CN115960516B - Polymer compound coating and preparation method thereof - Google Patents
Polymer compound coating and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a high molecular compound coating and a preparation method thereof, belonging to the technical field of coating compositions. The invention uses 6, 6-dimethyl bicyclo [3.1.1] hept-2-ene-2-ethanol and 2-ethoxy-5- (1-propenyl) phenol to respectively carry out esterification reaction with alkane chain acyl chloride under the action of an acid binding agent, and the obtained esterification product is subjected to epoxidation treatment to sequentially obtain a first polymerized monomer and a second polymerized monomer; the first polymeric monomer and the second polymeric monomer are mixed with epoxy monomer obtained by oxidizing 1-methoxy-4- [ (Z) -1-propenyl ] benzene according to a proportion to prepare the high molecular compound coating. After the high molecular compound coating is photo-cured, the surface of the coating is smooth and fine, has no structural defect and has excellent corrosion resistance.
Description
Technical Field
The invention relates to the technical field of coating compositions, in particular to a high molecular compound coating and a preparation method thereof.
Background
The epoxy resin has excellent physical properties such as electric, mechanical, heat resistance and the like, and has stable chemical properties, and is not corroded and damaged by common acid and alkali, chemical medicines and industrial solvents. Epoxy resins have excellent compatibility with many materials, have high strength mechanical properties, and can withstand long-term environmental stresses. The epoxy resin has strong variability, and products with different shapes can be manufactured according to actual requirements by adjusting the composition formula.
Chinese patent CN106398460a discloses a high weather resistance and flexibility epoxy resin composition and preparation method thereof, the composition comprises the following components in parts by mass: 10 to 20 parts of epoxy resin I, 20 to 40 parts of self-made high weather resistance and flexible epoxy resin, 1.5 to 25 parts of curing agent, 0.00 to 0.3 part of curing accelerator and 20 to 40 parts of inorganic filler. The self-made high-weatherability and high-flexibility epoxy resin adopts bulk polymerization, no volatile matters are generated in the synthesis process, and the environment friendliness is strong.
Chinese patent CN114133701a provides a preparation and application of a high-performance epoxy polymer material, which comprises the following steps: (1) preparing an epoxy polymer A; (2) preparing an epoxy polymer B; (3) preparing an arylsulfonamide compound; (4) Mixing the epoxy polymer A, the epoxy polymer B and the aryl sulfonamide compound prepared in the steps (1) to (3) according to the following parts by weight: 55-60 parts of: 45-50 parts of: 20-25 parts. The invention also relates to application of the high-performance epoxy polymer material, which is applied to the field of paint or epoxy terrace or building materials. The preparation method is simple, low in cost, and the prepared high-performance epoxy polymer material has high mechanical property, good adhesive force, excellent weather resistance and stable performance, and meets the requirement of outdoor application.
When the epoxy monomer adopted in the prior art forms a polymer, the reactivity is too high, the stability is poor, the polymerization rate is difficult to control, and the coating shrinkage and cracks caused by too high local polymerization rate can occur, so that the normal use is affected.
Disclosure of Invention
In view of the above-mentioned drawbacks of the prior art, the present invention provides a polymer coating and a preparation method thereof.
A preparation method of a high molecular compound coating comprises the following steps:
s1, uniformly mixing 6, 6-dimethyl bicyclo [3.1.1] hept-2-ene-2-ethanol, triethylamine and dichloromethane to obtain an alcohol amine mixture; mixing octanoyl chloride and dichloromethane uniformly, adding the alcohol amine mixture under the condition of no light and no oxygen, and carrying out a first esterification reaction; after the first esterification reaction is finished, pouring the reaction product into excessive deionized water, filtering and collecting precipitate, washing the precipitate with saturated saline water, and drying to obtain a first esterification reaction product for later use;
s2, taking the first esterification reaction product, uniformly mixing the first esterification reaction product with dichloromethane, adding m-chloroperoxybenzoic acid, and carrying out a first epoxidation reaction; after the first epoxidation reaction is finished, pouring the reaction product into excessive sodium hydroxide aqueous solution, collecting an organic phase, drying the organic phase, and distilling the organic phase under reduced pressure to remove dichloromethane to obtain a first polymerized monomer for later use;
s3, uniformly mixing 2-ethoxy-5- (1-propenyl) phenol, triethylamine and dichloromethane to obtain a phenolic amine mixture; uniformly mixing decanoyl chloride and dichloromethane, then adding the phenolic amine mixture under the dark and anaerobic conditions, and carrying out a second esterification reaction; after the second esterification reaction is finished, pouring the reaction product into excessive deionized water at the temperature of 0-4 ℃, filtering, collecting precipitate, washing the precipitate with saturated saline water, and drying to obtain a second esterification reaction product for later use;
s4, mixing the second esterification reaction product with dichloromethane uniformly, adding m-chloroperoxybenzoic acid, performing a second epoxidation reaction, pouring the reaction product into excessive sodium hydroxide aqueous solution after the second epoxidation reaction is finished, collecting an organic phase, drying the organic phase, and distilling under reduced pressure to remove dichloromethane to obtain a second polymer monomer for later use;
s5, uniformly mixing 1-methoxy-4- [ (Z) -1-propenyl ] benzene, sodium carbonate and methanol, adding hydrogen peroxide and carrying out oxidation reaction; after the oxidation reaction is finished, filtering a reaction product, collecting a precipitate, washing the precipitate by diethyl ether, and drying to obtain an epoxy monomer for later use;
s6, mixing the first polymerization monomer, the second polymerization monomer and the epoxy monomer according to a proportion until all components are uniformly dispersed, and obtaining the high polymer compound coating.
