An alicyclic vinyl resin, its preparation method, and its applications

Abstract

The application discloses a kind of alicyclic vinyl resins, with formula (I) or formula (II) structure shown in:Wherein, R1 And R independently selected from any one of ester group, ether bond, carbonyl, aromatic group, fatty chain segment.The application provides the preparation method of alicyclic vinyl resin, comprising: heating vinyl monomer to 65-95 DEG C dehydration, adding polymerization inhibitor, stirring uniformly, temperature is reduced to 65-75 DEG C after adding catalyst stirring uniformly;Temperature is raised to 65-95 DEG C after again slowly adding alicyclic epoxy resin, temperature is raised to 95-100 DEG C and keeps warm;Epoxy value is determined during keeping warm, when epoxy group residual amount reaches specified value, add remaining polymerization inhibitor, obtain just.The alicyclic vinyl resin obtained by the method has excellent properties, and the synthesis method has mild reaction conditions, low cost, simple post-treatment process, environmental friendly, suitable for industrial production.The application also provides the application of the above-mentioned alicyclic vinyl resin in the field of photocuring.

Description

Technical Field

[0001] This invention relates to the field of organic chemical synthesis, and in particular to an alicyclic vinyl resin, its preparation method, and its applications. Background Technology

[0002] Vinyl resins are a wide range of resins with diverse applications, including corrosion-resistant and high-strength fiberglass products, anti-corrosion engineering, thermosetting or UV-cured coatings, UV-cured inks, adhesives, and heavy-duty anti-corrosion flooring. They can be cured through thermosetting and radiation curing. With the development of environmental protection and a low-carbon economy, the application of UV-cured acrylic resins is increasing.

[0003] Traditional free radical curing systems have a large shrinkage rate and low adhesion to glass and ceramic substrates. Traditional vinyl resin (bisphenol A type) curing systems have brittle cured products with poor mechanical properties. Furthermore, epoxy-based curing systems containing aromatic rings have poor weather resistance, and the cured products are prone to yellowing and chalking, which limits the application range of coatings.

[0004] Alicyclic vinyl resins, as the main resin, can improve the mechanical properties of cured products, reduce system shrinkage, and have low color and high gloss. Their adhesion to substrates is significantly improved compared to traditional vinyl resins, which expands the range of substrates that can be selected. In addition, compared to traditional bisphenol A type vinyl resins, cycloalicyclic vinyl resins do not contain aromatic groups, and the system has better resistance to yellowing, aging, UV, and gloss and color retention, thus broadening its outdoor application fields.

[0005] However, the preparation cost of alicyclic vinyl resins in the existing technology is high, the yield is low, and the environmental pollution is significant, making them difficult to apply to industrial production. Summary of the Invention

[0006] The purpose of this invention is to solve the aforementioned technical problems in the prior art. This invention provides an alicyclic vinyl resin, its preparation method, and its applications, offering a low-cost, high-yield, and environmentally friendly alicyclic vinyl resin and its preparation method suitable for industrial production.

[0007] To solve the above-mentioned technical problems, embodiments of the present invention disclose an alicyclic vinyl resin having the structure shown in formula (I) or formula (II):

[0008]

[0009] R1 and R are independently selected from any one of ester group, ether bond, carbonyl group, aromatic group, and aliphatic chain segment.

[0010] According to another specific embodiment of the present invention, an alicyclic vinyl resin is disclosed, which is prepared from vinyl monomers and alicyclic epoxy resin under the action of a polymerization inhibitor and a catalyst;

[0011] The vinyl monomer comprises 15-75% by mass percentage, the alicyclic epoxy resin comprises 25-85%, the polymerization inhibitor comprises 0.02-1.2%, and the catalyst comprises 0.02-1%.

[0012] According to another specific embodiment of the present invention, an alicyclic vinyl resin is disclosed, which is prepared by the following method:

[0013] According to the mass percentage, the vinyl monomer is heated to 65-95℃ to dehydrate, 0.01-0.6% of polymerization inhibitor is added, and the mixture is stirred evenly. After cooling to 65-75℃, the catalyst is added and stirred evenly. The temperature is then raised to 65-95℃, and the alicyclic epoxy resin is slowly added. The temperature is then raised to 95-100℃ and held. During the holding process, samples are taken every 20-30 minutes to determine the epoxy value. When the epoxy residue is less than 10%, 0.01-0.6% of polymerization inhibitor is added to obtain the final product.

[0014] According to another specific embodiment of the present invention, an alicyclic vinyl resin is disclosed, wherein the vinyl monomer is a hydroxyl-containing vinyl monomer and / or a carboxyl-containing vinyl monomer.

[0015] According to another specific embodiment of the present invention, an alicyclic vinyl resin is disclosed, wherein the hydroxyl-containing vinyl monomer is one or a combination of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, and hydroxyethyl methacrylate, and the carboxyl-containing vinyl monomer is one or a combination of acrylic acid and methacrylic acid.

