CN117603418A - High-biobased UV resin containing imine bond, and preparation method and application thereof - Google Patents
High-biobased UV resin containing imine bond, and preparation method and application thereof Download PDFInfo
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- CN117603418A CN117603418A CN202311468818.1A CN202311468818A CN117603418A CN 117603418 A CN117603418 A CN 117603418A CN 202311468818 A CN202311468818 A CN 202311468818A CN 117603418 A CN117603418 A CN 117603418A
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- 239000011347 resin Substances 0.000 title claims abstract description 43
- 229920005989 resin Polymers 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 239000000463 material Substances 0.000 claims abstract description 43
- 239000004359 castor oil Substances 0.000 claims abstract description 37
- 235000019438 castor oil Nutrition 0.000 claims abstract description 37
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims abstract description 37
- FGQOOHJZONJGDT-UHFFFAOYSA-N vanillin Natural products COC1=CC(O)=CC(C=O)=C1 FGQOOHJZONJGDT-UHFFFAOYSA-N 0.000 claims abstract description 32
- 235000012141 vanillin Nutrition 0.000 claims abstract description 32
- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229920000768 polyamine Polymers 0.000 claims abstract description 23
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 6
- 239000000178 monomer Substances 0.000 claims abstract description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 72
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 24
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 22
- 239000003960 organic solvent Substances 0.000 claims description 22
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 18
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 18
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- CPOQZWDLPWEJET-UHFFFAOYSA-N (4-formyl-2-methoxyphenyl) 2-methylprop-2-enoate Chemical compound COC1=CC(C=O)=CC=C1OC(=O)C(C)=C CPOQZWDLPWEJET-UHFFFAOYSA-N 0.000 claims description 12
- -1 vanillin acrylic ester Chemical class 0.000 claims description 11
- 239000012074 organic phase Substances 0.000 claims description 10
- OGMADIBCHLQMIP-UHFFFAOYSA-N 2-aminoethanethiol;hydron;chloride Chemical compound Cl.NCCS OGMADIBCHLQMIP-UHFFFAOYSA-N 0.000 claims description 9
- 229940097265 cysteamine hydrochloride Drugs 0.000 claims description 9
- DCUFMVPCXCSVNP-UHFFFAOYSA-N methacrylic anhydride Chemical compound CC(=C)C(=O)OC(=O)C(C)=C DCUFMVPCXCSVNP-UHFFFAOYSA-N 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical class [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000000746 purification Methods 0.000 claims description 4
- 239000000376 reactant Substances 0.000 claims description 4
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 claims description 2
- 150000001299 aldehydes Chemical class 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims 1
- 238000003848 UV Light-Curing Methods 0.000 abstract description 29
- 238000001723 curing Methods 0.000 abstract description 22
- 238000011084 recovery Methods 0.000 abstract description 12
- 239000002994 raw material Substances 0.000 abstract description 8
- 238000012958 reprocessing Methods 0.000 abstract description 8
- 125000003172 aldehyde group Chemical group 0.000 abstract description 7
- 239000002028 Biomass Substances 0.000 abstract description 4
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 230000015556 catabolic process Effects 0.000 abstract description 2
- 238000006731 degradation reaction Methods 0.000 abstract description 2
- 238000002390 rotary evaporation Methods 0.000 description 15
- 239000000243 solution Substances 0.000 description 13
- 239000000047 product Substances 0.000 description 12
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 11
- 239000000126 substance Substances 0.000 description 11
- 238000000605 extraction Methods 0.000 description 10
- 238000002474 experimental method Methods 0.000 description 9
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 8
- 239000003999 initiator Substances 0.000 description 8
- 229920006395 saturated elastomer Polymers 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- PSGAAPLEWMOORI-PEINSRQWSA-N medroxyprogesterone acetate Chemical compound C([C@@]12C)CC(=O)C=C1[C@@H](C)C[C@@H]1[C@@H]2CC[C@]2(C)[C@@](OC(C)=O)(C(C)=O)CC[C@H]21 PSGAAPLEWMOORI-PEINSRQWSA-N 0.000 description 7
- 238000000465 moulding Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 125000003277 amino group Chemical group 0.000 description 5
- 239000002585 base Substances 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 230000009477 glass transition Effects 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 235000017557 sodium bicarbonate Nutrition 0.000 description 5
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- 239000002262 Schiff base Substances 0.000 description 4
- 150000004753 Schiff bases Chemical class 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 238000005520 cutting process Methods 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 238000007731 hot pressing Methods 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 230000002441 reversible effect Effects 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000007056 transamidation reaction Methods 0.000 description 4
