CN110294840B - Synthetic method of UV-LED curing vinyl-terminated water-based flame-retardant polyester - Google Patents
Synthetic method of UV-LED curing vinyl-terminated water-based flame-retardant polyester Download PDFInfo
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- 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
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/692—Polyesters containing atoms other than carbon, hydrogen and oxygen containing phosphorus
- C08G63/6924—Polyesters containing atoms other than carbon, hydrogen and oxygen containing phosphorus derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/6928—Polycarboxylic acids and polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
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- 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
- C08G63/91—Polymers modified by chemical after-treatment
- C08G63/914—Polymers modified by chemical after-treatment derived from polycarboxylic acids and polyhydroxy compounds
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- 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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Abstract
The invention discloses a UV-LED curing vinyl-terminated water-based flame-retardant polyester and a synthesis method thereof. The synthesis method comprises the following steps: adding polybasic acid, polyhydric alcohol, functional flame-retardant polyhydroxy compound and functional multi-double bond hydroxylated vegetable oil into a reaction kettle, adding an organic solvent as a water carrying agent, and heating to 180-210 ℃ under the protection of nitrogenoC, refluxing to react until the acid value is lower than 10mgKOH/g, and decompressing and extracting the organic solvent; cooling to 120-150 deg.CoC, adding maleic anhydride to react; keeping the temperature of the system unchanged, adding metered vinyl functional monomers containing hydroxyl structures and polymerization inhibitors, and reacting for 3-5 hours to obtain an adduct containing hydrophilic groups and vinyl groups; cooling to 40-60 deg.CoC, adding a neutralizing agent to obtain carboxylate type polyester containing vinyl groups; adding deionized water for emulsification and dispersion to obtain the UV-LED curing vinyl-terminated waterborne polyester. The vinyl waterborne polyester obtained by the invention has excellent medium resistance, coating film hardness and flexibility, and is very suitable for UV-LED curing waterborne coatings.
Description
Technical Field
The invention relates to the field of UV-LED curing water-based flame-retardant coatings, in particular to a preparation method of UV-LED curing vinyl-terminated water-based flame-retardant polyester.
Background
Polyester resin systems are widely used in the field of coatings because of their excellent gloss, fullness, impact resistance, flexibility, weatherability, adhesion, and the like. However, currently polyesters are still predominantly solvent based. With the increase of environmental awareness of people, environmental regulations have increasingly strict limits on the content of Volatile Organic Compounds (VOC) in the coating, and low-VOC and even zero-VOC coating products are increasingly favored by the market. On the other hand, the polyester resin belongs to a type which is extremely easy to burn, and the halogen-free flame retardant polyester resin is particularly urgent along with the increasing safety requirement. Therefore, the development of waterborne flame-retardant polyester coatings is urgent.
The water-based polyester resin is prepared by introducing a hydrophilic group containing carboxyl or sulfonic group into a resin structure, and adding organic amine or inorganic base for neutralization and salt formation to achieve the purpose of water-based resin. Chinese patent CN 104193973A discloses a hydroxyl-terminated water-based polyester resin and a preparation method thereof. By introducing the terminal hydroxyl, the molecular chain structure of the water-based polyester resin tends to be stable, and the bond energy of each group chemical bond in the molecular chain is improved. However, the introduction of hydroxyl group inevitably causes intermolecular hydrogen bonding, which results in too high viscosity of the resin system and is not suitable for industrial production. Chinese patent CN 10726668A discloses a hydrolysis resistant polyester and a preparation method thereof. The waterborne polyester resin is obtained by replacing the traditional trimellitic anhydride hydrophilic unit with dimethylolpropane acid. Although the hydrolysis resistance of trimellitic anhydride as a hydrophilic unit is improved to some extent, the defect of poor hydrolysis resistance of a multi-ester bond and a carboxylic acid type resin is not essentially solved. Chinese patent CN 106700050A discloses a composition for preparing hydrophilic polyester, hydrophilic polyester and a preparation method thereof. By incorporating sulfonic acid polycarboxylic acids in the molecular structure, highly hydrophilic and even water-soluble polyester resins are prepared. Although the problem of the hydration of polyester resins is solved, the stability of the polyester resins is remarkably reduced due to the introduction of sulfonate. Therefore, the development of water-based polyester coating with excellent comprehensive performance is required to meet the environmental protection regulations and market demands.
