CN102276508A - Low-cost functional monomer containing polymerizable double bonds and mercapto chain transfer and preparation method thereof - Google Patents
Low-cost functional monomer containing polymerizable double bonds and mercapto chain transfer and preparation method thereof Download PDFInfo
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- CN102276508A CN102276508A CN2011101643601A CN201110164360A CN102276508A CN 102276508 A CN102276508 A CN 102276508A CN 2011101643601 A CN2011101643601 A CN 2011101643601A CN 201110164360 A CN201110164360 A CN 201110164360A CN 102276508 A CN102276508 A CN 102276508A
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- polymerizable double
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Abstract
The invention provides a functional monomer containing polymerizable double bonds and mercapto chain transfer and a preparation method thereof, and belongs to the field of branched monomer molecule design and organic synthesis. The preparation method comprises the following steps: stirring (methyl) hydroxyethyl (hydroxypropyl) acrylate and mercaptopropionic acid which serve as raw materials, benzene (toluene and ethyl acetate) serving as a solvent and a water-carrying agent, p-toluenesulfonic acid serving as a catalyst and hydroquinone serving as a polymerization inhibitor to react for 5-18 hours in an oil bath temperature range from 70 DEG C to 130 DEG C; removing the solvent in a rotary evaporation way; washing with water to separate out an oil phase product; adding anhydrous sodium sulfate for drying to obtain the (methyl) acrylate functional monomer containing polymerizable double bonds and mercapto chain-transfer functional sulfydryl with yield of over 90 percent. According to the preparation method, the raw materials have wide sources, the cost is low, the product can be directly used for synthesizing a vinyl branched polymer without purification by a special method. Therefore, the price of the vinyl branched polymer can be greatly lowered, and the application range of the vinyl branched polymer can be greatly enlarged.
Description
Technical field
The present invention relates to a kind of preparation that contains (methyl) esters of acrylic acid sulfhydryl compound of polymerizable double bond and chain transfer function sulfydryl, belongs to the field of branched monomer molecular designing and organic synthesis.
Background technology
Branched polymer is because unique three-dimensional branched molecular structure and a large amount of intramolecularly hole existence, make at polymer blended, high solid coating, binding agent and matrix material matrix resin, medicine and support of the catalyst, aspects such as high molecule liquid crystal have broad application prospects.
Preparation vinyl branched polymer mainly adopts living polymerization at present, but its reaction conditions is harsh relatively, makes branched polymer will realize mass-producing application cost costliness.Therefore, the investigator attempts adopting the incompatible preparation branched polymer of radical polymerization, mainly by add the monomer that contains the chain transfer function in the radical polymerization system, makes polymkeric substance generation branching.Sulfydryl is typical chain transfer group, but sulfydryl can the Michael addition reaction take place with two keys, and reduces the monomeric chain transfer branching of chain-transfer agent efficient.Therefore to have the stability of the functional monomer of sulfydryl and two keys are its essential condition as branched monomer to this class.Simultaneously, such monomeric price will directly restrict the cost of branched polymer, thereby determine its Application Areas and scope.
Professor Shi Wenfang of Chinese University of Science and Technology adopts 4-chloromethylation vinylbenzene (CMS) to synthesize the chain-transfer agent monomer through thiocarbamide salt route two-step approach: 4-benzyl-mercapto vinylbenzene, synthesized branched polymer with this as the chain transfer monomer, but this monomer is extremely unstable.Professor Jiang Jinqiang of Southern Yangtze University designs and has synthesized the styrene monomer that contains alkyl thiosulfurie acid sodium (potassium) salt, utilize alkyl thiosulfurie acid sodium (potassium) salt at methyl-sulphoxide (DMSO) or N, can discharge this characteristic of generation chain transfer sulfydryl in the dinethylformamide intensive polar solvents such as (DMF), in DMSO or DMF, carry out the synthesizing branched polymkeric substance of solution polymerization.The thiosulfuric acid salt monomer is not quite similar with the solubility property of general vinyl monomer, and in as intensive polar solvents such as DMF or DMSO, just can generate sulfydryl, branching process and polymkeric substance degree of branching are discharged the speed and the degree of sulfydryl and are controlled, and therefore the operation of reaction and polymerization implementation method may be subjected to restriction to a certain degree.Our seminar successfully prepares own ester of branched monomer methacrylic acid sulfydryl and the mercaptan acid vinyl benzyl ester that two classes had both contained (its patent No. and title are respectively: the method for 201010117610.1 preparing branched polymer by conventional free radical polymerization and 201110000746.9 contains the styrene monomer and the preparation method of polymerizable double bond and chain transfer sulfydryl) polymerizable double bond and chain transfer function sulfydryl, purity all reaches more than 95%, and its stability in storage is better, successfully prepare branched polymer through radical polymerization, the degree of branching is higher.But its raw materials cost is all very high; the price of CMS wherein and sulfydryl hexanol all is 20 ~ 30 times (seeing Table 1 data) of conventional industrial chemicals; and subsequent purification process relative complex, make that the cost of the synthesizing branched polymkeric substance of employing chain-transfer agent monomer is too high, be unfavorable for realizing the mass-producing application.
