CN114940750B - Resin for metal coiled material and preparation method thereof - Google Patents
Resin for metal coiled material and preparation method thereof Download PDFInfo
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- CN114940750B CN114940750B CN202210749252.9A CN202210749252A CN114940750B CN 114940750 B CN114940750 B CN 114940750B CN 202210749252 A CN202210749252 A CN 202210749252A CN 114940750 B CN114940750 B CN 114940750B
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 27
- 239000002184 metal Substances 0.000 title claims abstract description 27
- 239000000463 material Substances 0.000 title claims abstract description 23
- 229920005989 resin Polymers 0.000 title claims abstract description 19
- 239000011347 resin Substances 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000010438 heat treatment Methods 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000002156 mixing Methods 0.000 claims abstract description 15
- 239000003112 inhibitor Substances 0.000 claims abstract description 13
- 229920001225 polyester resin Polymers 0.000 claims abstract description 13
- 239000004645 polyester resin Substances 0.000 claims abstract description 13
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 13
- 239000000243 solution Substances 0.000 claims abstract description 12
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 11
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- 239000012760 heat stabilizer Substances 0.000 claims abstract description 10
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 10
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims abstract description 7
- 239000002253 acid Substances 0.000 claims abstract description 7
- 239000008367 deionised water Substances 0.000 claims abstract description 7
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 7
- 238000004821 distillation Methods 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 7
- 238000001914 filtration Methods 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 7
- 238000004519 manufacturing process Methods 0.000 claims abstract description 6
- 239000012530 fluid Substances 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims abstract description 4
- 238000007599 discharging Methods 0.000 claims abstract description 4
- 239000011259 mixed solution Substances 0.000 claims abstract description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 30
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 18
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 12
- 150000002009 diols Chemical class 0.000 claims description 12
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 claims description 7
- 229920001610 polycaprolactone Polymers 0.000 claims description 7
- 239000004632 polycaprolactone Substances 0.000 claims description 7
- SPSPIUSUWPLVKD-UHFFFAOYSA-N 2,3-dibutyl-6-methylphenol Chemical compound CCCCC1=CC=C(C)C(O)=C1CCCC SPSPIUSUWPLVKD-UHFFFAOYSA-N 0.000 claims description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 6
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical group CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 6
- 235000010354 butylated hydroxytoluene Nutrition 0.000 claims description 6
- 229920000515 polycarbonate Polymers 0.000 claims description 6
- 239000004417 polycarbonate Substances 0.000 claims description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 6
- 238000013329 compounding Methods 0.000 claims description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 3
- 239000011964 heteropoly acid Substances 0.000 claims description 3
- 239000011973 solid acid Substances 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 3
- 238000000576 coating method Methods 0.000 abstract description 24
- 239000011248 coating agent Substances 0.000 abstract description 23
- -1 acrylic ester Chemical class 0.000 abstract description 13
- 238000005452 bending Methods 0.000 abstract description 6
- 229920000728 polyester Polymers 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 4
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 239000007788 liquid Substances 0.000 description 8
- 238000010992 reflux Methods 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000004721 Polyphenylene oxide Substances 0.000 description 3
- 239000012024 dehydrating agents Substances 0.000 description 3
- 238000005886 esterification reaction Methods 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229920000570 polyether Polymers 0.000 description 3
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- XOBOCRSRGDBOGH-UHFFFAOYSA-N 5-phenylnonan-5-ol Chemical compound CCCCC(O)(CCCC)C1=CC=CC=C1 XOBOCRSRGDBOGH-UHFFFAOYSA-N 0.000 description 1
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000003848 UV Light-Curing Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000012546 transfer Methods 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
- 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
-
- 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
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/42—Chemical after-treatment
-
- 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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/331—Polymers modified by chemical after-treatment with organic compounds containing oxygen
- C08G65/332—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof
- C08G65/3322—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof acyclic
-
- 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
- C09D167/06—Unsaturated polyesters having carbon-to-carbon unsaturation
-
- 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
- C09D169/00—Coating compositions based on polycarbonates; Coating compositions based on derivatives of polycarbonates
-
- 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
- C09D171/00—Coating compositions based on polyethers obtained by reactions forming an ether link in the main chain; Coating compositions based on derivatives of such polymers
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention discloses a resin for a metal coiled material and a preparation method thereof, and particularly relates to the field of resin preparation, comprising the following steps: s1, adding polyester resin, a heat stabilizer, acrylic acid, a water-carrying agent, a polymerization inhibitor and a catalyst into a reactor, heating, mixing and stirring, and stopping the reaction when the acid value in the reactor system is basically not reduced and no water is distilled out; s2, adding a pH value regulator into the reactor to neutralize when the temperature in the reactor system is reduced to below 60 ℃, and separating out a neutralization solution; s3, washing the mixed solution in the reactor with deionized water, separating out water solution, drying by anhydrous calcium chloride, and carrying out reduced pressure distillation, filtering and discharging to obtain the yellowish transparent viscous fluid acrylate oligomer. The synthetic polyester acrylic ester is used for modifying the coating, so that the bending resistance and the hardness of the coating are obviously improved, the energy consumption in the production process is effectively reduced, and the economic benefit is high.
