CN107090238B - A kind of POSS crosslinking polyarylate ultraviolet light solidified protection coating and preparation method thereof - Google Patents
A kind of POSS crosslinking polyarylate ultraviolet light solidified protection coating and preparation method thereof Download PDFInfo
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- 229920001230 polyarylate Polymers 0.000 title claims abstract description 81
- 238000000576 coating method Methods 0.000 title claims abstract description 34
- 239000011248 coating agent Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 238000004132 cross linking Methods 0.000 title abstract 3
- 239000000126 substance Substances 0.000 claims abstract description 24
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 14
- 239000002518 antifoaming agent Substances 0.000 claims abstract description 13
- 150000001336 alkenes Chemical group 0.000 claims abstract 2
- 239000000758 substrate Substances 0.000 claims abstract 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 84
- 239000000178 monomer Substances 0.000 claims description 64
- 238000006243 chemical reaction Methods 0.000 claims description 61
- 125000003118 aryl group Chemical group 0.000 claims description 43
- 239000000243 solution Substances 0.000 claims description 42
- 239000011253 protective coating Substances 0.000 claims description 31
- 238000001723 curing Methods 0.000 claims description 29
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical compound OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 claims description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 20
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 claims description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- 239000007789 gas Substances 0.000 claims description 16
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 16
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 16
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 claims description 16
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
- 239000003054 catalyst Substances 0.000 claims description 15
- 239000012074 organic phase Substances 0.000 claims description 14
- 239000007864 aqueous solution Substances 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 239000012071 phase Substances 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 5
- 238000012696 Interfacial polycondensation Methods 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 5
- 238000003618 dip coating Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 230000001678 irradiating effect Effects 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 238000010907 mechanical stirring Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 230000003472 neutralizing effect Effects 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 5
- 239000012429 reaction media Substances 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- 238000004528 spin coating Methods 0.000 claims description 5
- 238000005507 spraying Methods 0.000 claims description 5
- 238000012546 transfer Methods 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- YIKSHDNOAYSSPX-UHFFFAOYSA-N 1-propan-2-ylthioxanthen-9-one Chemical compound S1C2=CC=CC=C2C(=O)C2=C1C=CC=C2C(C)C YIKSHDNOAYSSPX-UHFFFAOYSA-N 0.000 claims description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 3
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- ZXDDPOHVAMWLBH-UHFFFAOYSA-N 2,4-Dihydroxybenzophenone Chemical compound OC1=CC(O)=CC=C1C(=O)C1=CC=CC=C1 ZXDDPOHVAMWLBH-UHFFFAOYSA-N 0.000 claims description 2
- RAWPGIYPSZIIIU-UHFFFAOYSA-N [benzoyl(phenyl)phosphoryl]-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)P(=O)(C=1C=CC=CC=1)C(=O)C1=CC=CC=C1 RAWPGIYPSZIIIU-UHFFFAOYSA-N 0.000 claims description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 2
- 239000012965 benzophenone Substances 0.000 claims description 2
- 229950005499 carbon tetrachloride Drugs 0.000 claims description 2
- 239000012949 free radical photoinitiator Substances 0.000 claims description 2
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical group O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 claims description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 2
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims 1
- 239000013530 defoamer Substances 0.000 claims 1
- 230000001376 precipitating effect Effects 0.000 claims 1
- 238000003756 stirring Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 21
- 238000005260 corrosion Methods 0.000 abstract description 9
- 230000007797 corrosion Effects 0.000 abstract description 8
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 abstract description 5
- 239000003063 flame retardant Substances 0.000 abstract description 5
- 230000002411 adverse Effects 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 239000002585 base Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 6
- 238000001556 precipitation Methods 0.000 description 6
- 239000002994 raw material Substances 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 150000001263 acyl chlorides Chemical class 0.000 description 4
- 239000003431 cross linking reagent Substances 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 239000011261 inert gas Substances 0.000 description 4
- 239000011256 inorganic filler Substances 0.000 description 4
