CN113402493A - Cyclocarboxylation soybean oil (methyl) acrylate resin and preparation method thereof - Google Patents
Cyclocarboxylation soybean oil (methyl) acrylate resin and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a cycloxarboxylated soybean oil (methyl) acrylate resin, which is obtained by reacting epoxidized soybean oil with aldehyde group (methyl) acrylate under the action of an onium salt catalyst, wherein a main body structure of the epoxidized soybean oil is connected with a (methyl) acrylate group through a dioxolane structure, and the dioxolane structure is obtained by reacting an epoxy group with the aldehyde group. The preparation method comprises the following steps: s1, feeding epoxidized soybean oil and aldehyde (meth) acrylate according to the molar ratio of epoxy groups to aldehyde groups of 1.0: 1.0-1.5, and feeding an onium salt catalyst according to the molar ratio of the onium salt catalyst to aldehyde (meth) acrylate of 1-10%; s2, mixing the raw materials, and stirring and reacting for 5-48 h at room temperature to 60 ℃. The cyclocarboxylation soybean oil (methyl) acrylate resin has high photocuring activity, can be used as a photocuring resin material, and has the advantages of simple preparation process and wide raw material selection.
Description
Technical Field
The invention belongs to the field of polymer materials, and relates to preparation of cyclocarboxylation soybean oil (methyl) acrylate resin.
Background
Vegetable oil, lignin, cellulose and the like belong to renewable resources, the research and development of new materials based on the renewable resources is called as an important research and development and application direction of the material field, and soybean oil is an important one of the renewable resources. Based on the transgenic planting technology, the global soybean oil yield is very high, less soybean oil is eaten, and more soybean oil is modified to be used as chemical raw materials including paint, printing ink, adhesive, plasticizer, lubricating oil and the like, so that the application and development characteristics of the bio-based materials in the field of chemical materials are met. Soybean oil is a triglyceride compound formed from oleic and linoleic acids and glycerol, rich in ester bonds and carbon-carbon double bonds, and also can be regarded as being rich in pseudo-allyl structures, which provide opportunities for chemical modification of soybean oil. The modification methods mainly comprise polyol ester exchange- (methyl) acrylic acid esterification, ester exchange-ammonia esterification, anhydride modification, epoxidation of carbon-carbon double bonds under the action of peroxide, graft modification, sulfydryl-alkene addition modification and the like, and the main aim of modification is to endow the soybean oil with a reactive group with higher activity or a hardness and toughness improvement structure. Modified soybean oil for photocuring applications is often prepared by ring-opening esterification of epoxidized soybean oil with (meth) acrylic acid or a carboxyl-based poly (meth) acrylate, and introducing a certain proportion of a highly reactive (meth) acrylate into the main structure of soybean oil to impart a certain photocuring activity. However, as a result of many modifications at present, the resulting modified (meth) acrylated soybean oil is not satisfactory in photocuring activity and poor in oxygen inhibition tack-free property. The adhesion and self-film-forming strength of the photocured coating are still poor.
Soybean oil and derivatives thereof, including epoxidized soybean oil and the like, belong to bio-based materials, have the characteristic of recycling, and the research and manufacture of high-biocompatibility recyclable high polymer materials based on bio-based renewable resources is one of the important directions for the development of future high polymer materials. However, the conventional vegetable oil modified product has the defects of poor cohesion, poor adhesion and the like, is difficult to use as a main material, and is generally only used in a small amount as an auxiliary material in a material formula system, for example, a small amount of modified vegetable oil is added in an ink formula to improve the wettability of a pigment. A few innovative researches show that the specially modified soybean oil can obtain better cohesiveness and is expected to be applied as a main material in the field of environment-friendly and renewable pressure-sensitive adhesives. For example, the modified vegetable oil-based green pressure-sensitive adhesive technology researched by Likeshi et al, Oregon university, USA, adopts a special high molecular weight cross-linking agent to perform tackifying modification on soybean oil, and obtains better cohesion performance, and basic performances such as initial adhesion, permanent adhesion and the like are obviously improved.
