CN105037158B - A kind of dibasic alcohol hyperbranched monomer based on maleic anhydride and preparation method thereof - Google Patents

Abstract

The invention relates to a dihydric alcohol hyperbranched monomer based on maleic anhydride. The structural formula of the monomer is shown in the description, wherein HO-(CH2)n-OH is divalent alcohol, and n is not smaller than 4. The dihydric alcohol hyperbranched monomer has the advantages as follows: (1) the monomer has four degree of functionality, is high in double bond conversion rate, and good in thermal stability; (2) the monomer is better in adhesive force and better in hardness, and can be applied to the field of paint; other advantages are also achieved. The invention also relates to a preparation method of the dihydric alcohol hyperbranched monomer based on maleic anhydride, and the preparation method has the advantages of being few in reaction steps, short in preparation cycle, simple and convenient to operate, easy to control and the like.

Description

A kind of dibasic alcohol hyperbranched monomer based on maleic anhydride and preparation method thereof

technical field

The invention relates to the technical field of photosensitive polymer materials, in particular to a hyperbranched acrylate based on maleic anhydride as a photopolymerizable monomer.

Background technique

Photopolymerization (also known as photocuring) technology is the process of using light (ultraviolet light or visible light) to trigger the rapid transformation of chemically reactive liquid substances into solid substances. It is a new green technology that came out in the 1960s. In 1946, Inmont Corporation of the United States published the patent for unsaturated polyester/styrene UV curing ink for the first time. By the end of the 1980s, UV curing technology had maintained an average annual growth rate of more than 15%. Since the mid-1990s, it has been growing rapidly at an annual rate of nearly 10%, and there is still a growing trend in some fields. Light curing technology has the characteristics of high efficiency, wide adaptability, economy, energy saving, and environmental friendliness. These characteristics meet the requirements of environmental protection and energy saving in various countries in the world today. fields of biomaterials.

The difference between photocuring technology and traditional thermal curing technology is that photocuring reaction is essentially a polymerization and crosslinking reaction initiated by ultraviolet light. Any photocuring system includes at least the following three parts: (1) oligomer (or (called prepolymer, resin), which endows the material with basic physical and chemical properties; (2) monomer, also known as reactive diluent, is mainly used to adjust the viscosity of the system, but it also affects the curing rate and the performance of the material; (3) ) Photoinitiator, used to generate active species (free radicals or cations) that initiate polymerization.

Reactive diluents are generally small molecules containing polymerizable functional groups, so they are also called "monomers" in the industry. Reactive diluents can usually participate in the polymerization and crosslinking process, unlike traditional solvent-based coatings and organic solvents in inks that volatilize into the air. Therefore, this advantage endows the photo-curing system with environmental protection characteristics. Reactive diluents can be divided into monofunctional reactive diluents and multifunctional reactive diluents according to the number of reactive groups contained in each molecule. Monofunctional reactive diluents contain only one group that can participate in the curing reaction in each molecule, such as β-hydroxyethyl methacrylate (HEMA). Multifunctional reactive diluents refer to reactive diluents that contain two or more groups that can participate in curing reactions in each molecule, such as 1,6-hexanediol diacrylate (HDDA). The use of monomers containing more functional groups can not only increase the reactivity, but also impart a cross-linked structure to the cured film.

In radiation curing compositions, monomers play a key role. In addition to adjusting the viscosity of the system, it can also affect the curing kinetics, the degree of polymerization, and the physical and mechanical properties of the resulting polymer. While the properties of the cured material are essentially determined by the oligomers used, major technical and safety concerns have to be taken into account with the properties of the monomers used.

According to the curing mechanism, reactive diluents can be divided into two types: free radical type and cationic type. (Meth) acrylates are typical free radical reactive diluents, and the curing reaction is carried out by free radical photopolymerization. Epoxy is a cationic reactive diluent, and its curing reaction mechanism is cationic polymerization. Vinyl ethers can participate in both free radical polymerization and cationic polymerization, so they can be used as reactive diluents for the two photocuring systems.

In the light-curing formulation system, reactive diluents and oligomers together account for more than 90% of the entire formulation quality, and determine the basic physical and chemical properties of the molded material. The ideal monomer has the following characteristics: (1) small polymerization shrinkage, high degree of curing (ie, high double bond conversion rate) and will not reduce the mechanical properties of the cured material; (2) good hydrophobicity; (3) cheap, synthetic Simple; (4) good stability, easy to store for a long time.

