CN110294840A - A kind of synthetic method solidifying end-vinyl waterborne flame retardant polyester for UV-LED - Google Patents
A kind of synthetic method solidifying end-vinyl waterborne flame retardant polyester for UV-LED Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—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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- 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
- C08G63/91—Polymers modified by chemical after-treatment
- C08G63/914—Polymers modified by chemical after-treatment derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/918—Polycarboxylic acids and polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
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- 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
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- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/18—Fireproof paints including high temperature resistant paints
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Abstract
The invention discloses one kind for UV-LED solidification end-vinyl waterborne flame retardant polyester and its synthetic method.Its synthetic method are as follows: polyacid, polyalcohol, functional flame retardant type polyol and functional more double bond hydroxylated vegetable oils are added in reaction kettle, organic solvent is added as water entrainer, under nitrogen protection, is warming up to 180 ~ 210oC, back flow reaction to acid value are lower than 10 mgKOH/g, decompression extraction organic solvent；It is cooled to 120 ~ 150oC is added maleic anhydride and is reacted；Maintenance system is temperature-resistant, and the vinyl function monomer and polymerization inhibitor containing hydroxyl structure of metering is added, and reacts 3 ~ 5 h, obtains the addition product containing hydrophilic radical and vinyl group；It is cooled to 40 ~ 60oC is added neutralizer, obtains the carboxylic acid type polyester containing vinyl group；Deionized water emulsification is added, dispersion obtains UV-LED solidification end-vinyl waterborne polyester.Gained vinyl waterborne polyester of the invention has excellent resistance to medium, hardness of film and flexibility, is highly suitable for UV-LED solidified aqueous coating.
Description
Technical field
The present invention relates to UV-LED curable water-borne anti-flaming dope fields, and in particular to one kind solidifies end ethylene for UV-LED
The preparation method of base waterborne flame retardant polyester.
Background technique
Polyester resin system is because it is with excellent glossiness, richness, impact resistance, flexibility, weatherability and attachment
Power etc., and it is widely used in paint field.However, polyester is still based on solvent type at present.With mentioning for people's environmental consciousness
Height, environmental regulation are more and more tighter to the limitation of organic volatile in coating (VOC) content, low the VOC even coating products of Diamond Search
It is increasingly subject to market favor.On the other hand, polyester resin belongs to easily incendiary type, with the increasingly raising of safety requirements, nothing
Halogen flame retardant type polyester resin seems especially urgent.Therefore, the flame retardant polyester coating for developing Water-borne modification seems especially urgent.
The Water-borne modification of polyester resin has by introducing in resin structure containing carboxyl or sulfonic hydrophilic radical, addition
Machine amine or inorganic base etc. are neutralized into salt, achieve the purpose that Water-borne modification.Chinese patent CN104193973 A discloses a kind of terminal hydroxy group
Aqueous polyester resin and preparation method thereof.By the introducing of terminal hydroxy group, so that aqueous polyester resin molecular chain structure is tended towards stability, mention
The bond energy of each group chemical key in high strand.But the introducing of hydroxyl, unavoidably causes intermolecular hydrogen bonding to act on, and causes
Resin system viscosity is excessive, is not suitable for industrialized production.Chinese patent CN10726668 A discloses a kind of hydrolytic resistance polyester
And preparation method thereof.Traditional trimellitic anhydride hydrophilic unit is replaced by dihydroxy methylpropane acid, obtains aqueous polyester resin.
Although improving anti-hydrolytic performance of the trimellitic anhydride as hydrophilic unit to a certain extent, do not solve inherently
The defect of the hydrolytic resistance of polyester key and carboxylic resin difference.Chinese patent CN106700050 A discloses one kind and is used to prepare
The composition of hydrophilic polyester, hydrophilic polyester and preparation method thereof.By the polynary carboxylic for introducing sulfonic acid in the molecular structure
Acid prepares highly-hydrophilic even water-soluble polyester resin.Although solving the Water-borne modification of polyester resin, however, due to sulfonic acid
The introducing of salt causes its stability to be remarkably decreased.Therefore, it is necessary to develop the waterborne polyester coating of excellent combination property to meet environmental protection
Regulation and the market demand.
