CN110229317B - UV-curable unsaturated polyester resin with high vinyl functionality, and preparation method and application thereof - Google Patents

UV-curable unsaturated polyester resin with high vinyl functionality, and preparation method and application thereof Download PDF

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CN110229317B
CN110229317B CN201910509998.0A CN201910509998A CN110229317B CN 110229317 B CN110229317 B CN 110229317B CN 201910509998 A CN201910509998 A CN 201910509998A CN 110229317 B CN110229317 B CN 110229317B
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polyester resin
unsaturated polyester
preparation
glycidyl ether
coating
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CN110229317A (en
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瞿金清
明姝婕
朱延安
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Beixin Jiabao Li Coatings Group Co ltd
South China University of Technology SCUT
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CARPOLY CHEMICAL GROUP CO LTD
South China University of Technology SCUT
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/24—Preparation of carboxylic acid esters by reacting carboxylic acids or derivatives thereof with a carbon-to-oxygen ether bond, e.g. acetal, tetrahydrofuran
    • C07C67/26—Preparation of carboxylic acid esters by reacting carboxylic acids or derivatives thereof with a carbon-to-oxygen ether bond, e.g. acetal, tetrahydrofuran with an oxirane ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/76—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring
    • C07C69/80—Phthalic acid esters
    • 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
    • C08G63/56—Polyesters derived from ester-forming derivatives of polycarboxylic acids or of polyhydroxy compounds other than from esters thereof
    • C08G63/58—Cyclic ethers; Cyclic carbonates; Cyclic sulfites ; Cyclic orthoesters
    • 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
    • C08G63/78—Preparation processes
    • C08G63/81—Preparation processes using solvents
    • 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
    • C09D167/07—Unsaturated polyesters having carbon-to-carbon unsaturation having terminal carbon-to-carbon unsaturated bonds
    • 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
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16

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Abstract

本发明公开了高乙烯基官能度的可UV固化不饱和聚酯树脂及其制备方法与应用。该制备方法是在氮气保护下，将酸酐、环氧化合物、催化剂和溶剂，搅拌并加热到90～120℃并保温1‑3h；然后在1‑2h内逐滴加溶有阻聚剂的乙烯基缩水甘油醚，在90～120℃下开环共聚反应4‑6h，测定反应体系酸值至15mg KOH/g以下，减压蒸馏脱除未反应的单体和溶剂，得到浅黄色透明不饱和聚酯。本发明的制备方法简单，所制备的高乙烯基官能度的可UV固化不饱和聚酯树脂，乙烯基官能度高，固体含量高达85％以上，黏度为2000～6000mPa·s。采用该聚酯制备UV固化涂料成本较低，涂膜具有优异的光泽度和耐介质性。

Figure 201910509998

The invention discloses a UV-curable unsaturated polyester resin with high vinyl functionality and a preparation method and application thereof. The preparation method is as follows: under nitrogen protection, acid anhydride, epoxy compound, catalyst and solvent are stirred and heated to 90-120° C. and kept for 1-3h; then ethylene with polymerization inhibitor dissolved therein is added dropwise within 1-2h base glycidyl ether, conduct a ring-opening copolymerization reaction at 90-120 ° C for 4-6 h, measure the acid value of the reaction system to below 15 mg KOH/g, and remove the unreacted monomer and solvent by vacuum distillation to obtain light yellow transparent unsaturated Polyester. The preparation method of the invention is simple, and the prepared UV-curable unsaturated polyester resin with high vinyl functionality has high vinyl functionality, a solid content of more than 85 percent, and a viscosity of 2000-6000 mPa·s. The use of the polyester to prepare the UV-curable coating is low in cost, and the coating film has excellent gloss and medium resistance.

Figure 201910509998

Description

UV-curable unsaturated polyester resin with high vinyl functionality, and preparation method and application thereof
Technical Field
The invention relates to a polyester resin, in particular to an unsaturated polyester resin capable of being cured by ultraviolet light, a preparation method and application thereof, belonging to the field of fine chemical engineering.
Background
The UV curing coating is an insoluble and infusible solid coating formed by polymerization of a monomer containing an active group through the polymerization reaction of a photoinitiator which is cracked into free radicals or anions and cations by UV irradiation. Compared with the traditional curing technology, the UV curing technology saves energy, has high curing speed and good film coating performance, and is suitable for large-scale industrial production. The preparation of the common polyester acrylate is that acrylic acid is introduced to a polyester chain through an esterification reaction on a hydroxyl polyester resin molecular chain, the esterification reaction at the temperature of 160-200 ℃ is needed, benzene and homologous compounds thereof used as a dehydration solvent are toxic and are not easy to remove from the resin. For example, in the Chinese patent application CN105061738A, terephthalic acid, 2,4, 4-tetramethyl-1, 3-cyclobutanediol and ethylene glycol are subjected to polycondensation reaction under the action of a catalyst at the reaction temperature of 200 ℃ and 260 ℃ to obtain a polycondensation product, and then acrylic acid or acrylic ester is added into the system after the reaction to obtain the polyester acrylic UV curing monomer. The Chinese patent application CN105504245A firstly prepares carboxyl-containing polyester resin, the esterification reaction temperature is 200 ℃, and then the carboxyl-containing polyester resin reacts with acrylic acid glycidyl ether or methacrylic acid glycidyl ether to prepare vinyl polyester resin, so that the raw material cost is high, the energy consumption is high, and the large-scale industrial production is not facilitated. The literature reports that the preparation of UV curable polyester resins requires esterification at higher temperatures (above 180 ℃), the process for introducing vinyl or acrylic monomers is complex and costly.
