CN117843865A - Amorphous fluororesin, preparation method and application thereof, light-transmitting oxygen-permeable release film, and preparation method and application thereof - Google Patents
Amorphous fluororesin, preparation method and application thereof, light-transmitting oxygen-permeable release film, and preparation method and application thereof Download PDFInfo
- Publication number
- CN117843865A CN117843865A CN202211342175.1A CN202211342175A CN117843865A CN 117843865 A CN117843865 A CN 117843865A CN 202211342175 A CN202211342175 A CN 202211342175A CN 117843865 A CN117843865 A CN 117843865A
- Authority
- CN
- China
- Prior art keywords
- formula
- transmitting
- amorphous fluororesin
- light
- release film
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000002360 preparation method Methods 0.000 title claims description 41
- 238000010146 3D printing Methods 0.000 claims abstract description 12
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 56
- 229910052731 fluorine Inorganic materials 0.000 claims description 56
- 239000011737 fluorine Substances 0.000 claims description 56
- YSYRISKCBOPJRG-UHFFFAOYSA-N 4,5-difluoro-2,2-bis(trifluoromethyl)-1,3-dioxole Chemical compound FC1=C(F)OC(C(F)(F)F)(C(F)(F)F)O1 YSYRISKCBOPJRG-UHFFFAOYSA-N 0.000 claims description 53
- 239000000178 monomer Substances 0.000 claims description 45
- 239000002904 solvent Substances 0.000 claims description 41
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 34
- 238000006116 polymerization reaction Methods 0.000 claims description 34
- 238000010926 purge Methods 0.000 claims description 31
- 238000001035 drying Methods 0.000 claims description 25
- 239000007789 gas Substances 0.000 claims description 19
- 238000005266 casting Methods 0.000 claims description 18
- 229910052757 nitrogen Inorganic materials 0.000 claims description 18
- 239000003999 initiator Substances 0.000 claims description 17
- 239000007788 liquid Substances 0.000 claims description 15
- 239000004014 plasticizer Substances 0.000 claims description 15
- 238000011282 treatment Methods 0.000 claims description 15
- -1 cyclic ether olefin Chemical class 0.000 claims description 13
- 238000001914 filtration Methods 0.000 claims description 13
- JQOUSYSYOSCMJZ-UHFFFAOYSA-N fluoro benzenecarboperoxoate Chemical compound FOOC(=O)C1=CC=CC=C1 JQOUSYSYOSCMJZ-UHFFFAOYSA-N 0.000 claims description 13
- 239000000126 substance Substances 0.000 claims description 13
- 238000001816 cooling Methods 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 238000007664 blowing Methods 0.000 claims description 11
- 238000005520 cutting process Methods 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 11
- 238000005096 rolling process Methods 0.000 claims description 10
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 8
- 239000000758 substrate Substances 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 7
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 6
- 238000000016 photochemical curing Methods 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 4
- 238000004334 fluoridation Methods 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 abstract description 19
- 230000035699 permeability Effects 0.000 abstract description 10
- 238000002834 transmittance Methods 0.000 abstract description 8
- 150000004292 cyclic ethers Chemical group 0.000 abstract description 4
- 239000011148 porous material Substances 0.000 abstract description 2
- 238000009825 accumulation Methods 0.000 abstract 1
- 230000002035 prolonged effect Effects 0.000 abstract 1
- 206010037544 Purging Diseases 0.000 description 18
- 239000010410 layer Substances 0.000 description 16
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 11
- 239000001301 oxygen Substances 0.000 description 11
- 229910052760 oxygen Inorganic materials 0.000 description 11
- 229910001220 stainless steel Inorganic materials 0.000 description 11
- 239000010935 stainless steel Substances 0.000 description 11
- 238000005481 NMR spectroscopy Methods 0.000 description 10
- 229910000831 Steel Inorganic materials 0.000 description 10
- 239000010959 steel Substances 0.000 description 10
- 238000001291 vacuum drying Methods 0.000 description 9
- 229920005989 resin Polymers 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 7
- 230000009477 glass transition Effects 0.000 description 7
- 238000004062 sedimentation Methods 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 230000005540 biological transmission Effects 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 6
- 238000011084 recovery Methods 0.000 description 6
- 238000012512 characterization method Methods 0.000 description 5
- 238000004090 dissolution Methods 0.000 description 5
- 239000012634 fragment Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000004381 surface treatment Methods 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 229910001873 dinitrogen Inorganic materials 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 4
- 238000005086 pumping Methods 0.000 description 4
- PPVPVKZXQJZBRA-UHFFFAOYSA-N (2,3,4,5,6-pentafluorobenzoyl) 2,3,4,5,6-pentafluorobenzenecarboperoxoate Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1C(=O)OOC(=O)C1=C(F)C(F)=C(F)C(F)=C1F PPVPVKZXQJZBRA-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- ZQBFAOFFOQMSGJ-UHFFFAOYSA-N hexafluorobenzene Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1F ZQBFAOFFOQMSGJ-UHFFFAOYSA-N 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- RIQRGMUSBYGDBL-UHFFFAOYSA-N 1,1,1,2,2,3,4,5,5,5-decafluoropentane Chemical compound FC(F)(F)C(F)C(F)C(F)(F)C(F)(F)F RIQRGMUSBYGDBL-UHFFFAOYSA-N 0.000 description 1
- RNECRRSAJGRDKN-UHFFFAOYSA-N 2,2,3,3,4,4-hexafluoro-5-methoxy-5-oxopentanoic acid Chemical compound COC(=O)C(F)(F)C(F)(F)C(F)(F)C(O)=O RNECRRSAJGRDKN-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 238000012660 binary copolymerization Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- UOBSVARXACCLLH-UHFFFAOYSA-N monomethyl adipate Chemical compound COC(=O)CCCCC(O)=O UOBSVARXACCLLH-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000000196 viscometry Methods 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Classifications
-
- 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
- C08F234/00—Copolymers of cyclic compounds having no unsaturated aliphatic radicals in a side chain and having one or more carbon-to-carbon double bonds in a heterocyclic ring
- C08F234/02—Copolymers of cyclic compounds having no unsaturated aliphatic radicals in a side chain and having one or more carbon-to-carbon double bonds in a heterocyclic ring in a ring containing oxygen
-
- 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
- C08F224/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a heterocyclic ring containing oxygen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2337/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a heterocyclic ring containing oxygen; Derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2345/00—Characterised by the use of homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic ring system; Derivatives of such polymers
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention provides an amorphous fluororesin with a structure shown in a formula 1, wherein five-membered or six-membered cyclic ether fragments Q1-Q5 with large volume are introduced into the amorphous fluororesin structure, so that the internal microstructure of the amorphous fluororesin polymer presents amorphous phases, molecular chains are in a disordered accumulation state, the refractive index of light is extremely low, the light transmittance is extremely high, in addition, the free volume among the molecular chains is larger, and a uniform pore diameter structure is formed in a light-transmitting oxygen-transmitting release film prepared from the amorphous fluororesin, so that the air permeability is improved, and the oxygen-transmitting quantity and the light transmittance of the light-transmitting oxygen-transmitting release film are improved; meanwhile, the introduction of the five-membered or six-membered cyclic ether segment improves the toughness of the light-transmitting oxygen-permeable release film, so that the film has excellent mechanical properties, low release force during use and prolonged service life, and can completely meet the current application of a large-scale continuous industrial 3D printing device.
