阅读说明：本技术 一种基于环氧大豆油的光固化树脂及其制备方法 (A kind of light-cured resin and preparation method thereof based on epoxidized soybean oil ) 是由 严文斌 欧阳丽伟 于 2019-09-24 设计创作，主要内容包括：本发明公开了一种基于环氧大豆油的光固化树脂,按质量百分数计,包括20-40％阳离子光固化组分A、10-20％阳离子光固化组分B1、15-50％自由基光固化组分、1-8％阳离子光引发剂、1-8％自由基光引发剂和0-10％增韧剂；其中,阳离子光固化组分A为环氧大豆油,阳离子光固化组分B包括脂环族环氧单体,环氧大豆油和脂环族环氧单体的质量比为2-4:1；本发明通过在环氧大豆油中加入脂环族环氧单体,进行光固化反应时,脂环族环氧单体可提高环氧大豆油阳离子光固化活性,使基于环氧大豆油制备的光固化树脂快速成型。本发明所提供的基于环氧大豆油的光固化树脂的制备方法,制备工艺简单且易于工业化生产,并且生产成本低。(The invention discloses a kind of light-cured resins based on epoxidized soybean oil, by mass percentage, including 20-40% cation photocuring component A, 10-20% cation photocuring component B1,15-50% radical UV curing component, 1-8% cation light initiator, 1-8% free radical photo-initiation and 0-10% toughener；Wherein, cation photocuring component A is epoxidized soybean oil, and cation photocuring component B includes cycloaliphatic epoxy monomer, and the mass ratio of epoxidized soybean oil and cycloaliphatic epoxy monomer is 2-4:1；The present invention in epoxidized soybean oil by being added cycloaliphatic epoxy monomer, and when carrying out photocuring reaction, epoxidized soybean oil cation photocuring activity is can be improved in cycloaliphatic epoxy monomer, makes the light-cured resin rapid shaping prepared based on epoxidized soybean oil.The preparation method of light-cured resin provided by the present invention based on epoxidized soybean oil, preparation process is simple and easy to industrialized production, and production cost is low.)

1. a kind of light-cured resin based on epoxidized soybean oil, which is characterized in that by mass percentage, including following components:

Wherein, the cation photocuring component A is epoxidized soybean oil, and the cation photocuring component B1 is alicyclic epoxy Monomer；The epoxidized soybean oil and the mass ratio of cycloaliphatic epoxy monomer are 2-4:1.

2. the light-cured resin according to claim 1 based on epoxidized soybean oil, which is characterized in that the epoxidized soybean oil Structure it is as shown in Equation 1:

3. the light-cured resin according to claim 1 or 2 based on epoxidized soybean oil, which is characterized in that described alicyclic Epoxy monomer is 3,4- epoxycyclohexyl-methyl 3,4- epoxycyclohexyl formic acid esters, and structure is as shown in Equation 2:

4. the light-cured resin according to claim 1 based on epoxidized soybean oil, which is characterized in that further include cationic photopolymerization Curing component B2, by mass percentage, the content of the cation photocuring component B2 are 0-40%, and the cationic photopolymerization is solid Change component B2 is aliphatic glycidyl ether monomer, and the aliphatic glycidyl ether monomer is benzyl glycidyl ether, phenyl The mixture of one or more of glycidol ether, 1,4 butanediol diglycidyl ethers.

5. the light-cured resin according to claim 1 based on epoxidized soybean oil, which is characterized in that the free radical light is solid Agent is made of acrylate monomer and acrylic ester prepolymer mixing.

6. the light-cured resin according to claim 5 based on epoxidized soybean oil, which is characterized in that the acrylate is pre- Polymers is the mixture of one or more of epoxy acrylate, urethane acrylate, polyester acrylate.

7. the light-cured resin according to claim 5 based on epoxidized soybean oil, which is characterized in that the acrylate is pre- Polymers is made of epoxy acrylate and polyester acrylate mixing.

8. the light-cured resin according to claim 1 based on epoxidized soybean oil, which is characterized in that the cationic photopolymerization draws Hair agent is the phosphate without antimony.

9. the light-cured resin according to claim 1 based on epoxidized soybean oil, which is characterized in that the free radical light draws Hair agent is cracking type free radical photo-initiation.

10. a kind of preparation method of the light-cured resin based on epoxidized soybean oil, which comprises the following steps:

S1: 20-40% cation photocuring component A, 10-20% cation photocuring component B1,15-50% free radical light is consolidated After agent, 1-8% free radical photo-initiation and the mixing of 0-10% toughener, it is warming up to 50-70 DEG C, isothermal reaction 0.5-5h stops Only heat；

S2: the temperature to the mixed material in step S1 is down to 35 DEG C hereinafter, addition 1-8% cation light initiator, reaction 0.5-5h obtains the light-cured resin based on epoxidized soybean oil.

Technical field

The present invention relates to Photocurable composition correlative technology fields, and in particular to a kind of photocuring based on epoxidized soybean oil Resin and preparation method thereof.

