CN102585050B - Preparation method of emulsion type tert-butyl peroxyneo-caprate with 50% mass fraction - Google Patents
Preparation method of emulsion type tert-butyl peroxyneo-caprate with 50% mass fraction Download PDFInfo
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Abstract
The invention relates to a preparation method of an initiating agent for synthesis of high polymers, in particular to a preparation method of emulsion type tert-butyl peroxyneo-caprate. The preparation method includes: adding tert-butyl hydroperoxide in alkaline solution, adding neodecanoyl chloride in the alkaline solution in dropwise mode, finishing adding of the neodecanoyl chloride in 40-120 minutes, stirring and reacting for 30-50 minutes, separating mother solution, and washing a reaction product to potential of hydrogen (pH) ranging from 5 to 7; mixing deionized water, an antifreezing agent, an emulsifying agent and an dispersing agent evenly to obtain water-phase solution; mixing the reaction product and the water-phase solution according to mass ratio of 1: (0.90-1.00), and stirring for 3-3.5 hours at the temperature of 0 DEG C to perform emulsifying synthesis. Content and yield of produces manufactured by the preparation method are improved greatly, the products are easy to store and transport. The preparation method of the emulsion type tert-butyl peroxyneo-caprate simplifies technological process, overcomes complicated requirements of reaction devices, and enables reaction to be performed under relatively temperate and safe conditions. Products yield can reach above 95%.
Description
Technical field
The present invention relates to the synthetic preparation method with initiator of a kind of superpolymer, particularly the preparation method of the special butyl ester of a kind of emulsion-type massfraction 50% peroxidation neodecanoic acid.
Background technology
Along with the fast development of the synthetic industry of domestic superpolymer, synthetic kind and the demand with initiator of superpolymer promotes rapidly.The special butyl ester of emulsion-type peroxidation neodecanoic acid synthesizes as a kind of superpolymer uses efficient initiator, in the polymerization process of superpolymer, compare with the solvent-borne type initiator, had the advantage that the solvent-borne type initiator amount is few, efficiency of initiation is high, the polyreaction heat release even, be convenient to control concurrently, after particularly water is cooked solvent, realized environmental protection, and effectively avoided the harm of flammable solvent to human body in production and the use, the products obtained therefrom excellent property is a kind of safety, environmental protection, the synthetic initiator of using of superpolymer efficient, constant product quality.
Summary of the invention
The object of the present invention is to provide a kind of easy to operate, process time short and be suitable for the preparation method of the special butyl ester of emulsion-type massfraction 50% peroxidation neodecanoic acid of industrial applications.
The invention provides the preparation method of the special butyl ester of a kind of emulsion-type massfraction 50% peroxidation neodecanoic acid, may further comprise the steps:
(1) tertbutyl peroxide is added in the basic solution, tertbutyl peroxide is 1: 0.45～0.9 with the massfraction ratio of alkali;
(2) new decanoyl chloride is added drop-wise in the solution of step (1) gained, stirs while dripping, temperature is controlled at 10～30 ℃, adds in 40～120min;
(3) after new decanoyl chloride dropwises, stirring reaction 30～50min;
(4) stop to stir after reaction finishes, leave standstill 20～40min, mother liquor is separated, resultant of reaction is washed till pH value 5～7;
(5) with deionized water, frostproofer, emulsifying agent and dispersion agent by mass ratio 1: (0.26～0.48): (0.026～0.065): (0.026～0.065) mixes, and makes aqueous phase solution;
(6) aqueous phase solution with step (5) gained mixes with the resultant of reaction (oil phase) of step (4) gained, and both mass ratioes are 1: (0.90～1.00), and it is synthetic to carry out emulsification 0～5 ℃ of temperature;
(7) obtain the special butyl ester of emulsion-type peroxidation neodecanoic acid after being cooled to-10 ℃～-15 ℃, concentration is 49%～51%.
Basic solution in the described step (1) is aqueous sodium hydroxide solution or potassium hydroxide aqueous solution, and concentration is 25%～35%.
The mass ratio of the solution of new decanoyl chloride and step (1) gained is 1: 1.27～2.7 in the described step (2).
Temperature control in the described step (2) is preferably 20～30 ℃.
The stirring reaction time in the described step (3) is preferably 40～45min.
Frostproofer preferred alcohol in the described step (5); The preferred milky white spirit of emulsifying agent, dispersion agent preferably polyethylene alcohol.