Description
Technical Field
The invention relates to the technical field of 3D printing materials, in particular to amorphous fluororesin, a preparation method and application thereof, a light-transmitting oxygen-permeable release film, and a preparation method and application thereof.
Background
At present, the 3D printing technology is involved in various fields of industrial design, footwear, education, constructional engineering, dental medical treatment, aerospace, jewelry and the like. 3D printing belongs to a rapid prototyping technology, also called additive manufacturing, and is a novel technology for constructing objects by using powdery metal or polymer resin and other materials in a layer-by-layer printing mode based on digital model files. Photo-curing molding is the earliest 3D printing molding technology and is also the current more mature 3D printing technology. The material is the basis and the restriction factor of 3D printing technology development, and one of the key components is a release film at the bottom of the liquid storage tank.
The professor DeSimone in 2015 proposes a continuous delamination-free liquid interface manufacturing technique CLIP (Continuous Liquid Interface Production) based on DLP (Digital LightProcess) technology, and at present, a release film in a liquid storage tank bottom of the technique is a film processed by taking fluororesin TeflonAF2400 of America mu company as a base material, so that light transmission and oxygen transmission can be combined at the same time. However, the flexibility and tear resistance of the Teflon AF2400 film are not ideal enough, which affects the service life. Therefore, the release film with high light and oxygen permeability and good mechanical property, which is applicable to a photo-curing 3D printer, is a problem to be solved in the prior art.
Disclosure of Invention
The invention aims to provide amorphous fluororesin, a preparation method and application thereof, a light-transmitting oxygen-permeable release film, and a preparation method and application thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides an amorphous fluororesin having a chemical structure shown in formula 1,
in the formula 1, Q is a repeating unit formed by five-membered or six-membered cyclic ether olefin monomers, x and y are polymerization degrees, x is more than 0 and y is more than 0, and the average relative molecular weight of the amorphous fluororesin is 10000 ～ 1000000.
The Q fragment in the formula 1 is a fragment with a chemical structure shown in a formula Q1, a formula Q2, a formula Q3, a formula Q4 or a formula Q5;
the invention also provides a preparation method of the amorphous fluororesin according to the technical scheme, which comprises the following steps:
mixing perfluoro-2, 2-dimethyl-1, 3-dioxole, Q' monomer, initiator perfluoro benzoyl peroxide and fluoridation liquid FC-72, and then carrying out polymerization reaction to obtain amorphous fluororesin;
the perfluoro-2, 2-dimethyl-1, 3-dioxole (namely PDD) is a compound with a chemical structure shown in a formula 2;
the Q 'monomer is a compound with a chemical structure shown in a formula Q1', a formula Q2', a formula Q3', a formula Q4 'or a formula Q5';
the polymerization reaction was carried out under a nitrogen atmosphere.
Preferably, the temperature of the polymerization reaction is 60-90 ℃, and the time of the polymerization reaction is 10-14 h.
The invention also provides application of the amorphous fluororesin or the amorphous fluororesin prepared by the preparation method in preparation of a release film.
The invention also provides a preparation method of the light-transmitting oxygen-transmitting release film, which comprises the following steps:
(1) Mixing the amorphous fluororesin prepared by the technical scheme or the amorphous fluororesin prepared by the preparation method with a fluorine-containing plasticizer and a fluorine-containing solvent to obtain a fluororesin solution;
(2) Filtering and purifying the fluororesin solution obtained in the step (1) to obtain a pretreatment solution;
(3) Casting the pretreatment solution obtained in the step (2) onto a substrate, sequentially performing drying and blowing treatment, and sequentially performing cooling, stripping, rolling and cutting to obtain the light-transmitting oxygen-permeable release film.
Preferably, the concentration of the amorphous fluororesin in the fluororesin solution in the step (1) is 1 to 15wt%.
Preferably, the purging treatment in the step (3) comprises a first purging and a second purging which are sequentially carried out, and the gas used for the first purging is F-containing 2 The gas used for the second purge is nitrogen.
The invention also provides the light-transmitting and oxygen-transmitting release film prepared by the preparation method.
The invention also provides a light-transmitting oxygen-permeable release film prepared by the preparation method of the technical scheme or application of the light-transmitting oxygen-permeable release film in photocuring 3D printing.
The invention provides an amorphous fluororesin with a structure shown in a formula 1, which is prepared by taking perfluoro-2, 2-dimethyl-1, 3-dioxole (PDD) as a monomer and selecting perfluoro five-membered cyclic ether olefin monomer (Q1 ' -Q4 ') or six-membered cyclic ether olefin monomer (Q5 ') as another monomer through binary copolymerization, and by introducing five-membered cyclic ether segments (Q1-Q4) or six-membered cyclic ether segments (Q5) with large volume into the amorphous fluororesin structure, the oxygen permeability and the light permeability of a light-transmitting oxygen-permeable release film prepared from the amorphous fluororesin are improved, because the internal microstructure of the obtained fluororesin polymer is in an amorphous phase, molecular chains are in a disordered stacking state, the refractive index of light is extremely low, the light transmittance is extremely high, and in addition, the free volume among the molecular chains is larger, thereby being beneficial to forming a uniform pore-size structure inside the film and improving the oxygen permeability. Meanwhile, five-membered ring ether segments (Q1-Q4) or six-membered ring ether segments (Q5) are introduced into the amorphous fluororesin structure, so that the toughness of the light-transmitting oxygen-permeable release film prepared from the amorphous fluororesin is improved, the light-transmitting oxygen-permeable release film is excellent in mechanical property, low in release force in use, and capable of fully meeting the current large-scale continuous industrial 3D printing device application. The results of the examples show that the oxygen permeability (Barrer) of the light-transmitting oxygen-permeable release film prepared by the amorphous fluororesin provided by the invention can reach 1260, the light transmittance can reach 98%, the tensile strength can reach 48Mpa, and the elongation at break (%) can reach 18.2.
Drawings
FIG. 1 is a graph showing glass transition temperatures of amorphous fluorine resins according to the present invention;
FIG. 2 is a flow chart of a method for preparing a light-transmitting oxygen-transmitting release film according to the invention;
FIG. 3 is a 10 μm-scale electron microscope image of the surface of the light-transmitting oxygen-transmitting release film prepared in product example 2 of the present invention;
FIG. 4 is a 300 nm-class electron microscope image of the surface of the light-transmitting oxygen-transmitting release film prepared in product example 2 of the present invention.