Specifically, the preparation method of the high molecular compound coating comprises the following steps in parts by weight:
s1, uniformly mixing 2.35-3.10 parts of 6, 6-dimethylbicyclo [3.1.1] hept-2-ene-2-ethanol, 1.65-2.15 parts of triethylamine and 10-15 parts of dichloromethane to obtain an alcohol amine mixture; uniformly mixing 2.80-3.65 parts of octanoyl chloride and 3-5 parts of dichloromethane, then adding the alcohol amine mixture under the protection of light shielding and nitrogen, and carrying out a first esterification reaction; after the first esterification reaction is finished, pouring the reaction product into excessive deionized water at the temperature of 0-4 ℃, filtering, collecting precipitate, washing the precipitate with saturated saline water, and drying to obtain a first esterification reaction product for later use;
s2, taking 3.30-4.35 parts of the first esterification reaction product and 30-40 parts of dichloromethane, uniformly mixing, adding 2.55-3.30 parts of m-chloroperoxybenzoic acid, and carrying out a first epoxidation reaction; after the first epoxidation reaction is finished, pouring the reaction product into excessive sodium hydroxide aqueous solution, collecting an organic phase, drying the organic phase, and distilling the organic phase under reduced pressure to remove dichloromethane to obtain a first polymerized monomer for later use;
s3, uniformly mixing 2.55-3.30 parts of 2-ethoxy-5- (1-propenyl) phenol, 1.65-2.15 parts of triethylamine and 10-15 parts of dichloromethane to obtain a phenolic amine mixture; uniformly mixing 3.25-4.30 parts of decanoyl chloride and 3-5 parts of dichloromethane, then adding the phenolic amine mixture under the protection of light shielding and nitrogen, and carrying out a second esterification reaction; after the second esterification reaction is finished, pouring the reaction product into excessive deionized water at the temperature of 0-4 ℃, filtering, collecting precipitate, washing the precipitate with saturated saline water, and drying to obtain a second esterification reaction product for later use;
s4, mixing 3.75-4.95 parts of the second esterification reaction product with 30-40 parts of dichloromethane uniformly, adding 2.55-3.30 parts of m-chloroperoxybenzoic acid and carrying out a second epoxidation reaction, pouring the reaction product into excessive sodium hydroxide aqueous solution after the second epoxidation reaction is finished, collecting an organic phase, drying the organic phase, and distilling the organic phase under reduced pressure to remove dichloromethane to obtain a second polymerization monomer for later use;
s5, uniformly mixing 1.90-2.50 parts of 1-methoxy-4- [ (Z) -1-propenyl ] benzene, 1.05-1.35 parts of sodium carbonate and 30-40 parts of methanol, adding 3.75-4.85 parts of hydrogen peroxide and carrying out oxidation reaction; filtering the reaction product after the oxidation reaction is finished, collecting the precipitate, washing the precipitate by diethyl ether at 0-4 ℃ and drying to obtain an epoxy monomer for later use;
s6, mixing the first polymerization monomer, the second polymerization monomer and the epoxy monomer according to a proportion until all components are uniformly dispersed, and obtaining the high polymer compound coating.
Preferably, the temperature of the first esterification reaction in the step S1 is 20-35 ℃, and the reaction time is 2-5 h.
Preferably, the temperature of the first epoxidation reaction in the step S2 is 0-5 ℃, and the reaction time is 18-36 h.
Preferably, the temperature of the second esterification reaction in the step S3 is 20-30 ℃, and the reaction time is 2-4 hours.
Preferably, the temperature of the second epoxidation reaction in the step S4 is 0-10 ℃, and the reaction time is 12-24 hours.
Preferably, the temperature of the oxidation reaction in the step S5 is 20-30 ℃ and the reaction time is 12-24 h.
In the high molecular compound coating, the mass ratio of the first polymerized monomer to the second polymerized monomer to the epoxy monomer is (1.1-1.7): (2.3-2.9): 1.
the concentration of the sodium hydroxide aqueous solution is 5-10wt% independently.
The concentration of the hydrogen peroxide is 27.5-35.0 wt%.
According to the application occasion or the storage requirement, the macromolecular compound coating can be added with auxiliary agents, solvents for dilution or pigments commonly used in the field.
The invention takes 6, 6-dimethyl bicyclo [3.1.1] hept-2-ene-2-ethanol and 2-ethoxy-5- (1-propenyl) phenol as reaction raw materials, and makes esterification reaction with alkane chain acyl chloride under the action of acid binding agent, and the obtained esterification product is subjected to epoxidation treatment to obtain a first and a second polymerization monomers respectively; the first and the second polymeric monomers are mixed with epoxy monomers obtained by oxidizing 1-methoxy-4- [ (Z) -1-propenyl ] benzene according to a proportion to prepare the high molecular compound coating.
