CN103232343A - Hydroxyl-comprising low-volume-shrinkage nonylphenyl acrylate monomer and preparation method thereof - Google Patents

Abstract

The invention relates to a hydroxyl-comprising low-volume-shrinkage nonylphenyl acrylate monomer and a preparation method thereof. The monomer has side group structure with larger volume, such that polymer free volume can be larger during photopolymerization, bond rotation and chain movement are inhibited, and molecule rigidity is increased. Therefore, when the macro-monomer is polymerized, volume shrinkage is low, polymerization product hydrophobicity is increased, and water-solubility is reduced. Also, the monomer comprises long alkyl branched chain, such that the polymerization product has good flexibility. The product comprises hydrophilic hydroxyl, such that the product has low volatility, high adhesion force, and good adhesion when used as paint.

Description

Hydroxyl-containing nonylphenyl acrylate monomer with low volume shrinkage and preparation method thereof

technical field

The invention relates to the technical field of photosensitive polymer materials, in particular to an acrylate containing a long alkyl benzene ring and a hydroxyl group as a photopolymerizable monomer.

Background technique

The photopolymerization process refers to the process in which liquid oligomers (including monomers) undergo cross-linking polymerization to form solid products under the action of light (including ultraviolet light, visible light) or high-energy rays (mainly electron beams), triggering A chemically reactive liquid substance rapidly transforms into a solid state. At the North American Radiation Curing International Conference held in May 2004, the technology was summarized as having "5E" characteristics: efficient (Efficient), wide adaptability (Enabling), economical (Economical), energy saving (Energy Saving) and environmental friendliness (Environmental Friendly). At the same time, in November 2005, the North American Radiation Curing Association (San Francisco) won the 17th "Clean Air Awards for UV&EBtechnology" (SCAQMD) in the United States. With the continuous development of science and technology and the increasing emphasis on environmental protection, environmentally friendly light curing technology has also developed rapidly, and has continued to develop at a high speed for more than 30 years, with an average annual growth rate of about 10%. Photocuring technology is known as a green technology because of its fast curing speed, less pollution, energy saving and excellent performance of cured products. And it is widely used in coatings, inks, printing plate making, stereolithography, adhesives, imaging, microelectronics and biomaterials and other fields.

The difference between photocuring technology and traditional thermal curing technology is that the essence of photocuring reaction is 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.

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 (that is, 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.

Since Inmont Corporation of the United States first published the unsaturated polyester/styrene ultraviolet (UV) photocuring ink technology patent in 1946, photocuring technology has maintained rapid development. In the technological progress of photocuring systems, the research and development of new photopolymerizable monomers has always occupied a very important position. Ordinary acrylate monomers have low viscosity and good adhesion, but are more toxic and irritating to the skin, such as isobutyl acrylate (IBA), cyclohexyl acrylate (CA), 2-ethyl acrylate Cyclohexyl ester (2-EHA), etc. If ethoxy and propoxy are introduced into the monomer molecule, the curing speed and shrinkage rate can be improved, irritation can be reduced, and the compatibility with various prepolymers is also greatly improved. Further, in acrylic acid The introduction of methoxy groups into ester monomer molecules can better solve the problem of curing degree, and has the characteristics of high activity, strong dilution ability, low toxicity, low irritation, and balance curing speed and shrinkage rate at the same time (Hou Youjun, 2011 "Painting Industry" in 2010: Research Progress of Special Acrylic Monomers, Volume 41, Issue 3, Page 75). A. Bendry disclosed a new method for the preparation of phenolic acrylate monomers (publication number: 102320961A), first reacting a polyhydroxyphenyl compound with an acid anhydride to form an intermediate benzene containing hydroxyl and ring substituents of the ester moiety Base compound; then use the intermediate phenyl compound to react with acrylate compound to form phenolic acrylate compound.

The hydroxyl-containing nonylphenyl acrylate monomer with low volume shrinkage and its preparation method have the following advantages: (1) The monomer has a large-volume side chain—a nonylbenzene ring, which not only increases The molecular rigidity makes the volume shrinkage of the polymer small during photopolymerization, improves the hydrophobicity, and increases the flexibility of the molecule. Because it has a hydrophilic hydroxyl group, when used as a coating, it reduces the volatility of the product and improves In addition, there is a methoxy structure in the monomer molecule, which better balances the curing speed and volume shrinkage; (2) During the reaction process, epichlorohydrin itself is a solvent, and there is no need to add other substances as solvents , to avoid the introduction of impurities; (3) less reaction steps, short preparation cycle, simple operation, easy to control, and less by-products, no complicated wastewater treatment, so it is more suitable for industrial production.

