CN115368542A - Light-cured resin and preparation method and application thereof - Google Patents

Light-cured resin and preparation method and application thereof Download PDF

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CN115368542A
CN115368542A CN202211148657.3A CN202211148657A CN115368542A CN 115368542 A CN115368542 A CN 115368542A CN 202211148657 A CN202211148657 A CN 202211148657A CN 115368542 A CN115368542 A CN 115368542A
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reactant
acid
reaction
resin
side chain
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崔同浩
赵云川
马培培
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Zhonghan New Material Technology Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/52—Polycarboxylic acids or polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D167/06—Unsaturated polyesters having carbon-to-carbon unsaturation

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  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
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Abstract

The invention provides a light-cured resin and a preparation method and application thereof. The main chain structure of the light-cured resin is a polyester structure, and the side chain contains a carbon-carbon double bond and an acyloxy group. According to the invention, the photocuring resin takes saturated polyester as a main chain, and a carbon-carbon double bond and an acyl oxygen group are introduced into a side chain of the photocuring resin, so that compared with a traditional unsaturated vinyl photocuring group, the photocuring resin has the advantages of high curing speed, adjustable photocuring speed and low viscosity. So that the coating containing the light-cured resin has high adhesion to a base material, is healthy and environment-friendly, and is suitable for batch production.

Description

Light-cured resin and preparation method and application thereof
Technical Field
The invention belongs to the technical field of coatings, and particularly relates to a light-cured resin, and a preparation method and application thereof.
Background
The UV light curable resin is a resin that can be cured by irradiation of ultraviolet light. The light curing technology has little or almost no VOCs emission in the cross-linking curing process, is an environment-friendly green technology, can save energy by ultraviolet irradiation curing, can be used for large-scale rapid production, and has great potential in the actual production process. Unsaturated polyester is one of the earliest used light-cured matrix resins, and the unsaturated polyester is still applied in large scale so far due to the advantages of convenient raw material source, low price, simple synthesis process, good hardness of the obtained cured coating and the like.
The unsaturated polyester has a photo-curing group of a vinyl group (C = C double bond), but the double bond is located on the polyester main chain, and the reaction activity is relatively low, so that the photo-curing speed is relatively slow, and in addition, the unsaturated polyester having a maleic acid and fumaric acid structure in the general main chain has the disadvantages of low adhesion and the like. Therefore, the problems that the curing speed of the light-cured resin is low and the adhesive force is poor are solved urgently.
For example, patent CN102838486a discloses a uv-curable polyester acrylate and a preparation method thereof, wherein the uv-curable polyester acrylate adopts phthalic anhydride or maleic anhydride and hydroxyethyl acrylate as synthetic monomers, by adopting a melt copolymerization method, the prepared ultraviolet curing resin has low viscosity and higher curing speed and adhesive force. However, the method adopts hydroxyethyl acrylate as a chain end, so that the synthesized UV light-cured resin has low functionality, only 2 and the synthesis process requires the use of carcinogenic substances such as epichlorohydrin, which can affect the large-scale use of the method.
CN110922603A discloses a different-chain-segment-modified photocuring resin, a preparation method and an application thereof, wherein the photocuring resin is prepared by reacting polycarbodiimide with a carboxyl-terminated compound, and introducing a compound containing carboxyl and an acrylic acid group on a terminal group, such as beta-acryloxypropionic acid, as a photocuring group, and the synthesized photocuring resin has good water resistance, flexibility, high temperature resistance and weather resistance. However, the resin functionality of the photocurable resin is also low and the photocuring speed is slow.
Therefore, it is an urgent technical problem to be solved in the art to develop a photocurable resin which has fast photocuring speed, large adhesion, environmental protection and mass production.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a light-cured resin and a preparation method and application thereof. The light-cured resin takes common polyester as a main chain, double bonds and acyl-oxygen groups are introduced into a side chain of the light-cured resin, compared with the traditional unsaturated vinyl photocuring group, the epoxy resin has the advantages of high curing speed, adjustable photocuring speed and low viscosity. So that the coating containing the light-cured resin has high adhesion to a base material, is healthy and environment-friendly, and is suitable for batch production.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a photocurable resin, the main chain structure of the light-cured resin is a polyester structure, and the side chain contains a carbon-carbon double bond and an acyloxy group.
