CN110272537A - A kind of synthetic method solidifying the modified end-vinyl waterborne polyester of aldehyde resin for UV-LED - Google Patents
A kind of synthetic method solidifying the modified end-vinyl waterborne polyester of aldehyde resin for UV-LED Download PDFInfo
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- CN110272537A CN110272537A CN201910555359.8A CN201910555359A CN110272537A CN 110272537 A CN110272537 A CN 110272537A CN 201910555359 A CN201910555359 A CN 201910555359A CN 110272537 A CN110272537 A CN 110272537A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/52—Polycarboxylic acids or polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
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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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- 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
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Abstract
The invention discloses the synthetic methods that a kind of UV-LED solidifies the modified end-vinyl waterborne polyester of aldehyde resin.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, and 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 ~ 150oMaleic anhydride is added in C, reacts 3 ~ 5 h；Vinyl function monomer and polymerization inhibitor containing hydroxyl structure are added, 3 ~ 5 h is reacted, obtains the addition product containing hydrophilic radical and vinyl group；Cool down 40 ~ 60 againoC is added neutralizer and neutralizes, obtains the carboxylic acid type polyester containing vinyl group；Deionized water emulsification is added, 15 ~ 30 min of high speed 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 solidified aqueous coating fields, and in particular to one kind changes for UV-LED solidification aldehyde resin
The preparation method of property end-vinyl waterborne 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 polyester key copolymer, and finished product film easily hydrolyzes, causes
The corrosion and destruction for protecting substrate, with the promotion of people's quality of the life, the polyester resin with excellent film performance seems outstanding
It is urgent.Therefore, the 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.It the characteristics of introducing of hydrophilic radical simultaneously and this body structure of polyester, necessarily leads
The medium-resistance for causing finished product film poor.Therefore, it is necessary to develop the waterborne polyester coating of excellent combination property to meet environmental protection rule
The fixed and market demand.105062341 B of Chinese patent CN discloses a kind of with the poly- ammonia of polyacetals modified water-soluble for helping film forming function
Ester and the preparation method and application thereof.By aldehyde resin modified aqueous polyurethane dispersoid, the medium-resistance of its film is improved.
South China Science & Engineering University Duan Xiaojun etc. has excellent by aldehyde resin modified water-soluble hydroxypropyl lotion, the two-component coating of preparation
Hardness of film, glossiness and medium-resistance.
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.
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 aldehyde resin and vinyl structure in waterborne polyester structure, and is applied to UV-LED solidified aqueous coating neck
Domain improves the resistance to medium of film and the UV-LED solidification aldehyde resin modified water-soluble end-vinyl waterborne polyester of film performance
Preparation method.
The object of the invention is achieved through the following technical solutions:
Solidify end-vinyl waterborne polyester and its synthetic method for UV-LED, comprising the following steps:
1) synthesis of aldehyde resin modified poly ester: in terms of mass fraction, take 20~40 parts of polyalcohols, 35~55 parts it is polynary
Acid, 5~10 parts of aldehyde resin and the more double bond hydroxylated vegetable oils of 5~10 parts of functionality and 10~30 parts of water entrainers, are added to band
Have in the reaction kettle of reflux unit, under nitrogen protection, is to slowly warm up to 110~140 DEG C, is completely dissolved to raw material, is warming up to
180~210 DEG C, back flow reaction to acid value is lower than 10mgKOH/g, is then cooled to 120~150 DEG C, and decompression extraction water entrainer closes
At more plant oil modified polyester of double bond hydroxyl out；
2) synthesis of the modified end-vinyl polyester of aldehyde resin: in terms of mass fraction, taking for preparing in step 1) is how double
2~6 parts of maleic anhydrides are added in the plant oil modified polyester of key hydroxyl, are added in reaction kettle, react 3~5h, are then added 2
The vinyl function monomer and 0.1~0.4 part of polymerization inhibitor of~6 parts of hydroxyl structures, heat preservation the reaction was continued 3~5h, obtain polyacetals
Resin modified vinyl polyester；
3) synthesis of aldehyde resin modified water-soluble end-vinyl polyester: in terms of mass fraction, in the polyacetals of step 2) preparation
0.5~3 part of neutralizer is added in resin modified vinyl polyester to neutralize, stirs 15~30min, product is transferred to dispersion bucket
It is interior, it is gradually added into 100~200 parts of deionized water, 15~30min of high speed dispersion obtains aldehyde resin modified water-soluble end ethylene
Base 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 and season penta
One of tetrol is a variety of.
