CN102659960B - Preparation method of solvent-type di-(2-ethylhexyl)peroxydicarbonate with mass fraction of 60% - Google Patents
Preparation method of solvent-type di-(2-ethylhexyl)peroxydicarbonate with mass fraction of 60% Download PDFInfo
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- CN102659960B CN102659960B CN201110442093.XA CN201110442093A CN102659960B CN 102659960 B CN102659960 B CN 102659960B CN 201110442093 A CN201110442093 A CN 201110442093A CN 102659960 B CN102659960 B CN 102659960B
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- solvent
- ethylhexyl
- reaction
- ester
- peroxydicarbonate
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- 238000002360 preparation method Methods 0.000 title abstract description 8
- ZACVGCNKGYYQHA-UHFFFAOYSA-N 2-ethylhexoxycarbonyloxy 2-ethylhexyl carbonate Chemical compound CCCCC(CC)COC(=O)OOC(=O)OCC(CC)CCCC ZACVGCNKGYYQHA-UHFFFAOYSA-N 0.000 title abstract 5
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- 238000003756 stirring Methods 0.000 claims abstract description 23
- 239000000243 solution Substances 0.000 claims abstract description 15
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000002904 solvent Substances 0.000 claims abstract description 10
- 150000001335 aliphatic alkanes Chemical class 0.000 claims abstract description 6
- 239000012452 mother liquor Substances 0.000 claims abstract description 5
- 150000002148 esters Chemical class 0.000 claims description 27
- -1 2-ethylhexyl Chemical group 0.000 claims description 21
- BEQKKZICTDFVMG-UHFFFAOYSA-N 1,2,3,4,6-pentaoxepane-5,7-dione Chemical compound O=C1OOOOC(=O)O1 BEQKKZICTDFVMG-UHFFFAOYSA-N 0.000 claims description 19
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- AOGYCOYQMAVAFD-UHFFFAOYSA-N chlorocarbonic acid Chemical compound OC(Cl)=O AOGYCOYQMAVAFD-UHFFFAOYSA-N 0.000 claims description 8
- 239000003637 basic solution Substances 0.000 claims description 4
- VKPSKYDESGTTFR-UHFFFAOYSA-N 2,2,4,6,6-pentamethylheptane Chemical compound CC(C)(C)CC(C)CC(C)(C)C VKPSKYDESGTTFR-UHFFFAOYSA-N 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000003999 initiator Substances 0.000 abstract description 7
- 238000006116 polymerization reaction Methods 0.000 abstract description 6
- 230000000977 initiatory effect Effects 0.000 abstract description 3
- 229920000642 polymer Polymers 0.000 abstract 3
- 239000000047 product Substances 0.000 abstract 3
- 230000015572 biosynthetic process Effects 0.000 abstract 2
- 239000007795 chemical reaction product Substances 0.000 abstract 2
- 238000003786 synthesis reaction Methods 0.000 abstract 2
- 239000012670 alkaline solution Substances 0.000 abstract 1
- 238000005406 washing Methods 0.000 abstract 1
- 239000000460 chlorine Substances 0.000 description 6
- RTGLJCSUKOLTEM-UHFFFAOYSA-N 2-ethylhexyl carbonochloridate Chemical compound CCCCC(CC)COC(Cl)=O RTGLJCSUKOLTEM-UHFFFAOYSA-N 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000003921 oil Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a preparation method of solvent-type di-(2-ethylhexyl)peroxydicarbonate with mass fraction of 60%, and belongs to the preparation method field of initiator used in synthesis of high polymer. The preparation method is characterized by: adding hydrogen peroxide into an alkaline solution; dropping 2-etylhexyl-chlorformiat into the obtained solution with stirring; carrying out a stirring reaction for 30-50 minutes after finishing dropping 2-etylhexyl-chlorformiat; stopping stirring after the reaction, separating mother liquor, washing reaction products till pH value ranges between 5-7; adding an alkane solvent into the obtained reaction products; and producing solvent-type di-(2-ethylhexyl)peroxydicarbonate. The prepared solvent-type di-(2-ethylhexyl)peroxydicarbonate is easily dispersible in a polymerization system and releases uniform heat in a polymerization reaction, has a high initiating efficiency and is easy to control, and assists in producing products of stable and decent performances. The prepared solvent-type di-(2-ethylhexyl)peroxydicarbonate is an initiator used in synthesis of high polymer, which is safe, highly efficient and has stable product quality, and can assist in producing high polymer products with better quality and stability.