According to the invention, the carbon-carbon double bond and the acyloxy group are introduced into the side chain, so that the curing speed of the resin can be improved, the curing speed of the resin can be controlled by adjusting the content of the carbon-carbon double bond and the acyloxy group, the photocuring resin is a short-chain polymer, the viscosity is low, and the coating containing the photocuring resin has high adhesive force to a substrate.
In the present invention, if an acyloxy group is introduced to the end of the main chain, the main chain is blocked, the photocuring speed of the resin is reduced, and the flexibility of the resin is poor.
Preferably, the polyester of the main chain structure of the photocurable resin is a saturated polyester.
Preferably, the raw materials of the light-curable resin include a reactant a and a reactant B; the raw materials of the reactant A comprise dihydric alcohol and dibasic acid; the raw material of the reactant B comprises polyols and side chain modifying substances; the side chain modifying substance comprises a carboxyl-containing substance carbon-carbon double bonds and acyloxy groups.
Preferably, the molar ratio of the reactant a to the reactant B is 1 (0.1 to 1), and may be, for example, 1.
In the invention, the reactant A and the reactant B are in a specific molar ratio range, so that the light-cured resin with proper curing speed and high adhesive force can be obtained; when the content of the reactant B is too small, the resin curing speed is slow, and the adhesive force to the base material is reduced; when the content of the reactant B is increased, the resin is too fast in curing speed, the internal stress is large, and cracks are easy to generate.
Preferably, the intrinsic viscosity of the photocurable resin is 0.3 to 0.5dl/g, and may be, for example, 0.31dl/g, 0.32dl/g, 0.33dl/g, 0.34dl/g, 0.35dl/g, 0.36dl/g, 0.37dl/g, 0.38dl/g, 0.39dl/g, 0.4dl/g, 0.41dl/g, 0.42dl/g, 0.43dl/g, 0.44dl/g, 0.45dl/g, 0.46dl/g, 0.47dl/g, 0.48dl/g, 0.49dl/g, or the like.
In the invention, the intrinsic viscosity of the light-cured resin is in a specific range, the curing speed of the resin is moderate, and the adhesive force to a base material is better; the intrinsic viscosity is less than 0.3dl/g, and the adhesive force is poor; if it exceeds 0.5dl/g, the processability is poor.
Preferably, the molar ratio of the diol to the dibasic acid in the raw materials of the reactant a is (1-2): 1, and may be, for example, 1.1.
Preferably, the dihydric alcohol in the raw materials of the reactant A comprises at least one of ethylene glycol, 1,2-propylene glycol, 2-methyl-1,3-propylene glycol, 2-butyl-2-ethyl-1,3-propylene glycol, 1,4-butanediol, pentanediol, neopentyl glycol, 1-5-pentanediol, 3-methyl-1,5-pentanediol, hexanediol, 1,4-cyclohexanedimethanol, diethylene glycol, 2,2,4-trimethyl-1,3-pentanediol.
Preferably, the diol comprises a combination of neopentyl glycol and ethylene glycol.
Preferably, the molar ratio of the neopentyl glycol to the ethylene glycol is 1 (1-2), and can be, for example, 1.
Preferably, the dibasic acid in the raw material of the reactant A comprises at least one of terephthalic acid, isophthalic acid, phthalic anhydride, sebacic acid, adipic acid, 1,4-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid or 2,6-naphthalenedicarboxylic acid.
Preferably, the dibasic acid comprises a combination of terephthalic acid, isophthalic acid and sebacic acid.
Preferably, the molar ratio of the terephthalic acid, the isophthalic acid and the sebacic acid is (1.5-2.5): (2-3): 1, wherein specific values in (1.5-2.5) can be, for example, 1.6, 1.7, 1.8, 1.9, 2, 2.1, 2.2, 2.3, 2.4, 2.45 and the like; specific values in (2 to 3) may be, for example, 2.05, 2.1, 2.15, 2.2, 2.25, 2.3, 2.35, 2.4, 2.45, 2.5, 2.55, 2.6, 2.65, 2.7, 2.75, 2.8, 2.85, 2.9, 2.95, and the like.
Preferably, the reactant a is prepared by a method comprising:
and carrying out esterification reaction on dihydric alcohol and dibasic acid to obtain a reactant A.