Background technique

In recent years, 3D printing technique is grown rapidly, in industrial modeling, machine-building, military affairs, building, video display, family It is all used widely in the fields such as electric light industry, medicine, archaeology, culture and arts, agricultural.Wherein, using photocuring as moulding process 3D printing technique, such as the molding of data photocuring, stereolithography, polymeric spray, continuous liquid level, have printing precision Height, product surface smooth finish, resolution ratio is outstanding, and details shows the advantages such as outstanding, becomes current high-end, Arts 3D printing One preferred technique.

Light-cured resin is the core of photocuring 3D printing technique, and it is to stablize beating for liquid under feed states that it, which is a kind of, Material is printed, composition may include the components such as polymer monomer, prepolymer, photoinitiator, promotor, diluent.It was printing Cheng Zhong, this resinoid can be fast curing-formed under the irradiation of ultraviolet light or visible light that printing device is launched.Currently Report that 3D printing is more with solidified resin type, research and development are also more active, but are able to enter using commercialized limited.Shadow at present Ringing the biggest obstacle that light-cured resin is applied in 3D printing is its high raw material and manufacturing cost, even generally the least expensive quotient Industry 3D printing light-cured resin, price cause the popularization of photocuring 3D printing technique and general also in 500 yuan/kilogram or more And there are certain difficulty.

Soybean oil is the big edible oil kind in China first, and from a wealth of sources, cheap, soybean oil belongs to the vegetable oil of semi-drying Rouge has more double bond on triglycerides chain, and the modification and derivatization to double bond on soybean oil can obtain a variety of valuable Derivative.Wherein, the broad interest that UV-cured resin has caused researchers is prepared by raw material of soybean oil.This The route of class light-cured resin is general are as follows: (1) first by soybean oil, epoxidation obtains epoxy under hydrogen peroxide and organic acid effect Soybean oil；(2) ring-opening reaction occurs for epoxidized soybean oil and acrylic acid, generates epoxy soybean oil acrylate；(3) it is added appropriate Photoinitiator is solidified under ultraviolet light.Used initiator is mainly ultraviolet initiator such as 1- hydroxy-cyclohexyl Phenyl ketone etc..In most report, used with light-cured resin prepared by soybean oil mainly as coating etc., but also have very Few example has studied application of the soybean oil light-cured resin in terms of 3D printing, such as Shida Miao report it is big with epoxy Soya bean oil acrylate is in the case where bis- (2,4, the 6- trimethylbenzoyl) phosphine oxides of ultraviolet initiator phenyl cause, with three-dimensional plate Photocuring mode is printed, carries out 3D printing under 355 ultraviolet laser irradiation.

But there are no actual applications on 3D printing resin for current epoxidized soybean oil, essentially consist in epoxidized soybean oil because of it Strand itself is longer, and steric hindrance is larger, is unfavorable for the attack of cation group, influences the reaction of cation photocuring part Activity causes product initial strength inadequate, or even can not form.

Summary of the invention

For above-mentioned technical problem of the existing technology, the present invention provides a kind of photocuring tree based on epoxidized soybean oil Cycloaliphatic epoxy monomer is added on the basis of using epoxidized soybean oil in rouge, and the cation photocuring of epoxidized soybean oil can be improved Partial reactivity promotes the rapid curing of light-cured resin；The present invention also provides the preparation method of the light-cured resin, Simple process is easy to industrialization production and at low cost.To achieve the goals above, technical scheme is as follows:

A kind of light-cured resin based on epoxidized soybean oil, by mass percentage, including following components:

Wherein, the cation photocuring component A is epoxidized soybean oil, and the cation photocuring component B1 is alicyclic Epoxy monomer；The epoxidized soybean oil and the mass ratio of the cycloaliphatic epoxy monomer are 2-4:1.

Further, the structure of the epoxidized soybean oil is as shown in Equation 1:

Further, the cycloaliphatic epoxy monomer be 3,4- epoxycyclohexyl-methyl 3,4- epoxycyclohexyl formic acid esters, Its structure is as shown in Equation 2:

It further, further include cation photocuring component B2, by mass percentage, the cation photocuring component The content of B2 is 0-40%, and the cation photocuring component B2 is aliphatic glycidyl ether monomer, and the aliphatic is shunk Glycerol ether monomer be benzyl glycidyl ether, phenyl glycidyl ether, the one of which in 1,4 butanediol diglycidyl ethers or Two or more mixtures.

Further, the radical UV curing agent is made of acrylate monomer and acrylic ester prepolymer mixing.

Further, the acrylic ester prepolymer is epoxy acrylate, urethane acrylate, polyester acrylate One or more of mixture.

Further, the acrylic ester prepolymer is made of epoxy acrylate and polyester acrylate mixing.

Further, the cation light initiator is the phosphate without antimony.

Further, the free radical photo-initiation is cracking type free radical photo-initiation.

The present invention also provides a kind of preparation methods of light-cured resin based on epoxidized soybean oil, comprising the following steps:

S1: by 20-40% cation photocuring component A, 10-20% cation photocuring component B1,15-50% free radical After light curing agent, 1-8% free radical photo-initiation and the mixing of 0-10% toughener, it is warming up to 50-70 DEG C, isothermal reaction 0.5- 5h stops heating；

S2: the temperature to the mixed material in step S1 is down to 35 DEG C hereinafter, 1-8% cation light initiator is added, instead 0.5-5h is answered, the light-cured resin based on epoxidized soybean oil is obtained.

