CN104058922B - A kind of synthetic method of 1,1,3-trimethylammonium-3-phenyl indan - Google Patents
A kind of synthetic method of 1,1,3-trimethylammonium-3-phenyl indan Download PDFInfo
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- CN104058922B CN104058922B CN201310086547.3A CN201310086547A CN104058922B CN 104058922 B CN104058922 B CN 104058922B CN 201310086547 A CN201310086547 A CN 201310086547A CN 104058922 B CN104058922 B CN 104058922B
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- methyl styrene
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Abstract
The present invention relates to a kind of alpha-methyl styrene cyclodimerisation body i.e. synthetic method of 1,1,3-trimethylammonium-3-phenyl indan.By a certain amount of 1,1,3-trimethylammonium-3-phenyl indan product or join in reactor containing the reaction solution of this product and an acidic catalyst of catalytic amount, add raw material alpha-methyl styrene again after heating, insulation reaction, react complete, crystallization or distillation obtain target product, and content is greater than 99%.The method has simple to operate, solvent-free consumption, and cost is low, the feature that product quality is high.
Description
Technical field
The present invention relates to a kind of alpha-methyl styrene cyclodimerisation body i.e. synthetic method of 1,1,3-trimethylammonium-3-phenyl indan.
Background technology
Alpha-methyl styrene cyclodimerisation body, also known as 1,1,3-trimethylammonium-3-phenyl indan, is clear crystal, is dissolved in the multiple organic solvents such as ethanol, ether, chloroform, water insoluble.Because it can have good consistency with many macromolecular materials, and form indane ring structure because of it, not easily degrade, thermostability and antioxidant property are all good, can be used for multiple special occasions, as as lubricant, heat-transfer medium, softening agent and processing aid, spicy filler etc., in addition, also can be used for the conveying medium of electronic industry inorganic particulate.
The synthesis of alpha-methyl styrene cyclodimerisation body take alpha-methyl styrene as raw material, under an acidic catalyst effect, carry out polymerization obtain, polyreaction is at normal pressure or add pressure and carry out, the temperature of reaction is relevant with catalyzer used, and in product, cyclodimerisation body is relevant with catalyzer and temperature with the dimeric composition of line.Reaction can be carried out having under solvent or condition of no solvent, and conventional nonpolar inert solvent is as benzene, dimethylbenzene, halogenated hydrocarbons etc.Conventional an acidic catalyst [document, permitted red building, Heilongjiang Bayi Agricultural Reclamation University's journal, 2006,18(2), 92-95] there is inorganic strong, the middle strong acid (as sulfuric acid or phosphoric acid etc.) of liquid or carry sour polynite, carclazyte, Fuller's earth, tosic acid, the mixture of oxyhalogenide and strong inorganic acid, or with resin cation (R.C.), heteropolyacid, ionic liquid etc.
In patent US4987159, take methylsulfonic acid as catalyzer, alpha-methyl styrene carries out polymerization and generates alpha-methyl styrene cyclodimerisation body, its synthetic method is, whole catalyzer and a small amount of alpha-methyl styrene are added in reactor, add thermal booster reaction, then add remaining alpha-methyl styrene gradually, react complete and obtain this product through filtration treatment.Alpha-methyl styrene polymerization is external except generating cyclodimerisation, also can generate linear dimerization body 2,4-phenylbenzene-4-methyl-1-pentene and 2,4-phenylbenzene-4-methyl-2-amylene and trimer by-products.Contriver synthesizes according to method described in US4987159, finds at reaction initiating stage and adds the surplus stock initial stage, system steep temperature rise, restive, and the product content obtained is only 60-70%, and by product is mainly linear dimerization body and tripolymer.Contriver also above-mentioned multiple different an acidic catalyst on probation tests, and ubiquity reaction compares violent, and steep temperature rise, generates a large amount of linear dimerization bodies and tripolymer, the problems such as cyclodimerisation body yield is low.Simultaneously due to initiation reaction steep temperature rise, restive, industrial implementation exists serious potential safety hazard, because which limit the enforcement industrially of such method.Because this polyreaction is strong exothermal reaction, although can be played a role to the generation of the control of temperature of reaction and minimizing by product by the method adding inert solvent, but after employing solvent, can cause and be separated trouble, cost increases and is unfavorable for the problems such as environmental protection.
Summary of the invention
The object of the present invention is to provide a kind of alpha-methyl styrene cyclodimerisation body i.e. synthetic method of 1,1,3-trimethylammonium-3-phenyl indan.The method had both overcome solventless method and had carried out the problems such as the reaction of alpha-methyl styrene polymerization is violent, by product is many, and turn avoid to adopt has solvent method to carry out being polymerized and the product separation trouble brought and cost is high, the problem such as not environmentally.The method has simple to operate, and cost is low, the high and feature of environmental protection of the cyclodimerisation body product quality obtained.