The main materials of the coating, the printing ink and the adhesive are high-performance materials which are obtained by modifying renewable vegetable oil with high-performance synthetic resin, and are research hotspots in the field of biological recyclable materials at home and abroad and are the entry point of the technology. The carbon-carbon double bond of oleate and linoleate in the soybean oil structure is easily oxidized to form an epoxy group on the chain, so that epoxidized soybean oil (ESO for short) is obtained, and the structure of the epoxidized soybean oil can be shown in a formula 3.
A large amount of epoxy groups rich in the epoxy group have relatively high reactivity, can react with active groups such as carboxyl, sulfydryl, amino and the like in a ring-opening way, and comprise the epoxy group ring-opening esterification reaction with acrylic acid and carboxyl polyacrylate (pentaerythritol triacrylate-anhydride adduct) to synthesize ESO acrylate resin, the acrylate group introduced on the soybean oil is suitable for free radical polymerization crosslinking, and the epoxy group can be used as an ultraviolet light curing material for UV curing coatings, printing ink, adhesives and the like. However, the ESO acrylate resin obtained by the traditional modification technology has low photocuring activity, serious oxygen inhibition and difficult thorough curing. Meanwhile, the strength of the curing film is poor, and the curing film is difficult to apply to a photocuring formula in a high proportion, so that the biological reproducibility and biocompatibility characteristics of modern high-performance photocuring formula materials are limited.
Disclosure of Invention
Based on the above, the primary object of the present invention is to overcome the disadvantages and drawbacks of the prior art and to provide a cyclocarboxylated soybean oil (meth) acrylate resin.
The technical scheme adopted by the invention is as follows:
the cyclocarboxylated soybean oil (methyl) acrylate resin is characterized by having a structural formula shown as a formula 1:
in the formula, R1Is any one of H and methyl; n is 1-5; l is any one of alkylene, alkylidene and hydrocarbon residue with 1-7 carbon atoms.
Further, the L group is phenylene
Methylene phenyl group
Methylphenylene group
Any of methylene and 1, 4-furylidene.
Further, the L group is a phenylene group
Tetramethylene phenyl
Six-fork n-pentyl group
Any one of (1).
The other purpose of the invention is to provide a preparation method of the cyclocarboxylation soybean oil (methyl) acrylate resin, which is obtained by reacting epoxidized soybean oil and aldehyde group (methyl) acrylate under the action of an onium salt catalyst, wherein a main structure of the epoxidized soybean oil is connected with a (methyl) acrylate group through a dioxolane structure, and the dioxolane structure is obtained by reacting an epoxy group with an aldehyde group.
Further, the method comprises the following steps:
s1: feeding epoxidized soybean oil and aldehyde (meth) acrylate according to the molar ratio of epoxy groups to aldehyde groups of 1.0: 1.0-1.5, and feeding an onium salt catalyst according to the molar ratio of the onium salt catalyst to aldehyde (meth) acrylate of 1-10%;
s2: mixing the raw materials, and stirring and reacting for 5-48 h at room temperature to 60 ℃.
Further, the aldehyde-based (meth) acrylate is selected from one or more of 4- (meth) acryloyloxybenzaldehyde, 3- (meth) acryloyloxybenzaldehyde, 2- (meth) acryloyloxybenzaldehyde, 3, 5-di (meth) acryloyloxybenzaldehyde, 3,4, 5-tri (meth) acryloyloxybenzaldehyde, (meth) acryloyloxyacetal, 4- (meth) acryloyloxyfuran formaldehyde, D-glucose penta (meth) acrylate.
Further, the onium salt catalyst is an imidazolium salt with a weak nucleophilic anion, and the structure of the imidazolium salt is shown as formula 2:
wherein R2 and R3 are alkyl with 1-6 carbon atoms; the anion X-is any one of PF6-, SbF6-, BF4-, (C6H5)4B-, (CF3SO2) 2N-.
