CN109749071B - Silicon-containing waterborne UV (ultraviolet) bio-based unsaturated polyester and preparation method thereof - Google Patents
Silicon-containing waterborne UV (ultraviolet) bio-based unsaturated polyester and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the field of coatings, and discloses silicon-containing water-based UV (ultraviolet) bio-based unsaturated polyester and a preparation method thereof. The method comprises the following steps: mixing bio-based dihydric alcohol and carboxyl-containing dihydric alcohol to form clear liquid, adding a silane coupling agent, a catalyst and a polymerization inhibitor into the clear liquid to perform modification reaction, adding bio-based dibasic acid, the catalyst and the polymerization inhibitor into the clear liquid after the modification reaction is finished to perform photocuring reaction, cooling a product after the photocuring reaction is finished to room temperature, adding a neutralizer into the product to perform neutralization, and then mixing the product with a photoinitiator to obtain the silicon-containing waterborne UV bio-based unsaturated polyester. According to the invention, through modification, Si-O bonds are introduced, so that the weather resistance, the thermal degradation temperature and the hardness are improved, the obtained product has no obvious change within 3 months, and the stability is good, which indicates that the comprehensive performance of the waterborne UV unsaturated polyester is improved.
Description
Technical Field
The invention belongs to the field of coatings, and particularly relates to silicon-containing water-based UV (ultraviolet) bio-based unsaturated polyester and a preparation method thereof.
Background
The water-based UV coating has the advantages of both water-based and ultraviolet-curable coatings, has excellent construction operability and environmental protection performance, and is a novel green material which is researched more.
At present, monomers for synthesizing the water-based paint oligomer are mostly derived from petroleum which is a fossil energy source. However, the petroleum-based polymer materials have long degradation period and even are difficult to degrade in natural environment, and can cause pollution to soil, water and the like after long-term use; on the other hand, fossil energy sources such as petroleum are not renewable, the utilization rate of the fossil energy sources such as petroleum in the world is increased year by year since the industrial revolution, and researchers predict that the fossil energy sources in the world will be exhausted in 2050 according to the current speed of human consumption of the fossil energy sources. Green, recyclable bio-based chemical materials are favored by industry and researchers. The bio-based material is a biomass synthetic material obtained by taking renewable resources such as crops, wastes, trees, other plants and residues and inclusions thereof as raw materials through processes of biosynthesis, biological processing and biorefinery, and the large-scale development and application of the bio-based material can reduce the dependence of chemical material industry on fossil resources, and is beneficial to environmental improvement and economic coordinated development.
Itaconic acid is evaluated by the U.S. department of energy as one of the most potential 12 bio-based chemical materials, has two-COOH and one alpha and beta unsaturated double bond, and is very active chemically. Besides bulk polymerization, the copolymer can also be copolymerized with other olefin monomers, and can be subjected to various esterification reactions, addition reactions and polymerization reactions, thereby preparing various novel high polymer materials. At present, itaconic acid is produced mainly by agricultural and sideline products such as cheap straws, sugarcane, beet, starch, vinasse and the like under the action of strains such as candida, aspergillus itaconate, aspergillus terreus and the like. The raw materials are widely available and renewable, and the prepared bio-based product has little pollution to the environment and has huge application potential and value.
The preparation method of the unsaturated polyester is simple, but has the defects of low hardness, poor weather resistance, poor hydrophobic property and the like, and the market space of the unsaturated polyester is limited. In the prior art, unsaturated polyester is relatively rarely modified, and the method mainly focuses on the following points: (1) long-chain dibasic acid or glycol is introduced, and although the flexibility can be improved by the mode, the crosslinking curing density is reduced and the hardness is reduced due to chain growth; (2) the inorganic nanoparticles are modified by utilizing good photoelectric effect, although the hardness can be improved by the mode, the prepared paint film has certain photoelectric property, the inorganic nanoparticles have the characteristic of easy agglomeration, and are difficult to be uniformly dispersed in resin, and even if the inorganic nanoparticles are uniformly dispersed, the storage time is also a problem; (3) the method is characterized in that partial large-chain silicon resin, fluorine resin or fluorine-silicon resin is modified by copolymerization and other modes, elements such as Si, F and the like are introduced, but the long chains of silicon and fluorine inevitably affect the photocuring density, so that the adhesion is affected, and the monomers have different chain lengths and different performances, so that the molecular chain structure of the synthesized resin cannot be well controlled.
