CN103980438B - The preparation of ultraviolet curing type soybean oil base compound resin - Google Patents

Abstract

The invention relates to the preparation of ultraviolet-curable soybean oil-based composite resin. Epoxidized soybean oil methacrylate was obtained by reacting epoxidized soybean oil with methacrylic acid. The hydroxyl-terminated polybutadiene is first reacted with diisocyanate, and then capped with hydroxyethyl acrylate or hydroxypropyl acrylate to obtain an oligomer containing terminal double bonds. The oligomer containing terminal double bonds and epoxy soybean oil methacrylate are uniformly mixed, and then cured by ultraviolet light. Oligomers containing terminal double bonds improved the mechanical properties of photocured films. Using epoxidized soybean oil as a synthetic raw material is beneficial to environmental protection and sustainable economic development.

Description

Preparation of Ultraviolet Curable Soybean Oil-based Composite Resin

technical field

The invention relates to the preparation of ultraviolet-curable soybean oil-based composite resin.

Background technique

With the development of society and the improvement of people's living standards, the demand for petrochemical products is increasing day by day. As a result, a series of problems such as environmental pollution and shortage of petroleum products have been caused. It also makes the research of bio-based materials more and more attention. Soybean oil is an unsaturated triglyceride whose fatty acid components mainly include stearic acid, oleic acid, linoleic acid and linolenic acid. In addition to being renewable, soybean oil also has the advantages of low price and biodegradability, and is an alternative resource for the production of polymer materials. The functionalized epoxidized soybean oil was obtained by introducing epoxy group modified soybean oil into the unsaturated free fatty acid of soybean oil. In the past, epoxidized soybean oil was mostly used as a plasticizer for polyvinyl chloride and as a starting material for the production of polyols and polyurethane foams. The ring-opening of epoxidized soybean oil with methacrylic acid can introduce active double bonds, so that it can undergo free radical UV curing reaction.

The UV-curable coating formulation is mainly composed of three parts: a prepolymer with a functional group (acrylic acid or methacrylic acid) at the end, a reactive diluent with a single or multiple functional groups, and a UV photoinitiator. Depending on the specific application, non-reactive substances such as pigments, tackifiers and surfactants can also be added to the formulation. Among them, the prepolymer, which determines the mechanical properties of the UV-cured film, is the most important component in the formulation. UV curing technology is a promising coating technology that is rapidly growing due to its low environmental impact, low energy consumption, high efficiency, and a safer and healthier working environment.

Epoxy soybean oil methacrylate as a free radical photocuring system has the advantages of fast curing speed, low price and environmental protection, but its mechanical properties need to be further improved for application.

Contents of the invention

The object of the present invention is to provide the preparation of ultraviolet light-curable soybean oil-based composite resin, and obtain the ultraviolet light-curable soybean oil-based composite resin with improved mechanical properties.

The preparation of the described UV-curable soybean oil-based composite resin of the present invention, the specific operation steps are as follows:

Step a, adding epoxidized soybean oil, methacrylic acid, triphenylphosphine and p-hydroxymethylanisole with more than 2 epoxy groups per molecule into the reaction kettle, controlling the reaction temperature at 90-110°C, and the reaction time is 4 ~6h to obtain epoxy soybean oil methacrylate;

Step b, adding hydroxyl-terminated polybutadiene and diisocyanate into the reaction kettle, controlling the reaction temperature at 40-80°C, and the reaction time is 1.5-3 hours to obtain the intermediate product, then, adding hydroxyethyl acrylate or hydroxypropyl acrylate, the reaction temperature Control 70-80°C, and the reaction time is 1.5-2 hours to obtain oligomers containing terminal double bonds;

Step c, the oligomer containing terminal double bonds obtained by step a to obtain epoxy soybean oil methacrylate and step b to carry out ultraviolet light curing, and the curing formula is as follows:

The material ratio of epoxidized soybean oil, methacrylic acid, triphenylphosphine and p-hydroxymethyl anisole in step a is 1:2～4:0.03:0.1.