Further, the anion X-is any one of PF6-, SbF 6-.
Further, the epoxidized soybean oil has an epoxy value greater than 0.060mol/100 g.
Furthermore, the epoxidized soybean oil and the aldehyde (meth) acrylate are fed according to the molar ratio of the epoxy group to the aldehyde group of 1.0: 1.0-1.1, and the onium salt catalyst is fed according to the molar ratio of the onium salt catalyst to the aldehyde (meth) acrylate of 1-5%.
Compared with the prior art, the invention has the beneficial effects that:
according to the invention, the modified soybean oil rich in dioxolane structure and acrylate group is obtained by introducing acrylate group and endowing the soybean oil with dioxolane structure with high activity. The acetal active hydrogen on the dioxolane structure can improve the free radical photocuring activity, accelerate the curing rate, inhibit the oxygen inhibition which is commonly existed in the UV curing process, improve the UV curing, and enhance the solvent resistance and the strength of a cured film. The cyclic structure of dioxolane itself can also improve the mechanical strength of the cured film and improve the overall properties such as hardness and adhesion of the cured film. Therefore, the cyclocarboxylation soybean oil (methyl) acrylate resin has relatively high photocuring activity and can be used as a photocuring resin material, including an ultraviolet curing adhesive material. In addition, the preparation process of the cyclocarboxylation soybean oil (methyl) acrylate resin is simple and the raw materials are widely selected.
For a better understanding and practice, the invention is described in detail below with reference to specific examples.
Detailed Description
The following examples are provided to facilitate understanding of the present invention, but are not intended to limit the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
In order to overcome the common defects of low photocuring reaction activity and poor film forming strength of common ESO (ethylene styrene-acrylate copolymer) acrylate, the invention provides that a dioxolane structure with high activity is endowed to soybean oil while an acrylate group is introduced, so that modified soybean oil rich in the dioxolane structure and the acrylate group is obtained, the structure of the modified soybean oil is shown as a formula 1, wherein L is a residue derived from benzene rings, furan and alkane, R1 is methyl or hydrogen, and n is 1-5. The acetal active hydrogen on the dioxolane structure can improve the free radical photocuring activity, accelerate the curing rate, inhibit the oxygen inhibition which is commonly existed in the UV curing process, improve the UV curing, and enhance the solvent resistance and the strength of a cured film. The cyclic structure of dioxolane itself can also improve the mechanical strength of the cured film and improve the overall properties such as hardness and adhesion of the cured film.
In order to achieve the synthesis of the materials, the technical route of the implementation of the invention refers to a newer result in the basic research of organic chemistry, namely, the mild cyclization reaction of the epoxy group and the aldehyde group under the action of the catalyst forms a dioxolane acetal structure, and the reaction is typically represented as follows.
The acetal active hydrogen is easy to participate in free radical reaction, and can play a role in accelerating polymerization and inhibiting oxygen polymerization in photocuring reaction. The above catalysts in basic organic chemistry research include methyl rhenium trioxide (MTO), phosphomolybdovanadate, aromatic ring quaternary ammonium salts, and the like. These catalysts have the characteristics that methyl rhenium trioxide catalyst is expensive, common materials are difficult to bear, the catalytic reaction time is too long, and a reaction at normal temperature of several days is required. The catalytic efficiency of the phosphomolybdovanadophosphoric acid catalyst can reach a higher level, but the phosphomolybdovanadophosphoric acid catalyst is still in a laboratory research stage, a mature industrial product is not formed, and the darker color of the phosphomolybdovanadophosphoric acid catalyst is not easy to remove in subsequent treatment. The catalytic reproducibility of the phosphomolybdovanadophosphoric acid catalyst is also unstable. The aromatic ring quaternary ammonium salt mainly comprises pyridinium salt, and the catalyst has the main defects of poor thermal stability and easy thermal decomposition to generate unpleasant odor. Further, these pyridinium salt catalysts have poor solubility in the reaction system, and require heating to promote compatibility, which in turn tends to cause thermal decomposition of the pyridinium salt catalyst.