- 229910003475 inorganic filler Inorganic materials 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- 239000012716 precipitator Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000012295 chemical reaction liquid Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- LNBMZFHIYRDKNS-UHFFFAOYSA-N 2,2-dimethoxy-1-phenylethanone Chemical compound COC(OC)C(=O)C1=CC=CC=C1 LNBMZFHIYRDKNS-UHFFFAOYSA-N 0.000 description 1
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- FDQSRULYDNDXQB-UHFFFAOYSA-N benzene-1,3-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC(C(Cl)=O)=C1 FDQSRULYDNDXQB-UHFFFAOYSA-N 0.000 description 1
- KXHPPCXNWTUNSB-UHFFFAOYSA-M benzyl(trimethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC1=CC=CC=C1 KXHPPCXNWTUNSB-UHFFFAOYSA-M 0.000 description 1
- 229960001701 chloroform Drugs 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- MQAYPFVXSPHGJM-UHFFFAOYSA-M trimethyl(phenyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)C1=CC=CC=C1 MQAYPFVXSPHGJM-UHFFFAOYSA-M 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
Classifications
-
- 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
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
- C09D167/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/91—Polymers modified by chemical after-treatment
- C08G63/914—Polymers modified by chemical after-treatment derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/916—Dicarboxylic acids and dihydroxy compounds
-
- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
-
- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/18—Fireproof paints including high temperature resistant paints
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2312/00—Crosslinking
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polyesters Or Polycarbonates (AREA)
- Paints Or Removers (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
The invention discloses a kind of POSS to be crosslinked polyarylate ultraviolet light solidified protection coating comprising following component and its mass content: alkene end group polyarylate oligomer: 70~99%；Eight vinyl-POSS:0.5~28%；Photoinitiator: 0.05~2%；Defoaming agent: 0.1~0.5%；Levelling agent: 0.1~0.5%.The invention also discloses the preparation methods of above-mentioned POSS crosslinking polyarylate ultraviolet light solidified protection coating.POSS crosslinking polyarylate coating of the present invention not only maintains the excellent chemical corrosion resistance of polyarylate material, weatherability, high and low temperature resistance and good flame retardant property and extremely low hygroscopicity, also because POSS there are due to there is high hardness and excellent anti-wear property, be highly suitable for the wear-and corrosion-resistant coating material of substrate under adverse circumstances.
Description
Technical Field
The invention relates to a POSS (polyhedral oligomeric silsesquioxane) crosslinked polyarylate ultraviolet curing protective coating and a preparation method thereof, belonging to the field of preparation of photocuring coatings.
Background
Abrasion, breakage and corrosion are three main forms of material failure, so that the development of an anti-corrosion and wear-resistant high-performance protective coating material has important significance for prolonging the service life of a base material.
Polyarylate is a polymer having aromatic rings connected to both ends of an ester group, and is industrially a polyarylate resin obtained by polycondensation of bisphenol a, terephthalic acid (or terephthaloyl chloride), and isophthalic acid (or isophthaloyl chloride) as raw materials. The polyarylate has excellent chemical resistance, weather resistance, good flame retardant performance and extremely low moisture absorption rate due to the fact that a molecular chain contains a large number of aromatic units and ester bonds with stable performance are used for connecting the aromatic rings, has wide use temperature, can be used for a long time at minus 70 to plus 180 ℃, and is very suitable for an anticorrosive coating material of a base material under severe environment (high temperature, low temperature, chemical corrosion, moisture and the like). However, polyarylates are currently less useful in the field of protective coatings due to their poor solubility in organic solvents.
Disclosure of Invention
The invention aims to provide an ultraviolet curing polyhedral oligomeric silsesquioxane (POSS) filled and crosslinked polyarylate protective coating and a preparation method thereof. The POSS nano particles in the ultraviolet curing coating have excellent dispersibility, and the prepared polyarylate coating has extremely high hardness, outstanding chemical corrosion resistance and wear resistance, and also has excellent high and low temperature resistance, weather resistance and flame retardant property. The prepared ultraviolet curing coating has the advantages of high curing speed, low energy consumption, simple operation, excellent coating performance and practical application value.
The purpose of the invention is realized by the following technical scheme:
a POSS crosslinked polyarylate ultraviolet curing protective coating comprises the following components in percentage by mass:
alkene-terminated polyarylate oligomer: 70-99%;
octavinyl-POSS: 0.5-28%;
photoinitiator (2): 0.05-2%;
defoaming agent: 0.1-0.5%;
leveling agent: 0.1 to 0.5 percent.