The hydroxyl groups in the raw materials have adverse effects on the epoxidation reaction, and the invention converts the hydroxyl groups into ester groups, so that the corresponding monomers are smoothly prepared. The high molecular compound coating is oily liquid at room temperature, is easy to mix with a photoinitiator and participates in curing. In the photocuring process, the photoinitiator is excited and light-induced electron transfer occurs, so that conjugated acid is formed to initiate polymerization of the high-molecular compound coating. The high molecular compound coating has good polymerization rate and stability, and the reason is that carbocations formed after the ring-opening reaction of the conjugated acid on the epoxy group have better stability; in addition, direct bonding of the epoxy groups to the aromatic rings between the monomers can also lead to this effect. The methylene and long alkane chain substituent between the epoxy group and the aromatic ring can properly reduce the reactivity, and the electron-withdrawing ester substituent on the benzene ring at the p-position of the epoxy group can reduce the stabilizing effect of carbocations formed by conjugate acid after the ring-opening reaction of the benzene ring and the epoxy group, so that the shrinkage and cracks of the coating are prevented from being caused by the excessively high local polymerization rate.
The invention provides a use method of the polymer compound coating, which comprises the following steps:
adding a photoinitiator into the high polymer compound coating, wherein the addition amount of the photoinitiator is 2-4wt%; then transferring the mixture into a photo-curing device for photo-curing, wherein the irradiation wavelength is 350-395 nm, and the treatment time is 30-90 s.
On the basis of conforming to the common knowledge in the field, the above preferred conditions can be arbitrarily combined to obtain the preferred embodiments of the invention.
The invention has the following description and functions of partial raw materials in the formula:
triethylamine: an organic compound of the formula C 6 H 15 N is colorless oily liquid, is slightly soluble in water, is soluble in most organic solvents such as ethanol, diethyl ether, acetone and the like, and is mainly used as a solvent, a polymerization inhibitor and a preservative, and can also be used for synthesizing dyes and the like. The acid binding agent is used for neutralizing the generated acid to prevent further electrophilic addition reaction, so that the reactant is successfully esterified.
M-chloroperoxybenzoic acid: the organic matter has a chemical formula of C 7 H 5 ClO 3 Is a white powdery crystal, is almost insoluble in water, is easily soluble in ethanol and ethers, and is soluble in chloroform and dichloroethane. The heat stability and the annual decomposition rate at room temperature are below 1 percent. The decomposition rate is accelerated in the liquid state. And (3) carrying out stereoselective epoxidation reaction on the carbon-carbon double bond.
The invention has the beneficial effects that:
compared with the prior art, the invention uses the esterification reaction of the 6, 6-dimethyl bicyclo [3.1.1] hept-2-ene-2-ethanol and the 2-ethoxy-5- (1-propenyl) phenol with the alkane chain acyl chloride under the action of the acid binding agent to convert the hydroxyl into the ester group, thereby reducing the adverse effect of the hydroxyl existing in the raw materials on the epoxidation reaction. The obtained esterified product is subjected to epoxidation treatment to sequentially obtain a first polymerized monomer and a second polymerized monomer; the first polymeric monomer and the second polymeric monomer are mixed with epoxy monomer obtained by oxidizing 1-methoxy-4- [ (Z) -1-propenyl ] benzene according to a proportion to prepare the high molecular compound coating.
Compared with the prior art, the invention has good photo-curing reactivity and stability, and the carbocation formed by the conjugate acid after the ring-opening reaction of the epoxy group has better stability, and the direct bonding of the epoxy group and the aromatic ring between monomers also improves the utility. The methylene and long alkane chain substituent between the epoxy group and the aromatic ring can properly reduce the reactivity, and the electron-withdrawing ester substituent on the benzene ring at the p-position of the epoxy group can reduce the stabilizing effect of carbocations formed by conjugate acid after the ring-opening reaction of the benzene ring and the epoxy group, so that the shrinkage and cracks of the coating are prevented from being caused by the excessively high local polymerization rate.
Detailed Description
The invention is further illustrated by means of the following examples, which are not intended to limit the scope of the invention. The experimental methods, in which specific conditions are not noted in the following examples, were selected according to conventional methods and conditions, or according to the commercial specifications.
The comparative example and the examples of the present invention have the following parameters of part of raw materials:
sodium hydroxide aqueous solution, concentration: 10wt% of Jinan Ming Wei chemical Co., ltd;
hydrogen peroxide, concentration: 35.0wt%, jinan Kunfeng chemical Co., ltd;
photoinitiator ITX, south beijing milan chemical company.