Description
Technical field
The present invention relates to the method for making of a kind of solvent-borne type massfraction 60% peroxy dicarbonate two (2-ethylhexyl) ester, belong to the synthetic preparation method field with initiator of superpolymer.
Background technology
Along with the fast development of the synthetic industry of domestic superpolymer, superpolymer is synthetic to be promoted rapidly by kind and the demand of initiator.Solvent-borne type peroxy dicarbonate two (2-ethylhexyl) ester (EHP)-60 synthesizes and uses efficient initiator as a kind of superpolymer, in polymerization process, consumption is few, in polymerization system, easily disperse, in polymerization, exothermic heat of reaction is even, and efficiency of initiation is higher, is convenient to control, products obtained therefrom excellent property is the synthetic initiator of using of a kind of superpolymer safe, efficient, constant product quality.
Summary of the invention
According to the deficiencies in the prior art, the technical problem to be solved in the present invention is: the method for making of a kind of solvent-borne type massfraction 60% peroxy dicarbonate two (2-ethylhexyl) ester is provided, and easy to operate, the process time is short and be suitable for industrial applications.
The technical solution adopted for the present invention to solve the technical problems is: the method for making of a kind of solvent-borne type massfraction 60% peroxy dicarbonate two (2-ethylhexyl) ester is provided, it is characterized in that following steps:
(1) hydrogen peroxide is added in basic solution, the mass ratio of hydrogen peroxide and alkali is 1: 2.0～4.0;
(2) chloroformic acid 2-(ethyl hexyl) ester is added drop-wise in the solution of step (1) gained, stir on dropping limit, limit, temperature is controlled at 20～30 DEG C, chloroformic acid 2-(ethyl hexyl) ester added in 2 hours at 40 minutes, and the mass ratio of the solution of chloroformic acid 2-(ethyl hexyl) ester and step (1) gained is 1: 1.3～4.0;
(3) after chloroformic acid 2-(ethyl hexyl) ester dropwises, then stirring reaction 30～50 minutes;
(4) reaction stops after finishing stirring leaving standstill 20～40 minutes, mother liquor is separated, till resultant of reaction is washed till to pH value 5～7;
(5) in the resultant of reaction of step (4) gained, add alkane solvent, at 0 DEG C of temperature, stir 1～3.5 hour; Obtain solvent-borne type peroxy dicarbonate two (2-ethylhexyl) ester.
Basic solution in described step (1) is aqueous sodium hydroxide solution or potassium hydroxide aqueous solution, and its mass percent is 10%～20%;
Temperature in described step (2) is controlled at 20～30 DEG C.
The stirring reaction time in described step (3) is 40～45 minutes.
The resultant of reaction of the gained of step (4) described in described step (5) and the mass ratio of alkane solvent are 1: 0.5～1: 0.7.
Solvent in described step (5) is solvent oil or Permethyl 99A..
The invention has the beneficial effects as follows:
(1) in polymerization system, easily disperse and in polyreaction heat release even, efficiency of initiation is high, be convenient to control, products obtained therefrom stable performance, good, be that a kind of superpolymer safe, efficient, constant product quality is synthetic with initiator, and can produce the higher more stable superpolymer product of quality.
(2) preparation method of solvent-borne type peroxy dicarbonate two provided by the invention (2-ethylhexyl) ester, simplify technical process, overcome the complicated requirement to conversion unit, reaction is carried out under gentle, safe environment, product content and yield increase substantially, and yield can reach more than 95%.It is identical with same kind of products at abroad that product quality level can reach.
Product quality indicator is in table 1:
Table 1
| Project | Index |
| Outward appearance | Colourless transparent liquid, machinery-free impurity |
| Colourity, Pt-Co≤ | 20 |
| Active oxygen massfraction, % | 2.77±0.05 |
| EHP massfraction, % | 60.0±1.0 |
| Chlorine (in Cl) massfraction, %≤ | 0.05 |
Embodiment
Below in conjunction with embodiment, the present invention is described further.
