CN109180480A - A kind of acrylate-based hydroxyalkyl acid esters reactive diluent and its preparation method and application - Google Patents
A kind of acrylate-based hydroxyalkyl acid esters reactive diluent and its preparation method and application Download PDFInfo
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- CN109180480A CN109180480A CN201810878047.6A CN201810878047A CN109180480A CN 109180480 A CN109180480 A CN 109180480A CN 201810878047 A CN201810878047 A CN 201810878047A CN 109180480 A CN109180480 A CN 109180480A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/24—Preparation of carboxylic acid esters by reacting carboxylic acids or derivatives thereof with a carbon-to-oxygen ether bond, e.g. acetal, tetrahydrofuran
- C07C67/26—Preparation of carboxylic acid esters by reacting carboxylic acids or derivatives thereof with a carbon-to-oxygen ether bond, e.g. acetal, tetrahydrofuran with an oxirane ring
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
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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
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
- C09D163/10—Epoxy resins modified by unsaturated compounds
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Abstract
The invention discloses a kind of acrylate-based hydroxyalkyl acid esters reactive diluents and its preparation method and application, the preparation method of the acrylate-based hydroxyalkyl acid esters reactive diluent includes esterification and alkoxylation, specially under polymerization inhibitor, catalyst action, esterification first is carried out using acid anhydrides and hydroxy acryl acid ester as raw material, then carries out alkoxylation with ethylene oxide or propylene oxide and target product is made.Acrylate-based hydroxyalkyl acid esters reactive diluent of the present invention is novel green compound, it is used as a kind of novel coating material solidified reactive diluent of UV, it is halogen-free, nontoxic non-stimulated, curing rate is fast, practicability is very strong, various aspects of performance is better than common acrylate monomer, and its stable preparation process, reaction condition are mild, easy to operate, it is no postprocessing working procedures, no waste discharge, environmentally protective.
Description
Technical field
The present invention relates to useless UV curing field more particularly to a kind of acrylate-based hydroxyalkyl acid esters reactive diluents
And its preparation method and application.
Background technique
Ultraviolet photocureable material (hereinafter referred to as UV curing materials) is research hotspot in recent years, it have it is at low cost, Gu
It is fast, high-efficient to change speed, without volatile solvent, pollutes the features such as small and low energy consumption, is widely used in coating, binder, print
The fields such as brush ink.Reactive diluent is a coating material solidified important component of UV, and 40~60% are accounted for about in product formula, is lived
Property diluent is a kind of substance containing polymerizable functional group, not only can may also participate in light with letdown resin, regulation system viscosity
Photosensitive polymerization reaction, the laser curing velocity coating material solidified to UV and curing membrane performance all have a major impact.
Reactive diluent presses the number of contained reactive group, can be divided into mono-functional reactive's diluent, di-functional reactive
Diluent and polyfunctional group reactive diluent, such as monofunctional butyl acrylate (BA), Isooctyl acrylate monomer, (methyl) propylene
Sour hydroxy ester (HEA, HPA, HEMA, HPMA), styrene (St), vinyl pyrrolidone (NVP) and vinylacetate (VA) etc.,
Many monofunctional diluent molecular weight are lower, and volatility is larger, and corresponding toxicities are larger, smell is big, inflammable etc., such as early application
N-butyl acrylate, isobutyl acrylate etc., the St including non-acrylic compounds due to its volatility, inflammability and toxicity by
Walk photocureable coating system of fading out；NVP because it is under a cloud be carcinogen due to do not used in UV system；It is bifunctional to have second
Omega-diol diacrylate (EGDA), triethylene-glycol diacrylate (TEGDA) and tripropylene glycol diacrylate (TPGDA)
Deng, many difunctional product itselfs and nontoxicity, but have human body compared with strong stimulation, there is certain wound to skin after contacting for a long time
Evil；Trifunctional refer to containing there are three or the above reaction active groups, this kind of reactive diluent laser curing velocity is fast, crosslink density
Greatly, viscosity is high, and dilution effect is poor.
Currently, monofunctional diluent is widely used in UV coating, based on (methyl) acrylic compounds.Because of (first
Base) the aggregated reaction of carbon-to-carbon double bond in acrylate, acrylate is generated, there is extremely strong light, heat and chemical stabilization
Property, so UV prepared therefrom is coating material solidified to have the performances such as excellent weatherability, acid and alkali-resistance.