[0016] According to another specific embodiment of the present invention, an alicyclic vinyl resin is disclosed, the alicyclic epoxy resin having the structure shown in formula (III) or formula (IV):

[0017]

[0018] Wherein, R is any one of ester group, ether bond, carbonyl group, aromatic group, or aliphatic chain segment.

[0019] According to another specific embodiment of the present invention, an alicyclic vinyl resin is disclosed, wherein the alicyclic epoxy resin is any one or more of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate, bis((3,4-epoxycyclohexyl)methyl)adipate, 1,2-epoxy-4-vinylcyclohexane, dicyclopentenyl ether dioxide, dicyclopentadiene dioxide, vinylcyclohexene dioxide, and tetrahydroindene dialicyclic compounds.

[0020] According to another specific embodiment of the present invention, an alicyclic vinyl resin is disclosed, wherein the polymerization inhibitor is any one or more of hydroquinone, p-tert-butylresorcinol, and p-hydroxyanisole.

[0021] The catalyst is any one or more of triethylamine, quaternary ammonium salt, tin tetrachloride pentahydrate, and boron trifluoride diethyl ether.

[0022] The embodiments of the present invention also disclose a method for preparing the above-mentioned alicyclic vinyl resin, comprising the following steps:

[0023] (1) Heat the vinyl monomer to 65-95℃ to dehydrate it, add a certain amount of polymerization inhibitor, stir evenly, cool to 65-75℃ and then add catalyst and stir evenly.

[0024] (2) After heating to 65-95℃, slowly add the alicyclic epoxy resin, and then heat to 95-100℃ and keep warm.

[0025] (3) During the heat preservation process, samples are taken at regular intervals to determine the epoxy value. When the residual amount of epoxy groups reaches the specified value, the remaining polymerization inhibitor is added.

[0026] According to another specific embodiment of the present invention, an embodiment of the present invention discloses a method for preparing an alicyclic vinyl resin, wherein in step (1), the vinyl monomer is dehydrated to below 0.05%, and after adding a catalyst, it is stirred for 5-10 min;

[0027] In step (2), the alicyclic epoxy resin is added dropwise over a period of 90-120 minutes;

[0028] In step (3), during the heat preservation process, samples are taken every 20-30 minutes to determine the epoxy value, and the specified value for the residual epoxy group content is less than 10%;

[0029] The polymerization inhibitor added in step (1) is 0.01-0.6%, and the polymerization inhibitor added in step (3) is 0.01-0.6%.

[0030] The embodiments of the present invention also disclose the application of the above-mentioned alicyclic vinyl resin in the field of photocuring.

[0031] Compared with the prior art, the present invention has the following technical effects:

[0032] The alicyclic vinyl resin obtained by this method has excellent properties. Furthermore, the synthesis method has mild reaction conditions, low cost, simple post-processing, and is environmentally friendly, making it suitable for industrial production. Detailed Implementation

[0033] The following specific embodiments illustrate the implementation of the present invention. Those skilled in the art can easily understand other advantages and effects of the present invention from the content disclosed in this specification. Although the description of the present invention is presented in conjunction with preferred embodiments, this does not mean that the features of the invention are limited to these embodiments. On the contrary, the purpose of describing the invention in conjunction with embodiments is to cover other options or modifications that may be derived based on the claims of the present invention. To provide a deep understanding of the invention, many specific details will be included in the following description. The invention may also be implemented without using these details. Furthermore, to avoid confusion or obscuring the focus of the invention, some specific details will be omitted in the description. It should be noted that, unless otherwise specified, the embodiments and features in the embodiments of the present invention can be combined with each other.

[0034] Example 1

[0035] (a) 232g of hydroxyethyl acrylate was put into a four-necked round-bottom flask equipped with a stirrer and a thermometer, and the temperature was raised to 85°C and then dehydrated under reduced pressure.

[0036] (b) After the temperature drops to 65°C, add 1.5g of boron trifluoride ether and slowly drip in the alicyclic epoxy resin over approximately 2 hours. Probe with nitrogen gas for protection. The structural formula of the alicyclic epoxy resin is as follows:

[0037]

[0038] (c) After the alicyclic epoxy resin was added, 500 ppm of p-hydroxyanisole was added, and the epoxy value was measured after keeping it warm for 30 min.

[0039] (d) The epoxy value of the reaction was determined to be 0.087 mol / 100g. The reaction was stopped, and the product was cooled to room temperature before being discharged. The structural formula of the alicyclic vinyl resin is:

[0040]

[0041] Example 2

[0042] (a) 288g of hydroxypropyl methacrylate was put into a four-necked round-bottom flask equipped with a stirrer and a thermometer, and the temperature was raised to 85°C and then dehydrated under reduced pressure.

[0043] (b) After the temperature drops to 70°C, add 0.8g of boron trifluoride ether and slowly drip in 260g of alicyclic epoxy resin over approximately 2 hours. Probe with nitrogen gas for protection. The structural formula of the alicyclic epoxy resin is as follows:

[0044]

[0045] (c) After the alicyclic epoxy resin was added, 500 ppm of p-hydroxyanisole was added, and the epoxy value was measured after keeping it warm for 30 min.