Beneficial effect of the present invention is:
The special butyl ester of the emulsion-type peroxidation neodecanoic acid of preparing has overcome solvent-borne type initiator (mainly referring to organic solvent) power consumption height, not environmental protection, inflammable dangerous, and the shortcoming that easily human body is worked the mischief in process of production.In the superpolymer polyreaction, the special butyl ester of the emulsion-type peroxidation neodecanoic acid that this method is prepared has had solvent-borne type initiator stable polymerization reaction, constant product quality concurrently, consumption is few, initiation is quick, the uniform advantage of heat release, and the harm to human body has been avoided in production and the use in environmental protection.In addition, the preparation method of the special butyl ester of emulsion-type peroxidation neodecanoic acid of the present invention has overcome the complicated requirement to conversion unit, makes under the environment that is reflected at gentleness, safety and carries out, and product content and yield increase substantially, and yield can reach more than 95%.Product stock, the convenient transportation of preparation can be applicable to suitability for industrialized production in a large number.
Embodiment
The invention will be further described below by embodiment.
Embodiment 1
(1) in the 250ml flask, adding content is 90% sodium hydroxide 22.5 grams, and water 40 grams stir and are cooled to 5 ℃, make alkaline solution of sodium hydroxide, and concentration is about 32.4%;
(2) dripping purity in the solution that makes to step (1) is 70.5% tertbutyl peroxide 38 grams, reaction 30min, and temperature is controlled at 25 ℃;
(3) stir that slowly to drip concentration in the flask be that 99% new decanoyl chloride solution 50 restrains in the back, temperature of reaction is controlled at 20 ℃, and 2h adds, then stirring reaction 30min;
(4) stop to stir after reaction finishes, leave standstill 20min, reaction mother liquor is separated, with resultant of reaction wash to pH value be 5.2, making content is that 98% new peroxide tert-butyl caprate 62.2 restrains totally;
(5) with deionized water, ethanol, milky white spirit, polyvinyl alcohol by mass ratio 1: 0.4: 0.05: 0.05 mixes, and makes aqueous phase solution 60 and restrains;
(6) be to mix at 1: 0.92 the resultant of reaction of the aqueous phase solution of step (5) gained and step (4) gained by mass ratio, stir 3h down at 0 ℃, it is synthetic to carry out emulsification;
(7) obtain the special butyl ester of emulsion-type peroxidation neodecanoic acid, concentration is 51%.
| Project | Index |
| Outward appearance | Colourless transparent liquid does not have mechanical impurity |
| Colourity, Pt-Co | 30 |
| The active oxygen massfraction, % | 3.65 |
| Massfraction, % | 51 |
Embodiment 2
(1) in the 250ml flask, the adding mass content is 90% sodium hydroxide 22.5 grams, and water 40 grams stir and are cooled to 5 ℃, make alkaline solution of sodium hydroxide, and concentration is about 32.4%;
(2) dripping purity in the solution that makes to step (1) is 70.5% tert-butyl hydroperoxide potassium 38 grams, reaction 30min, and temperature is controlled at 35 ℃;
(3) stir that slowly to drip concentration in the flask be that 99% new decanoyl chloride solution 60 restrains in the back, temperature of reaction is controlled at 25 ℃, and 40min adds, then stirring reaction 50min;
(4) stop to stir after reaction finishes, leave standstill 40min, reaction mother liquor is separated, with resultant of reaction wash to pH value be 6, making mass content is that 99% new peroxide tert-butyl caprate 62.2 restrains;
(5) with deionized water, ethanol, milky white spirit, polyvinyl alcohol by mass ratio 1: 0.26: 0.05: 0.065 mixes, and makes aqueous phase solution 60 and restrains;
(6) be that 1: 0.98 quality is mixed with the resultant of reaction of the aqueous phase solution of step (5) gained and step (4) gained by mass ratio, stir down at 0 ℃ that to carry out emulsification in 3 hours synthetic;
(7) cooling obtains the special butyl ester of emulsion-type peroxidation neodecanoic acid after-3 ℃, and concentration is about 50%.