With the coating material solidified development of UV, the exploitation of simple function group (methyl) acrylic compounds reactive diluent is concerned,
Simple function group (methyl) acrylic compounds reactive diluent of many low volatilities, low toxicity, but because price has now been developed
Factor also limits the application of a part of product in terms of high, complex process and industrialization difficulty.Document " solidifies ultraviolet light
The research of middle photosensitive resin diluent " in (" material science and technique ", 2004,12 (3): 238-241), Xie Xuan et al. synthesis
A kind of photosensitive resin diluent-long-chain fat hydrocarbon glycidyl ether acrylate, photosensitive resin made of this kind of diluent have
Good storage stability, and the flexibility of solidfied material is good, cubical contraction is small.Chinese invention patent (application number:
201710338723.6 applyings date: 2017-05-15) in disclose a kind of cashew nut phenolic group acrylate reactive diluent, the dilution
Agent biomass content is high, and volatility is low, and toxicity is smaller, and film shrinking percentage is small, and partially biodegradable.Said two products work
Skill is more complex, the purification process such as is extracted, distilled.Chinese invention patent (application number: 200510031419.4 applications
Day: a kind of 1- hydroxy-ethyl acrylate base, 4- hydroxyl chloropropyl maleate and synthetic method are disclosed in 2005-04-05),
Have curing rate fast as the coating material solidified reactive diluent of UV, it is non-stimulated to human body, cheap, there is the features such as film forming；
But wherein use the virose epoxychloropropane of tool for raw material, even if having minimal residue is also to have certain harmfulness to body.
Meanwhile as environmentally friendly new policy is frequently put into effect, product containing halogen will be substituted gradually.
In view of this, low cost, high-performance, nontoxic nonirritant, simple process reactive diluent, still have very big
Research space.
Summary of the invention
Based on the above the deficiencies in the prior art, technical problem solved by the invention is to provide a kind of acrylate-based hydroxyl
Alkyl acid ester activated diluting agent and its preparation method and application, which is novel green
Color compound is used as a kind of novel coating material solidified reactive diluent of UV, be halogen-free, nontoxic non-stimulated, curing rate is fast,
Practicability is very strong, various aspects of performance is better than common acrylate monomer, and its stable preparation process, reaction condition are mild, operation
Simply, no postprocessing working procedures, no waste discharge, environmentally protective.
In order to solve the above technical problem, the present invention provides a kind of acrylate-based hydroxyalkyl acid esters reactive diluent, one
The novel UV of kind is coating material solidified to use reactive diluent, the structural formula with following I or II:
Wherein R1For-H or-CH3, R2For-H or-CH3。
In order to solve the above-mentioned technical problem, the present invention also provides a kind of acrylate-based hydroxyalkyl acid esters reactive diluents
Preparation method includes the following steps:
(1) esterification: by molfraction be 1 acid anhydrides and molfraction be 1.0~1.5 hydroxy acryl acid ester into
Row mixing, is then added catalyst and polymerization inhibitor, and 1~5h, sampling monitoring acid value to theoretical value model are reacted at 60~100 DEG C
It encloses；Reaction equation is as shown in III.
(2) alkoxylation: being added proper catalyst into step (1) products therefrom, and control reaction temperature is 70~
120 DEG C, it is first slowly added to a small amount of ethylene oxide into above-mentioned reaction system or propylene oxide carries out initiation reaction, causes wait react
The ethylene oxide or propylene oxide progress alkoxylation that molfraction is 1.0~2.0 are continuously added into again afterwards, after charging
1~3h of aging monitors acid value≤2.0mgKOH/g, is cooled to 50~60 DEG C, N2Three times, completion discharges to be produced up to target for displacement
Object；Reaction equation is as shown in IV.
As a preferred embodiment of the above technical solution, acrylate-based hydroxyalkyl acid esters reactive diluent provided by the invention is into one
Step includes some or all of following technical characteristic:
As an improvement of the above technical solution, in step (1), the catalyst, polymerization inhibitor dosage be respectively acid anhydrides and
0.5~5.0%, the 0.1~1.0% of hydroxy acryl acid ester total amount.
As an improvement of the above technical solution, in step (2), the dosage of the catalyst is target product gross mass
0.2~2.0%.
As an improvement of the above technical solution, in step (1), the acid anhydrides is maleic anhydride, phthalic anhydride
One of or it is a variety of.