Detailed Description
The invention provides an amorphous fluororesin having a chemical structure shown in formula 1,
in the present invention, in the formula 1, x and y are polymerization degrees, x > 0 and y > 0, preferably x > 1 and y > 1. In the present invention, the average relative molecular weight of the amorphous fluororesin is 10000 ～ 1000000, preferably 200000 ～ 500000. The invention controls the average relative molecular weight of the amorphous fluororesin in the above range so as to ensure the oxygen permeability and the light transmittance of the amorphous fluororesin and simultaneously have higher mechanical property and solubility.
In the present invention, the Q fragment in formula 1 is a fragment having a chemical structure represented by formula Q1, formula Q2, formula Q3, formula Q4 or formula Q5, preferably a fragment having a chemical structure represented by formula Q2.
The invention also provides a preparation method of the amorphous fluororesin according to the technical scheme, which comprises the following steps:
and mixing perfluoro-2, 2-dimethyl-1, 3-dioxole, Q' monomer, initiator perfluoro benzoyl peroxide and fluoridation liquid FC-72, and performing polymerization reaction to obtain the amorphous fluororesin.
The perfluoro-2, 2-dimethyl-1, 3-dioxole (namely PDD) is a compound with a chemical structure shown in a formula 2;
in the present invention, the Q ' monomer is a compound having a structure represented by formula Q1', formula Q2', formula Q3', formula Q4', or formula Q5', preferably a compound having a chemical structure represented by formula Q2 '.
In the present invention, the molar ratio of the perfluoro-2, 2-dimethyl-1, 3-dioxole (i.e., PDD) monomer to the Q' monomer is preferably (0.1 to 10): 1, more preferably (0.8 to 5): 1, more preferably 1:1. The molar ratio of the perfluoro-2, 2-dimethyl-1, 3-dioxole monomer to the Q' monomer is controlled within the range so as to ensure that the prepared fluororesin has high molecular weight and proper glass transition temperature and is easy to process.
In the present invention, the mass ratio of the total mass of the perfluoro-2, 2-dimethyl-1, 3-dioxole and the Q' monomer to the initiator perfluorobenzoyl peroxide is preferably (400 to 600): 1, more preferably (450 to 550): 1, still more preferably 500:1. the invention controls the mass ratio of the total mass of perfluoro-2, 2-dimethyl-1, 3-dioxole and Q' monomer (namely all monomers) to the mass ratio of initiator perfluoro benzoyl peroxide in the above range so as to ensure that all monomers reach the maximum conversion rate in the polymerization process.
In the present invention, the fluorinated liquid FC-72 is preferably a fluorinated solvent produced by 3M company.
In the present invention, the ratio of the total mass of the perfluoro-2, 2-dimethyl-1, 3-dioxole and the Q' monomer to the mass of the fluorinated liquid FC-72 is preferably (0.6 to 2): 1, more preferably (0.8 to 1.6): 1, more preferably 1:1. the invention controls the mass ratio of the total mass of perfluoro-2, 2-dimethyl-1, 3-dioxole and Q' monomer (namely all monomers) to the fluorinated liquid FC-72 in the above range to ensure that all components are uniformly mixed.
The invention has no special limitation on the mixing mode of the perfluoro-2, 2-dimethyl-1, 3-dioxole, the Q' monomer, the initiator perfluoro benzoyl peroxide and the fluoride solution FC-72, and can realize uniform mixing of the components.
In the present invention, the polymerization reaction is preferably carried out under stirring in a nitrogen atmosphere. In the present invention, the polymerization reaction is carried out under stirring to ensure the sufficiency of polymerization and to block air in nitrogen to prevent the reaction from being affected.
In the present invention, the polymerization reaction temperature is 60 to 90 ℃, preferably 63 to 85 ℃, more preferably 65 ℃. In the present invention, the polymerization time is 10 to 14 hours, preferably 11 to 13 hours, more preferably 12 hours. The present invention controls the temperature and time of the polymerization reaction within the above ranges to ensure the sufficiency of the polymerization reaction and the molecular weight of the polymer.
After the polymerization reaction is completed, the invention preferably mixes the product of the polymerization reaction with acetone to sequentially perform sedimentation and washing to obtain a washing product.
The invention is beneficial to removing impurities in the products of the polymerization reaction by mixing the products of the polymerization reaction with acetone and sequentially carrying out sedimentation and washing.
After the washed product is obtained, the washed product is preferably subjected to vacuum drying to obtain the amorphous fluororesin.
In the present invention, the temperature of the vacuum drying is preferably 90 to 120 ℃, more preferably 95 to 115 ℃, and still more preferably 100 ℃. In the present invention, the time for the vacuum drying is preferably 3 to 8 hours, more preferably 4 to 6 hours, and still more preferably 5 hours. The invention controls the temperature and time of vacuum drying in the above range to ensure that the amorphous fluororesin is completely dried.
The preparation method of the amorphous fluororesin provided by the invention is simple to operate, mild in reaction condition and suitable for large-scale production. According to the preparation method provided by the invention, the amorphous fluororesin with the structure shown in the formula 1 is obtained as a random copolymer, and the molecular weight of the polymer and the molecular weight distribution range thereof can be controlled by controlling the proportion of the fed monomers, the temperature and time of the polymerization reaction, the quality of the initiator and the quality of the fluorinated solution, so that the amorphous fluororesin with good comprehensive performance is obtained.
The invention also provides the amorphous fluororesin prepared by the preparation method of the technical scheme or the application of the amorphous fluororesin in preparing the release film.
The invention also provides a preparation method of the light-transmitting oxygen-transmitting release film, which comprises the following steps:
(1) Mixing the amorphous fluororesin prepared by the technical scheme or the amorphous fluororesin prepared by the preparation method with a fluorine-containing plasticizer and a fluorine-containing solvent to obtain a fluororesin solution;
(2) Filtering and purifying the fluororesin solution obtained in the step (1) to obtain a pretreatment solution;
(3) Casting the pretreatment solution obtained in the step (2) onto a substrate, sequentially performing drying and blowing treatment, and sequentially performing cooling, stripping, rolling and cutting to obtain the light-transmitting oxygen-permeable release film.
According to the invention, the amorphous fluororesin prepared by the technical scheme or the amorphous fluororesin prepared by the preparation method is mixed with a fluorine-containing plasticizer and a fluorine-containing solvent to obtain a fluororesin solution.
In the present invention, the fluorine-containing plasticizer is preferably any one of methyl perfluoro glutarate, methyl perfluoro adipate and methyl perfluoro suberate.
In the present invention, the mass ratio of the amorphous fluororesin to the fluorine-containing plasticizer is preferably (30 to 80): 1, more preferably (40 to 60): 1, more preferably (50:1). The present invention controls the mass ratio of the amorphous fluororesin to the fluorine-containing plasticizer within the above range to reduce the viscosity of the amorphous fluororesin solution and to increase the fluidity of the fluororesin solution.
In the present invention, the fluorine-containing solvent is preferably one or more of perfluorobenzene, SF-10, FC-75, vertrel XF and FC-72. In the present invention, both VertrelXF and SF-10 are preferably fluorine-containing solvents manufactured by Chemours, inc. of America. In the present invention, the FC-75 and FC-72 are preferably fluorine-containing solvents manufactured by 3M company.