- 235000015112 vegetable and seed oil Nutrition 0.000 description 4
- 239000008158 vegetable oil Substances 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000006870 function Effects 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000010146 3D printing Methods 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 239000008157 edible vegetable oil Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012949 free radical photoinitiator Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000003847 radiation curing Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- XHFLOLLMZOTPSM-UHFFFAOYSA-M sodium;hydrogen carbonate;hydrate Chemical class [OH-].[Na+].OC(O)=O XHFLOLLMZOTPSM-UHFFFAOYSA-M 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000003549 soybean oil 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
- C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
- C08G12/04—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds
- C08G12/06—Amines
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a high bio-based UV resin containing imine bonds, and a preparation method and application thereof. The invention takes castor oil polyamine prepared from renewable biomass resource castor oil and vanillin-based acrylate monomer containing only one aldehyde group prepared from renewable biomass resource vanillin as raw materials to prepare the high bio-based UV resin containing imine bonds. The high bio-based UV resin containing imine bonds provided by the invention can be subjected to UV curing, has short curing time and low energy consumption, and the cured UV curing material has high bio-based content, good mechanical properties and reprocessing and degradation recovery capabilities.
Description
Technical Field
The invention belongs to the technical field of preparation of UV (ultraviolet) curing materials, and relates to a high-biobased UV resin containing imine bonds, and a preparation method and application thereof.
Background
Ultraviolet light curing (UV curing) technology is widely applied to the fields of paint, 3D printing, adhesives and the like because of the five advantages of environmental protection (Environmental Friendly), energy Saving (Energy Saving), economy (Economy), high efficiency (efficiency) and universality (Enabled), wherein the light-cured resin plays a key role on the final performance of the material. The traditional ultraviolet light curing resin is difficult to realize recovery after being subjected to ultraviolet light curing, and meanwhile, most of the ultraviolet light curing resin is synthesized by petrochemical raw materials, so that under the dual pressures of increasingly exhaustion of petroleum resources and environmental protection, the development of the bio-based ultraviolet resin with dynamic reversible bonds is an important direction for realizing sustainable development of the radiation curing material industry.
In recent years, the introduction of dynamic reversible chemical bonds into polymers has become a research hotspot. Chinese patent application CN113004477B discloses a vegetable oil-based self-repairing polymer based on schiff base, the preparation method of which comprises the following steps: according to the mass ratio of 3: (0.1-2) dissolving vegetable oil-based polyamine and a multi-component aldehyde compound in an organic solvent, standing at room temperature to 100 ℃ for 4-48 hours to volatilize the solvent, and then continuously standing under vacuum for 12-24 hours to remove trace amount of the solvent to obtain the modified vegetable oil-based polyamine. The patent adopts a curing molding mode of condensing, curing and molding multifunctional aldehyde and polyamine in a solvent to prepare the vegetable oil-based self-repairing polymer based on Schiff base, which has the functions of self-healing, reprocessing, recycling and shape memory, but the mechanical property of the prepared self-repairing polymer based on Schiff base is poor when the castor oil-based polyamine is used as a raw material to prepare the castor oil-based self-repairing polymer based on Schiff base.
Castor oil is an important non-edible vegetable oil, hydroxyl and unsaturated double bonds in the structure provide sites for chemical modification, and the castor oil is an ideal raw material for preparing high polymer materials. Starting from castor oil, a high bio-based Virimer material with good mechanical properties is developed, and the material has important environmental protection and economic value.
Disclosure of Invention
The first object of the present invention is to provide a high bio-based UV resin containing an imine bond. The invention takes castor oil polyamine prepared from renewable biomass resource castor oil and vanillin-based acrylate monomer containing only one aldehyde group prepared from renewable biomass resource vanillin as raw materials to prepare the high bio-based UV resin containing imine bonds. The high bio-based UV resin containing imine bonds provided by the invention can be subjected to UV curing, has short curing time and low energy consumption, and the cured UV curing material has high bio-based content, good mechanical properties and reprocessing and degradation recovery capabilities.