Description
Technical Field
The invention relates to the technical field of resin preparation, in particular to a resin for a metal coiled material and a preparation method thereof.
Background
The metal material is a material with the properties of gloss, ductility, easy conduction, heat transfer and the like, and is generally divided into ferrous metal and nonferrous metal, wherein the ferrous metal comprises iron, chromium, manganese and the like, steel is a basic structural material, namely an industrial skeleton, and the metal coiled material is a coiled metal material, and the surface of the metal coiled material is required to be coated with resin coating in the production and processing process so as to improve the comprehensive performance of the metal coiled material and play a certain protection role on the metal coiled material, so that the metal coiled material is more practical in the subsequent use;
most of the existing resin coatings for metal coiled materials have single component, and the prepared resin has poor comprehensive performance, low bending strength and insufficient hardness, and when the resin coating is impacted, the coating is easy to crack, so that the protection performance of the base material is affected.
Disclosure of Invention
The invention provides a resin for a metal coiled material and a preparation method thereof, which aims to solve the problems that: the existing resin coating for the metal coiled material has low bending strength and hardness.
In order to achieve the above purpose, the present invention provides the following technical solutions: a preparation method of resin for metal coiled materials comprises the following steps:
s1, mixing polyester resin, a heat stabilizer and acrylic acid according to a molar ratio of 11:1:17-12:1:16.5, adding a water-carrying agent, a polymerization inhibitor and a catalyst into the reactor, heating, mixing and stirring, and stopping the reaction when the acid value in the reactor system is basically not reduced and no water is distilled out;
s2, adding a pH value regulator into the reactor to neutralize when the temperature in the reactor system is reduced to below 60 ℃, and separating out a neutralization solution;
s3, washing the mixed solution in the reactor with deionized water, separating out water solution, drying by using anhydrous calcium chloride, heating the reactor for the second time, and carrying out reduced pressure distillation, filtering and discharging to obtain the yellowish transparent viscous liquid acrylic ester oligomer.
In a preferred embodiment, in step S1, the temperature of the heating, mixing and stirring is 98-137 ℃ and the heating time is 3-6h.
In a preferred embodiment, in step S1, the polyester resin is one or more of polycaprolactone diol, polycarbonate diol, polyether diol, and the mass fraction of the added polyester resin is 20-30wt%; the heat stabilizer is trimethylolpropane, and the mass fraction of the added heat stabilizer is 0.5-1.8wt%; the mass fraction of the added acrylic acid is 18-26wt%; the water-carrying agent is one of toluene, dimethylbenzene and cyclohexane, and the mass fraction of the added water-carrying agent is 40-50wt%; the polymerization inhibitor is one or more of p-methoxyphenol, dibutyl hydroxyl toluene and hydroquinone, and the mass fraction of the added polymerization inhibitor is 0.2-0.5wt%; the catalyst is one of p-toluenesulfonic acid, concentrated sulfuric acid, p-toluenesulfonic acid, heteropolyacid and super solid acid, and the mass fraction of the added catalyst is 2-3wt%.
In a preferred embodiment, in step S2, the ph adjuster is 10% sodium carbonate or 5% sodium hydroxide.
In a preferred embodiment, in step S3, the secondary heating reactor is operated at a temperature of 98-137℃for a period of 30-45 minutes.