Example 1
The high molecular compound coating is prepared by the following method:
s1, uniformly mixing 2.35kg of 6, 6-dimethylbicyclo [3.1.1] hept-2-ene-2-ethanol, 1.65kg of triethylamine and 10kg of dichloromethane to obtain an alcohol amine mixture; uniformly mixing 2.80kg of octanoyl chloride and 3kg of dichloromethane, then adding the alcohol amine mixture under the protection of light shielding and nitrogen, and performing a first esterification reaction, wherein the temperature of the first esterification reaction is 30 ℃, and the reaction time is 4 hours; after the first esterification reaction is finished, pouring the reaction product into excessive deionized water at the temperature of 0 ℃, filtering and collecting precipitate, washing the precipitate by saturated saline water, and drying to obtain a first esterification reaction product for later use;
s2, taking 3.30kg of the first esterification reaction product, uniformly mixing with 30kg of dichloromethane, adding 2.55kg of m-chloroperoxybenzoic acid, and carrying out a first epoxidation reaction, wherein the temperature of the first epoxidation reaction is 0 ℃, and the reaction time is 24 hours; after the first epoxidation reaction is finished, pouring the reaction product into excessive sodium hydroxide aqueous solution, collecting an organic phase, drying the organic phase, and distilling the organic phase under reduced pressure to remove dichloromethane to obtain a first polymerized monomer for later use;
s3, uniformly mixing 2.55kg of 2-ethoxy-5- (1-propenyl) phenol, 1.65kg of triethylamine and 10kg of dichloromethane to obtain a phenolic amine mixture; uniformly mixing 3.25kg of decanoyl chloride and 3kg of dichloromethane, then adding the phenolic amine mixture under the protection of light shielding and nitrogen, and performing a second esterification reaction, wherein the temperature of the second esterification reaction is 25 ℃, and the reaction time is 3 hours; after the second esterification reaction is finished, pouring the reaction product into excessive deionized water at the temperature of 0 ℃, filtering and collecting precipitate, washing the precipitate with saturated saline water, and drying to obtain a second esterification reaction product for later use;
s4, mixing 3.75kg of the second esterification reaction product with 30kg of dichloromethane uniformly, adding 2.55kg of m-chloroperoxybenzoic acid, and carrying out a second epoxidation reaction, wherein the temperature of the second epoxidation reaction is 5 ℃, and the reaction time is 18 hours; after the second epoxidation reaction is finished, pouring the reaction product into excessive sodium hydroxide aqueous solution, collecting an organic phase, drying the organic phase, and distilling the organic phase under reduced pressure to remove dichloromethane to obtain a second polymer monomer for later use;
s5, uniformly mixing 1.90kg of 1-methoxy-4- [ (Z) -1-propenyl ] benzene, 1.05kg of sodium carbonate and 30kg of methanol, adding 3.75kg of hydrogen peroxide, and carrying out oxidation reaction at 20 ℃ for 18 hours; after the oxidation reaction is finished, filtering a reaction product, collecting a precipitate, washing the precipitate by diethyl ether at 0 ℃, and drying to obtain an epoxy monomer for later use;
s6, mixing the first polymerization monomer, the second polymerization monomer and the epoxy monomer according to the mass ratio of 1.1:2.9:1, mixing until all the components are uniformly dispersed, and obtaining the high molecular compound coating.
Example 2
The high molecular compound coating is prepared by the following method:
s1, uniformly mixing 2.35kg of 6, 6-dimethylbicyclo [3.1.1] hept-2-ene-2-ethanol, 1.65kg of triethylamine and 10kg of dichloromethane to obtain an alcohol amine mixture; uniformly mixing 2.80kg of octanoyl chloride and 3kg of dichloromethane, then adding the alcohol amine mixture under the protection of light shielding and nitrogen, and performing a first esterification reaction, wherein the temperature of the first esterification reaction is 30 ℃, and the reaction time is 4 hours; after the first esterification reaction is finished, pouring the reaction product into excessive deionized water at the temperature of 0 ℃, filtering and collecting precipitate, washing the precipitate by saturated saline water, and drying to obtain a first esterification reaction product for later use;
s2, taking 3.30kg of the first esterification reaction product, uniformly mixing with 30kg of dichloromethane, adding 2.55kg of m-chloroperoxybenzoic acid, and carrying out a first epoxidation reaction, wherein the temperature of the first epoxidation reaction is 0 ℃, and the reaction time is 24 hours; after the first epoxidation reaction is finished, pouring the reaction product into excessive sodium hydroxide aqueous solution, collecting an organic phase, drying the organic phase, and distilling the organic phase under reduced pressure to remove dichloromethane to obtain a first polymerized monomer for later use;
s3, uniformly mixing 2.55kg of 2-ethoxy-5- (1-propenyl) phenol, 1.65kg of triethylamine and 10kg of dichloromethane to obtain a phenolic amine mixture; uniformly mixing 3.25kg of decanoyl chloride and 3kg of dichloromethane, then adding the phenolic amine mixture under the protection of light shielding and nitrogen, and performing a second esterification reaction, wherein the temperature of the second esterification reaction is 25 ℃, and the reaction time is 3 hours; after the second esterification reaction is finished, pouring the reaction product into excessive deionized water at the temperature of 0 ℃, filtering and collecting precipitate, washing the precipitate with saturated saline water, and drying to obtain a second esterification reaction product for later use;
s4, mixing 3.75kg of the second esterification reaction product with 30kg of dichloromethane uniformly, adding 2.55kg of m-chloroperoxybenzoic acid, and carrying out a second epoxidation reaction, wherein the temperature of the second epoxidation reaction is 5 ℃, and the reaction time is 18 hours; after the second epoxidation reaction is finished, pouring the reaction product into excessive sodium hydroxide aqueous solution, collecting an organic phase, drying the organic phase, and distilling the organic phase under reduced pressure to remove dichloromethane to obtain a second polymer monomer for later use;
s5, uniformly mixing 1.90kg of 1-methoxy-4- [ (Z) -1-propenyl ] benzene, 1.05kg of sodium carbonate and 30kg of methanol, adding 3.75kg of hydrogen peroxide, and carrying out oxidation reaction at 20 ℃ for 18 hours; after the oxidation reaction is finished, filtering a reaction product, collecting a precipitate, washing the precipitate by diethyl ether at 0 ℃, and drying to obtain an epoxy monomer for later use;
s6, mixing the first polymerization monomer, the second polymerization monomer and the epoxy monomer according to a mass ratio of 1.7:2.3:1, mixing until all the components are uniformly dispersed, and obtaining the high molecular compound coating.
