CN114213292A - Dual-curable vegetable oil modified isocyanate curing agent and preparation method thereof - Google Patents
Dual-curable vegetable oil modified isocyanate curing agent and preparation method thereof Download PDFInfo
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- CN114213292A CN114213292A CN202111365480.8A CN202111365480A CN114213292A CN 114213292 A CN114213292 A CN 114213292A CN 202111365480 A CN202111365480 A CN 202111365480A CN 114213292 A CN114213292 A CN 114213292A
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- vegetable oil
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- 235000015112 vegetable and seed oil Nutrition 0.000 title claims abstract description 45
- 239000008158 vegetable oil Substances 0.000 title claims abstract description 45
- 239000012948 isocyanate Substances 0.000 title claims abstract description 33
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 32
- 150000002513 isocyanates Chemical class 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title abstract description 9
- -1 mercapto compound Chemical class 0.000 claims abstract description 23
- 239000005058 Isophorone diisocyanate Substances 0.000 claims abstract description 15
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000012650 click reaction Methods 0.000 claims abstract description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 30
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 15
- VPASWAQPISSKJP-UHFFFAOYSA-N ethyl prop-2-enoate;isocyanic acid Chemical compound N=C=O.CCOC(=O)C=C VPASWAQPISSKJP-UHFFFAOYSA-N 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 11
- 235000005687 corn oil Nutrition 0.000 claims description 11
- 239000002285 corn oil Substances 0.000 claims description 11
- 238000010521 absorption reaction Methods 0.000 claims description 10
- 238000012360 testing method Methods 0.000 claims description 10
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 9
- 235000019484 Rapeseed oil Nutrition 0.000 claims description 6
- 230000009977 dual effect Effects 0.000 claims description 6
- 239000003549 soybean oil Substances 0.000 claims description 6
- 235000012424 soybean oil Nutrition 0.000 claims description 6
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 5
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- 239000001110 calcium chloride Substances 0.000 claims description 5
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 230000001678 irradiating effect Effects 0.000 claims description 5
- PJUIMOJAAPLTRJ-UHFFFAOYSA-N monothioglycerol Chemical compound OCC(O)CS PJUIMOJAAPLTRJ-UHFFFAOYSA-N 0.000 claims description 5
- 238000002390 rotary evaporation Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000004448 titration Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 235000013311 vegetables Nutrition 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 2
- 239000004006 olive oil Substances 0.000 claims description 2
- 235000008390 olive oil Nutrition 0.000 claims description 2
- 239000002383 tung oil Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 abstract description 13
- 239000011248 coating agent Substances 0.000 abstract description 10
- 239000003973 paint Substances 0.000 abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 6
- 239000002932 luster Substances 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 238000001723 curing Methods 0.000 description 28
- 230000008859 change Effects 0.000 description 8
- 238000003848 UV Light-Curing Methods 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- FEWFXBUNENSNBQ-UHFFFAOYSA-N 2-hydroxyacrylic acid Chemical compound OC(=C)C(O)=O FEWFXBUNENSNBQ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 229920000180 alkyd Polymers 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000013068 control sample Substances 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 description 2
- YXRKNIZYMIXSAD-UHFFFAOYSA-N 1,6-diisocyanatohexane Chemical compound O=C=NCCCCCCN=C=O.O=C=NCCCCCCN=C=O.O=C=NCCCCCCN=C=O YXRKNIZYMIXSAD-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229920005628 alkoxylated polyol Polymers 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000011152 fibreglass Substances 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
- C07C319/16—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides by addition of hydrogen sulfide or its salts to unsaturated compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
- C07C319/20—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides by reactions not involving the formation of sulfide groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
- C07C323/50—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton
- C07C323/51—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton
- C07C323/54—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being acyclic and unsaturated
-
- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
Abstract
The invention discloses a vegetable oil modified isocyanate curing agent capable of being cured doubly and a preparation method thereof, and relates to the vegetable oil modified isocyanate curing agent capable of being cured doubly, which takes unsaturated vegetable oil as a main body, and specifically comprises three steps of carrying out mercapto-alkene click reaction on the unsaturated vegetable oil and a mercapto compound, and grafting an isocyanate compound with an unsaturated double bond and isophorone diisocyanate; the main raw materials used in the manufacturing process are environment-friendly and pollution-free, the conditions in the whole preparation process are mild, the post-treatment is simple, and the synthesized vegetable oil modified isocyanate curing agent is used for paint products, so that the thickness of the coating is obviously improved, the luster of the product is ensured, and the water resistance is greatly improved.
