CN113150283A - Fluorosilicone polymer capable of being subjected to UV light and thermal curing, preparation method thereof and coating - Google Patents
Fluorosilicone polymer capable of being subjected to UV light and thermal curing, preparation method thereof and coating Download PDFInfo
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- CN113150283A CN113150283A CN202110504295.6A CN202110504295A CN113150283A CN 113150283 A CN113150283 A CN 113150283A CN 202110504295 A CN202110504295 A CN 202110504295A CN 113150283 A CN113150283 A CN 113150283A
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- 229920000642 polymer Polymers 0.000 title claims abstract description 49
- 238000000576 coating method Methods 0.000 title claims abstract description 29
- 239000011248 coating agent Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 6
- 238000003848 UV Light-Curing Methods 0.000 title abstract description 10
- 238000001029 thermal curing Methods 0.000 title abstract description 7
- -1 cyclic siloxane Chemical class 0.000 claims abstract description 30
- ZHPNWZCWUUJAJC-UHFFFAOYSA-N fluorosilicon Chemical compound [Si]F ZHPNWZCWUUJAJC-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000001723 curing Methods 0.000 claims abstract description 24
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 15
- 239000011737 fluorine Substances 0.000 claims abstract description 15
- 239000003054 catalyst Substances 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims abstract description 10
- 239000002253 acid Substances 0.000 claims abstract description 9
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 9
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 7
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 7
- 239000003513 alkali Substances 0.000 claims abstract description 6
- 239000012974 tin catalyst Substances 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims description 12
- 239000010703 silicon Substances 0.000 claims description 12
- 229910052710 silicon Inorganic materials 0.000 claims description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000000016 photochemical curing Methods 0.000 claims description 10
- 229920002799 BoPET Polymers 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical group CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 6
- 238000009835 boiling Methods 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 229920002545 silicone oil Polymers 0.000 claims description 6
- 230000003472 neutralizing effect Effects 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 4
- 239000003292 glue Substances 0.000 claims description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 4
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 4
- ISPWSRVEMSGMKS-UHFFFAOYSA-N 3-[[3-hydroxypropyl(dimethyl)silyl]oxy-dimethylsilyl]propan-1-ol Chemical compound OCCC[Si](C)(C)O[Si](C)(C)CCCO ISPWSRVEMSGMKS-UHFFFAOYSA-N 0.000 claims description 2
- OWJKJLOCIDNNGJ-UHFFFAOYSA-N 4-[[4-hydroxybutyl(dimethyl)silyl]oxy-dimethylsilyl]butan-1-ol Chemical compound OCCCC[Si](C)(C)O[Si](C)(C)CCCCO OWJKJLOCIDNNGJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 2
- 239000000159 acid neutralizing agent Substances 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 239000012949 free radical photoinitiator Substances 0.000 claims description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 2
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 claims 2
- 239000005020 polyethylene terephthalate Substances 0.000 claims 2
- 229920001187 thermosetting polymer Polymers 0.000 abstract description 3
- 239000011253 protective coating Substances 0.000 abstract description 2
- 239000002904 solvent Substances 0.000 abstract description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 abstract 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- 238000012360 testing method Methods 0.000 description 8
- UKKQXBZHCNDFKQ-UHFFFAOYSA-N 1-[dimethylsilyloxy(dimethyl)silyl]propane-1,3-diol Chemical compound C[SiH](C)O[Si](C)(C)C(O)CCO UKKQXBZHCNDFKQ-UHFFFAOYSA-N 0.000 description 4
- BVTLTBONLZSBJC-UHFFFAOYSA-N 2,4,6-tris(ethenyl)-2,4,6-trimethyl-1,3,5,2,4,6-trioxatrisilinane Chemical compound C=C[Si]1(C)O[Si](C)(C=C)O[Si](C)(C=C)O1 BVTLTBONLZSBJC-UHFFFAOYSA-N 0.000 description 4
- FGZFESWHQXSPJU-UHFFFAOYSA-N 2-methyl-2-(3,3,3-trifluoropropyl)-1,3,5,2,4,6-trioxatrisilinane Chemical compound FC(F)(F)CC[Si]1(C)O[SiH2]O[SiH2]O1 FGZFESWHQXSPJU-UHFFFAOYSA-N 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 4
- 239000002390 adhesive tape Substances 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 4
- 239000010452 phosphate Substances 0.000 description 4
