A twelve-functionality photocurable acrylate and a method for its preparation

Abstract

The application provides a kind of twelve functional light-curable acrylate and its preparation method, specifically relates to UV light curing technical field.The synthesis of the twelve functional light-curable acrylate is mainly divided into two steps, the intermediate product side double bond ikon diol in the first step is made from the following mass fraction components: 26.02 mass parts of ikon acid, 45.66 mass parts of allyl glycidyl ether, 0.8-1.0 mass parts of N, N-dimethylformamide, 0.7-0.8 mass parts of tetrabutylammonium bromide, 0.1-0.3 mass parts of methoxyphenol;The twelve functional light-curable acrylate in the second step is made from the following mass fraction components: 35.84 mass parts of side double bond ikon diol, 33.34 mass parts of isophorone diisocyanate, 29.83 mass parts of pentaerythritol triacrylate, 0.1-0.3 mass parts of isooctanoic acid stannous and 0.1-0.3 mass parts of p-methoxyphenol.The twelve functional light-curable acrylate prepared by the application has fast UV curing speed, high efficiency, and the coating after curing has high hardness.

Description

TECHNICAL FIELD

[0001] The application relates to the technical field of UV light curing, in particular to a twelve-functionality light-curable acrylate and a preparation method thereof. TECHNICAL BACKGROUND

[0002] A synthesis method of a commercial multi-functionality light-curable acrylate is as follows: one is to generate polydipentaerythritol hexaacrylate through intermolecular dehydration reaction of pentaerythritol triacrylate, the obtained six-functionality light-curable acrylate only contains six carbon-carbon double bonds in the molecular structure, and the molecular weight is small, so the added amount of the light-curable acrylate in the UV curing product accounts for a large proportion; the other is to generate nine-functionality light-curable acrylate through the following method: 2,2-dimethylol propionic acid is reacted with ethylene oxide or propylene oxide to obtain a trihydroxy polyether ester, the trihydroxy polyether ester is reacted with diisocyanate and pentaerythritol triacrylate or bishydroxymethyl propane triacrylate to obtain a nine-functionality polyurethane acrylate. However, the molecular weight of the obtained acrylate is relatively large, the UV crosslinking density is not enough, and the performance of the cured product is affected. Therefore, a multi-functionality acrylate with relatively small molecular weight and containing more carbon-carbon double bonds in the molecular structure is needed. The twelve-functionality light-curable acrylate in the application belongs to an oligomer, has relatively small molecular weight, and contains 12 carbon-carbon double bonds in the molecular structure, so the UV curing speed is fast, and the crosslinking density of the cured product is high. SUMMARY

[0003] In view of this, the application provides a twelve-functionality light-curable acrylate and a preparation method thereof, which can be applied to the field of UV light curing.

[0004] The first aspect of the application provides a twelve-functionality light-curable acrylate.

[0005] The second aspect of the application provides a preparation method of a twelve-functionality light-curable acrylate.

[0006] The side double bond icodextrin, isophorone diisocyanate, pentaerythritol triacrylate, a catalyst and a polymerization inhibitor are reacted at a certain temperature to obtain the twelve-functionality light-curable acrylate.

[0007] Preferably, in the preparation method of the twelve-functionality light-curable acrylate, the preparation method of the side double bond icodextrin includes the following steps.

[0008] Step S1, in mass parts, 26.02 mass parts of itaconic acid, 45.66 mass parts of allyl glycidyl ether, 0.8-1.0 mass parts of N,N-dimethylformamide, 0.7-0.8 mass parts of tetrabutylammonium bromide, and 0.1-0.3 mass parts of methoxyphenol are mixed to react for a period of time to obtain itaconyl alcohol containing a side double bond.

[0009] Preferably, in the preparation method of the one twelve-functionality photocurable acrylate, the preparation method of itaconyl alcohol containing a side double bond comprises the following steps:

[0010] Step S2, in the preparation method of the one twelve-functionality photocurable acrylate, the preparation step of itaconyl alcohol containing a side double bond, the itaconyl alcohol containing a side double bond obtained in step S1 is subjected to water removal at 95°C under reduced pressure for 1-2 hours to remove N,N-dimethylformamide and unreacted allyl glycidyl ether.

[0011] Step S3, in the preparation method of the one twelve-functionality photocurable acrylate, itaconyl alcohol containing a side double bond is washed with two volumes of ultrapure deionized water three times to remove unreacted itaconic acid.

[0012] Step S4, in the preparation method of the one twelve-functionality photocurable acrylate, the preparation step of itaconyl alcohol containing a side double bond, the itaconyl alcohol containing a side double bond obtained in step S3 is added with 0.1-0.3 mass parts of p-methoxyphenol at 85°C under reduced pressure for 2 hours to remove water to obtain itaconyl alcohol containing a side double bond.