Description
Technical Field
The invention belongs to the technical field of coating curing agents, and particularly relates to a vegetable oil modified isocyanate curing agent capable of being cured doubly and a preparation method thereof.
Background
The curing agent is widely applied to high-performance coatings, paints, adhesives, decorative building materials, elastomers, household goods and the like, has simple and convenient resin curing and using process and excellent performance compared with the prior chemical curing agent coatings, and is widely applied to adhesives, coatings and glass fiber reinforced plastic composite materials, such as Chinese patent publication No. CN 103421156B, which discloses a UV curing resin and a preparation method thereof and application in UV curing colored paint. Then mixing the ester compound with isophorone diisocyanate, adding a polymerization inhibitor and a catalyst, and reacting to obtain acrylic modified polyurethane; and (3) reacting the acrylic modified polyurethane with the alkyd resin at the temperature of between 60 and 100 ℃ for 2 to 3 hours to obtain the UV curing resin. The UV curing paint is prepared by reacting UV curing resin, acrylic acid alkoxylated polyol ester reactive diluent, pigment, thermoplastic acrylic resin, photoinitiator, alkyd resin drier, dispersant, foaming agent and flatting agent.
The technical means can reduce pollution, and overcome the problems that the paint system can not be completely cured due to the shielding effect of the pigment filler to ultraviolet light in the existing ultraviolet light curing colored paint system, and the wetting of the UV curing resin to the pigment filler is not good, and the adhesion of a coating film is not good. However, when the pure UV curable resin coating is used for coating regular workpieces, the curing effect in a local groove region is not ideal, and the hardness, gloss and water resistance of the coating are seriously reduced, which affects the overall performance.
Disclosure of Invention
The invention aims to solve the defects of the prior art and provides a vegetable oil modified isocyanate curing agent capable of being cured doubly and a preparation method thereof.
In order to achieve the purpose, the invention designs a vegetable oil modified isocyanate curing agent capable of being cured doubly, which comprises a mercapto-alkene click reaction of unsaturated vegetable oil and a mercapto compound, and then a reaction of the unsaturated vegetable oil and an isophorone diisocyanate grafted with an isocyanate compound with an unsaturated double bond, wherein the vegetable oil has the following general structural formula:
wherein
The dual-curable vegetable oil modified isocyanate curing agent has the following structural formula:
preferably, the vegetable oil modified isocyanate curing agent capable of double curing further comprises that the unsaturated vegetable oil is one or a mixture of more than one of soybean oil, corn oil, rapeseed oil, tung oil and olive oil.
Preferably, the vegetable oil modified isocyanate curing agent capable of dual curing further comprises that the mercapto compound is 3-mercapto-1, 2-propanediol.
Preferably, the dual-curable vegetable oil modified isocyanate curing agent further comprises that R1 in the structural formula is isophorone diisocyanate, and R2 in the structural formula is isocyanate ethyl acrylate.