Preferably, the starting materials for the reaction also include a catalyst.
Preferably, the catalyst comprises at least one of sodium acetate, zinc acetate, manganese acetate, antimony acetate, tetrabutyl titanate or isopropyl titanate.
The catalyst is preferably 0.01 to 0.02% by mass of the total mass of the dibasic acid and the glycol, and may be, for example, 0.012%, 0.014%, 0.016%, 0.018%, or the like.
Preferably, the reaction is carried out in the presence of a protective atmosphere.
Preferably, the protective atmosphere comprises nitrogen.
Preferably, the reaction comprises mixing dibasic acid and dihydric alcohol, and then carrying out a first-stage reaction and a second-stage reaction to obtain the reactant A.
Preferably, the mixing temperature is 100 ~ 150 ℃, for example can be 110 ℃, 120 ℃, 130 ℃, 140 ℃ etc..
Preferably, the rotation speed of the mixing is 60 to 120rpm, and may be, for example, 70rpm, 80rpm, 90rpm, 100rpm, 110rpm, or the like.
Preferably, the temperature of the first stage reaction is 160 to 195 ℃, for example 165 ℃, 170 ℃, 175 ℃, 180 ℃, 185 ℃, 190 ℃ and the like.
Preferably, the time of the first stage reaction is 1.5 to 2.5h, for example, 1.6h, 1.8h, 2h, 2.2h, 2.4h, etc.
The temperature of the second-stage reaction is preferably 200 to 225 ℃ and may be, for example, 205 ℃, 210 ℃, 215 ℃, 220 ℃ or the like.
Preferably, the time of the second stage reaction is 2 to 3 hours, and may be, for example, 2.2 hours, 2.4 hours, 2.6 hours, 2.8 hours, etc.
In the preparation method of the reactant A, the reaction is stopped when the esterification rate is more than 95% in the second stage of reaction; the esterification rate was calculated from the outflow volume of by-product water.
The molar ratio of the polyhydric alcohol to the side chain-modifying substance in the raw material of the reactant B is preferably 1 (1 to 1.5), and may be, for example, 1:1, 1.
Preferably, the functionality of the polyol in the starting material of the reactant B is 3 or more, and may be, for example, 3, 4, 5, etc.
Preferably, the polyhydric alcohol in the raw materials of the reactant B comprises at least one of trimethylolpropane, pentaerythritol or glycerol.
Preferably, the polyhydric alcohol in the raw material of the reactant B is trimethylolpropane.
Preferably, the side chain-modifying substance comprises at least one of β - (acryloyloxy) propionic acid, 6- (acryloyloxy) hexanoic acid, mono-2- (methacryloyloxy) ethyl maleate, 4- (4-acryloyloxy-tert-butoxy) -benzoic acid, 4- (3- (acryloyloxy) propoxy) benzoic acid, mono (2-acryloyloxyethyl succinate), 4- [4- (acryloyloxy) phenylazo ] benzoic acid or 3- (propionyloxy) benzoic acid.
Preferably, the reactant B is prepared by a method comprising:
and carrying out esterification reaction on the polyhydric alcohol and the side chain modified substance to obtain a reactant B.
Preferably, the feedstock for the reaction further comprises a catalyst.
Preferably, the catalyst comprises at least one of sodium acetate, zinc acetate, manganese acetate, antimony acetate, tetrabutyl titanate or isopropyl titanate.
Preferably, the catalyst accounts for 0.01 to 0.02% of the total mass of the polyol and the side chain-modified substance, and may be, for example, 0.012%, 0.014%, 0.016%, 0.018%, or the like.
Preferably, the reaction is carried out in the presence of a protective atmosphere.
Preferably, the protective atmosphere comprises nitrogen.
Preferably, the reaction comprises mixing the polyol and the side chain modification substance, and then reacting to obtain the reactant B.
Preferably, the mixing temperature is 100-150 ℃, for example, can be 110 ℃, 120 ℃, 130 ℃, 140 ℃.
Preferably, the mixing time is 0.5 to 1.5h, for example, 0.6h, 0.8h, 1h, 1.2h, 1.4h, etc.