Summary of the invention
At above-mentioned the deficiencies in the prior art, we design equally contains polymerizable double bond, have chain transfer group sulfydryl simultaneously, and have good preservation stability, but selected starting material is more cheap relatively, the simple target branched monomer of building-up process.The selected raw material of design synthetic branched monomer is cheap industrial goods (methyl) vinylformic acid hydroxyl second (third) ester and thiohydracrylic acid among the present invention, the product stability in storage is better, productive rate is higher, effective constituent is about 60% in the thick product, and need not to be further purified, be directly used in radical polymerization and prepare branched polymer.
The invention discloses preparation one class (methyl) esters of acrylic acid sulfhydryl compound that contains polymerizable double bond and have chain transfer function sulfydryl with low cost.It is characterized in that with (methyl) vinylformic acid hydroxyl second (third) ester and thiohydracrylic acid be raw material, prepare the acrylic ester monomer that contains the chain transfer sulfydryl, cost of material is cheap, preparation technology is simple, the product yield height, and have stability in storage preferably, need not purifying, can be directly used in the synthesizing branched polymkeric substance of conventional radical polymerization.
Contain polymerizable double bond and the function monomer with (methyl) esters of acrylic acid sulfydryl of chain transfer function sulfydryl, its structural formula is as follows:
R wherein
1For-H or-CH
3; R
2For-CH
2CH
2-or-CH
2CH (CH
3)-; R
3For-CH
2CH
2-or-CH (CH
3)-; R
4For-CH
2CH
2-or-CH (CH
3)-or-C (CH
3)
2-; N=0,1,2,3,4.
The above-mentioned polymerizable double bond and have the preparation method of (methyl) esters of acrylic acid sulfhydryl compound of chain transfer function sulfydryl of containing, carry out according to following step:
(1) with (methyl) vinylformic acid hydroxyl second (third) ester, thiohydracrylic acid, catalyzer and stopper are 1:(0.8 ~ 1.2 according to mol ratio): 0.04:0.002 adds the reactor that contains solvent, wherein said solvent quality is 1 ~ 3 times of (methyl) vinylformic acid hydroxyl second (third) ester quality, and stirring reaction is 5 ~ 18 hours in 70 ~ 130 ℃ of oil bath temperature scopes; (2) remove with Rotary Evaporators behind the stopped reaction and desolvate, and, be washed till water and clarify, isolate oil phase with a large amount of distillation washings; (3) in oil phase, add an amount of anhydrous Na
2SO
4Drying obtains colourless transparent liquid.
Wherein said solvent is benzene, toluene or ethyl acetate,
Wherein said catalyzer is a tosic acid,
Wherein said stopper is a Resorcinol.
Advantage of the present invention: (methyl) esters of acrylic acid sulfhydryl compound cost of material that this method obtains is cheap, the product yield height, polymer (the n=1 that forms, 2,3,4) also has the effect of polymerizable and chain transfer, its stability in storage is good, thick product need not to purify and can be directly used in polymerization, can obtain branched polymer under the conventional radical polymerization condition, and thick product also can separate the pure product (n=0) that obtain by simple post.
Description of drawings
Fig. 1, Fig. 2 be respectively typical case's (methyl) esters of acrylic acid sulfydryl function monomer of gained nucleus magnetic resonance (
1H-NMR) spectrogram.
Fig. 3 is the liquid chromatograph mass spectrography (HLPC-MS) of thick product.
Embodiment
Example 1
With reactant hydroxyethyl methylacrylate (2.6005g, 0.02mol), the 3-thiohydracrylic acid (2.1201g, 0.02mol), solvent toluene (6.0474g), a small amount of hydroquinone of polymerization retarder (0.0044g, 0.04mmol) join the there-necked flask that is connected to water trap, and then the adding tosic acid (0.1523g, 0.8mmol), the bubbling stirring reaction is 10 hours under 100 ℃ of oil bath temperatures, and reaction produces water and obviously takes system out of.Remove with Rotary Evaporators behind the stopped reaction and desolvate, and, be washed till water and clarify, isolate oil phase with a large amount of distillation washings.Add an amount of anhydrous Na
2SO
4Drying obtains oil-phase product, total recovery 95.43%.