Example 3
The high molecular compound coating is prepared by the following method:
s1, uniformly mixing 2.35kg of 6, 6-dimethylbicyclo [3.1.1] hept-2-ene-2-ethanol, 1.65kg of triethylamine and 10kg of dichloromethane to obtain an alcohol amine mixture; uniformly mixing 2.80kg of octanoyl chloride and 3kg of dichloromethane, then adding the alcohol amine mixture under the protection of light shielding and nitrogen, and performing a first esterification reaction, wherein the temperature of the first esterification reaction is 30 ℃, and the reaction time is 4 hours; after the first esterification reaction is finished, pouring the reaction product into excessive deionized water at the temperature of 0 ℃, filtering and collecting precipitate, washing the precipitate by saturated saline water, and drying to obtain a first esterification reaction product for later use;
s2, taking 3.30kg of the first esterification reaction product, uniformly mixing with 30kg of dichloromethane, adding 2.55kg of m-chloroperoxybenzoic acid, and carrying out a first epoxidation reaction, wherein the temperature of the first epoxidation reaction is 0 ℃, and the reaction time is 24 hours; after the first epoxidation reaction is finished, pouring the reaction product into excessive sodium hydroxide aqueous solution, collecting an organic phase, drying the organic phase, and distilling the organic phase under reduced pressure to remove dichloromethane to obtain a first polymerized monomer for later use;
s3, uniformly mixing 2.55kg of 2-ethoxy-5- (1-propenyl) phenol, 1.65kg of triethylamine and 10kg of dichloromethane to obtain a phenolic amine mixture; uniformly mixing 3.25kg of decanoyl chloride and 3kg of dichloromethane, then adding the phenolic amine mixture under the protection of light shielding and nitrogen, and performing a second esterification reaction, wherein the temperature of the second esterification reaction is 25 ℃, and the reaction time is 3 hours; after the second esterification reaction is finished, pouring the reaction product into excessive deionized water at the temperature of 0 ℃, filtering and collecting precipitate, washing the precipitate with saturated saline water, and drying to obtain a second esterification reaction product for later use;
s4, mixing 3.75kg of the second esterification reaction product with 30kg of dichloromethane uniformly, adding 2.55kg of m-chloroperoxybenzoic acid, and carrying out a second epoxidation reaction, wherein the temperature of the second epoxidation reaction is 5 ℃, and the reaction time is 18 hours; after the second epoxidation reaction is finished, pouring the reaction product into excessive sodium hydroxide aqueous solution, collecting an organic phase, drying the organic phase, and distilling the organic phase under reduced pressure to remove dichloromethane to obtain a second polymer monomer for later use;
s5, uniformly mixing 1.90kg of 1-methoxy-4- [ (Z) -1-propenyl ] benzene, 1.05kg of sodium carbonate and 30kg of methanol, adding 3.75kg of hydrogen peroxide, and carrying out oxidation reaction at 20 ℃ for 18 hours; after the oxidation reaction is finished, filtering a reaction product, collecting a precipitate, washing the precipitate by diethyl ether at 0 ℃, and drying to obtain an epoxy monomer for later use;
s6, mixing the first polymerization monomer, the second polymerization monomer and the epoxy monomer according to the mass ratio of 1.4:2.6:1, mixing until all the components are uniformly dispersed, and obtaining the high molecular compound coating.