In the present invention, the ratio of the mass of the amorphous fluororesin to the mass of the fluorine-containing solvent is preferably (1 to 15): (85 to 99), more preferably (2 to 10): (90-98). The invention controls the ratio of the mass of the amorphous fluorine resin and the mass of the fluorine-containing solvent in the range so as to ensure that the amorphous fluorine resin is completely dissolved in the fluorine-containing solvent and ensure the fluidity of the amorphous fluorine resin solution so as to facilitate the subsequent processing.
In the present invention, the temperature at which the amorphous fluororesin is mixed with the fluorine-containing plasticizer and the fluorine-containing solvent is preferably 25 to 100 ℃, more preferably 30 to 90 ℃, and still more preferably 80 ℃. The invention controls the mixing temperature in the above range to ensure that the components are completely dissolved.
In the present invention, the mass concentration of the amorphous fluororesin in the fluororesin solution is preferably 1 to 15wt%, more preferably 1.5 to 12wt%, and still more preferably 2 to 10wt%. The invention controls the mass concentration of the amorphous fluororesin in the fluororesin solution within the above range so as to ensure that the amorphous fluororesin is completely dissolved in the fluorine-containing solvent.
In the present invention, the fluorine-containing plasticizer is used only as an additive, and does not account for the total mass of the fluororesin solution.
After the fluororesin solution is obtained, the fluororesin solution is filtered and purified to obtain a pretreatment solution.
In the present invention, the pore size of the filter for filtration and purification is preferably 3 to 18. Mu.m, more preferably 5 to 15. Mu.m, and still more preferably 9. Mu.m. In the present invention, the pressure of the filtration purification is preferably 0.8 to 10atm, more preferably 1 to 8atm, and still more preferably 5atm. The invention controls the aperture of the filter screen used for filtering and purifying and the pressure of the filtering in the range so as to ensure that the prepared pretreatment solution has no impurities and gel, thereby being beneficial to improving the performance of the light-transmitting and oxygen-transmitting release film prepared subsequently.
After the pretreatment solution is obtained, the pretreatment solution is cast on a substrate, and then is subjected to drying and blowing treatment in sequence, and then is subjected to cooling, stripping, rolling and cutting in sequence, so that the light-transmitting oxygen-permeable release film is obtained.
In the present invention, the temperature of the pretreatment solution at the time of casting is preferably 40 to 110 ℃, more preferably 50 to 100 ℃, and still more preferably 80 ℃. The invention controls the temperature of the pretreatment solution in casting in the range so as to ensure the fluidity of the pretreatment solution to facilitate the subsequent processing. The thickness of the cast product, i.e., the cast film, in the present invention is controlled by the movement rate of the substrate, the casting coating rate, the distance between the casting die and the surface of the substrate, the mass concentration of the amorphous fluororesin in the pretreatment solution, and the like.
In the present invention, the substrate is preferably made of stainless steel.
In the present invention, the temperature of the drying is preferably 100 to 200 ℃, more preferably 120 to 180 ℃, and even more preferably 140 ℃. The invention controls the drying temperature in the above range to effectively remove the organic solvent. The drying time is not particularly limited, and the purpose of removing the organic solvent can be achieved.
In the present invention, in the drying process, the present invention preferably recovers the solvent volatilized in the drying process by using a solvent recovery device.
In the present invention, the purge treatment includes a first purge and a second purge which are sequentially performed. In the present invention, the gas used for the first purge is a mixed gas of fluorine-containing gases. In the present invention, the mixed gas of fluorine-containing gas preferably comprises (15 to 25) by volume: 100 or a mixed gas consisting of fluorine gas and nitrogen gas in a volume ratio of (15-25): 100, more preferably a mixed gas consisting of fluorine gas and argon gas in a volume ratio of 20:100 or a mixed gas consisting of fluorine gas and nitrogen gas with the volume ratio of 20:100, and argon. In the present invention, the time of the first purge is preferably 20 to 40 seconds, more preferably 30 seconds. The invention controls the time of the first blowing in the range so as to ensure that the prepared release film has good uniformity of the inside and the surface and reduce the release force of the surface of the release film.
In the present invention, the gas used for the second purge is preferably nitrogen. In the present invention, the time of the second purge is preferably 20 to 40 seconds, and more preferably 30 seconds. The invention controls the time of the second purging in the above range so as to make the surface of the release film smoother.
In the present invention, the thickness of the light-transmitting oxygen-transmitting release film is preferably 20 to 400. Mu.m, more preferably 40 to 300. Mu.m, still more preferably 60 to 200. Mu.m. The thickness of the light-transmitting oxygen-permeable release film is controlled in the range, so that the flatness and the supporting strength of the light-transmitting oxygen-permeable release film are ensured. In the invention, the light-transmitting oxygen-permeable release film is preferably a perfluorinated cyclic ether copolymer film with a single-layer structure.
After the purging treatment is completed, the film after the purging treatment is sequentially cooled, peeled, rolled and cut.
The cooling mode is not particularly limited, and the cooling mode is a mode which is well known to those skilled in the art. The stripping, winding and cutting modes are not particularly limited, and the technical scheme well known to the person skilled in the art can be adopted.
The invention also provides the light-transmitting and oxygen-transmitting release film prepared by the preparation method.
According to the preparation method provided by the invention, the amorphous fluororesin is used as a raw material, and the prepared light-transmitting oxygen-transmitting release film has the advantages of high oxygen transmission, good light transmission, good toughness, excellent mechanical property and long service life.
The invention also provides an application of the light-transmitting oxygen-permeable release film prepared by the technical scheme or the preparation method in photocuring 3D printing.
The light-transmitting oxygen-transmitting release film provided by the invention can completely meet the application of the current large-scale continuous industrial 3D printing device, and has excellent comprehensive performance.
The technical solutions of the present invention will be clearly and completely described in the following in connection with the embodiments of the present invention. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
An amorphous fluororesin having a structure represented by the formula 1-1, denoted as FR-1, prepared by the steps of:
122g (0.5 mol) of perfluoro-2, 2-dimethyl-1, 3-dioxole (namely PDD), 122g (0.5 mol) of Q1' monomer, 488mg of initiator perfluoro benzoyl peroxide and 244g of FC-72 fluorine-containing solvent are added into a 1000ml polymerization kettle, after liquid nitrogen is cooled, vacuumizing and nitrogen exchanging are carried out for three deoxidization operations, after the polymerization reaction is carried out for 12 hours under the condition of nitrogen atmosphere and stirring, white viscous polymer is obtained, the initial product is poured into 1000ml of acetone for sedimentation and washing, the operation is repeated twice, and then the vacuum drying is carried out for 5 hours at 100 ℃,223g of white amorphous fluororesin product, designated FR-1, was obtained, and the average relative molecular weight of the polymer FR-1 was 4.18X10 as measured by the viscometry 5 。
The molar ratio of perfluoro-2, 2-dimethyl-1, 3-dioxole (i.e. PDD) to Q1' monomer is 1:1, a step of; the mass ratio of the total mass of the perfluoro-2, 2-dimethyl-1, 3-dioxole and the Q1' monomer to the initiator perfluoro benzoyl peroxide is 500:1; the mass ratio of the total mass of the perfluoro-2, 2-dimethyl-1, 3-dioxole and the Q1' monomer to the fluorine-containing solvent FC-72 is 1:1.