Among the monofunctional monomers used in the early days, such as n-butyl acrylate (n-BA) and isobutyl acrylate (i-BA) are highly volatile diluents, they were mainly used in the preparation of wood lacquers in the early days, and they are flammable, It has defects such as strong odor and low curing speed, so it is rarely used now. On the other hand, difunctional monomers contain two photoactive (meth)acrylate functional groups. The curing speed is faster than that of monofunctional monomers, and the crosslinking density of the film increases with the increase of crosslinking points, but it still maintains a good dilution effect. In addition, as the functionality of the monomer increases, the molecular weight becomes larger, its volatility gradually decreases, and the odor also decreases. DuyguAvci et al. used EHMA, HEA and HEMA as raw materials to react with _C18 bisacryloyl chloride to obtain a series of difunctional (meth)acrylate monomers with methylol groups. At the same time, its photopolymerization behavior was studied by DSC. This type of monomer contains a flexible long-chain structure, which can enhance the impact resistance and toughness of the material, and broaden its application field. (Duygu A, Jennifer N, Lon J M. Synthesis and photopolymerization kinetics of new flexible diacrylate crosslinkers based on C18diacid [J]. Polymer, 2003, 44:963-968) Generally speaking, acrylate monomers have a large shrinkage after photocuring and are resistant to Poor thermal performance affects the application fields of photocurable materials. Therefore, the design and development of new functional acrylate photoactive monomers is of great significance for expanding the application field of photocurable materials and preparing high-performance photocurable materials. Traditional urethane (meth)acrylates are generally prepared by the addition reaction of isocyanate and hydroxyl-bearing compounds. However, isocyanate has a pungent smell, has a strong stimulating effect on the skin, eyes and respiratory tract, and has relatively large toxic and side effects.

Contents of the invention

The object of the present invention is to provide a kind of dibasic alcohol branched monomer based on maleic anhydride, which has the following advantages:

(1) The monomer is tetrafunctional, with high double bond conversion rate and good thermal stability;

(2) The monomer has good adhesion and good hardness, and can be used in the field of coatings;

The object of the present invention is to provide a kind of preparation method of the dibasic alcohol branched monomer based on maleic anhydride, has the following advantages:

(1) The reaction steps are few, the preparation cycle is short, the operation is simple and easy to control.

The technical scheme that the present invention solves its technical problem is: a kind of glycol hyperbranched monomer based on maleic anhydride, its structural formula is as follows:

in It is dibasic alcohol, n≥4.

Specifically, the dihydric alcohol is one of ethylene glycol, propylene glycol, butanediol, pentanediol, hexylene glycol, and polyethylene glycol.

A kind of preparation method of the dibasic alcohol hyperbranched monomer based on maleic anhydride as above, comprises the steps:

Step 1: Prepare the first-generation product with dihydric alcohol, maleic anhydride and glycerol methacrylate as raw materials, and its structural formula is:

Step 2: take the first-generation product, maleic anhydride and glycerol methacrylate as raw materials to prepare the second-generation product, which is the target product: a dibasic alcohol hyperbranched monomer based on maleic anhydride, whose structural formula is:

As preferably, the concrete steps of described step one are:

(1) Add 1 part of dihydric alcohol and 3-4 parts of maleic anhydride into the reaction vessel, mix well, heat up to 60-70°C, and add catalyst and polymerization inhibitor, after the maleic anhydride melts, heat up to 80-85°C, continue to stir for 4 hours, cool to room temperature, extract the product with ethyl acetate, wash with water 2 to 3 times, filter, dry, and remove the solvent to obtain an intermediate product;

(2) Add 2-3 parts of glycidyl methacrylate, catalyst and solvent into the reaction vessel, raise the temperature to 70°C, and drop 1 part of the intermediate product in step (1) into the reactor dropwise, at 0.5 The drop was completed within -1 hour, then the reaction system was heated to 85°C, continued to stir for 5 hours, then cooled to room temperature, the product was extracted with ethyl acetate, washed 2 to 3 times with water, filtered, dried, and the solvent was removed to obtain the first generation product.

As preferably, the concrete steps of described step 2 are:

(1) Add 1 part of the first-generation product G1 and 3-4 parts of maleic anhydride into the reaction vessel, mix well, heat up to 60-70°C, add catalyst and polymerization inhibitor, after the maleic anhydride melts, heat up to 80-85°C, continue to stir for 4 hours, cool to room temperature, extract the product with ethyl acetate, wash with water 2 to 3 times, filter, dry, and remove the solvent to obtain an intermediate product;

(2) Add 2-3 parts of glycidyl methacrylate, catalyst and solvent into the reaction vessel, raise the temperature to 70°C, and drop 1 part of the intermediate product in step (1) into the reactor dropwise, at 0.5 Dropping is completed within -1 hour, then the temperature of the reaction system is raised to 85°C, and after stirring for 5 hours, it is cooled to room temperature, the product is extracted with ethyl acetate, washed with water for 2 to 3 times, filtered, dried, and the solvent is removed to obtain the second generation product.

Specifically, the catalyst in the step (1) is one of concentrated sulfuric acid, concentrated hydrochloric acid, p-toluenesulfonic acid, methanesulfonic acid and thionyl chloride, and its added weight is 2-5wt% of the reaction system.

Specifically, the polymerization inhibitor in the step (1) is one of p-hydroxyanisole, cuprous chloride, hydroquinone, p-benzoquinone and 2,5-dimethylhydroquinone, which The added weight is 1-5wt‰ of the reaction system.