Chinese patent application 2016111382348(CN106748765A, 2017.5.31) discloses a UV-curable polyester, and a preparation method and application thereof. The preparation method comprises the following steps: 1) mixing 1 part of triglycidyl ether and 3-4 parts of acrylic acid monomer in terms of mole fraction in a reaction kettle, adding a quaternary ammonium salt catalyst and a polymerization inhibitor organic solvent, and reacting at 105-125 ℃ until the acid value is lower than 10 mgKOH/g; 2) adding anhydride, a polymerization inhibitor and p-toluenesulfonic acid into the substrate prepared in the step 1), reacting for 2-4h at the temperature of 105-130 ℃, then adding an epoxy compound which is 0.9-1.2 times of the mole number of the anhydride, adding a quaternary ammonium salt catalyst and an organic solvent, reacting until the acid value is less than 10mgKOH/g, removing the solvent by reduced pressure distillation, cooling and discharging; the resin has a solid content of more than 100% and a viscosity of 3000-30000 mPas. The UV curing coating prepared from the polyester has excellent film coating performance and lower cost. However, the polyester acrylic resin prepared by the technology has low vinyl content, and as one part of triglycidyl ether reacts with acrylic acid, at most 3 vinyl groups can be introduced into the molecular chain of the resin, namely the vinyl functionality of the product resin is 3, the crosslinking density of the coating film at the later stage of UV curing is low, and the chemical resistance of the coating film is reduced. Most of the starting triglycidyl ethers are expensive, which increases the cost of the UV-curable polyester acrylic resins.
Disclosure of Invention
The invention aims to provide the UV-curable unsaturated polyester resin with relatively low cost, high crosslinking density, good chemical resistance and energy saving and high vinyl functionality and the preparation method thereof; the invention can obtain the UV-cured polyester with the solid content of more than 85 wt% and the viscosity of 2000-6000 mPa & s (25 ℃).
The invention also aims to provide application of the UV-curable resin prepared by the method in coating. The coating prepared by the UV-curable resin has excellent performance, and the hardness of the coating can reach 2H.
The purpose of the invention is realized by the following technical scheme:
the preparation method of the UV-curable unsaturated polyester resin with high vinyl functionality comprises the following components in percentage by mass: acid anhydride: 33-42%, vinyl glycidyl ether: 11-24%, epoxy compound: 18-34%, polymerization inhibitor 0.1-0.5% and organic solvent 10-20%. The preparation method comprises the following steps: adding acid anhydride, an epoxy compound, a catalyst and a solvent into a three-neck flask provided with a stirrer and a thermometer under the protection of nitrogen, stirring and heating to 90-120 ℃, and preserving heat for 1-3 hours; and then, dropwise adding vinyl glycidyl ether dissolved with a polymerization inhibitor within 1-2h, opening ring and copolymerizing for 4-6h at 90-120 ℃, measuring the acid value of a reaction system to be below 15mg KOH/g, and removing unreacted monomers and solvents by reduced pressure distillation to obtain the light yellow transparent unsaturated polyester.
The acid anhydride comprises one or more than two of phthalic anhydride, trimellitic anhydride, hexahydrophthalic anhydride, methyl hexahydrophthalic anhydride, pyromellitic dianhydride and the like.
The epoxy compound comprises epoxy chloropropane, n-butyl glycidyl ether, octyl glycidyl ether, benzyl glycidyl ether, tertiary carbonic acid glycidyl ester and C12～14One or more of glycidyl ethers.
The vinyl glycidyl ether comprises one or more than two of glycidyl methacrylate, allyl glycidyl ether, 4-vinylbenzyl glycidyl ether and 4-hydroxybutyl acrylate glycidyl ether.
The solvent comprises one or more than two of ethyl acetate, butyl acetate, butanone and cyclohexanone.
The catalyst comprises one or more than two of tetraethyl ammonium bromide, tetrabutyl ammonium bromide, tetraoctyl ammonium bromide and zinc acetate. The dosage of the catalyst is 1-5% of the mass of the acid anhydride.
The polymerization inhibitor comprises one or more than two of hydroquinone, p-hydroxyanisole and tert-butyl catechol.
The UV-curable unsaturated polyester resin with high vinyl functionality is prepared by the preparation method, and the viscosity is 2000-6000 mPa & s at 25 ℃.
The high-vinyl-functionality UV-curable unsaturated polyester resin is applied to coating, and an active diluent and a photoinitiator are added into polyester, and the coating comprises the following components in percentage by mass: 65-75% of polyester resin, 20-35% of reactive diluent, 2-5% of photoinitiator and 0.1-0.5% of other auxiliary agents, and forming a film through UV curing. The active diluent comprises one or more than two of trimethylolpropane triacrylate, tripropylene glycol diacrylate, hexanediol diacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, acryloyl morpholine and the like;
the photoinitiator comprises one or more than two of 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide (Lucirin TPO), 2-hydroxy-2-methyl-1-phenyl-1-acetone (Darocur 1173), 1-hydroxycyclohexyl phenyl ketone and the like;
the other auxiliary agents comprise one or more than two of a leveling agent, a base material wetting agent and a defoaming agent.