The glass transition temperature tg=215 ℃ of FR-1 was detected using a differential scanning calorimeter DSC, as shown in fig. 1.
Nuclear magnetic resonance 19 F NMR) characterization of the structure of the polymer FR-1, the proportion of repeat units formed by PDD and Q1' respectively in the copolymer was determined to be 0.86:1.
example 2
An amorphous fluororesin having a structure represented by the formula 1-2, denoted as FR-2, prepared by the steps of:
122g (0.5 mol) of perfluoro-2, 2-dimethyl-1, 3-dioxole (PDD), 147g (0.5 mol) of Q2' monomer, 538mg of initiator perfluoro benzoyl peroxide and 269g of FC-72 fluorine-containing solvent are added into a 1000ml polymerization kettle, liquid nitrogen is cooled, vacuum pumping and nitrogen exchange are carried out for three deoxidization operations, polymerization reaction is carried out for 12 hours under the condition of nitrogen atmosphere and stirring after heating to 65 ℃, white viscous polymer is obtained, the initial product is poured into 1000ml of acetone for sedimentation and washing, the operation is repeated for two times, the vacuum drying is carried out for 5 hours at 100 ℃ to obtain 248g of white amorphous fluororesin product which is named FR-2, and the average relative molecular weight of the polymer FR-2 is 4.93 multiplied by 10 measured by adopting a viscosity method 5 。
The molar ratio of perfluoro-2, 2-dimethyl-1, 3-dioxole (i.e. PDD) to Q2' monomer is 1:1, a step of; the mass ratio of the total mass of the perfluoro-2, 2-dimethyl-1, 3-dioxole and the Q2' monomer to the initiator perfluoro benzoyl peroxide is 500:1; the mass ratio of the total mass of the perfluoro-2, 2-dimethyl-1, 3-dioxole and the Q2' monomer to the fluorine-containing solvent FC-72 is 1:1.
The glass transition temperature tg=221℃offr-2 was detected by a differential scanning calorimeter DSC as shown in FIG. 1.
Nuclear magnetic resonance 19 F NMR) characterization of the structure of the polymer FR-2, the ratio of repeat units formed by PDD and Q2' respectively in the copolymer was determined to be 0.89:1.
example 3
An amorphous fluororesin having a structure represented by the formula 1-3, denoted as FR-3, prepared by the steps of:
122g (0.5 mol) PDD perfluoro-2, 2-dimethyl-1, 3-dioxole, 153g (0.5 mol) Q3' monomer, 550mg initiator perfluoro benzoyl peroxide and 275g FC-72 fluorine-containing solvent are added into a 1000ml polymerization kettle, after liquid nitrogen is cooled, vacuum pumping and nitrogen exchange are carried out for three deoxidization operations, the polymerization reaction is carried out for 12 hours under the condition of nitrogen atmosphere and stirring, white viscous polymer is obtained, the initial product is poured into 1000ml acetone for sedimentation and washing, the operation is repeated twice, the vacuum drying is carried out for 5 hours at 100 ℃ to obtain 261g white amorphous fluorine resin, named FR-3, and the average relative molecular weight of the polymer FR-3 is 3.26 multiplied by 10 measured by adopting a viscosity method 5 。
The molar ratio of the perfluoro-2, 2-dimethyl-1, 3-dioxole (namely PDD) to the Q3' monomer is 1:1; the mass ratio of the total mass of the perfluoro-2, 2-dimethyl-1, 3-dioxole and the Q3' monomer to the initiator perfluoro benzoyl peroxide is 500:1; the mass ratio of the total mass of the perfluoro-2, 2-dimethyl-1, 3-dioxole and the Q3' monomer to the fluorine-containing solvent FC-72 is 1:1;
the glass transition temperature tg=228℃offr-3 was measured by a differential scanning calorimeter DSC as shown in FIG. 1.
Nuclear magnetic resonance 19 F NMR) characterization of the structure of the polymer FR-3, the ratio of repeat units formed by PDD and Q3' respectively in the copolymer was determined to be 1.07:1.
example 4
An amorphous fluororesin having a structure represented by the formula 1-4, denoted as FR-4, prepared by the steps of:
122g (0.5 mol) PDD perfluoro-2, 2-dimethyl-1, 3-dioxole, 178g (0.5 mol) Q4' monomer, 600mg initiator perfluoro-benzoyl peroxide and 300g FC-72 fluorine-containing solvent are added into a 1000ml polymerization kettle, after liquid nitrogen is cooled, vacuum pumping and nitrogen exchange are carried out for three deoxidization operations, polymerization reaction is carried out for 12 hours under the condition of nitrogen atmosphere and stirring, white viscous polymer is obtained, the initial product is poured into 1000ml acetone for sedimentation and washing, the operation is repeated twice, vacuum drying is carried out for 5 hours at 100 ℃ to obtain 283.5g white amorphous fluorine resin which is named FR-4, and the average relative molecular weight of the polymer FR-4 is 2.05x10 measured by adopting a viscosity method 5 。
The molar ratio of the perfluoro-2, 2-dimethyl-1, 3-dioxole (namely PDD) to the Q3' monomer is 1:1; the mass ratio of the total mass of the perfluoro-2, 2-dimethyl-1, 3-dioxole and the Q3' monomer to the initiator perfluoro benzoyl peroxide is 500:1; the mass ratio of the total mass of the perfluoro-2, 2-dimethyl-1, 3-dioxole and the Q3' monomer to the fluorine-containing solvent FC-72 is 1:1.
The glass transition temperature tg=235℃offr-4 was detected by a differential scanning calorimeter DSC as shown in FIG. 1.
Nuclear magnetic resonance 19 F NMR) characterization of the structure of the polymer FR-3, the ratio of repeat units formed by PDD and Q4' respectively in the copolymer was determined to be 1.15:1.
example 5
An amorphous fluororesin having a structure represented by the formula 1-5, denoted as FR-5, prepared by the steps of:
122g (0.5 mol) PDD perfluoro-2, 2-dimethyl-1, 3-dioxole, 147g (0.5 mol) Q5' monomer, 538mg initiator perfluoro-benzoyl peroxide and 269g FC-72 fluorine-containing solvent are added into a 1000ml polymerization kettle, after liquid nitrogen is cooled, the vacuum pumping and nitrogen exchange are carried out for three deoxidization operations, the polymerization reaction is carried out for 12 hours under the condition of heating to 65 ℃ under the nitrogen atmosphere and stirring, white viscous polymer is obtained, the initial product is poured into 1000ml acetone for sedimentation and washing, the operation is repeated twice, the vacuum drying is carried out for 5 hours at 100 ℃ to obtain 248g white amorphous fluorine resin which is named FR-5, and the average relative molecular weight of the polymer FR-5 is 3.25 multiplied by 10 measured by adopting a viscosity method 5 。
The molar ratio of the perfluoro-2, 2-dimethyl-1, 3-dioxole (namely PDD) to the Q5' monomer is 1:1; the mass ratio of the total mass of the perfluoro-2, 2-dimethyl-1, 3-dioxole and the Q5' monomer to the initiator perfluoro benzoyl peroxide is 500:1; the mass ratio of the total mass of the perfluoro-2, 2-dimethyl-1, 3-dioxole and the Q5' monomer to the fluorine-containing solvent FC-72 is 1:1.