The flame retardant modification of polyester resin is mostly modified by adopting an external flame retardant. Chinese patent CN201610550744.X discloses an inorganic flame-retardant water-based polyester coating and a preparation method thereof. The polyester fiber is modified by water and zinc borate, so that the flame retardant property of the finished coating film is improved, however, inorganic matter is doped and does not participate in the curing film forming of polyester, and the performance of the polyester resin is influenced to a certain degree. The phosphorus-containing flame retardant is copolymerized and modified to become a research hotspot of the current flame-retardant polyester, and Chinese patent CN 104558569A discloses flame-retardant polyester and a preparation method thereof. However, the increase of the phosphorus content in the polyester significantly reduces the crystallization properties of the polyester, and ultimately affects the fullness of the finished coating film. The functional multi-double bond hydroxylated vegetable oil can overcome the defects, so that the flame-retardant polyester resin with excellent coating performance can be effectively prepared by adjusting the proportion of the functional multi-double bond hydroxylated vegetable oil and the functional flame-retardant polyhydroxy compound.
The UV-LED curing coating has the advantages of energy conservation, environmental protection, high curing speed, excellent coating performance, suitability for large-scale construction and the like, and is increasingly concerned by people. At present, the commonly used UV-LED curing water-based paint mainly comprises water-based polyurethane acrylate resin, water-based epoxy acrylate resin, water-based polyacrylate resin and the like. Wherein, the waterborne polyurethane acrylate resin is expensive; the paint prepared from the water-based epoxy acrylate resin has high viscosity and poor flexibility. The UV-LED curing water-based polyester has the advantages of polyester and acrylate, and can effectively overcome the defects.
Disclosure of Invention
Aiming at the defects of poor hydrolysis resistance, poor film coating performance and poor flame retardant property of the existing waterborne polyester resin, the invention provides a preparation method of UV-LED curing waterborne vinyl-terminated waterborne flame retardant polyester, which introduces phosphate and a vinyl structure into a waterborne polyester structure, applies the phosphate and the vinyl structure to the field of UV-LED curing waterborne flame retardant coating and improves the medium resistance, the film coating performance and the flame retardant performance of a coating film.
The purpose of the invention is realized by the following technical scheme:
a vinyl-terminated water-based flame-retardant polyester for UV-LED curing and a synthetic method thereof comprise the following steps:
1) synthesizing multi-double bond hydroxyl vegetable oil modified flame-retardant polyester: taking 20-40 parts by mass of polyol, 35-55 parts by mass of polybasic acid, 5-10 parts by mass of functional flame-retardant polyhydroxy compound, 5-10 parts by mass of functional multi-double bond hydroxylated vegetable oil and 10-30 g of water-carrying agent, adding the mixture into a reaction kettle with a reflux device, slowly heating the mixture to 110-140 ℃ under the protection of nitrogen, heating the mixture to 180-210 ℃ until the raw materials are completely dissolved, carrying out reflux reaction until the acid value is lower than 10mg KOH/g, then cooling the mixture to 120-150 ℃, and extracting the water-carrying agent by reduced pressure distillation at the vacuum degree of 0.04-0.1 MPa to synthesize the multi-double bond hydroxyl vegetable oil modified polyester;
2) synthesis of vinyl-terminated polyester: adding 2-6 parts by mass of maleic anhydride into the multi-double bond hydroxyl vegetable oil modified polyester prepared in the step 1), adding the mixture into a reaction kettle, reacting for 3-5 hours, adding 2-6 parts by mass of a hydroxyl structure-containing vinyl functional monomer and 0.1-0.4 part by mass of a polymerization inhibitor, and keeping the temperature to continue reacting for 3-5 hours to obtain vinyl polyester;
3) synthesis of aqueous vinyl-terminated polyester: adding 0.5-3 parts of neutralizing agent into the vinyl polyester prepared in the step 2) for neutralization, stirring for 15-30 min, transferring the product into a dispersing barrel, gradually adding 100-200 parts of deionized water, and dispersing at high speed for 15-30 min to obtain the water-based vinyl-terminated polyester.