| Project | Index |
| Outward appearance | Colourless transparent liquid does not have mechanical impurity |
| Colourity, Pt-Co | 29 |
| The active oxygen massfraction, % | 3.60 |
| Massfraction, % | 50 |
Embodiment 3
(1) in the 250ml flask, adding content is 90% sodium hydroxide 22.5 grams, and water 40 grams stir and are cooled to 5 ℃, make alkaline solution of sodium hydroxide, and concentration is about 32.4%;
(2) dripping purity in the solution that makes to step (1) is 70.5% tertbutyl peroxide 42 grams, reaction 30min, and temperature is controlled at 25 ℃;
(3) stir that slowly to drip concentration in the flask be that 99% new decanoyl chloride solution 50 restrains in the back, temperature of reaction is controlled at 20 ℃, and 1.5h adds, then stirring reaction 40min;
(4) stop to stir after reaction finishes, leave standstill 20min, reaction mother liquor is separated, with resultant of reaction wash to pH value be 7, making content is that 98% new peroxide tert-butyl caprate 62.2 restrains totally;
(5) with deionized water, ethanol, milky white spirit, polyvinyl alcohol by mass ratio 1: 0.48: 0.026: 0.05 mixes, and makes aqueous phase solution 60 and restrains;
(6) be to mix at 1: 1 the resultant of reaction of the aqueous phase solution of step (5) gained and step (4) gained by mass ratio, stirring 3.5h down at 0 ℃, to carry out emulsification synthetic;
(7) cool to-10 ℃ and obtain the special butyl ester of emulsion-type peroxidation neodecanoic acid, concentration is about 49%.
| Project | Index |
| Outward appearance | Colourless transparent liquid does not have mechanical impurity |
| Colourity, Pt-Co | 29 |
| The active oxygen massfraction, % | 3.70 |
| Massfraction, % | 49 |
Claims (7)
1. the preparation method of the special butyl ester of emulsion-type massfraction 50% a peroxidation neodecanoic acid is characterized in that may further comprise the steps:
(1) tertbutyl peroxide is added in the basic solution, tertbutyl peroxide is 1: 0.45～0.9 with the massfraction ratio of alkali;
(2) new decanoyl chloride is added drop-wise in the solution of step (1) gained, stirs while dripping, temperature is controlled at 10～30 ℃, adds in 40～120min;
(3) after new decanoyl chloride dropwises, stirring reaction 30～50min;
(4) stop to stir after reaction finishes, leave standstill 20～40min, mother liquor is separated, resultant of reaction is washed till pH value 5～7;
(5) with deionized water, frostproofer, emulsifying agent and dispersion agent by mass ratio 1: (0.26～0.48): (0.026～0.065): (0.026～0.065) mixes, and makes aqueous phase solution;
(6) aqueous phase solution with step (5) gained mixes with the resultant of reaction of step (4) gained, and both mass ratioes are 1: (0.90～1.00), and it is synthetic to carry out emulsification at 0 ℃ of stirring 3～3.5h;
(7) be cooled to 0 ℃～-15 ℃ and obtain the emulsion-type new peroxide tert-butyl caprate, concentration is 49%～51%.
2. according to the preparation method of the special butyl ester of the described emulsion-type massfraction 50% peroxidation neodecanoic acid of claim 1, it is characterized in that, basic solution in the described step (1) is aqueous sodium hydroxide solution or potassium hydroxide aqueous solution, and its alkali lye massfraction is 20%～35%.
3. according to the preparation method of the special butyl ester of the described emulsion-type massfraction 50% peroxidation neodecanoic acid of claim 1, it is characterized in that the mass ratio of the solution of new decanoyl chloride and step (1) gained is 1: 1.27～2.7 in the described step (2).
4. according to the preparation method of the special butyl ester of the described emulsion-type massfraction 50% peroxidation neodecanoic acid of claim 1, it is characterized in that the stirring reaction time in the described step (3) is 40～45min.
5. according to the preparation method of the special butyl ester of the described emulsion-type massfraction 50% peroxidation neodecanoic acid of claim 1, it is characterized in that the frostproofer in the described step (5) is ethanol.
6. according to the preparation method of the special butyl ester of the described emulsion-type massfraction 50% peroxidation neodecanoic acid of claim 1, it is characterized in that the emulsifying agent in the described step (5) is milky white spirit.
7. according to the preparation method of the special butyl ester of the described emulsion-type massfraction 50% peroxidation neodecanoic acid of claim 1, it is characterized in that the dispersion agent in the described step (5) is polyvinyl alcohol.
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Non-Patent Citations (3)
| Title |
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| 卫生级聚氯乙烯树脂的研制;孙光远;《齐鲁石油化工》;20041231;第32卷(第2期);79-80 * |
| 孙光远.卫生级聚氯乙烯树脂的研制.《齐鲁石油化工》.2004,第32卷(第2期),79-80. |
| 赵玉英.过氧化新癸酸叔丁酯（BNP）的合成.《浙江化工》.2003,第34卷(第7期),17，26. * |
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