Therefore, it is necessary to develop a bio-based aqueous UV resin with good combination of properties.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention mainly aims to provide a preparation method of silicon-containing water-based UV bio-based unsaturated polyester. The invention adopts a monomer containing active functional groups, firstly synthesizes a micromolecule modifier with a fixed chain length and a chain segment with active groups, and then carries out block copolymerization, thereby not only avoiding the problem of inorganic nano materials, but also well controlling the molecular chain structure of the resin and fully playing the performance of introduced Si.
Another object of the present invention is to provide the silicon-containing aqueous UV bio-based unsaturated polyester prepared by the above method
It is still another object of the present invention to provide the use of the above silicon-containing aqueous UV bio-based unsaturated polyester for paper finishing, leather finishing, glass and tile finishing underlayers.
The purpose of the invention is realized by the following scheme:
a preparation method of silicon-containing water-based UV bio-based unsaturated polyester comprises the following steps:
(1) mixing bio-based diol and carboxyl-containing diol to form a clear liquid;
(2) adding a silane coupling agent, a catalyst and a polymerization inhibitor into the clear liquid obtained in the step (1) to perform modification reaction;
(3) adding bio-based dibasic acid, a catalyst and a polymerization inhibitor into the product obtained after the modification reaction in the step (2) to perform a photocuring reaction;
(4) and (4) cooling the product obtained after the photocuring reaction in the step (3) to room temperature, adding a neutralizer for neutralization, and then mixing with a photoinitiator to obtain the silicon-containing waterborne UV bio-based unsaturated polyester.
The bio-based diol in the step (1) is at least one of 1, 4-butanediol, 1, 3-propanediol and 2, 3-butanediol, and is preferably 1, 4-butanediol; the dihydric alcohol containing carboxyl is at least one of 2, 2-dimethylolpropionic acid and dimethylolbutyric acid, and preferably 2, 2-dimethylolpropionic acid;
the using amount of the bio-based diol and the carboxyl-containing diol in the step (1) is 5-30% of the total molar amount of the bio-based diol and the carboxyl-containing diol;
the silane coupling agent in the step (2) is a silane coupling agent containing an epoxy functional group, and preferably at least one of a silane coupling agent KH560, a silane coupling agent SCA-403 and a silane coupling agent A-186; the dosage of the silane coupling agent meets the condition that the molar ratio of the silane coupling agent to the dihydric alcohol containing carboxyl is 1: 1;
the catalyst in the step (2) is at least one of concentrated sulfuric acid (96 wt% -98 wt%), p-toluenesulfonic acid, N dimethyl benzylamine and triphenylphosphine; preferably at least one of N, N dimethyl benzylamine and triphenylphosphine; the dosage of the catalyst is 0.5-1.0% of the total mass of the carboxyl-containing dihydric alcohol and the silane coupling agent.
The polymerization inhibitor in the step (2) is at least one of hydroquinone (1, 4-dihydroxybenzene); the dosage of the polymerization inhibitor is 0.5 to 1.0 percent of the total mass of the carboxyl-containing dihydric alcohol and the silane coupling agent.
The modification reaction in the step (2) is carried out at 85-95 ℃ for 1.5-2.5 h until the acid value is reduced to 25-35 mg (KOH)/g.
The bio-based dibasic acid in the step (3) is itaconic acid (methylene succinic acid, itaconic acid), and the using amount of the bio-based dibasic acid is 1.1-1.5 times of the total molar amount of the bio-based dibasic acid and the carboxyl-containing dihydric alcohol in the step (1);
the catalyst in the step (3) is at least one of concentrated sulfuric acid (96 wt% -98 wt%), p-toluenesulfonic acid, N dimethyl Benzylamine (BDMA) and triphenylphosphine; preferably at least one of concentrated sulfuric acid and p-toluenesulfonic acid (PTSA); the dosage of the catalyst is 0.5-1.0% of the total mass of the itaconic acid, the bio-based dihydric alcohol and the dihydric alcohol containing carboxyl.