To further achieve the object of the present invention, preferably, the polybasic acid is one or more of adipic acid, terephthalic acid, isophthalic acid, phthalic acid, and tetrahydrophthalic acid.
Preferably, the polyhydric alcohol is one or more of propylene glycol, butanediol, neopentyl glycol, hexanediol, trimethylolpropane and pentaerythritol.
Preferably, the functional flame-retardant polyhydroxy compound is one or more of phosphoric acid, hydroxyethylidene diphosphonic acid, 2-hydroxyphosphonoacetic acid and phenylphosphoric acid diethylene glycol.
Preferably, the functional multi-double bond hydroxylated vegetable oil is one or more of multi-double bond hydroxyl tung oil, multi-double bond hydroxyl linseed oil and castor oil.
Preferably, the vinyl functional monomer containing a hydroxyl structure is one or more of hydroxyethyl acrylate (HEA), hydroxypropyl acrylate (HPA), hydroxyethyl methacrylate (HEMA) and hydroxypropyl methacrylate (HPMA).
Preferably, the water-carrying agent is toluene and/or xylene.
Preferably, the polymerization inhibitor is one or more of p-methoxyphenol, 2-tert-butylhydroquinone and methylhydroquinone.
Preferably, the neutralizing agent is one or more of ammonia, triethylamine and N, N-dimethylethanolamine.
Preferably, the addition amount of the neutralizing agent is 80-120% of the molar amount of the maleic anhydride.
The waterborne vinyl-terminated polyester for UV-LED curing is prepared by the synthesis method, the solid content is 35-55%, the viscosity is 100-3500 cP, and the particle size of the emulsion is 30-130 nm.
The invention discloses an application of UV-LED curing vinyl-terminated water-based flame-retardant polyester in the field of coatings, which is characterized in that 1-5% of photoinitiator is added into a polyester system in parts by mass, and a film is formed through UV-LED curing. The photoinitiator is one or more of 4-methylbenzophenone, 2-hydroxy-2-methyl-1-phenyl acetone, thioxanthone and ethyl 2,4, 6-trimethylbenzoyl phenyl phosphonate.
The water-based flame-retardant polyester for UV-LED curing terminal vinyl has the advantages that a paint film prepared by UV-LED curing has excellent medium resistance, good flexibility, high film hardness, high flame-retardant grade and the like, and can be applied to the fields of water-based wood coatings, water-based adhesives, water-based ink and the like.
Compared with the prior art, the vinyl-terminated water-based flame-retardant polyester for UV-LED curing has the following advantages and beneficial effects:
1) the water-based polyester is modified by adopting natural raw materials such as functional multi-double-bond hydroxylated vegetable oil, so that the process is simple, safe and environment-friendly, and the cost is low; the introduction of the long-chain alkyl chain can effectively weaken the hydrogen bond effect between the water-based polyester structures and reduce the viscosity of a resin system.
2) According to the invention, through double chains in a resin main chain structure, a Diels-Alder reaction is utilized to graft a terminal vinyl group and a hydrophilic group, the grafting rate is high, and heavy metal catalysis is not needed.
3) The vinyl-terminated water-based flame-retardant polyester integrates the performances of phosphorus-containing compounds and polyhydroxylated vegetable oil, so that a coating film has excellent flame-retardant performance and fullness.
4) The vinyl-terminated waterborne flame-retardant polyester is cured into a film through the UV-LED, so that the medium resistance, the flexibility and the hardness of the film are improved; meanwhile, the method is energy-saving and suitable for large-scale construction.
Detailed Description
The invention will be further described with reference to the following examples for better understanding, but the scope of the invention as claimed is not limited to the examples.