In a preferred embodiment of the present invention, the above components preferably comprise, by mass:
alkene-terminated polyarylate oligomer: 90-98 percent;
octavinyl-POSS: 1-8%;
photoinitiator (2): 0.5-1%;
defoaming agent: 0.1-0.5%;
leveling agent: 0.1 to 0.5 percent.
On the premise that POSS can be well dispersed, the higher the POSS content is, the higher the hardness of the coating is. However, excessive amounts of POSS tend to cause them to aggregate and fail to form a good dispersion in the polyarylate matrix. Thus, the proper mass content of the alkenyl-terminated polyarylate oligomer and the octavinyl-POSS is critical to the performance of the protective coating of the present invention.
Preferably, the number average molecular weight of the alkene-terminated polyarylate oligomer is 1000-6000 g/mol.
The molecular structure schematic diagram of the POSS crosslinked polyarylate ultraviolet curing protective coating is shown in figure 1.
Thus, POSS acts as a stereo crosslinker to crosslink polyarylate oligomers into an integral network, and POSS also acts as an inorganic filler, and since it reacts with polyarylate molecules, POSS has good dispersibility as an inorganic filler.
In a preferred embodiment of the present invention, the preparation of the ene-terminated polyarylate oligomer is as follows:
(1) placing a three-mouth bottle provided with a condenser pipe and an inert gas protection device on a magnetic stirrer, and adding a reaction medium dichloromethane and a small amount of catalyst triethylamine into the reaction bottle; dissolving terephthaloyl chloride and hydroxyethyl acrylate in an equal molar ratio in dichloromethane, wherein the concentration of the terephthaloyl chloride is 0.4-0.6 mol/L, transferring the prepared solution to a constant-pressure dropping funnel, gradually dropping the solution into a reaction bottle, and maintaining the reaction temperature at 40-50 ℃; after the liquid dropping is finished, continuing the reaction at the reflux temperature, stopping heating when no hydrogen chloride gas is discharged from the reaction system, and continuing introducing nitrogen until the reaction system is cooled to the room temperature to obtain a dichloromethane solution of the alkene-terminated benzoyl chloride monomer; the chemical structural formula of the alkene-terminated benzoyl chloride monomer is as follows:
the preparation of the alkenyl-terminated benzoyl chloride monomer is referred to an existing Master thesis which has demonstrated the success of preparing the alkenyl-terminated benzoyl chloride monomer using the above preparation method;
adding an aromatic diphenol monomer and a quaternary ammonium salt phase transfer interfacial polycondensation catalyst into an aqueous solution of alkali to form an aqueous solution with the monomer molar concentration of 0.4-1.0 mol/L, wherein the alkali is usually sodium hydroxide or potassium hydroxide; the chemical structure of the aromatic diphenol monomer is one of the following:
adding an aromatic diformyl chloride monomer into dichloromethane to dissolve to form an organic phase solution of acyl chloride, and preparing the solution with the monomer concentration of 0.2-0.8 mol/L; the chemical structure of the aromatic diacid chloride monomer is one of the following:
the preparation of the 3 raw materials is not in sequence;
(2) gradually adding an organic phase solution of an aromatic diacid chloride monomer into an alkali water solution of the aromatic diphenol monomer and a catalyst under the condition of rapid mechanical stirring, controlling the molar ratio of the aromatic diphenol monomer to the aromatic diacid chloride to be 1.1-1.2, controlling the reaction temperature to be 10-50 ℃, dropwise adding a dichloromethane solution of the alkene-terminated benzoyl chloride monomer prepared in the step (1) into the reaction system when no hydrogen chloride gas escapes from the reaction system, carrying out end-capping reaction, and stopping dropwise adding the alkene-terminated benzoyl chloride monomer until no hydrogen chloride gas is generated in the reaction system; after the reaction is finished, neutralizing the reaction solution to be neutral by using acid, standing the reaction solution, after two phases of the reaction solution are layered, dropwise adding a lower organic phase into a strongly stirred precipitator for precipitation, respectively washing the precipitation product by using ethanol and distilled water, carrying out vacuum filtration by using a Buchner funnel, and finally drying the precipitation product in a vacuum oven at the temperature of 60 ℃ for 8-12 hours to obtain the alkene-terminated polyarylate oligomer.
