CN102229532B - Preparation method of diallyl phthalate - Google Patents
Preparation method of diallyl phthalate Download PDFInfo
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- CN102229532B CN102229532B CN 201110142479 CN201110142479A CN102229532B CN 102229532 B CN102229532 B CN 102229532B CN 201110142479 CN201110142479 CN 201110142479 CN 201110142479 A CN201110142479 A CN 201110142479A CN 102229532 B CN102229532 B CN 102229532B
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- diallyl ester
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Abstract
The invention belongs to the field of chemical synthesis. The invention discloses a preparation method of diallyl phthalate. The method comprises the following steps that phthalic anhydride, allyl alcohol and a polymerization inhibitor are heated to undergo a reaction in the presence of a Lewis acid catalyst; an inorganic phase is separated out from reaction products obtained from the previous step, and a Lewis acid catalyst and allyl alcohol are added into an organic phase of the reaction products and are heated to undergo a reaction; and an inorganic phase is separated out from reaction products obtained from the previous step, and an organic phase of the reaction products is washed and distilled to form diallyl phthalate. The preparation method has the advantages of simple process, high reaction efficiency, easy post-treatment, good product quality and high yield.
Description
Technical field
The invention belongs to the field of chemical synthesis, relate to a kind of preparation method of Phthalic acid, diallyl ester.
Background technology
In the sixties in 20th century, dially phthalate (DAP) resin, m-phthalic acid two allyl vinegar (DAI) resins just obtain general application and research, DAP resin, DAI resin all have the performances such as good resistance toheat, weather resistance, dielectric properties as the allyl ester resin, the maximum characteristics of DAP resin after the curing are the good and higher dimensional stabilitys of electrical insulating property, can at-66 ℃～180 ℃ life-time service, be widely used in aircraft, boats and ships; Wiring board, switch, the transmodulator of electric and electronic products; The electrical equipment such as automobile, railway part, electron device etc.; Strengthen the DAP plastics as glass fibre, have good chemical resistance, be used for radome, insulcrete, decorative sheet, airplane self-control device, switch element, electric elements, military machinery, communication instrument etc.In addition, this resinoid can also be applied to the precision electronic element that requires tolerance variation especially little in the computer, and can use in severe environment.
Just have the scholar to begin DAP is studied as far back as nineteen forty-two, nineteen forty-six W.Simpson has made detailed report in its research paper.The DAP resin starts from the middle of last century in industrial application, and the fifties aerospace industry flourish proposed very harsh requirement to material, in order to adapt to severe environment for use, just arises at the historic moment take DAP as the allyl ester class on basis.The Shell Co. Ltd of the U.S. just produces the DAP resin solution since nineteen forty-six, and U.S. FMC Corp. had synthesized white powder DAP performed polymer with the DAP monomer under superoxide, water and polymerization regulator effect in 1958, produces powdery resin and has begun industrialization.Because relative and polymerization of vinyl monomer is difficult to use free radical polymerisation process direct polymerization allylic cpd, the research of relevant allyl monomer polyreaction does not receive investigators' too many concern.The existence of chain transfer reaction is the major cause that causes this difficulty; Side reaction problem another one aspect when cyclization is two propylene ester group class monomer polymerizations simultaneously.
The DAP monomer belongs to the allyl ester compounds, has two unsaturated double-bonds, and monomer can make two unsaturated double-bond all open under the effect of light, heat, initiator etc. to carry out polyaddition reaction.Generally speaking, DAP monomer polymerization process is divided into two stages, the reaction fs: only allow a unsaturated link(age) of DAP molecule participate in reaction, aggregate into thermoplastic simple linear polymer, the DAP performed polymer, heating can be softened, melting, and DAP is water insoluble, ethanol isopolarity solvent, but can be dissolved in DAP monomer and acetone equal solvent.In addition, the DAP performed polymer is not linear structure completely, and also have following two kinds of forms: (1) has the polymkeric substance of side chain; (2) polymkeric substance of formation ring-type in the molecule; The reaction subordinate phase: second two key in the monomer molecule participate in polyreaction, and intermolecular cross-linking reaction forms tridimensional network, insoluble not molten polymkeric substance, i.e. γ-polymer, i.e. curing reaction.Usually, the activity of other vinyl monomer of DAP monomer reaction specific activity is lower, because allyl group has very strong chain transfer tendency and molecule space steric effect thereof.The impact of the steric effect of second two key reaction when especially reacting subordinate phase is more obvious, and the vinyl-based difficulty of radical polymerization composition and division in a proportion of DAP monomer is used more widely thereby limited DAP.
