addition mode, and the phenyl salicylate can continuously and effectively play a role in ultraviolet light absorption. The inventor also finds that the fluorinated ester chain transfer agent introduces high polymer end group fluorine in the polymerization process, improves the stability of the end group and the oxidation resistance and heat resistance, and can improve the yellowing resistance of the polyvinylidene fluoride resin.
In summary, the invention provides a compound chain transfer agent, which enables the end group of the polyvinylidene fluoride resin to contain an ultraviolet light absorption group and a yellowing resistant group, so that the prepared polyvinylidene fluoride resin has excellent ultraviolet light resistance and yellowing resistance.
In one aspect, the invention provides a preparation method of polyvinylidene fluoride resin, which is prepared by suspension polymerization of vinylidene fluoride monomer, a compound chain transfer agent, an initiator and a dispersing agent.
In a specific embodiment, the method comprises the steps of:
(a) Adding a compound chain transfer agent, an initiator, a dispersing agent and deionized water into a reactor, and starting stirring; (b) Adding vinylidene fluoride monomers into a reactor, and starting polymerization reaction after heating to a polymerization temperature; (c) And after the polymerization is finished, performing post-treatment to obtain the polyvinylidene fluoride resin.
In the invention, the reactor in the step (a) is selected from a vertical reaction kettle or a horizontal reaction kettle.
In the invention, the compound chain transfer agent comprises an ultraviolet light absorbing chain transfer agent and a yellowing resistant chain transfer agent, and the dosage of the compound chain transfer agent is 0.45-1.75wt% of that of vinylidene fluoride monomer.
The ultraviolet light absorbing chain transfer agent is phenyl salicylate, and the yellowing-resistant transfer agent is fluorinated esters, including but not limited to methyl trifluoroacetate, ethyl trifluoroacetate, methyl pentafluoropropionate, ethyl pentafluoropropionate, methyl heptafluorobutynate, and ethyl heptafluorobutynate; the addition ratio of the ultraviolet light absorption chain transfer agent to the yellowing resistant chain transfer agent is 1.2-2.0:1, preferably 1.6-1.8:1.
The suspension polymerization initiator is one or more of diethyl peroxydicarbonate, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate and tert-amyl peroxypivalate, and the use level of the initiator is 0.10-0.42 wt% of vinylidene fluoride monomer.
The dispersing agent is one or more of methyl cellulose, hydroxyethyl cellulose, hydroxypropyl methyl cellulose, sodium carboxymethyl cellulose and polyethylene glycol 600, and the adding amount of the dispersing agent is 0.22-0.38wt% of vinylidene fluoride monomer.
The dosage of the deionized water is 1.2-2.3 times of that of the vinylidene fluoride monomer.
The suspension polymerization temperature is 42-55 ℃, the reaction time is 5-10 hours, preferably 6-8 hours, and the reaction pressure is 10.5-13.2MPaG, preferably 11.6-12.6MPaG.
The post-treatment process in the step (c) comprises the processes of discharging unreacted monomers, washing, filtering and drying.
In the present invention, an operation of removing oxygen is further included before the reaction, and the oxygen content is controlled to 20ppm or less by performing nitrogen substitution in a negative pressure environment.
On the other hand, the invention also provides polyvinylidene fluoride resin prepared by the preparation method.
Finally, the invention also provides application of the polyvinylidene fluoride resin in the aspect of solar back plates.
The invention has the beneficial effects that: the ultraviolet light absorption group and the yellowing resistance group are introduced into the polymer end group of the polyvinylidene fluoride resin by adopting the compound chain transfer agent, so that the polyvinylidene fluoride resin is endowed with excellent ultraviolet light resistance and yellowing resistance, and the polyvinylidene fluoride resin prepared by the compound chain transfer agent has excellent and long-acting protection effect when being used for a solar backboard.
Detailed Description
The process according to the invention is further illustrated by the following specific examples, but the invention is not limited to the examples listed but encompasses any other known modifications within the scope of the claims.