At least one of p-hydroxyanisole polymerization inhibitor and hydroquinone (1, 4-dihydroxybenzene) polymerization inhibitor in the step (3); the dosage of the polymerization inhibitor is 0.5 to 1.0 percent of the total mass of the itaconic acid, the bio-based dihydric alcohol and the dihydric alcohol containing carboxyl.
The photocuring reaction in the step (3) is carried out for 2-3 h at 135 ℃ under the protection of inert gas until the acid value reaches 200-240 mg (KOH)/g, then the temperature is kept at 135 ℃, and the vacuum pumping reaction is continued for 1-1.5 h, wherein the pressure is 0.085-0.095 MPa.
The neutralizing agent in the step (4) is at least one of triethylamine, triethanolamine, N-dimethylethanolamine and ammonia water; the dosage of the neutralizer meets the requirement that the neutralization degree of the obtained target product is 30-45%;
the photoinitiator in the step (4) is at least one of 1173 (2-hydroxy-2-methyl-1-phenyl-1-acetone), 2959 (2-hydroxy-4' - (2-hydroxyethoxy) -2-methyl propiophenone) and polyethylene glycol (beta-4- [ p- (2-dimethylamine-2-benzyl) butyrylphenyl ] piperazine) propionate; the using amount of the photoinitiator meets the requirement that the mass fraction of the photoinitiator in the silicon-containing waterborne UV bio-based unsaturated polyester is 3-6%.
In the preparation method, in order to ensure mild and controllable reaction and lower viscosity of the prepared resin, the raw materials to be added are preferably uniformly mixed in the step (2) and the step (3) and then added in batches; when the silane coupling agent, the catalyst and the polymerization inhibitor are added as in the step (2), it is preferable to mix them uniformly and add them in portions.
The silicon-containing water-based UV bio-based unsaturated polyester prepared by the method.
The silicon-containing water-based UV bio-based unsaturated polyester is applied to paper varnish, leather surface coating, glass and ceramic tile coating base layers.
The mechanism of the invention is as follows:
taking the bio-based diol as 1, 4-butanediol, the diol containing carboxyl as 2, 2-dimethylolpropionic acid, the bio-based diacid as itaconic acid, and the silane coupling agent as KH560 as an example, the reaction mechanism is as follows:
compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the traditional petroleum-based monomer is abandoned, the main reactants are mainly itaconic acid and 1,4 butanediol which are obtained by microbial fermentation, the cost of the two materials is low, and the two materials have important significance for relieving the consumption pressure of fossil energy and sustainable development;
(2) aiming at the defects of poor high temperature resistance, hydrophobicity, hardness and other performances of the unsaturated polyester, the Si-O bond is introduced through modification, so that the weather resistance, the thermal degradation temperature and the hardness are improved, the obtained product has no obvious change within 3 months and good stability, and the comprehensive performance of the water-based UV unsaturated polyester is improved.
(3) In addition, the invention adds the monomer mode in batches through multistep, make the appearance color of polyester prepared light yellow and clear, the viscosity is reduced to some extent than the traditional one-step addition method.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
The reagents used in the examples are commercially available without specific reference.