The leveling agent comprises one or more than two of Germany BYK 358N, BYK 306 and BYK 371;
the defoaming agent comprises one or more than two of BYK 024, BYK 028 and BYK 141 of Bick company of Germany;
the substrate wetting agent comprises one or more than two of TEGO 2250, TEGO 270 and TEGO245 of Windowski. The UV curing coating film has the pencil hardness of 2H and excellent water resistance and alcohol resistance.
The technical principle of the invention is as follows:
the unsaturated aliphatic polyester is prepared by ring-opening polymerization of an epoxy group of anhydride and vinyl glycidyl ether; in a polymerization reaction system, firstly, acid anhydride is coordinated, activated and ring-opened with a catalyst to generate ester-based anions, the anions attack epoxy groups coordinated and activated by the catalyst to cause the epoxy groups to be inserted into a polymer main chain in a ring-opening manner, the acid anhydride and vinyl glycidyl ether are alternately inserted into a polymer chain-lengthening chain to generate polyester containing a large amount of vinyl, the polyester molecular chain contains a large amount of vinyl glycidyl ether, the vinyl has high functionality, and UV curing can be carried out; in order to regulate and control the vinyl functionality of the unsaturated polyester, an epoxy compound without vinyl is adopted to participate in polymerization reaction, so that the addition amount of vinyl glycidyl ether is reduced, and the viscosity and the cost of the resin are also reduced.
Compared with the prior art, the invention has the following advantages:
1. the unsaturated polyester with high vinyl functionality is prepared by ring-opening polymerization of anhydride and vinyl glycidyl ether and is used for UV curable coating; the method has the advantages of wide raw material source, low price, few reaction steps, simple formula and low industrial operation difficulty, can save a large amount of cost compared with the prior art, and is very suitable for industrial large-scale production;
2. compared with the traditional reaction for generating polyester by acid and alcohol, the reaction does not produce water as a by-product, does not need benzene substances as a water-carrying agent and a solvent, has the reaction temperature of not more than 120 ℃, and has simpler process, energy conservation, consumption reduction, safety and environmental protection;
3. after the polyester resin prepared by the invention is subjected to UV curing film forming, the coating film has high hardness and excellent adhesion, and the coating film has high gloss and good medium resistance.
Drawings
FIG. 1 is an infrared spectrum of a UV-curable polyester of the product of example 1.
FIG. 2A block diagram of a UV curable polyester prepared in example 1. Wherein the structural formula 1 is a structural formula of a product polymer obtained by reacting phthalic anhydride with glycidyl methacrylate; the structural formula 2 is the structural formula of the product obtained by adding the n-butyl glycidyl ether in the reaction of the example 1.
Detailed Description
For a better understanding of the present invention, the present invention will be further described with reference to the accompanying drawings and examples, but the embodiments of the present invention are not limited thereto.
The Pasteur Laromer LR 9004 in the examples is an elastic polyester acrylate produced by Pasteur Germany, mainly used for the production of radiation-cured gloss oil and printing ink for paper, PVC, wood and wood products, has good stability and low-temperature flexibility, and belongs to a class of polyester acrylic resin with larger market share.
In the following examples, the properties of the UV-curable polyester resin and the photocurable coating were measured according to the following methods: the resin viscosity was measured using a rotational viscometer of type NDJ-1 according to GB/T21059-2007; the acid value of the resin is determined according to GB/T6743-2008; the coating hardness is measured according to GB/T6739-; the coating adhesion was determined according to GB/T9286-1998; the gloss of the coating film was measured according to GB/T9754-2007 using a gloss meter model WGG60-E4 at an angle of 60 °; the water resistance of the coating is determined by adopting a room temperature soaking method according to GB/T5209-1985; the alcohol resistance of the coating film was determined according to GB/T4893.1-2005.
Example 1
1) A high vinyl functionality UV curable unsaturated polyester resin having the composition in mass percent of the raw material formulation shown in Table 1 (excluding catalyst):
TABLE 1
Figure BDA0002093145240000051
2) The process for preparing a UV curable unsaturated polyester resin of high vinyl functionality comprises the steps of:
in FIG. 2, molecular formula 1 is a structural formula of a polymer obtained by reacting phthalic anhydride with glycidyl methacrylate, wherein n is the number of repeating units and is generally greater than 6; the molecular weight of the product is regulated and controlled to be generally above 2000 by adjusting the ratio of the mass of phthalic anhydride and glycidyl methacrylate, namely n is 6-10. The structural formula 2 in fig. 2 is a structural formula of a product obtained by adding n-butyl glycidyl ether in the reaction, and the structural formula is mainly used for regulating and controlling the functionality of vinyl in unsaturated polyester, namely vinyl content, so as to regulate and control the crosslinking density of a coating film, and further regulate and control the hardness, chemical resistance and cost of the coating film.