The main raw material sources are as follows:
vinylidene fluoride: vanhua chemical group Co., ltd., industrial products;
Hydroxypropyl methylcellulose: aladine, analytically pure;
polyethylene glycol 600: beijing enokie, analytically pure;
Phenyl salicylate: beijing enokie, analytically pure;
ethyl heptafluorobutyrate: beijing enokie, analytically pure;
methyl trifluoroacetate: beijing enokie, analytically pure;
Tertiary amyl peroxypivalate: beijing enokie, analytically pure;
Diisopropyl peroxydicarbonate: zibo Red chemical Co., ltd.
The main test method is as follows:
preparing a polyvinylidene fluoride fluorine film: and adding polyvinylidene fluoride resin particles into a casting extruder, controlling the rotating speed of a screw to be 100r/min, the material temperature to be 200-210 ℃, the machine head pressure to be 10MPa, and controlling the linear speed of a casting film to be 45m/min to obtain the fluorine film with the thickness of 20 um.
1. Ultraviolet resistance
And placing the polyvinylidene fluoride resin prepared fluorine film in a UV aging machine (Haida instrument HD-E802), and testing the ultraviolet light transmittance, wherein the lower the ultraviolet light transmittance is, the better the ultraviolet light resistance is.
2. Yellowing resistance
About 15g of the polymer powder was weighed into a 20ml container and heated in an oven at 230℃for 30min. And a Hunterlab Labscan XE yellow index instrument is selected for testing, the yellow index is used for representing the yellowing degree, and the lower the index is, the better the yellowing resistance degree is.
3. Tensile Strength
The tensile strength of the polyvinylidene fluoride resin after the preparation of the fluorine film was measured according to astm d 882 standard (tensile strength test). The test was performed using a Shenzhen Kexing 98-HJ tensile strength tester.
Example 1
The experiment was performed in a 5L reactor equipped with a stirrer, the reactor was evacuated and then filled with nitrogen to positive pressure, and the experiment was started after several cycles of testing the oxygen content in the reactor below 20 ppm. 1920g of deionized water, 2.64g of dispersant hydroxypropyl methylcellulose, 3.2g of chain transfer agent phenyl salicylate, 2.56g of chain transfer agent ethyl heptafluorobutyrate (0.48% of the mass of vinylidene fluoride is added in total by the compound chain transfer agent, the addition proportion of the ultraviolet light absorption chain transfer agent and the yellowing-resistant chain transfer agent is 1.25), 4.92g of initiator tert-amyl peroxypivalate, 1200g of vinylidene fluoride monomer are added, the temperature is raised to 46 ℃, the reaction pressure is 12MPaG, the reaction is carried out for 8 hours, the unreacted monomer is cooled and discharged, and the product is filtered, washed and dried to obtain the polyvinylidene fluoride resin.
Example 2
The experiment was performed in a 5L reactor equipped with a stirrer, the reactor was evacuated and then filled with nitrogen to positive pressure, and the experiment was started after several cycles of testing the oxygen content in the reactor below 20 ppm. 1440g of deionized water, 600.56 g of dispersing agent polyethylene glycol, 8.5g of chain transfer agent phenyl salicylate, 5.9g of chain transfer agent methyl trifluoroacetate (1.2% of the mass of vinylidene fluoride is added in the total amount of the compound chain transfer agent, the addition ratio of the ultraviolet light absorption chain transfer agent and the yellowing-resistant chain transfer agent is 1.4), 1.56g of tert-amyl peroxypivalate as an initiator, 1200g of vinylidene fluoride monomer, heating to the reaction temperature of 54 ℃, reacting for 5h under the reaction pressure of 10.5MPaG, cooling, discharging unreacted monomer, and filtering, washing and drying the product to obtain the polyvinylidene fluoride resin.