The chemical structural formula of the octavinyl-POSS is shown in figure 2.
The photoinitiator is a free radical photoinitiator, and specifically may be one or more selected from 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide, bis-benzoylphenylphosphine oxide, 2-dimethoxy-acetophenone, benzophenone, 2, 4-dihydroxybenzophenone, thiopropoxy thioxanthone and isopropyl thioxanthone.
The invention also provides a preparation method of the POSS crosslinked polyarylate ultraviolet curing protective coating, which comprises the following steps:
dissolving the alkenyl-terminated polyarylate oligomer, octavinyl-POSS, the photoinitiator, the defoaming agent and the leveling agent in an organic solvent according to the mass percentage to prepare a solution with the mass fraction of 5-40%, uniformly mixing at 30-50 ℃, coating the solution on the surface of a base material in a spraying, dip-coating or spin-coating manner, drying the surface at room temperature, and irradiating for 5-30 minutes under ultraviolet light to obtain the POSS crosslinked polyarylate ultraviolet curing protective coating.
The preparation method of the POSS crosslinked polyarylate ultraviolet curing protective coating adopts one of dichloromethane, trichloromethane, tetrachloromethane, tetrahydrofuran and acetone as a solvent.
The invention provides a POSS (polyhedral oligomeric silsesquioxane) crosslinked polyarylate ultraviolet curing protective coating and a preparation method thereof. The coating is prepared by using octavinyl POSS as a cross-linking agent, using polyarylate oligomer with an end group as an alkenyl group as a main component and initiating a polymer to cross-link and solidify through ultraviolet light. The organic-inorganic nano hybrid material POSS is introduced into a polyarylate system as a cross-linking agent, so that the coating material not only retains excellent chemical corrosion resistance, weather resistance, high temperature resistance, low temperature resistance, size stability, good flame retardant property and extremely low hygroscopicity of polyarylate, but also endows the coating with extremely high hardness and wear resistance and durability. The prepared POSS crosslinked polyarylate coating is very suitable for coating protective materials of base materials in harsh environments (high temperature, low temperature, humidity, chemical corrosion and the like). The prepared ultraviolet curing coating has the advantages of high curing speed, low energy consumption, simple operation, excellent coating performance and practical application value.
Compared with the prior art, the invention has the following beneficial effects:
(1) POSS is introduced into a polyarylate coating material as a cross-linking agent, and due to the existence of chemical bonds between POSS and polymers, the POSS is well dispersed in a polyarylate matrix and is not easy to agglomerate;
(2) the POSS crosslinked polyarylate coating not only maintains the excellent chemical corrosion resistance, weather resistance, high and low temperature resistance, good flame retardant property and extremely low moisture absorption of polyarylate materials, but also has extremely high hardness and excellent wear resistance due to the POSS, and is very suitable for the wear-resistant anticorrosive coating material of the base material in severe environment;
(3) the ultraviolet curing coating prepared by the invention has the advantages of high curing speed, low energy consumption, simple operation, excellent coating performance and practical application value.
Of course, it is not necessary for any product in which the invention is practiced to achieve all of the above-described advantages at the same time.
Drawings
FIG. 1 is a schematic molecular structure diagram of a POSS crosslinked polyarylate UV-curable protective coating of the present invention;
FIG. 2 is a chemical structure of the octavinyl-POSS of the present invention.
Detailed Description
In this context, a range of values from one value to another is a general expression avoiding any recitation of all values in the range in the specification. Thus, recitation of a range of values herein is intended to encompass any value within the range and any smaller range defined by any value within the range, as if the range and smaller range were explicitly recited in the specification.
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are only for illustrating the present invention and are not intended to limit the scope of the present invention. In practice, the technical personnel according to the invention make improvements and modifications, which still belong to the protection scope of the invention. The defoaming agent and the leveling agent in the following examples are all commercially available.