Example 4
The high molecular compound coating is prepared by the following method:
s1, uniformly mixing 3.10kg of 6, 6-dimethylbicyclo [3.1.1] hept-2-ene-2-ethanol, 2.15kg of triethylamine and 15kg of dichloromethane to obtain an alcohol amine mixture; uniformly mixing 2.80kg of octanoyl chloride and 5kg of dichloromethane, then adding the alcohol amine mixture under the protection of light shielding and nitrogen, and performing a first esterification reaction, wherein the temperature of the first esterification reaction is 30 ℃, and the reaction time is 4 hours; after the first esterification reaction is finished, pouring the reaction product into excessive deionized water at the temperature of 0 ℃, filtering and collecting precipitate, washing the precipitate by saturated saline water, and drying to obtain a first esterification reaction product for later use;
s2, taking 4.35kg of the first esterification reaction product, uniformly mixing with 40kg of dichloromethane, adding 3.30kg of m-chloroperoxybenzoic acid, and carrying out a first epoxidation reaction, wherein the temperature of the first epoxidation reaction is 0 ℃, and the reaction time is 24 hours; after the first epoxidation reaction is finished, pouring the reaction product into excessive sodium hydroxide aqueous solution, collecting an organic phase, drying the organic phase, and distilling the organic phase under reduced pressure to remove dichloromethane to obtain a first polymerized monomer for later use;
s3, uniformly mixing 3.30kg of 2-ethoxy-5- (1-propenyl) phenol, 2.15kg of triethylamine and 15kg of dichloromethane to obtain a phenolic amine mixture; uniformly mixing 3.25kg of decanoyl chloride and 3kg of dichloromethane, then adding the phenolic amine mixture under the protection of light shielding and nitrogen, and performing a second esterification reaction, wherein the temperature of the second esterification reaction is 25 ℃, and the reaction time is 3 hours; after the second esterification reaction is finished, pouring the reaction product into excessive deionized water at the temperature of 0 ℃, filtering and collecting precipitate, washing the precipitate with saturated saline water, and drying to obtain a second esterification reaction product for later use;
s4, mixing 4.95kg of the second esterification reaction product with 40kg of dichloromethane uniformly, adding 3.30kg of m-chloroperoxybenzoic acid, and carrying out a second epoxidation reaction, wherein the temperature of the second epoxidation reaction is 5 ℃, and the reaction time is 18 hours; after the second epoxidation reaction is finished, pouring the reaction product into excessive sodium hydroxide aqueous solution, collecting an organic phase, drying the organic phase, and distilling the organic phase under reduced pressure to remove dichloromethane to obtain a second polymer monomer for later use;
s5, uniformly mixing 2.50kg of 1-methoxy-4- [ (Z) -1-propenyl ] benzene, 1.35kg of sodium carbonate and 40kg of methanol, adding 4.85kg of hydrogen peroxide, and carrying out oxidation reaction at 20 ℃ for 18 hours; after the oxidation reaction is finished, filtering a reaction product, collecting a precipitate, washing the precipitate by diethyl ether at 0 ℃, and drying to obtain an epoxy monomer for later use;
s6, mixing the first polymerization monomer, the second polymerization monomer and the epoxy monomer according to the mass ratio of 1.4:2.6:1, mixing until all the components are uniformly dispersed, and obtaining the high molecular compound coating.
Comparative example 1
The high molecular compound coating is prepared by the following method:
s1, uniformly mixing 2.35kg of 6, 6-dimethylbicyclo [3.1.1] hept-2-ene-2-ethanol, 1.65kg of triethylamine and 10kg of dichloromethane to obtain an alcohol amine mixture; uniformly mixing 2.80kg of octanoyl chloride with 3kg of dichloromethane, then adding the alcohol amine mixture under the protection of light shielding and nitrogen for esterification reaction, wherein the temperature of the esterification reaction is 30 ℃, and the reaction time is 4 hours; after the esterification reaction is finished, pouring the reaction product into excessive deionized water at 0 ℃, filtering and collecting precipitate, washing the precipitate with saturated saline water, and drying to obtain an esterification reaction product for later use;
s2, mixing 3.30kg of the esterification reaction product with 30kg of dichloromethane uniformly, adding 2.55kg of m-chloroperoxybenzoic acid, and performing epoxidation reaction at a temperature of 0 ℃ for 24 hours; after the epoxidation reaction is finished, pouring the reaction product into excessive sodium hydroxide aqueous solution, collecting an organic phase, drying the organic phase, and distilling under reduced pressure to remove dichloromethane to obtain a polymerized monomer for later use;
s3, uniformly mixing 1.90kg of 1-methoxy-4- [ (Z) -1-propenyl ] benzene, 1.05kg of sodium carbonate and 30kg of methanol, adding 3.75kg of hydrogen peroxide, and carrying out oxidation reaction at 20 ℃ for 18 hours; after the oxidation reaction is finished, filtering a reaction product, collecting a precipitate, washing the precipitate by diethyl ether at 0 ℃, and drying to obtain an epoxy monomer for later use;
s4, mixing the polymerized monomer with the epoxy monomer according to the mass ratio of 4:1, mixing until all the components are uniformly dispersed, and obtaining the high molecular compound coating.
Comparative example 2
The high molecular compound coating is prepared by the following method:
s1, uniformly mixing 2.55kg of 2-ethoxy-5- (1-propenyl) phenol, 1.65kg of triethylamine and 10kg of dichloromethane to obtain a phenolic amine mixture; uniformly mixing 3.25kg of decanoyl chloride and 3kg of dichloromethane, and then adding the phenolic amine mixture under the protection of light shielding and nitrogen for esterification reaction, wherein the temperature of the esterification reaction is 25 ℃, and the reaction time is 3 hours; after the esterification reaction is finished, pouring the reaction product into excessive deionized water at 0 ℃, filtering and collecting precipitate, washing the precipitate with saturated saline water, and drying to obtain an esterification reaction product for later use;
s2, mixing 3.75kg of the esterification reaction product with 30kg of dichloromethane uniformly, adding 2.55kg of m-chloroperoxybenzoic acid, and performing epoxidation reaction at a temperature of 5 ℃ for 18 hours; after the epoxidation reaction is finished, pouring the reaction product into excessive sodium hydroxide aqueous solution, collecting an organic phase, drying the organic phase, and distilling under reduced pressure to remove dichloromethane to obtain a polymerized monomer for later use;
s3, uniformly mixing 1.90kg of 1-methoxy-4- [ (Z) -1-propenyl ] benzene, 1.05kg of sodium carbonate and 30kg of methanol, adding 3.75kg of hydrogen peroxide, and carrying out oxidation reaction at 20 ℃ for 18 hours; after the oxidation reaction is finished, filtering a reaction product, collecting a precipitate, washing the precipitate by diethyl ether at 0 ℃, and drying to obtain an epoxy monomer for later use;
s4, mixing the polymerized monomer with the epoxy monomer according to the mass ratio of 4:1, mixing until all the components are uniformly dispersed, and obtaining the high molecular compound coating.