Example 3
The experiment was performed in a 5L reactor equipped with a stirrer, the reactor was evacuated and then filled with nitrogen to positive pressure, and the experiment was started after several cycles of testing the oxygen content in the reactor below 20 ppm. Adding 2760g of deionized water into a reaction kettle, adding 3.6g of dispersant hydroxypropyl methylcellulose, 13.4g of chain transfer agent phenyl salicylate, 7g of chain transfer agent ethyl heptafluorobutyrate (1.7% of the mass of vinylidene fluoride is added in total by the compound chain transfer agent, the addition ratio of the ultraviolet light absorption chain transfer agent to the yellowing-resistant chain transfer agent is 1.9), adding 2.16g of initiator diisopropyl peroxydicarbonate, adding 1200g of vinylidene fluoride monomer, heating to the reaction temperature of 42 ℃, reacting for 10 hours under the reaction pressure of 13.2MPaG, cooling, discharging unreacted monomer, and filtering, washing and drying the product to obtain the polyvinylidene fluoride resin.
Example 4
The experiment was performed in a 5L reactor equipped with a stirrer, the reactor was evacuated and then filled with nitrogen to positive pressure, and the experiment was started after several cycles of testing the oxygen content in the reactor below 20 ppm. 1920g of deionized water, 3.6g of dispersant hydroxypropyl methylcellulose, 5.1g of chain transfer agent phenyl salicylate, 3.1g of chain transfer agent ethyl heptafluorobutyrate (0.68% of the mass of vinylidene fluoride is added in total by the compound chain transfer agent, the addition proportion of ultraviolet light absorption chain transfer agent and yellowing-resistant chain transfer agent is 1.6), 3.24g of initiator tert-amyl peroxypivalate, 1200g of vinylidene fluoride monomer are added, the temperature is raised to 52 ℃, the reaction pressure is 12MPaG, the reaction is carried out for 8 hours, the unreacted monomer is cooled and discharged, and the product is filtered, washed and dried to obtain the polyvinylidene fluoride resin.
Example 5
The experiment was performed in a 5L reactor equipped with a stirrer, the reactor was evacuated and then filled with nitrogen to positive pressure, and the experiment was started after several cycles of testing the oxygen content in the reactor below 20 ppm. 1920g of deionized water, 3.8g of dispersant hydroxypropyl methylcellulose, 5.7g of chain transfer agent phenyl salicylate, 3.2g of chain transfer agent methyl trifluoroacetate (the mass ratio of the compound chain transfer agent to the added vinylidene fluoride is 0.74 percent, the addition amount of the ultraviolet light absorbing chain transfer agent and the yellowing-resistant chain transfer agent is 1.8), 3.0g of initiator tert-amyl peroxypivalate, 1200g of vinylidene fluoride monomer, heating to the reaction temperature of 50 ℃, reacting for 9 hours under the reaction pressure of 12.6MPaG, cooling, discharging unreacted monomer, and filtering, washing and drying the product to obtain the polyvinylidene fluoride resin.
Comparative example 1
The phenyl salicylate of example 1 was replaced with an equal amount of ethyl acetate, with the other experimental conditions unchanged.
Comparative example 2
The ethyl heptafluorobutyrate in example 1 was replaced with an equal amount of diethyl carbonate, and the other experimental conditions were unchanged.
Comparative example 3
The phenyl salicylate and ethyl heptafluorobutyrate in example 1 were each replaced with equal amounts of acetone, with the other experimental conditions unchanged.
Comparative example 4
The experiment was performed in a 5L reactor equipped with a stirrer, the reactor was evacuated and then filled with nitrogen to positive pressure, and the experiment was started after several cycles of testing the oxygen content in the reactor below 20 ppm. Adding 1920g of deionized water into a reaction kettle, adding 2.64g of dispersant hydroxypropyl methylcellulose, 2.56g of chain transfer agent ethyl heptafluorobutyrate (the addition amount of the chain transfer agent is 0.21 percent of the mass of vinylidene fluoride monomers), adding 4.92g of initiator tert-amyl peroxypivalate, adding 1200g of vinylidene fluoride monomers, heating to the reaction temperature of 46 ℃, reacting for 8 hours under the reaction pressure of 12MPaG, cooling, discharging unreacted monomers, filtering, washing and drying the product to obtain polyvinylidene fluoride resin, adding the prepared polyvinylidene fluoride resin into a mixer, heating the mixer to 80 ℃, adding 3.2g of phenyl salicylate (the addition amount is 0.27 percent of the vinylidene fluoride monomers), mixing for 20 minutes, and discharging the materials to obtain the final product.