Preferably, the reaction temperature is 200 ~ 250 ℃, for example can be 205 degrees, 210 degrees, 215 degrees, 220 degrees, 225 degrees, 230 degrees, 235 degrees, 240 degrees, 245 degrees C.
Preferably, the reaction is carried out to an esterification rate of greater than 98%.
In the present invention, the reaction is carried out until the esterification rate is more than 98%, wherein the esterification rate is determined according to the volume of water, a by-product of the reaction.
In a second aspect, the present invention provides a method for producing a photocurable resin according to the first aspect, the method comprising the steps of:
and carrying out polycondensation reaction on the reactant A and the reactant B to obtain the photocuring resin.
The temperature of the polycondensation reaction is preferably 225 to 240 ℃ and may be, for example, 228 ℃, 230 ℃, 232 ℃, 234 ℃, 236 ℃, 238 ℃ or the like.
Preferably, the pressure of the polycondensation reaction is 100Pa or less, and may be, for example, 10Pa, 20Pa, 40Pa, 60Pa, 80Pa, or the like.
The rotational speed of the polycondensation reaction is preferably 60 to 120rpm, and may be, for example, 70rpm, 80rpm, 90rpm, 100rpm, 110rpm, or the like.
Preferably, the raw materials for the polycondensation reaction further include a catalyst.
Preferably, the catalyst comprises at least one of dibutyltin oxide, dibutyltin dilaurate, antimony ethylene glycol, or antimony trioxide.
Preferably, the catalyst is 0.0033 to 0.0055% of the total molar amount of the reactant a and the reactant B, and may be, for example, 0.0034%, 0.0036%, 0.0038%, 0.004%, 0.0042%, 0.0044%, 0.0046%, 0.0048%, 0.005%, 0.0052%, 0.0054%, or the like.
Preferably, the polycondensation is carried out to a system intrinsic viscosity of 0.3 to 0.5dl/g, for example, 0.31dl/g, 0.32dl/g, 0.33dl/g, 0.34dl/g, 0.35dl/g, 0.36dl/g, 0.37dl/g, 0.38dl/g, 0.39dl/g, 0.4dl/g, 0.41dl/g, 0.42dl/g, 0.43dl/g, 0.44dl/g, 0.45dl/g, 0.46dl/g, 0.47dl/g, 0.48dl/g, 0.49dl/g, etc.
In a third aspect, the present invention provides a photocurable coating comprising the photocurable resin according to the first aspect, a reactive diluent and a photoinitiator.
Preferably, the photocurable coating comprises, in parts by weight, 45 to 55 parts (e.g., 46 parts, 48 parts, 50 parts, 52 parts, 54 parts, etc.) of the photocurable resin according to the first aspect, 25 to 35 parts (e.g., 26 parts, 28 parts, 30 parts, 32 parts, 34 parts, etc.) of a reactive diluent, and 4.5 to 5.5 parts (e.g., 4.6 parts, 4.8 parts, 5 parts, 5.2 parts, 5.4 parts, etc.) of a photoinitiator.
Preferably, the photo-curing coating further comprises 0.005-0.015 parts of leveling agent, such as 0.006 parts, 0.008 parts, 0.01 parts, 0.012 parts, 0.014 parts and the like.
The recitation of numerical ranges herein includes not only the above-recited values, but also any values between any of the above-recited numerical ranges not recited, and for brevity and clarity, is not intended to be exhaustive of the specific values encompassed within the range.
Compared with the prior art, the invention has the following beneficial effects:
the invention provides a light-cured resin and a preparation method and application thereof. The light-cured resin takes saturated polyester as a main chain, and carbon-carbon double bonds and acyloxy groups are introduced into a side chain of the light-cured resin, so that the curing speed of the resin can be improved. So that the coating comprising the light-cured resin has high adhesion to a substrate, is healthy and environment-friendly, and is suitable for batch production.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
The embodiment provides a light-cured resin, the main chain structure of the light-cured resin is saturated polyester, and the side chain of the light-cured resin contains acryloxy; the raw materials of the light-cured resin comprise a reactant A and a reactant B in a molar ratio of 5.27; the raw material of the reactant A comprises dibasic acid and dihydric alcohol with the molar ratio of 5.27; the dibasic acids comprise terephthalic acid, isophthalic acid and sebacic acid in a molar ratio of 2.05; the dihydric alcohol comprises neopentyl glycol and ethylene glycol in a molar ratio of 3.16; the raw materials of the reactant B comprise beta-acryloxypropionic acid and trimethylolpropane with the molar ratio of 1:1.