Example 1
The POSS crosslinked polyarylate ultraviolet curing protective coating provided by the embodiment is prepared by the following method:
first step, preparation of an ene-terminated polyarylate oligomer:
(1) placing a three-mouth bottle provided with a condenser pipe and an inert gas protection device on a magnetic stirrer, and adding a reaction medium dichloromethane and a small amount of catalyst triethylamine into the reaction bottle; dissolving terephthaloyl chloride and hydroxyethyl acrylate in an equal molar ratio in dichloromethane, wherein the concentration of the terephthaloyl chloride is 0.4mol/L, transferring the terephthaloyl chloride to a constant-pressure dropping funnel, gradually dropping the terephthaloyl chloride into a reaction bottle, and maintaining the reaction temperature at 40-50 ℃; after the liquid dropping is finished, continuing the reaction at the reflux temperature, stopping heating when no hydrogen chloride gas is discharged from the reaction system, and continuing introducing nitrogen until the reaction system is cooled to the room temperature to obtain a dichloromethane solution of the alkene-terminated benzoyl chloride monomer; the chemical structural formula of the alkene-terminated benzoyl chloride monomer is as follows:
adding an aromatic diphenol monomer and a quaternary ammonium salt phase transfer interfacial polycondensation catalyst cetyl trimethyl ammonium bromide into an aqueous solution of sodium hydroxide to form an aqueous solution with the monomer molar concentration of 0.4 mol/L; the chemical structure of the aromatic diphenol monomer is:
adding an aromatic diacid chloride monomer into dichloromethane to dissolve to form an organic phase solution of acyl chloride, and preparing the solution with the monomer concentration of 0.2 mol/L; the chemical structural formula of the aromatic diacid chloride monomer is as follows:
the preparation of the 3 raw materials is not in sequence;
(2) gradually adding an organic phase solution of an aromatic diacid chloride monomer into a sodium hydroxide aqueous solution of an aromatic diphenol monomer and a catalyst under the condition of rapid mechanical stirring, controlling the molar ratio of the aromatic diphenol monomer to the aromatic diacid chloride at 1.1, controlling the reaction temperature to be 10-20 ℃, continuously dropwise adding a dichloromethane solution of the alkene-terminal benzoyl chloride monomer prepared in the step (1) into the reaction system until no hydrogen chloride gas is generated in the reaction system when no hydrogen chloride gas escapes from the reaction system; after the reaction is finished, neutralizing the mixture to be neutral by using acid, standing the mixture, dropwise adding a lower organic phase into a strongly stirred precipitator for precipitation after two phases of reaction liquid are layered, washing the precipitated product by using ethanol and distilled water respectively, filtering the product in vacuum by using a Buchner funnel, and finally drying the product in a vacuum oven at the temperature of 60 ℃ for 8 hours to obtain the alkene-terminated polyarylate oligomer. The number average molecular weight of the olefin-terminated polyarylate oligomer was tested to be 6000 g/mol.
Step two, preparing the POSS crosslinked polyarylate ultraviolet curing protective coating:
dissolving the alkenyl-terminated polyarylate oligomer, octavinyl-POSS, a photoinitiator, a defoaming agent and a leveling agent in dichloromethane according to the following weight percentage to prepare a solution with the mass fraction of 10%, uniformly mixing at 30-40 ℃, coating the solution on the surface of a base material in a spraying, dip-coating or spin-coating manner, drying the surface at room temperature, and irradiating for 5 minutes under ultraviolet light to obtain the POSS crosslinked polyarylate ultraviolet light curing protective coating:
alkene-terminated polyarylate oligomer: 90 percent;
octavinyl-POSS: 7 percent;
photoinitiator 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide: 2 percent;
defoaming agent: 0.5 percent;
leveling agent: 0.5 percent.