Because the DAP resin price is expensive, from the seventies, the market of DAP series products has greatly been impacted in the appearance of low price Resins, epoxy, vibrin, urethane and various new thermoplastic engineering plastic.The producer of late nineteen seventies worldwide production DAP monomer only has one, and producer's entire United States of producing its moulding compound only has two.After the eighties, DAP basic mode plastics price reduces gradually, and has developed on conventional moulded and injection-molded basis and to be economic moulding technology, and the resinoid market of DAP has obtained recovering and development.The viewpoint of the spacial framework of allylic cpd when the people such as Simpson propose cyclization and changed gelation point.Oiwa and Matsumoto have studied the polyreaction of diallyl compound, and kinetics, gelation, cyclopolymerization and the copolymerization phenomenon of this class reaction has been discussed.The kinetic equation that proposes is respectively computing to be carried out in cyclisation and non-cyclisation free radical.Thermopolymerization DAP monomer was along with the corresponding raising of raising double bond conversion rate of polymerization temperature when Kostanki observed polymerization temperature and is higher than 200 ℃.Yet DAP just has the crosslinked trend that occurs in the very low situation of level of response, the restriction that this is serious the development of relevant DAP research.Previous result of study also only limits to the research to character before the DAP polymeric gel.Along with the application and development of many advanced persons' measuring technology, the needs of research DAP polymeric gel afterreaction character have been helped to have solved.
Spurr and Yoshida etc. change to characterize the level of response of DAP monomer polymerization by the absorption peak at the stretching vibration peak 1645cm place of the allyl double bonds in the measurement DAP monomer with infrared spectroscopy.The people such as Warfield and Petree, Yamawaki and Willard all use dsc to study the mass polymerization of DAP.Warfield, the people such as Petree and Yamawaki use dsc (DSC) by the thermopolymerization of unreacted pair of key in the research polydiallyl phthalate, have inquired into the variation of specific resistance in the DAP bulk polymerisation process.Willard then is the solidification process when adopting dsc to study DCP initiation DAP mass polymerization.
During the allylic monomers polymerization, chain transfer reaction has limited the carrying out of transfer reaction.Bartlett and Altschul and Gaylord point out that allylic decay chain transfer reaction is the hydrogen atom of capturing on the carbon atom adjacent with two keys, and allyl radical becomes the group of resonance stabilized.With respect to allyl radical, the new free radical of formation is very stable, and activity is very little when carrying out transfer reaction, does not trend towards increasing chain length and causes new reaction chain.Therefore, the decay chain transfer reaction is in fact chain termination reaction.Gaylord also points out to also have a kind of effective chain transfer reaction, and this reaction then forms alkoxy free group, and alkoxy free group has reactive behavior, can the trigger monomer polymerization produce new molecular chain as the free radical that initiator produces.The existence of chain transfer reaction has explained that allylic monomers (such as the DAP monomer) reactive behavior compares the lower major cause of activity of vinyl monomer.On the other hand, cyclization is another important side reaction of allylic compound polymerization reaction.W.simpson, T.Holt point out the increase along with the distance between the allyl group, the to some extent decline of monomer cyclisation trend.The cyclization of allylic compound has two kinds of situations, i.e. continuous intramolecular cyclization and discrete intramolecular cyclization.Continuously intramolecular cyclization is non-cyclisation free radical to be added on two keys of same monomeric unit form ring texture.Discontinuous intramolecular cyclization is that a non-cyclisation free radical is added on two keys of any non-same monomeric unit on the reaction chain.There is ring texture in the people such as W.Simpson when thinking owing to the DAP monomer polymerization, and there are larger difference in the DAP polyreaction degree when reaction arrives gel and theoretical value, and the cyclisation type of DAP monomer mainly is continuous intramolecular cyclization reaction.The people such as Matsumoto adopt nuclear magnetic resonance research to find that the DAP intramolecular cyclization reaction mainly is mode of connection and 11 yuan of structure of rings of the easiest formation end to end.