The embodiment provides a preparation method of the light-cured resin, which specifically comprises the following steps:
(1) Putting 0.08g of terephthalic acid, isophthalic acid, sebacic acid, neopentyl glycol, ethylene glycol and tetrabutyl titanate and 0.10g of zinc acetate (the total amount of tetrabutyl titanate and zinc acetate accounts for 0.012 percent of the total mass of dibasic acid and dihydric alcohol) into a 2L stainless steel reaction kettle, stirring at the rotating speed of 100rpm under the protection of nitrogen, rapidly heating to 150 ℃, fully mixing, gradually heating to 180 ℃ for reaction for 2 hours, then heating to 210 ℃ for reaction for 2.5 hours, and finishing the reaction when the esterification rate is more than 95 percent to obtain a reactant A; (ii) a
(2) Adding 0.12g of beta-acryloxypropionic acid, trimethylolpropane and zinc acetate (the zinc acetate accounts for 0.012 percent of the total mass of the beta-acryloxypropionic acid and the trimethylolpropane) into a 1L stainless steel reaction kettle, stirring under the protection of nitrogen, wherein the stirring speed is 100rpm, keeping the temperature unchanged when the temperature is raised to 150 ℃, stirring for 1h, then gradually raising the temperature to 240 ℃ for reaction, and finishing the reaction when the esterification rate is more than 98 percent to obtain a reactant B;
(3) Adding the reactant A obtained in the step (1) and the reactant B obtained in the step (2) into a 2L stainless steel kettle, mixing, fully stirring for 30min, adding 0.1g of antimony trioxide, continuously heating, slowly reducing the pressure, adjusting the rotating speed to 60rpm, controlling the temperature to be between 225 and 240 ℃, gradually reducing the pressure to be below 100Pa to perform polycondensation reaction, sampling and analyzing, stopping stirring when the viscosity of a polymer reaches 0.3 to 0.5dl/g, eliminating vacuum, pressurizing and discharging to obtain the light-cured resin.
Example 2
The embodiment provides a light-cured resin, the main chain structure of the light-cured resin is polyester, and the side chain of the light-cured resin contains acryloxy; the raw materials of the light-cured resin comprise a reactant A and a reactant B in a molar ratio of 5.27; the raw material of the reactant A comprises dibasic acid and dihydric alcohol with the molar ratio of 5.27; the dibasic acids comprise terephthalic acid, isophthalic acid and sebacic acid in a molar ratio of 2.05; the dihydric alcohol comprises neopentyl glycol and ethylene glycol in a molar ratio of 3.16; the raw materials of the reactant B comprise beta-acryloxy propionic acid and trimethylolpropane with the molar ratio of 1:1.
This example provides a method for preparing the photocurable resin, which includes the same steps as example 1.
Example 3
The embodiment provides a light-cured resin, the main chain structure of the light-cured resin is polyester, and the side chain of the light-cured resin contains acryloxy; the raw materials of the light-cured resin comprise a reactant A and a reactant B in a molar ratio of 5.27; the raw material of the reactant A comprises a dibasic acid and a dihydric alcohol which have a molar ratio of 5.27; the dibasic acids comprise terephthalic acid, isophthalic acid and sebacic acid in a molar ratio of 2.05; the diols comprise neopentyl glycol and ethylene glycol in a molar ratio of 3.16; the raw materials of the reactant B comprise beta-acryloxypropionic acid and trimethylolpropane with the molar ratio of 1:1.
This example provides a method for preparing the photocurable resin, which includes the same steps as example 1.
Example 4
The embodiment provides a light-cured resin, the main chain structure of the light-cured resin is polyester, and the side chain of the light-cured resin contains acryloxy; the raw materials of the light-cured resin comprise a reactant A and a reactant B in a molar ratio of 5.27; the raw materials of the reactant A comprise polybasic acid and polyhydric alcohol in a molar ratio of 5.27; the polybasic acid comprises terephthalic acid, isophthalic acid and sebacic acid in a molar ratio of 2.05; the polyol comprises neopentyl glycol and ethylene glycol in a molar ratio of 3.16; the raw materials of the reactant B comprise beta-acryloxy propionic acid and trimethylolpropane with the molar ratio of 1:1.