Example 2
With reactant hydroxyethyl methylacrylate (2.6132g, 0.02mol), the 3-thiohydracrylic acid (2.1243g, 0.02mol), solvent ethyl acetate (7.1034g), a small amount of hydroquinone of polymerization retarder (0.0041g, 0.04mmol) join the there-necked flask that is connected to water trap, and then the adding tosic acid (0.1517g, 0.8mmol), the bubbling stirring reaction is 5 hours under 100 ℃ of oil bath temperatures, and reaction produces water and obviously takes system out of.Remove with Rotary Evaporators behind the stopped reaction and desolvate, and, be washed till water and clarify, isolate oil phase with a large amount of distillation washings.Add an amount of anhydrous Na
2SO
4Drying obtains oil-phase product, total recovery 98.15%.
Example 3
With reactant Propylene glycol monoacrylate (2.6054g, 0.02mol), the 3-thiohydracrylic acid (1.7021g, 0.016mol), solvent ethyl acetate (7.0056g), a small amount of hydroquinone of polymerization retarder (0.0043g, 0.04mmol) join the there-necked flask that is connected to water trap, and then the adding tosic acid (0.1601g, 0.8mmol), the bubbling stirring reaction is 16 hours under 100 ℃ of oil bath temperatures, and reaction produces water and obviously takes system out of.Remove with Rotary Evaporators behind the stopped reaction and desolvate, and, be washed till water and clarify, isolate oil phase with a large amount of distillation washings.Add an amount of anhydrous Na
2SO
4Drying obtains oil-phase product, total recovery 96.93%.
Example 4
With reactant Hydroxyethyl acrylate (2.3182g, 0.02mol), the 3-thiohydracrylic acid (2.1186g, 0.02mol), solvent toluene (4.6070g), a small amount of hydroquinone of polymerization retarder (0.0043g, 0.04mmol) join the there-necked flask that is connected to water trap, and then the adding tosic acid (0.1536g, 0.8mmol), the bubbling stirring reaction is 18 hours under 80 ℃ of oil bath temperatures, and reaction produces water and obviously takes system out of.Remove with Rotary Evaporators behind the stopped reaction and desolvate, and, be washed till water and clarify, isolate oil phase with a large amount of distillation washings.Add an amount of anhydrous Na
2SO
4Drying obtains oil-phase product, total recovery 97.22%.
Example 5
With reactant Propylene glycol monoacrylate (2.6038g, 0.02mol), the 3-thiohydracrylic acid (2.1265g, 0.02mol), solvent toluene (5.3474g), a small amount of hydroquinone of polymerization retarder (0.0047g, 0.04mmol) join the there-necked flask that is connected to water trap, and then the adding tosic acid (0.1534g, 0.8mmol), the bubbling stirring reaction is 10 hours under 70 ℃ of oil bath temperatures, and reaction produces water and obviously takes system out of.Remove with Rotary Evaporators behind the stopped reaction and desolvate, and, be washed till water and clarify, isolate oil phase with a large amount of distillation washings.Add an amount of anhydrous Na
2SO
4Drying obtains oil-phase product, total recovery 95.43%.
Example 6
With reactant hydroxyethyl methylacrylate (2.6079g, 0.02mol), the 3-thiohydracrylic acid (2.3321g, 0.022mol), solvent benzol (5.4237g), a small amount of hydroquinone of polymerization retarder (0.0045g, 0.04mmol) join the there-necked flask that is connected to water trap, and then the adding tosic acid (0.1540g, 0.8mmol), the bubbling stirring reaction is 13 hours under 100 ℃ of oil bath temperatures, and reaction produces water and obviously takes system out of.Remove with Rotary Evaporators behind the stopped reaction and desolvate, and, be washed till water and clarify, isolate oil phase with a large amount of distillation washings.Add an amount of anhydrous Na
2SO
4Drying obtains oil-phase product, total recovery 97.92%.
Example 7
With reactant Rocryl 410 (2.9008g, 0.02mol), the 3-thiohydracrylic acid (2.5441g, 0.024mol), solvent benzol (6.0276g), a small amount of hydroquinone of polymerization retarder (0.0046g, 0.04mmol) join the there-necked flask that is connected to water trap, and then the adding tosic acid (0.1529g, 0.8mmol), the bubbling stirring reaction is 10 hours under 120 ℃ of oil bath temperatures, and reaction produces water and obviously takes system out of.Remove with Rotary Evaporators behind the stopped reaction and desolvate, and, be washed till water and clarify, isolate oil phase with a large amount of distillation washings.Add an amount of anhydrous Na
2SO
4Drying obtains oil-phase product, total recovery 95.82%.