As an improvement of the above technical solution, in step (1), the hydroxy acryl acid ester is hydroxy-ethyl acrylate, third
Olefin(e) acid hydroxypropyl acrylate, acrylic acid alcoxylates, hydroxyethyl methacrylate, hydroxy propyl methacrylate, methacrylic acid alcoxyl
One of glycolylate is a variety of.
As an improvement of the above technical solution, in step (1) and step (2), the catalyst is independently triethylamine, crow
One of Lip river tropine, p-methyl benzenesulfonic acid, triphenylphosphine are a variety of.
As an improvement of the above technical solution, in step (1), the polymerization inhibitor is p-hydroxyanisole, hydroquinone, right
One of tert-butyl catechol, phenthazine are a variety of.
A kind of application of acrylate-based hydroxyalkyl acid esters reactive diluent, the acrylate-based hydroxyalkyl acid esters activity
Diluent is applied to UV curing field.
Compared with prior art, technical solution of the present invention has the following beneficial effects:
1) acrylate-based hydroxyalkyl acid esters reactive diluent of the present invention is a kind of coating material solidified work of novel UV
Property diluent, is halogen-free, is nontoxic, harmless non-stimulated, and curing rate is fast, and practicability is very strong, various aspects of performance
Better than common acrylate monomer.
2) the corresponding UV of reactive diluent of the present invention is coating material solidified is made after paint film with excellent adhesive force, Gu
Change speed is fast, and hardness is moderate, and flow leveling is excellent.
3) stable preparation process, the reaction condition temperature of acrylate-based hydroxyalkyl acid esters reactive diluent of the present invention
With it is low for equipment requirements, easy to operate, without postprocessing working procedures, low energy consumption for material consumption, no waste discharge, environmentally protective.
The above description is only an overview of the technical scheme of the present invention, in order to better understand the technical means of the present invention,
And it can be implemented in accordance with the contents of the specification, and in order to allow above and other objects, features and advantages of the invention can
It is clearer and more comprehensible, below in conjunction with preferred embodiment, detailed description are as follows.
Detailed description of the invention
Fig. 1 is acrylate-based hydroxyalkyl acid esters reactive diluent1H-NMR spectrum.
Specific embodiment
The following detailed description of a specific embodiment of the invention, as part of this specification, by embodiment come
Illustrate that the principle of the present invention, other aspects of the present invention, feature and its advantage will become apparent by the detailed description.
Embodiment 1
1- hydroxy-ethyl acrylate base, the preparation method of 4- ethoxy maleate:
(1) esterification: 97g maleic anhydride solid, 116g hydroxy-ethyl acrylate are weighed respectively, then by 116g's
Hydroxy-ethyl acrylate is added in dry reactor, and adding quality is esterification feed (maleic anhydride and acrylic acid hydroxyl
Ethyl ester) 2.0% triethylamine and 0.3% p-hydroxyanisole, stir and are warming up to 70 DEG C, put into 97g maleic in several times
Dicarboxylic anhydride solid, 75~85 DEG C of 1~3h of insulation reaction, until acid value within the scope of 261~264mgKOH/g, is considered as esterification
Terminate.
(2) it alkoxylation: is added into carboxylate obtained by step (1) and is equivalent to the 0.8% of target product gross mass
Triphenylphosphine, reaction temperature control at 80~90 DEG C, first a small amount of ethylene oxide is slowly added into above-mentioned reactant, wait react
Be continuously added into again after initiation 44g ethylene oxide carry out alkoxylation, 1~2h of aging after charging, monitoring acid value≤
2.0mgKOH/g is cooled to 50~60 DEG C, N2Three times, completion discharges up to the acrylate-based hydroxyalkyl acid esters of target product for displacement
Reactive diluent.
Embodiment 2
1- hydroxypropyl acrylate base, the preparation method of 4- hydroxypropyl maleate:
(1) esterification: 97g maleic anhydride solid, 130g hydroxypropyl acrylate are weighed respectively, then by 130g's
Hydroxypropyl acrylate is added in dry reactor, and adding quality is esterification feed (maleic anhydride and acrylic acid hydroxyl
Propyl ester) 1.0% p-methyl benzenesulfonic acid and 0.8% hydroquinone, stir and are warming up to 75 DEG C, put into 97g maleic in several times
Dicarboxylic anhydride solid, 75~85 DEG C of 1~3h of insulation reaction, until acid value within the scope of 245~250mg KOH/g, is considered as esterification instead
It should terminate.