[0046] (d) The epoxy value of the reaction was determined to be 0.066 mol / 100g. The reaction was stopped, and the product was cooled to room temperature before being discharged. The structural formula of the alicyclic vinyl resin is:

[0047]

[0048] Example 3

[0049] (a) 144g of acrylic acid was put into a four-necked round-bottom flask equipped with a stirrer and a thermometer, and the temperature was raised to 90°C and then dehydrated under reduced pressure.

[0050] (b) Add 1.5g of triphenylphosphine and 1.0g of triethylamine, and slowly add alicyclic epoxy resin dropwise over approximately 2 hours, while purging with nitrogen gas for protection. The structural formula of the alicyclic epoxy resin is as follows:

[0051]

[0052] (c) After the alicyclic epoxy resin was added, 500 ppm hydroquinone was added, and the epoxy value was measured after keeping it warm for 30 min.

[0053] (d) The epoxy value of the reaction was determined to be 0.05 mol / 100g. The reaction was stopped, and the product was cooled to room temperature before being discharged. The structural formula of the alicyclic vinyl resin is:

[0054]

[0055] Example 4

[0056] (a) 260g of hydroxyethyl methacrylate was put into a four-necked round-bottom flask equipped with a stirrer and a thermometer, and the temperature was raised to 85°C and then dehydrated under reduced pressure.

[0057] (b) After the temperature drops to 70°C, add 1.0 g of boron trifluoride ether and slowly add the alicyclic epoxy resin dropwise over approximately 2 hours. Nitrogen gas is then introduced for protection. The structural formula of the alicyclic epoxy resin is as follows:

[0058]

[0059] (c) After the alicyclic epoxy resin was added, 1000 ppm hydroquinone was added, and the epoxy value was measured after keeping it warm for 30 min.

[0060] (d) The epoxy value of the reaction was determined to be 0.075 mol / 100g. The reaction was stopped, and the product was cooled to room temperature before being discharged. The structural formula of the alicyclic vinyl resin is:

[0061]

[0062] Performance testing:

[0063] This invention not only synthesizes different alicyclic epoxy-modified vinyl resins, but also applies them to UV curing formulations to prepare UV resins, and tests the weather resistance, temperature change resistance, heat resistance, and adhesion of the cured film of the corresponding resins.

[0064] 1. Preparation of UV resin: Take 100 parts of the alicyclic epoxy vinyl resin prepared in Examples 1-4, and then add 2 parts by weight of 2-hydroxy-2-methyl-1-phenyl-1-propanone and 2 parts by weight of diphenyl-(2,4,6-trimethylbenzoyl)phosphorus oxide, and stir with a planetary mixer to mix evenly.

[0065] 2. Test sample preparation: Apply the mixture solution from step 1 to a 100*100*1 mm aluminum sheet using a roller coating method, and then cure it for 20 seconds using a 1000W mercury lamp at a distance of 10 cm.

[0066] 3. Weather resistance of paint film: Weather resistance was tested according to GB / T 1767-1979;

[0067] 4. Heat resistance of the paint film: The heat resistance was tested at 200℃ according to GB / T 1735-1979;

[0068] 5. Temperature resistance of paint film: Place it in an 85℃ oven for 1 hour, then place it at 25℃ for 15 minutes. Repeat this cycle four times. The paint film is considered qualified if it does not change color, crack, or peel off.

[0069] 6. Coating adhesion: Adhesion was tested according to GB / T 9286-1998, and the test results are shown in Table 1.

[0070] Table 1

[0071]

[0072] As shown in Table 1, the alicyclic vinyl resin of the present invention has good weather resistance, good heat resistance, good temperature change resistance, and good adhesion after curing.

[0073] While the present invention has been described with reference to certain preferred embodiments, those skilled in the art should understand that the above description is a further detailed explanation of the invention in conjunction with specific embodiments, and should not be construed as limiting the specific implementation of the invention to these descriptions. Various changes in form and detail can be made by those skilled in the art, including several simple deductions or substitutions, without departing from the spirit and scope of the invention.

Claims

1. A cycloaliphatic vinyl resin characterized in that, having the following structure: The method for producing the resin is characterized by comprising the steps of, comprising the following steps: (a) 260 g of hydroxyethyl methacrylate is put into a four-port round-bottom flask equipped with a stirrer and a thermometer, and after being warmed to 85°C, it is dehydrated under reduced pressure; (b) after the temperature is reduced to 70°C, 1.0 g of boron trifluoride etherate is put in, and the alicyclic epoxy resin is slowly dripped in, the dripping time is about 2 h, and nitrogen is introduced for protection, the alicyclic epoxy resin has the following structural formula: ； (c) after the alicyclic epoxy resin is completely dripped in, 1000 ppm of hydroquinone is added, and the epoxy value is measured after being kept for 30 min; (d) the reaction epoxy value is 0.075 mol / 100 g, the reaction is stopped, and the product is cooled to room temperature and discharged.

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