Based on the previous manual work, the invention discovers that the aromatic ring quaternary ammonium salt ionic liquid compound carrying weak nucleophilic anions has better catalytic activity and compatibility, mainly comprises imidazolium salt ionic liquid, and the general structure of the compound is shown as a formula 2.
Wherein R is2、R3Is an alkyl group having 1 to 6 carbon atoms; anion XˉIs PF6 -、SbF6 -、BF4 -、(C6H5)4B-、(CF3SO2)2N-Etc. and optimized to PF6 -，SbF6 -. The catalyst is liquid at ambient temperature or when heated to about 60 ℃, is compatible with ESO, and is commercially available.
In order to obtain a dioxolane structure on modified soybean oil, the invention adopts the action of aldehyde acrylate and ESO. The aldehyde acrylate comprises aldehyde methacrylate, which is (methyl) acrylate with aldehyde, and the structural general formula is shown as formula 4.
Wherein R is1Is H or methyl CH3(ii) a n is 1-5; l is an alkylene group, an alkylidene group, or a hydrocarbon residue having a higher degree of substitution (i.e., a polynary group) of 1 to 7 carbon atoms. More particularly, when n ═ 1, the L group predominantly comprises phenylene groups
Methylene phenyl group
Methylphenylene group
Methylene, 1, 4-furylidene, and the like. When n is 2 to 5, the L group includes a phenylene group
Tetramethylene phenyl
Six-fork n-pentyl group
And the like.
More specifically, the aldehyde acrylate includes, but is not limited to, the following compounds.
4- (meth) acryloyloxybenzaldehyde
3- (meth) acryloyloxybenzaldehyde
2- (meth) acryloyloxybenzaldehyde
3, 5-di (meth) acryloyloxybenzaldehyde
3,4, 5-tri (meth) acryloyloxybenzaldehyde
(meth) acryloyloxyacetaldehyde
4- (meth) acryloyloxyfuran formaldehyde
D-glucose penta (meth) acrylate.
Wherein R is1The groups are as described in formula 1. The aldehyde (meth) acrylates used in the present invention are custom made from Guangdong Boxing New materials, Inc.
The ESO raw material used in the present invention has an epoxy value of more than 0.060mol/100 g.
The synthetic conditions of the soybean oil (methyl) acrylate resin containing a dioxolane structure synthesized by the invention are that the aldehyde group is slightly excessive relative to the epoxy group, and the raw materials are fed. Preferably, the epoxy soybean oil and the aldehyde group (methyl) acrylate are fed according to the molar ratio of the epoxy group to the aldehyde group of 1.0 to (1.0-1.5), and the molar ratio is optimized to be 1.0 to (1.0-1.1). The onium salt catalyst is added in a proportion of 1-10% by mole of the aldehyde (meth) acrylate, and the proportion is optimized to 1-5%.
The synthesis conditions of the invention also comprise that the epoxy soybean and the aldehyde group (methyl) acrylate are mixed according to a proportion and stirred for reaction for 5-48 hours at the temperature of room temperature to 60 ℃. The reaction can be accelerated by raising the temperature, but the side reactions are increased correspondingly, and the content of active hydrogen of the obtained cyclic acetal is not increased in equal proportion along with the consumption of epoxy groups.
The synthesis of the invention is carried out under the condition of no solvent, the epoxy group in the final reaction system is used up, the infrared absorption spectrum tracks and checks the reaction system, when the infrared spectrum shows 823cm-1And (4) completely eliminating the characteristic absorption peak of the epoxy group, namely the reaction completion mark. The length of this reaction time depends on the temperature, the catalyst and the aldehyde (meth) acrylate structure used.