Under the protection of nitrogen, phthalic anhydride, n-butyl glycidyl ether, ethyl acetate and tetraethyl ammonium bromide (1.0 percent of the mass fraction of the anhydride) are added into a flask with a stirrer and a thermometer according to given mass and mixed uniformly, the temperature is raised to 90 ℃, the temperature is kept for 1h, then glycidyl methacrylate dissolved with hydroquinone is added dropwise, the dripping is completed within 1.5h, ring opening copolymerization is carried out for 4h at 100 ℃ until the acid value is reduced to 15mgKOH/g, the temperature is reduced, and discharging is carried out, thus obtaining the UV-curable unsaturated aliphatic polyester.
3) The physical and chemical properties of the UV-curable polyester resin prepared by the preparation method are as follows: appearance: light yellow and transparent; solid content: 88.41 percent; acid value: 8.5mgKOH/g, viscosity (25 ℃ C.): 4075 mPas.
4) Preparation and performance of UV curing coating
The formulation composition of the UV curable coating in parts by mass is as follows:
TABLE 2
Figure BDA0002093145240000061
Adding the formula materials into a container, dispersing at a low speed of 600r/min for 10-15 min, and filtering through 300-mesh filter cloth to obtain the UV curing coating. The coating is respectively coated on a wood plate and a glass plate at the energy of 600mJ/cm2Curing under a UV curing machine.
The coating properties were measured and compared to the properties of basf Laromer LR 9004 as shown in table 3 below:
TABLE 3
Figure BDA0002093145240000062
Table 3 shows that the UV-curable polyester resin film prepared in this example has high gloss, high hardness and excellent water resistance.
FIG. 1 is an infrared spectrum of the UV-curable polyester resin thus prepared, in which phthalic anhydride was not present at 1760cm-1、1850cm-1The absorption peak of the vibration of the carbonyl group of the acid anhydride proves that the acid anhydride reacts during the ring-opening copolymerization; at 905, 913cm-1Characteristic absorption peaks of epoxy groups do not exist at the left and right parts, and the fact that the epoxy compound and the acid anhydride have ring-opening reaction is proved to generate a structure shown as a structural formula 2 in figure 2; at 1726cm-1Shows a strong and sharp ester carbonyl peak at 1640cm-1A characteristic absorption peak of-C ═ C-appears, confirming the formation of the UV-curable unsaturated polyester. In FIG. 2, molecular formula 1 is a structural formula of a polymer obtained by reacting phthalic anhydride with glycidyl methacrylate, wherein n is the number of repeating units and is generally greater than 6; the molecular weight of the product is regulated and controlled to be generally above 2000 by adjusting the ratio of the mass of phthalic anhydride and glycidyl methacrylate, namely n is 6-10. The structural formula 2 in fig. 2 is a structural formula of a product obtained by adding n-butyl glycidyl ether in the reaction, and the structural formula is mainly used for regulating and controlling the functionality of vinyl in unsaturated polyester, namely vinyl content, so as to regulate and control the crosslinking density of a coating film, and further regulate and control the hardness, chemical resistance and cost of the coating film.
Compared with the Chinese patent application 2016111382348(CN106748765A, 2017.5.31), the vinyl functionality of the present example is increased from 3 to more than 6, the preparation process is changed from a two-step process to a one-step process, and expensive triglycidyl ether is not needed to be used as a starting material; by changing the type and proportion of the epoxy monomers, the vinyl functionality, viscosity and performance of the unsaturated polyester can be effectively regulated and controlled, and the UV curing polyester with high solid content and low viscosity is prepared. Therefore, the embodiment has the advantages of high vinyl functionality of the UV-curable unsaturated resin, high hardness of the UV-curable coating, good chemical resistance, simple process and low cost. Compared with the traditional reaction (CN105061738A and CN105504245A) for generating polyester by alcohol and acid, the method does not need to react at the temperature of 180-240 ℃, has lower reaction temperature which is not more than 120 ℃, does not produce water as a by-product, does not need benzene substances as a water-carrying agent, is more environment-friendly, has simple process, saves energy and saves energy.
Example 2
1) A high vinyl functionality UV curable unsaturated polyester resin having the composition in mass percent of the raw material formulation shown in Table 4 (excluding catalyst):
TABLE 4
Figure BDA0002093145240000071
Figure BDA0002093145240000081
2) A process for the preparation of a UV curable unsaturated polyester resin of high vinyl functionality comprising the steps of:
under the protection of nitrogen, phthalic anhydride, octyl glycidyl ether, butyl acetate and tetrabutylammonium bromide (1.2 percent of the mass fraction of the anhydride) are added into a flask with a stirrer and a thermometer according to given mass and are uniformly mixed, the temperature is raised to 100 ℃, the temperature is kept for 2.5 hours, then glycidyl methacrylate dissolved with hydroquinone is dropwise added, the dripping is finished for 1 hour, the ring opening copolymerization reaction is carried out for 4.5 hours at 110 ℃ until the acid value is reduced to 15mgKOH/g, the temperature is reduced, and the material is discharged, so that the unsaturated aliphatic polyester capable of being cured by UV is obtained.
3) The physical and chemical properties of the UV-curable polyester resin prepared by the preparation method are as follows: appearance: light yellow and transparent; solid content: 89.25 percent; acid value: 9.6mgKOH/g, viscosity (25 ℃ C.): 3560 mPas.