The methacrylic acid in step a also can be replaced with acrylic acid, obtains epoxy soybean oil acrylate.

The diisocyanate in step b is hexamethylene diisocyanate or toluene-2,4-diisocyanate or isophorone diisocyanate or 4,4'-diphenylmethane diisocyanate or 4,4'-dicyclohexyl methane diisocyanate.

The molar ratio of hydroxyl-terminated polybutadiene and diisocyanate in step b is 1:2.

The material ratio of the intermediate product in step b to hydroxyethyl acrylate or hydroxypropyl acrylate is 1:2.

The reactive diluent in step c is one or any combination of hydroxyethyl acrylate, hydroxypropyl acrylate, hexanediol dimethacrylate and trimethylolpropane trimethacrylate.

The photoinitiator in step c is a free radical photoinitiator 1-hydroxycyclohexyl phenyl ketone or benzophenone or 2-hydroxy-2-methyl-1-phenyl-1-propanone.

The advantages and innovations of the present invention are as follows: ① Adding oligomers containing terminal double bonds can significantly improve the mechanical properties of the UV-curable soybean oil-based composite resin, and hydroxyl-terminated polybutadiene containing a large number of double bonds can also produce more multiple cross-linking reactions. ② Using epoxidized soybean oil as a synthetic raw material is beneficial to environmental protection and sustainable economic development. ③ According to different operating temperatures, different reactive diluents and different amounts of reactive diluents can be added to facilitate the operation and the performance of the final product.

detailed description

The present invention will be further described below by specific embodiment:

The preparation of UV-curable soybean oil-based composite resin is carried out according to the following steps:

Step a, adding epoxidized soybean oil, methacrylic acid, triphenylphosphine and p-hydroxymethyl anisole with a substance ratio of 1:2 to 4:0.03:0.1 and epoxy groups greater than 2 In the reaction kettle, the reaction temperature is controlled at 90-110°C, and after the reaction time is 4-6 hours, epoxy soybean oil methacrylate is obtained; in other embodiments, methacrylic acid can also be replaced with acrylic acid, and the final result is Epoxy soybean oil acrylate, this embodiment is also feasible.

Step b, adding hydroxyl-terminated polybutadiene and diisocyanate with a substance ratio of 1:2 into the reaction kettle, the diisocyanate can be hexamethylene diisocyanate or toluene-2,4-diisocyanate or isophor Ketone diisocyanate or 4,4'-diphenylmethane diisocyanate or 4,4'-dicyclohexylmethane diisocyanate, the reaction temperature is controlled at 40-80°C, the reaction time is 1.5-3h, and the intermediate product is obtained. Then, add Hydroxyethyl acrylate or hydroxypropyl acrylate, the molar ratio of the intermediate product to hydroxyethyl acrylate or hydroxypropyl acrylate is 1:2, the reaction temperature is controlled at 70-80°C, and after 1.5-2 hours of reaction time, the compound containing Oligomers with terminal double bonds;

Step c, the epoxidized soybean oil methacrylate obtained in step a and the oligomer containing double bonds at the end obtained in step b are subjected to ultraviolet light curing, and the curing formula is as follows:

Wherein, the reactive diluent is one or any combination of hydroxyethyl acrylate, hydroxypropyl acrylate, hexanediol dimethacrylate and trimethylolpropane trimethacrylate, and the photoinitiator is Free radical type photoinitiator 1-hydroxycyclohexyl phenyl ketone or benzophenone or 2-hydroxy-2-methyl-1-phenyl-1-propanone.

Concrete embodiment is as follows:

Example 1

Step a, add epoxidized soybean oil, methacrylic acid, triphenylphosphine and p-hydroxymethyl anisole into the reactor according to the ratio of substances 1:2:0.03:0.1, the reaction temperature is controlled at 110°C, and the reaction time is 4h;

Step b, adding hydroxyl-terminated polybutadiene and hexamethylene diisocyanate into the reaction kettle, the reaction temperature is controlled at 45°C, and the reaction time is 3h. Then, hydroxyethyl acrylate is added, the reaction temperature is controlled at 70°C, and the reaction time is 2h to obtain Oligomers containing terminal double bonds.