The molecular formula of the acrylic ester oligomer of the resin for the metal coiled material prepared by the preparation method is [ -CH2-CH- ] n-COOR.
In a preferred embodiment, n has a value in the range of 11 to 18.
The invention has the technical effects and advantages that:
1. the synthetic polyester acrylic ester is used for modifying the coating, so that the bending resistance and the hardness of the coating are obviously improved, the energy consumption in the production process is effectively reduced, and the economic benefit is high.
Drawings
FIG. 1 is a schematic flow chart of a preparation method according to an embodiment of the present invention.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. 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.
Referring to the drawing x of the specification, a preparation method of resin for metal coiled materials comprises the following steps:
s1, mixing polyester resin, a heat stabilizer and acrylic acid according to a molar ratio of 11:1:17-12:1:16.5 is added to the reactor, preferably at 11:1:17, adding the water-carrying agent, the polymerization inhibitor and the catalyst into the reactor, heating, mixing and stirring, and stopping the reaction when the acid value in the reactor system is basically not reduced and no water is distilled;
s2, adding a pH value regulator into the reactor to neutralize when the temperature in the reactor system is reduced to below 60 ℃, and separating out a neutralization solution;
s3, washing the mixed solution in the reactor with deionized water, separating out water solution, drying by using anhydrous calcium chloride, heating the reactor for the second time, and carrying out reduced pressure distillation, filtering and discharging to obtain the yellowish transparent viscous liquid acrylic ester oligomer.
In step S1, the temperature of heating, mixing and stirring is 98-137 ℃, preferably 110 ℃, and the heating time is 3-6h, preferably 4h.
In the step S1, the polyester resin is one or more of polycaprolactone diol, polycarbonate diol and polyether diol, and the mass fraction of the added polyester resin is 20-30wt%, preferably the two components are compounded according to the ratio of 1:1, and the mass fraction is 27.5wt%; the heat stabilizer is trimethylolpropane, and the mass fraction of the added heat stabilizer is 0.5-1.8wt%, preferably 0.5wt%; the mass fraction of the acrylic acid added is 18-26wt%, preferably 24wt%; the water-carrying agent is one of toluene, dimethylbenzene and cyclohexane, and the mass fraction of the added water-carrying agent is 40-50wt%, preferably toluene, and 45wt%; the polymerization inhibitor is one or more of p-methoxyphenol, dibutyl hydroxy toluene and hydroquinone, the mass fraction of the added polymerization inhibitor is 0.2-0.5wt%, preferably the dibutyl hydroxy toluene and the p-methoxyphenol are compounded according to the mass fraction of 1:1 to form the polymerization inhibitor, and the mass fraction is 0.5wt%; the catalyst is one of p-toluenesulfonic acid, concentrated sulfuric acid, p-toluenesulfonic acid, heteropolyacid and super solid acid, the mass fraction of the catalyst is 2-3wt%, preferably the dosage of p-toluenesulfonic acid, and the mass fraction is 2.5wt%.
In the step S2, the pH value regulator is 10% sodium carbonate or 5% sodium hydroxide.
In step S3, the temperature of the secondary heating reactor is 98-137 ℃, preferably 110 ℃, and the heating time is 30-45min, preferably 30min.
The molecular formula of the acrylic ester oligomer of the resin for the metal coiled material prepared by the preparation method is [ -CH2-CH- ] n-COOR.
The value range of n is 11-18.
The preparation method of the acrylate oligomer of the present invention will be described in detail with reference to specific examples.
Example 1
Adding a mixture of two polycaprolactone diols with the mass fraction of 20wt% into a reactor according to the ratio of 1:1, adding trimethylolpropane with the mass fraction of 0.5wt% and acrylic acid with the mass fraction of 26wt% into the reactor for mixing, adding a polymerization inhibitor prepared by compounding toluene with the mass fraction of 50wt% and dibutylhydroxytoluene with the mass fraction of 0.5wt% and p-methoxyphenol according to the ratio of 1:1 and p-toluenesulfonic acid with the mass fraction of 3wt% into the reactor, introducing micro compressed air, heating to 98 ℃ for reflux esterification reaction for 6 hours, and detecting that the acid value in the reactor is basically not reduced and is the end point when no water is distilled;
when the temperature in the reactor system is reduced to below 60 ℃, 10% sodium carbonate or 5% sodium hydroxide is used for neutralization, and the neutralization liquid is separated;
washing with deionized water for 3-5 times, separating out water solution, drying overnight by using anhydrous calcium chloride, heating to 98 ℃ and refluxing for 45min, vacuumizing, distilling off the dehydrating agent toluene by using a reduced pressure distillation mode, and filtering by using 400-mesh filter cloth to obtain the yellowish transparent viscous fluid acrylic ester oligomer product a.