4) Preparation and performance of UV curing coating
The formulation composition of the UV curable coating in parts by mass is as follows:
TABLE 5
Figure BDA0002093145240000082
Adding the formula materials into a container, dispersing at a low speed of 600r/min for 10-15 min, and filtering through 300-mesh filter cloth to obtain the UV curing coating. Coating the paint on wood plates and glass plates respectively at high energyIs 600mJ/cm2Curing under a UV curing machine.
The coating properties were measured and compared to the properties of basf Laromer LR 9004 as shown in table 6 below:
TABLE 6
Figure BDA0002093145240000091
Example 3
1) A high vinyl functionality UV curable unsaturated polyester resin having the composition in weight percent of the raw material formulation shown in Table 7 (excluding catalyst):
TABLE 7
Figure BDA0002093145240000092
2) The process for preparing a UV curable unsaturated polyester resin of high vinyl functionality comprises the steps of:
under the protection of nitrogen, hexahydrophthalic anhydride, benzyl glycidyl ether, butyl acetate and tetrabutylammonium bromide (1.5 percent of the mass fraction of anhydride) are added into a flask with a stirrer and a thermometer according to given mass and are uniformly mixed, the temperature is raised to 110 ℃, the temperature is kept for 3 hours, then allyl glycidyl ether dissolved with tert-butyl catechol is added dropwise, the dripping is finished for 1 hour, the ring opening copolymerization reaction is carried out for 6 hours at the temperature of 110 ℃ until the acid value is reduced to 15mgKOH/g, the temperature is reduced, and the material is discharged, so that the unsaturated aliphatic polyester capable of being cured by UV is obtained.
3) The physical and chemical properties of the UV-curable polyester resin prepared by the preparation method are as follows: appearance: light yellow and transparent; solid content: 87.92 percent; acid value: 9.5mgKOH/g, viscosity (25 ℃ C.): 4580 mPas.
4) Preparation and performance of UV curing coating
The formulation composition of the UV curable coating in parts by mass is as follows:
TABLE 8
Figure BDA0002093145240000101
Adding the above materials into containerDispersing at low speed for 10-15 min at the rotating speed of 600r/min in a device, and filtering through 300-mesh filter cloth to obtain the UV curing coating. The coating is respectively coated on a wood plate and a glass plate at the energy of 600mJ/cm2Curing under a UV curing machine.
The coating properties were measured and compared to the properties of basf Laromer LR 9004 as shown in table 9 below:
TABLE 9
Figure BDA0002093145240000102
Example 4
1) A high vinyl functionality UV curable unsaturated polyester resin having the composition in weight percent of the raw material formulation shown in Table 10 (excluding catalyst):
watch 10
Figure BDA0002093145240000103
Figure BDA0002093145240000111
2) The preparation process of the UV-cured polyester resin comprises the following steps:
under the protection of nitrogen, succinic anhydride, n-butyl glycidyl ether, butanone and zinc acetate (1.5 percent of the mass fraction of the anhydride) are added into a flask with a stirrer and a thermometer according to given mass and are uniformly mixed, the temperature is raised to 90 ℃, the temperature is kept for 3 hours, then 4-vinylbenzyl glycidyl ether dissolved with p-hydroxyanisole is added dropwise, the dripping is completed within 2 hours, ring opening copolymerization is carried out for 4 hours at 100 ℃ until the acid value is reduced to 15mgKOH/g, the temperature is reduced, discharging is carried out, and the unsaturated aliphatic polyester capable of being cured by UV is obtained.
(3) The physical and chemical properties of the UV-curable polyester resin prepared by the preparation method are as follows: appearance: light yellow and transparent; solid content: 86.98 percent; acid value: 11.3mgKOH/g, viscosity (25 ℃ C.): 2750 mPas.
(4) Preparation and performance of UV curing coating
The formulation composition of the UV curable coating in parts by mass is as follows:
TABLE 11
Figure BDA0002093145240000112
Adding the formula materials into a container, dispersing at a low speed of 600r/min for 10-15 min, and filtering through 300-mesh filter cloth to obtain the UV curing coating. The coating is respectively coated on a wood plate and a glass plate at the energy of 600mJ/cm2Curing under a UV curing machine.
The coating properties were measured and compared to basf Laromer LR 9004 properties as shown in table 12 below:
TABLE 12
Figure BDA0002093145240000121
Example 5
1) A high vinyl functionality UV curable unsaturated polyester resin having the composition in weight percent of the raw material formulation shown in Table 13 (excluding catalyst):
watch 13
Figure BDA0002093145240000122
2) A process for the preparation of a UV curable unsaturated polyester resin of high vinyl functionality comprising the steps of:
under the protection of nitrogen, adding phthalic anhydride, n-butyl glycidyl ether, tertiary carbonic acid glycidyl ester, ethyl acetate and tetrabutylammonium bromide (the mass fraction of the anhydride is 3.0%) according to given mass into a flask provided with a stirrer and a thermometer, uniformly mixing, heating to 110 ℃, keeping the temperature for 2 hours, then dropwise adding 4-hydroxybutyl acrylate glycidyl ether dissolved with p-hydroxyanisole, finishing dripping for 1 hour, carrying out ring opening copolymerization reaction for 5 hours at 110 ℃ until the acid value is reduced to 15mgKOH/g, cooling and discharging to obtain the UV-curable unsaturated aliphatic polyester.