(2) it alkoxylation: is added into carboxylate obtained by step (1) and is equivalent to the 0.5% of target product gross mass
Triphenylphosphine, reaction temperature control at 75~85 DEG C, first a small amount of propylene oxide is slowly added into above-mentioned reactant, wait react
Be continuously added into again after initiation 60g propylene oxide carry out alkoxylation, 1~2h of aging after charging, monitoring acid value≤
2.0mgKOH/g is cooled to 50~60 DEG C, N2Three times, completion discharges up to the acrylate-based hydroxyalkyl acid esters of target product for displacement
Reactive diluent.
Embodiment 3
1- hydroxyethyl methacrylate base, the preparation method of 4- hydroxypropylphthalate:
(1) esterification: 148g phthalic anhydride solid, 132.6g hydroxyethyl methacrylate are weighed respectively, then
The hydroxyethyl methacrylate of 132.6g is added in dry reactor, adding quality is esterification feed (O-phthalic
Acid anhydrides and hydroxyethyl methacrylate) 1.0% triphenylphosphine and 1.0% p-tert-Butylcatechol, stir and are warming up to
70 DEG C, put into 148g phthalic anhydride solid in several times, 80~90 DEG C of 1~3h of insulation reaction, until acid value 200~
Within the scope of 204mgKOH/g, being considered as esterification terminates.
(2) it alkoxylation: is added into carboxylate obtained by step (1) and is equivalent to the 1.0% of target product gross mass
Methenamine, reaction temperature control at 70~80 DEG C, first a small amount of propylene oxide is slowly added into above-mentioned reactant, wait react
Be continuously added into again after initiation 61g propylene oxide carry out alkoxylation, 1~2h of aging after charging, monitoring acid value≤
2.0mgKOH/g is cooled to 50~60 DEG C, N2Three times, completion discharges up to target product methacrylate hydroxyalkyl for displacement
Acid esters reactive diluent.
Embodiment 4
1- hydroxy propyl methacrylate base, the preparation method of 4- ethoxy phthalic acid ester:
(1) esterification: weighing 144g phthalic anhydride solid, 144g hydroxy propyl methacrylate respectively, then will
The hydroxy propyl methacrylate of 144g is added in dry reactor, and adding quality is esterification feed (phthalic anhydride
And hydroxy propyl methacrylate) 2.0% triphenylphosphine, 0.2% p-hydroxyanisole and 0.1% phenthazine, stirring simultaneously
70 DEG C are warming up to, puts into 144g phthalic anhydride solid, 70~80 DEG C of 1~3h of insulation reaction in several times, until acid value is 190
Within the scope of~195mgKOH/g, being considered as esterification terminates.
(2) it alkoxylation: is added into carboxylate obtained by step (1) and is equivalent to the 1.0% of target product gross mass
Triethylamine, reaction temperature control at 70~80 DEG C, first a small amount of ethylene oxide is slowly added into above-mentioned reactant, draw wait react
Be continuously added into again after hair 45.5g ethylene oxide carry out alkoxylation, 1~2h of aging after charging, monitoring acid value≤
2.0mgKOH/g is cooled to 50~60 DEG C, N2Three times, completion discharges up to target product methacrylate hydroxyalkyl for displacement
Acid esters reactive diluent.
Table 1 lists acrylate-based hydroxyalkyl acid esters reactive diluent index ginseng prepared by each embodiment (methyl)
Number.It can be seen that (methyl) acrylate-based hydroxyalkyl acid esters reactive diluent color prepared by each embodiment from table (1)
Shallowly, good fluidity, for carboxylate acid value close to theoretical value, finished product acid value is low, illustrates that raw material residual is low, obtains high conversion production
Product.
(methyl) acrylate-based hydroxyalkyl acid esters reactive diluent index parameter prepared by each embodiment of table 1
Embodiment 5:
It is configured to the coating material solidified group of the UV of evaluation and test (methyl) acrylate-based hydroxyalkyl acid esters reactive diluent performance
Point and dosage:
By above-mentioned formula ratio, reaction is added in acrylic acid epoxy resin, reactive diluent, photosensitizer and other auxiliary agents and is held
Device carries out high speed dispersion and is uniformly mixed, it is coating material solidified to be made into UV.It is being plated by paint film property standard method of test measurement paint film
Main performance on zinc-iron plate.
Table 2 provides the coating material solidified performance ginseng being made after paint film of the corresponding UV of reactive diluent prepared by each embodiment
Number.From in table (2) it can be seen that each embodiment prepared by the corresponding UV of reactive diluent is coating material solidified paint film is made after have
Excellent adhesive force, curing rate is fast, and hardness is moderate, and flow leveling is excellent.
