CN109776340A - A kind of methacrylate monomers and preparation method thereof with resistance to the oxygen inhibiting polymerization performance - Google Patents
A kind of methacrylate monomers and preparation method thereof with resistance to the oxygen inhibiting polymerization performance Download PDFInfo
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- CN109776340A CN109776340A CN201910062268.0A CN201910062268A CN109776340A CN 109776340 A CN109776340 A CN 109776340A CN 201910062268 A CN201910062268 A CN 201910062268A CN 109776340 A CN109776340 A CN 109776340A
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- resistance
- inhibiting polymerization
- methacrylate monomers
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- oxygen inhibiting
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Abstract
The present invention discloses a kind of methacrylate monomers with resistance to the oxygen inhibiting polymerization performance, is related to synthesis of polymer material field, there are problems that surface oxygen inhibition based on existing radical UV curing coating and proposes, with following chemical structural formula:
Description
Technical field
The present invention relates to synthesis of polymer material fields, and in particular to a kind of methacrylic acid with resistance to the oxygen inhibiting polymerization performance
Ester monomer and preparation method thereof.
Background technique
There is table mostly to the oxygen sensitive in air, free radical type light solidifying coating in the Light Curing of free radical polymerization
The problem of face oxygen inhibition.Due to the effect of oxygen inhibition, the decline of coating surface performance, such as coating surface hardness, scratch resistance is wear-resisting
Property and gloss etc..The surface oxygen inhibition problem in Light Curing how is effectively avoided, becomes light polymerization technique and is badly in need of solution
Critical issue certainly.
There is resistance to the oxygen inhibiting polymerization method reported in the literature more, such as realize photocuring under nitrogen atmosphere, or keeps coating surface floating
One layer of liquid wax layer and the method for avoiding curing system from contacting with oxygen.Also have and tended to using low-surface energy substance on low surface
The characteristic of energy interface enrichment, prepares fluorine-containing or siliceous photoinitiator, the free radical that generation is largely decomposed using initiator is disappeared
Oxygen consumption gas, and avoid the process of oxygen inhibition.For hydrogen-capture-type light initiator system, amine aided initiating produces after acting on main initiator
Raw free radical has certain resistance to the oxygen inhibiting polymerization, hinders so having and alleviating light solidifying coating surface oxygen using reactive amines aided initiating
Poly- report.But largely can cause the xanthochromia of coating using aminated compounds, and reduce coating is used for a long time performance and beauty
Sight degree.
According to the generation place of oxygen inhibition mainly in the interface of coating, so if aminated compounds can be made in coating surface
Enrichment, can be greatly reduced the dosage of aminated compounds, and reach corresponding oxygen inhibition performance.
Summary of the invention
The problem to be solved by the present invention is that there is surface oxygen inhibition in existing radical UV curing coating.
The present invention adopts the following technical solutions solves above-mentioned technical problem:
A kind of methacrylate monomers with resistance to the oxygen inhibiting polymerization performance, with following chemical structural formula:
Wherein p=4-9.
The present invention also provides a kind of preparation method of methacrylate monomers with resistance to the oxygen inhibiting polymerization performance, including it is following
Step:
(1) acrylated acrylic's ethylene oxidic ester is used；
(2) under condition of ice bath, fluorine-containing primary amine is added dropwise into the product of step (1), after being added dropwise, is warming up to 60-80 DEG C,
The reaction was continued；
(3) after reaction, reaction product is washed, and be dried.
Preferably, glycidyl methacrylate and the molar ratio of acrylic acid are 1:1.05-1.1 in the step (1).
Preferably, the catalyst in the step (1) is tetramethyl ammonium chloride, in tetrabutylammonium bromide, triphenyl phosphorus
One or two, the additional amount of the catalyst are the 1-3wt% of glycidyl methacrylate and acrylic acid gross mass.
Preferably, the polymerization inhibitor in the step (1) is hydroxyanisol, and additional amount is methyl propenoic acid glycidyl
The 0.1-0.5wt% of ester and acrylic acid gross mass.
Preferably, the reaction temperature in the step (1) is 90-120 DEG C, reaction time 4-5h.
Preferably, the rate of addition of acrylic acid is 0.5-1.5g/min in the step (1).
Preferably, the fluorine-containing primary amine is the perfluoro primary amine compound of 5-10 carbon atom.
Preferably, the rate of addition of the fluorine-containing primary amine is 0.5-1.5g/min.