Preferably, aldehyde resin is urea formaldehyde A81, aldehyde ketone resin KR-80F, aldehyde ketone resin KR-120, aldehyde ketone resin
KR120B, aldehyde ketone resin KR-120W, aldehyde ketone resin UK-100, aldehyde ketone resin UK-300, aldehyde ketone resin UK-500, aldehyde ketone resin
One of YHKR-1210, aldehyde ketone resin YHKR-1218 or 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
It is oily, castor oil one or more.
Preferably, the vinyl function monomer of the hydroxyl structure is hydroxy-ethyl acrylate (HEA), acrylic acid hydroxypropyl
Ester (HPA), hydroxyethyl methacrylate (HEMA), hydroxy propyl methacrylate (HPMA) it is one or more.
Preferably, the water entrainer is the one or more of toluene and dimethylbenzene.
Preferably, the polymerization inhibitor be p methoxy phenol, 2- tert-butyl hydroquinone and methylnaphthohydroquinone one kind or
It is a variety of.
Preferably, the neutralizer be ammonium hydroxide, triethylamine, N, N- dimethylethanolamine it is one or more.
Preferably, vacuum distillation temperature described in step (1) is 120~150 DEG C and vacuum degree is 0.04~0.1MPa
Under conditions of carry out.
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 400~5000cP, and emulsion particle diameter is 60~200nm.
It is of the present invention for UV-LED solidify aldehyde resin modification end-vinyl waterborne polyester paint field application,
In terms of mass fraction, 1~5% photoinitiator is added in polyester system, through UV-LED film-forming.The photoinitiator
For 4- methyl benzophenone, 2-hydroxyl-2-methyl-1-phenylacetone, thioxanthone, 2,4,6- trimethylbenzoyl phenyl phosphine
Acetoacetic ester it is one or more.
It is of the present invention to be modified end-vinyl waterborne polyester for UV-LED solidification aldehyde resin, solidify through UV-LED and prepares
Paint film have excellent medium-resistance, flexibility good and the advantages such as hardness of film height, can be applied to water-borne wood coating,
The numerous areas such as aqueous binder and water-based ink.
Of the invention is modified end-vinyl waterborne polyester compared with prior art for UV-LED solidification aldehyde resin, has
As follows a little and 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) aldehyde resin end-vinyl waterborne polyester of the invention, the property of comprehensive aldehyde resin and polyhydroxylated vegetable oil
Can, so that film is had both excellent medium-resistance and hardness.
4) the modified end-vinyl waterborne polyester of aldehyde resin of the invention improves film by UV-LED film-forming
Medium-resistance, 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 the modified end-vinyl waterborne polyester of aldehyde resin for UV-LED, the type of feed of each component
And dosage such as table 1 (dimethylbenzene is as water entrainer):
Table 1:
Preparation process: in terms of mass fraction, by 50.9 parts of phthalic acids, 35 parts of trimethylolpropanes, 5 parts of castor oil and
5 parts of KR-80F are added in reaction kettle, and dimethylbenzene is added as water entrainer, under nitrogen protection, is warming up to 190 DEG C, reflux is anti-
10mgKOH/g, decompression extraction dimethylbenzene should be lower than to acid value；130 DEG C are cooled to, is added 2 parts of maleic anhydrides, reaction 3~
5h；Maintenance system is temperature-resistant, and 2 parts of hydroxy-ethyl acrylates and 0.1 part of p methoxy phenol are added, and reacts 3~5h, is contained
The addition product of hydrophilic radical and vinyl group；40~60 DEG C of cooling is added 0.8 part of triethylamine and neutralizes, obtains containing vinyl group
Carboxylic acid type polyester；150 parts of deionized water emulsifications are added, 15~30min of high speed dispersion obtains UV-LED solidification end-vinyl
Waterborne polyester.