Example 1:
the synthesis of the UV-LED curing vinyl-terminated waterborne flame-retardant polyester comprises the following raw materials in types and using amounts shown in Table 1 (dimethylbenzene is taken as a water-carrying agent):
table 1:
the preparation process comprises the following steps: adding 50.9g of phthalic acid, 35g of trimethylolpropane, 5g of castor oil and 5g of phosphoric acid into a reaction kettle in parts by mass, adding dimethylbenzene serving as a water-carrying agent, heating to 190 ℃ under the protection of nitrogen, carrying out reflux reaction until the acid value is 9mgKOH/g, and decompressing and extracting the dimethylbenzene; cooling to 130 ℃, decompressing and extracting xylene as a water-carrying agent under the vacuum degree of 0.04-0.1 MPa, adding 2g of maleic anhydride, and reacting for 3-5 h; maintaining the temperature of the system unchanged, adding 2g of hydroxyethyl acrylate and 0.1g of p-methoxyphenol, and reacting for 4 hours to obtain an adduct containing a hydrophilic group and a vinyl group; cooling to 50 ℃, adding 0.8g of triethylamine for neutralization to obtain carboxylate type polyester containing ethylene groups; adding 150g of deionized water for emulsification, and dispersing at high speed for 15-30 min to obtain the UV-LED cured vinyl-terminated waterborne polyester.
The performances of the vinyl-terminated water-based flame-retardant polyester for UV-LED curing are as follows: solid content, 40%; viscosity, 900 cP; emulsion particle size, 105 nm.
The preparation composition conditions of the UV-LED curing vinyl-terminated water-based flame-retardant polyester coating are shown in the following table 2:
table 2:
the preparation process comprises the following steps: the components are mixed according to the formula in parts by weight, dispersed uniformly at a high speed, and cured to form a film under the irradiation of a UV-LED.
The coating properties were determined as in table 3:
table 3:
as can be seen from Table 3, the vinyl-terminated water-based flame-retardant polyester for UV-LED curing has the properties of high film hardness, good flexibility, high glossiness, excellent adhesion, excellent water resistance, high flame-retardant grade and the like. The vinyl-terminated waterborne flame-retardant polyester is prepared by firstly using castor oil, trimethylolpropane, phosphoric acid and phthalic acid for esterification reaction, introducing carbon-carbon double bonds and phosphate into a main resin structure to prepare the functional multi-double bond vegetable oil modified flame-retardant polyester, and regulating the viscosity, reaction sites and flame retardant property of the resin by regulating the using amounts of the castor oil and a flame retardant; then, by utilizing Diels-Alder reaction, maleic anhydride is introduced, the dosage of the maleic anhydride is regulated and controlled, the flame-retardant polyester with the main chain structure containing the anhydride group is prepared, and no catalyst is added for catalysis in the reaction process; finally, preparing the flame-retardant polyester with terminal vinyl and carboxyl structural units by adjusting the using amount of the functional hydroxyl acrylate; finally neutralizing and emulsifying to obtain the high-performance vinyl-terminated water-based flame-retardant polyester for UV-LED curing. The invention has the advantages of energy saving, environmental protection, low cost and the like.
Example 2:
the synthesis of the UV-LED curing vinyl-terminated waterborne flame-retardant polyester comprises the following raw materials in types and using amounts shown in Table 4 (dimethylbenzene as a water-carrying agent):
table 4:
the preparation process comprises the following steps: adding 50.9g of phthalic acid, 5g of phosphoric acid, 35g of trimethylolpropane and 5g of multi-double-bond hydroxylated tung oil into a reaction kettle in parts by mass, adding dimethylbenzene serving as a water-carrying agent, heating to 190 ℃ under the protection of nitrogen, carrying out reflux reaction until the acid value is 8mgKOH/g, cooling to 130 ℃, and extracting the dimethylbenzene serving as the water-carrying agent under the vacuum degree of 0.04-0.1 MPa; adding 2g of maleic anhydride, and reacting for 3 hours; maintaining the temperature of the system unchanged, adding 2g of hydroxyethyl acrylate and 0.1g of p-methoxyphenol, and reacting for 4 hours to obtain an adduct containing a hydrophilic group and a vinyl group; cooling to 50 ℃, adding 0.8g of triethylamine for neutralization to obtain carboxylate type polyester containing ethylene groups; adding 150g of deionized water for emulsification, and dispersing at high speed for 15-30 min to obtain the UV-LED cured vinyl-terminated water-based flame-retardant polyester.