The glass transition temperature tg=217 ℃ of FR-5 was detected by differential scanning calorimeter DSC, as shown in fig. 1.
Nuclear magnetic resonance 19 F NMR) characterization of the structure of the polymer FR-5, the ratio of repeat units formed by PDD and Q5' respectively in the copolymer was determined to be 0.93:1.
the flow chart of the preparation method of the light-transmitting oxygen-transmitting release film is shown in fig. 2, and specifically comprises the following steps: firstly, mixing amorphous fluororesin with a fluorine-containing plasticizer and a fluorine-containing solvent to obtain a fluororesin solution, then filtering and purifying to obtain a pretreatment solution, casting the pretreatment solution onto a substrate, sequentially performing drying and purging treatments, and sequentially performing cooling, stripping, rolling and cutting to obtain the light-transmitting oxygen-permeable release film.
Product example 1
A preparation method of a light-transmitting oxygen-transmitting release film is characterized in that the FR-1 release film comprises the following steps:
(1) 20 g of dried amorphous fluororesin prepared by the preparation method described in the example 1, namely FR-1 and 0.4 g of perfluor adipic acid methyl ester, are added into 980 g of perfluor benzene, heated to 80 ℃ and stirred for dissolution, so as to obtain a transparent fluororesin solution with the mass concentration of FR-1 of 2 wt%;
the mass ratio of the amorphous fluororesin to the fluorine-containing plasticizer in the step (1) is 50:1; the mass ratio of the amorphous fluororesin to the fluorine-containing solvent is 2:98;
(2) Filtering and purifying the fluororesin solution obtained in the step (1) by a stainless steel filter screen with a 9-micrometer aperture by a pressurizing pump with the pressure of 5atm to obtain a pretreatment solution;
(3) Casting and coating the pretreatment solution obtained in the step (2) on a continuously running stainless steel belt through a casting die head to form a gelatinous solution layer, then entering a closed drying area, reversely blowing hot air at 140 ℃ into the drying area, drying at 140 ℃, connecting a solvent recovery device at the top to recover the volatilized solvent, continuously running the formed film layer along with the steel belt, entering a film surface treatment, namely a purging treatment area, and firstly introducing the film layer with the volume ratio of 20:100, and then passivating the surface of the film, and then carrying out second purging by using nitrogen, cooling the film on the steel belt, and then stripping, rolling and cutting to obtain the FR-1 release film with the thickness of 60 mu m.
Product example 2
A preparation method of a light-transmitting oxygen-transmitting release film is characterized in that the FR-2 release film comprises the following steps:
(1) 30 g of amorphous fluororesin prepared by the preparation method described in example 2, namely FR-2 and 0.6 g of methyl perfluorosuberate, are added into 970 g of SF-10, heated to 80 ℃ and stirred for dissolution, so as to obtain a transparent fluororesin solution with the mass concentration of FR-2 of 3 wt%;
the mass ratio of the amorphous fluororesin to the fluorine-containing plasticizer in the step (1) is 50:1; the mass ratio of the amorphous fluororesin to the fluorine-containing solvent is 3:97;
(2) Filtering and purifying the fluororesin solution obtained in the step (1) by a stainless steel filter screen with a 9-micrometer aperture by a pressurizing pump with the pressure of 5atm to obtain a pretreatment solution;
(3) Casting and coating the pretreatment solution obtained in the step (2) on a continuously running stainless steel belt through a casting die head to form a gelatinous solution layer, then entering a closed drying area, reversely blowing hot air at 140 ℃ into the drying area, drying at 140 ℃, connecting a solvent recovery device at the top to recover the volatilized solvent, continuously running the formed film layer along with the steel belt, entering a film surface treatment, namely a purging treatment area, and firstly introducing the film layer with the volume ratio of 20:100, and then passivating the surface of the film, and then carrying out second purging by using nitrogen, and then peeling, rolling and cutting the film on the steel belt after cooling to obtain the FR-2 release film with the thickness of 80 mu m.
The film surface of the light-transmitting oxygen-permeable release film prepared in the product example 2 is observed by using a 10-micron scanning electron microscope, and a 10-micron electron microscope image is obtained, as shown in fig. 3, and as can be seen from fig. 3, the film surface of the light-transmitting oxygen-permeable release film prepared in the product example 2 is uniform and has no flaws.
The surface of the light-transmitting oxygen-permeable release film prepared in the product example 2 is observed by using a 300-nanometer scanning electron microscope, a 300-nanometer scanning electron microscope image is obtained, as shown in fig. 4, and as can be seen from fig. 4, the nanometer micropores on the surface of the light-transmitting oxygen-permeable release film prepared in the product example 2 are uniformly distributed.
Product example 3
A preparation method of a light-transmitting oxygen-transmitting release film is characterized in that the FR-3 release film comprises the following steps:
(1) 50 g of amorphous fluororesin prepared by the preparation method described in example 3, namely FR-3 and 1g of perfluoro-glutarate methyl ester, are added into 950 g of FC-75, and heated to 80 ℃ and stirred for dissolution, so as to obtain transparent fluororesin solution with FR-3 mass concentration of 5 wt%;
the mass ratio of the amorphous fluororesin to the fluorine-containing plasticizer in the step (1) is 50:1; the mass ratio of the amorphous fluororesin to the fluorine-containing solvent is 5:95;
(2) Filtering and purifying the fluororesin solution obtained in the step (1) by a stainless steel filter screen with a 9-micrometer aperture by a pressurizing pump with the pressure of 5atm to obtain a pretreatment solution;
(3) Casting and coating the pretreatment solution obtained in the step (2) on a continuously running stainless steel belt through a casting die head to form a gelatinous solution layer, then entering a closed drying area, reversely blowing hot air at 140 ℃ into the drying area, drying at 140 ℃, connecting a solvent recovery device at the top to recover the volatilized solvent, continuously running the formed film layer along with the steel belt, entering a film surface treatment, namely a purging treatment area, and firstly introducing the film layer with the volume ratio of 20: and (3) carrying out first purging on the mixed gas consisting of fluorine gas and nitrogen gas at 100 to passivate the surface of the film, and then carrying out second purging on the film by nitrogen gas, cooling the film on the steel belt, and then stripping, rolling and cutting to obtain the FR-3 release film with the thickness of 100 mu m.