Polyester resin it is flame-retardant modified, mostly use additional fire retardant modified.Chinese patent CN201610550744.X is disclosed
A kind of inorganic fire-retarded waterborne polyester coating and preparation method thereof.By water and zinc borate modified polyester fiber, improve at
The flame retardant property of product film, however the inorganics doped film-forming for being not engaged in polyester, make the performance of polyester resin itself
At a degree of influence.Modification by copolymerization containing phosphorus flame retardant becomes the research hotspot of current flame retardant polyester, Chinese patent
CN104558569 A discloses a kind of flame retardant polyester and its manufacturing method, passes through and introduces hydroxyl or carboxylic acid type phosphoric acid ester chemical combination
Object participates in copolymerization, prepares flame retardant polyester.However, in polyester phosphorus content increase, the crystal property of polyester is remarkably decreased, finally
Influence the richness of finished product film.Functional more double bond hydroxylated vegetable oils can overcome drawbacks described above, therefore how adjust function
The ratio of the energy more double bond hydroxylated vegetable oils of property and functional flame retardant type polyol, can effectively prepare with excellent painting
The fire retardant polyester resin of film properties.
UV-LED is coating material solidified to have that energy-saving and environmental protection, curing rate is fast, film performance is excellent, is suitable for extensive construction
Etc. advantages, the growing interest by people.Currently, common UV-LED solidified aqueous coating mainly has watersoluble polyurethane acrylic acid
Ester resin, waterborne epoxy acrylate resin, water polyacrylic acid resin etc..Wherein, aqueous urethane acrylate
Resin price is expensive；The viscosity of the coating of waterborne epoxy acrylate resin preparation is big, flexibility is poor.UV-LED curable water-borne polyester
The advantages of having both polyester and acrylate can effectively overcome drawbacks described above.
Summary of the invention
The present invention is directed to the defect of existing aqueous polyester resin hydrolytic resistance, film performance and poor flame retardant properties, provides one
Kind introduces phosphate and vinyl structure in waterborne polyester structure, and is applied to UV-LED curable water-borne anti-flaming dope neck
Domain, the UV-LED curable water-borne end-vinyl waterborne flame retardant for improving the resistance to medium of film, film performance and flame retardant property are poly-
The preparation method of ester.
The object of the invention is achieved through the following technical solutions:
One kind is for UV-LED solidification end-vinyl waterborne flame retardant polyester and its synthetic method, comprising the following steps:
1) in terms of mass fraction, 20~40 parts of polyalcohols, 35 synthesis of more plant oil modified flame retardant polyesters of double bond hydroxyl: are taken
~55 parts of polyacids, 5~10 parts of functional flame retardant type polyols and the more double bond hydroxylated vegetable oils of 5~10 parts of functionality
And 10~30g water entrainer, it is added in the reaction kettle with reflux unit, under nitrogen protection, is to slowly warm up to 110~140
DEG C, it is completely dissolved to raw material, is warming up to 180~210 DEG C, back flow reaction to acid value is lower than 10mg KOH/g, is then cooled to 120
~150 DEG C, it is 0.04~0.1MPa vacuum distillation extraction water entrainer in vacuum degree, it is plant oil modified poly- synthesizes more double bond hydroxyls
Ester；
2) synthesis of end-vinyl polyester: in terms of mass fraction, what is prepared in step 1) takes more double bond hydroxyl vegetable oil
2~6 parts of maleic anhydrides are added in modified poly ester, are added in reaction kettle, react 3~5h, and 2~6 parts of hydroxyls are then added
The vinyl function monomer of structure and 0.1~0.4 part of polymerization inhibitor, heat preservation the reaction was continued 3~5h, obtain vinyl polyester；
3) it the synthesis of aqueous end-vinyl polyester: in terms of mass fraction, is added in the vinyl polyester of step 2) preparation
0.5~3 part of neutralizer neutralizes, stir 15~30min, product is transferred in dispersion bucket, is gradually added into 100~200 parts and goes
Ionized water, 15~30min of high speed dispersion obtain aqueous end-vinyl polyester.
To further realize the object of the invention, it is preferable that the polyacid is adipic acid, terephthalic acid (TPA), isophthalic two
One of formic acid, phthalic acid, tetrahydrophthalic acid are a variety of.
Preferably, the polyalcohol is propylene glycol, butanediol, neopentyl glycol, hexylene glycol, trimethylolpropane, season penta
One of tetrol is a variety of.