This example provides a method for preparing the photocurable resin, which includes the same steps as example 1.
Example 5
The embodiment provides a light-cured resin, the main chain structure of the light-cured resin is polyester, and the side chain of the light-cured resin contains acryloxy; the raw materials of the light-cured resin comprise a reactant A and a reactant B in a molar ratio of 5.27; the raw materials of the reactant A comprise polybasic acid and polyhydric alcohol in a molar ratio of 5.27; the polybasic acid comprises terephthalic acid, isophthalic acid and sebacic acid in a molar ratio of 2.05; the polyol comprises neopentyl glycol and ethylene glycol in a molar ratio of 3.16; the raw materials of the reactant B comprise beta-acryloxy propionic acid and trimethylolpropane with the molar ratio of 1:1.
This example provides a method for preparing the photocurable resin, which includes the same steps as example 1.
Example 6
This example provides a photocurable resin, which is different from example 1 only in that the amount of the reactant B is reduced so that the molar ratio of the reactant a to the reactant B is 5.27.
Example 7
This example provides a photocurable resin, which is different from example 1 only in that the amount of the reactant B is increased so that the molar ratio of the reactant a to the reactant B is 5.27.
Example 8
This example provides a photocurable resin which differs from example 1 only in that the above trimethylolpropane is replaced with glycerol in an equal molar amount of hydroxyl groups, and the other raw materials, the amount ratio, and the preparation method are the same as those of example 1.
Comparative example 1
This comparative example provides a photocurable resin which differs from example 1 only in that the β -acryloxypropionic acid was replaced with an equimolar amount of acrylic acid, and the other raw materials, the amount ratio, and the preparation method were the same as those of example 1.
Comparative example 2
This comparative example provides a photocurable resin that is the unsaturated polyester provided in patent document CN103059285a, example 1.
Application example
A photocuring coating comprises 50 parts of photocuring resin provided by examples 1-8 and comparative examples 1-2, 30 parts of reactive diluent (hexanediol diacrylate), 184 parts of photoinitiator and 0.01 part of leveling agent (Solvesso 150).
Performance testing
(1) Intrinsic viscosity: adopts GB/T14190-2008 fiber grade polyester the test was performed by the chip on (PET) test method;
(2) Curing speed: delivering a photocurable coating comprising the photocurable resin provided in examples 1-8 and comparative examples 1-2 under a Hg lamp light source, repeatedly embossing and scratching with a fingernail without generating imprint as a complete curing standard, and determining a belt speed of a completely cured sample; wherein, the larger the value is, the longer the photocuring time is, the slower the photocuring speed is;
(3) Adhesion force: coating a photocuring paint comprising the photocuring resin provided by the examples 1-8 and the comparative examples 1-2 on an ABS plate, baking for 3 minutes at 60 ℃, curing by using UV light with the wavelength of 300nm, and testing the performance of the coating according to GB/T9286-1998 standard;
(4) Appearance: after curing, observing whether the surface of the coating cracks or not; if there is no crack, then mark as "pass"; if there is a crack, the mark is "fail".
The specific test results are shown in table 1:
TABLE 1
Figure BDA0003854460250000121
Figure BDA0003854460250000131
As can be seen from the table above, the photocuring resin provided by the invention takes saturated polyester as a main chain, and introduces carbon-carbon double bonds and acyloxy groups into side chains, so that the problem of slow curing speed of unsaturated polyester is effectively solved, and the adhesive force of a coating is improved; as can be seen from examples 1 to 5, the coating comprising the photocurable resin had a photocuring speed of 51 to 97m/min and an adhesion of 4B to 5B.
As is clear from comparison between example 1 and examples 6 and 7, when the amount of the reactant B is not within a specific range, that is, when the content of the acryloyloxy group is not within a specific range, the photocuring rate of the coating is lowered, the adhesion is lowered, or the photocuring rate is too high, and cracks are likely to occur.
As is clear from comparison between example 1 and example 8, when the trimethylolpropane is replaced with glycerol in an equal molar amount of hydroxyl groups, the coating material is slower in photocuring speed and the adhesion is lowered.