- 230000000379 polymerizing effect Effects 0.000 description 4
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 3
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000013005 condensation curing Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000004447 silicone coating Substances 0.000 description 2
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229920001688 coating polymer Polymers 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229920001558 organosilicon polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920005573 silicon-containing polymer Polymers 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
- C08G77/24—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen halogen-containing groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/06—Preparatory processes
- C08G77/08—Preparatory processes characterised by the catalysts used
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
- C08G77/26—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen nitrogen-containing groups
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
- C09D183/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
Abstract
The invention discloses a fluorine-silicon polymer capable of being subjected to UV light and thermosetting and a preparation method and a coating thereof, wherein the fluorine-silicon polymer capable of being subjected to UV light and thermosetting is polymerized by the following components in parts by weight: 10-80 parts of fluorine-containing cyclic siloxane; 10-80 parts of vinyl-containing cyclic siloxane; 0-80 parts of dimethyl cyclosiloxane mixture; 0.1-10 parts of 1, 3-dihydroxyalkyl-1, 1,3, 3-tetramethyldisiloxane; 1-1000ppm of alkali catalyst; 1-1000ppm of acid neutralizer; 0.1-10 parts of diisocyanate; 1-1000ppm of organic tin catalyst; 0.1-10 parts of hydroxyalkyl methacrylate or hydroxyalkyl acrylate. The fluorine-silicon polymer provided by the invention has good solvent resistance and heat resistance, is suitable for two curing modes of thermal curing and UV (ultraviolet) light curing, and has the priority of short curing period and high efficiency when UV light curing is utilized, so that the application field of the fluorine-silicon polymer is greatly expanded, such as the field of electronic protective coatings and the like.
Description
Technical Field
The invention relates to the field of preparation of organic silicon high polymer materials, in particular to a fluorine-silicon polymer capable of being subjected to UV light and thermal curing, a preparation method thereof and a coating.
Background
At present, coatings applied in the market are various, wherein silicone coatings of polysiloxane type occupy an extremely important position due to a plurality of application products and a wide application field. At present, the curing modes of the organic silicon coating polymer mainly comprise condensation curing and thermal curing, and the two traditional curing modes have more or less defects, such as a long period of about 2-3d during condensation curing, a high curing temperature required by thermal curing, and more than 100 ℃, so that the organic silicon polymer coating cannot be applied to some specific fields, such as substrates requiring short operation period or being sensitive to temperature.
The UV light curing can be carried out at normal temperature, and the curing only needs tens of seconds. The advantages of the UV light curing technology enable the UV light curing technology to have great potential application value in the field of coatings, and if the UV light curing technology is introduced into a silicone coating, the application field of the UV light curing technology can be greatly expanded, such as electronic protection coatings.
Disclosure of Invention
In order to overcome the above defects of the conventional silicone polymer coating, the first aspect of the present invention provides a UV-curable and thermosetting fluorosilicone polymer, which has the following specific technical scheme:
a fluorine-silicon polymer capable of being cured by UV light and heat has a molecular structure as follows:
wherein:
r is
Or
Wherein: x is an integer not less than 3, y is an integer not less than 2,
is composed of
One of (1);
pf is fluorine-containing alkyl and has a structural general formula of-C2H4CnF2n+1Wherein: n is an integer of 1 to 3000, m is an integer of 1 to 3000, and p is an integer of 0 to 3000.
In some embodiments, the fluorosilicone polymer is polymerized from the following components, by mass:
in some embodiments, the fluorine-containing cyclic siloxane is
Wherein: n is an integer of 1 or more.