3) The physical and chemical properties of the UV-curable polyester resin prepared by the preparation method are as follows: appearance: light yellow and transparent; solid content: 88.86 percent; acid value: 8.4mgKOH/g, viscosity (25 ℃ C.): 3925 mPas.
4) Preparation and performance of UV curing coating
The formulation composition of the UV curable coating in parts by mass is as follows:
TABLE 14
Figure BDA0002093145240000131
Adding the formula materials into a container, dispersing at a low speed of 600r/min for 10-15 min, and filtering through 300-mesh filter cloth to obtain the UV curing coating. The coating is respectively coated on a wood plate and a glass plate at the energy of 600mJ/cm2Curing under a UV curing machine.
The coating properties were measured and compared to the properties of basf Laromer LR 9004 as shown in table 15 below:
watch 15
Figure BDA0002093145240000132
Example 6
1) A high vinyl functionality UV curable unsaturated polyester resin having the composition in weight percent of the raw material formulation shown in Table 16 (excluding catalyst):
TABLE 16
Figure BDA0002093145240000141
2) A process for the preparation of a UV curable unsaturated polyester resin of high vinyl functionality comprising the steps of:
under the protection of nitrogen, succinic anhydride, benzyl glycidyl ether, epichlorohydrin, ethyl acetate and zinc acetate (2.5 percent of the mass fraction of the anhydride) are added into a flask with a stirrer and a thermometer according to given mass and are uniformly mixed, the temperature is raised to 90 ℃, the temperature is kept for 2 hours, then glycidyl methacrylate dissolved with hydroquinone is added dropwise, the dripping is finished for 1 hour, ring opening copolymerization reaction is carried out for 6 hours at 90 ℃ until the acid value is reduced to 15mgKOH/g, the temperature is reduced, discharging is carried out, and the unsaturated aliphatic polyester capable of being cured by UV is obtained.
(3) The physical and chemical properties of the UV-curable polyester resin prepared by the preparation method are as follows: appearance: light yellow and transparent; solid content: 90.32 percent; acid value: 9.7mgKOH/g, viscosity (25 ℃ C.): 2855 mPas.
(4) Preparation and performance of UV curing coating
The formulation composition of the UV curable coating in parts by mass is as follows:
TABLE 17
Figure BDA0002093145240000142
Figure BDA0002093145240000151
Adding the formula materials into a container, dispersing at a low speed of 600r/min for 10-15 min, and filtering through 300-mesh filter cloth to obtain the UV curing coating. The coating is respectively coated on a wood plate and a glass plate at the energy of 600mJ/cm2Curing under a UV curing machine.
The coating properties were measured and compared to the properties of basf Laromer LR 9004 as shown in table 18 below:
watch 18
Figure BDA0002093145240000152
Example 7
1) A high vinyl functionality UV curable unsaturated polyester resin having the composition in weight percent of the raw material formulation shown in Table 19 (excluding catalyst):
watch 19
Figure BDA0002093145240000153
2) A process for the preparation of a UV curable unsaturated polyester resin of high vinyl functionality comprising the steps of:
under the protection of nitrogen, a stirrer is arranged in the nitrogen gasA thermometer is arranged in a flask, methyl hexahydrophthalic anhydride, benzyl glycidyl ether and C are added according to given mass12～14Uniformly mixing glycidyl ether, butanone and tetrabutylammonium bromide (1.2 percent of the mass fraction of anhydride), heating to 100 ℃, preserving heat for 2.5 hours, then dropwise adding allyl glycidyl ether dissolved with hydroquinone, completing the dropwise addition for 1 hour, opening ring copolymerization for 6 hours at 100 ℃ until the acid value is reduced to 15mgKOH/g, cooling and discharging to obtain the unsaturated aliphatic polyester capable of being UV cured.
3) The physical and chemical properties of the UV-curable polyester resin prepared by the preparation method are as follows: appearance: light yellow and transparent; solid content: 90.02 percent; acid value: 10.5mgKOH/g, viscosity (25 ℃ C.): 3365 mPas.
4) Preparation and performance of UV curing coating
The formulation composition of the UV curable coating in parts by mass is as follows:
watch 20
Figure BDA0002093145240000161
Adding the formula materials into a container, dispersing at a low speed of 600r/min for 10-15 min, and filtering through 300-mesh filter cloth to obtain the UV curing coating. The coating is respectively coated on a wood plate and a glass plate at the energy of 600mJ/cm2Curing under a UV curing machine.