[0013] Step S5, in mass parts, in the preparation method of the one twelve-functionality photocurable acrylate, isophorone diisocyanate is added dropwise in two batches of 11.11 mass parts and 22.23 mass parts into 35.84 mass parts of itaconyl alcohol containing a side double bond containing 0.1-0.3 mass parts of stannous isooctoate and 0.1-0.3 mass parts of p-methoxyphenol to react for a period of time, and then 29.83 mass parts of pentaerythritol triacrylate is added dropwise into the system to react for a period of time to obtain the twelve-functionality photocurable acrylate.

[0014] Preferably, the preparation method of the twelve-functionality photocurable acrylate comprises the following steps:

[0015] Preferably, in step S1, the reaction temperature is 80-85°C, and the reaction time is 2-3 hours.

[0016] Preferably, in step S5, the reaction temperatures are 65-70°C, 70-75°C, and 75-80°C, respectively, and each reaction is performed for 3-4 hours, and the reaction at 75-80°C is performed for 4-5 hours.

[0017] Preferably, the dicarboxylic acid is selected from itaconic acid.

[0018] Preferably, in step S1, the epoxy olefin monomer is selected from at least one of allyl glycidyl ether and glycidyl methacrylate.

[0019] Preferably, in step S1, the solvent is selected from at least one of dimethylformamide and acetone.

[0020] Preferably, in step S5, the isocyanate is selected from at least one of isophorone diisocyanate, toluene diisocyanate, and diphenylmethane diisocyanate.

[0021] Preferably, in step S5, the blocking agent is selected from pentaerythritol triacrylate.

[0022] Preferably, in step S1, the quaternary ammonium salt catalyst is selected from at least one of tetrabutylammonium bromide and tetraethylammonium bromide.

[0023] Preferably, in step S5, the catalyst is selected from at least one of isooctoate stannous, octoate stannous.

[0024] Preferably, in steps S1 and S5, the polymerization inhibitor is selected from at least one of p-methoxyphenol, hydroquinone, and p-benzoquinone.

[0025] Preferably, the photoinitiator is selected from at least one of diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-methylphenylpropan-1-one, 2-methyl-1-(4-methylthiophenyl)-2-morpholinyl-1-propanone, benzoin dimethyl ether, benzophenone, 2-isopropylthioxanthone phenyl, 2,4,6-trimethylbenzoyl phenyl phosphinic acid ethyl ester, and bis(2,4,6-trimethylbenzoyl)phosphine oxide.

[0026] With the rapid development of the UV light curing industry, the application field is becoming more and more wide. The twelve-functionality light-curable acrylate provided by the present application, i.e., an acrylate molecule structure containing twelve carbon-carbon double bonds, can be used in the UV light curing field. The carbon-carbon double bonds can be crosslinked under the induction of ultraviolet light (UV) after being mixed with a photoinitiator, forming a three-dimensional network structure, so that it is solidified. The twelve-functionality light-curable acrylate prepared by the present application contains 12 carbon-carbon double bonds in each molecular structure, has fast UV light curing speed and high efficiency, and has high hardness of the cured coating.

[0027] In summary, the present application provides a twelve-functionality light-curable acrylate and a preparation method thereof. BRIEF DESCRIPTION OF DRAWINGS

[0028] In order to more clearly illustrate the technical solutions in the specific embodiments or prior art of the present application, the drawings required to be used in the specific embodiments or prior art description will be briefly introduced below. Obviously, the drawings described below are some embodiments of the present application, and all other drawings obtained by those skilled in the art without creative labor based on these drawings also belong to the protection scope of the present application.

[0029] Figure 1 NMR chart of the twelve-functionality photocurable acrylate prepared in the preparation method described in the present application. DETAILED DESCRIPTION

[0030] The technical solutions of the present application will be described clearly and completely below in combination with the drawings. Obviously, the described embodiments are some embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor also belong to the protection scope of the present application.

[0031] Embodiment 1

[0032] The synthesis of the twelve-functionality photocurable acrylate includes the following specific steps:

[0033] The 26.02 parts by mass of itaconic acid, 45.66 parts by mass of allyl glycidyl ether, 0.8-1.0 parts by mass of dimethylformamide, 0.7-0.8 parts by mass of tetrabutylammonium bromide, and 0.1-0.3 parts by mass of methoxyphenol are mixed at 80-85°C for 2-3 hours, and N,N-dimethylformamide and incompletely reacted allyl glycidyl ether are removed by vacuum at 95°C for 1-2 hours. It is washed with three times of water to remove incompletely reacted itaconic acid, and 0.1-0.3 parts by mass of p-methoxyphenol is added to remove water at 85°C for 2 hours, to obtain the side double bond itaconyl glycol.