Example 1
100g of ESO (epoxy value of 0.065mol/100g), 11.5g (0.067mol) of 4-acryloyloxybenzaldehyde and 0.20g (0.67mmol) of 1-n-butyl-3-methyl hexafluorophosphate are added into a reactor, the mixture is mechanically stirred uniformly and reacted for 48 hours at the room temperature of 26 ℃, and the epoxy group infrared characteristic absorption peak in the system completely disappears. The reaction system is not separated, and a nuclear magnetic hydrogen spectrum test is directly carried out, wherein a delta 2.85-3.12 ppm multiplet on a hydrogen spectrum is originally attributed to an ESO epoxy group C-H bond, completely disappears in a nuclear magnetic hydrogen spectrum of a product, and a cyclic acetal active hydrogen-O-CH (Ar) -O-unimodal signal appears in the product near delta 5.85 ppm.
Example 2
100g of ESO (epoxy value of 0.065mol/100g), 12.7g (0.067mol) of 4-methacryloyloxybenzaldehyde and 0.20g (0.67mmol) of 1-n-butyl-3-methyl hexafluorophosphate are added into a reactor, the mixture is mechanically stirred uniformly and reacted for 48 hours at the room temperature of 26 ℃, and the epoxy group infrared characteristic absorption peak in the system completely disappears. The reaction system is not separated, and a nuclear magnetic hydrogen spectrum test is directly carried out, wherein a delta 2.85-3.12 ppm multiplet on a hydrogen spectrum is originally attributed to an ESO epoxy group C-H bond, completely disappears in a nuclear magnetic hydrogen spectrum of a product, and a cyclic acetal active hydrogen-O-CH (Ar) -O-unimodal signal appears in the product near delta 5.85 ppm.
Example 3
100g of ESO (epoxy value of 0.065mol/100g), 12.7g (0.067mol) of 2-methacryloyloxybenzaldehyde and 0.25g (0.67mmol) of 1-n-butyl-3-methyl hexafluoroantimonate are added into a reactor, the mixture is mechanically stirred uniformly and reacts for 5 hours at 60 ℃, and the epoxy group infrared characteristic absorption peak in the system completely disappears. The reaction system is not separated, and a nuclear magnetic hydrogen spectrum test is directly carried out, wherein a delta 2.85-3.12 ppm multiplet on a hydrogen spectrum is originally attributed to an ESO epoxy group C-H bond, completely disappears in a nuclear magnetic hydrogen spectrum of a product, and a cyclic acetal active hydrogen-O-CH (Ar) -O-unimodal signal appears in the product near delta 5.91 ppm.
Example 4
100g of ESO (epoxy value of 0.065mol/100g), 17.6g (0.072mol) of 3, 5-bisacryloxybenzaldehyde and 1.1g (3.6mmol) of 1-n-hexyl-3-methyl hexafluorophosphate are added into a reactor, the mixture is mechanically stirred uniformly, and the mixture is stirred and reacted for 32 hours at the room temperature of 26 ℃, so that the epoxy group infrared characteristic absorption peak in the system completely disappears. The reaction system is not separated, and a nuclear magnetic hydrogen spectrum test is directly carried out, wherein a delta 2.85-3.12 ppm multiplet on a hydrogen spectrum is originally attributed to an ESO epoxy group C-H bond, completely disappears in a nuclear magnetic hydrogen spectrum of a product, and a cyclic acetal active hydrogen-O-CH (Ar) -O-unimodal signal appears in the product near delta 5.77 ppm.
Example 5
100g of ESO (epoxy value 0.065mol/100g), 20.5g (0.065mol) of 3,4, 5-triacryloxybenzaldehyde and 0.18g (0.65mmol) of 1-n-butyl-3-methyl hexafluorophosphate are added into a reactor, the mixture is mechanically stirred uniformly, the mixture is stirred at 45 ℃ for reaction for 31 hours, and the epoxy group infrared characteristic absorption peak in the system completely disappears. The reaction system is not separated, and a nuclear magnetic hydrogen spectrum test is directly carried out, wherein a delta 2.85-3.12 ppm multiplet on a hydrogen spectrum is originally attributed to an ESO epoxy group C-H bond, completely disappears in a nuclear magnetic hydrogen spectrum of a product, and a cyclic acetal active hydrogen-O-CH (Ar) -O-unimodal signal appears in the product near delta 5.71 ppm.