As can be seen from the comparison of example 1 with comparative example 1, when the photo-curable resin has no acyloxy group, the photo-curing speed of the coating is reduced, and the coating has cracks; the performance of the light-cured resin provided by the invention is superior to that of the conventional unsaturated polyester resin.
In conclusion, the photocuring resin provided by the invention has the advantages that the photocuring double-bond monomer is introduced into the side chain instead of two ends of the main chain, so that the photocuring resin with controllable functionality, high curing speed and strong adhesive force is obtained.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are only exemplary embodiments of the present invention, and are not intended to limit the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. The photocuring resin is characterized in that the main chain structure of the photocuring resin is a polyester structure, and a side chain contains a carbon-carbon double bond and an acyloxy group.
2. The photocurable resin according to claim 1, wherein the polyester of the main chain structure of the photocurable resin is a saturated polyester;
preferably, the raw materials of the light-curable resin include a reactant a and a reactant B;
the raw materials of the reactant A comprise dihydric alcohol and dibasic acid; the raw materials of the reactant B comprise polyhydric alcohol and a side chain modification substance; the side chain modifying substance comprises a compound containing carboxyl, a carbon-carbon double bond and an acyloxy group;
preferably, the molar ratio of the reactant A to the reactant B is 1 (0.1-1);
preferably, the intrinsic viscosity of the photocurable resin is 0.3 to 0.5dl/g.
3. The photocurable resin of claim 2, wherein the molar ratio of the diol to the diacid in the starting materials of reactant a is (1-2): 1;
preferably, the dihydric alcohol in the raw material of the reactant A comprises at least one of ethylene glycol, 1,2-propylene glycol, 2-methyl-1,3-propylene glycol, 2-butyl-2-ethyl-1,3-propylene glycol, 1,4-butanediol, pentanediol, neopentyl glycol, 1-5-pentanediol, 3-methyl-1,5-pentanediol, hexanediol, 1,4-cyclohexanedimethanol, diethylene glycol, 2,2,4-trimethyl-1,3-pentanediol;
preferably, the glycol comprises a combination of neopentyl glycol and ethylene glycol;
preferably, the molar ratio of the neopentyl glycol to the ethylene glycol is 1 (1-2);
preferably, the dibasic acid in the raw material of the reactant A comprises at least one of terephthalic acid, isophthalic acid, phthalic anhydride, sebacic acid, adipic acid, 1,4-naphthalene dicarboxylic acid, 2,7-naphthalene dicarboxylic acid or 2,6-naphthalene dicarboxylic acid;
preferably, the dibasic acid comprises a combination of terephthalic acid, isophthalic acid, and sebacic acid;
preferably, the molar ratio of the terephthalic acid, the isophthalic acid and the sebacic acid is (1.5-2.5): (2-3): 1.
4. The photocurable resin of claim 2 or 3, wherein the reactant A is prepared by a method comprising:
carrying out esterification reaction on dihydric alcohol and dibasic acid to obtain a reactant A;
preferably, the feedstock for the reaction further comprises a catalyst;
preferably, the catalyst comprises at least one of sodium acetate, zinc acetate, manganese acetate, antimony acetate, tetrabutyl titanate or isopropyl titanate;
preferably, the catalyst accounts for 0.01-0.02% of the total mass of the dibasic acid and the dihydric alcohol;
preferably, the reaction is carried out in the presence of a protective atmosphere;
preferably, the reaction comprises mixing dibasic acid and dihydric alcohol, and then carrying out a first-stage reaction and a second-stage reaction to obtain the reactant A;
preferably, the temperature of the mixing is 100 to 150 ℃;
preferably, the temperature of the first stage reaction is 160-195 ℃;
preferably, the time of the first stage reaction is 1.5-2.5 h;
preferably, the temperature of the second-stage reaction is 200-225 ℃;
preferably, the time of the second stage reaction is 2 to 3 hours.