Example 1
(1) Weighing 8.56g of 1, 4-butanediol and 0.67g of 2, 2-dimethylolpropionic acid, adding into a four-neck flask provided with a circulating condensing device, heating to 60 ℃, and uniformly stirring until the 2, 2-dimethylolpropionic acid is dissolved, and clarifying the flask solution;
(2) heating to 90 ℃, weighing KH560 with the same molar weight as that of 2, 2-dimethylolpropionic acid in a beaker, wherein the mass of the KH560 is 1.18g, weighing 0.02g of N, N-dimethyl benzylamine and 0.02g of p-hydroxyanisole simultaneously, stirring and mixing with the KH560 uniformly, then slowly dripping the KH560 mixed with a catalyst and a polymerization inhibitor into a four-neck flask in four batches on average, dripping the KH560 into the four-neck flask within 8 minutes, adding the KH560 into the four-neck flask at an interval of 10 minutes, and keeping the temperature for 1.5 hours until the acid value is reduced to 30mg (KOH)/g;
(3) heating to 135 ℃, introducing nitrogen, weighing 16.01g of itaconic acid, 0.245g of p-toluenesulfonic acid and 0.245g of p-hydroxyanisole, evenly dividing the 3 into 3 parts, adding one part of the itaconic acid into a reactor, stirring uniformly, keeping the temperature for reaction for 2.5h after all the itaconic acid is dissolved, clarifying the flask solution, adding the next batch of itaconic acid, keeping the temperature for reaction for 2.5h after all the itaconic acid is added until the acid value is 220mg (KOH)/g, vacuumizing, keeping the pressure at 0.090MPa, keeping the temperature for reaction for 1h under the vacuum condition, cooling to 60 ℃, adding N, N-dimethylethanolamine, neutralizing the acid value to 40%, adding a photoinitiator 1173, and mixing to obtain the silicon-containing waterborne UV bio-unsaturated polyester, wherein the mass fraction of the photoinitiator 1173.
The prepared polyester was measured for appearance, viscosity and stability, and the synthesized unsaturated polyester was coated on a polished tinplate sticker using a paint film coater, cured for 40 seconds by a 300nm ultraviolet curing machine, and measured for adhesion, hardness, water contact angle and thermal degradation properties, with the results shown in table 1 below:
table 1 performance test results of silicon-containing aqueous UV bio-based unsaturated polyester prepared in example 1
Example 2
(1) Weighing 8.11g of 1, 4-butanediol and 1.34g of 2, 2-dimethylolpropionic acid, adding into a four-neck flask provided with a circulating condensing device, heating to 60 ℃, uniformly stirring until the 2, 2-dimethylolpropionic acid is dissolved, and clarifying the flask solution;
(2) heating to 90 ℃, weighing KH560 with the same molar weight as that of 2, 2-dimethylolpropionic acid in a beaker, wherein the mass of the KH560 is 2.36g, weighing 0.03g of N, N-dimethyl benzylamine and 0.03g of p-hydroxyanisole simultaneously, stirring and mixing with the KH560 uniformly, slowly dripping the KH560 mixed with a catalyst and a polymerization inhibitor into a four-neck flask in four batches, finishing the dripping within 8 minutes of each batch, adding the next batch at an interval of 12 minutes, and after finishing the dripping, keeping the temperature for reaction for 1.5 hours until the acid value is reduced to 30mg (KOH)/g;
(3) heating to 135 ℃, introducing nitrogen, weighing 16.39g of itaconic acid, 0.24g of p-toluenesulfonic acid and 0.24g of hydroquinone, evenly dividing the 3 into 3 parts, adding one part of the itaconic acid into a reactor, stirring uniformly, standing until all the itaconic acid is dissolved, clarifying the solution in the flask, adding the next batch of itaconic acid, after all the itaconic acid is added, carrying out heat preservation reaction for 2.5h until the acid value is 220mg (KOH)/g, then vacuumizing, keeping the pressure at 0.090MPa, continuing the heat preservation reaction for 1h under the vacuum condition, then cooling to 60 ℃, adding triethanolamine, adding 40% of neutralization degree, adding a photoinitiator 1173, and mixing to obtain the silicon-containing waterborne UV bio-based unsaturated polyester, wherein the mass fraction of the photoinitiator 1173.