The second object of the present invention is to provide a method for producing the above-mentioned high bio-based UV resin containing an imine bond.
A third object of the present invention is to provide the use of the above-mentioned high bio-based UV resin containing an imine bond for preparing UV curable materials.
The fourth object of the present invention is to provide a UV curable composition comprising the above-mentioned high biobased UV resin containing an imine bond as a curing raw material.
According to one aspect of the present invention, there is provided a method for preparing an imine bond-containing high bio-based UV resin, comprising the steps of:
the molar ratio of the amine groups of the castor oil polyamine to the aldehyde groups of the vanillin acrylic ester monomers is 1: (0.8-1.2) adding the mixture into an organic solvent, reacting for 4-12 hours at room temperature, and removing the organic solvent to obtain the high biological base UV resin containing dynamic reversible chemical bonds (imine bonds); wherein the vanillin acrylic ester monomer is vanillin acrylic ester or vanillin methacrylic ester.
The preparation method of the high bio-based UV resin containing the imine bond has the advantages of simple process, no need of a catalyst and environment-friendly preparation process.
In some embodiments, the organic solvent may be selected from one or more of dichloromethane, chloroform, ethyl acetate, acetone.
In some embodiments, a method of preparing a castor oil polyamine may include the steps of:
dissolving castor oil and cysteamine hydrochloride in absolute ethyl alcohol, adding 2, 2-dimethoxy-2-phenyl acetophenone (photo initiator DMPA), reacting for 12-24 h under ultraviolet light, removing absolute ethyl alcohol, and purifying. Therefore, the preparation process of the castor oil polyamine is more environment-friendly and efficient by selecting the absolute ethyl alcohol which is an environment-friendly solvent as a reaction solvent and using the DMPA which is a photoinitiator with higher efficiency as a catalyst.
In some embodiments, the molar ratio of double bonds in castor oil to cysteamine hydrochloride may be 1: (2-4).
In some embodiments, the molar ratio of double bonds in castor oil to the photoinitiator DMPA may be 1: (0.05-0.1).
In some embodiments, purification of castor oil and cysteamine hydrochloride reaction products may include the steps of:
dissolving the product in an organic solvent, extracting for 3-5 times by using a saturated sodium carbonate aqueous solution, performing organic phase drying to remove water, and removing the organic solvent to obtain the product; wherein the organic solvent can be selected from one or more of dichloromethane, chloroform, ethyl acetate and acetone.
In some embodiments, the method of preparing vanillin acrylate may comprise the steps of:
adding vanillin, acryloyl chloride and triethylamine into an organic solvent, reacting for 12-24 hours at room temperature, and purifying to obtain the product; wherein the organic solvent can be selected from one or more of dichloromethane, chloroform, ethyl acetate and acetone.
In some embodiments, the molar ratio of vanillin to acrylic acid chloride can be 1: (1.0 to 1.2); the amount of triethylamine may be 40% to 60% of the total mass of the reactants (i.e., the total mass of vanillin, acryloyl chloride, and triethylamine).
In some embodiments, the purification of vanillin acrylate may comprise the steps of: extracting the product with saturated sodium bicarbonate water solution for several times until no carbon dioxide is produced, extracting with saturated saline water until the organic phase is neutral, collecting organic phase, drying to remove water, and rotary evaporating to remove organic solvent.
In some embodiments, the method of preparing vanillin methacrylate may include the steps of:
mixing vanillin, methacrylic anhydride and 4-dimethylaminopyridine, reacting at 55-65 ℃ for 12-24 h, and purifying to obtain the product.
In some embodiments, the molar ratio of vanillin to methacrylic anhydride can be 1 (1-1.2); the amount of 4-Dimethylaminopyridine (DMAP) used is 0.1% to 0.5% of the total mass of the reactants (i.e. the total mass of vanillin, methacrylic anhydride and DMAP).