Example 2
Adding a mixture of 30wt% of polycaprolactone dihydric alcohol and 2wt% of polycarbonate dihydric alcohol into a reactor according to the ratio of 1:1, adding 1.8wt% of trimethylolpropane and 16wt% of acrylic acid into the reactor for mixing, adding 50wt% of toluene, 0.2wt% of polymerization inhibitor compounded by 0.2wt% of dibutylhydroxytoluene and p-methoxyphenol according to the ratio of 1:1, adding 2wt% of p-toluenesulfonic acid into the reactor, introducing a small amount of compressed air, heating to 137 ℃ for reflux esterification reaction for 3 hours, and detecting that the acid value in the reactor is basically not reduced when no water is distilled out;
when the temperature in the reactor system is reduced to below 60 ℃, 10% sodium carbonate or 5% sodium hydroxide is used for neutralization, and the neutralization liquid is separated;
washing with deionized water for 3-5 times, separating out water solution, drying overnight by using anhydrous calcium chloride, heating to 137 ℃ and refluxing for 30min, vacuumizing, distilling off the dehydrating agent toluene by using a reduced pressure distillation mode, and filtering by using 400-mesh filter cloth to obtain the yellowish transparent viscous fluid acrylic ester oligomer product b.
Example 3
Adding a mixture of polycaprolactone dihydric alcohol and polycarbonate dihydric alcohol with the mass fraction of 27.5wt% into a reactor according to the ratio of 1:1, adding trimethylolpropane with the mass fraction of 0.5wt% and acrylic acid with the mass fraction of 24wt% into the reactor for mixing, adding a polymerization inhibitor prepared by compounding toluene with the mass fraction of 45wt% and dibutylhydroxytoluene with the mass fraction of 0.5wt% and p-methoxyphenol according to the ratio of 1:1 and p-toluenesulfonic acid with the mass fraction of 2.5wt% into the reactor, introducing a small amount of compressed air, heating to 110 ℃, carrying out reflux esterification for 4 hours, and detecting that the acid value in the reactor is basically not reduced and is the end point when no water is distilled;
when the temperature in the reactor system is reduced to below 60 ℃, 10% sodium carbonate or 5% sodium hydroxide is used for neutralization, and the neutralization liquid is separated;
washing with deionized water for 3-5 times, separating out water solution, drying overnight by using anhydrous calcium chloride, heating to 110 ℃ and refluxing for 30min, vacuumizing, distilling off the dehydrating agent toluene by using a reduced pressure distillation mode, and filtering by using 400-mesh filter cloth to obtain the yellowish transparent viscous fluid acrylic ester oligomer product c.
Example 4
In this example, the addition components, proportions, and implementation steps and conditions were the same as in example 3; unlike example 3, the polyester resin added in this example was a single polycaprolactone diol, and a yellowish transparent viscous liquid acrylate oligomer product d was prepared.
Example 5
In this example, the addition components, proportions, and implementation steps and conditions were the same as in example 3; unlike example 3, the polyester resin added in this example was a single polycarbonate diol, and a yellowish transparent viscous liquid acrylate oligomer product e was produced.
Example 6
In this example, the addition components, proportions, and implementation steps and conditions were the same as in example 3; unlike example 3, the polyester resin added in this example was a polyether diol alone, and a yellowish transparent viscous liquid acrylate oligomer product f was produced.
Comparative example
In this example, the addition components, proportions, and implementation steps and conditions were the same as in example 3; unlike example 3, the polyester resin added in this example was a common polyester acrylate.