Preferably, the functional flame retardant type polyol is phosphoric acid, 1-hydroxy ethylidene-1,1-diphosphonic acid, 2- di
One of guanidine-acetic acid, diphenylphosphoryl propionic acid diethylene glycol are a variety of.
Preferably, the more double bond hydroxylated vegetable oils of functionality are more double bond hydroxyl tung oil, more double bond hydroxyl flax
One of oil, castor oil are a variety of.
Preferably, the vinyl function monomer of the hydroxyl structure is hydroxy-ethyl acrylate (HEA), acrylic acid hydroxypropyl
One of ester (HPA), hydroxyethyl methacrylate (HEMA), hydroxy propyl methacrylate (HPMA) are a variety of.
Preferably, the water entrainer is toluene and/or dimethylbenzene.
Preferably, the polymerization inhibitor be one of p methoxy phenol, 2- tert-butyl hydroquinone, methylnaphthohydroquinone or
It is a variety of.
Preferably, the neutralizer is ammonium hydroxide, triethylamine, N, one of N- dimethylethanolamine or a variety of.
Preferably, the additional amount of the neutralizer is the 80~120% of maleic anhydride mole.
One kind for UV-LED solidify end-vinyl waterborne polyester, be made by above-mentioned synthetic method, solid content be 35~
55%, viscosity is 100~3500cP, and emulsion particle diameter is 30~130nm.
It is of the present invention to solidify end-vinyl waterborne flame retardant polyester in the application of paint field, with mass parts for UV-LED
1~5% photoinitiator is added, through UV-LED film-forming in number meter in polyester system.The photoinitiator is 4- methyl
Benzophenone, 2-hydroxyl-2-methyl-1-phenylacetone, thioxanthone, in 2,4,6- trimethylbenzoyl phenyl phosphinic acid ethyl ester
It is one or more.
Of the present invention to solidify end-vinyl waterborne flame retardant polyester for UV-LED, the paint film for solidifying preparation through UV-LED has
There are the advantages such as excellent medium-resistance, flexibility are good, hardness of film is high and flame retardant rating is high, can be applied to aqueous wooden ware painting
The numerous areas such as material, aqueous binder and water-based ink.
Of the invention solidifies end-vinyl waterborne flame retardant polyester compared with prior art for UV-LED, has as follows a little
With the utility model has the advantages that
1) using the natural materials modified water-soluble polyester such as functional more double bond hydroxylated vegetable oils, simple process, safety collar
It protects, is low in cost；The introducing of chain alkyl chain can effectively weaken the interstructural hydrogen bond action of waterborne polyester, reduce resin system
Viscosity.
2) present invention by the double-strand in resin backbone structure, reacted using Diels-Alder, be grafted end-vinyl and
Hydrophilic radical, grafting rate is high, and is not necessarily to heavy metal catalyst.
3) end-vinyl waterborne flame retardant polyester of the invention, the comprehensive property containing phosphorus series compound and polyhydroxylated vegetable oil
Can, so that film is had both excellent flame retardant property and richness.
4) end-vinyl waterborne flame retardant polyester of the invention improves the media-resistant of film by UV-LED film-forming
Performance, flexibility and hardness of film；Energy conservation simultaneously is suitable for extensive construction.
Specific embodiment
For a better understanding of the present invention, below with reference to embodiment, the invention will be further described, but the present invention claims guarantors
The range of shield is not limited to the scope of the embodiments.
Embodiment 1:
A kind of synthesis solidifying end-vinyl waterborne flame retardant polyester for UV-LED, the type of feed and dosage of each component are such as
Table 1 (dimethylbenzene is as water entrainer):
Table 1:
Preparation process: in terms of mass fraction, by 50.9g phthalic acid, 35g trimethylolpropane, 5g castor oil and 5g
Phosphoric acid is added in reaction kettle, and dimethylbenzene is added as water entrainer, under nitrogen protection, is warming up to 190 DEG C, back flow reaction to acid
Value is 9mgKOH/g, decompression extraction dimethylbenzene；130 DEG C are cooled to, is 0.04~0.1MPa decompression extraction water entrainer in vacuum degree
2g maleic anhydride is added in dimethylbenzene, reacts 3~5h；Maintenance system is temperature-resistant, and 2g hydroxy-ethyl acrylate and 0.1g is added
P methoxy phenol reacts 4h, obtains the addition product containing hydrophilic radical and vinyl group；Tri- second of 0.8g is added in 50 DEG C of cooling
Amine neutralizes, and obtains the carboxylic acid type polyester containing vinyl group；150g deionized water is added to emulsify, 15~30min of high speed dispersion,
Obtain UV-LED solidification end-vinyl waterborne polyester.