In some embodiments, purification of vanillin methacrylate may include the steps of: dissolving the product in an organic solvent, extracting for a plurality of times by using a saturated sodium bicarbonate aqueous solution until no carbon dioxide is generated, extracting until an organic phase is neutral by using a saturated saline solution, collecting organic phase, drying and removing water, and removing the organic solvent by rotary evaporation to obtain the product; wherein the organic solvent can be selected from one or more of dichloromethane, chloroform, ethyl acetate and acetone.
According to another aspect of the invention, there is provided the use of the imine bond-containing high bio-based UV resin prepared by the above preparation method of the imine bond-containing high bio-based UV resin in the preparation of UV curable materials. The high bio-based UV resin containing the imine bond can be cured and formed by adopting a UV light curing forming process, the curing time is short, the energy consumption is low, and the cured UV curing material has high crosslinking density and good mechanical property. Therefore, the high bio-based UV resin containing the imine bond can be used as a curing raw material to prepare a UV curing material.
According to still another aspect of the present invention, there is provided a UV-curable composition comprising the high bio-based UV resin having an imine bond provided by the present invention and a photoinitiator, wherein the photoinitiator is used in an amount of 3 to 7% by mass of the high bio-based UV resin having an imine bond.
In some embodiments, the photoinitiator is selected from free radical photoinitiators, and may specifically be selected from at least one of the photoinitiators TPO, photoinitiator 1173, and the like.
Drawings
FIG. 1 is a schematic diagram of the synthetic route of the imine bond containing high biobased UV resin of the present invention.
Detailed Description
The present invention will be described in further detail with reference to the following embodiments. The examples are for illustration only and are not intended to limit the invention in any way. The raw materials and reagents used in the examples were conventional products which were obtained commercially, unless otherwise specified; the experimental methods for which specific conditions are not specified in the examples are generally in accordance with the conditions conventional in the art or in accordance with the manufacturer's recommendations.
Example 1
(1) Preparation of castor oil polyamine
46.7g of castor oil (0.15 mol of double bond), 51.2g of cysteamine hydrochloride (0.45 mol) and 3.5g of photo initiator DMPA (0.015 mol) are stirred and dissolved in 150mL of absolute ethyl alcohol, the mixture is reacted for 18 hours under a 30W ultraviolet lamp, the absolute ethyl alcohol is removed by rotary evaporation, the product is dissolved in chloroform, 150mL of saturated sodium carbonate aqueous solution is added for extraction for 5 times, an organic phase is collected, and the solvent is removed by rotary evaporation to obtain castor oil polyamine with an amine value of 2.28mmol/g.
(2) Preparation of vanillin methacrylate
30.3g of vanillin (0.2 mol), 33.2g of methacrylic anhydride (0.22 mol) and 0.17g of catalyst DMAP (0.0014 mol) were taken and reacted at 60℃for 24 hours, then 150mL of methylene chloride was added for dissolution, 3 times of extraction with 150mL of saturated aqueous sodium bicarbonate solution, 3 times of extraction with saturated aqueous sodium bicarbonate solution, and dried overnight with anhydrous magnesium sulfate, and then methylene chloride was distilled off to obtain vanillin methacrylate.
(3) Preparation of high biobased UV resin containing imine bond
20g of the castor oil polyamine prepared in the step (1) and 10.03g of the vanillin methacrylate prepared in the step (2) (the molar ratio of amine groups to aldehyde groups is about 1:1) are taken and dissolved in 150mL of dichloromethane, the mixture is stirred and reacted for 6 hours at room temperature, and the dichloromethane is removed by rotary evaporation to obtain the high bio-based UV resin containing imine bonds.
(5) UV curing
And (3) adding 0.15g of photo-initiator TPO into 5g of the high biological base UV resin containing imine bonds prepared in the step (3), uniformly stirring, coating the mixture on a glass plate by a wet method, curing the mixture on a 2.5kW ultraviolet curing machine for 30s, wherein the thickness of a film coater is 1000 micrometers, and obtaining the UV curing material.
The biobased content of the UV curing material is 88.2%, and the glass transition temperature is 38 ℃; the tensile strength can reach 15.3MPa.
And (3) reprocessing experiments: cutting the UV cured material, hot-pressing for 30 minutes at 150 ℃ and a hot press of 30MPa, and re-molding the UV cured material into a complete sample, wherein the prepared UV cured material has reworkability.