Specifically, the catalyst in the step (2) is one of tetrabutylammonium bromide, tetramethylammonium chloride, triethylamine, N,N-dimethylaniline and triphenylphosphine, which The added weight is 2-5wt% of the reaction system.

The present invention starts from molecular structure design, (taking butanediol as an example) at first two hydroxyl groups on the dibasic alcohol open the acid anhydride structure on the maleic anhydride, generate intermediate product G0.5, then through the two hydroxyl groups on G0.5 The carboxyl group opens the epoxy structure on GMA to obtain the first-generation product G1, and then the two hydroxyl groups on G1 open the anhydride structure on the maleic anhydride to generate the intermediate product G1.5, and then the two carboxyl groups on G1.5 open the GMA. Epoxy structure, to obtain the second generation product, the final product G2.

The whole reaction equation of a kind of glycol branched monomer based on maleic anhydride prepared by the present invention can be expressed as: (taking 1,4-butanediol as example)

Description of drawings

The present invention will be further described below in conjunction with the accompanying drawings and embodiments.

Fig. 1 is the photopolymerization double bond conversion rate-time diagram of the G2 that cleavage type initiator 184 triggers embodiment 1 to obtain;

Fig. 2 is the thermogravimetric curve graph of each formulation along with temperature increasing.

detailed description

The present invention is described in further detail now in conjunction with accompanying drawing. These drawings are all simplified schematic diagrams, which only illustrate the basic structure of the present invention in a schematic manner, so they only show the configurations related to the present invention.

Example 1

(1) Add 0.1mol (9.1g) butanediol and 0.3mol (29.4g) maleic anhydride into the reaction vessel, mix well, stir and heat up to 60°C, and add the catalyst p-toluenesulfonic acid (0.77g, react 2wt% of the system) and polymerization inhibitor p-hydroxyanisole (0.19g, 5wt‰ of the reaction system), after the maleic anhydride melted, the temperature was raised to 80°C, and after stirring for 4h, the product was extracted with ethyl acetate, and then Wash with water 2 to 3 times, filter, dry over anhydrous sodium sulfate, and distill off the solvent under reduced pressure to obtain the first-generation product G0.5.

(2) Glycidyl methacrylate (GMA) of 0.2mol (28.4g), catalyst tetrabutylammonium chloride (1.14g, 2wt% of the reaction system) and inhibitor p-hydroxyanisole (0.29g , 5wt‰ of the reaction system) was added to the reaction vessel, the temperature was raised to 70°C, and 1 part of G0.5 (0.1mol, 28.8g) was dropped into the reactor drop by drop, and the drop was completed within 0.5h, and then the reaction system Raise the temperature to 80°C, continue to stir for 4 hours, then cool to room temperature, extract the product with ethyl acetate, wash 2 to 3 times with water, filter, dry with anhydrous sodium sulfate, and rotary evaporate to obtain the first generation product G1.

(3) Add 0.1mol (57.05g) of the first generation product G1, 0.3mol (29.4g) of maleic anhydride into the reaction vessel, mix well, stir and heat up to 60°C, and add the catalyst p-toluenesulfonic acid ( 1.73g, 2wt% of the reaction system) and polymerization inhibitor p-hydroxyanisole (0.43g, 5wt‰ of the reaction system), after the maleic anhydride melted, the temperature was raised to 80°C, and after continuing to stir for 4h, it was cooled to room temperature. The product was extracted with ethyl acetate, washed 2-3 times with water, filtered, dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure to obtain the intermediate product G1.5.

(4) Glycidyl methacrylate (GMA) of 0.2mol (28.4g), catalyst tetrabutylammonium chloride (1.98g, 2wt% of the reaction system) and inhibitor p-hydroxyanisole (0.49g , 5wt‰ of the reaction system) was added to the reaction vessel, the temperature was raised to 70°C, and 1 part of G1.5 (0.1mol, 70.6g) was dropped into the reactor drop by drop, and the drop was completed within 0.5h, and then the reaction system Heat up to 80°C, continue stirring for 4 hours, cool to room temperature, extract the product with ethyl acetate, wash with water 2 to 3 times, filter, dry over anhydrous sodium sulfate, and distill off the solvent under reduced pressure to obtain the second-generation product G2. That is, 105.1 g of the target product.

The basic physical properties of the product are tested: viscosity (cps@25°C) 1010, chromaticity (APHA/Gardner) 380, refractive index 1.517, surface tension (Dynes/cm@20°C) 82.3.

Example 2

(1) Add 0.1mol (9.1g) butanediol and 0.3mol (29.4g) maleic anhydride into the reaction vessel, mix well, stir and heat up to 60°C, and add the catalyst p-toluenesulfonic acid (0.77g, react 2wt% of the system) and polymerization inhibitor p-hydroxyanisole (0.19g, 5wt‰ of the reaction system), after the maleic anhydride melted, the temperature was raised to 80°C, and after stirring for 4h, the product was extracted with ethyl acetate, and then Wash with water 2 to 3 times, filter, dry over anhydrous sodium sulfate, and distill off the solvent under reduced pressure to obtain the first-generation product G0.5. .