The following test experiments were conducted on the coating of the acrylate oligomer obtained in each of the above examples on the surface of a metal coil, and the method of coating the surface of the coil was conducted:
the acrylate prepolymer a, b, c, d, e, f with the mass fraction of 85.5wt% prepared in the embodiment is uniformly mixed with 1, 6-hexanediol diacrylate with the mass fraction of 10wt%, a photoinitiator TPO with the mass fraction of 2wt%, a photoinitiator 819 with the mass fraction of 2wt% and a leveling agent 358 with the mass fraction of 0.5wt% respectively to prepare a coating, then the coating is uniformly scraped on a test substrate by a scraper, and a metal aluminum coiled sheet is selected as the test substrate;
the coating film thickness was about 10 μm, and was cured by UV curing to form a film, and the cured film was subjected to performance test.
The results of the performance test experiments on the acrylate oligomers obtained in the examples are shown in table 1 below:
by observing the test experimental results, the application of the modified acrylic ester coating to the metal coiled material can be seen, and the acrylic ester oligomer coating prepared by the invention sacrifices the leveling property of the coating to a certain extent, but the coating formed by coating the prepared coating on the metal coiled material has certain bending resistance, and the hardness of the coating is greatly improved compared with that of the conventional polyester acrylic ester.
In conclusion, the synthetic polyester acrylic ester is used for modifying the coating, and the result shows that the coating preliminarily meets the standard of a metal coiled material, particularly, the bending resistance and the hardness of the coating are obviously improved, the energy consumption in the production process is effectively reduced, and the preparation method has higher economic benefit.
Finally: the foregoing description of the preferred embodiments of the invention is not intended to limit the invention to the precise form disclosed, and any such modifications, equivalents, and alternatives falling within the spirit and principles of the invention are intended to be included within the scope of the invention.
Claims (3)
1. The preparation method of the resin for the metal coiled material is characterized by comprising the following steps of:
s1, mixing polyester resin, a heat stabilizer and acrylic acid according to a molar ratio of 11:1:17-12:1:16.5, adding a water carrying agent, a polymerization inhibitor and a catalyst into the reactor, heating, mixing and stirring, and stopping the reaction when the acid value in the reactor system is not reduced and no water is distilled;
s2, adding a pH value regulator into the reactor to neutralize when the temperature in the reactor system is reduced to below 60 ℃, and separating out a neutralization solution;
s3, washing the mixed solution in the reactor with deionized water, separating out water solution, drying by using anhydrous calcium chloride, heating the reactor for the second time, and carrying out reduced pressure distillation, filtration and discharging to obtain the yellowish transparent viscous fluid acrylate oligomer;
in the step S1, heating, mixing and stirring are carried out for 3-6 hours at the temperature of 98-137 ℃;
in the step S1, the heat stabilizer is trimethylolpropane, and the mass fraction of the added heat stabilizer is 0.5-1.8wt%; the mass fraction of the added acrylic acid is 18-26wt%; the water-carrying agent is one of toluene, dimethylbenzene and cyclohexane, and the mass fraction of the added water-carrying agent is 40-50wt%; the catalyst is one of p-toluenesulfonic acid, concentrated sulfuric acid, heteropolyacid and super solid acid, and the mass fraction of the added catalyst is 2-3wt%;
in the step S1, the polyester resin is prepared by compounding and mixing polycaprolactone diol and polycarbonate diol with the mass fraction of 27.5wt% according to the ratio of 1:1;
in the step S1, the polymerization inhibitor is prepared by compounding and mixing dibutyl hydroxy toluene and p-methoxyphenol according to a ratio of 1:1.
2. The method for producing a resin for a metal coil according to claim 1, wherein: in the step S2, the pH value regulator is 10% sodium carbonate or 5% sodium hydroxide.
3. The method for producing a resin for a metal coil according to claim 2, characterized in that: in the step S3, the temperature of the secondary heating reactor is 98-137 ℃ and the heating time is 30-45min.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03181517A (en) * | 1989-12-08 | 1991-08-07 | Daicel Chem Ind Ltd | Polycarbonate acrylate resin or polycarbonate methacrylate resin |
| JP2001151730A (en) * | 1999-11-19 | 2001-06-05 | Ube Ind Ltd | Method for producing polycarbonatediol acrylate compound |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03181517A (en) * | 1989-12-08 | 1991-08-07 | Daicel Chem Ind Ltd | Polycarbonate acrylate resin or polycarbonate methacrylate resin |
| JP2001151730A (en) * | 1999-11-19 | 2001-06-05 | Ube Ind Ltd | Method for producing polycarbonatediol acrylate compound |
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