Solidify the performance of end-vinyl waterborne flame retardant polyester: solid content for UV-LED, 40%；Viscosity, 1500cP；Lotion
Partial size, 135nm.
In terms of mass fraction, solidify the preparation composition of the modified end-vinyl waterborne polyester coating of aldehyde resin for UV-LED
Situation such as table 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 solidification aldehyde resin that is used for of the invention is modified end-vinyl waterborne polyester, has film
The performances such as hardness is high, flexibility is good, glossiness is high, adhesive force is excellent and water resistance is superior.The modified end of aldehyde resin of the invention
Vinyl waterborne polyester is reacted with castor oil, trimethylolpropane, aldehyde resin, phthalate first, by carbon carbon
Double bond and aldehyde resin are introduced into resin body structure, are prepared functional more plant oil modified polyester of double bond, are passed through adjusting
Castor oil and aldehyde resin dosage, can regulate and control resin viscosity, reaction site and film performance；Then Diels-Alder is utilized
Reaction introduces maleic anhydride, regulates and controls its dosage, prepare polyester of the backbone structure containing anhydride group, nothing in reaction process
Extra catalyst is needed to be catalyzed；Finally by regulatory function hydroxy acrylate dosage, the modified end ethylene of aldehyde resin is prepared
The polyester of base and carboxyl structural element；Finally neutralizing emulsification can be obtained for the modified end of UV-LED solidification high-performance aldehyde resin
Vinyl waterborne polyester.The present invention has many advantages, such as energy-saving and environmental protection, low in cost.
Embodiment 2:
A kind of synthesis solidifying the modified end-vinyl waterborne polyester of aldehyde resin for UV-LED, the type of feed of each component
And dosage such as table 4 (dimethylbenzene is as water entrainer):
Table 4:
Preparation process: in terms of mass fraction, by 50.9 parts of phthalic acids, 5 parts of KR-80F, 35 parts of trimethylolpropanes and
Double bond hydroxylated tung oil is added in reaction kettle more than 5 parts, 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；130 DEG C are cooled to, 2 parts of maleic acids are added
Acid anhydride reacts 3~5h；Maintenance system is temperature-resistant, is added 2 parts of hydroxy-ethyl acrylates and 0.1 part of p methoxy phenol, and reaction 3~
5h obtains the addition product containing hydrophilic radical and vinyl group；40~60 DEG C of cooling is added 0.8 part of triethylamine and neutralizes, contained
There is the carboxylic acid type polyester of vinyl group；150 parts of deionized water emulsifications are added, it is solid to obtain UV-LED by 15~30min of high speed dispersion
Change end-vinyl waterborne flame retardant polyester.
Solidify the performance of end-vinyl waterborne flame retardant polyester: solid content for UV-LED, 40%；Viscosity, 1750cP；Lotion
Partial size, 150nm.
In terms of mass fraction, solidify the preparation composition of the modified end-vinyl waterborne polyester coating of aldehyde resin for UV-LED
Situation such as table 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 the modified end-vinyl waterborne polyester of aldehyde resin for UV-LED, the type of feed of each component
And dosage such as table 7 (dimethylbenzene is as water entrainer):
Table 7:
Preparation process: in terms of mass fraction, by 51.8 parts of phthalic acids, 6 parts of UK-100,30 parts of pentaerythrites and 6 parts
Castor oil 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 is extremely
Acid value is lower than 10mgKOH/g, decompression extraction dimethylbenzene；130 DEG C are cooled to, 3 parts of maleic anhydrides are added, reacts 3~5h；Dimension
It is constant to hold system temperature, 3 parts of hydroxypropyl acrylates and 0.2 part of p methoxy phenol are added, reacts 3~5h, obtains containing hydrophilic
The addition product of group and vinyl group；40~60 DEG C of cooling is added 1.1 parts of triethylamines and neutralizes, obtains the carboxylic containing vinyl group
Hydrochlorate type polyester；100 parts of deionized water emulsifications are added, it is modified to obtain UV-LED solidification aldehyde resin by 15~30min of high speed dispersion
End-vinyl waterborne polyester.
Solidify the performance of the modified end-vinyl waterborne polyester of aldehyde resin: solid content for UV-LED, 50%；Viscosity,
4500cP；Emulsion particle diameter, 190nm.