Product example 4
A preparation method of a light-transmitting oxygen-transmitting release film is characterized in that the FR-4 release film comprises the following steps:
(1) 65 g of the amorphous fluororesin prepared by the preparation method described in example 4, namely FR-4 and 1.3 g of methyl perfluorosuberate, were added to 935 g of SF-10, heated to 80 ℃ and stirred for dissolution to obtain a transparent fluororesin solution having a concentration of 6.5wt% of FR-4;
the mass ratio of the amorphous fluororesin to the fluorine-containing plasticizer in the step (1) is 50:1; the mass ratio of the amorphous fluororesin to the fluorine-containing solvent is 6.5:93.5;
(2) Filtering and purifying the fluororesin solution obtained in the step (1) by a stainless steel filter screen with a 9-micrometer aperture by a pressurizing pump with the pressure of 5atm to obtain a pretreatment solution;
(3) Casting and coating the pretreatment solution obtained in the step (2) on a continuously running stainless steel belt through a casting die head to form a gelatinous solution layer, then entering a closed drying area, reversely blowing hot air at 140 ℃ into the drying area, drying at 140 ℃, connecting a solvent recovery device at the top to recover the volatilized solvent, continuously running the formed film layer along with the steel belt, entering a film surface treatment, namely a purging treatment area, and firstly introducing the film layer with the volume ratio of 20:100, and then passivating the surface of the film, and then carrying out second purging by using nitrogen, and then peeling, rolling and cutting the film on the steel belt after cooling to obtain the FR-4 release film with the thickness of 130 mu m.
Product example 5
A preparation method of a light-transmitting oxygen-transmitting release film is characterized in that the FR-5 release film comprises the following steps:
(1) 100 g of dried amorphous fluororesin prepared by the preparation method described in example 5, namely FR-5 resin particles and 2g of perfluoro-suberate methyl ester, are added into 900 g of SF-10, heated to 80 ℃ and stirred for dissolution, so as to obtain a transparent fluororesin solution with the FR-5 mass concentration of 10 wt%;
the mass ratio of the amorphous fluororesin to the fluorine-containing plasticizer in the step (1) is 50:1; the mass ratio of the amorphous fluororesin to the fluorine-containing solvent is 10:90;
(2) Filtering and purifying the fluororesin solution obtained in the step (1) by a stainless steel filter screen with a 9-micrometer aperture by a pressurizing pump with the pressure of 5atm to obtain a pretreatment solution;
(3) Casting and coating the pretreatment solution obtained in the step (2) on a continuously running stainless steel belt through a casting die head to form a gelatinous solution layer, then entering a closed drying area, reversely blowing hot air at 140 ℃ into the drying area, drying at 140 ℃, connecting a solvent recovery device at the top to recover the volatilized solvent, continuously running the formed film layer along with the steel belt, entering a film surface treatment, namely a purging treatment area, and firstly introducing the film layer with the volume ratio of 20:100, and then passivating the surface of the film, and then carrying out second blowing by using nitrogen, and then peeling, rolling and cutting the film on the steel belt after cooling to obtain the FR-5 release film with the thickness of 200 mu m.
The oxygen permeability of the release films prepared in examples 1 to 5 was measured by the differential pressure method according to the same standard as that of the TeflonAF2400 film, the light transmittance was measured by an ultraviolet spectrophotometer, and the tensile strength and elongation at break were measured by a universal material tester, and the test results are shown in Table 1 below.
Table 1 results statistics of oxygen permeability, light transmittance, tensile Strength and elongation at break of light-transmitting oxygen-permeable Release films and TeflonAF2400 films prepared respectively in product examples 1 to 5
In conclusion, the surface of the light-transmitting oxygen-permeable release film prepared from the amorphous fluororesin provided by the invention is uniform and free of any flaws, nano micropores are uniformly distributed, the oxygen permeability (Barrer) of the film can reach 1260, the light transmittance can reach 98%, the tensile strength can reach 48MPa, and the elongation at break can reach 18.2%. The light-transmitting oxygen-transmitting release film prepared by taking the amorphous fluororesin provided by the invention as a raw material has the advantages of high oxygen transmission, good light transmission, good toughness, excellent mechanical property and long service life.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (10)
1. An amorphous fluororesin having a chemical structure represented by formula 1,
in the formula 1, Q is a repeating unit formed by five-membered or six-membered cyclic ether olefin monomers, x and y are polymerization degrees, x is more than 0 and y is more than 0, and the average relative molecular weight of the amorphous fluororesin is 10000 ～ 1000000.
2. The amorphous fluororesin according to claim 1, wherein the Q segment in formula 1 is a segment having a chemical structure represented by formula Q1, formula Q2, formula Q3, formula Q4 or formula Q5;
3. the method for producing an amorphous fluororesin according to claim 1 or 2, comprising the steps of:
mixing perfluoro-2, 2-dimethyl-1, 3-dioxole, Q' monomer, initiator perfluoro benzoyl peroxide and fluoridation liquid FC-72, and then carrying out polymerization reaction to obtain amorphous fluororesin;
the perfluoro-2, 2-dimethyl-1, 3-dioxole (namely PDD) is a compound with a chemical structure shown in a formula 2;
the Q 'monomer is a compound with a chemical structure shown in a formula Q1', a formula Q2', a formula Q3', a formula Q4 'or a formula Q5';
the polymerization reaction was carried out under a nitrogen atmosphere.
4. The method according to claim 3, wherein the polymerization reaction is carried out at a temperature of 60 to 90℃for a time of 10 to 14 hours.
5. Use of the amorphous fluororesin according to claim 1 or 2 or the amorphous fluororesin prepared by the preparation method according to claim 3 or 4 for preparing a release film.
6. A preparation method of a light-transmitting oxygen-transmitting release film comprises the following steps:
(1) Mixing the amorphous fluororesin according to claim 1 or 2 or the amorphous fluororesin prepared by the preparation method according to claim 3 or 4 with a fluorine-containing plasticizer and a fluorine-containing solvent to obtain a fluororesin solution;
(2) Filtering and purifying the fluororesin solution obtained in the step (1) to obtain a pretreatment solution;
(3) Casting the pretreatment solution obtained in the step (2) onto a substrate, sequentially performing drying and blowing treatment, and sequentially performing cooling, stripping, rolling and cutting to obtain the light-transmitting oxygen-permeable release film.
7. The method according to claim 6, wherein the concentration of the amorphous fluororesin in the fluororesin solution in the step (1) is 1 to 15% by weight.
8. The method according to claim 6, wherein the purging in the step (3) comprises a first purging and a second purging which are sequentially performed, and the gas used for the first purging is F-containing 2 The gas used for the second purge is nitrogen.
9. The light-transmitting and oxygen-transmitting release film prepared by the preparation method of any one of claims 6 to 8.