In some embodiments, the vinyl-containing cyclic siloxane is
In some embodiments, the 1, 3-dihydroxyalkyl-1, 1,3, 3-tetramethyldisiloxane has the following general structural formula:
wherein: x is an integer of 3 or more.
In some embodiments, the 1, 3-dihydroxyalkyl-1, 1,3, 3-tetramethyldisiloxane is one of 1, 3-bis (hydroxypropyl) -1,1,3, 3-tetramethyldisiloxane, 1, 3-bis (hydroxybutyl) -1,1,3, 3-tetramethyldisiloxane.
In some embodiments, the base catalyst is one or more of sodium hydroxide, tetramethylammonium hydroxide, and silicon alkoxide; the acid neutralizer is one of phosphoric acid, hydrochloric acid, silicon-based acid ester glue and fluorine-containing silicon-based acid ester glue.
In some embodiments, the diisocyanate is one of isophorone diisocyanate, hexamethylene diisocyanate, toluene diisocyanate.
In some embodiments, the organotin-based catalyst is dibutyltin dilaurate.
The second aspect of the present invention provides a method for preparing a UV-curable and thermally curable fluorosilicone polymer, comprising:
weighing 10-80 parts of fluorine-containing cyclic siloxane, 10-80 parts of vinyl-containing cyclic siloxane, 0-80 parts of dimethylcyclosiloxane mixture, 0.1-10 parts of 1, 3-dihydroxyalkyl-1, 1,3, 3-tetramethyldisiloxane, 1-1000ppm of alkali catalyst (calculated by the total amount of the components), 1-1000ppm of acid neutralizing agent (calculated by the total amount of the components), 0.1-10 parts of diisocyanate, 1-1000ppm of organic tin catalyst (calculated by the total amount of the components), and 0.1-10 parts of hydroxyalkyl methacrylate or hydroxyalkyl acrylate;
adding fluorine-containing cyclic siloxane, vinyl-containing cyclic siloxane, dimethyl cyclosiloxane mixture and 1, 3-dihydroxyalkyl-1, 1,3, 3-tetramethyl disiloxane into a reactor, and dehydrating at 40-70 ℃ for 0.5-3 h;
adding an alkali catalyst, and carrying out polymerization reaction for 1-72h at 40-150 ℃;
adding an acid neutralizer, and neutralizing for 1-72 h;
heating to 180 ℃ and 200 ℃, decompressing to more than-0.09 MPa, decompressing and removing low boiling point for 1-3 h.
Cooling to 30-90 deg.C, adding diisocyanate, tin catalyst, hydroxyalkyl methacrylate or hydroxyalkyl acrylate, and reacting for 1-72h to obtain colorless transparent dual-curable fluorosilicone polymer.
In a third aspect of the invention, there is provided a coating prepared by the process of:
uniformly mixing a free radical photoinitiator with the fluorosilicone polymer of the first aspect of the invention, coating the mixture on a PET film, and carrying out UV (ultraviolet) photocuring to obtain the coating, or
The coating is obtained by uniformly mixing hydrogen-containing silicone oil, a platinum catalyst and the fluorosilicone polymer of the first aspect of the invention, coating the mixture on a PET film, and thermally curing the mixture.
The fluorine-silicon polymer provided by the invention has good solvent resistance and heat resistance, is suitable for two curing modes of thermal curing and UV (ultraviolet) light curing, and has the priority of short curing period and high efficiency when UV light curing is utilized, so that the application field of the fluorine-silicon polymer is greatly expanded, such as the field of electronic protective coatings and the like.
Detailed Description
The present invention is described in detail below with reference to examples, and the description in this section is only exemplary and explanatory and should not be construed as limiting the scope of the present invention in any way.
It should be noted that the experimental methods used in the examples are all conventional methods unless otherwise specified, and the materials, reagents, and the like used in the examples are commercially available unless otherwise specified.