In terms of mass fraction, solidify the preparation composition of the modified end-vinyl waterborne polyester coating of aldehyde resin for UV-LED
Situation such as table 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 the modified end-vinyl waterborne polyester of aldehyde resin for UV-LED, the type of feed of each component
And dosage such as table 10 (toluene is as water entrainer):
Table 10:
Preparation process: in terms of mass fraction, by 41.6 parts of M-phthalic acids, 10 parts of UK-200,30 parts of neopentyl glycols and 10
The more double bond hydroxylated tung oils of part 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；130 DEG C are cooled to, 4 parts of maleic anhydrides are added, instead
Answer 3~5h；Maintenance system is temperature-resistant, is added 4 parts of hydroxyethyl methacrylates and 0.4 part of p methoxy phenol, and reaction 3~
5h obtains the addition product containing hydrophilic radical and vinyl group；40~60 DEG C of cooling is added 2 parts of triethylamines and neutralizes, contained
The carboxylic acid type flame retardant polyester of vinyl group；120 parts of deionized water emulsifications are 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, 45%；Viscosity, 3200cP；Lotion
Partial size, 175nm.
In terms of mass fraction, solidify the preparation composition of the modified end-vinyl waterborne polyester coating of aldehyde resin for UV-LED
Situation such as table 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 the modified end-vinyl waterborne polyester of aldehyde resin for UV-LED, the type of feed of each component
And dosage such as table 13 (toluene is as water entrainer):
Table 13:
Preparation process: in terms of mass fraction, by 50.9 parts of phthalic acids, 5 parts of YHKR-1210,25 parts of trihydroxy methyls third
Alkane, 10 parts of propylene glycol and 5 parts of 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；130 DEG C are cooled to, 2 parts of maleics two are added
Acid anhydrides reacts 3~5h；Maintenance system is temperature-resistant, and 2 parts of hydroxy-ethyl acrylates and 0.1 part of p methoxy phenol, reaction 3 is added
~5h obtains the addition product containing hydrophilic radical and vinyl group；40~60 DEG C of cooling is added 0.8 part of triethylamine and neutralizes, obtains
Carboxylic acid type polyester containing vinyl group；150 parts of deionized water emulsifications are added, 15~30min of high speed dispersion obtains UV-LED
Solidify the modified end-vinyl waterborne polyester of aldehyde resin.
Solidify the performance of the modified end-vinyl waterborne polyester of aldehyde resin: solid content for UV-LED, 40%；Viscosity,
2600cP；Emulsion particle diameter, 155nm.
In terms of mass fraction, solidify the preparation composition of the modified end-vinyl waterborne polyester coating of aldehyde resin for UV-LED
Situation such as table 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 the modified end-vinyl waterborne polyester of aldehyde resin for UV-LED, the type of feed of each component
And dosage such as table 4 (dimethylbenzene is as water entrainer):
Table 16:
Preparation process: in terms of mass fraction, by 47.9 parts of phthalic acids, 35 parts of trimethylolpropanes, 2 parts of castor oil, 3
The more double bond hydroxylated tung oils of part and 8 parts of YHKR-1218 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, is added 2
Part maleic anhydride, reacts 3~5h；Maintenance system is temperature-resistant, and 2 parts of hydroxy-ethyl acrylates and 0.1 part is added to methoxyl group
Phenol reacts 3~5h, obtains the addition product containing hydrophilic radical and vinyl group；0.8 part of three second is added in 40~60 DEG C of cooling
Amine neutralizes, and obtains the carboxylic acid type polyester containing vinyl group；150 parts of deionized waters are added to emulsify, high speed dispersion 15~
30min obtains the modified end-vinyl waterborne polyester of UV-LED solidification aldehyde resin.
Solidify the performance of the modified end-vinyl waterborne polyester of aldehyde resin: solid content for UV-LED, 40%；Viscosity,
27000cP；Emulsion particle diameter, 175nm.