[0034] The isophorone diisocyanate is added dropwise in two batches of 11.11 parts by mass and 22.23 parts by mass to 35.84 parts by mass of the side double bond itaconyl glycol containing 0.1-0.3 parts by mass of isooctanoic acid stannous isooctanoate and 0.1-0.3 parts by mass of p-methoxyphenol at 65-70°C and 70-75°C respectively for 3-4 hours, and 29.83 parts by mass of pentaerythritol triacrylate is added dropwise to the system at 75-80°C for 4-5 hours, to obtain the twelve-functionality photocurable acrylate.

[0035] Raw materials:

[0036] Twelve functional light curable acrylate, tetrahydrofuran acrylate (THFA, Guangzhou Lihou Trading Co., Ltd.), photoinitiator (TPO-L, Tianjin Jiurixin Material Co., Ltd.).

[0037] Preparation of the coating:

[0038] Take 4.8 parts by mass of twelve functional light curable acrylate, 3.0 parts by mass of tetrahydrofuran acrylate and 0.16 (2wt%) parts by mass of photoinitiator, stir evenly, and prepare the coating.

[0039] Preparation of the coating:

[0040] Select test level tinplate, rub it horizontally and vertically with 400 mesh and 600 mesh sandpaper respectively, and then wipe it with acetone and dry it. Then use a coating applicator with a thickness of 50um to coat the coating on the degreased tinplate, and then UV cure it.

[0041] Instruments and equipment:

[0042] The UV curing machine is selected from the UV belt type light curing machine LT-UV102 curing machine (405nm) of Zhuozhou Lantian Special Lamp Development Co., Ltd., and the light intensity is 120mW / cm 2 .

[0043] Coating performance:

[0044] The pencil hardness of the coating after UV curing of the twelve functional light curable acrylate component is 3H, and the pencil hardness of the coating after UV curing of the polydiisopentaerythritol hexaacrylate component is 2H.

[0045] Example 2

[0046] The synthesis of twelve functional light curable acrylate includes the following specific steps:

[0047] Mix 26.02 parts by mass of itaconic acid, 45.66 parts by mass of allyl glycidyl ether, 0.8-1.0 parts by mass of dimethylformamide, 0.7-0.8 parts by mass of tetrabutylammonium bromide, and 0.1-0.3 parts by mass of methoxyphenol at 80-85°C for 2-3 hours, and remove N,N-dimethylformamide and unreacted allyl glycidyl ether at 95°C under reduced pressure for 1-2 hours; wash it with two volumes of ultrapure deionized water three times to remove unreacted itaconic acid; then add 0.1-0.3 parts by mass of p-methoxyphenol to it at 85°C under reduced pressure for 2 hours to remove water, and prepare a side double bond itaconyl alcohol.

[0048] Isoflorone diisocyanate was added dropwise in two batches of 11.11 parts by mass and 22.23 parts by mass to 35.84 parts by mass of side double bond isosorbide containing 0.1-0.3 parts by mass of isooctanoic acid stannous isooctanoate and 0.1-0.3 parts by mass of p-methoxyphenol at 65-70°C and 70-75°C respectively for 3-4 hours, and then 29.83 parts by mass of pentaerythritol triacrylate was added dropwise at 75-80°C for 4-5 hours to obtain a twelve-functionality photocurable acrylate.

[0049] Raw materials:

[0050] Twelve-functionality photocurable acrylate, tetrahydrofurfuryl acrylate (THFA, Guangzhou Lihou Trading Co., Ltd.), photoinitiator (TPO-L, Tianjin Jiurixin New Material Co., Ltd.).

[0051] Preparation of the coating:

[0052] 5.8 parts by mass of twelve-functionality photocurable acrylate, 3.0 parts by mass of tetrahydrofurfuryl acrylate and 0.18 (2 wt%) parts by mass of photoinitiator were weighed and stirred uniformly to prepare the coating.

[0053] Preparation of the coating:

[0054] Test-grade tinplate was selected, and the tinplate was rubbed horizontally and vertically with 400-mesh and 600-mesh sandpaper respectively, cleaned with acetone and dried, and then the coating was coated on the degreased tinplate with a coater with a thickness of 50 um, and UV light curing was performed.

[0055] Instruments and equipment:

[0056] The UV light curing machine was selected from the UV belt type light curing machine LT-UV102 curing machine (405 nm) of Zhuozhou Lantian Special Lamp Development Co., Ltd., and the light intensity was 120 mW / cm 2 .

[0057] Coating performance:

[0058] The pencil hardness of the coating after UV light curing of the twelve-functionality photocurable acrylate component was 3H, and the pencil hardness of the coating after UV light curing of the polydi-pentaerythritol hexaacrylate component was 3H.