Also comprises a vegetable oil modified isocyanate curing agent capable of dual curing and a preparation method thereof, and the preparation method comprises the following steps:
(1) respectively adding unsaturated vegetable oil, a sulfhydryl compound, a photoinitiator and dichloromethane into a reaction bottle, irradiating for 2-16 hours by using a 1.8mw/cm2 ultraviolet lamp under the state of stirring at room temperature to ensure that an unsaturated double bond on the unsaturated vegetable oil acid reacts with the sulfhydryl compound, testing the compound by using an infrared spectrometer, washing out excessive sulfhydryl compound when an absorption peak of an unsaturated carbon-carbon double bond on a 1760cm & lt-1 & gt disappears, removing the dichloromethane by rotary evaporation to obtain sulfhydryl modified vegetable oil, and drying overnight by using calcium chloride for later use; wherein the molar ratio content of the sulfhydryl compound to the unsaturated vegetable oil is determined to be 3.5:1-6: 1;
(2) adding the obtained mercapto-modified vegetable oil, isophorone diisocyanate R1 and dibutyltin laurate into acetone, reacting for 3-6 hours at 80 ℃, testing a compound by using an infrared spectrometer, stopping the reaction when an isocyanate absorption peak on 2275cm & lt-1 & gt disappears, and carrying out the next reaction, wherein the molar ratio content of isophorone diisocyanate R1 to the mercapto-modified vegetable oil is determined to be 3:1-5: 1;
(3) slowly dripping the mercapto modified vegetable oil grafted by the isophorone diisocyanate R1 prepared in the second step into isocyanate ethyl acrylate R2 at the temperature of 80 ℃, setting the dripping time to be 3 hours, and continuously keeping the temperature for 5 hours, wherein the molar ratio content of the isocyanate ethyl acrylate R2 to the mercapto modified vegetable oil is determined to be 3:1-5:1, determining the content of NCO by using a titration mode, and removing acetone in vacuum after the NCO content is qualified, so that the dual-cured vegetable oil modified isocyanate curing agent can be obtained.
Compared with the prior art, the invention has the following advantages:
1. the main raw material is environment-friendly and pollution-free, and the post treatment is simple and easy to purify;
2. the activation period is long, and the activity is mild;
3. the product acts on the coating, the hardness of the coating film is obviously improved, and the luster and the water resistance of the product are greatly enhanced.
Detailed Description
The present invention will be further described with reference to the following examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention.
The specific steps of examples 1 to 3 and comparative examples 1 to 3 were as follows:
example 1;
(1) respectively adding 0.3mol of soybean oil, 1.5mol of 3-mercapto-1, 2-propanediol, 0.1g of photoinitiator (UV1173) and 100ml of dichloromethane into a reaction bottle, irradiating for 12 hours by using a 1.8mw/cm2 ultraviolet lamp under the state of stirring at room temperature to ensure that unsaturated double bonds on the soybean oil react with mercapto compounds, testing the compounds by using an infrared spectrometer, and when the wavelength is 1760cm-1When the absorption peak of the unsaturated carbon-carbon double bond disappears, washing out excessive sulfhydryl compound, removing dichloromethane by rotary evaporation to obtain sulfhydryl modified corn oil, and drying with calcium chloride overnight for later use;
(2) adding 0.2mol of the obtained sulfhydryl modified soybean oil, 0.8mol of isocyanate ethyl acrylate and 0.06g of dibutyltin laurate into 100ml of acetone, reacting at 80 ℃ for 3 hours, and testing the compound by using an infrared spectrometer when the concentration is 2275cm-1When the absorption peak of the isocyanate disappears, the reaction is terminated;
(3) slowly dripping 0.1mol of isocyanate ethyl acrylate grafted mercapto-modified corn oil prepared in the second step into 0.3mol of isophorone diisocyanate at the temperature of 80 ℃, continuously preserving the heat for 5 hours, determining the NCO content by using a titration mode, and removing acetone in vacuum after the NCO content is qualified to obtain the dual-curable soybean oil modified isocyanate curing agent.