Example 8
With reactant hydroxyethyl methylacrylate (2.6027g, 0.02mol), 2 mercaptopropionic acid (2.1201g, 0.02mol), solvent benzol (5.2427g), a small amount of hydroquinone of polymerization retarder (0.0043g, 0.04mmol) join the there-necked flask that is connected to water trap, and then the adding tosic acid (0.1519g, 0.8mmol), the bubbling stirring reaction is 8 hours under 120 ℃ of oil bath temperatures, and reaction produces water and obviously takes system out of.Remove with Rotary Evaporators behind the stopped reaction and desolvate, and, be washed till water and clarify, isolate oil phase with a large amount of distillation washings.Add an amount of anhydrous Na
2SO
4Drying obtains oil-phase product, total recovery 94.82%.
Example 9
With reactant Rocryl 410 (2.8904g, 0.02mol), 2 mercaptopropionic acid (2.1197g, 0.02mol), solvent benzol (6.0032g), a small amount of hydroquinone of polymerization retarder (0.0047g, 0.04mmol) join the there-necked flask that is connected to water trap, and then the adding tosic acid (0.1530g, 0.8mmol), the bubbling stirring reaction is 6 hours under 130 ℃ of oil bath temperatures, and reaction produces water and obviously takes system out of.Remove with Rotary Evaporators behind the stopped reaction and desolvate, and, be washed till water and clarify, isolate oil phase with a large amount of distillation washings.Add an amount of anhydrous Na
2SO
4Drying obtains oil-phase product, total recovery 92.77%.
Three kinds of cost overviews that contain the function monomer of polymerizable double bond and chain transfer sulfydryl of table 1
Claims (3)
1. the cheap function monomer that contains polymerizable double bond and chain transfer sulfydryl is characterized in that its structural formula is as follows:
R wherein
1For-H or-CH
3; R
2For-CH
2CH
2-or-CH
2CH (CH
3)-; R
3For-CH
2CH
2-or-CH (CH
3)-; R
4For-CH
2CH
2-or-CH (CH
3)-or-C (CH
3)
2-; N=0,1,2,3,4.
2. the described cheapness of claim 1 contains the preparation method of the function monomer of polymerizable double bond and chain transfer sulfydryl, it is characterized in that carrying out according to following step:
(1) be 1:(0.8 ~ 1.2 with (methyl) vinylformic acid hydroxyl second (third) ester, thiohydracrylic acid, catalyzer and stopper according to mol ratio): 0.04:0.002 adds the reactor that contains solvent, wherein said solvent quality is 1 ~ 3 times of (methyl) vinylformic acid hydroxyl second (third) ester quality, and stirring reaction is 5 ~ 18 hours in 70 ~ 130 ℃ of oil bath temperature scopes; (2) remove with Rotary Evaporators behind the stopped reaction and desolvate, and, be washed till water and clarify, isolate oil phase with a large amount of distillation washings; (3) in oil phase, add an amount of anhydrous Na
2SO
4Drying obtains colourless transparent liquid.
3. cheapness according to claim 2 contains the preparation method of the function monomer of polymerizable double bond and chain transfer sulfydryl, it is characterized in that wherein said solvent is benzene, toluene or ethyl acetate, wherein said catalyzer is a tosic acid, and wherein said stopper is a Resorcinol.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102924640A (en) * | 2012-10-30 | 2013-02-13 | 常州大学 | Method for preparing branched polystyrene by emulsion polymerization |
| CN110183664A (en) * | 2019-04-30 | 2019-08-30 | 常州大学 | A kind of preparation method and application of ultraviolet curing type silicone oil containing methacrylate |
| CN112479952A (en) * | 2020-12-02 | 2021-03-12 | 江汉大学 | Preparation method of nonamercapto compound monomer |
-
2011
- 2011-06-20 CN CN2011101643601A patent/CN102276508A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102924640A (en) * | 2012-10-30 | 2013-02-13 | 常州大学 | Method for preparing branched polystyrene by emulsion polymerization |
| CN102924640B (en) * | 2012-10-30 | 2014-12-03 | 常州大学 | Method for preparing branched polystyrene by emulsion polymerization |
| CN110183664A (en) * | 2019-04-30 | 2019-08-30 | 常州大学 | A kind of preparation method and application of ultraviolet curing type silicone oil containing methacrylate |
| CN110183664B (en) * | 2019-04-30 | 2021-09-28 | 常州大学 | Preparation method and application of ultraviolet-curing methacrylate-containing silicone oil |
| CN112479952A (en) * | 2020-12-02 | 2021-03-12 | 江汉大学 | Preparation method of nonamercapto compound monomer |
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Application publication date: 20111214 |