The prepared polyester is subjected to appearance, viscosity and stability measurement, in addition, the synthesized unsaturated polyester is coated on a polished tinplate paster by using a paint film coater, and is cured for 40s by a 300nm ultraviolet curing machine, and the adhesive force, the hardness, the water contact angle and the thermal degradation performance of the polyester are measured. The performance results are shown in table 2 below:
table 2 results of performance test of silicon-containing aqueous UV bio-based unsaturated polyester prepared in example 2
Example 3:
(1) weighing 7.21g of 1, 4-butanediol and 2.68g of 2, 2-dimethylolpropionic acid, adding into a four-neck flask provided with a circulating condensing device, heating to 60 ℃, and uniformly stirring until the 2, 2-dimethylolpropionic acid is dissolved, and clarifying the flask solution;
(2) heating to 90 ℃, weighing KH560 with the same molar weight as that of 2, 2-dimethylolpropionic acid in a beaker, wherein the mass of the KH560 is 4.72g, weighing 0.07g of N, N-dimethyl benzylamine and 0.07g of p-hydroxyanisole simultaneously, stirring and mixing with the KH560 uniformly, slowly dripping the KH560 mixed with a catalyst and a polymerization inhibitor in four batches, adding the KH560 into the four-neck flask within 8 minutes, adding the KH560 into the four-neck flask at an interval of 15 minutes, adding the next batch again, and after finishing the dripping, keeping the temperature for reaction for 1.5 hours until the acid value is reduced to 30mg (KOH)/g;
(3) heating to 135 ℃, introducing nitrogen, weighing 17.17g of itaconic acid, 0.27g of p-toluenesulfonic acid and 0.27g of p-hydroxyanisole, evenly dividing the 3 into 3 parts, adding one part of the itaconic acid into a reactor, stirring uniformly, standing until all the itaconic acid is dissolved, clarifying the flask solution, adding the next batch of itaconic acid, after all the itaconic acid is added, carrying out heat preservation reaction for 2.5h until the acid value is 220mg (KOH)/g, then vacuumizing, keeping the pressure at 0.090MPa, continuing the heat preservation reaction for 1h under the vacuum condition, cooling to 60 ℃, adding N, N-dimethylethanolamine to enable the neutralization degree to be 40%, adding a photoinitiator 1173, and mixing to obtain the silicon-containing waterborne UV bio-based unsaturated polyester, wherein the mass fraction of the photoinitiator 1173.
The prepared polyester is subjected to appearance, viscosity and stability measurement, in addition, the synthesized unsaturated polyester is coated on a polished tinplate paster by using a paint film coater, and is cured for 40s by a 300nm ultraviolet curing machine, and the adhesive force, the hardness, the water contact angle and the thermal degradation performance of the polyester are measured. The performance results are shown in table 3 below:
table 3 performance test results of the silicon-containing aqueous UV bio-based unsaturated polyester prepared in example 3
Example 4:
(1) weighing 6.3g of 1, 4-butanediol and 4.02g of 2, 2-dimethylolpropionic acid, adding into a four-neck flask provided with a circulating condensing device, heating to 60 ℃, uniformly stirring until the 2, 2-dimethylolpropionic acid is dissolved, and clarifying the flask solution;
(2) heating to 90 ℃, weighing KH560 with the same molar weight as that of 2, 2-dimethylolpropionic acid in a beaker, wherein the mass of the KH560 is 7.08g, meanwhile, weighing 0.11g of N, N-dimethyl benzylamine and 0.11g of p-hydroxyanisole, uniformly stirring and mixing with the KH560, then slowly dripping the KH560 mixed with a catalyst and a polymerization inhibitor into a four-neck flask in four batches, wherein each batch is about 10 minutes, adding the next batch at an interval of 15 minutes, and after the dripping is completed, carrying out heat preservation reaction for about 1.5 hours until the acid value is reduced to 30mg (KOH)/g; (ii) a
(3) Heating to 135 ℃, introducing nitrogen, weighing 17.95g of itaconic acid, 0.28g of p-toluenesulfonic acid and 0.28g of p-hydroxyanisole, equally dividing the 3 into 3 parts, adding one part of itaconic acid into a reactor, uniformly stirring, after all the itaconic acid is dissolved, clarifying the flask solution, adding the next batch of itaconic acid, after all the itaconic acid is added, carrying out heat preservation reaction for 2.5h until the acid value is 220mg (KOH)/g, then vacuumizing, keeping the pressure at 0.090MPa, continuing the heat preservation reaction for 1h under the vacuum condition, then cooling to 60 ℃, adding triethylamine, adding 40% of neutralization degree, and adding photoinitiator 1173 for mixing to obtain the silicon-containing waterborne UV bio-based unsaturated polyester, wherein the mass fraction of the photoinitiator 1173%.