Contents of the invention

The present invention provides a low volume shrinkage nonylphenyl acrylate monomer containing hydroxyl groups and a preparation method thereof. The present invention starts from molecular structure design and connects the large side group of nonylbenzene ring to acrylic acid through molecular design. It forms an acrylate monomer with greater rigidity, flexibility and higher hydrophobicity, and also has good adhesion. Moreover, the preparation cost is low and the operation is simple.

The chemical structural formula of the low volume shrinkage nonylphenyl acrylate monomer containing hydroxyl of the present invention is as follows:

The preparation method of the monomer is as follows (the following are expressed in mole fractions):

The first step reaction: Add 1 part of nonylphenol and 2 to 4 parts of epichlorohydrin into the reaction vessel, mix well, heat up to 55-65 °C in the bottle, and start to drop 1-2 parts of alkaline Solution, control the dripping speed, 3 ~ 4h dripping. Stirring was continued for 5h, and the epoxy value was measured. When it reached the maximum value, the reaction was terminated and cooled to room temperature. Suction filtration to remove the NaCl crystals produced by the reaction; then wash the organic phase twice with deionized water, and then dry overnight with anhydrous sodium sulfate; distill under reduced pressure to remove excess unreacted epichlorohydrin.

The second-step reaction: add 1 part of the first-step reaction product, 1-2 parts of acrylic acid, a small amount of polymerization inhibitor and catalyst into the reaction vessel, and raise the temperature to 85-90°C. The reaction was tested by FTIR every 0.5h. When the infrared absorption peak of the epoxy group at 910cm ^-1 disappeared, the reaction was terminated. The excess acrylic acid was removed to obtain the target product.

A method for synthesizing nonylphenyl acrylate monomers containing hydroxyl groups with low volume shrinkage according to the present invention is characterized in that the basic solution used in the first step reaction is sodium hydroxide solution.

A kind of synthetic method of nonylphenyl acrylate monomer containing hydroxyl group with low volume shrinkage of the present invention is characterized in that the polymerization inhibitor used in the second step reaction is p-hydroxyanisole, and the catalyst is tetrabutyl bromide ammonium chloride.

The whole reaction equation of the low volume shrinkage nonylphenyl acrylate monomer containing hydroxyl prepared by the present invention can be expressed as:

In the preparation method, sodium hydroxide solution is used to provide alkaline conditions, and p-hydroxyanisole and tetrabutylammonium bromide are used as catalysts for polymerization inhibitors. The reaction does not additionally use other solvents, and epichlorohydrin is used as both a reactant and a solvent.

Detailed ways

Example 1

The first step reaction: mix 0.2mol (44.0g) nonylphenol with 0.4mol (37g) epichlorohydrin, and add it to a 250ml four-necked flask equipped with a condenser tube, a thermometer, a stirring rod and a constant pressure dropping funnel , stirred and raised the temperature to 58°C, began to add NaOH solution (45wt%, 9.8g) dropwise, the dropping rate was controlled at 2 drops/min, and the drop was completed in about 2 hours. After the dropwise addition, continue to stir for 4 hours to measure the epoxy value. When it reaches the maximum value, the reaction is terminated and cooled to room temperature. Post-processing: filter with suction to remove the NaCl crystals produced by the reaction, wash the organic phase twice with deionized water, and then dry it overnight with anhydrous sodium sulfate. Distill under reduced pressure to remove excess unreacted epichlorohydrin in the product.

The second step reaction: take 0.1mol (27.62g) of the first step reaction product, add 0.1mol (7.2g) of acrylic acid to a three-necked flask, then add 0.34g (1wt% of the reaction system) of p-hydroxyanisole and 0.19g (0.3%mol of the reaction system) of tetrabutylammonium bromide was heated up to 90°C. The reaction was tested by FTIR every half hour. If the infrared absorption peak of the epoxy group at 910 cm ^-1 disappeared, it indicated that the reaction was over. After about 5 hours, the infrared absorption peak of the epoxy group disappeared. The excess acrylic acid was removed to obtain the target product. The product is a light yellow clear liquid with a viscosity of about 1210cps, a refractive index of 1.4536 and a surface tension of 33.5dynes/cm.