Solidify the performance of end-vinyl waterborne flame retardant polyester: solid content for UV-LED, 40%；Viscosity, 900cP；Lotion
Partial size, 105nm.
In terms of mass fraction, situation such as table is formed for the UV-LED preparation for solidifying end-vinyl waterborne flame retardant polyester coating
2:
Table 2:
Preparation process: in terms of mass fraction, mixing according to above-mentioned formula, and high speed dispersion is uniform, under being irradiated through UV-LED, Gu
It is melted into film.
Film performance is measured, such as table 3:
Table 3:
As shown in Table 3, the UV-LED that is used for of the invention solidifies end-vinyl waterborne flame retardant polyester, high with hardness of film,
The performances such as flexibility is good, glossiness is high, adhesive force is excellent, water resistance is superior and flame retardant rating is high.End-vinyl water of the invention
Property flame retardant polyester first be with castor oil, trimethylolpropane, phosphoric acid, phthalate reaction, by carbon-carbon double bond and phosphorus
Acid esters is introduced into resin body structure, functional more plant oil modified flame retardant polyesters of double bond is prepared, by adjusting castor oil
And amount of flame-retardant agent, resin viscosity, reaction site and flame retardant property can be regulated and controled；Then it is reacted, is introduced using Diels-Alder
Maleic anhydride regulates and controls its dosage, prepares flame retardant polyester of the backbone structure containing anhydride group, is not necessarily in reaction process additional
Catalyst；Finally by regulatory function hydroxy acrylate dosage, end-vinyl and carboxyl structural element are prepared
Flame retardant polyester；It finally neutralizes emulsification and can be obtained and solidify high-performance end-vinyl waterborne flame retardant polyester for UV-LED.The present invention
Have many advantages, such as energy-saving and environmental protection, low in cost.
Embodiment 2:
A kind of synthesis solidifying end-vinyl waterborne flame retardant polyester for UV-LED, the type of feed and dosage of each component are such as
Table 4 (dimethylbenzene is as water entrainer):
Table 4:
Preparation process: in terms of mass fraction, 50.9g phthalic acid, 5g phosphoric acid, 35g trimethylolpropane and 5g is more
Double bond hydroxylated tung oil is added in reaction kettle, and dimethylbenzene is added as water entrainer, under nitrogen protection, is warming up to 190 DEG C, returns
Stream reaction is cooled to 130 DEG C, is 0.04~0.1MPa decompression extraction water entrainer dimethylbenzene in vacuum degree to acid value 8mgKOH/g；
2g maleic anhydride is added, reacts 3h；Maintenance system is temperature-resistant, and 2g hydroxy-ethyl acrylate and 0.1g is added to methoxybenzene
Phenol reacts 4h, obtains the addition product containing hydrophilic radical and vinyl group；50 DEG C of cooling is added 0.8g triethylamine and neutralizes, obtains
Carboxylic acid type polyester containing vinyl group；The emulsification of 150g deionized water is added, 15~30min of high speed dispersion obtains UV-LED
Solidify end-vinyl waterborne flame retardant polyester.
Solidify the performance of end-vinyl waterborne flame retardant polyester: solid content for UV-LED, 40%；Viscosity, 1250cP；Lotion
Partial size, 125nm.
In terms of mass fraction, situation such as table is formed for the UV-LED preparation for solidifying end-vinyl waterborne flame retardant polyester coating
5:
Table 5:
Preparation process: in terms of mass fraction, mixing according to above-mentioned formula, and high speed dispersion is uniform, under being irradiated through UV-LED, Gu
It is melted into film.