DAP resin monomer Phthalic acid, diallyl ester is colourless or the pale yellow oily liquid body, and smell is gentle, has tearing property.
Phthalic acid, diallyl ester
The synthetic method report of Phthalic acid, diallyl ester is a lot, as: the dehydration of acid (sulfuric acid, phosphoric acid, sodium pyrosulfate, iron(ic) chloride, tin chloride, ferric sulfate, methylsulfonic acid, tosic acid, resin cation (R.C.)) catalytic esterification; Under the alkaline condition, the etherificate of haloalkane (chlorallylene, allyl bromide 98 and allyl iodide) and phthalate; The transesterify under acid/base catalysis of Methyl Benzene-o-dicarboxylate or ethyl ester and vinyl carbinol; The esterification and etherification of phthalic anhydride and vinyl carbinol; The etherification oxidation of phthalic acid and propylene etc.
1) phthalic anhydride and vinyl carbinol direct esterification dehydration under acid catalysis:
Nineteen fifty-one, the Derr of Shell Co. Ltd, Elwood L. and Illman, the US Patent No. 2557639 of John C. application studies show that, phthalic anhydride, vinyl carbinol, sulfuric acid are heated to 140 ℃ of reflux water-dividing products obtained therefroms, than higher take benzene as solvent products obtained therefrom purity, less side products (impurity lacks 30% when participating in without benzene) shows solvent-free participation better effects if.
Nineteen fifty-two, the Pourrat of France State Scientific Research Centre, H. applied for French Patent FR1012528, it has invented the method for a kind of solvent-free preparation DAP, be about to phthalic anhydride and ℃ dehydration of vinyl carbinol direct heating to 135, or under the catalysis of tosic acid the method for preparing product, products obtained therefrom has higher transparency and refraction coefficient.
Nineteen fifty-three, Japanese scholars Yoshida, Yasushi; Oshima, Keiji. in " technical chemistry magazine ", reported vinyl carbinol, phthalic anhydride, quinoline have been mixed, take benzene as solvent, respectively take tosic acid, sulfuric acid as catalyzer, reflux 6 hours, crude product washs through 5% aqueous sodium carbonate, anhydrous sodium sulfate drying, vacuum distilling, the cut of collection 175-85/15mmHg, the result shows the good catalytic activity of sulfuric acid, yield higher (about 95%).
Nineteen fifty-five, Taiwan Chia, K.S.; Cheng, T.Y.; Chen, Shang-I; Chao, Fu-Yong; Hsia, Yao; Chu, the scholars such as Chin-Chiun. have reported with phthalic anhydride, excessive 10% vinyl carbinol, toluene and tosic acid back flow reaction 20 hours, prepare the method for DAP, yield is 97.6%.
1958, Weigner, J.A.; Kudlacek, Vl.; Baca, J.; Havel, St. wait the people to publish thesis at Chemicky Prumysl magazine, when studies show that direct esterification, the effect of dimethylbenzene is that solvent is good than toluene and benzene, and the catalytic efficiency of sulfuric acid is better than tosic acid, Katex FN, ion exchange resin texts.
Nineteen fifty-nine, the Lindeman of Germany, Janusz; Trochimezuk, Witold. wait the people to introduce a kind of homemade ion exchange resin comes catalysis phthalic anhydride and vinyl carbinol esterification as catalyzer method at Chemische Technik magazine, namely take benzene as solvent, phthalic anhydride, vinyl carbinol, ion exchange resin reflux 3 hours, dehydration obtains product, yield is about 95%, claims that this catalyzer can Reusability and can inactivation.