Example 2

The first step reaction: mix 0.2mol (44.0g) nonylphenol with 0.8mol (74.0g) epichlorohydrin, and add it to a 250ml four-necked flask equipped with a condenser tube, a thermometer, a stirring rod and a constant pressure dropping funnel , stirred and heated to 58°C, started to add NaOH solution (45wt%, 9.8g) dropwise, and the drop rate was controlled at 2 drops/min, and the drop was completed in about 2 hours. After the dropwise addition, continue to stir for 4 hours to measure the epoxy value. When it reaches the maximum value, the reaction is terminated and cooled to room temperature. Post-processing: filter with suction to remove the NaCl crystals produced by the reaction, wash the organic phase twice with deionized water, and then dry it overnight with anhydrous sodium sulfate. Distill under reduced pressure to remove excess unreacted epichlorohydrin in the product.

The second step reaction: take 0.1mol (27.62g) of the first step reaction product, add 0.1mol (7.2g) of acrylic acid to a three-necked flask, then add 0.34g (1wt% of the reaction system) of p-hydroxyanisole and 0.19g (0.3%mol of the reaction system) of tetrabutylammonium bromide was heated up to 90°C. The reaction was tested by FTIR every half hour. If the infrared absorption peak of the epoxy group at 910 cm ^-1 disappeared, it indicated that the reaction was over. After about 5 hours, the infrared absorption peak of the epoxy group disappeared. The excess acrylic acid was removed to obtain the target product. The product is a light yellow to colorless transparent liquid with a viscosity of about 1150cps, a refractive index of 1.4221 and a surface tension of 33.1dynes/cm.

Example 3

The first step reaction: mix 0.2mol (44.0g) nonylphenol with 0.4mol (37.0g) epichlorohydrin, and add it to a 250ml four-necked flask equipped with a condenser tube, a thermometer, a stirring rod and a constant pressure dropping funnel , stirred and heated to 60°C, started to add NaOH solution (45wt%, 17.6g) dropwise, the dropping rate was controlled at 2 drops/min, and the drop was completed in about 3 hours. After the dropwise addition, continue to stir for 5 hours, measure the epoxy value, when it reaches the maximum value, end the reaction, and cool to room temperature. Post-processing: filter with suction to remove the NaCl crystals produced by the reaction, wash the organic phase twice with deionized water, and then dry it overnight with anhydrous sodium sulfate. Distill under reduced pressure to remove excess unreacted epichlorohydrin in the product.

The second step reaction: take 0.1mol (27.62g) of the first step reaction product, add 0.1mol (7.2g) of acrylic acid to a three-necked flask, then add 0.34g (1wt% of the reaction system) of p-hydroxyanisole and 0.19g (0.3%mol of the reaction system) of tetrabutylammonium bromide was heated up to 90°C. The reaction was tested by FTIR every half hour. If the infrared absorption peak of the epoxy group at 910 cm ^-1 disappeared, it indicated that the reaction was over. After about 5 hours, the infrared absorption peak of the epoxy group disappeared. The excess acrylic acid was removed to obtain the target product. The product is a light yellow clear liquid with a viscosity of about 1171cps, a refractive index of 1.3937 and a surface tension of 32.9dynes/cm.

Example 4

The first step reaction: mix 0.2mol (44.0g) nonylphenol with 0.8mol (74.0g) epichlorohydrin, and add it to a 250ml four-necked flask equipped with a condenser tube, a thermometer, a stirring rod and a constant pressure dropping funnel , stirred and heated to 60°C, started to add NaOH solution (45wt%, 17.6g) dropwise, the dropping rate was controlled at 2 drops/min, and the drop was completed in about 3 hours. After the dropwise addition, continue to stir for 5 hours, measure the epoxy value, when it reaches the maximum value, end the reaction, and cool to room temperature. Post-processing: filter with suction to remove the NaCl crystals produced by the reaction, wash the organic phase twice with deionized water, and then dry it overnight with anhydrous sodium sulfate. Distill under reduced pressure to remove excess unreacted epichlorohydrin in the product.