Embodiment mono-
The preparation process of solvent-borne type peroxy dicarbonate two (2-ethylhexyl) ester is as follows:
(1) in 500ml flask, adding content is 100 grams of 25% sodium hydroxide solutions, and 100 grams, water, stirs and be cooled to 5 DEG C;
(2) in the solution making to step (1), drip purity and be 38 grams of 27.5% hydrogen peroxide, react 30 minutes, temperature is controlled at 25 DEG C;
(3) stir that slowly to drip concentration in backward flask be 75 grams of 98% chloroformic acid 2-ethylhexyl ester solutions, temperature of reaction is controlled at 20～30 DEG C, and 1.5 hours used times added, and adds after chloroformic acid 2-ethylhexyl ester solution stirring reaction 50 minutes;
(4) reaction stops after finishing stirring, and leaves standstill 20 minutes, reaction mother liquor is separated, by resultant of reaction wash to pH value be till 5;
(5) making content is 65.8 grams of 98.87% peroxy dicarbonate two (2-ethylhexyl) esters, and yield is 98.5%;
(6) in the peroxy dicarbonate two making (2-ethylhexyl) ester, add 40.8 grams of solvent oils, in 0 DEG C of stirring 3 hours, obtain solvent-borne type peroxy dicarbonate two (2-ethylhexyl) ester, concentration is about 61%.All other indexs all reach product quality indicator requirement.
| Project | Index |
| Outward appearance | Colourless transparent liquid, machinery-free impurity |
| Colourity, Pt-Co | 18 |
| Active oxygen massfraction, % | 2.74 |
| EHP massfraction, % | 60.5 |
| Chlorine (in Cl) massfraction, % | 0.04 |
Embodiment bis-
The preparation process of solvent-borne type peroxy dicarbonate two (2-ethylhexyl) ester is as follows:
(1) in 500ml flask, adding content is 100 grams, 25% potassium hydroxide, and 100 grams, water, stirs and be cooled to 5 DEG C;
(2) in the solution making to step (1), drip concentration and be 38 grams of 27.5% hydrogen peroxide, react 30 minutes, temperature is controlled at 25 DEG C;
(3) stir that slowly to drip concentration in backward flask be 75 grams of 98% chloroformic acid 2-ethylhexyl ester solutions, temperature of reaction is controlled at 20～30 DEG C, and 2 hours used times added, and adds after chloroformic acid 2-ethylhexyl ester solution stirring reaction 30 minutes;
(4) reaction stops after finishing stirring, and leaves standstill 40 minutes, reaction mother liquor is separated, by resultant of reaction wash to pH value be till 7;
(5) making content is 65.9 grams of 98.2% peroxy dicarbonate two (2-ethylhexyl) esters (EHP), and yield is 98%;
(6) in the peroxy dicarbonate two making (2-ethylhexyl) ester (EHP), add 38.6 grams of Permethyl 99A.s, stir 3.5 hours in 0 DEG C, obtain solvent-borne type peroxy dicarbonate two (2-ethylhexyl) ester, concentration is about 61.93%.All other indexs all reach product quality indicator requirement.
| Project | Index |
| Outward appearance | Colourless transparent liquid, machinery-free impurity |
| Colourity, Pt-Co | 19 |
| Active oxygen massfraction, % | 2.80 |
| EHP massfraction, % | 69.5 |
| Chlorine (in Cl) massfraction, % | 0.05 |
Claims (3)
1. a method for making for solvent-borne type massfraction 60% peroxy dicarbonate two (2-ethylhexyl) ester, is characterized in that following steps:
(1) hydrogen peroxide is added in basic solution, the mass ratio of hydrogen peroxide and alkali is 1:2.0～4.0;
(2) chloroformic acid 2-(ethyl hexyl) ester is added drop-wise in the solution of step (1) gained, stir on dropping limit, limit, temperature is controlled at 20～30 DEG C, chloroformic acid 2-(ethyl hexyl) ester added in 2 hours at 40 minutes, and the mass ratio of the solution of chloroformic acid 2-(ethyl hexyl) ester and step (1) gained is 1:1.3～4.0;
(3) after chloroformic acid 2-(ethyl hexyl) ester dropwises, then stirring reaction 30～50 minutes;
(4) reaction stops after finishing stirring leaving standstill 20～40 minutes, mother liquor is separated, till resultant of reaction is washed till to pH value 5～7;
(5) in the resultant of reaction of step (4) gained, add alkane solvent, at 0 DEG C of temperature, stir 3～3.5 hours; Obtain solvent-borne type peroxy dicarbonate two (2-ethylhexyl) ester;
The resultant of reaction of the gained of step (4) described in described step (5) and the mass ratio of alkane solvent are 1:0.5～1:0.7;
Alkane solvent in described step (5) is solvent oil or Permethyl 99A..