Preferably, reaction product is washed with deionized 2-3 times in the step (3), is washed with 1wt%NaOH solution
After 2 times, anhydrous sodium sulfate is added and is dried.
The beneficial effects of the present invention are:
The amine-containing methacrylate monomers containing long fluorocarbon chain prepared in the present invention, may participate in Light Curing,
Before solidification, the fluorocarbon chain of low-surface-energy makes the compound tend to the surface enrichment in coating, to improve the antioxygen resistance of coating
Poly- performance.
Specific embodiment
Below with reference to saying that embodiment is described in further details the present invention.
Test material and reagent as used in the following examples etc., unless otherwise specified, commercially obtain.
Embodiment 1
A kind of reaction equation of the methacrylate monomers preparation process with resistance to the oxygen inhibiting polymerization performance is as follows:
Wherein p=4-9；
Acrylic acid and glycidyl methacrylate be subjected to reacting for carboxyl open loop oxygen, then with containing long fluorocarbon chain
Primary amine carries out Michael addition reaction, and the work of Michael addition reaction occurs using acrylate and methacrylate and amino
Sex differernce makes acrylic double bond react and prepare the methacrylate monomers of bifunctionality with amino.
Embodiment 2
A kind of preparation method of the methacrylate monomers with resistance to the oxygen inhibiting polymerization performance, comprising the following steps:
(1) glycidyl methacrylate 64g is weighed, tetramethyl ammonium chloride 3.0g, hydroxyanisol 0.1g is added, in
In three-necked flask, stirring is warming up to 90 DEG C, and acrylic acid 37.8g is added dropwise into reaction system using constant pressure funnel, drips
Acid value is tested after Bi Hou, the reaction was continued 4h, when acid value is less than 10mg KOH/g, stops reaction；
(2) it after cooling, in ice bath, is added dropwise in perfluoro amylamine 79.8g, 60min and is added dropwise into reaction system, drip
After adding, 60 DEG C are warming up to, the reaction was continued 2h；
(3) after reaction, product is washed with deionized 2-3 times, then is washed 2-3 times with 1wt%NaOH aqueous solution,
Finally be washed with deionized to neutrality, be transferred in beaker, be added suitable anhydrous sodium sulfate, it is dry for 24 hours, filtering to get
To the methacrylate monomers with resistance to the oxygen inhibiting polymerization.
The chemical structural formula of the monomer is as follows:
Embodiment 3
A kind of preparation method of the methacrylate monomers with resistance to the oxygen inhibiting polymerization performance, comprising the following steps:
(1) glycidyl methacrylate 64g is weighed, tetrabutylammonium bromide 1.2g, hydroxyanisol 0.5g is added, in
In three-necked flask, stirring is warming up to 120 DEG C, and acrylic acid 43.2g is added dropwise into reaction system using constant pressure funnel, drips
Acid value is tested after Bi Hou, the reaction was continued 4h, when acid value is less than 10mgKOH/g, stops reaction；
(2) it under condition of ice bath, is added dropwise in perfluoro hexylamine 106.2g, 1.5h and is added dropwise into reaction system, be added dropwise
After, 80 DEG C are warming up to, the reaction was continued 2h；
(3) after reaction, it is cooled to room temperature, product is washed with deionized 2-3 times, then is water-soluble with 1wt%NaOH
Liquid washs 2-3 times, is finally washed with deionized to neutrality, is transferred in beaker, suitable anhydrous sodium sulfate is added, dry
For 24 hours, it filters to get the methacrylate monomers with resistance to the oxygen inhibiting polymerization are arrived.
The chemical structural formula of the monomer is as follows:
Embodiment 4
A kind of preparation method of the methacrylate monomers with resistance to the oxygen inhibiting polymerization performance, comprising the following steps:
(1) glycidyl methacrylate 64g is weighed, tetramethyl ammonium chloride 2.5g, hydroxyanisol 0.3g is added, in
In three-necked flask, stirring is warming up to 100 DEG C, and acrylic acid 39.6g, 40min are added dropwise into reaction system using constant pressure funnel
It is inside added dropwise, after being added dropwise, tests acid value after the reaction was continued 4h, when acid value is less than 10mg KOH/g, stop reaction；
(2) it under condition of ice bath, is added dropwise in perfluoro heptyl amice 106.1g, 1.5h and is added dropwise into reaction system, be added dropwise
After, 70 DEG C are warming up to, the reaction was continued 2h；
(3) after reaction, product is washed with deionized 2-3 times, then is washed 2-3 times with 1wt%NaOH aqueous solution,
Finally be washed with deionized to neutrality, be transferred in beaker, be added suitable anhydrous sodium sulfate, it is dry for 24 hours, filtering to get
To the methacrylate monomers with resistance to the oxygen inhibiting polymerization.