(2) Glycidyl methacrylate (GMA) of 0.21mol (29.9g), catalyst tetrabutylammonium chloride (1.17g, 2wt% of reaction system) and polymerization inhibitor p-hydroxyanisole (0.29g , 5wt‰ of the reaction system) was added to the reaction vessel, the temperature was raised to 70°C, and 1 part of the reaction product (0.1mol, 28.8g) in step (1) was dropped into the reactor dropwise, and the dropwise was completed within 0.5h , then the reaction system was heated up to 80°C, continued to stir for 4 hours, cooled to room temperature, extracted the product with ethyl acetate, washed 2 to 3 times with water, filtered, dried over anhydrous sodium sulfate, and distilled off the solvent under reduced pressure to obtain the first The first generation product G1.

(3) Add 0.1mol (50.05g) of the first generation product G1, 0.3mol (29.4g) of maleic anhydride into the reaction vessel, mix well, stir and heat up to 60°C, and add the catalyst p-toluenesulfonic acid ( 1.59g, 2wt% of the reaction system) and polymerization inhibitor p-hydroxyanisole (0.39g, 5wt‰ of the reaction system), after the maleic anhydride melted, the temperature was raised to 80°C, and after continuing to stir for 4h, it was cooled to room temperature. The product was extracted with ethyl acetate, washed 2-3 times with water, filtered, dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure to obtain the intermediate product G1.5.

(4) Glycidyl methacrylate (GMA) of 0.21mol (29.9), catalyst tetrabutylammonium chloride (2.04g, 2wt% of reaction system) and polymerization inhibitor p-hydroxyanisole (0.51g, 5wt‰) of the reaction system was added to the reaction vessel, and the temperature was raised to 70°C, and 1 part of G1.5 (0.1mol, 72.2g) was dropped into the reactor dropwise, and the drop was completed within 0.5h, and then the temperature of the reaction system was raised to 80°C, continue stirring for 4 hours, cool to room temperature, extract the product with ethyl acetate, wash with water 2 to 3 times, filter, dry over anhydrous sodium sulfate, and distill off the solvent under reduced pressure to obtain the second-generation product G2, namely Target product 103.2 g.

The basic physical properties of the product are tested: viscosity (cps@25°C) 1005, chromaticity (APHA/Gardner) 374, refractive index 1.613, surface tension (Dynes/cm@20°C) 81.3.

Example 3

(1) Add 0.1mol (9.1g) butanediol and 0.3mol (29.4g) maleic anhydride into the reaction vessel, mix well, stir and heat up to 60°C, and add the catalyst p-toluenesulfonic acid (0.77g, react 2wt% of the system) and polymerization inhibitor p-hydroxyanisole (0.19g, 5wt‰ of the reaction system), after the maleic anhydride melted, the temperature was raised to 80°C, and after stirring for 4h, the product was extracted with ethyl acetate, and then Wash with water 2 to 3 times, filter, dry over anhydrous sodium sulfate, and distill off the solvent under reduced pressure to obtain the first-generation product G0.5. .

(2) Glycidyl methacrylate (GMA) of 0.22mol (31.28g), catalyst tetrabutylammonium chloride (1.21g, 2wt% of reaction system) and polymerization inhibitor p-hydroxyanisole (0.30g , 5wt‰ of the reaction system) was added to the reaction vessel, the temperature was raised to 70°C, and 1 part of the reaction product (0.1mol, 28.8g) in step (1) was dropped into the reactor dropwise, and the dropwise was completed within 0.5h , then the reaction system was heated up to 80°C, continued to stir for 4 hours, cooled to room temperature, extracted the product with ethyl acetate, washed 2 to 3 times with water, filtered, dried over anhydrous sodium sulfate, and distilled off the solvent under reduced pressure to obtain the first The first generation product G1.

(3) Add 0.1mol (48.01g) of the first generation product G1, 0.3mol (29.4g) of maleic anhydride into the reaction vessel, mix well, stir and heat up to 60°C, and add the catalyst p-toluenesulfonic acid ( 1.55g, 2wt% of the reaction system) and polymerization inhibitor p-hydroxyanisole (0.39g, 5wt‰ of the reaction system), after the maleic anhydride melted, the temperature was raised to 80°C, and after continuing to stir for 4h, it was cooled to room temperature. The product was extracted with ethyl acetate, washed 2-3 times with water, filtered, dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure to obtain the intermediate product G1.5.

(4) Glycidyl methacrylate (GMA) of 0.22mol (31.28g), catalyst tetrabutylammonium chloride (2.03g, 2wt% of reaction system) and polymerization inhibitor p-hydroxyanisole (0.51g , 5wt‰ of the reaction system) was added to the reaction vessel, the temperature was raised to 70°C, and 1 part of G1.5 (0.1mol, 70.6g) was dropped into the reactor drop by drop, and the drop was completed within 0.5h, and then the reaction system Heat up to 80°C, continue stirring for 4 hours, cool to room temperature, extract the product with ethyl acetate, wash with water 2 to 3 times, filter, dry over anhydrous sodium sulfate, and distill off the solvent under reduced pressure to obtain the second-generation product G2. That is, 104.9 g of the target product.