The coating properties were measured and compared to basf Laromer LR 9004 properties as shown in table 21 below:
TABLE 21
Figure BDA0002093145240000162
Figure BDA0002093145240000171
Example 8
1) A high vinyl functionality UV curable unsaturated polyester resin having the composition in weight percent of the raw material formulation shown in Table 22 (excluding catalyst):
TABLE 22
Figure BDA0002093145240000172
2) The process for preparing a UV curable unsaturated polyester resin of high vinyl functionality comprises the steps of:
under the protection of nitrogen, adding trimellitic anhydride, n-butyl glycidyl ether and C according to given mass into a flask provided with a stirrer and a thermometer12～14Uniformly mixing glycidyl ether, cyclohexanone and tetraoctylammonium bromide (the weight percentage of anhydride is 4.0 percent), heating to 120 ℃, keeping the temperature for 3 hours, then dropwise adding glycidyl methacrylate dissolved with tert-butyl catechol, completing dripping for 1 hour, opening ring copolymerization at 120 ℃ for 6 hours until the acid value is reduced to 15mgKOH/g, cooling and discharging to obtain the unsaturated aliphatic polyester capable of being UV cured.
(3) The physical and chemical properties of the UV-curable polyester resin prepared by the preparation method are as follows: appearance: light yellow and transparent; solid content: 90.25 percent; acid value: 7.8mgKOH/g, viscosity (25 ℃ C.): 5275 mPas.
(4) Preparation and performance of UV curing coating
The formulation composition of the UV curable coating in parts by mass is as follows:
TABLE 23
Figure BDA0002093145240000173
Figure BDA0002093145240000181
Adding the formula materials into a container, dispersing at a low speed of 600r/min for 10-15 min, and filtering through 300-mesh filter cloth to obtain the UV curing coating. The coating is respectively coated on a wood plate and a glass plate at the energy of 600mJ/cm2Curing under a UV curing machine.
The coating properties were measured and compared to basf Laromer LR 9004 properties as shown in table 24 below:
watch 24
Figure BDA0002093145240000182
The UV-curable polyester prepared by the invention has the characteristics of simple preparation process, low VOC (volatile organic compounds) emission, energy conservation and environmental protection, and the prepared coating has the advantages of high glossiness, good water resistance, high hardness and the like.
It should be noted that the present invention is not limited to the above-mentioned embodiments, and any other changes, modifications, substitutions, combinations and simplifications which are made without departing from the spirit and principle of the present invention should be regarded as equivalent alternatives which are included in the protection scope of the present invention.

Claims (9)

1.高乙烯基官能度的可UV固化不饱和聚酯树脂的制备方法，其特征在于，以质量百分比计，其原料组成为：酸酐33~42%、乙烯基缩水甘油醚11~24%、环氧化合物18~34%、阻聚剂0.1~0.5%、有机溶剂10~20%；制备时，在氮气保护下，将酸酐、环氧化合物、催化剂和溶剂搅拌并加热到90~120℃并保温1-3h；然后在1-2h内逐滴加溶有阻聚剂的乙烯基缩水甘油醚，在90~120℃下开环共聚反应4-6h，测定反应体系酸值至15mg KOH/g以下，减压蒸馏脱除未反应的单体和溶剂，得到可UV固化不饱和聚酯树脂；1. the preparation method of the UV-curable unsaturated polyester resin of high vinyl functionality, is characterized in that, in mass percent, its raw material consists of: acid anhydride 33～42%, vinyl glycidyl ether 11～24%, Epoxy compound 18~34%, polymerization inhibitor 0.1~0.5%, organic solvent 10~20%; during preparation, under nitrogen protection, the acid anhydride, epoxy compound, catalyst and solvent are stirred and heated to 90~120 ℃ and Incubate for 1-3h; then dropwise add vinyl glycidyl ether with polymerization inhibitor dissolved within 1-2h, conduct ring-opening copolymerization at 90~120℃ for 4-6h, measure the acid value of the reaction system to 15mg KOH/g Below, the unreacted monomer and solvent are removed by distillation under reduced pressure to obtain UV-curable unsaturated polyester resin; 所述的酸酐为邻苯二甲酸酐、丁二酸酐、偏苯三酸酐、六氢苯酐、甲基六氢苯酐和均苯四甲酸二酐中的一种或两种以上；Described acid anhydride is one or more in phthalic anhydride, succinic anhydride, trimellitic anhydride, hexahydrophthalic anhydride, methyl hexahydrophthalic anhydride and pyromellitic dianhydride; 所述的环氧化合物为环氧氯丙烷、正丁基缩水甘油醚、辛基缩水甘油醚、苄基缩水甘油醚、叔碳酸缩水甘油酯及C12~14缩水甘油醚中的一种或两种以上；Described epoxy compound is one or two in epichlorohydrin, n-butyl glycidyl ether, octyl glycidyl ether, benzyl glycidyl ether, tertiary carbonic acid glycidyl ester and C 12～14 glycidyl ether. more than one species; 所述的乙烯基缩水甘油醚为甲基丙烯酸缩水甘油酯、烯丙基缩水甘油醚、4-乙烯基苄基缩水甘油醚及4-羟基丁基丙烯酸酯缩水甘油醚中的一种或两种以上；Described vinyl glycidyl ether is one or both of glycidyl methacrylate, allyl glycidyl ether, 4-vinylbenzyl glycidyl ether and 4-hydroxybutyl acrylate glycidyl ether above; 所述的催化剂为四丁基溴化铵、四乙基溴化铵、四辛基溴化铵及醋酸锌中的一种或两种以上。