Film performance is measured, such as table 6:
Table 6:
Embodiment 3:
A kind of synthesis solidifying end-vinyl waterborne flame retardant polyester for UV-LED, the type of feed and dosage of each component are such as
Table 7 (dimethylbenzene is as water entrainer):
Table 7:
Preparation process: in terms of mass fraction, by 51.8g phthalic acid, 6g phosphoric acid, 30g pentaerythrite and 6g castor oil
It is added in reaction kettle, dimethylbenzene is added as water entrainer, under nitrogen protection, is warming up to 190 DEG C, back flow reaction is low to acid value
In 10mgKOH/g, decompression extraction dimethylbenzene；130 DEG C are cooled to, is 0.04~0.1MPa decompression extraction water entrainer two in vacuum degree
3g maleic anhydride is added in toluene, reacts 3~5h；Maintenance system is temperature-resistant, and 3g hydroxypropyl acrylate and 0.2g pairs is added
Metoxyphenol reacts 3~5h, obtains the addition product containing hydrophilic radical and vinyl group；1.1g is added in 40~60 DEG C of cooling
Triethylamine neutralizes, and obtains the carboxylic acid type flame retardant polyester containing vinyl group；The emulsification of 100g deionized water, high speed dispersion 15 is added
~30min obtains UV-LED solidification end-vinyl waterborne flame retardant polyester.
Solidify the performance of end-vinyl waterborne flame retardant polyester: solid content for UV-LED, 50%；Viscosity, 2300cP；Lotion
Partial size, 130nm.
In terms of mass fraction, situation such as table is formed for the UV-LED preparation for solidifying end-vinyl waterborne flame retardant polyester coating
8:
Table 8:
Preparation process: in terms of mass fraction, mixing according to above-mentioned formula, and high speed dispersion is uniform, under being irradiated through UV-LED, Gu
It is melted into film.
Film performance is measured, such as table 9:
Table 9:
Embodiment 4:
A kind of synthesis solidifying end-vinyl waterborne flame retardant polyester for UV-LED, the type of feed and dosage of each component are such as
Table 10 (toluene is as water entrainer):
Table 10:
Preparation process: in terms of mass fraction, by 41.6g M-phthalic acid, 10g 1-hydroxy ethylidene-1,1-diphosphonic acid, 30g neopentyl glycol
And the more double bond hydroxylated tung oils of 10g are added in reaction kettle, and toluene is added as water entrainer, under nitrogen protection, is warming up to 190
DEG C, back flow reaction to acid value is lower than 10mgKOH/g, decompression extraction dimethylbenzene；Be cooled to 130 DEG C, vacuum degree be 0.04~
0.1MPa decompression extraction water entrainer dimethylbenzene, is added 4g maleic anhydride, reacts 3~5h；Maintenance system is temperature-resistant, is added
4g hydroxyethyl methacrylate and 0.4g p methoxy phenol react 3~5h, obtain it is containing hydrophilic radical and vinyl group plus
At object；40~60 DEG C of cooling is added 2g triethylamine and neutralizes, obtains the carboxylic acid type flame retardant polyester containing vinyl group；It is added
The emulsification of 120g deionized water, 15~30min of high speed dispersion obtain UV-LED solidification end-vinyl waterborne flame retardant polyester.
Solidify the performance of end-vinyl waterborne flame retardant polyester: solid content for UV-LED, 45%；Viscosity, 900cP；Lotion
Partial size, 95nm.
In terms of mass fraction, situation such as table is formed for the UV-LED preparation for solidifying end-vinyl waterborne flame retardant polyester coating
11:
Table 11:
Preparation process: in terms of mass fraction, mixing according to above-mentioned formula, and high speed dispersion is uniform, under being irradiated through UV-LED, Gu
It is melted into film.
Film performance is measured, such as table 12:
Table 12:
Embodiment 5:
A kind of synthesis solidifying end-vinyl waterborne flame retardant polyester for UV-LED, the type of feed and dosage of each component are such as
Table 13 (toluene is as water entrainer):
Table 13:
Preparation process: in terms of mass fraction, by 50.9g phthalic acid, 5g 1-hydroxy ethylidene-1,1-diphosphonic acid, 25g trihydroxy methyl
Propane, 10g propylene glycol and 5g castor oil are added in reaction kettle, and toluene is added as water entrainer, under nitrogen protection, is warming up to
190 DEG C, back flow reaction to acid value is lower than 10mgKOH/g, decompression extraction dimethylbenzene；Be cooled to 130 DEG C, vacuum degree be 0.04~
0.1MPa decompression extraction water entrainer dimethylbenzene, is added 2g maleic anhydride, reacts 3~5h；Maintenance system is temperature-resistant, is added
2g hydroxy-ethyl acrylate and 0.1g p methoxy phenol react 3~5h, obtain the addition containing hydrophilic radical and vinyl group
Object；40~60 DEG C of cooling is added 0.8g triethylamine and neutralizes, obtains the carboxylic acid type flame retardant polyester containing vinyl group；It is added
The emulsification of 150g deionized water, 15~30min of high speed dispersion obtain UV-LED solidification end-vinyl waterborne flame retardant polyester.