The basic physical properties of the product are tested: viscosity (cps@25°C) 1003, chromaticity (APHA/Gardner) 372, refractive index 1.601, surface tension (Dynes/cm@20°C) 80.3.

Example 4

(1) Add 0.1mol (9.1g) butanediol and 0.3mol (29.4g) maleic anhydride into the reaction vessel, mix well, stir and heat up to 70°C, and add catalyst p-toluenesulfonic acid (0.77g, react 2wt% of the system) and the polymerization inhibitor p-hydroxyanisole (0.19g, 5wt‰ of the reaction system), after the maleic anhydride melted, the temperature was raised to 80°C, and after stirring for 4h, it was cooled to room temperature and washed with ethyl acetate The product was extracted, washed with water for 2-3 times, filtered, dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure to obtain the intermediate product G0.5.

(2) Glycidyl methacrylate (GMA) of 0.22mol (31.28g), catalyst tetrabutylammonium chloride (2.03g, 2wt% of reaction system) and polymerization inhibitor p-hydroxyanisole (0.51g , 5wt‰ of the reaction system) was added to the reaction vessel, the temperature was raised to 70°C, and 1 part of the reaction product (0.1mol, 28.8g) in step (1) was dropped into the reactor dropwise, and the dropwise was completed within 0.5h , then the reaction system was heated up to 80°C, continued to stir for 4 hours, cooled to room temperature, extracted the product with ethyl acetate, washed 2 to 3 times with water, filtered, dried over anhydrous sodium sulfate, and distilled off the solvent under reduced pressure to obtain the first The first generation product G1.

(3) Add 0.1mol (48.01g) of the first generation product G1, 0.3mol (29.4g) of maleic anhydride into the reaction vessel, mix well, stir and heat up to 70°C, and add the catalyst p-toluenesulfonic acid ( 1.55g, 2wt% of the reaction system) and polymerization inhibitor p-hydroxyanisole (0.39g, 5wt‰ of the reaction system), after the maleic anhydride melted, the temperature was raised to 80°C, and after continuing to stir for 4h, it was cooled to room temperature. The product was extracted with ethyl acetate, washed 2-3 times with water, filtered, dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure to obtain the intermediate product G1.5.

(4) Glycidyl methacrylate (GMA) of 0.22mol (31.28g), catalyst tetrabutylammonium chloride (2.03g, 2wt% of reaction system) and polymerization inhibitor p-hydroxyanisole (0.51g , 5wt‰ of the reaction system) was added to the reaction vessel, the temperature was raised to 70°C, and 1 part of G1.5 (0.1mol, 70.6g) was dropped into the reactor drop by drop, and the drop was completed within 0.5h, and then the reaction system Heat up to 80°C, continue stirring for 4 hours, cool to room temperature, extract the product with ethyl acetate, wash with water 2 to 3 times, filter, dry over anhydrous sodium sulfate, and distill off the solvent under reduced pressure to obtain the second-generation product G2. That is, 104.1 g of the target product.

The basic physical properties of the product are tested: viscosity (cps@25°C) 1008, chromaticity (APHA/Gardner) 381, refractive index 1.589, surface tension (Dynes/cm@20°C) 84.3.

Example 5

(1) Add 0.1mol (9.1g) butanediol and 0.33mol (32.34g) maleic anhydride into the reaction vessel, mix well, stir and heat up to 70°C, and add the catalyst p-toluenesulfonic acid (1.24g, react 3wt% of the system) and the polymerization inhibitor p-hydroxyanisole (0.17g, 4wt‰ of the reaction system), after the maleic anhydride melted, the temperature was raised to 80°C, and after stirring for 4h, it was cooled to room temperature and washed with ethyl acetate The product was extracted, washed with water for 2-3 times, filtered, dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure to obtain the intermediate product G0.5.

(2) Glycidyl methacrylate (GMA) of 0.22mol (31.28g), catalyst tetrabutylammonium chloride (2.03g, 2wt% of reaction system) and polymerization inhibitor p-hydroxyanisole (0.51g , 5wt‰ of the reaction system) was added to the reaction vessel, the temperature was raised to 70°C, and 1 part of the reaction product (0.1mol, 28.8g) in step (1) was dropped into the reactor dropwise, and the dropwise was completed within 0.5h , then the reaction system was heated up to 85°C, continued to stir for 4 hours, cooled to room temperature, extracted the product with ethyl acetate, washed with water 2 to 3 times, filtered, dried over anhydrous sodium sulfate, and distilled off the solvent under reduced pressure to obtain the first The first generation product G1.