Step c, the oligomer containing terminal double bonds obtained by step a to obtain epoxy soybean oil methacrylate and step b to carry out ultraviolet light curing, and the curing formula is as follows:

60% Epoxy Soybean Oil Methacrylate

20% oligomers with terminal double bonds

17% Hexylene Glycol Dimethacrylate

3% 1-Hydroxycyclohexyl phenyl ketone

Example 2

Step a, adding epoxidized soybean oil, acrylic acid, triphenylphosphine and p-hydroxymethyl anisole into the reaction kettle according to the ratio of substances 1:3:0.03:0.1, the reaction temperature is controlled at 100°C, and the reaction time is 6h;

Step b. Add hydroxyl-terminated polybutadiene and toluene-2,4-diisocyanate into the reaction kettle. The reaction temperature is controlled at 60°C, and the reaction time is 2.5h. Then, hydroxypropyl acrylate is added, and the reaction temperature is controlled at 75°C. After 2h, an oligomer containing terminal double bonds was obtained.

Step c, carry out ultraviolet light curing to the oligomer containing terminal double bonds obtained by step a obtained epoxy soybean oil acrylate and step b, and the curing formula is as follows:

50% Epoxy Soybean Oil Acrylate

20% oligomers with terminal double bonds

25% Hydroxyethyl Acrylate

5% Benzophenone

Example 3

Step a, add epoxidized soybean oil, methacrylic acid, triphenylphosphine and p-hydroxymethylanisole into the reactor according to the ratio of substances 1:4:0.03:0.1, the reaction temperature is controlled at 110°C, and the reaction time is 4.5 hours;

Step b. Add hydroxyl-terminated polybutadiene and isophorone diisocyanate into the reaction kettle. The reaction temperature is controlled at 70°C, and the reaction time is 2h. Then, hydroxyethyl acrylate is added, and the reaction temperature is controlled at 80°C, and the reaction time is 1.5h. Oligomers containing terminal double bonds are obtained.

Step c, the oligomer containing terminal double bonds obtained by step a to obtain epoxy soybean oil methacrylate and step b to carry out ultraviolet light curing, and the curing formula is as follows:

40% Epoxy Soybean Oil Methacrylate

30% oligomers with terminal double bonds

27% Hydroxypropyl Acrylate

3% 1-Hydroxycyclohexyl phenyl ketone

Example 4

Step a, add epoxidized soybean oil, methacrylic acid, triphenylphosphine and p-hydroxymethyl anisole into the reactor according to the ratio of substances 1:2:0.03:0.1, the reaction temperature is controlled at 110°C, and the reaction time is 4.5 hours;

Step b. Add hydroxyl-terminated polybutadiene and 4,4'-diphenylmethane diisocyanate into the reaction kettle, control the reaction temperature at 50°C, and the reaction time is 3h, add hydroxypropyl acrylate, control the reaction temperature at 70°C, and react Time 2h yields oligomers containing terminal double bonds.

Step c, the oligomer containing terminal double bonds obtained by step a to obtain epoxy soybean oil methacrylate and step b to carry out ultraviolet light curing, and the curing formula is as follows:

50% Epoxy Soybean Oil Methacrylate

40% oligomers with terminal double bonds

7% Trimethylolpropane Trimethacrylate

3% 2-Hydroxy-2-methyl-1-phenyl-1-propanone

Example 5

Step a, add epoxidized soybean oil, methacrylic acid, triphenylphosphine and p-hydroxymethylanisole into the reactor according to the ratio of substances 1:3:0.03:0.1, the reaction temperature is controlled at 100°C, and the reaction time is 6h;

Step b. Add hydroxyl-terminated polybutadiene and toluene-2,4-diisocyanate into the reaction kettle, the reaction temperature is controlled at 40°C, and the reaction time is 3h. Then, hydroxyethyl acrylate is added, the reaction temperature is controlled at 80°C, and the reaction time is After 2h, an oligomer containing a terminal double bond was obtained.