Solidify the performance of end-vinyl waterborne flame retardant polyester: solid content for UV-LED, 40%；Viscosity, 600cP；Lotion
Partial size, 85nm.
In terms of mass fraction, situation such as table is formed for the UV-LED preparation for solidifying end-vinyl waterborne flame retardant polyester coating
14:
Table 14:
Preparation process: in terms of mass fraction, mixing according to above-mentioned formula, and high speed dispersion is uniform, under being irradiated through UV-LED, Gu
It is melted into film.
Film performance is measured, such as table 15:
Table 15:
Embodiment 6:
A kind of synthesis solidifying end-vinyl waterborne flame retardant polyester for UV-LED, the type of feed and dosage of each component are such as
Table 4 (dimethylbenzene is as water entrainer):
Table 16:
Preparation process: in terms of mass fraction, 47.9g phthalic acid, 35g trimethylolpropane, 2g castor oil, 3g is more
Double bond hydroxylated tung oil and 8g 1-hydroxy ethylidene-1,1-diphosphonic acid are added in reaction kettle, and dimethylbenzene is added as water entrainer, protects in nitrogen
Under shield, 190 DEG C are warming up to, back flow reaction to acid value is lower than 10mgKOH/g, decompression extraction dimethylbenzene；130 DEG C are cooled to, true
Reciprocal of duty cycle is 0.04~0.1MPa decompression extraction water entrainer dimethylbenzene, and 2g maleic anhydride is added, reacts 3~5h；Maintenance system
It is temperature-resistant, 2g hydroxy-ethyl acrylate and 0.1g p methoxy phenol is added, reacts 3~5h, obtains containing hydrophilic radical and second
The addition product of alkenyl group；40~60 DEG C of cooling is added 0.8g triethylamine and neutralizes, it is fire-retardant to obtain the carboxylic acid type containing vinyl group
Polyester；The emulsification of 150g deionized water is added, it is poly- to obtain UV-LED solidification end-vinyl waterborne flame retardant by 15~30min of high speed dispersion
Ester.
Solidify the performance of end-vinyl waterborne flame retardant polyester: solid content for UV-LED, 40%；Viscosity, 1050cP；Lotion
Partial size, 105nm.
In terms of mass fraction, situation such as table is formed for the UV-LED preparation for solidifying end-vinyl waterborne flame retardant polyester coating
17:
Table 17:
Preparation process: in terms of mass fraction, mixing according to above-mentioned formula, and high speed dispersion is uniform, under being irradiated through UV-LED, Gu
It is melted into film.
Film performance is measured, such as table 18:
Table 18:
Embodiment 7:
A kind of synthesis solidifying end-vinyl waterborne flame retardant polyester for UV-LED, the type of feed and dosage of each component are such as
Table 19 (dimethylbenzene is as water entrainer):
Table 19:
Preparation process: in terms of mass fraction, by 25.9g phthalic acid, 20g terephthalic acid (TPA), 35g trihydroxy methyl third
Alkane, 10g2- di guanidine-acetic acid and 5g castor oil are added in reaction kettle, and dimethylbenzene is added as water entrainer, protects in nitrogen
Under shield, 190 DEG C are warming up to, back flow reaction to acid value is lower than 10mgKOH/g, decompression extraction dimethylbenzene；130 DEG C are cooled to, true
Reciprocal of duty cycle is 0.04~0.1MPa decompression extraction water entrainer dimethylbenzene, and 2g maleic anhydride is added, reacts 3~5h；Maintenance system
It is temperature-resistant, 2g hydroxy-ethyl acrylate and 0.1g p methoxy phenol is added, reacts 3~5h, obtains containing hydrophilic radical and second
The addition product of alkenyl group；40~60 DEG C of cooling is added 0.8g triethylamine and neutralizes, it is fire-retardant to obtain the carboxylic acid type containing vinyl group
Polyester；The emulsification of 150g deionized water is added, it is poly- to obtain UV-LED solidification end-vinyl waterborne flame retardant by 15~30min of high speed dispersion
Ester.