The present invention realizes object of the present invention by method below, by a certain amount of 1,1,3-trimethylammonium-3-phenyl indan product, and an acidic catalyst of catalytic amount joins in reactor, is heated to 100-180 DEG C and keeps, add raw material alpha-methyl styrene again, keep set temperature by heating or lowering the temperature, reinforced complete, temperature 100-180 DEG C is kept to continue reaction, react complete and obtain reaction solution, recrystallization or underpressure distillation obtain 1, and 1,3-trimethylammonium-3-phenyl indan, content is greater than 99%.
Method of the present invention can also be, contains 1,1 by a certain amount of, the reaction solution of 3-trimethylammonium-3-phenyl indan and an acidic catalyst of catalytic amount join in reactor, are heated to 100-180 DEG C and keep, then adding raw material alpha-methyl styrene, set temperature is kept by heating or lowering the temperature, reinforced complete, keep temperature 100-180 DEG C to continue reaction, react complete and obtain reaction solution, recrystallization or underpressure distillation obtain 1,1,3-trimethylammonium-3-phenyl indan, content is greater than 99%.
In method of the present invention, join 1 in reactor, 1, the weight of 3-trimethylammonium-3-phenyl indan or containing in the reaction solution of 1,1,3-trimethylammonium-3-phenyl indan, the weight of 1,1,3-trimethylammonium-3-phenyl indan is the 5-20% of input raw material alpha-methyl styrene weight.
In the method for the invention, an acidic catalyst adopted is the vitriol oil, 85% phosphoric acid, polyphosphoric acid, tosic acid or methylsulfonic acid, preferred methylsulfonic acid.
In the method for the invention, charge temperature and the preferred 140-150 DEG C of temperature of reaction.
At reaction initial period, a certain amount of 1 is added in reactor, 1,3-trimethylammonium-3-phenyl indan or containing 1,1, the reaction solution of 3-trimethylammonium-3-phenyl indan, can dispersed catalyst effectively, reduce its concentration, simultaneously also to after the raw material alpha-methyl styrene concentration that adds effectively dilute, what effectively control polyreaction carries out degree, avoids polymerization system steep temperature rise and the by product linear dimerization body that causes and tripolymer increase, thus improves more than the in-situ transesterification rate to 98% of product.Simultaneously, owing to introducing the target product for synthesis of system itself, so do not need to carry out extra separating treatment to it, react complete material straight run distillation or add solvent and carry out recrystallization and just can obtain product, the content of product is greater than 99%, and productive rate reaches more than 96%.Synthetic method of the present invention is simple to operate, and exothermic heat of reaction is easy to control, and production cost is low, easily realizes industrialization, is a kind of environmental friendliness and has the method for commercial value.
Embodiment
Embodiment 1
By 10g1,1,3-trimethylammonium-3-phenyl indan, 0.5g methylsulfonic acid join in reactor, be heated to 100 DEG C, more slowly add 100g raw material alpha-methyl styrene, reinforced complete, keep temperature of reaction 100-120 DEG C to continue reaction 3h, react complete, obtain reaction solution A, ethyl alcohol recrystallization obtains 1,1,3-trimethylammonium-3-phenyl indan white crystal 108g, content 99.2%, fusing point 51-53 DEG C, yield 97.4%.
Comparative examples 1(patent US4987159 method)
Be dissolved in 9.3g isopropenylbenzene by 1g methylsulfonic acid, be heated to 80 DEG C, now reaction starts to carry out and heat release, and system temperature rises to 160 DEG C, after exothermic process terminates, and system temperature is down to 100 DEG C.In 2 hours, in system, add 65g isopropenylbenzene, and keep system temperature to be about 100 DEG C.Mixture is cooled, filters through atlapulgite, obtain 73g white solid, 1,1,3-trimethylammonium-3-phenyl indan content 68%.
Embodiment 2
Reaction solution A is obtained by embodiment 1 operation, getting 20g joins in reactor, add 1g methylsulfonic acid again, be heated to 140 DEG C, more slowly add 100g raw material alpha-methyl styrene, keep 140 DEG C always, reinforced complete, keep temperature of reaction 140-150 DEG C, continue reaction 3h, react complete, purity assay 98.2%.Ethyl alcohol recrystallization obtains 1,1,3-trimethylammonium-3-phenyl indan white crystal 118g, content 99.4%, yield 97.6%.