In terms of mass fraction, solidify the preparation composition of the modified end-vinyl waterborne polyester coating of aldehyde resin for UV-LED
Situation such as table 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 the modified end-vinyl waterborne polyester of aldehyde resin for UV-LED, the type of feed of each component
And dosage such as table 19 (dimethylbenzene is as water entrainer):
Table 19:
Preparation process: in terms of mass fraction, by 25.9 parts of phthalic acids, 20 parts of terephthalic acid (TPA)s, 35 parts of trihydroxy methyls
Propane, 10 parts of KR-120W and 5 part of castor oil are added in reaction kettle, and addition dimethylbenzene is as water entrainer, under nitrogen protection,
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, 2 parts of addition is suitable
Anhydride maleique reacts 3~5h；Maintenance system is temperature-resistant, and 2 parts of hydroxy-ethyl acrylates and 0.1 part of p methoxy phenol are added,
3~5h is reacted, the addition product containing hydrophilic radical and vinyl group is obtained；40~60 DEG C of cooling, is added in 0.8 part of triethylamine
With obtain the carboxylic acid type polyester containing vinyl group；150 parts of deionized water emulsifications are added, 15~30min of high speed dispersion is obtained
To the modified end-vinyl waterborne polyester of UV-LED solidification aldehyde resin.
Solidify the performance of the modified end-vinyl waterborne polyester of aldehyde resin: solid content for UV-LED, 40%；Viscosity,
3250cP；Emulsion particle diameter, 185nm.
In terms of mass fraction, solidify the preparation composition of the modified end-vinyl waterborne polyester coating of aldehyde resin for UV-LED
Situation such as table 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 the modified end-vinyl waterborne polyester of aldehyde resin for UV-LED, the type of feed of each component
And dosage such as table 4 (dimethylbenzene is as water entrainer):
Table 22:
Preparation process: in terms of mass fraction, by 47.9 parts of phthalic acids, 35 parts of trimethylolpropanes, 5 parts of castor oil, 4
UK-200 and 4 part of YHKR-1218 of part 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 lower than 10mgKOH/g, decompression extraction dimethylbenzene；130 DEG C are cooled to, 2 parts of maleics two are added
Acid anhydrides reacts 3~5h；Maintenance system is temperature-resistant, and 1 part of hydroxy-ethyl acrylate, 1 part of hydroxyethyl methacrylate and 0.1 is added
Part p methoxy phenol, reacts 3~5h, obtains the addition product containing hydrophilic radical and vinyl group；40~60 DEG C of cooling is added
0.8 part of triethylamine neutralizes, and obtains the carboxylic acid type polyester containing vinyl group；150 parts of deionized water emulsifications, high speed dispersion is added
15~30min obtains the modified end-vinyl waterborne polyester of UV-LED solidification aldehyde resin.
Solidify the performance of the modified end-vinyl waterborne polyester of aldehyde resin: solid content for UV-LED, 50%；Viscosity,
4200cP；Emulsion particle diameter, 195nm.
In terms of mass fraction, solidify the preparation composition of the modified end-vinyl waterborne polyester coating of aldehyde resin for UV-LED
Situation such as table 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:
Embodiment of the present invention are not limited by the above embodiments, other it is any away from Spirit Essence of the invention with
Modification made by principle changes, substitution, combines and simplify, and should be equivalent substitute mode, should all be included in guarantor of the invention
Within the scope of shield.
Claims (10)
1. the synthetic method that a kind of UV-LED solidifies the modified end-vinyl waterborne polyester of aldehyde resin, which is characterized in that including such as
Lower step:
1) polyalcohol, polyacid, aldehyde resin and functional more double bond hydroxylating plants the synthesis of aldehyde resin modified poly ester: are taken
Oil and water entrainer, are added in the reaction kettle with reflux unit, under nitrogen protection, are to slowly warm up to 110 ~ 140oC, to
Raw material is completely dissolved, and is warming up to 180 ~ 210oC, back flow reaction to acid value are lower than 10 mgKOH/g, are then cooled to 120 ~ 150oC, under the conditions of vacuum degree is 0.04 ~ 0.1 Mpa, decompression extraction water entrainer synthesizes more plant oil modified polyester of double bond hydroxyl；
2) synthesis of the modified end-vinyl polyester of aldehyde resin: the more plant oil modified polyester of double bond hydroxyl prepared in step 1)
Maleic anhydride is added, reacts 3 ~ 5 h, then the vinyl function monomer and polymerization inhibitor of addition hydroxyl structure, 120 ~ 150oUnder C, the reaction was continued 3 ~ 5 h obtain aldehyde resin modified vinyl polyester；
3) synthesis of aldehyde resin modified water-soluble end-vinyl polyester: in the aldehyde resin modified vinyl polyester of step 2 preparation
Middle addition neutralizer neutralizes, and stirs 15 ~ 30 min, product is transferred in dispersion bucket, after deionized water is added, 600 ~ 1500
Under r/min revolving speed, 15 ~ 30 min obtain aldehyde resin modified water-soluble end-vinyl polyester.