The performances of the vinyl-terminated water-based flame-retardant polyester for UV-LED curing are as follows: solid content, 40%; viscosity, 1250 cP; the emulsion particle size is 125 nm.
The formulation composition conditions of the UV-LED curing vinyl-terminated waterborne flame-retardant polyester coating are shown in the following table 5:
table 5:
the preparation process comprises the following steps: the components are mixed according to the formula in parts by weight, dispersed uniformly at a high speed, and cured to form a film under the irradiation of a UV-LED.
The coating properties were determined as in table 6:
table 6:
example 3:
the synthesis of the UV-LED curing vinyl-terminated waterborne flame-retardant polyester comprises the following raw materials in types and using amounts shown in Table 7 (dimethylbenzene is taken as a water-carrying agent):
table 7:
the preparation process comprises the following steps: adding 51.8g of phthalic acid, 6g of phosphoric acid, 30g of pentaerythritol and 6g of castor oil into a reaction kettle in parts by mass, adding xylene as a water-carrying agent, heating to 190 ℃ under the protection of nitrogen, carrying out reflux reaction until the acid value is lower than 10mgKOH/g, and extracting xylene under reduced pressure; cooling to 130 ℃, decompressing and extracting xylene as a water-carrying agent under the vacuum degree of 0.04-0.1 MPa, adding 3g of maleic anhydride, and reacting for 3-5 h; maintaining the temperature of the system unchanged, adding 3g of hydroxypropyl acrylate and 0.2g of p-methoxyphenol, and reacting for 3-5 h to obtain an adduct containing hydrophilic groups and vinyl groups; cooling to 40-60 ℃, and adding 1.1g of triethylamine for neutralization to obtain carboxylate type flame-retardant polyester containing ethylene groups; and adding 100g of deionized water for emulsification, and dispersing at a high speed for 15-30 min to obtain the UV-LED cured vinyl-terminated water-based flame-retardant polyester.
The performances of the vinyl-terminated water-based flame-retardant polyester for UV-LED curing are as follows: solid content, 50%; viscosity, 2300 cP; emulsion particle size, 130 nm.
The formulation composition conditions for the UV-LED cured vinyl terminated waterborne flame retardant polyester coating are as follows, in parts by mass, in table 8:
table 8:
the preparation process comprises the following steps: the components are mixed according to the formula in parts by weight, dispersed uniformly at a high speed, and cured to form a film under the irradiation of a UV-LED.
The coating properties were determined as in table 9:
table 9:
example 4:
the synthesis of the UV-LED curing vinyl-terminated waterborne flame-retardant polyester comprises the following raw materials in types and dosage as shown in Table 10 (toluene as a water-carrying agent):
table 10:
the preparation process comprises the following steps: adding 41.6g of isophthalic acid, 10g of hydroxyethylidene diphosphonic acid, 30g of neopentyl glycol and 10g of multi-double bond hydroxylated tung oil into a reaction kettle in parts by mass, adding toluene as a water-carrying agent, heating to 190 ℃ under the protection of nitrogen, carrying out reflux reaction until the acid value is lower than 10mgKOH/g, and decompressing and extracting xylene; cooling to 130 ℃, decompressing and extracting xylene as a water-carrying agent under the vacuum degree of 0.04-0.1 MPa, adding 4g of maleic anhydride, and reacting for 3-5 h; maintaining the temperature of the system unchanged, adding 4g of hydroxyethyl methacrylate and 0.4g of p-methoxyphenol, and reacting for 3-5 h to obtain an addition product containing a hydrophilic group and a vinyl group; cooling to 40-60 ℃, adding 2g of triethylamine for neutralization to obtain carboxylate type flame-retardant polyester containing ethylene groups; adding 120g of deionized water for emulsification, and dispersing at high speed for 15-30 min to obtain the UV-LED cured vinyl-terminated water-based flame-retardant polyester.