10. The application of the light-transmitting oxygen-transmitting release film prepared by the preparation method of any one of claims 6 to 8 or the light-transmitting oxygen-transmitting release film of claim 9 in photo-curing 3D printing.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2022112243193 | 2022-10-09 | ||
| CN202211224319 | 2022-10-09 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN117843865A true CN117843865A (en) | 2024-04-09 |
| CN117843865B CN117843865B (en) | 2024-09-20 |
Family
ID=90540644
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211342175.1A Active CN117843865B (en) | 2022-10-09 | 2022-10-31 | Amorphous fluororesin, preparation method and application thereof, light-transmitting oxygen-permeable release film, and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117843865B (en) |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5276121A (en) * | 1992-05-05 | 1994-01-04 | E. I. Du Pont De Nemours And Company | Amorphous copolymers of two fluorinated ring monomers |
| US5408020A (en) * | 1994-05-09 | 1995-04-18 | E. I. Du Pont De Nemours And Company | Copolymers of perhalo-2,2-di-loweralkyl-1,3-dioxole, and perfluoro-2-methylene-4-methyl-1,3-dioxolane |
| CN1213677A (en) * | 1997-10-02 | 1999-04-14 | 旭硝子株式会社 | Refractivity distributing optical resin material |
| CN102471412A (en) * | 2009-07-31 | 2012-05-23 | 旭硝子株式会社 | Electrolyte material, liquid composition, and membrane electrode assembly for solid polymer fuel cell |
| JP2017214478A (en) * | 2016-05-31 | 2017-12-07 | ダイキン工業株式会社 | Release film |
| CN108047189A (en) * | 2017-12-11 | 2018-05-18 | 博容新材料（深圳）有限公司 | A kind of own cycloolefin of fluorine-containing dioxa, its homopolymer and preparation method thereof |
| CN108517025A (en) * | 2018-03-23 | 2018-09-11 | 博容新材料（深圳）有限公司 | A kind of amorphous fluoropolymer and preparation method thereof |
| CN112375173A (en) * | 2020-11-23 | 2021-02-19 | 杭州师范大学 | Low-refractive-index transparent material and preparation method and application thereof |
| CN112771086A (en) * | 2018-09-28 | 2021-05-07 | 东曹株式会社 | Fluororesin, fluororesin particles, and processes for producing these |
| WO2022245887A2 (en) * | 2021-05-18 | 2022-11-24 | Chromis Fiberoptics, Inc. | Gas separation articles composed of amorphous fluorinated copolymers of dioxolanes and other fluorinated ring monomers and methods of making and using thereof |
-
2022
- 2022-10-31 CN CN202211342175.1A patent/CN117843865B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5276121A (en) * | 1992-05-05 | 1994-01-04 | E. I. Du Pont De Nemours And Company | Amorphous copolymers of two fluorinated ring monomers |
| US5408020A (en) * | 1994-05-09 | 1995-04-18 | E. I. Du Pont De Nemours And Company | Copolymers of perhalo-2,2-di-loweralkyl-1,3-dioxole, and perfluoro-2-methylene-4-methyl-1,3-dioxolane |
| CN1213677A (en) * | 1997-10-02 | 1999-04-14 | 旭硝子株式会社 | Refractivity distributing optical resin material |
| CN102471412A (en) * | 2009-07-31 | 2012-05-23 | 旭硝子株式会社 | Electrolyte material, liquid composition, and membrane electrode assembly for solid polymer fuel cell |
| JP2017214478A (en) * | 2016-05-31 | 2017-12-07 | ダイキン工業株式会社 | Release film |
| CN108047189A (en) * | 2017-12-11 | 2018-05-18 | 博容新材料（深圳）有限公司 | A kind of own cycloolefin of fluorine-containing dioxa, its homopolymer and preparation method thereof |
| CN108517025A (en) * | 2018-03-23 | 2018-09-11 | 博容新材料（深圳）有限公司 | A kind of amorphous fluoropolymer and preparation method thereof |
| CN112771086A (en) * | 2018-09-28 | 2021-05-07 | 东曹株式会社 | Fluororesin, fluororesin particles, and processes for producing these |
| CN112375173A (en) * | 2020-11-23 | 2021-02-19 | 杭州师范大学 | Low-refractive-index transparent material and preparation method and application thereof |
| WO2022245887A2 (en) * | 2021-05-18 | 2022-11-24 | Chromis Fiberoptics, Inc. | Gas separation articles composed of amorphous fluorinated copolymers of dioxolanes and other fluorinated ring monomers and methods of making and using thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN117843865B (en) | 2024-09-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5399098B2 (en) | Block copolymer and method for producing the same | |
| CN101293185A (en) | Method for producing polyvinylidene fluoride porous membrane | |
| JP3021979B2 (en) | Polyimide precursor solution, method for producing the same, molded body and coating obtained therefrom | |
| JP5338660B2 (en) | Method for producing fluorinated perfluoropolymer | |
| JP2001511210A (en) | Method for producing fluorocarbon polymer | |
| CN113698599B (en) | Polyimide resin and preparation method thereof | |
| CN111617641B (en) | Imidazole functionalized ionic liquid copolymer synthesis and alloy ultrafiltration membrane preparation method | |
| CN117843865B (en) | Amorphous fluororesin, preparation method and application thereof, light-transmitting oxygen-permeable release film, and preparation method and application thereof | |
| JP2951484B2 (en) | Powder and granules of polyimide precursor, mixture thereof and production method thereof | |
| JP5633793B2 (en) | Method for producing stretched polytetrafluoroethylene film and stretched polytetrafluoroethylene film | |
| KR101144833B1 (en) | Perfluorinated polymers | |
| JP4996784B2 (en) | (Per) fluorinated amorphous polymer film | |
| JP2022179573A (en) | Production method of fluororesin particles containing fluorine-containing aliphatic ring structure | |
| CN107261863B (en) | Preparation method of anti-pollution polyvinyl chloride film | |
| JPH0824602A (en) | Surface-improve gas separation membrane and its preparation | |
| JP2012251022A (en) | Polyphenylene sulfide resin foam and method of producing the same | |
| WO2020075724A1 (en) | Fluororesin, method for producing same, and method for producing fluororesin particles | |
| JPH03287630A (en) | Production of polyvinyl alcohol film and production of polarizing film | |
| CN111992055A (en) | Preparation method of organic-inorganic composite ultrafiltration membrane based on carboxyl-containing polyaryletherketone and graphene oxide | |
| Wang et al. | Preparation, characterisation and gas transport properties of trifluoroacetylated ethyl cellulose | |
| JP7553859B2 (en) | Modified polytetrafluoroethylene and aqueous dispersion | |
| JPS61266442A (en) | Production of porous fluorinated polyolefin article | |
| JP5332076B2 (en) | Method for producing recycled polyindigo film | |
| WO2024034677A1 (en) | Modified polytetrafluoroethylene | |
| CN117323844A (en) | High-toughness chlorine-containing copolymer-based filtering membrane and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CB02 | Change of applicant information |
Country or region after: China Address after: Room 1309, Room 112, Building 10, No. 21, Lane 689, Changxing Road, Jiangbei District, Ningbo City, Zhejiang Province, 315000 Applicant after: NINGBO JIAMA MATERIAL TECHNOLOGY Co.,Ltd. Address before: 200241, No. 77, Lane 500, Zilong Road, Minhang District, Shanghai, 1001 Applicant before: NINGBO JIAMA MATERIAL TECHNOLOGY Co.,Ltd. Country or region before: China |
|
| CB02 | Change of applicant information |