The second step reaction: take 0.1mol (27.62g) of the first step reaction product, add 0.1mol (7.2g) of acrylic acid to a three-necked flask, then add 0.34g (1wt% of the reaction system) of p-hydroxyanisole and 0.19g (0.3%mol of the reaction system) of tetrabutylammonium bromide was heated up to 90°C. The reaction was tested by FTIR every half hour. If the infrared absorption peak of the epoxy group at 910 cm ^-1 disappeared, it indicated that the reaction was over. After about 5 hours, the infrared absorption peak of the epoxy group disappeared. The excess acrylic acid was removed to obtain the target product. The product is a light yellow transparent liquid with a viscosity of about 1095cps, a refractive index of 1.5136 and a surface tension of 32.2dynes/cm

Example 5

The first step reaction: mix 0.2mol (44.0g) nonylphenol with 0.4mol (37.0g) epichlorohydrin, and add it to a 250ml four-necked flask equipped with a condenser tube, a thermometer, a stirring rod and a constant pressure dropping funnel , stirred and heated to 60°C, started to add NaOH solution (45wt%, 9.8g) dropwise, and the drop rate was controlled at 2 drops/min, and the drop was completed in about 2 hours. After the dropwise addition, continue to stir for 4 hours to measure the epoxy value. When it reaches the maximum value, the reaction is terminated and cooled to room temperature. Post-processing: filter with suction to remove the NaCl crystals produced by the reaction, wash the organic phase twice with deionized water, and then dry it overnight with anhydrous sodium sulfate. Distill under reduced pressure to remove excess unreacted epichlorohydrin in the product.

The second step reaction: take 0.1mol (27.62g) of the first step reaction product, add 0.2mol (14.4g) of acrylic acid to a three-necked flask, and then add 0.42g (1wt% of the reaction system) of p-hydroxyanisole and 0.29g (0.3%mol of the reaction system) of tetrabutylammonium bromide was heated to 90°C. The reaction was tested by FTIR every half hour. If the infrared absorption peak of the epoxy group at 910 cm ^-1 disappeared, it indicated that the reaction was over. After about 5 hours, the infrared absorption peak of the epoxy group disappeared. The excess acrylic acid was removed to obtain the target product. The product is a light yellow clear liquid with a viscosity of about 1210cps, a refractive index of 1.4577 and a surface tension of 32.8dynes/cm.

Example 6

The first step reaction: mix 0.2mol (44.0g) nonylphenol with 0.8mol (74.0g) epichlorohydrin, and add it to a 250ml four-necked flask equipped with a condenser tube, a thermometer, a stirring rod and a constant pressure dropping funnel , stirred and heated to 60°C, started to add NaOH solution (45wt%, 9.8g) dropwise, and the drop rate was controlled at 2 drops/min, and the drop was completed in about 2 hours. After the dropwise addition, continue to stir for 4 hours to measure the epoxy value. When it reaches the maximum value, the reaction is terminated and cooled to room temperature. Post-processing: filter with suction to remove the NaCl crystals produced by the reaction, wash the organic phase twice with deionized water, and then dry it overnight with anhydrous sodium sulfate. Distill under reduced pressure to remove excess unreacted epichlorohydrin in the product.

The second step reaction: take 0.1mol (27.62g) of the first step reaction product, add 0.2mol (14.4g) of acrylic acid to a three-necked flask, and then add 0.42g (1wt% of the reaction system) of p-hydroxyanisole and 0.29g (0.3%mol of the reaction system) of tetrabutylammonium bromide was heated to 90°C. The reaction was tested by FTIR every half hour. If the infrared absorption peak of the epoxy group at 910 cm ^-1 disappeared, it indicated that the reaction was over. After about 5 hours, the infrared absorption peak of the epoxy group disappeared. The excess acrylic acid was removed to obtain the target product. The product is a light yellow clear liquid with a viscosity of about 1208cps, a refractive index of 1.4611 and a surface tension of 33.1dynes/cm.

Example 7

The first step reaction: mix 0.2mol (44.0g) nonylphenol with 0.4mol (37.0g) epichlorohydrin, and add it to a 250ml four-necked flask equipped with a condenser tube, a thermometer, a stirring rod and a constant pressure dropping funnel , stirred and heated to 60°C, started to add NaOH solution (45wt%, 17.6g) dropwise, the dropping rate was controlled at 2 drops/min, and the drop was completed in about 3 hours. After the dropwise addition, continue to stir for 5 hours, measure the epoxy value, when it reaches the maximum value, end the reaction, and cool to room temperature. Post-processing: filter with suction to remove the NaCl crystals produced by the reaction, wash the organic phase twice with deionized water, and then dry it overnight with anhydrous sodium sulfate. Distill under reduced pressure to remove excess unreacted epichlorohydrin in the product.