Step c, the oligomer containing terminal double bonds obtained by step a to obtain epoxy soybean oil methacrylate and step b to carry out ultraviolet light curing, and the curing formula is as follows:

60% Epoxy Soybean Oil Methacrylate

37% oligomers with terminal double bonds

3% 1-Hydroxycyclohexyl phenyl ketone

The UV-curable soybean oil-based composite resins prepared by the above-mentioned different examples all have the following advantages: ① The mechanical properties of UV-curable soybean oil-based composite resins are significantly improved by adding oligomers containing terminal double bonds; Butadiene contains a large number of double bonds and more cross-linking reactions can occur. ② Using epoxidized soybean oil as a synthetic raw material is beneficial to environmental protection and sustainable economic development. ③ According to different operating temperatures, different reactive diluents and different amounts of reactive diluents can be added to facilitate the operation and the performance of the final product.

Claims (8)

1. the preparation of ultraviolet curing type soybean oil base compound resin, it is characterised in that comprise the following steps:

Step a, by the epoxy radix of the per molecule epoxidized soybean oil more than 2, methacrylic acid, triphenylphosphine and to methylol Methyl phenyl ethers anisole adds in reactor, and reaction temperature controls 90～110 DEG C, and the reaction time 4～6h obtains epoxidized soybean oil metering system Acid esters；

Step b, adding in reactor by end hydroxy butadiene and diisocyanate, reaction temperature controls 40～80 DEG C, reaction Time 1.5～3h obtains intermediate product, then, adds hydroxy-ethyl acrylate or hydroxypropyl acrylate, and reaction temperature controls 70～80 DEG C, the reaction time 1.5～2h obtains the oligomer containing terminal double bond；

Step c, step a is obtained epoxidized soybean oil methacrylate and the oligomer containing terminal double bond that step b obtains is carried out Ultraviolet light polymerization, curing formula is as follows:

The preparation of ultraviolet curing type soybean oil base compound resin the most according to claim 1, it is characterised in that: step a In epoxidized soybean oil, methacrylic acid, triphenylphosphine and the amount ratio to the material of methylol methyl phenyl ethers anisole be 1: 2～4: 0.03: 0.1。

The preparation of ultraviolet curing type soybean oil base compound resin the most according to claim 1, it is characterised in that: step a In methacrylic acid can also replace to acrylic acid, obtain epoxy soybean oil acrylate.

The preparation of ultraviolet curing type soybean oil base compound resin the most according to claim 1, it is characterised in that: step b In diisocyanate be hexamethylene diisocyanate or Toluene-2,4-diisocyanate, 4-diisocyanate or IPDI or 4,4 '-methyl diphenylene diisocyanate or 4,4 '-dicyclohexyl methyl hydride diisocyanate.

The preparation of ultraviolet curing type soybean oil base compound resin the most according to claim 1, it is characterised in that: step b In end hydroxy butadiene and the amount ratio of material of diisocyanate be 1: 2.

The preparation of ultraviolet curing type soybean oil base compound resin the most according to claim 1, it is characterised in that: step b In intermediate product and the amount ratio of material of hydroxy-ethyl acrylate or hydroxypropyl acrylate be 1: 2.

The preparation of ultraviolet curing type soybean oil base compound resin the most according to claim 1, it is characterised in that: step c In reactive diluent be hydroxy-ethyl acrylate, hydroxypropyl acrylate, hexanediol dimethacrylate and trimethylolpropane tris A kind of or the most several combination in methacrylate.

The preparation of ultraviolet curing type soybean oil base compound resin the most according to claim 1, it is characterised in that: step c In light trigger be radical photoinitiator 1-hydroxycyclohexyl phenyl ketone or benzophenone or 2-hydroxy-2-methyl-1-benzene Base-1-acetone.