Example 1
Adding 1mol of trifluoropropylmethylcyclotrisiloxane, 0.1mol of trimethyltrivinylcyclotrisiloxane and 0.01mol of 1, 3-dihydroxypropyl-1, 1,3, 3-tetramethyldisiloxane into a reactor, dehydrating for 1h at 45 ℃, then adding 20ppm of tetramethylammonium hydroxide silicon alkoxide, polymerizing for 1h at 45 ℃, and then adding 200ppm of fluorine-containing silicon-based phosphate for neutralization for 1 h. Then heating to 180 ℃, decompressing to more than-0.09 MPa, decompressing and removing low boiling point for 1 h. Then cooling to 30-90 ℃, adding 0.005mol of toluene diisocyanate, 100ppm of dibutyltin dilaurate and 0.01mol of hydroxyethyl methacrylate, and reacting for 24h to obtain the colorless and transparent fluorine-silicon polymer capable of being cured doubly.
The molecular structure of the obtained fluorosilicone polymer is as follows:
the prepared fluorine-silicon polymer and a photoinitiator 1173 are uniformly mixed and coated on a PET film, and the mixing ratio is that the fluorine-silicon polymer: photoinitiator 1173 — 100: 5; and (4) carrying out photocuring by using a UV photocuring machine to obtain the fluorine-silicon coating.
Uniformly mixing the prepared fluorine-silicon polymer with a Kaster catalyst, hydrogen-containing silicone oil and ethyl acetate according to the mass ratio of 5:0.7:1:10, and curing for 1.5min at 150 ℃ by an oven to obtain a fluorine-silicon coating curing degree test, wherein the fluorine-silicon coating is adhered by a standard release tape 7475 and then is removed, so that the surface has no trace and the curing is complete.
And (3) testing the hardness of the film: measured according to GB/T6739-2006, HV 880 multiplied by 10-7MPa
Example 2
Adding 1mol of trifluoropropylmethyl cyclotrisiloxane, 0.1mol of trimethyl trivinyl cyclotrisiloxane, 0.5mol of DMC0.5mol and 0.01mol of 1, 3-dihydroxypropyl-1, 1,3, 3-tetramethyl disiloxane into a reactor, dehydrating for 1h at 45 ℃, then adding 20ppm of tetramethyl ammonium hydroxide silicon alkoxide, polymerizing for 1h at 45 ℃, and then adding 200ppm of fluorine-containing silicon-based phosphate for neutralizing for 1 h. Then heating to 180 ℃, decompressing to more than-0.09 MPa, decompressing and removing low boiling point for 1 h. Then cooling to 30-90 ℃, adding 0.005mol of toluene diisocyanate, 100ppm of dibutyltin dilaurate and 0.01mol of hydroxyethyl methacrylate, and reacting for 24h to obtain the colorless and transparent fluorine-silicon polymer capable of being cured doubly.
The molecular structure of the obtained fluorosilicone polymer is as follows:
the prepared fluorosilicone polymer and a photoinitiator 1173 are uniformly mixed and coated on a PET film, and the mixing ratio is that the fluorosilicone polymer: photoinitiator 1173 — 100: 5; and (4) carrying out photocuring by using a UV photocuring machine to obtain the fluorine-silicon coating.
Uniformly mixing the prepared fluorine-silicon polymer with a Kaster catalyst, hydrogen-containing silicone oil and ethyl acetate according to the mass ratio of 5:0.7:1:10, and curing for 1.5min at 150 ℃ by an oven to obtain a fluorine-silicon coating curing degree test, wherein the fluorine-silicon coating is adhered by a standard release tape 7475 and then is removed, so that the surface has no trace and the curing is complete.