Solidify the performance of end-vinyl waterborne flame retardant polyester: solid content for UV-LED, 40%；Viscosity, 1250cP；Lotion
Partial size, 115nm.
In terms of mass fraction, situation such as table is formed for the UV-LED preparation for solidifying end-vinyl waterborne flame retardant polyester coating
20:
Table 20:
Preparation process: in terms of mass fraction, mixing according to above-mentioned formula, and high speed dispersion is uniform, under being irradiated through UV-LED, Gu
It is melted into film.
Film performance is measured, such as table 21:
Table 21:
Embodiment 8:
A kind of synthesis solidifying end-vinyl waterborne flame retardant polyester for UV-LED, the type of feed and dosage of each component are such as
Table 4 (dimethylbenzene is as water entrainer):
Table 22:
Preparation process: in terms of mass fraction, by 47.9g phthalic acid, 35g trimethylolpropane, 5g castor oil, 4g phosphorus
Acid and 4g2- di guanidine-acetic acid are added in reaction kettle, and dimethylbenzene is added as water entrainer, under nitrogen protection, is warming up to
190 DEG C, back flow reaction to acid value is lower than 10mgKOH/g, decompression extraction dimethylbenzene；Be cooled to 130 DEG C, vacuum degree be 0.04~
0.1MPa decompression extraction water entrainer dimethylbenzene, is added 2g maleic anhydride, reacts 3~5h；Maintenance system is temperature-resistant, is added
1g hydroxy-ethyl acrylate, 1g hydroxyethyl methacrylate and 0.1g p methoxy phenol react 3~5h, obtain containing hydrophilic group
The addition product of group and vinyl group；40~60 DEG C of cooling is added 0.8g triethylamine and neutralizes, obtains the carboxylate containing vinyl group
Type polyester；The emulsification of 150g deionized water is added, 15~30min of high speed dispersion obtains UV-LED solidification end-vinyl waterborne flame retardant
Polyester.
Solidify the performance of end-vinyl waterborne flame retardant polyester: solid content for UV-LED, 50%；Viscosity, 1200cP；Lotion
Partial size, 120nm.
In terms of mass fraction, situation such as table is formed for the UV-LED preparation for solidifying end-vinyl waterborne flame retardant polyester coating
23:
Table 23:
Preparation process: in terms of mass fraction, mixing according to above-mentioned formula, and high speed dispersion is uniform, under being irradiated through UV-LED, Gu
It is melted into film.
Film performance is measured, such as table 24:
Table 24:
Claims (10)
1. a kind of synthetic method for UV-LED curable water-borne flame retardant polyester, which comprises the steps of:
1) synthesis of more plant oil modified flame retardant polyesters of double bond hydroxyl: polyalcohol, polyacid, functional flame retardant type is polyhydroxylated
Object, functional more double bond hydroxylated vegetable oils and water entrainer are closed, is added in the reaction kettle with reflux unit, in nitrogen protection
Under, it is to slowly warm up to 110 ~ 140oC is completely dissolved to raw material, is warming up to 180 ~ 210oC, back flow reaction to acid value are lower than 10
Mg KOH/g, is then cooled to 120 ~ 150oC, under the conditions of vacuum degree is 0.04 ~ 0.1 Mpa, decompression extraction water entrainer is closed
At more plant oil modified polyester of double bond hydroxyl out；
2) synthesis of end-vinyl flame retardant polyester: what is prepared in step 1) takes the plant oil modified polyester addition of more double bond hydroxyls suitable
Anhydride maleique is added in reaction kettle, reacts 3 ~ 5 h, and the vinyl function monomer and polymerization inhibitor of hydroxyl structure is then added
Agent, 120 ~ 150oUnder C, the reaction was continued 3 ~ 5 h obtain vinyl polyester；
3) synthesis of aqueous end-vinyl flame retardant polyester: being added in neutralizer in the vinyl polyester of step 2 preparation and stirs
15 ~ 30 min are mixed, product is transferred in dispersion bucket, are gradually added into deionized water, under 600 ~ 1500 r/min revolving speeds, high speed point
15 ~ 30 min are dissipated, aqueous end-vinyl polyester is obtained.