The performances of the vinyl-terminated water-based flame-retardant polyester for UV-LED curing are as follows: solid content, 45%; viscosity, 900 cP; emulsion particle size, 95 nm.
The formulation composition conditions for the UV-LED cured vinyl terminated waterborne flame retardant polyester coating are as follows, in parts by mass, in table 11:
table 11:
the preparation process comprises the following steps: the components are mixed according to the formula in parts by weight, dispersed uniformly at a high speed, and cured to form a film under the irradiation of a UV-LED.
The coating properties were measured as in table 12:
table 12:
example 5:
the synthesis of the UV-LED curing vinyl-terminated waterborne flame-retardant polyester comprises the following raw materials in types and dosage as shown in Table 13 (toluene as a water-carrying agent):
table 13:
the preparation process comprises the following steps: adding 50.9g of phthalic acid, 5g of hydroxyethylidene diphosphonic acid, 25g of trimethylolpropane, 10g of propylene glycol and 5g of castor oil into a reaction kettle in parts by mass, adding toluene as a water-carrying agent, heating to 190 ℃ under the protection of nitrogen, carrying out reflux reaction until the acid value is lower than 10mgKOH/g, and decompressing and extracting xylene; cooling to 130 ℃, decompressing and extracting xylene as a water-carrying agent under the vacuum degree of 0.04-0.1 MPa, adding 2g of maleic anhydride, and reacting for 3-5 h; maintaining the temperature of the system unchanged, adding 2g of hydroxyethyl acrylate and 0.1g of p-methoxyphenol, and reacting for 3-5 h to obtain an adduct containing a hydrophilic group and a vinyl group; cooling to 40-60 ℃, and adding 0.8g of triethylamine for neutralization to obtain carboxylate type flame-retardant polyester containing ethylene groups; adding 150g of deionized water for emulsification, and dispersing at high speed for 15-30 min to obtain the UV-LED cured vinyl-terminated water-based flame-retardant polyester.
The performances of the vinyl-terminated water-based flame-retardant polyester for UV-LED curing are as follows: solid content, 40%; viscosity, 600 cP; the emulsion particle size is 85 nm.
The formulation composition conditions for the UV-LED cured vinyl terminated waterborne flame retardant polyester coating in parts by mass are as shown in table 14:
table 14:
the preparation process comprises the following steps: the components are mixed according to the formula in parts by weight, dispersed uniformly at a high speed, and cured to form a film under the irradiation of a UV-LED.
The coating properties were determined as in table 15:
table 15:
example 6:
the synthesis of the UV-LED curing vinyl-terminated waterborne flame-retardant polyester comprises the following raw materials in types and using amounts shown in Table 4 (dimethylbenzene as a water-carrying agent):
table 16:
the preparation process comprises the following steps: adding 47.9g of phthalic acid, 35g of trimethylolpropane, 2g of castor oil, 3g of multi-double bond hydroxylated tung oil and 8g of hydroxyethylidene diphosphonic acid into a reaction kettle, adding xylene as a water carrying agent, heating to 190 ℃ under the protection of nitrogen, carrying out reflux reaction until the acid value is lower than 10mgKOH/g, and decompressing and extracting the xylene; cooling to 130 ℃, decompressing and extracting xylene as a water-carrying agent under the vacuum degree of 0.04-0.1 MPa, adding 2g of maleic anhydride, and reacting for 3-5 h; maintaining the temperature of the system unchanged, adding 2g of hydroxyethyl acrylate and 0.1g of p-methoxyphenol, and reacting for 3-5 h to obtain an adduct containing a hydrophilic group and a vinyl group; cooling to 40-60 ℃, and adding 0.8g of triethylamine for neutralization to obtain carboxylate type flame-retardant polyester containing ethylene groups; adding 150g of deionized water for emulsification, and dispersing at high speed for 15-30 min to obtain the UV-LED cured vinyl-terminated water-based flame-retardant polyester.
The performances of the vinyl-terminated water-based flame-retardant polyester for UV-LED curing are as follows: solid content, 40%; viscosity, 1050 cP; emulsion particle size, 105 nm.