The second step reaction: take 0.1mol (27.62g) of the first step reaction product, add 0.2mol (14.4g) of acrylic acid to a three-necked flask, and then add 0.42g (1wt% of the reaction system) of p-hydroxyanisole and 0.29g (0.3%mol of the reaction system) of tetrabutylammonium bromide was heated to 90°C. The reaction was tested by FTIR every half hour. If the infrared absorption peak of the epoxy group at 910 cm ^-1 disappeared, it indicated that the reaction was over. After about 5 hours, the infrared absorption peak of the epoxy group disappeared. The excess acrylic acid was removed to obtain the target product. The product is a light yellow clear liquid with a viscosity of about 1120cps, a refractive index of 1.4536 and a surface tension of 32.5dynes/cm.

Example 8

The first step reaction: mix 0.2mol (44.0g) nonylphenol with 0.8mol (74.0g) epichlorohydrin, and add it to a 250ml four-necked flask equipped with a condenser tube, a thermometer, a stirring rod and a constant pressure dropping funnel , stirred and heated to 60°C, started to add NaOH solution (45wt%, 17.6g) dropwise, the dropping rate was controlled at 2 drops/min, and the drop was completed in about 3 hours. After the dropwise addition, continue to stir for 5 hours, measure the epoxy value, when it reaches the maximum value, end the reaction, and cool to room temperature. Post-processing: filter with suction to remove the NaCl crystals produced by the reaction, wash the organic phase twice with deionized water, and then dry it overnight with anhydrous sodium sulfate. Distill under reduced pressure to remove excess unreacted epichlorohydrin in the product.

The second step reaction: take 0.1mol (27.62g) of the first step reaction product, add 0.2mol (14.4g) of acrylic acid to a three-necked flask, and then add 0.42g (1wt% of the reaction system) of p-hydroxyanisole and 0.29g (0.3%mol of the reaction system) of tetrabutylammonium bromide was heated to 90°C. The reaction was tested by FTIR every half hour. If the infrared absorption peak of the epoxy group at 910 cm ^-1 disappeared, it indicated that the reaction was over. After about 5 hours, the infrared absorption peak of the epoxy group disappeared. The excess acrylic acid was removed to obtain the target product. The obtained product is a light yellow to colorless transparent liquid with a viscosity of about 1216 cps, a refractive index of 1.4536 and a surface tension of 33.6 dynes/cm.

Claims (4)

1. a nonylphenyl acrylate monomer containing hydroxyl group with low volume shrinkage, its structural formula is as follows:

Among them, the methoxy group is located at the para position of the nonyl group on the benzene ring. 2. the preparation method of the nonylphenyl acrylate monomer of the low volume shrinkage containing hydroxyl described in claim 1, is characterized in that comprising the steps: The following are expressed in mole fractions The first step reaction: Add 1 part of nonylphenol and 2-4 parts of epichlorohydrin into the reaction container, mix well, heat up to the temperature in the bottle of 55-65°C, and start to drop 1-2 parts of alkaline solution , Control the drop rate, 2 ~ 3h drop. Stirring was continued for 5h, and the epoxy value was measured. When it reached the maximum value, the reaction was terminated and cooled to room temperature. Suction filtration to remove the NaCl crystals produced by the reaction; then wash the organic phase twice with deionized water, and then dry overnight with anhydrous sodium sulfate; distill under reduced pressure to remove excess unreacted epichlorohydrin. The second-step reaction: add 1 part of the first-step reaction product, 1-2 parts of acrylic acid, a small amount of polymerization inhibitor and catalyst into the reaction vessel, and raise the temperature to 85-90°C. The reaction was tested by FTIR every 0.5h. When the infrared absorption peak of the epoxy group at 910cm ^-1 disappeared, the reaction was terminated. The excess acrylic acid was removed to obtain the target product. 3. the preparation method of the nonylphenyl acrylate monomer of a kind of hydroxyl-containing low volume shrinkage according to claim 2, it is characterized in that used alkaline solution is sodium hydroxide solution in the first step reaction. 4. the preparation method of the nonylphenyl acrylate monomer of a kind of hydroxyl-containing low volume shrinkage according to claim 2 is characterized in that used polymerization inhibitor is p-hydroxyanisole in the second step reaction, and catalyzer is Tetrabutylammonium bromide.