The prepared polyester is subjected to appearance, viscosity and stability measurement, in addition, the synthesized unsaturated polyester is coated on a polished tinplate paster by using a paint film coater, and is cured for 40s by a 300nm ultraviolet curing machine, and the adhesive force, the hardness, the water contact angle and the thermal degradation performance of the polyester are measured. The performance results are shown in table 4 below:
table 4 results of performance test of silicon-containing aqueous UV bio-based unsaturated polyester prepared in example 4
Comparative example 1 (no silicon, no carboxyl group containing diol modification):
(1) weighing 10.32g of 1, 4-butanediol, adding the 1, 4-butanediol into a four-neck flask provided with a circulating condensing device, heating to 135 ℃, and introducing nitrogen;
(2) weighing 17.95g of itaconic acid, 0.28g of p-toluenesulfonic acid and 0.28g of p-hydroxyanisole, adding the itaconic acid, the p-toluenesulfonic acid and the p-hydroxyanisole into a four-neck flask provided with a circulating condensing device at one time, carrying out heat preservation reaction for 2.5 hours, then vacuumizing, carrying out heat preservation reaction under the vacuum condition for 1 hour, cooling to 60 ℃, adding triethylamine, neutralizing the degree of 40%, adding a photoinitiator 1173, and mixing to obtain the waterborne UV bio-based unsaturated polyester, wherein the mass fraction of the photoinitiator 1173 is 3%.
The prepared polyester is subjected to appearance, viscosity and stability measurement, in addition, the synthesized unsaturated polyester is coated on a polished tinplate paster by using a paint film coater, and is cured for 40s by a 300nm ultraviolet curing machine, and the adhesive force, the hardness, the water contact angle and the thermal degradation performance of the polyester are measured. The performance results are shown in table 5 below:
TABLE 5 Performance test results for aqueous UV biobased unsaturated polyester prepared in comparative example 1
Comparative example 2 (no silicon, with carboxyl group containing diol):
(1) weighing 6.30g of 1, 4-butanediol and 4.02g of 2, 2-dimethylolpropionic acid, adding into a four-neck flask provided with a circulating condensing device, heating to 135 ℃, and introducing nitrogen;
weighing 17.95g of itaconic acid, 0.28g of p-toluenesulfonic acid and 0.28g of p-hydroxyanisole, adding the itaconic acid, the p-toluenesulfonic acid and the p-hydroxyanisole into a four-neck flask provided with a circulating condensing device at one time, carrying out heat preservation reaction for 2.5 hours, then vacuumizing, carrying out heat preservation reaction under the vacuum condition for 1 hour, cooling to 60 ℃, adding triethylamine, neutralizing the degree of 40%, adding a photoinitiator 1173, and mixing to obtain the waterborne UV bio-based unsaturated polyester, wherein the mass fraction of the photoinitiator 1173 is 3%.