The chemical structural formula of the monomer is as follows:
Embodiment 5
A kind of preparation method of the methacrylate monomers with resistance to the oxygen inhibiting polymerization performance, comprising the following steps:
(1) glycidyl methacrylate 64g is weighed, tetramethyl ammonium chloride 2.0g, hydroxyanisol 0.3g is added, in
In three-necked flask, stirring is warming up to 100 DEG C, and acrylic acid 37.8g, 40min are added dropwise into reaction system using constant pressure funnel
It is inside added dropwise, after being added dropwise, after the reaction was continued 4h, tests acid value, when acid value is less than 10mgKOH/g, stop reaction；
(2) it under condition of ice bath, is added dropwise in perfluoro octylame 119.2g, 2h and is added dropwise into reaction system, drip
Bi Hou is warming up to 70 DEG C, the reaction was continued 2h；
(3) after reaction, it is washed with deionized 2-3 times in separatory funnel, then washs 2- with 1wt%NaOH aqueous solution
It 3 times, is finally washed with deionized to neutrality, is transferred in beaker, suitable anhydrous sodium sulfate is added, it is dry to filter for 24 hours,
Obtain the methacrylate monomers with resistance to the oxygen inhibiting polymerization.
The chemical structural formula of the monomer is as follows:
Embodiment 6
A kind of preparation method of the methacrylate monomers with resistance to the oxygen inhibiting polymerization performance, comprising the following steps:
(1) glycidyl methacrylate 64g is weighed, triphenyl phosphorus 3.0g, hydroxyanisol 0.1g, Yu Sankou is added
In flask, stirring is warming up to 90 DEG C, and acrylic acid 39.6g is added dropwise into reaction system using constant pressure funnel, after being added dropwise,
Acid value is tested after the reaction was continued 4h, when acid value is less than 10mgKOH/g, stops reaction；
(2) it under condition of ice bath, is added dropwise in perfluoro nonyl amine 138.6g, 2h and is added dropwise into reaction system, be added dropwise
Afterwards, 70 DEG C are warming up to, the reaction was continued 2h；
(3) after reaction, it is cooled to room temperature, product is washed with deionized 2-3 times, then with 1wt%NaOH aqueous solution
Washing 2-3 times, is finally washed with deionized to neutrality, is transferred in beaker, and suitable anhydrous sodium sulfate is added, and dries for 24 hours,
It filters to get the methacrylate monomers with resistance to the oxygen inhibiting polymerization are arrived.
The chemical structural formula of the monomer is as follows:
Embodiment 7
A kind of preparation method of the methacrylate monomers with resistance to the oxygen inhibiting polymerization performance, comprising the following steps:
(1) glycidyl methacrylate 64g is weighed, triphenyl phosphorus 3.0g, hydroxyanisol 0.1g, Yu Sankou is added
In flask, stirring is warming up to 90 DEG C, and acrylic acid 37.8g is added dropwise into reaction system using constant pressure funnel, after being added dropwise,
Acid value is tested after the reaction was continued 4h, when acid value is less than 10mgKOH/g, stops reaction；
(2) it under condition of ice bath, is added dropwise in perfluoro decyl amine 158.6g, 2.5h and is added dropwise into reaction system, drip
Bi Hou is warming up to 70 DEG C, the reaction was continued 2h；
(3) after reaction, it is cooled to room temperature, product is washed with deionized 2-3 times, then with 1wt%NaOH aqueous solution
Washing 2-3 times, is finally washed with deionized to neutrality, is transferred in beaker, and suitable anhydrous sodium sulfate is added, and dries for 24 hours,
It filters to get the methacrylate monomers with resistance to the oxygen inhibiting polymerization are arrived.
The chemical structural formula of the monomer is as follows:
The above is only the preferred embodiment of the present invention, protection scope of the present invention is not limited merely to above-described embodiment,
It is within the scope of the invention with present inventive concept without the various process programs of substantial differences.
Claims (10)
1. a kind of methacrylate monomers with resistance to the oxygen inhibiting polymerization performance, it is characterised in that: have following chemical structural formula:
Wherein p=4-9.