2. UV-LED according to claim 1 solidifies the synthetic method of the modified end-vinyl waterborne polyester of aldehyde resin,
It is characterized in that, according to the mass fraction, the mass fraction of the raw material is polyalcohol 20-40 parts, 35-55 parts of polyacid, polyacetals tree
5-10 parts of rouge, 10-30 parts of water entrainer, 2-6 parts of maleic anhydride, contains hydroxyl at functional more 5-10 parts of double bond hydroxylated vegetable oils
100-200 parts of 0.5 ~ 3 part of 0.1 ~ 0.4 part of 2-6 parts of vinyl function monomer, polymerization inhibitor, the neutralizer of based structures, deionized water.
3. UV-LED according to claim 1 solidifies the synthetic method of the modified end-vinyl waterborne polyester of aldehyde resin,
It is characterized in that, polyacid as described in step (1) is adipic acid, terephthalic acid (TPA), M-phthalic acid, phthalic acid or tetrahydro
One of phthalic acid is a variety of.
4. UV-LED according to claim 1 solidifies the synthetic method of the modified end-vinyl waterborne polyester of aldehyde resin,
Be characterized in that, polyalcohol as described in step (1) be propylene glycol, butanediol, neopentyl glycol, hexylene glycol, trimethylolpropane or
One of pentaerythrite is a variety of.
5. UV-LED according to claim 1 solidifies the synthetic method of the modified end-vinyl waterborne polyester of aldehyde resin,
It is characterized in that, aldehyde resin as described in step (1) is urea formaldehyde A81, aldehyde ketone resin KR-80F, aldehyde ketone resin KR-120, aldehyde
Ketone resin KR120B, aldehyde ketone resin KR-120W, aldehyde ketone resin UK-100, aldehyde ketone resin UK-300, aldehyde ketone resin UK-500, aldehyde
One of ketone resin YHKR-1210, aldehyde ketone resin YHKR-1218 or a variety of.
6. UV-LED according to claim 1 solidifies the synthetic method of the modified end-vinyl waterborne polyester of aldehyde resin,
It is characterized in that, the more double bond hydroxylated vegetable oils of functionality as described in step (1) are more double bond hydroxyl tung oil, more double bond hydroxyls Asia
One of sesame oil, castor oil are a variety of.
7. UV-LED according to claim 1 solidifies the synthetic method of the modified end-vinyl waterborne polyester of aldehyde resin,
It is characterized in that, water entrainer as described in step (1) is toluene and/or dimethylbenzene.
8. UV-LED according to claim 1 solidifies the synthetic method of the modified end-vinyl waterborne polyester of aldehyde resin,
It is characterized in that, the vinyl function monomer of hydroxyl structure described in step (2) is hydroxy-ethyl acrylate, acrylic acid hydroxypropyl
One of ester, hydroxyethyl methacrylate or hydroxy propyl methacrylate are a variety of.
9. UV-LED according to claim 1 solidifies the synthetic method of the modified end-vinyl waterborne polyester of aldehyde resin,
It is characterized in that, polymerization inhibitor described in step (2) is p methoxy phenol, 2- tert-butyl hydroquinone, one in methylnaphthohydroquinone
Kind is a variety of.
10. UV-LED according to claim 1 solidifies the synthetic method of the modified end-vinyl waterborne polyester of aldehyde resin,
It is characterized in that, neutralizer described in step (3) is ammonium hydroxide, triethylamine, N, one of N- dimethylethanolamine or a variety of.
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