1979, the former Russian scholar Savos ' kin, V.M.; Protsenko, E.I.; Borbulevich, A.I.; Gontarevskaya, N.P.; Shevchuk, L.N. etc. have reported it also is method take sulfuric acid as catalyst for making direct esterification in Soviet Union magazine Plasticheskie Massy, product yield is greater than 90%.
2) phthalic anhydride and propylene halide etherificate under the alkali effect:
1964, Borsini, Giancarlo; Sinatti, Giuseppe; Cossi, Giovanni. wait the people in French Patent FR1372967, to report for work phthalic acid or phthalic anhydride, yellow soda ash, chlorallylene, tertiary amine or quaternary amine are made catalyzer, be heated to 120～140 ℃ of reactions 5.25 hours, reaction solution through washing, dry, distill to get product, yield is about 91%.
Nineteen sixty-five, the Oshima of Japanese ponding chemical industry, Teruo; Okagami, Tomoya; Yoshitake, Hiroshi. wait the people to apply for Japanese Patent JP40023494, disclose take ethyltriphenylphosphiodide iodide phosphorus as phase-transfer catalyst, dimethylbenzene is solvent, during the phthalic anhydride and the rare propyl chloride etherification reaction that have stopper to participate in, reaction finish to fall back, washing, reclaim solvent, distillation namely gets product.
Nineteen sixty-five, the Schweizerische Aluminium of Switzerland Co., Ltd has applied for a patent NL6501098, has studied chloropropene alcohol and phthalic acid under the phase-transfer catalyst effect, reflux to 130～300 ℃, reacted 7 hours, the yield of the finished product is about 97%.
1966, the expert Stange of U.S. FMC Corp., Hugo; Tuemmler, William B. etc. has applied for US Patent No. 3250801, studied the method that phthalic anhydride and one step of propylene halide in the autoclave pressure prepare DAP, being about to phthalic anhydride, propenyl chloride, water, yellow soda ash and allyl group chlorination triethylamine is phase-transfer catalyst, the method that in the presence of stopper, prepares DAP, temperature of reaction is 130 ℃, and 4.3 hours time, peak pressure is 235psig.The gained crude product is through washing, and sodium bicarbonate washs, and yield is about 95%.
1966, the Oils ﹠amp of Japan; The Sugimoto of Fats company, Hiroaki; Bessho, Hidekazu; Koshimura, Masamitsu. etc. have applied for patent JP41000096, and research ammonium salt, alkaline carbonate or supercarbonate are alkali, and under 120～130 ℃ of conditions, reaction prepared the method for DAP in 4 hours.Applied for again patent JP41000095 the same year, studied the method for preparing DAP take liquefied ammonia as alkali, and reaction was carried out 4 hours at 120 ℃, namely gets product through sodium hydroxide neutralization, washing, distillation again.
Nineteen sixty-eight, the Kato of the Nitto Electric Industry company of Japan, Fumihiko; Yoshihara, the people such as Mitsuo., it is solvent that the Japanese Patent JP43027849 of application has disclosed spent glycol, basic metal halides catalysis chlorallylene and phthalic acid prepare the method for DAP, and reaction solution is heated to 100 ℃, add potassiumiodide catalysis, reacted 5 hours, yield only is 40%.
1972, Santa, Toshihiro; Tsunawaki, Kiyokazu; Nawata, the people such as Kiyoshi are in Japanese Patent JP49030310, introduced a kind of basic metal or alkaline-earth metal prepare DAP as the base catalysis etherificate method, invention is take DMF as solvent, magnesium oxide is acid constraint agent, temperature of reaction is 97～120 ℃, and with allyl bromide 98 and phthalic acid reflux 3 hours, gained DAP yield was about 93%.