The formulation composition conditions for the UV-LED cured vinyl terminated waterborne flame retardant polyester coating in parts by weight are as follows in table 17:
table 17:
the preparation process comprises the following steps: the components are mixed according to the formula in parts by weight, dispersed uniformly at a high speed, and cured to form a film under the irradiation of a UV-LED.
The coating properties were measured as in table 18:
table 18:
example 7:
the synthesis of the UV-LED curing vinyl-terminated waterborne flame-retardant polyester comprises the following raw materials in types and dosage as shown in Table 19 (dimethylbenzene as a water-carrying agent):
table 19:
the preparation process comprises the following steps: adding 25.9g of phthalic acid, 20g of terephthalic acid, 35g of trimethylolpropane, 10g of 2-hydroxyphosphonoacetic acid and 5g of castor oil into a reaction kettle in parts by mass, adding xylene as a water-carrying agent, heating to 190 ℃ under the protection of nitrogen, carrying out reflux reaction until the acid value is lower than 10mgKOH/g, and decompressing and extracting the xylene; cooling to 130 ℃, decompressing and extracting xylene as a water-carrying agent under the vacuum degree of 0.04-0.1 MPa, adding 2g of maleic anhydride, and reacting for 3-5 h; maintaining the temperature of the system unchanged, adding 2g of hydroxyethyl acrylate and 0.1g of p-methoxyphenol, and reacting for 3-5 h to obtain an adduct containing a hydrophilic group and a vinyl group; cooling to 40-60 ℃, and adding 0.8g of triethylamine for neutralization to obtain carboxylate type flame-retardant polyester containing ethylene groups; adding 150g of deionized water for emulsification, and dispersing at high speed for 15-30 min to obtain the UV-LED cured vinyl-terminated water-based flame-retardant polyester.
The performances of the vinyl-terminated water-based flame-retardant polyester for UV-LED curing are as follows: solid content, 40%; viscosity, 1250 cP; emulsion particle size, 115 nm.
The formulation composition conditions for the UV-LED cured vinyl terminated waterborne flame retardant polyester coating are given in table 20:
table 20:
the preparation process comprises the following steps: the components are mixed according to the formula in parts by weight, dispersed uniformly at a high speed, and cured to form a film under the irradiation of a UV-LED.
The coating properties were determined as in table 21:
table 21:
example 8:
the synthesis of the UV-LED curing vinyl-terminated waterborne flame-retardant polyester comprises the following raw materials in types and using amounts shown in Table 4 (dimethylbenzene as a water-carrying agent):
table 22:
the preparation process comprises the following steps: adding 47.9g of phthalic acid, 35g of trimethylolpropane, 5g of castor oil, 4g of phosphoric acid and 4g of 2-hydroxyphosphorylacetic acid into a reaction kettle, adding dimethylbenzene serving as a water-carrying agent, heating to 190 ℃ under the protection of nitrogen, carrying out reflux reaction until the acid value is lower than 10mgKOH/g, and decompressing and extracting the dimethylbenzene; cooling to 130 ℃, decompressing and extracting xylene as a water-carrying agent under the vacuum degree of 0.04-0.1 MPa, adding 2g of maleic anhydride, and reacting for 3-5 h; maintaining the temperature of the system unchanged, adding 1g of hydroxyethyl acrylate, 1g of hydroxyethyl methacrylate and 0.1g of p-methoxyphenol, and reacting for 3-5 hours to obtain an adduct containing a hydrophilic group and a vinyl group; cooling to 40-60 ℃, and adding 0.8g of triethylamine for neutralization to obtain carboxylate type polyester containing ethylene groups; adding 150g of deionized water for emulsification, and dispersing at high speed for 15-30 min to obtain the UV-LED cured vinyl-terminated water-based flame-retardant polyester.
The performances of the vinyl-terminated water-based flame-retardant polyester for UV-LED curing are as follows: solid content, 50%; viscosity, 1200 cP; the emulsion particle size is 120 nm.
The formulation composition conditions for the UV-LED cured vinyl terminated waterborne flame retardant polyester coating in parts by mass are given in table 23:
table 23:
the preparation process comprises the following steps: the components are mixed according to the formula in parts by weight, dispersed uniformly at a high speed, and cured to form a film under the irradiation of a UV-LED.