The prepared polyester is subjected to appearance, viscosity and stability measurement, in addition, the synthesized unsaturated polyester is coated on a polished tinplate paster by using a paint film coater, and is cured for 40s by a 300nm ultraviolet curing machine, and the adhesive force, the hardness, the water contact angle and the thermal degradation performance of the polyester are measured. The performance results are shown in table 6 below:
TABLE 6 Performance test results for aqueous UV biobased unsaturated polyester prepared in comparative example 2
As can be seen from tables 1-6, the carboxyl-containing dihydric alcohol is modified by the silane coupling agent, the Si-O bond is introduced into the unsaturated polyester, the weather resistance, the thermal degradation temperature and the hardness are improved, the viscosity is reduced, the obtained product has no obvious change in 3 months, and the stability is good, so that the comprehensive performance of the waterborne UV unsaturated polyester is improved.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A preparation method of silicon-containing waterborne UV bio-based unsaturated polyester is characterized by comprising the following steps:
(1) mixing bio-based diol and carboxyl-containing diol to form a clear liquid;
(2) adding a silane coupling agent, a catalyst and a polymerization inhibitor into the clear liquid obtained in the step (1) to perform modification reaction;
(3) adding bio-based dibasic acid, a catalyst and a polymerization inhibitor into the product obtained after the modification reaction in the step (2) to perform a photocuring reaction;
(4) cooling the product obtained after the photocuring reaction in the step (3) to room temperature, adding a neutralizer for neutralization, and then mixing with a photoinitiator to obtain silicon-containing waterborne UV (ultraviolet) bio-based unsaturated polyester;
the bio-based diol in the step (1) is at least one of 1, 4-butanediol, 1, 3-propanediol and 2, 3-butanediol; the dihydric alcohol containing carboxyl in the step (1) is at least one of 2, 2-dimethylolpropionic acid and dimethylolbutyric acid;
the silane coupling agent in the step (2) is a silane coupling agent containing epoxy functional groups;
the bio-based dibasic acid in the step (3) is itaconic acid.
2. The method for preparing silicon-containing aqueous UV bio-based unsaturated polyester according to claim 1, wherein:
the using amount of the bio-based diol and the carboxyl-containing diol in the step (1) is 5-30% of the total molar amount of the bio-based diol and the carboxyl-containing diol.
3. The method for preparing silicon-containing aqueous UV bio-based unsaturated polyester according to claim 1, wherein:
the catalyst in the step (2) is at least one of concentrated sulfuric acid, p-toluenesulfonic acid, N dimethyl benzylamine and triphenylphosphine;
the polymerization inhibitor in the step (2) is at least one of p-hydroxyanisole and hydroquinone (1, 4-dihydroxybenzene);
the dosage of the silane coupling agent in the step (2) meets the condition that the molar ratio of the silane coupling agent to the dihydric alcohol containing carboxyl is 1: 1;
the dosage of the catalyst in the step (2) is 0.5-1.0% of the total mass of the carboxyl-containing dihydric alcohol and the silane coupling agent;
the using amount of the polymerization inhibitor in the step (2) is 0.5-1.0% of the total mass of the carboxyl-containing dihydric alcohol and the silane coupling agent.
4. The method for preparing the silicon-containing aqueous UV bio-based unsaturated polyester according to claim 3, wherein:
the silane coupling agent in the step (2) is at least one of a silane coupling agent KH560, a silane coupling agent SCA-403 and a silane coupling agent A-186;
the catalyst in the step (2) is at least one of N, N dimethyl benzylamine and triphenylphosphine.
5. The method for preparing silicon-containing aqueous UV bio-based unsaturated polyester according to claim 1, wherein:
the modification reaction in the step (2) is carried out at 85-95 ℃ for 1.5-2.5 h until the acid value is reduced to 25-35 mg (KOH)/g.
6. The method for preparing silicon-containing aqueous UV bio-based unsaturated polyester according to claim 1, wherein:
the using amount of the bio-based dibasic acid in the step (3) is 1.1-1.5 times of the total molar amount of the bio-based dibasic acid and the carboxyl-containing dihydric alcohol in the step (1);
the catalyst in the step (3) is at least one of concentrated sulfuric acid, p-toluenesulfonic acid, N dimethyl benzylamine and triphenylphosphine; the dosage of the catalyst is 0.5-1.0% of the total mass of the itaconic acid, the bio-based dihydric alcohol and the carboxyl-containing dihydric alcohol;
at least one of p-hydroxyanisole polymerization inhibitor and hydroquinone (1, 4-dihydroxybenzene) polymerization inhibitor in the step (3); the dosage of the polymerization inhibitor is 0.5-1.0% of the total mass of the itaconic acid, the bio-based dihydric alcohol and the carboxyl-containing dihydric alcohol.