(3) Add 0.1mol (48.01g) of the first generation product G1, 0.33mol (32.34g) of maleic anhydride into the reaction vessel, mix well, stir and heat up to 70°C, and add the catalyst p-toluenesulfonic acid ( 2.41g, 3wt% of the reaction system) and the polymerization inhibitor p-hydroxyanisole (0.32g, 4wt‰ of the reaction system), after the maleic anhydride melts, the temperature is raised to 80°C, and after continuing to stir for 4h, it is cooled to room temperature. The product was extracted with ethyl acetate, washed with water 2-3 times, filtered, dried over anhydrous sodium sulfate, and solvent G1.5 was distilled off under reduced pressure.

(4) Glycidyl methacrylate (GMA) of 0.22mol (31.28g), catalyst tetrabutylammonium chloride (2.03g, 2wt% of reaction system) and polymerization inhibitor p-hydroxyanisole (0.51g , 5wt‰ of the reaction system) was added to the reaction vessel, the temperature was raised to 70°C, and 1 part of G1.5 (0.1mol, 70.6g) was dropped into the reactor drop by drop, and the drop was completed within 0.5h, and then the reaction system Heat up to 85°C, continue stirring for 4 hours, cool to room temperature, extract the product with ethyl acetate, wash with water 2 to 3 times, filter, dry over anhydrous sodium sulfate, and distill off the solvent under reduced pressure to obtain the second-generation product G2, namely 100.4 g of the target product.

The basic physical properties of the product are tested: viscosity (cps@25°C) 1008, chromaticity (APHA/Gardner) 381, refractive index 1.589, surface tension (Dynes/cm@20°C) 84.3.

Example 6

(1) Add 0.1mol (9.1g) butanediol and 0.35mol (34.3g) maleic anhydride into the reaction vessel, mix well, stir and heat up to 70°C, and add the catalyst p-toluenesulfonic acid (1.74g, react 4wt% of the system) and the polymerization inhibitor p-hydroxyanisole (0.22g, 5wt‰ of the reaction system), after the maleic anhydride melted, the temperature was raised to 80°C, and after stirring for 4h, it was cooled to room temperature and washed with ethyl acetate The product was extracted, washed with water for 2-3 times, filtered, dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure to obtain the intermediate product G0.5.

(2) Glycidyl methacrylate (GMA) of 0.25mol (35.55g), catalyst tetrabutylammonium chloride (1.29g, 2wt% of reaction system) and polymerization inhibitor p-hydroxyanisole (0.32g , 5wt‰ of the reaction system) was added to the reaction vessel, the temperature was raised to 70°C, and 1 part of the reaction product (0.1mol, 28.8g) in step (1) was dropped within 0.5h, and then the reaction system was heated to After continuing to stir for 4 hours at 85°C, cool to room temperature, extract the product with ethyl acetate, wash with water 2 to 3 times, filter, dry over anhydrous sodium sulfate, and distill off the solvent under reduced pressure to obtain the first-generation product G1.

(3) 0.1mol (48.01g) of the first-generation product G1, 0.35mol (34.3g) of maleic anhydride are added to the reaction vessel, mixed uniformly, stirred and heated to 70°C, and the catalyst p-toluenesulfonic acid ( 3.29g, 4wt% of the reaction system) and polymerization inhibitor p-hydroxyanisole (0.41g, 5wt‰ of the reaction system), after the maleic anhydride melted, the temperature was raised to 80°C, and after stirring for 4h, it was cooled to room temperature. The product was extracted with ethyl acetate, washed 2-3 times with water, filtered, dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure to obtain the intermediate product G1.5.

(4) Glycidyl methacrylate (GMA) of 0.25mol (31.28g), catalyst tetrabutylammonium chloride (2.04g, 2wt% of reaction system) and polymerization inhibitor p-hydroxyanisole (0.51g , 5wt‰ of the reaction system) was added to the reaction vessel, the temperature was raised to 70°C, and 1 part of G1.5 (0.1mol, 70.6g) was dropped into the reactor drop by drop, and the drop was completed within 0.5h, and then the reaction system Heat up to 85°C, continue stirring for 4 hours, cool to room temperature, extract the product with ethyl acetate, wash with water 2 to 3 times, filter, dry over anhydrous sodium sulfate, and distill off the solvent under reduced pressure to obtain the second-generation product G2. That is, 101.8 g of the target product.

The basic physical properties of the product are tested: viscosity (cps@25°C) 1001, chromaticity (APHA/Gardner) 376, refractive index 1.591, surface tension (Dynes/cm@20°C) 85.1.

Example 7

(1) Add 0.1mol (9.1g) butanediol and 0.4mol (39.2g) maleic anhydride into the reaction vessel, mix well, stir and heat up to 70°C, and add catalyst p-toluenesulfonic acid (0.97g, react 2wt% of the system) and the polymerization inhibitor p-hydroxyanisole (0.24g, 5wt‰ of the reaction system), after the maleic anhydride melted, the temperature was raised to 80°C, and after stirring for 4h, it was cooled to room temperature and washed with ethyl acetate The product was extracted, washed with water for 2-3 times, filtered, dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure to obtain the intermediate product G0.5.