Example 2:
(1) respectively adding 0.3mol of corn oil, 1.2mol of 3-mercapto-1, 2-propanediol, 0.1g of photoinitiator (UV1173) and 100ml of dichloromethane into a reaction bottle, and irradiating for 8 hours at room temperature under stirring by using a 1.8mw/cm2 ultraviolet lamp to ensure unsaturation on the corn oilReacting the double bond with a mercapto compound, and measuring the compound by using an infrared spectrometer at a wavelength of 1760cm-1When the absorption peak of the unsaturated carbon-carbon double bond disappears, washing out excessive sulfhydryl compound, removing dichloromethane by rotary evaporation to obtain sulfhydryl modified corn oil, and drying with calcium chloride overnight for later use;
(2) adding 0.2mol of the obtained sulfhydryl modified corn oil, 0.7mol of isocyanate ethyl acrylate and 0.06g of dibutyltin laurate into 100ml of acetone, reacting at 80 ℃ for 3 hours, and testing the compound by using an infrared spectrometer when the concentration is 2275cm-1When the absorption peak of the isocyanate disappears, the reaction is terminated;
(3) slowly dripping 0.1mol of the mercapto-modified corn oil grafted by the isocyanate ethyl acrylate prepared in the second step into 0.3mol of isophorone diisocyanate at the temperature of 80 ℃, continuously preserving the heat for 5 hours, determining the NCO content by using a titration mode, and removing acetone in vacuum after the NCO content is qualified to obtain the dual-curable corn oil modified isocyanate curing agent.
Example 3:
(1) respectively adding 0.3mol of rapeseed oil, 1.3mol of 3-mercapto-1, 2-propylene glycol, 0.1g of photoinitiator (UV1173) and 100ml of dichloromethane into a reaction bottle, irradiating for 16 hours by using a 1.8mw/cm2 ultraviolet lamp under the state of stirring at room temperature to ensure that unsaturated double bonds on the corn oil react with mercapto compounds, testing the compounds by using an infrared spectrometer, and when the wavelength is 1760cm-1When the absorption peak of the unsaturated carbon-carbon double bond disappears, washing out excessive sulfhydryl compound, removing dichloromethane by rotary evaporation to obtain sulfhydryl modified rapeseed oil, and drying with calcium chloride overnight for later use;
(2) adding 0.2mol of the obtained sulfydryl modified rapeseed oil, 0.8mol of isocyanate ethyl acrylate and 0.06g of dibutyltin laurate into 100ml of acetone, reacting at 80 ℃ for 3 hours, and testing the compound by using an infrared spectrometer when the concentration is 2275cm-1When the absorption peak of the isocyanate disappears, the reaction is terminated;
(3) slowly dripping 0.1mol of mercapto-modified corn oil grafted by isocyanate ethyl acrylate prepared in the second step into 0.4mol of isophorone diisocyanate at the temperature of 80 ℃, continuously preserving heat for 5 hours, determining the content of NCO by using a titration mode, and removing acetone in vacuum after the NCO content is qualified to obtain the rapeseed oil modified isocyanate curing agent capable of being dual-cured.
The dual-curable vegetable oil-modified isocyanate curing agent prepared in examples 1 to 3 and the HDI trimer curing agent as a comparative sample were diluted with PMA respectively until the solid content was 60%, and were formulated with a commercially available hydroxyacrylic acid emulsion (Xifeng chemical B18 hydroxyacrylic acid dispersion: hydroxyl content 3.8% solid content: 50%) to prepare a white paint, and the results were as follows:
| numbering | Example 1 | Example 2 | Example 3 | Control sample |
| Activation period (Normal temperature 4) Hour) | The change of the gloss is less than 5 percent, KU viscosity change < 8% | The change of the gloss is less than 5 percent, KU viscosity change < 8% | The change of the gloss is less than 5 percent, KU viscosity change < 8% | The change of the gloss is less than 15 percent, KU viscosity change < 17% |
| Gloss (. degree) | 93 | 92.5 | 93.1 | 89 |
| Water resistance (Normal temperature) 168h） | OK | OK | OK | OK |
| Acid resistance (5% sulfur) Acid 72 h) | OK | OK | OK | OK |
| Alkali resistance (5% hydrogen and oxygen) Sodium salt 72 h) | OK | OK | OK | OK |