2. a kind of preparation method for preparing the methacrylate monomers as described in claim 1 with resistance to the oxygen inhibiting polymerization performance,
It is characterized by comprising following steps:
(1) acrylated acrylic's ethylene oxidic ester is used；
(2) under condition of ice bath, fluorine-containing primary amine is added dropwise into the product of step (1), after being added dropwise, is warming up to 60-80 DEG C, continues
Reaction；
(3) after reaction, reaction product is washed, and be dried.
3. the preparation method of the methacrylate monomers according to claim 2 with resistance to the oxygen inhibiting polymerization performance, feature
Be: glycidyl methacrylate and the molar ratio of acrylic acid are 1:1.05-1.1 in the step (1).
4. the preparation method of the methacrylate monomers according to claim 2 with resistance to the oxygen inhibiting polymerization performance, feature
Be: catalyst in the step (1) is one or both of tetramethyl ammonium chloride, tetrabutylammonium bromide, triphenyl phosphorus,
The additional amount of the catalyst is the 1-3wt% of glycidyl methacrylate and acrylic acid gross mass.
5. the preparation method of the methacrylate monomers according to claim 2 with resistance to the oxygen inhibiting polymerization performance, feature
Be: the polymerization inhibitor in the step (1) is hydroxyanisol, and additional amount is glycidyl methacrylate and acrylic acid
The 0.1-0.5wt% of gross mass.
6. the preparation method of the methacrylate monomers according to claim 2 with resistance to the oxygen inhibiting polymerization performance, feature
Be: the reaction temperature in the step (1) is 90-120 DEG C, reaction time 4-5h.
7. the preparation method of the methacrylate monomers according to claim 2 with resistance to the oxygen inhibiting polymerization performance, feature
Be: the rate of addition of acrylic acid is 0.5-1.5g/min in the step (1).
8. the preparation method of the methacrylate monomers according to claim 2 with resistance to the oxygen inhibiting polymerization performance, feature
Be: the fluorine-containing primary amine is the perfluoro primary amine compound of 5-10 carbon atom.
9. the preparation method of the methacrylate monomers according to claim 2 with resistance to the oxygen inhibiting polymerization performance, feature
Be: the rate of addition of the fluorine-containing primary amine is 0.5-1.5g/min.
10. the preparation method of the methacrylate monomers according to claim 2 with resistance to the oxygen inhibiting polymerization performance, feature
It is: reaction product is washed with deionized 2-3 times in the step (3), after washing 2 times with 1wt%NaOH solution, is added
Anhydrous sodium sulfate is dried.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114292183A (en) * | 2021-12-29 | 2022-04-08 | 徐州博康信息化学品有限公司 | Preparation method of photoresist resin monomer containing hydroxyl structure |
| CN114874694A (en) * | 2022-05-17 | 2022-08-09 | 广东希贵光固化材料有限公司 | Anti-oxygen polymerization-inhibiting UVLED coating |
| CN115626984A (en) * | 2022-12-19 | 2023-01-20 | 暨南大学附属第一医院（广州华侨医院） | Fluorinated polymer, synthetic method thereof and application thereof in gene delivery |
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| CN105051082A (en) * | 2013-03-22 | 2015-11-11 | 第一毛织株式会社 | Photocurable composition and enveloped device including same |
| CN108409688A (en) * | 2018-02-12 | 2018-08-17 | 中山大学 | A kind of perfluorinated alkyl sulfonamide reactive amines acrylate compounds and preparation method |
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Patent Citations (2)
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| CN105051082A (en) * | 2013-03-22 | 2015-11-11 | 第一毛织株式会社 | Photocurable composition and enveloped device including same |
| CN108409688A (en) * | 2018-02-12 | 2018-08-17 | 中山大学 | A kind of perfluorinated alkyl sulfonamide reactive amines acrylate compounds and preparation method |
Non-Patent Citations (1)
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114292183A (en) * | 2021-12-29 | 2022-04-08 | 徐州博康信息化学品有限公司 | Preparation method of photoresist resin monomer containing hydroxyl structure |
| CN114874694A (en) * | 2022-05-17 | 2022-08-09 | 广东希贵光固化材料有限公司 | Anti-oxygen polymerization-inhibiting UVLED coating |
| CN115626984A (en) * | 2022-12-19 | 2023-01-20 | 暨南大学附属第一医院（广州华侨医院） | Fluorinated polymer, synthetic method thereof and application thereof in gene delivery |
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Application publication date: 20190521 |