2. the method for making of solvent-borne type massfraction 60% peroxy dicarbonate two (2-ethylhexyl) ester according to claim 1, it is characterized in that the basic solution in described step (1) is aqueous sodium hydroxide solution or potassium hydroxide aqueous solution, its mass percent is 10%～20%.
3. the method for making of solvent-borne type massfraction 60% peroxy dicarbonate two (2-ethylhexyl) ester according to claim 1, is characterized in that the stirring reaction time in described step (3) is 40～45 minutes.
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| CN104370789A (en) * | 2014-11-26 | 2015-02-25 | 淄博正华助剂股份有限公司 | Method for preparing peroxidized dicarbonate (2-ethylhexyl) ester (EHP) by continuous flow |
| CN109180549A (en) * | 2018-09-12 | 2019-01-11 | 蓝凤祥 | A kind of Safe production technology of dicetyl peroxydicarbonate ethylhexyl initiator |
| CN111548295B (en) * | 2020-04-02 | 2022-03-01 | 鄂尔多斯市瀚博科技有限公司 | Preparation method of di (2-ethylhexyl) peroxydicarbonate |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2464062A (en) * | 1947-11-26 | 1949-03-08 | Pittsburgh Plate Glass Co | Polymerization with a peroxydicar-bonate catalyst |
| GB2024224A (en) * | 1978-06-30 | 1980-01-09 | Ppg Industries Inc | Production of peroxydicarbonates |
| CN1387511A (en) * | 1999-11-04 | 2002-12-25 | 氧化乙烯公司 | Method for producing peroxydicarbonates and their use in radical polymerization of monomers |
| CN101287704A (en) * | 2005-10-14 | 2008-10-15 | 埃尔费尔德微技术Bts有限责任公司 | Method for the production of organic peroxides by means of a microreaction technique |
-
2011
- 2011-12-26 CN CN201110442093.XA patent/CN102659960B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2464062A (en) * | 1947-11-26 | 1949-03-08 | Pittsburgh Plate Glass Co | Polymerization with a peroxydicar-bonate catalyst |
| GB2024224A (en) * | 1978-06-30 | 1980-01-09 | Ppg Industries Inc | Production of peroxydicarbonates |
| CN1387511A (en) * | 1999-11-04 | 2002-12-25 | 氧化乙烯公司 | Method for producing peroxydicarbonates and their use in radical polymerization of monomers |
| CN101287704A (en) * | 2005-10-14 | 2008-10-15 | 埃尔费尔德微技术Bts有限责任公司 | Method for the production of organic peroxides by means of a microreaction technique |
Non-Patent Citations (2)
| Title |
|---|
| 吕海金.过氧化二碳酸(2-乙基)己酯的合成研究.《青岛职业技术学院学报》.2004,第17卷(第4期), |
| 过氧化二碳酸(2-乙基)己酯的合成研究;吕海金;《青岛职业技术学院学报》;20041231;第17卷(第4期);第69－70页 * |
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Denomination of invention: Preparation of 60% solvent based bis (2-ethylhexyl) peroxydicarbonate Effective date of registration: 20230511 Granted publication date: 20140820 Pledgee: Zibo Linzi District sub branch of China Post Savings Bank Co.,Ltd. Pledgor: ZIBO ZHENGHUA AUXILIARY Co.,Ltd. Registration number: Y2023980040339 |
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