During the curing of the coating, after a double curing with an ultraviolet lamp, the performance tests were carried out again, with the following results:
| numbering | Example 1 | Example 2 | Example 3 | Control sample |
| Water resistance (Normal temperature 360 h) | OK | OK | OK | × |
| Acid resistance (5% sulfuric acid 168 h) | OK | OK | OK | × |
| Alkali resistance (5% sodium hydroxide 168 h) | OK | OK | OK | × |
The results show that the dual-curable vegetable oil modified isocyanate curing agent prepared by the invention has mild activity and long activation period, is used as a curing agent for coating products, obviously improves the construction open time, and greatly improves the luster and the water resistance of the products.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (5)
1. A dual-curable vegetable oil modified isocyanate curing agent comprises a mercapto-alkene click reaction of unsaturated vegetable oil and a mercapto compound, and then a reaction of the unsaturated vegetable oil and an isophorone diisocyanate, wherein the vegetable oil has the following structural general formula:
wherein
The dual-curable vegetable oil modified isocyanate curing agent has the following structural formula:
2. the dual curable vegetable oil modified isocyanate curing agent of claim 1, wherein the unsaturated vegetable oil is one or more of soybean oil, corn oil, rapeseed oil, tung oil and olive oil.
3. The dual curable vegetable oil-modified isocyanate curing agent of claim 1, wherein the mercapto compound is 3-mercapto-1, 2-propanediol.
4. The dual curable vegetable oil-modified isocyanate curing agent of claim 1, wherein R in the formula1Is isophorone diisocyanate, and R in the structural formula2Is isocyanate ethyl acrylate.
5. A method for preparing the dual curable vegetable oil-modified isocyanate curing agent according to any one of claims 1 to 4, comprising the following three synthetic steps:
(1) respectively adding unsaturated vegetable oil, a sulfhydryl compound, a photoinitiator and dichloromethane into a reaction bottle, irradiating for 2-16 hours by using an ultraviolet lamp of 1.8mw/cm2 under the state of stirring at room temperature to ensure that an unsaturated double bond on the unsaturated vegetable oil acid reacts with the sulfhydryl compound, testing the compound by using an infrared spectrometer, and testing the compound when the wavelength is 1760cm-1When the absorption peak of the unsaturated carbon-carbon double bond disappears, washing out excessive sulfhydryl compound, removing dichloromethane by rotary evaporation to obtain sulfhydryl modified vegetable oil, and drying with calcium chloride overnight for use; wherein the molar ratio content of the mercapto compound to the unsaturated vegetable oil is determined to be 3.5:1-6: 1;
(2) the obtained sulfhydryl modified vegetable oil and isophorone diisocyanate R1Adding dibutyltin laurate into acetone, reacting for 3-6 hours at 80 ℃, and testing the compound by using an infrared spectrometer when the concentration is 2275cm-1When the absorption peak of the isocyanate disappears, the reaction is terminated, and the next reaction is carried out to obtain isophorone diisocyanate R1The molar ratio content of the modified vegetable oil to the sulfydryl is determined to be 3:1-5: 1;
(3) at the temperature of 80 ℃, the isophorone diisocyanate R prepared in the second step1The grafted mercapto-modified vegetable oil was slowly added dropwise to the isocyanate ethyl acrylate R2In the reaction, the dropping time was set to 3 hours, and the heat was kept for 5 hours, wherein the isocyanate ethyl acrylate R was2The molar ratio content of the modified vegetable oil and the mercapto group is determined to be 3:1-5:1, the NCO content is determined by a titration mode, and acetone is removed in vacuum after the NCO content is qualified, so that the dual-cured vegetable oil modified isocyanate curing agent can be obtained.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| CN116376409A (en) * | 2023-03-01 | 2023-07-04 | 长沙学院 | Anticorrosive paint and preparation method and application thereof |
| CN116376409B (en) * | 2023-03-01 | 2024-04-19 | 长沙学院 | Anticorrosive paint and preparation method and application thereof |
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