Adding a photoinitiator ITX into the macromolecular compound coatings prepared in the above examples and comparative examples, wherein the addition amount is 3wt%; and after being uniformly mixed, the mixture is transferred into a photo-curing device for photo-curing, wherein the irradiation wavelength is 395nm, and the treatment time is 45s. The coating samples meeting the test case requirements were cured and tested accordingly, with a coating thickness of 100 μm.
Test example 1
After the high molecular compound coating is solidified into a coating, the corrosion resistance of the coating is tested by referring to the specific method and steps in the artificial atmosphere corrosion test salt spray test of the standard GB/T10125-2021. The test adopts a neutral salt spray test (NSS test), the spray pressure is 126kPa, the hot water temperature of a saturation tower is 50 ℃, the test temperature is 35 ℃ and the test is 80cm 2 The average sedimentation rate of the horizontal area of (2) was 1.5mL/h, the solubility of the sodium chloride solution was 50g/L, and the test period was 168h. After the salt spray test is finished, part 4 is marked according to GB/T30789.4-2015, number and size of evaluation defects of ageing of color paint and varnish coating and uniform change degree of appearance: evaluation of cracking ratings "GB/T30789.5-2015" number and size of defects and evaluation of ageing of paint and varnish coatingsMark of degree of uniform change in appearance part 5: evaluation criteria in evaluation of peel level coating defects were evaluated and the corrosion resistance test results of the coating are shown in table 1.
Table 1:
from the above test results, it can be seen that example 3 has the lowest amount of flaking, number of cracks, and smallest cracks. The coating of example 3 has the best corrosion resistance.
Test example 2
After the high molecular compound coating is cured into a coating, the scratch resistance test of the coating is described in section 1 of the determination of the scratch resistance of paints and varnishes according to GB/T9279.1-2015: the specific method and steps in the constant load method are carried out. The test environment temperature is 23 ℃ and the relative humidity is 50%; the test type is a "pass/fail" test. The scratch resistance test results of the coatings are shown in table 2.
Table 2:
as can be seen from the above test results, example 3 has a dense and defect-free surface and has an optimal scratch resistance.
As can be seen from the test results of the above test examples, the coating of example 3 has the best overall properties. The reason for this result may be that the presence of hydroxyl groups in the starting materials adversely affects the progress of the epoxidation reaction, and the conversion of hydroxyl groups to ester groups in the present invention gives a smooth preparation of the corresponding monomers. The high molecular compound coating is oily liquid at room temperature, is easy to mix with a photoinitiator and participates in curing. In the photocuring process, the photoinitiator is excited and light-induced electron transfer occurs, so that conjugated acid is formed to initiate polymerization of the high-molecular compound coating. The high molecular compound coating has good polymerization rate and stability, and the reason is that carbocations formed after the ring-opening reaction of the conjugated acid on the epoxy group have better stability; in addition, direct bonding of the epoxy groups to the aromatic rings between the monomers can also lead to this effect. The methylene and long alkane chain substituent between the epoxy group and the aromatic ring can properly reduce the reactivity, and the electron-withdrawing ester substituent on the benzene ring at the p-position of the epoxy group can reduce the stabilizing effect of carbocations formed by conjugate acid after the ring-opening reaction of the benzene ring and the epoxy group, so that the shrinkage and cracks of the coating are prevented from being caused by the excessively high local polymerization rate.
Claims (9)
1. The preparation method of the high molecular compound coating is characterized by comprising the following steps: esterification reaction is carried out on 6, 6-dimethyl bicyclo [3.1.1] hept-2-ene-2-ethanol and 2-ethoxy-5- (1-propenyl) phenol respectively with alkane chain acyl chloride under the action of an acid binding agent, and the obtained esterification product is subjected to epoxidation treatment to obtain a first polymerized monomer and a second polymerized monomer in sequence; the first polymerization monomer and the second polymerization monomer are mixed with an epoxy monomer obtained by oxidizing 1-methoxy-4- [ (Z) -1-propenyl ] benzene according to a proportion to prepare a high molecular compound coating;
in the high molecular compound coating, the mass ratio of the first polymeric monomer to the second polymeric monomer to the epoxy monomer is (1.1-1.7): (2.3 to 2.9): 1.