Example 2
The POSS crosslinked polyarylate ultraviolet curing protective coating provided by the embodiment is prepared by the following method:
first step, preparation of an ene-terminated polyarylate oligomer:
(1) placing a three-mouth bottle provided with a condenser pipe and an inert gas protection device on a magnetic stirrer, and adding a reaction medium dichloromethane and a small amount of catalyst triethylamine into the reaction bottle; dissolving terephthaloyl chloride and hydroxyethyl acrylate in an equal molar ratio in dichloromethane, wherein the concentration of the terephthaloyl chloride is 0.6mol/L, transferring the terephthaloyl chloride to a constant-pressure dropping funnel, gradually dropping the terephthaloyl chloride into a reaction bottle, and maintaining the reaction temperature at 40-50 ℃; after the liquid dropping is finished, continuing the reaction at the reflux temperature, stopping heating when no hydrogen chloride gas is discharged from the reaction system, and continuing introducing nitrogen until the reaction system is cooled to the room temperature to obtain a dichloromethane solution of the alkene-terminated benzoyl chloride monomer; the chemical structural formula of the alkene-terminated benzoyl chloride monomer is as follows:
adding an aromatic diphenol monomer and a quaternary ammonium salt phase transfer interfacial polycondensation catalyst benzyltrimethylammonium chloride into an aqueous solution of sodium hydroxide to form an aqueous solution with the monomer molar concentration of 1.0 mol/L; the chemical structure of the aromatic diphenol monomer is:
adding an aromatic diacid chloride monomer into dichloromethane to dissolve to form an organic phase solution of acyl chloride, and preparing the solution with the monomer concentration of 0.8 mol/L; the chemical structural formula of the aromatic diacid chloride monomer is as follows:
the preparation of the 3 raw materials is not in sequence;
(2) gradually adding an organic phase solution of an aromatic diacid chloride monomer into a sodium hydroxide aqueous solution of an aromatic diphenol monomer and a catalyst under the condition of rapid mechanical stirring, controlling the molar ratio of the aromatic diphenol monomer to the aromatic diacid chloride to be 1.2, controlling the reaction temperature to be 40-50 ℃, continuously dropwise adding a dichloromethane solution of the alkene-terminal benzoyl chloride monomer prepared in the step (1) into the reaction system until no hydrogen chloride gas is generated in the reaction system when no hydrogen chloride gas escapes from the reaction system; after the reaction is finished, neutralizing the mixture to be neutral by using acid, standing the mixture, dropwise adding a lower organic phase into a strongly stirred precipitator for precipitation after two phases of reaction liquid are layered, washing the precipitated product by using ethanol and distilled water respectively, filtering the product in vacuum by using a Buchner funnel, and finally drying the product in a vacuum oven at the temperature of 60 ℃ for 12 hours to obtain the alkene-terminated polyarylate oligomer. The number average molecular weight of the olefin-terminated polyarylate oligomer was tested to be 1000 g/mol.
Step two, preparing the POSS crosslinked polyarylate ultraviolet curing protective coating:
dissolving the alkenyl-terminated polyarylate oligomer, octavinyl-POSS, a photoinitiator, a defoaming agent and a leveling agent in acetone to prepare a solution with the mass fraction of 40%, uniformly mixing at 40-50 ℃, coating the solution on the surface of a base material in a spraying, dip-coating or spin-coating manner, drying the surface at room temperature, and irradiating the surface for 30 minutes under ultraviolet light to obtain the POSS crosslinked polyarylate ultraviolet light curing protective coating:
alkene-terminated polyarylate oligomer: 98 percent;
octavinyl-POSS: 1.3 percent;
photoinitiator isopropyl thioxanthone: 0.5 percent;
defoaming agent: 0.1 percent;
leveling agent: 0.1 percent.
Example 3
The POSS crosslinked polyarylate ultraviolet curing protective coating provided by the embodiment is prepared by the following method:
first step, preparation of an ene-terminated polyarylate oligomer:
(1) placing a three-mouth bottle provided with a condenser pipe and an inert gas protection device on a magnetic stirrer, and adding a reaction medium dichloromethane and a small amount of catalyst triethylamine into the reaction bottle; dissolving terephthaloyl chloride and hydroxyethyl acrylate in an equal molar ratio in dichloromethane, wherein the concentration of the terephthaloyl chloride is 0.5mol/L, transferring the terephthaloyl chloride to a constant-pressure dropping funnel, gradually dropping the terephthaloyl chloride into a reaction bottle, and maintaining the reaction temperature at 40-50 ℃; after the liquid dropping is finished, continuing the reaction at the reflux temperature, stopping heating when no hydrogen chloride gas is discharged from the reaction system, and continuing introducing nitrogen until the reaction system is cooled to the room temperature to obtain a dichloromethane solution of the alkene-terminated benzoyl chloride monomer; the chemical structural formula of the alkene-terminated benzoyl chloride monomer is as follows:
adding aromatic diphenol monomer and quaternary ammonium salt phase transfer interfacial polycondensation catalyst phenyltrimethylammonium chloride into aqueous solution of sodium hydroxide to form aqueous solution with monomer molar concentration of 0.6 mol/L; the chemical structure of the aromatic diphenol monomer is:
adding an aromatic diacid chloride monomer into dichloromethane to dissolve to form an organic phase solution of acyl chloride, and preparing the solution with the monomer concentration of 0.4 mol/L; the chemical structural formula of the aromatic diacid chloride monomer is as follows:
the preparation of the 3 raw materials is not in sequence;
(2) gradually adding an organic phase solution of an aromatic diacid chloride monomer into a sodium hydroxide aqueous solution of an aromatic diphenol monomer and a catalyst under the condition of rapid mechanical stirring, controlling the molar ratio of the aromatic diphenol monomer to the aromatic diacid chloride at 20-30 ℃, continuously dropwise adding a dichloromethane solution of the alkene-terminal benzoyl chloride monomer prepared in the step (1) into a reaction system until no hydrogen chloride gas is generated in the reaction system when no hydrogen chloride gas escapes from the reaction system, and carrying out end-capping reaction until no hydrogen chloride gas is generated in the reaction system; after the reaction is finished, neutralizing the mixture to be neutral by using acid, standing the mixture, dropwise adding a lower organic phase into a strongly stirred precipitator for precipitation after two phases of reaction liquid are layered, washing the precipitated product by using ethanol and distilled water respectively, filtering the product in vacuum by using a Buchner funnel, and finally drying the product in a vacuum oven at the temperature of 60 ℃ for 10 hours to obtain the alkene-terminated polyarylate oligomer. The number average molecular weight of the olefin-terminated polyarylate oligomer was tested to be 3000 g/mol.
Step two, preparing the POSS crosslinked polyarylate ultraviolet curing protective coating:
dissolving an olefin-terminated polyarylate oligomer, octavinyl-POSS, a photoinitiator, a defoaming agent and a leveling agent in tetrahydrofuran according to the following weight percentage to prepare a solution with the mass fraction of 5%, uniformly mixing at 30-40 ℃, coating the solution on the surface of a base material in a spraying, dip-coating or spin-coating manner, drying the surface at room temperature, and irradiating for 15 minutes under ultraviolet light to obtain the POSS crosslinked polyarylate ultraviolet light curing protective coating:
alkene-terminated polyarylate oligomer: 70 percent;
octavinyl-POSS: 28%;
photoinitiator 2, 2-dimethoxy-acetophenone: 1.4 percent;
defoaming agent: 0.3 percent;
leveling agent: 0.3 percent.
The molecular structure schematic diagram of the POSS crosslinked polyarylate ultraviolet curing protective coating is shown in figure 1.
Therefore, the POSS is used as a stereo cross-linking agent to cross-link different polyarylate molecules into an integral network, and the POSS is also used as an inorganic filler at the same time, and reacts with polyarylate molecules, so that the POSS has good dispersity as the inorganic filler, and the hardness and the wear resistance of the obtained POSS cross-linked polyarylate protective coating are greatly improved.
The protective coatings obtained in examples 1 to 3 were subjected to a performance test:
microhardness testing of the coatings was performed using a microhardness tester (model 71, shanghai first optics works, applied load 0.0981N). The polyarylate coatings containing POSS in examples 1-3 were found to have vickers microhardness 34-52% higher than the polyarylate coatings without POSS.
The coating was subjected to a wear resistance test using a paint film wear resistance tester (manufactured by Shanghai modern environmental engineering technology Co., Ltd.) with reference to national Standard GB1768-79 (load 1000g, diameter of rubber grinding wheel 50mm, thickness 13mm, turntable speed 10.99 m/s). The test results show that the abrasion resistance of the polyarylate coatings of examples 1-3 is improved by 10% to 70% after the addition of POSS.
In light of the above teachings, those skilled in the art will readily appreciate that the materials and their equivalents, the processes and their equivalents, as listed or exemplified herein, are capable of performing the invention in any of its several forms, and that the upper and lower limits of the parameters of the materials and processes, and the ranges of values between these limits are not specifically enumerated herein.