The coating properties were measured as in table 24:
table 24:
Claims (7)
1. a synthetic method for UV-LED curing water-based flame-retardant polyester is characterized by comprising the following steps:
1) hydroxy with multiple double bondsSynthesizing base vegetable oil modified flame-retardant polyester: adding polyhydric alcohol, polybasic acid, functional flame-retardant polyhydroxy compound, functional multi-double bond hydroxylated vegetable oil and water-carrying agent into a reaction kettle with a reflux device, and slowly heating to 110-140 ℃ under the protection of nitrogenoC, after the raw materials are completely dissolved, heating to 180-210 DEGoC, refluxing to react until the acid value is lower than 10mg KOH/g, and then cooling to 120-150%oC, under the condition that the vacuum degree is 0.04-0.1 Mpa, decompressing and extracting a water-carrying agent to synthesize multi-double-bond hydroxyl vegetable oil modified polyester, wherein the functional flame-retardant polyhydroxy compound is one or more of phosphoric acid, hydroxy ethylidene diphosphonic acid, 2-hydroxy phosphoacetic acid and phenyl phosphopropionic acid diethylene glycol;
2) synthesis of vinyl-terminated flame-retardant polyester: adding maleic anhydride into the multi-double-bond hydroxyl vegetable oil modified polyester prepared in the step 1), adding the polyester into a reaction kettle, reacting for 3-5 hours, adding a hydroxyl structure-containing vinyl functional monomer and a polymerization inhibitor, and adding 120-150 parts of the polymerization inhibitoroC, continuously reacting for 3-5 h to obtain vinyl polyester;
3) synthesis of aqueous vinyl-terminated flame-retardant polyester: adding a neutralizing agent into the vinyl polyester prepared in the step 2) for neutralization, stirring for 15-30 min, transferring the product into a dispersing barrel, gradually adding deionized water, and dispersing at a high speed of 600-1500 r/min for 15-30 min to obtain the water-based vinyl-terminated polyester, wherein the vinyl functional monomer containing a hydroxyl structure is one or more of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate and hydroxypropyl methacrylate, and the polymerization inhibitor is one or more of p-methoxyphenol, 2-tert-butylhydroquinone and methylhydroquinone.
2. The synthesis method of the UV-LED curing water-based flame-retardant polyester is characterized in that the materials comprise, by mass, 20-40 parts of polyol, 35-55 parts of polybasic acid, 5-10 parts of functional flame-retardant polyhydroxy compound, 5-10 parts of functional double-bond hydroxylated vegetable oil, 10-30 parts of water-carrying agent, 2-6 parts of maleic anhydride, 2-6 parts of hydroxyl-structure-containing vinyl functional monomer, 0.1-0.4 part of polymerization inhibitor, 0.5-3 parts of neutralizer and 100-200 parts of deionized water.
3. The synthesis method of the UV-LED curing water-based flame retardant polyester as claimed in claim 1 or 2, wherein the polybasic acid is one or more of adipic acid, terephthalic acid, isophthalic acid, phthalic acid and tetrahydrophthalic acid.
4. The method for synthesizing UV-LED curing water-based flame retardant polyester as claimed in claim 1 or 2, wherein the polyalcohol is one or more of propylene glycol, butanediol, neopentyl glycol, hexanediol, trimethylolpropane and pentaerythritol.
5. The method for synthesizing the UV-LED curing water-based flame-retardant polyester as claimed in claim 1 or 2, wherein the functional multi-double bond hydroxylated vegetable oil is one or more of multi-double bond hydroxyl tung oil, multi-double bond hydroxyl linseed oil and castor oil.
6. The synthesis method of the UV-LED curing water-based flame retardant polyester as claimed in claim 1 or 2, wherein the water carrying agent is toluene and/or xylene.
7. The method for synthesizing the UV-LED curing water-based flame-retardant polyester as claimed in claim 1 or 2, wherein the neutralizing agent is one or more of ammonia, triethylamine and N, N-dimethylethanolamine.
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