2. the method for producing a polymer compound coating according to claim 1, comprising the steps of, in parts by weight:
s1, uniformly mixing 2.35-3.10 parts of 6, 6-dimethylbicyclo [3.1.1] hept-2-ene-2-ethanol, 1.65-2.15 parts of triethylamine and 10-15 parts of dichloromethane to obtain an alcohol amine mixture; uniformly mixing 2.80-3.65 parts of octanoyl chloride and 3-5 parts of dichloromethane, then adding the alcohol amine mixture under the protection of light shielding and nitrogen, and carrying out a first esterification reaction; after the first esterification reaction is finished, pouring the reaction product into excessive deionized water at 0-4 ℃, filtering, collecting precipitate, washing the precipitate with saturated saline water, and drying to obtain a first esterification reaction product for later use;
s2, taking 3.30-4.35 parts of the first esterification reaction product and 30-40 parts of dichloromethane, uniformly mixing, adding 2.55-3.30 parts of m-chloroperoxybenzoic acid, and carrying out a first epoxidation reaction; after the first epoxidation reaction is finished, pouring the reaction product into excessive sodium hydroxide aqueous solution, collecting an organic phase, drying the organic phase, and distilling the organic phase under reduced pressure to remove dichloromethane to obtain a first polymerized monomer for later use;
s3, uniformly mixing 2.55-3.30 parts of 2-ethoxy-5- (1-propenyl) phenol, 1.65-2.15 parts of triethylamine and 10-15 parts of dichloromethane to obtain a phenolic amine mixture; uniformly mixing 3.25-4.30 parts of decanoyl chloride and 3-5 parts of dichloromethane, adding the phenolic amine mixture under the protection of light shielding and nitrogen, and performing a second esterification reaction; after the second esterification reaction is finished, pouring the reaction product into excessive deionized water at 0-4 ℃, filtering, collecting precipitate, washing the precipitate with saturated saline water, and drying to obtain a second esterification reaction product for later use;
s4, mixing 3.75-4.95 parts of the second esterification reaction product with 30-40 parts of dichloromethane uniformly, adding 2.55-3.30 parts of m-chloroperoxybenzoic acid and carrying out a second epoxidation reaction, pouring the reaction product into excessive sodium hydroxide aqueous solution after the second epoxidation reaction is finished, collecting an organic phase, drying the organic phase, and distilling the organic phase under reduced pressure to remove dichloromethane to obtain a second polymerization monomer for later use;
s5, uniformly mixing 1.90-2.50 parts of 1-methoxy-4- [ (Z) -1-propenyl ] benzene, 1.05-1.35 parts of sodium carbonate and 30-40 parts of methanol, and adding 3.75-4.85 parts of hydrogen peroxide for oxidation reaction; after the oxidation reaction is finished, filtering a reaction product, collecting a precipitate, washing the precipitate by diethyl ether at 0-4 ℃ and drying to obtain an epoxy monomer for later use;
s6, mixing the first polymerization monomer, the second polymerization monomer and the epoxy monomer according to a proportion until all components are uniformly dispersed, and obtaining the high polymer compound coating.
3. The method for producing a polymer compound coating according to claim 2, characterized in that: the temperature of the first esterification reaction in the step S1 is 20-35 ℃, and the reaction time is 2-5 h.
4. The method for producing a polymer compound coating according to claim 2, characterized in that: and in the step S2, the temperature of the first epoxidation reaction is 0-5 ℃ and the reaction time is 18-36 h.
5. The method for producing a polymer compound coating according to claim 2, characterized in that: and in the step S3, the temperature of the second esterification reaction is 20-30 ℃, and the reaction time is 2-4 hours.
6. The method for producing a polymer compound coating according to claim 2, characterized in that: and in the step S4, the temperature of the second epoxidation reaction is 0-10 ℃ and the reaction time is 12-24 hours.
7. The method for producing a polymer compound coating according to claim 2, characterized in that: and in the step S5, the temperature of the oxidation reaction is 20-30 ℃ and the reaction time is 12-24 hours.
8. A high molecular compound coating is characterized in that: the method according to any one of claims 1 to 7.
9. Use of the polymer coating according to claim 8 for preparing a photo-curable coating, comprising the steps of: adding a photoinitiator into the high polymer compound coating, wherein the addition amount of the photoinitiator is 2-4wt%; and then transferring the material to a photo-curing device for photo-curing, wherein the irradiation wavelength is 350-390 nm, and the treatment time is 30-90 s.
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| JPH10330370A (en) * | 1997-05-26 | 1998-12-15 | Daicel Chem Ind Ltd | Epoxy compound, its production and photosetting resin composition |
| CN102503911A (en) * | 2011-12-01 | 2012-06-20 | 江苏三木化工股份有限公司 | Cation light-cured alicyclic epoxy compound and preparation method thereof |
| CN106589317A (en) * | 2016-12-03 | 2017-04-26 | 苏州大学 | Biomass-based epoxy resin and preparation method thereof |
| CN108299343A (en) * | 2018-02-09 | 2018-07-20 | 江苏泰特尔新材料科技有限公司 | It is a kind of to be prepared with micro passage reaction（Methyl）The method of acrylic acid -3,4- epoxycyclohexanecarboxylates |
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Patent Citations (4)
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| JPH10330370A (en) * | 1997-05-26 | 1998-12-15 | Daicel Chem Ind Ltd | Epoxy compound, its production and photosetting resin composition |
| CN102503911A (en) * | 2011-12-01 | 2012-06-20 | 江苏三木化工股份有限公司 | Cation light-cured alicyclic epoxy compound and preparation method thereof |
| CN106589317A (en) * | 2016-12-03 | 2017-04-26 | 苏州大学 | Biomass-based epoxy resin and preparation method thereof |
| CN108299343A (en) * | 2018-02-09 | 2018-07-20 | 江苏泰特尔新材料科技有限公司 | It is a kind of to be prepared with micro passage reaction（Methyl）The method of acrylic acid -3,4- epoxycyclohexanecarboxylates |
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