(2) Glycidyl methacrylate (GMA) of 0.3mol (42.66g), catalyst tetrabutylammonium chloride (1.43g, 2wt% of reaction system) and polymerization inhibitor p-hydroxyanisole (0.36g , 5wt‰ of the reaction system) was added to the reaction vessel, the temperature was raised to 70°C, and 1 part of the reaction product (0.1mol, 28.8g) in step (1) was dropped within 0.5h, and then the reaction system was heated to After continuing to stir for 4 hours at 85°C, cool to room temperature, extract the product with ethyl acetate, wash with water 2 to 3 times, filter, dry with anhydrous sodium sulfate, and rotary evaporate to obtain the first-generation product G1.

(3) 0.1mol (48.01g) of the first-generation product G1 and 0.4mol (39.2g) of maleic anhydride are added to the reaction vessel, mixed uniformly, stirred and heated to 70°C, and the catalyst p-toluenesulfonic acid ( 1.74g, 2wt% of the reaction system) and the polymerization inhibitor p-hydroxyanisole (0.16g, 5wt‰ of the reaction system), after the maleic anhydride melted, the temperature was raised to 80°C, and after continuing to stir for 4h, the mixture was mixed with ethyl acetate The product was extracted, washed with water for 2-3 times, filtered, dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure to obtain the intermediate product G1.5.

(4) Glycidyl methacrylate (GMA) of 0.3mol (42.66g), catalyst tetrabutylammonium chloride (2.27g, 2wt% of the reaction system) and inhibitor p-hydroxyanisole (0.57g , 5wt‰ of the reaction system) was added to the reaction vessel, the temperature was raised to 70°C, and 1 part of G1.5 (0.1mol, 70.6g) was dropped into the reactor drop by drop, and in 0.5h After the internal drop is completed, the temperature of the reaction system is raised to 85°C, and after stirring for 4 hours, it is cooled to room temperature, and the product is extracted with ethyl acetate, washed with water for 2 to 3 times, filtered, dried over anhydrous sodium sulfate, and the solvent is removed by distillation under reduced pressure , to obtain the second-generation product G2, namely the target product 102.6g.

The basic physical properties of the product are tested: viscosity (cps@25°C) 418, chromaticity (APHA/Gardner) 169, refractive index 1.3208, surface tension (Dynes/cm@20°C) 44.8.

Application example:

Curing rate:

With the second-generation hyperbranched monomer obtained in Example 1, the second-generation hyperbranched monomer of butanediol and the cleavage-type photoinitiator 184 of different concentrations are formulated into a polymerization system (initiator concentration: 0.5%, 1%, 2%, 3%, 4%), and ultrasonically oscillate for 2 minutes to ensure that the system is evenly mixed. Then, take a small amount of sample and smear it on the potassium bromide tablet. / ^cm2 light intensity irradiates the sample for 5 minutes, and the RTIR equipped with a horizontal sample stage can intuitively reflect the degree of the polymerization system by monitoring the change of the peak area of the characteristic absorption peak of 800-850cm- ¹ acrylate double bond. Its specific formula is as follows:

formula Second generation hyperbranched monomer Initiator 184 1 4.0g 0.5% 2 4.0g 1% 3 4.0g 2% 4 4.0g 3% 5 4.0g 4%

The results are shown in Figure 1. As can be seen from Figure 1, the hyperbranched second-generation monomer G2 can be completely polymerized by ultraviolet light irradiation for 300 seconds. When the initiator concentration is 4%, the conversion rate of the acrylate double bond is close to 72.5%.

Thermodynamic properties:

The present invention carries out thermogravimetric analysis on the formula system prepared by G3, and adopts a general dental resin formula system (Guangzhou Chenfa Medical Instrument Co., Ltd.-resin CN1005, 60 parts; Sartomer Guangdong Chemical Co., Ltd.-thinner PETTA, 40 parts; Jining Mingda New Material Co., Ltd.-initiator camphorkun CQ, 1.5 parts; Tongqi Chemical Industry (Shanghai) Co., Ltd.-inorganic filler SiO ₂ , 50 parts), change the composition of the monomer (PETTA) and G2 therein Part and content, observe the thermal stability of the system. The results are shown in Figure 2. When G2 replaces the monomer PETTA, the thermal stability of the whole system is better, and it begins to decompose at about 330°C.