The properties of the super absorbent resins obtained in the above examples and comparative examples are shown in Table 1 below:
table 1 example and comparative example performance parameters
As can be seen from the table, the compound chain transfer agent introduces an ultraviolet light absorption group and a yellowing resistance group into the polymer end group of the polyvinylidene fluoride resin to prepare the polyvinylidene fluoride resin for the solar back plate with excellent ultraviolet light resistance and heat resistance.
Those skilled in the art will appreciate that certain modifications and adaptations of the invention are possible and can be made under the teaching of the present specification. Such modifications and adaptations are intended to be within the scope of the present invention as defined in the appended claims.
Claims (9)
1. The preparation method comprises the steps of preparing a polyvinylidene fluoride resin through suspension polymerization of a vinylidene fluoride monomer, a compound chain transfer agent, an initiator and a dispersing agent, wherein the compound chain transfer agent comprises an ultraviolet light absorption chain transfer agent and a yellowing resistant chain transfer agent; the ultraviolet light absorbing chain transfer agent is phenyl salicylate, and the yellowing-resistant transfer agent is fluorinated esters selected from methyl trifluoroacetate, ethyl trifluoroacetate, methyl pentafluoropropionate, ethyl pentafluoropropionate, methyl heptafluorobutynate and ethyl heptafluorobutynate; the addition ratio of the ultraviolet light absorption chain transfer agent to the yellowing resistant chain transfer agent is 1.2-2.0:1, the dosage of the compound chain transfer agent is 0.45-1.75 wt% of the vinylidene fluoride monomer.
2. The method of claim 1, wherein the ultraviolet light absorbing chain transfer agent and the yellowing resistant chain transfer agent are added in a ratio of 1.6 to 1.8:1.
3. The preparation method according to claim 1, wherein the suspension polymerization initiator is one or more of diethyl peroxydicarbonate, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate and tert-amyl peroxypivalate, and the initiator is 0.10-0.42 wt% of vinylidene fluoride monomer.
4. A method according to any one of claims 1 to 3, wherein the dispersing agent is one or more of methylcellulose, hydroxyethyl cellulose, hydroxypropyl methylcellulose, sodium carboxymethyl cellulose, and polyethylene glycol 600, and the dispersing agent is added in an amount of 0.22 to 0.38wt% of the vinylidene fluoride monomer.
5. A method of preparation according to any one of claims 1 to 3, wherein the method of preparation comprises the steps of: (a) Adding a compound chain transfer agent, an initiator, a dispersing agent and deionized water into a reactor, and starting stirring; (b) Adding vinylidene fluoride monomers into a reactor, and starting polymerization reaction after heating to a polymerization temperature; (c) And after the polymerization is finished, performing post-treatment to obtain the polyvinylidene fluoride resin.
6. The method of claim 5, wherein the reactor in step (a) is selected from a vertical reactor or a horizontal reactor; and/or the dosage of the deionized water is 1.2-2.3 times of that of the vinylidene fluoride monomer.
7. The process according to claim 5, wherein the suspension polymerization is carried out at a temperature of 42 to 55℃for a period of 5 to 10 hours and at a pressure of 10.5 to 13.2MPaG.
8. The method of claim 5, wherein the post-treatment process in step (c) comprises a process of discharging unreacted monomers, washing, filtering, and drying.
9. A polyvinylidene fluoride resin produced by the production method according to any one of claims 1 to 8.
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