7. The method for preparing silicon-containing aqueous UV bio-based unsaturated polyester according to claim 1, wherein:
the photocuring reaction in the step (3) is carried out for 2-3 h at 135 ℃ under the protection of inert gas until the acid value reaches 200-240 mg (KOH)/g, then the temperature is kept at 135 ℃, and the vacuum pumping reaction is continued for 1-1.5 h, wherein the pressure is 0.085-0.095 MPa.
8. The method for preparing the silicon-containing aqueous UV bio-based unsaturated polyester according to claim 1, wherein:
the neutralizing agent in the step (4) is at least one of triethylamine, triethanolamine, N-dimethylethanolamine and ammonia water; the dosage of the neutralizer meets the requirement that the neutralization degree of the obtained target product is 30-45%;
the photoinitiator in the step (4) is at least one of 1173 (2-hydroxy-2-methyl-1-phenyl-1-acetone), 2959 (2-hydroxy-4' - (2-hydroxyethoxy) -2-methyl propiophenone) and polyethylene glycol (beta-4- [ p- (2-dimethylamine-2-benzyl) butyrylphenyl ] piperazine) propionate; the using amount of the photoinitiator meets the requirement that the mass fraction of the photoinitiator in the silicon-containing waterborne UV bio-based unsaturated polyester is 3-6%.
9. A silicon-containing aqueous UV bio-based unsaturated polyester prepared according to the method of any one of claims 1 to 8.
10. Use of the silicon-containing aqueous UV bio-based unsaturated polyester according to claim 9 in paper finishing, leather finishing, glass and tile finishing underlayments.
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| CN201910095973.0A Active CN109749071B (en) | 2019-01-31 | 2019-01-31 | Silicon-containing waterborne UV (ultraviolet) bio-based unsaturated polyester and preparation method thereof |
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Citations (4)
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|---|---|---|---|---|
| JPH04198313A (en) * | 1990-11-28 | 1992-07-17 | Dainippon Ink & Chem Inc | Unsaturated polyester resin composition and gel coating agent produced by using the same |
| CN103576457A (en) * | 2012-08-10 | 2014-02-12 | 株式会社日本触媒 | Solid resin compound and purpose thereof |
| CN105061727A (en) * | 2015-07-23 | 2015-11-18 | 广州大学 | Ultraviolet cured water-borne epoxy itaconic acid resin and preparation method thereof |
| CN107674189A (en) * | 2017-09-30 | 2018-02-09 | 合众（佛山）化工有限公司 | A kind of height divides hyperbranched Si modification unsaturated polyester resin and preparation method thereof admittedly |
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2019
- 2019-01-31 CN CN201910095973.0A patent/CN109749071B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04198313A (en) * | 1990-11-28 | 1992-07-17 | Dainippon Ink & Chem Inc | Unsaturated polyester resin composition and gel coating agent produced by using the same |
| CN103576457A (en) * | 2012-08-10 | 2014-02-12 | 株式会社日本触媒 | Solid resin compound and purpose thereof |
| CN105061727A (en) * | 2015-07-23 | 2015-11-18 | 广州大学 | Ultraviolet cured water-borne epoxy itaconic acid resin and preparation method thereof |
| CN107674189A (en) * | 2017-09-30 | 2018-02-09 | 合众（佛山）化工有限公司 | A kind of height divides hyperbranched Si modification unsaturated polyester resin and preparation method thereof admittedly |
Non-Patent Citations (3)
| Title |
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| Unsaturated polyester resin/epoxy-functionalised nanosilica composites constructed by in situ polymerisation;Pan Hao;《IET Micro & Nano Letter》;20151231;第10卷(第9期);第427-431页 * |
| 有机硅改性紫外光固化水性环氧衣康酸树脂的制备及性能研究;韦星船等;《电镀与涂饰》;20161231;第35卷(第6期);第275-280页 * |
| 衣康酸酯基聚氨酯乳液的制备及其性能;王阳等;《青岛科技大学学报 自然科学版》;20180831;第39卷;第41-45、48页 * |
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