Chemical recovery experiment: 2g of UV curing material is placed in 20mL of mixed solution of hexylamine and THF (1:2, v/v), and after being soaked for 24 hours at room temperature, imine bonds can be subjected to a transamidation reaction with hexylamine, and solids are completely dissolved in the solution, so that chemical recovery of the prepared UV curing material under mild conditions can be realized.
Example 2
(1) Preparation of castor oil polyamine
46.7g of castor oil, 51.2g of cysteamine hydrochloride and 3.5g of photo initiator DMPA are stirred and dissolved in 150mL of absolute ethyl alcohol, the mixture is reacted for 24 hours under a 30W ultraviolet lamp, the absolute ethyl alcohol is removed by rotary evaporation, the product is dissolved in chloroform, 150mL of saturated sodium carbonate aqueous solution is added for extraction for 5 times, an organic phase is collected, water is removed by rotary evaporation, and the solvent is removed to obtain castor oil polyamine with an amine value of 2.38mmol/g.
(2) Preparation of vanillin methacrylate
30.3g of vanillin, 33.2g of methacrylic anhydride and 0.17g of catalyst DMAP are taken and reacted for 24 hours at 60 ℃, 150mL of methylene chloride is added for dissolution, 150mL of saturated aqueous sodium bicarbonate solution is used for extraction for 3 times, saturated aqueous sodium chloride solution is used for extraction for 3 times, anhydrous magnesium sulfate is added for drying overnight, and methylene chloride is removed by rotary evaporation to obtain vanillin methacrylate.
(3) Preparation of high biobased UV resin containing imine bond
20g of the castor oil polyamine prepared in the step (1) and 10.5g of the vanillin methacrylate prepared in the step (2) (the molar ratio of amine groups to aldehyde groups is about 1:1) are taken and dissolved in 150mL of dichloromethane, the mixture is stirred and reacted for 4 hours at room temperature, and the dichloromethane is removed by rotary evaporation to obtain the high bio-based UV resin containing imine bonds.
(5) UV curing
And (3) adding 0.15g of photo-initiator TPO into 5g of the high biological base UV resin containing imine bonds prepared in the step (3), uniformly stirring, coating the mixture on a glass plate by a wet method, curing the mixture on a 2.5kW ultraviolet curing machine for 30s, wherein the thickness of a film coater is 1000 micrometers, and obtaining the UV curing material.
The biobased content of the UV curing material is 88.2%, and the glass transition temperature is 42 ℃; the tensile strength can reach 16.5MPa.
And (3) reprocessing experiments: cutting the UV cured material, hot-pressing for 30 minutes at 150 ℃ and a hot press of 30MPa, and re-molding the UV cured material into a complete sample, wherein the prepared UV cured material has reworkability.
Chemical recovery experiment: 2g of UV curing material is placed in 20mL of mixed solution of hexylamine and THF (1:2, v/v), and after being soaked for 24 hours at room temperature, imine bonds can be subjected to a transamidation reaction with hexylamine, and solids are completely dissolved in the solution, so that chemical recovery of the prepared UV curing material under mild conditions can be realized.
Example 3
(1) Preparation of castor oil polyamine
46.7g of castor oil, 51.2g of cysteamine hydrochloride and 3.5g of photo initiator DMPA are stirred and dissolved in 150mL of absolute ethyl alcohol, the mixture is reacted for 24 hours under a 30W ultraviolet lamp, the absolute ethyl alcohol is removed by rotary evaporation, the product is dissolved in chloroform, 150mL of saturated sodium carbonate aqueous solution is added for extraction for 5 times, an organic phase is collected, water is removed by rotary evaporation, and the solvent is removed to obtain castor oil polyamine with an amine value of 2.38mmol/g.
(2) Preparation of vanillin methacrylate
30.3g of vanillin, 33.2g of methacrylic anhydride and 0.17g of catalyst DMAP are taken and reacted for 24 hours at 60 ℃, 150mL of methylene chloride is added for dissolution, 150mL of saturated aqueous sodium bicarbonate solution is used for extraction for 3 times, saturated aqueous sodium chloride solution is used for extraction for 3 times, anhydrous magnesium sulfate is added for drying overnight, and methylene chloride is removed by rotary evaporation to obtain vanillin methacrylate.