Example 6
100g of ESO (epoxy value of 0.065mol/100g), 12.1g (0.067mol) of 4-acryloyloxyfuran formaldehyde and 0.18g (0.65mmol) of 1-n-butyl-3-methyl hexafluorophosphate are added into a reactor, the mixture is mechanically stirred uniformly and reacted for 45 hours at the room temperature of 26 ℃, and the epoxy group infrared characteristic absorption peak in the system completely disappears. The reaction system is not separated, and a nuclear magnetic hydrogen spectrum test is directly carried out, wherein a delta 2.85-3.12 ppm multiplet on a hydrogen spectrum is originally attributed to an ESO epoxy group C-H bond, completely disappears in a nuclear magnetic hydrogen spectrum of a product, and a cyclic acetal active hydrogen-O-CH (Ar) -O-unimodal signal appears in the product near delta 6.35 ppm.
Example 7
100g of ESO (epoxy value of 0.065mol/100g), 30.2g (0.067mol) of D-glucose pentaacrylate and 0.18g (0.65mmol) of 1-n-butyl-3-methyl hexafluorophosphate are added into a reactor, the mixture is mechanically stirred uniformly and reacted for 48 hours at the room temperature of 26 ℃, and the epoxy group infrared characteristic absorption peak in the system completely disappears. The reaction system is not separated, and a nuclear magnetic hydrogen spectrum test is directly carried out, wherein a delta 2.85-3.12 ppm multiplet on a hydrogen spectrum is originally attributed to an ESO epoxy group C-H bond, completely disappears in a nuclear magnetic hydrogen spectrum of a product, and a cyclic acetal active hydrogen-O-CH (Ar) -O-unimodal signal appears in the product near delta 5.53 ppm.
Comparative example:
100g of ESO (epoxy value 0.065mol/100g), 11.5g (0.067mol) of 4-acryloyloxybenzaldehyde and 0.21g (0.67mmol) of tetrabutylammonium bromide are added into a reactor, the mixture is mechanically stirred uniformly, and the reaction is stirred at 60 ℃ for 72 hours, so that the characteristic absorption peak of epoxy group infrared in the system is hardly changed. The reaction system is not subjected to separation treatment, a nuclear magnetic hydrogen spectrum test is directly carried out, a delta 2.85-3.12 ppm multiplet on a hydrogen spectrum is originally attributed to an ESO epoxy group C-H bond, the reduction is hardly caused in the nuclear magnetic hydrogen spectrum of the system, and a product does not have a due cyclic acetal active hydrogen-O-CH (Ar) -O-unimodal signal near delta 5.85 ppm.
Example 8
10g of each product obtained in examples 1 to 7 and 10g of conventional epoxidized soybean oil acrylate B-106 (New Material Co., Ltd., Guangdong Boxing), 0.20g of photoinitiator D1173 and 0.10g of benzophenone were added, the mixture was uniformly stirred and coated on a polished tinplate, and the thickness of the coating was controlled to be 25 μm. The radiation was carried out for 10sec with a 2000W medium pressure mercury lamp. The surface dryness of the coating was evaluated by a cotton blowing method, the adhesion of the cured coating was measured by a check method, and the solvent resistance of the cured film was measured by a butanone cotton wiping method, and the results are shown in Table 1.
TABLE 1
| Modified epoxidized soybean oil resin | Surface drying agent | Grade of adhesion | Butanone wiping frequency resistance |
| Example 1 product | Complete surface drying | 1 | 80 |
| Example 2 product | Basic surface stem | 2 | 56 |
| Example 3 product | Basic surface stem | 2 | 62 |
| Example 4 product | Complete surface drying | 0 | 120 |
| Example 5 product | Complete surface drying | 0 | 155 |
| Example 6 product | Complete surface drying | 0 | 162 |
| Example 7 product | Complete surface drying | 0 | 182 |
| Example 8 product | Complete surface drying | 1 | 200+ |
| B-106 | Basic surface stem | 3 | 25 |
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. 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.