5. The photocurable resin of claim 2, wherein the molar ratio of the polyol to the side chain-modifying substance in the raw materials of the reactant B is 1 (1-1.5);
preferably, the functionality of the polyhydric alcohol in the raw materials of the reactant B is more than or equal to 3;
preferably, the polyhydric alcohol in the raw materials of the reactant B comprises at least one of trimethylolpropane, pentaerythritol or glycerol;
preferably, the polyhydric alcohol in the raw materials of the reactant B is trimethylolpropane;
preferably, the side chain-modifying substance comprises at least one of β - (acryloyloxy) propionic acid, 6- (acryloyloxy) hexanoic acid, mono-2- (methacryloyloxy) ethyl maleate, 4- (4-acryloyloxy-tert-butoxy) -benzoic acid, 4- (3- (acryloyloxy) propoxy) benzoic acid, mono (2-acryloyloxyethyl succinate), 4- [4- (acryloyloxy) phenylazo ] benzoic acid or 3- (propionyloxy) benzoic acid.
6. The photocurable resin of claim 2 wherein the reactant B is prepared by a process comprising:
carrying out esterification reaction on polyol and a side chain modified substance to obtain a reactant B;
preferably, the feedstock for the reaction further comprises a catalyst;
preferably, the catalyst comprises at least one of sodium acetate, zinc acetate, manganese acetate, antimony acetate, tetrabutyl titanate or isopropyl titanate;
preferably, the catalyst accounts for 0.01-0.02% of the total mass of the polyalcohol and the side chain modification substance;
preferably, the reaction is carried out in the presence of a protective atmosphere;
preferably, the reaction comprises mixing a polyol with a side chain modification substance, and then reacting to obtain the reactant B;
preferably, the temperature of the mixing is 100 to 150 ℃;
preferably, the mixing time is 0.5-1.5 h;
preferably, the temperature of the reaction is 200-250 ℃;
preferably, the reaction is carried out to an esterification rate of greater than 98%.
7. A method for producing a photocurable resin according to any one of claims 1-6, comprising the steps of:
and carrying out polycondensation reaction on the reactant A and the reactant B to obtain the photocuring resin.
8. The method according to claim 7, wherein the temperature of the polycondensation reaction is 225 to 240 ℃;
preferably, the pressure of the polycondensation reaction is less than or equal to 100Pa;
preferably, the rotation speed of the polycondensation reaction is 60-120 rpm;
preferably, the raw materials for the polycondensation reaction further include a catalyst;
preferably, the catalyst comprises at least one of dibutyltin oxide, dibutyltin dilaurate, ethylene glycol antimony, or antimony trioxide;
preferably, the catalyst accounts for 0.0033 to 0.0055 percent of the total molar amount of the reactant A and the reactant B;
preferably, the polycondensation is carried out until the intrinsic viscosity of the system is 0.3 to 0.5dl/g.
9. A photocurable coating comprising the photocurable resin according to any one of claims 1-6, a reactive diluent and a photoinitiator.
10. The photocurable coating according to claim 9, wherein the photocurable coating comprises, in parts by weight, 45 to 55 parts of the photocurable resin according to any one of claims 1 to 6, 25 to 35 parts of a reactive diluent, and 4.5 to 5.5 parts of a photoinitiator;
preferably, the photocureable coating also comprises 0.005-0.015 part of a leveling agent.
CN202211148657.3A 2022-09-20 2022-09-20 Light-cured resin and preparation method and application thereof Pending CN115368542A (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105601900A (en) * 2016-01-29 2016-05-25 深圳市容大感光科技股份有限公司 Polyester-type alkaline-water-soluble photocuring resin and preparation method thereof, and photoinduced imaging agent
CN105669962A (en) * 2016-03-16 2016-06-15 无锡海特圣大光电材料科技有限公司 Preparation method of novel ultraviolet light curing powder coating resin
CN111925702A (en) * 2020-08-25 2020-11-13 江南大学 Photocurable coating containing hyperbranched polyester ether type photocureable resin and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105601900A (en) * 2016-01-29 2016-05-25 深圳市容大感光科技股份有限公司 Polyester-type alkaline-water-soluble photocuring resin and preparation method thereof, and photoinduced imaging agent
CN105669962A (en) * 2016-03-16 2016-06-15 无锡海特圣大光电材料科技有限公司 Preparation method of novel ultraviolet light curing powder coating resin
CN111925702A (en) * 2020-08-25 2020-11-13 江南大学 Photocurable coating containing hyperbranched polyester ether type photocureable resin and preparation method thereof

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Application publication date: 20221122