(3) Preparation of high biobased UV resin containing imine bond
20g of the castor oil polyamine prepared in the step (1) and 10.5g of the vanillin methacrylate prepared in the step (2) (the molar ratio of amine groups to aldehyde groups is about 1:1) are taken and dissolved in 150mL of dichloromethane, the mixture is stirred and reacted for 4 hours at room temperature, and the dichloromethane is removed by rotary evaporation to obtain the high bio-based UV resin containing imine bonds.
(5) UV curing
And (3) adding 0.15g of photoinitiator 1173 into 5g of the high biological base UV resin containing the imine bond prepared in the step (3), uniformly stirring, coating the mixture on a glass plate by a wet method, curing the mixture on a 2.5kW ultraviolet curing machine for 30s, wherein the thickness of a film coater is 1000 micrometers, and obtaining the UV curing material.
The biobased content of the UV curing material is 88.2%, and the glass transition temperature is 38 ℃; the tensile strength can reach 15.1MPa.
And (3) reprocessing experiments: cutting the UV cured material, hot-pressing for 30 minutes at 150 ℃ and a hot press of 30MPa, and re-molding the UV cured material into a complete sample, wherein the prepared UV cured material has reworkability.
Chemical recovery experiment: 2g of UV curing material is placed in 20mL of mixed solution of hexylamine and THF (1:2, v/v), and after being soaked for 24 hours at room temperature, imine bonds can be subjected to a transamidation reaction with hexylamine, and solids are completely dissolved in the solution, so that chemical recovery of the prepared UV curing material under mild conditions can be realized.
Example 4
(1) Preparation of castor oil polyamine
46.7g of castor oil, 51.2g of cysteamine hydrochloride and 3.5g of photo initiator DMPA are stirred and dissolved in 150mL of absolute ethyl alcohol, the mixture is reacted for 24 hours under a 30W ultraviolet lamp, the absolute ethyl alcohol is removed by rotary evaporation, the product is dissolved in chloroform, 150mL of saturated sodium carbonate aqueous solution is added for extraction for 5 times, an organic phase is collected, water is removed by rotary evaporation, and the solvent is removed to obtain castor oil polyamine with an amine value of 2.38mmol/g.
(2) Preparation of vanillin acrylic ester
40g of vanillin (0.26 mol), 51.4g of triethylamine (0.51 mol) and 26.9g of acryloyl chloride (0.29 mol) were dissolved in 200mL of methylene chloride with stirring in an ice water bath, reacted at room temperature for 24 hours, and then the filtrate was collected by filtration, extracted 3 times with 150mL of saturated aqueous sodium bicarbonate solution, extracted 3 times with saturated aqueous sodium chloride solution, dried overnight with anhydrous magnesium sulfate, and the methylene chloride was removed by spin evaporation to give vanillin acrylate.
(3) Preparation of high biobased UV resin containing imine bond
20g of the castor oil polyamine prepared in the step (1) and 9.4g of the vanillin acrylic ester prepared in the step (2) (the molar ratio of amine groups to aldehyde groups is about 1:1) are taken and dissolved in 150mL of dichloromethane, the mixture is stirred and reacted for 6 hours at room temperature, and the dichloromethane is removed by rotary evaporation to obtain the high-biobased UV resin containing imine bonds.
(5) UV curing
And (3) adding 0.15g of photoinitiator 1173 into 5g of the high biological base UV resin containing the imine bond prepared in the step (3), uniformly stirring, coating the mixture on a glass plate by a wet method, curing the mixture on a 2.5kW ultraviolet curing machine for 30s, wherein the thickness of a film coater is 1000 micrometers, and obtaining the UV curing material.
The biobased content of the UV curing material is 92.5%, and the glass transition temperature is 40 ℃; the tensile strength can reach 15.8MPa.
And (3) reprocessing experiments: cutting the UV cured material, hot-pressing for 30 minutes at 150 ℃ and a hot press of 30MPa, and re-molding the UV cured material into a complete sample, wherein the prepared UV cured material has reworkability.