Claims (10)
1. The cyclocarboxylated soybean oil (methyl) acrylate resin is characterized by having a structural formula shown as a formula 1:
in the formula, R1Is any one of H and methyl; n is 1-5; l is any one of alkylene, alkylidene and hydrocarbon residue with 1-7 carbon atoms.
2. The cyclocarboxylated soybean oil (meth) acrylate resin of claim 1 wherein: the L group in the structural formula is phenylene
Methylene phenyl group
Methylphenylene group
Any of methylene and 1, 4-furylidene.
3. The cyclocarboxylated soybean oil (meth) acrylate resin of claim 1 wherein the group L in the formula is a phenylene group
Tetramethylene phenyl
Six-fork n-pentyl group
Any one of (1).
4. The method for preparing a cyclocarboxylated soybean oil (meth) acrylate resin according to claim 1, wherein said epoxidized soybean oil is obtained by reacting epoxidized soybean oil with aldehyde (meth) acrylate in the presence of an onium salt catalyst, and the main structure of said epoxidized soybean oil is connected to the (meth) acrylate group by means of a dioxolane structure obtained by reacting an epoxy group with an aldehyde group.
5. The method for preparing the cyclocarboxylated soybean oil (meth) acrylate resin according to claim 4, comprising the steps of:
s1: feeding epoxidized soybean oil and aldehyde (meth) acrylate according to the molar ratio of epoxy groups to aldehyde groups of 1.0: 1.0-1.5, and feeding an onium salt catalyst according to the molar ratio of the onium salt catalyst to aldehyde (meth) acrylate of 1-10%;
s2: mixing the raw materials, and stirring and reacting for 5-48 h at room temperature to 60 ℃.
6. The method of claim 4, wherein the aldehyde-based (meth) acrylate is selected from one or more of 4- (meth) acryloyloxybenzaldehyde, 3- (meth) acryloyloxybenzaldehyde, 2- (meth) acryloyloxybenzaldehyde, 3, 5-di (meth) acryloyloxybenzaldehyde, 3,4, 5-tri (meth) acryloyloxybenzaldehyde, (meth) acryloyloxyacetal, 4- (meth) acryloyloxyfurfural, and D-glucose penta (meth) acrylate.
7. The method for preparing the cyclocarboxylated soybean oil (meth) acrylate resin according to claim 4, wherein the onium salt catalyst is an imidazolium salt with a weak nucleophilic anion, and the structure of the onium salt is shown as formula 2:
wherein R2 and R3 are alkyl with 1-6 carbon atoms; anion X-Is PF6-、SbF6-、BF4-、(C6H5)4B-、(CF3SO2)2N-Any one of (1).
8. The method of claim 7, wherein the anion X is selected from the group consisting of-Is PF6-，SbF6-Any one of (1).
9. The method of claim 4, wherein the epoxidized soybean oil has an epoxy value of greater than 0.060mol/100 g.
10. The method for preparing a cyclocarboxylated soybean oil (meth) acrylate resin according to claim 5, wherein the epoxidized soybean oil and the aldehyde (meth) acrylate are fed in a molar ratio of 1.0 to (1.0 to 1.1) of epoxy groups to aldehyde groups, and the onium salt catalyst is fed in a molar amount of 1 to 5% of the aldehyde (meth) acrylate.
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| CN110945045A (en) * | 2017-09-19 | 2020-03-31 | 三菱瓦斯化学株式会社 | Epoxy (meth) acrylate resin, curable resin composition, and cured product |
Non-Patent Citations (2)
| Title |
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| SANG-BONG LEE等: "N-Benzylpyridinium salts as new useful catalysts for transformation of epoxides to cyclic acetals, ortho esters, and ortho carbonates", CHEMISTRY LETTERS, no. 11, pages 2019 - 2022, XP002994521, DOI: 10.1246/cl.1990.2019 * |
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