Claims (6)
1. The POSS crosslinked polyarylate ultraviolet curing protective coating is characterized by comprising the following components in percentage by mass:
alkene-terminated polyarylate oligomer: 70-99%;
octavinyl-POSS: 0.5-28%;
photoinitiator (2): 0.05-2%;
defoaming agent: 0.1-0.5%;
leveling agent: 0.1-0.5%;
wherein,
the preparation method of the alkene-terminated polyarylate oligomer comprises the following steps:
(1) preparation of an ene-terminated benzoyl chloride monomer: under the condition of stirring, adding a reaction medium dichloromethane and a small amount of catalyst triethylamine into a reaction bottle; dissolving terephthaloyl chloride and hydroxyethyl acrylate in an equal molar ratio in dichloromethane, and gradually dropwise adding the solution into a reaction bottle, wherein the reaction temperature is maintained at 40-50 ℃; after the liquid dropping is finished, continuing the reaction at the reflux temperature, stopping heating when no hydrogen chloride gas is discharged from the reaction system, and continuing introducing nitrogen until the reaction system is cooled to the room temperature to obtain a dichloromethane solution of the alkene-terminated benzoyl chloride monomer; the chemical structural formula of the alkene-terminated benzoyl chloride monomer is as follows:
adding an aromatic diphenol monomer and a quaternary ammonium salt phase transfer interfacial polycondensation catalyst into an aqueous solution of alkali to form an aqueous solution with the monomer molar concentration of 0.4-1.0 mol/L; the chemical structural formula of the aromatic diphenol monomer is one of the following:
adding an aromatic diformyl chloride monomer into dichloromethane to dissolve to form an organic phase solution, and preparing a monomer with the concentration of 0.2-0.8 mol/L; the aromatic diacid chloride monomer is one of the following:
(2) gradually adding an organic phase solution of an aromatic diacid chloride monomer into an alkali water solution of the aromatic diphenol monomer and a catalyst under the condition of rapid mechanical stirring, controlling the molar ratio of the aromatic diphenol to the aromatic diacid chloride to be 1.1-1.2, controlling the reaction temperature to be 10-50 ℃, dropwise adding a dichloromethane solution of the alkene-terminated benzoyl chloride monomer prepared in the step (1) into the reaction system when no hydrogen chloride gas escapes from the reaction system, carrying out end-capping reaction, and stopping dropwise adding the alkene-terminated benzoyl chloride monomer until no hydrogen chloride gas is generated in the reaction system; and after the reaction is finished, neutralizing, precipitating, cleaning, filtering and drying to obtain the alkene end group polyarylate oligomer.
2. The POSS crosslinked polyarylate ultraviolet light cured protective coating of claim 1, wherein the weight content of each component is:
alkene-terminated polyarylate oligomer: 90-98 percent;
octavinyl-POSS: 1-8%;
photoinitiator (2): 0.5-1%;
defoaming agent: 0.1-0.5%;
leveling agent: 0.1 to 0.5 percent.
3. The POSS crosslinked polyarylate UV cured protective coating of claim 1 or 2, wherein the number average molecular weight of the ene-terminated polyarylate oligomer is 1000 to 6000 g/mol.
4. The POSS crosslinked polyarylate uv curable protective coating of claim 1 or 2, wherein the photoinitiator is a free radical photoinitiator selected from one or more of 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide, bis-benzoylphenylphosphine oxide, 2-dimethoxy-acetophenone, benzophenone, 2, 4-dihydroxybenzophenone, thiopropoxy thioxanthone and isopropyl thioxanthone.
5. A preparation method of the POSS crosslinked polyarylate ultraviolet curing protective coating as claimed in any one of claims 1 to 4, characterized by dissolving the ene-terminated polyarylate oligomer, octavinyl-POSS, the photoinitiator, the defoamer and the leveling agent in the organic solvent according to the above mass percentage to prepare a solution with a mass fraction of 5-40%, uniformly mixing at 30-50 ℃, coating the solution on the surface of a substrate by means of spraying, dip-coating or spin-coating, drying at room temperature, and irradiating for 5-30 minutes under ultraviolet light to obtain the POSS crosslinked polyarylate ultraviolet curing protective coating.
6. The method of claim 5, wherein the organic solvent is one of dichloromethane, chloroform, tetrachloromethane, tetrahydrofuran, or acetone.
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| CN109554107A (en) * | 2018-11-27 | 2019-04-02 | 深圳市高域化学材料有限公司 | A kind of UV light-cured type elasticity self-healing coatings |
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