Table 2 using reactive diluent prepared by each embodiment the coating material solidified performance parameter being made after paint film of UV
The bound of each raw material cited by the present invention and each raw material of the present invention, section value and technological parameter
Bound, the section value of (such as temperature, time) can realize the present invention, embodiment numerous to list herein.
The above is a preferred embodiment of the present invention, cannot limit the right model of the present invention with this certainly
It encloses, it is noted that for those skilled in the art, without departing from the principle of the present invention, may be used also
To make several improvement and variation, these, which improve and change, is also considered as protection scope of the present invention.
Claims (9)
1. a kind of acrylate-based hydroxyalkyl acid esters reactive diluent, it is characterised in that: a kind of coating material solidified activity of novel UV
Diluent, the structural formula with following I or II:
Wherein R1For-H or-CH3, R2For-H or-CH3。
2. a kind of preparation method of acrylate-based hydroxyalkyl acid esters reactive diluent, characterized by the following steps:
(1) esterification: by molfraction be 1 acid anhydrides and molfraction be 1.0~1.5 hydroxy acryl acid ester mix
It closes, catalyst and polymerization inhibitor is then added, 1~5h, sampling monitoring acid value to theoretical range are reacted at 60~100 DEG C；
(2) alkoxylation: proper catalyst being added into step (1) products therefrom, and control reaction temperature is 70~120
DEG C, it is first slowly added to a small amount of ethylene oxide into above-mentioned reaction system or propylene oxide carries out initiation reaction, after reacting initiation
It is continuously added into the ethylene oxide or propylene oxide progress alkoxylation that molfraction is 1.0~2.0 again, it is old after charging
Change 1~3h, monitors acid value≤2.0mgKOH/g, be cooled to 50~60 DEG C, N2Three times, completion discharges up to target product for displacement.
3. the preparation method of acrylate-based hydroxyalkyl acid esters reactive diluent as claimed in claim 2, it is characterised in that: step
Suddenly in (1), the catalyst, polymerization inhibitor dosage be respectively 0.5~5.0%, the 0.1 of acid anhydrides and hydroxy acryl acid ester total amount
~1.0%.
4. the preparation method of acrylate-based hydroxyalkyl acid esters reactive diluent as claimed in claim 2, it is characterised in that: step
Suddenly in (2), the dosage of the catalyst is the 0.2~2.0% of target product gross mass.
5. the preparation method of acrylate-based hydroxyalkyl acid esters reactive diluent as claimed in claim 2, it is characterised in that: step
Suddenly in (1), the acid anhydrides is one of maleic anhydride, phthalic anhydride or a variety of.
6. the preparation method of acrylate-based hydroxyalkyl acid esters reactive diluent as claimed in claim 2, it is characterised in that: step
Suddenly in (1), the hydroxy acryl acid ester is hydroxy-ethyl acrylate, hydroxypropyl acrylate, acrylic acid alcoxylates, methyl-prop
One of olefin(e) acid hydroxyl ethyl ester, hydroxy propyl methacrylate, methacrylic compound are a variety of.
7. the preparation method of acrylate-based hydroxyalkyl acid esters reactive diluent as claimed in claim 2, it is characterised in that: step
Suddenly in (1) and step (2), the catalyst is independently triethylamine, methenamine, p-methyl benzenesulfonic acid, one in triphenylphosphine
Kind is a variety of.
8. the preparation method of acrylate-based hydroxyalkyl acid esters reactive diluent as claimed in claim 2, it is characterised in that: step
Suddenly in (1), the polymerization inhibitor is one of p-hydroxyanisole, hydroquinone, p-tert-Butylcatechol, phenthazine or more
Kind.
9. a kind of application of acrylate-based hydroxyalkyl acid esters reactive diluent, it is characterised in that: the acrylate-based hydroxyl alkane
Base acid esters reactive diluent is applied to UV curing field.
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Cited By (3)
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| CN109912412A (en) * | 2019-03-06 | 2019-06-21 | 西安交通大学 | Non-volatile solubilized diluent of one kind and its preparation method and application |
| CN111234198A (en) * | 2020-03-09 | 2020-06-05 | 浙江皇马新材料科技有限公司 | Preparation method of reactive acrylate crosslinking agent |
| CN114479052A (en) * | 2020-10-26 | 2022-05-13 | 中国石油化工股份有限公司 | Photocuring diluent and preparation method and application thereof |
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