[0059] Example 3

[0060] The synthesis of the twelve-functionality photocurable acrylate included the following specific steps:

[0061] The 26.02 parts by mass of itaconic acid, 45.66 parts by mass of allyl glycidyl ether, 0.8-1.0 parts by mass of dimethylformamide, 0.7-0.8 parts by mass of tetrabutylammonium bromide, and 0.1-0.3 parts by mass of methoxyphenol are mixed at 80-85°C for 2-3 hours, and N,N-dimethylformamide and unreacted allyl glycidyl ether are removed by vacuum at 95°C for 1-2 hours; the mixture is washed with two volumes of ultrapure deionized water three times to remove unreacted itaconic acid; 0.1-0.3 parts by mass of p-methoxyphenol is added to the mixture, and water is removed by vacuum at 85°C for 2 hours to obtain the side double bond itaconyl glycol.

[0062] The isophorone diisocyanate is added dropwise in two batches of 11.11 parts by mass and 22.23 parts by mass to 35.84 parts by mass of the side double bond itaconyl glycol containing 0.1-0.3 parts by mass of isooctanoic acid stannous isooctanoate and 0.1-0.3 parts by mass of p-methoxyphenol at 65-70°C and 70-75°C, respectively, for 3-4 hours, and 29.83 parts by mass of pentaerythritol triacrylate is added dropwise to the system at 75-80°C for 4-5 hours to obtain the twelve-functionality photocurable acrylate.

[0063] Raw materials:

[0064] Twelve-functionality photocurable acrylate, tetrahydrofurfuryl acrylate (THFA, Guangzhou Lihou Trading Co., Ltd.), photoinitiator (TPO-L, Tianjin Jiurixin Material Co., Ltd.).

[0065] Preparation of the coating:

[0066] The coating is prepared by stirring 6.8 parts by mass of the twelve-functionality photocurable acrylate, 3.0 parts by mass of the tetrahydrofurfuryl acrylate, and 0.2 (2 wt%) parts by mass of the photoinitiator.

[0067] Preparation of the coating:

[0068] The test-grade tinplate is first rubbed horizontally and vertically with 400-mesh and 600-mesh sandpaper, respectively, and then cleaned with acetone and dried, and then the coating is applied to the degreased tinplate using a 50-μm-thick applicator, and then UV light curing is performed.

[0069] Instruments and equipment:

[0070] The UV light curing machine is selected from the UV belt-type light curing machine LT-UV102 (405 nm) of the Blue Sky Special Lamp Development Co., Ltd. of Zhuozhou City, with a light intensity of 120 mW / cm 2 .

[0071] Coating performance:

[0072] The pencil hardness of the coating of the twelve-functionality photocurable acrylate component after UV light curing is 4H, and the pencil hardness of the coating of the polydipentaerythritol hexaacrylate component after UV light curing is 3H.

[0073] The above embodiments are only used to illustrate the technical solutions of the present application, rather than to limit them. Although the present application has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or replace some or all of the technical features therein with equivalents. However, these modifications or replacements do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present application.

Claims

1. A method for preparing a twelve-functionality photocurable acrylate, characterized in that: Its preparation comprises the following steps: The invention relates to a method for preparing a double-bond itaconic acid diol having a side double bond. The method comprises mixing 26.02 parts by mass of itaconic acid, 45.66 parts by mass of allyl glycidyl ether, 0.7-1.0 parts by mass of dimethylformamide, 0.7-0.8 parts by mass of tetrabutylammonium bromide, and 0.1-0.3 parts by mass of methoxyphenol, and reacting the mixture at 80-85°C for 2-3 hours to obtain itaconic acid diol containing a side double bond. The method comprises adding 11.11 parts by mass and 22.23 parts by mass of isophorone diisocyanate dropwise in two batches to 35.84 parts by mass of itaconic acid diol containing 0.1-0.3 parts by mass of stannous isooctanoate and 0.1-0.3 parts by mass of p-methoxyphenol, reacting the mixture at 65-70°C and 70-75°C for 3-4 hours, respectively, and then adding 29.83 parts by mass of pentaerythritol triacrylate dropwise to the system, and reacting the mixture at 75-80°C for 4-5 hours to obtain a twelve-functionality photocurable acrylate.

2. The method for preparing a twelve-functionality photocurable acrylate according to claim 1, characterized in that: Itacondiol containing a side double bond is subjected to reduced pressure at 95°C for 1 to 2 hours to remove dimethylformamide and unreacted allyl glycidyl ether.

3. The method for preparing a twelve-functionality photocurable acrylate according to claim 1, characterized in that: Itaconic acid diol containing a side double bond was washed three times with twice the volume of ultrapure deionized water to remove unreacted itaconic acid.

4. The method for preparing a twelve-functionality photocurable acrylate according to claim 1, characterized in that: Itacondiol containing a lateral double bond is prepared by adding 0.1 to 0.3 parts by mass of p-methoxyphenol and removing water at 85° C. under reduced pressure for 2 hours to obtain itacondiol containing a lateral double bond.

Images