And (3) testing the hardness of the film: measured according to GB/T6739-2006, HV 780 multiplied by 10-7MPa。
Example 3
Adding 1mol of trifluoropropylmethylcyclotrisiloxane, 0.1mol of trimethyltrivinylcyclotrisiloxane, 0.5mol of DMC0.5mol and 0.01mol of 1, 3-dihydroxypropyl-1, 1,3, 3-tetramethyldisiloxane into a reactor, dehydrating for 1h at 45 ℃, then adding 20ppm of tetramethylammonium hydroxide silicon alkoxide, polymerizing for 1h at 45 ℃, then adding fluorine-containing silicon-based phosphate (200ppm), and neutralizing for 1 h. Then heating to 180 ℃, decompressing to more than-0.09 MPa, decompressing and removing low boiling point for 1 h. Then cooling to 30-90 ℃, adding 0.005mol of hexamethyl diisocyanate, 100ppm of dibutyltin dilaurate and 0.01mol of hydroxyethyl methacrylate, and reacting for 24h to obtain the colorless and transparent fluorine-silicon polymer capable of being cured in two ways.
The molecular structure of the obtained fluorosilicone polymer is as follows:
the prepared fluorosilicone polymer and a photoinitiator 1173 are uniformly mixed and coated on a PET film, and the mixing ratio is that the fluorosilicone polymer: photoinitiator 1173 — 100: 5; and (4) carrying out photocuring by using a UV photocuring machine to obtain the fluorine-silicon coating.
Uniformly mixing the prepared fluorine-silicon polymer with a Kanst catalyst, hydrogen-containing silicone oil and ethyl acetate according to the mass ratio of 5:0.7:1:10, and curing for 1.5min at 150 ℃ in an oven to obtain the fluorine-silicon coating.
And testing the curing degree, namely, the adhesive tape is pasted by a standard release adhesive tape 7475 and then is taken off, the surface has no trace, and the curing is complete.
And (3) testing the hardness of the film:measured according to GB/T6739-2006, HV 750X 10-7MPa。
Example 4
Adding 1mol of trifluoropropylmethylcyclotrisiloxane, 0.1mol of trimethyltrivinylcyclotrisiloxane, 0.5mol of DMC0.5mol and 0.01mol of 1, 3-dihydroxypropyl-1, 1,3, 3-tetramethyldisiloxane into a reactor, dehydrating for 1h at 45 ℃, then adding 20ppm of tetramethylammonium hydroxide silicon alkoxide, polymerizing for 1h at 45 ℃, then adding 200ppm of fluorine-containing silicon-based phosphate, and neutralizing for 1 h. Then heating to 180 ℃, decompressing to more than-0.09 MPa, decompressing and removing low boiling point for 1 h. Then cooling to 30-90 ℃, adding 0.005mol of hexamethyl diisocyanate, 100ppm of dibutyltin dilaurate and 0.01mol of hydroxypropyl acrylate, and reacting for 24h to obtain the colorless and transparent fluorine-silicon polymer capable of being cured in two ways.
The molecular structure of the obtained fluorosilicone polymer is as follows:
the prepared fluorosilicone polymer and a photoinitiator 1173 are uniformly mixed and coated on a PET film, and the mixing ratio is that the fluorosilicone polymer: photoinitiator 1173 — 100: 5; and (4) carrying out photocuring by using a UV photocuring machine to obtain the fluorine-silicon release coating.
Uniformly mixing the prepared fluorine-silicon polymer with a Kanst catalyst, hydrogen-containing silicone oil and ethyl acetate according to the mass ratio of 5:0.7:1:10, and curing for 1.5min at 150 ℃ in an oven to obtain the fluorine-silicon coating.
And testing the curing degree, namely, the adhesive tape is pasted by a standard release adhesive tape 7475 and then is taken off, the surface has no trace, and the curing is complete.
And (3) testing the hardness of the film: measured according to GB/T6739-2006, HV 800X 10-7MPa。
The above description is only an embodiment of the present invention, and not intended to limit the scope of the present invention, and all modifications of equivalent structures and equivalent processes, which are made by the present specification, or directly or indirectly applied to other related technical fields, are included in the scope of the present invention.