Chemical recovery experiment: 2g of UV curing material is placed in 20mL of mixed solution of hexylamine and THF (1:2, v/v), and after being soaked for 24 hours at room temperature, imine bonds can be subjected to a transamidation reaction with hexylamine, and solids are completely dissolved in the solution, so that chemical recovery of the prepared UV curing material under mild conditions can be realized.
Comparative example 1
Taking 5g of epoxy soybean oil acrylic resin, adding 0.15g of photo initiator TPO, uniformly stirring, coating on a glass plate by a wet method, wherein the thickness of a film coater is 1000 micrometers, and curing for 30s on a 2.5kW ultraviolet curing machine.
The biobased content of the UV curing material is 83%, and the glass transition temperature is 15 ℃; the tensile strength can reach 2.45MPa.
Because the material does not contain dynamic reversible imine bonds, the prepared UV cured material cannot realize the functions of hot press reprocessing and chemical recovery.
What has been described above is merely some embodiments of the present invention. It will be apparent to those skilled in the art that various modifications and improvements can be made without departing from the spirit of the invention.
Claims (10)
1. The preparation method of the high bio-based UV resin containing the imine bond is characterized by comprising the following steps of:
castor oil polyamine and vanillin acrylic ester monomer are mixed according to the molar ratio of amino to aldehyde of 1: (0.8-1.2) adding the mixture into an organic solvent, reacting for 4-12 hours at room temperature, and removing the organic solvent to obtain the catalyst; wherein the vanillin acrylic ester monomer is vanillin acrylic ester or vanillin methacrylic ester.
2. The preparation method according to claim 1, wherein the organic solvent is one or more selected from dichloromethane, chloroform, ethyl acetate and acetone.
3. The preparation method of the castor oil polyamine according to claim 1, comprising the following steps:
dissolving castor oil and cysteamine hydrochloride in absolute ethyl alcohol, adding 2, 2-dimethoxy-2-phenylacetophenone, reacting for 12-24 hours under ultraviolet light, removing absolute ethyl alcohol, and purifying to obtain the product;
the molar ratio of the double bond in the castor oil to the cysteamine hydrochloride is 1: (2-4); the molar ratio of the double bond in the castor oil to the 2, 2-dimethoxy-2-phenylacetophenone is 1: (0.05-0.1).
4. A method of preparation according to claim 3, wherein the purification comprises the steps of:
dissolving the product in an organic solvent, extracting for 3-5 times by using a saturated sodium carbonate aqueous solution, performing organic phase drying to remove water, and removing the organic solvent to obtain the product;
the organic solvent is selected from one or more of dichloromethane, chloroform, ethyl acetate and acetone.
5. The method according to any one of claims 1 to 4, wherein the method for producing vanillin acrylate comprises the steps of:
adding vanillin, acryloyl chloride and triethylamine into an organic solvent, reacting for 12-24 hours at room temperature, and purifying to obtain the product;
the organic solvent is selected from one or more of dichloromethane, chloroform, ethyl acetate and acetone;
the molar ratio of vanillin to acrylic chloride is 1: (1.0 to 1.2); the dosage of the triethylamine is 40-60% of the total mass of the reactants.
6. The method according to any one of claims 1 to 4, wherein the method for producing vanillin methacrylate comprises the steps of:
mixing vanillin, methacrylic anhydride and 4-dimethylaminopyridine, reacting for 12-24 hours at 55-65 ℃, and purifying to obtain the product;
the organic solvent is selected from one or more of dichloromethane, chloroform, ethyl acetate and acetone;
the mol ratio of vanillin to methacrylic anhydride is 1 (1-1.2); the dosage of the 4-dimethylaminopyridine is 0.1-0.5% of the total mass of the reactants.
7. The high bio-based UV resin containing an imine bond prepared according to the preparation method of any one of claims 1 to 6.
8. Use of the high biobased UV resin containing imine bonds according to claim 7, in the preparation of UV curable materials.
A UV curable composition comprising the imine bond-containing high bio-based UV resin according to claim 7 and a photoinitiator in an amount of 3% to 7% by mass of the imine bond-containing high bio-based UV resin according to claim 7.
10. The UV-curable composition according to claim 9, wherein the photoinitiator is selected from at least one of the photoinitiators TPO, 1173.
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