Compared to the prior art, beneficial effects of the present invention are as follows:

The present invention is by mixing cycloaliphatic epoxy monomer with epoxidized soybean oil, when carrying out photocuring reaction, because epoxy is big Soya-bean oil and the active constituent of cycloaliphatic epoxy monomer are all epoxy groups, and wherein the epoxy group in epoxidized soybean oil is due to being in Among chain, the epoxy group that steric hindrance is unfavorable in the attack of cationic species, especially long-chain is had occurred and that After cross-linking reaction, the steric hindrance of remaining epoxy group can be bigger, be less useful for reacting, and cycloaliphatic epoxy monomer due to The ring strain of its hexatomic ring, the epoxy group being attached thereto are particularly easy to ring-opening polymerisation, therefore the addition energy of cycloaliphatic epoxy monomer The activity for enough increasing epoxidized soybean oil cationic portion (i.e. epoxy group), so that light-cured resin be made to form rapidly；Moreover, choosing Use epoxidized soybean oil as the raw material of light-cured resin, raw material sources are easy to get extensively, and price is low, and cost is small, and And because its chain length is longer, there is better flexibility and more environmentally-friendly compared to traditional bisphenol A type epoxy resin.

In addition, the preparation method of the light-cured resin provided by the invention based on epoxidized soybean oil, preparation process and preparation Condition is simple, and easy to industrialized production, and production cost is low.

Specific embodiment

The present invention is intended to provide a kind of light-cured resin based on epoxidized soybean oil, the light-cured resin is with epoxidized soybean oil For reaction raw materials, the reactivity of cycloaliphatic epoxy monomer excitation epoxidized soybean oil is added, it can rapid curing and with higher Mechanical performance, by mass percentage, which includes following components:

Wherein, the cation photocuring component A is epoxidized soybean oil, and the cation photocuring component B1 is alicyclic Epoxy monomer；The epoxidized soybean oil and the mass ratio of the cycloaliphatic epoxy monomer are 2-4:1.

Further, the structure of the epoxidized soybean oil is as shown in Equation 1:

Further, the cycloaliphatic epoxy monomer be 3,4- epoxycyclohexyl-methyl 3,4- epoxycyclohexyl formic acid esters, Its structure is as shown in Equation 2:

It further, further include cation photocuring component B2, by mass percentage, the cation photocuring component The content of B2 is 0-40%, and the cation photocuring component B2 is aliphatic glycidyl ether monomer；Preferably, the fat Degree of functionality≤2 of race's glycidyl ether monomers；It is further preferable that aliphatic glycidyl ether monomer be benzyl glycidyl ether, The mixture of one or more of phenyl glycidyl ether, 1,4 butanediol diglycidyl ethers.

Further, the radical UV curing agent is made of acrylate monomer and acrylic ester prepolymer mixing.

Further, degree of functionality >=3 of the acrylate monomer.

Further, the acrylic ester prepolymer is epoxy acrylate, urethane acrylate, polyester acrylate One or more of mixture；Preferably, the acrylic ester prepolymer is by epoxy acrylate and polyacrylic acid Ester mixing composition.

Further, the cation light initiator is the phosphate without antimony, and general cation light initiator is containing a huge sum of money Belong to antimony, it is larger to environmental hazard, and the phosphate without antimony is used to avoid the harm to environment, make the light-cured resin more Environmental protection；Preferably, using the hexafluorophosphate for being free of antimony, the absorption to light can be increased, to improve consolidating for light-cured resin Change efficiency.

Further, the free radical photo-initiation is cracking type free radical photo-initiation, including but not limited to.

Further, the toughener is white toughener.

The present invention also provides the preparation methods of the above-mentioned light-cured resin based on epoxidized soybean oil, include the following steps:

S1: 20-40% cation photocuring component A, 10-20% cation photocuring component B1,15-50% is free After base, 1-8% free radical photo-initiation and the mixing of 0-10% toughener, it is warming up to 50-70 DEG C, isothermal reaction 0.5-5h, is stopped Heating；

S2: 35 DEG C are down to hereinafter, addition 1-8% cation light initiator, reaction to the mixed material temperature in step S1 0.5-5h obtains the light-cured resin based on epoxidized soybean oil.

The preparation method of the light-cured resin provided by the present invention, preparation process is simple and raw material sources are extensive, production It is at low cost.

Below in conjunction in specific embodiments of the present invention, technical solution in the embodiment of the present invention carries out clear, complete Site preparation description, it is clear that described embodiment is only a part of the embodiments of the present invention, instead of all the embodiments.Base Embodiment in the present invention, it is obtained by those of ordinary skill in the art without making creative efforts it is all its His embodiment, shall fall within the protection scope of the present invention.

For the effect of product used in clear embodiment, applicant lists the common product of related component, specifically As shown in table 1.

Name of product used in 1 embodiment of table and its corresponding ingredient names