Claims (10)
1. A fluorine-silicon polymer capable of being cured by UV light and heat is characterized in that the molecular structure is as follows:
wherein:
r is
Wherein: x is an integer not less than 3, y is an integer not less than 2,
is composed of
One of (1);
pf is fluorine-containing alkyl and has a structural general formula of-C2H4CnF2n+1Wherein: n is an integer of 1 to 3000, m is an integer of 1 to 3000, and p is an integer of 0 to 3000.
2. The fluorosilicone polymer of claim 1, wherein the fluorosilicone polymer is polymerized from the following components, by mass:
3. the fluorosilicone polymer of claim 2, wherein the fluorine-containing cyclic siloxane is
Wherein: n is an integer of 1 or more.
4. The fluorosilicone polymer of claim 2, wherein the vinyl-containing cyclic siloxane is
5. The fluorosilicone polymer of claim 2, wherein the 1, 3-dihydroxyalkyl-1, 1,3, 3-tetramethyldisiloxane has the following general structural formula:
wherein: x is an integer of 3 or more.
6. The fluorosilicone polymer of claim 5, wherein the 1, 3-dihydroxyalkyl-1, 1,3, 3-tetramethyldisiloxane is one of 1, 3-bis (hydroxypropyl) -1,1,3, 3-tetramethyldisiloxane and 1, 3-bis (hydroxybutyl) -1,1,3, 3-tetramethyldisiloxane.
7. The fluorosilicone polymer of claim 2, wherein:
the alkali catalyst is one of sodium hydroxide, tetramethyl ammonium hydroxide and silicon alkoxide.
The acid neutralizer is one of phosphoric acid, hydrochloric acid, silicon-based acid ester glue and fluorine-containing silicon-based acid ester glue.
8. The fluorosilicone polymer of claim 2, wherein:
the diisocyanate is one of isophorone diisocyanate, hexamethylene diisocyanate and toluene diisocyanate;
the organic tin catalyst is dibutyltin dilaurate.
9. A preparation method of a fluorosilicone polymer is characterized by comprising the following steps:
weighing 10-80 parts of fluorine-containing cyclic siloxane, 10-80 parts of vinyl-containing cyclic siloxane, 0-80 parts of dimethylcyclosiloxane mixture, 0.1-10 parts of 1, 3-dihydroxyalkyl-1, 1,3, 3-tetramethyldisiloxane, 1-1000ppm of alkali catalyst, 1-1000ppm of acid neutralizing agent, 0.1-10 parts of diisocyanate, 1-1000ppm of organic tin catalyst and 0.1-10 parts of hydroxyalkyl methacrylate or hydroxyalkyl acrylate;
adding fluorine-containing cyclic siloxane, vinyl-containing cyclic siloxane, dimethyl cyclosiloxane mixture and 1, 3-dihydroxyalkyl-1, 1,3, 3-tetramethyl disiloxane into a reactor, and dehydrating at 40-70 ℃ for 0.5-3 h;
adding an alkali catalyst, and carrying out polymerization reaction for 1-72h at 40-150 ℃;
adding an acid neutralizer, and neutralizing for 1-72 h;
heating to 180 ℃ and 200 ℃, decompressing to more than-0.09 MPa, decompressing and removing low boiling point for 1-3 h.
Cooling to 30-90 deg.C, adding diisocyanate, tin catalyst, hydroxyalkyl methacrylate or hydroxyalkyl acrylate, and reacting for 1-72h to obtain colorless transparent dual-curable fluorosilicone polymer.
10. A coating, characterized in that it is prepared as follows:
uniformly mixing a free radical photoinitiator with the fluorosilicone polymer of claim 1, coating the mixture on a PET (polyethylene terephthalate) film, and carrying out UV (ultraviolet) photocuring to obtain the coating, or
Uniformly mixing hydrogen-containing silicone oil, a platinum catalyst and the fluorosilicone polymer of claim 1, coating the mixture on a PET film, and thermally curing to obtain the coating.
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