Embodiment 3
By 5g1,1,3-trimethylammonium-3-phenyl indan (embodiment 1 gained), the 0.5g vitriol oil join in reactor, be heated to 130 DEG C, more slowly add 100g raw material alpha-methyl styrene, reinforced complete, keep temperature of reaction 130-140 DEG C to continue reaction 4h, react complete, stop stirring, the vitriol oil is separated after leaving standstill, underpressure distillation obtains 1,1,3-trimethylammonium-3-phenyl indan white solid 103g, content 99.3%, yield 97.1%.
Embodiment 4
By 10g1,1,3-trimethylammonium-3-phenyl indan, 0.5g tosic acid join in reactor, be heated to 180 DEG C, slowly add 100g raw material alpha-methyl styrene again, reinforced complete, keep temperature of reaction 160-180 DEG C to continue reaction 2h, react complete, ethyl alcohol recrystallization obtains 1,1,3-trimethylammonium-3-phenyl indan white crystal 107g, content 99.2%, yield 96.8%.
Claims (6)
1. one kind 1, the synthetic method of 3-trimethylammonium-3-phenyl indan, it is characterized in that: by a certain amount of 1, 1, the an acidic catalyst of 3-trimethylammonium-3-phenyl indan and catalytic amount joins in reactor, be heated to 100-180 DEG C, add raw material alpha-methyl styrene again, then react at 100-180 DEG C, react complete, obtain containing 1, 1, the reaction solution of 3-trimethylammonium-3-phenyl indan, purifiedly obtain 1, 1, 3-trimethylammonium-3-phenyl indan, wherein add in advance 1, 1, the weight of 3-trimethylammonium-3-phenyl indan is the 5-20% of raw material alpha-methyl styrene weight.
2. one kind 1, 1, the synthetic method of 3-trimethylammonium-3-phenyl indan, it is characterized in that: by described in a certain amount of claim 1 containing 1, 1, the reaction solution of 3-trimethylammonium-3-phenyl indan and an acidic catalyst of catalytic amount join in reactor, be heated to 100-180 DEG C, add raw material alpha-methyl styrene again, then react at 100-180 DEG C, react complete, the reaction solution obtained is purified obtains 1, 1, 3-trimethylammonium-3-phenyl indan, what wherein add in advance contains 1, 1, in the reaction solution of 3-trimethylammonium-3-phenyl indan 1, 1, the weight of 3-trimethylammonium-3-phenyl indan is the 5-20% of raw material alpha-methyl styrene weight.
3. synthetic method according to claim 1 and 2, wherein said an acidic catalyst is sulfuric acid, phosphoric acid, tosic acid or methylsulfonic acid.
4. synthetic method according to claim 3, wherein an acidic catalyst is methylsulfonic acid.
5. the arbitrary synthetic method according to claim 1,2 or 4, charge temperature and temperature of reaction are 140-150 DEG C.
6. synthetic method according to claim 3, charge temperature and temperature of reaction are 140-150 DEG C.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4987159A (en) * | 1990-04-11 | 1991-01-22 | Fratelli Lamberti S.P.A. | Carbonyl derivatives of 1-phenylindan suitable for use as polymerization photoinitiators, their preparation and use |
| CN1541989A (en) * | 2003-11-04 | 2004-11-03 | 华东师范大学 | Catalytic synthesis method of 1,3,3-trimethyl-1-phenyl indan |
| CN102603509A (en) * | 2011-12-20 | 2012-07-25 | 常州大学 | Preparation method of bifunctional phenylindane photoinitiator |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4987159A (en) * | 1990-04-11 | 1991-01-22 | Fratelli Lamberti S.P.A. | Carbonyl derivatives of 1-phenylindan suitable for use as polymerization photoinitiators, their preparation and use |
| CN1541989A (en) * | 2003-11-04 | 2004-11-03 | 华东师范大学 | Catalytic synthesis method of 1,3,3-trimethyl-1-phenyl indan |
| CN102603509A (en) * | 2011-12-20 | 2012-07-25 | 常州大学 | Preparation method of bifunctional phenylindane photoinitiator |
Non-Patent Citations (2)
| Title |
|---|
| 1, 1, 3-三甲基-3-苯基茚满的合成及表征;王文涛等;《塑料工业》;20030831;第31卷(第8期);6-8 * |
| An Efficient and Selective Hydroarylation of Styrenes with Electron-Rich Arenes, Catalyzed by Bismuth(III) Chloride and Affording Markovnikov Adducts;Hong-Bin Sun et al.;《Eur. J. Org. Chem.》;20061231;4231–4236 * |
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