The catalyst is one or more of tetrabutylammonium bromide, tetraethylammonium bromide, tetraoctylammonium bromide and zinc acetate. 2.根据权利要求1所述的高乙烯基官能度的可UV固化不饱和聚酯树脂的制备方法，其特征在于：所述的溶剂为乙酸乙酯、乙酸丁酯、丁酮及环己酮中的一种或两种以上。2. the preparation method of the UV-curable unsaturated polyester resin of high vinyl functionality according to claim 1, is characterized in that: described solvent is ethyl acetate, butyl acetate, butanone and cyclohexanone one or more of them. 3.根据权利要求1所述的高乙烯基官能度的可UV固化不饱和聚酯树脂的制备方法，其特征在于：所述的阻聚剂为对苯二酚、对羟基苯甲醚及叔丁基邻苯二酚中的一种或两种以上。3. the preparation method of the UV-curable unsaturated polyester resin of high vinyl functionality according to claim 1, is characterized in that: described polymerization inhibitor is hydroquinone, p-hydroxyanisole and tertiary One or more of butylcatechol. 4.根据权利要求1所述的高乙烯基官能度的可UV固化不饱和聚酯树脂的制备方法，其特征在于：所述的催化剂的用量为酸酐质量的1%~5%。4. the preparation method of the UV-curable unsaturated polyester resin of high vinyl functionality according to claim 1, is characterized in that: the consumption of described catalyst is 1%～5% of acid anhydride quality. 5.一种高乙烯基官能度的可UV固化不饱和聚酯树脂，其特征在于：其由权利要求1-4任一项所述的制备方法制得，25℃下黏度为2000~6000mPa·s。5. A UV-curable unsaturated polyester resin with high vinyl functionality, characterized in that: it is prepared by the preparation method described in any one of claims 1-4, and the viscosity is 2000-6000 mPa at 25°C. s. 6.权利要求5所述的高乙烯基官能度的可UV固化不饱和聚酯树脂在涂料中的应用，其特征在于：在可UV固化不饱和聚酯树脂中添加活性稀释剂、光引发剂和其他助剂；质量百分计，涂料的原料组成为：可UV固化不饱和聚酯树脂65~75%，活性稀释剂20~30%，光引发剂2~5%，其他助剂0.1~0.5%，所得UV固化涂膜铅笔硬度达2H，耐水性和耐醇性好。6. the application of the UV-curable unsaturated polyester resin of high vinyl functionality as claimed in claim 5 in coating, it is characterized in that: adding reactive diluent, photoinitiator in UV-curable unsaturated polyester resin and other additives; in terms of mass percentage, the raw material composition of the coating is: UV curable unsaturated polyester resin 65~75%, reactive diluent 20~30%, photoinitiator 2~5%, other additives 0.1~ 0.5%, the pencil hardness of the UV-cured coating film obtained is 2H, and the water resistance and alcohol resistance are good. 7.根据权利要求6所述的高乙烯基官能度的可UV固化不饱和聚酯树脂在涂料中的应用，其特征在于：所述的光引发剂为2,4,6-三甲基苯甲酰基-二苯基氧化膦、2-羟基-2-甲基-1-苯基-1-丙酮及1-羟基环己基苯基甲酮中的一种或两种以上。7. the application of the UV-curable unsaturated polyester resin of high vinyl functionality according to claim 6 in coating, it is characterized in that: described photoinitiator is 2,4,6-trimethylbenzene One or more of formyl-diphenylphosphine oxide, 2-hydroxy-2-methyl-1-phenyl-1-propanone and 1-hydroxycyclohexyl phenyl ketone. 8.根据权利要求6所述的高乙烯基官能度的可UV固化不饱和聚酯树脂在涂料中的应用，其特征在于：所述的活性稀释剂为三羟甲基丙烷三丙烯酸酯、三丙二醇二丙烯酸酯、己二醇二丙烯酸酯、甲基丙烯酸羟乙酯、甲基丙烯酸羟丙酯及丙烯酰吗啉中的一种或两种以上。8. the application of the UV-curable unsaturated polyester resin of high vinyl functionality according to claim 6 in coating, it is characterized in that: described reactive diluent is trimethylolpropane triacrylate, trimethylolpropane triacrylate, trimethylolpropane triacrylate, trimethylolpropane triacrylate One or more of propylene glycol diacrylate, hexanediol diacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate and acryloyl morpholine. 9.根据权利要求6所述的高乙烯基官能度的可UV固化不饱和聚酯树脂在涂料中的应用，其特征在于：所述的其他助剂为流平剂、基材润湿剂及消泡剂中的一种或两种以上；9. the application of the UV-curable unsaturated polyester resin of high vinyl functionality according to claim 6 in coating, it is characterized in that: described other auxiliary agent is leveling agent, base material wetting agent and One or more of defoamer; 所述的流平剂为德国BYK 358N、BYK 306及BYK 371中的一种或两种以上；Described leveling agent is one or more of German BYK 358N, BYK 306 and BYK 371; 所述的消泡剂为德国毕克公司的BYK 024、BYK 028及BYK 141中的一种或两种以上；The defoamer is one or more of BYK 024, BYK 028 and BYK 141 from BYK, Germany; 所述的基材润湿剂为赢创德固赛公司的TEGO 2250、TEGO 270及TEGO 245中的一种或两种以上。The substrate wetting agent is one or more of TEGO 2250, TEGO 270 and TEGO 245 from Evonik Degussa.
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