2. the synthetic method according to claim 1 for UV-LED curable water-borne flame retardant polyester, which is characterized in that each object
Material is in terms of mass fraction, 20 ~ 40 parts of polyalcohol, 35 ~ 55 parts of polyacid, functional 5 ~ 10 parts of flame retardant type polyol, function
Can more 5 ~ 10 parts of the double bond hydroxylated vegetable oils of property, 10 ~ 30 parts of water entrainer, 2 ~ 6 parts of maleic anhydride, hydroxyl structure ethylene
2 ~ 6 parts of base function monomer, 0.1 ~ 0.4 part of polymerization inhibitor, 0.5 ~ 3 part of neutralizer, 100 ~ 200 parts of deionized water.
3. the synthetic method according to claim 1 or 2 for UV-LED curable water-borne flame retardant polyester, which is characterized in that
The polyacid is one of adipic acid, terephthalic acid (TPA), M-phthalic acid, phthalic acid, tetrahydrophthalic acid
Or it is a variety of.
4. the synthetic method according to claim 1 or 2 for UV-LED curable water-borne flame retardant polyester, which is characterized in that
The polyalcohol is one of propylene glycol, butanediol, neopentyl glycol, hexylene glycol, trimethylolpropane, pentaerythrite or more
Kind.
5. the synthetic method according to claim 1 or 2 for UV-LED curable water-borne flame retardant polyester, which is characterized in that
The functional flame retardant type polyol is phosphoric acid, 1-hydroxy ethylidene-1,1-diphosphonic acid, 2- di guanidine-acetic acid, diphenylphosphoryl
One of propionic acid diethylene glycol is a variety of.
6. the synthetic method according to claim 1 or 2 for UV-LED curable water-borne flame retardant polyester, which is characterized in that
The described more double bond hydroxylated vegetable oils of functionality are more double bond hydroxyl tung oil, more double bond hydroxyl linseed oil, one in castor oil
Kind is a variety of.
7. the synthetic method according to claim 1 or 2 for UV-LED curable water-borne flame retardant polyester, which is characterized in that
The vinyl function monomer of the hydroxyl structure be hydroxy-ethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate,
One of hydroxy propyl methacrylate is a variety of.
8. the synthetic method according to claim 1 or 2 for UV-LED curable water-borne flame retardant polyester, which is characterized in that
The water entrainer is toluene and/or dimethylbenzene.
9. the synthetic method according to claim 1 or 2 for UV-LED curable water-borne flame retardant polyester, which is characterized in that
The polymerization inhibitor is one of p methoxy phenol, 2- tert-butyl hydroquinone, methylnaphthohydroquinone or a variety of.
10. the synthetic method according to claim 1 or 2 for UV-LED curable water-borne flame retardant polyester, which is characterized in that
The neutralizer is ammonium hydroxide, triethylamine, N, one of N- dimethylethanolamine or a variety of.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116082613A (en) * | 2023-02-03 | 2023-05-09 | 江苏纳欧新材料有限公司 | Preparation method of biodegradable copolyester with flame retardant and plasticizing functions |
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| CN107325271A (en) * | 2017-07-20 | 2017-11-07 | 汕头大学 | A kind of macromolecular flame retardant polyester and its preparation and application |
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| JPS58189212A (en) * | 1982-04-28 | 1983-11-04 | Hitachi Chem Co Ltd | Photocurable resin composition |
| CN104558569A (en) * | 2013-10-16 | 2015-04-29 | 东丽纤维研究所（中国）有限公司 | Flame-retardant polyester and producing method thereof |
| CN103980470A (en) * | 2014-06-04 | 2014-08-13 | 青岛科技大学 | Phosphorus-containing flame-retardant alkyd resin and preparation method thereof |
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| CN116082613A (en) * | 2023-02-03 | 2023-05-09 | 江苏纳欧新材料有限公司 | Preparation method of biodegradable copolyester with flame retardant and plasticizing functions |
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