The present invention carries out adhesion performance test to the formula system prepared by G3, and the formula system adopted is:

The system formula is as follows: (Guangzhou Chenfa Medical Instrument Co., Ltd.-resin CN1005, 60 parts; Diluent G2, 40 parts; Jining Mingda New Material Co., Ltd.-initiator Camphorkun CQ, 1.5 parts; Tongqi Chemical (Shanghai) Co., Ltd. - inorganic filler SiO2, 50 parts)

Adhesion test of different materials: (ISO standard-T9999358)

Sample material grade PP 4 Iron sheets 0 100mm PET 0 200mmPET 0 50mmPET 0 Tinplate 2 Ordinary glass 1

Pencil hardness test:

The present invention carries out the pencil hardness test to the formula system prepared by G3, and the formula system adopted is:

The formula of the system is as follows: (Guangzhou Chenfa Medical Instrument Co., Ltd.-Resin CN1005, 60 parts; Diluent G2, 40 parts; Jining Mingda New Material Co., Ltd.-Initiator Camphorkun CQ, 1.5 parts; Tongqi Chemical (Shanghai) Co., Ltd. - inorganic filler SiO2, 50 parts)

pencil specification Test Results 6H break 5H break 4H not broken 3H not broken 2H not broken h not broken B not broken HB not broken

Inspired by the above-mentioned ideal embodiment according to the present invention, through the above-mentioned description content, relevant workers can make various changes and modifications within the scope of not departing from the technical idea of the present invention. The technical scope of the present invention is not limited to the content in the specification, but must be determined according to the scope of the claims.

Claims (8)

1. a kind of glycol hyperbranched monomer based on maleic anhydride, its structural formula is as follows: in It is dibasic alcohol, n≥4. 2. a kind of dibasic alcohol hyperbranched monomer based on maleic anhydride as claimed in claim 1, is characterized in that: described dibasic alcohol is the one in butanediol, pentanediol, hexanediol. 3. a kind of preparation method of the dibasic alcohol hyperbranched monomer based on maleic anhydride as claimed in claim 1, comprises the steps: Step 1: Prepare the first-generation product with dihydric alcohol, maleic anhydride and glycerol methacrylate as raw materials, and its structural formula is: n≥4 Step 2: take the first generation product, maleic anhydride and glycerol methacrylate as raw materials to prepare the second generation product, its structural formula is: n≥4. 4. a kind of preparation method based on the dibasic alcohol hyperbranched monomer of maleic anhydride as claimed in claim 3, is characterized in that: the concrete steps of described step 1 are: (1) Add 1 part of dihydric alcohol and 3-4 parts of maleic anhydride into the reaction vessel, mix well, heat up to 60-70°C, and add catalyst and polymerization inhibitor, after the maleic anhydride melts, heat up to 80-85°C, continue to stir for 4 hours, cool to room temperature, extract the product with ethyl acetate, wash with water 2 to 3 times, filter, dry, and remove the solvent to obtain an intermediate product; (2) Add 2-3 parts of glycidyl methacrylate, catalyst and solvent into the reaction vessel, raise the temperature to 70°C, and drop 1 part of the intermediate product in step (1) into the reactor dropwise, at 0.5 The drop was completed within -1 hour, then the reaction system was heated to 85°C, continued to stir for 5 hours, then cooled to room temperature, the product was extracted with ethyl acetate, washed 2 to 3 times with water, filtered, dried, and the solvent was removed to obtain the first generation product. 5. the preparation method of a kind of dibasic alcohol hyperbranched monomer based on maleic anhydride as claimed in claim 3, is characterized in that: the concrete steps of described step 2 are: (1) Add 1 part of the first generation product and 3-4 parts of maleic anhydride into the reaction vessel, mix well, heat up to 60-70°C, add catalyst and polymerization inhibitor, after the maleic anhydride melts, heat up to 80-85°C, continue to stir for 4 hours, cool to room temperature, extract the product with ethyl acetate, wash with water 2 to 3 times, filter, dry, and remove the solvent to obtain an intermediate product; (2) Add 2-3 parts of glycidyl methacrylate, catalyst and solvent into the reaction vessel, raise the temperature to 70°C, and drop 1 part of the intermediate product in step (1) into the reactor dropwise, at 0.5 After the drop is completed within -1 hour, the temperature of the reaction system is raised to 85°C, and after stirring for 4 hours, it is cooled to room temperature, the product is extracted with ethyl acetate, washed with water for 2 to 3 times, filtered, dried, and the solvent is removed to obtain the second generation product. 6. the preparation method of a kind of dibasic alcohol hyperbranched monomer based on maleic anhydride as any one of claim 4-5, it is characterized in that: the catalyzer in the described step (1) is the vitriol oil, concentrated One of hydrochloric acid, p-toluenesulfonic acid, methanesulfonic acid and thionyl chloride, the added weight is 2-5wt% of the reaction system. 7. a kind of preparation method based on the dibasic alcohol hyperbranched monomer of maleic anhydride as described in any one of claim 4-5, it is characterized in that: described step (1) stopper is p-hydroxybenzoic acid One of ether, cuprous chloride, hydroquinone, p-benzoquinone and 2,5-dimethylhydroquinone, the added weight is 1-5wt‰ of the reaction system. 8. the preparation method of a kind of dibasic alcohol hyperbranched monomer based on maleic anhydride as described in any one of claim 4-5, it is characterized in that: the catalyzer in the described step (2) is tetrabutyl bromide One of Ammonium Chloride, Tetramethylammonium Chloride, Triethylamine, N,N-Dimethylaniline and Triphenylphosphine, the added weight is 2-5wt% of the reaction system.