1976, the Suzui of Osaka Soda company, Akio. in JP51008212, introduced the method for carrying out etherificate by dripping chlorallylene to the DMF solution of phthalic anhydride, salt of wormwood, temperature of reaction is 137～143 ℃, dripped off in 3 hours, and then continue reaction 3 hours, getting the DAP yield is 96%.1978, Suzui, the people such as Akio are again in patent JP53108914, introduced under the condition that Potassium ethanoate exists, with phthalic acid dipotassium or sodium and allyl group chlorine or bromine under the catalysis of hexaoxacyclooctadecane-6-6 or dicyclohexyl-hexaoxacyclooctadecane-6-6, reflux prepared the method for DAP in 5 hours, yield medium (82%～88%).1979, the Iio of Osaka Soda company, Katsumi; Harada, Yasuhiko; Goto, Akira. wait the people in patent JP54130528, introduce a kind of serialization and produced the method for DAP, with the two salt of the basic metal of phthalic acid and propylene halide in the presence of cupric chloride, the pH value is controlled at (20% sodium hydroxide) 6.5～8 times, in 45～50 ℃ of reactions 10 hours, yield was 96.7%.
3) phthalic ester and vinyl carbinol carry out transesterify:
Nineteen sixty-five, belgian patent BE660259 has reported dimethyl phthalate or ethyl ester and vinyl carbinol at magnesium alkoxide, MAGNESIUM METAL or tetrabutyl titanate, be heated to 130～170 ℃ and carry out transesterify, steam simultaneously methyl alcohol or the ethanol of generation, make molecular balance constantly break the method that obtains high conversion, can reach 99.6% through distillation the finished product yield.
1993, the Japanese Daisow expert Yoshinobu of company, Mitsutoshi; Shimizu, the patent JP05025093 of Yasumi etc. has introduced the method for carrying out transesterify take alkaline-earth metal as catalyzer, with calcium hydroxide and the composite catalyzer that forms of first (second) sodium alkoxide, temperature of reaction rises to 120 ℃, be incubated 8 hours, constantly divide exactly simultaneously first (second) alcohol of generation, the products obtained therefrom yield is 96.2%, and purity is 98%.
4) get with the propylene halide etherificate again behind phthalic anhydride and the vinyl carbinol mono-esterification:
Nineteen sixty-five, Goldberg, Geoffrey. etc. have introduced in English Patent GB992296 phthalic anhydride and vinyl carbinol esterification in 1: 1 have been generated first monoesters, the gained monoesters is without separation and purification, in the presence of quaternary amine, alkali, be heated to 60～70 ℃ of reactions 3 hours with chlorallylene again, yield is about 85%.
Nineteen sixty-five, the patent FR1396837 of CIBA company has introduced first phthalic anhydride and 120 ℃ of lower heating of vinyl carbinol was made monoesters in 3 hours, then adds chlorallylene, yellow soda ash, triethylamine, and reflux prepared the method for DAP in 24 hours.
1994, Zienko, Jaroslaw; Antoszczyszyn, Milka; Myszkowski, the people's such as Jerzy. Poland Patent PL164333 have studied phthalic anhydride, vinyl carbinol, chlorallylene in the presence of tetramethyl ammonium chloride, and 110 ℃ of lower methods that prepare DAP in the aqueous solution obtain purity greater than 99% product.
5) phthalic acid and propylene catalyzed oxidation under the palladium effect:
Nineteen sixty-five, the German patent NL6514335 of Bayer AG has introduced under palladium catalysis, and phthalic acid, propylene and oxygen coexistence are lower, are heated to 120 ℃, and stoichiometric number got final product to get the mixture of DAP, acetone and carbonic acid gas in ten minutes.Owing to adopt precious metal catalyst, there are the characteristics such as equipment requirements is high, cost is high, operation easier is large, this technique is not widely adopted.
Summary of the invention
The objective of the invention is the above-mentioned deficiency for prior art, a kind of preparation method of Phthalic acid, diallyl ester is provided.
Purpose of the present invention can be achieved through the following technical solutions:
A kind of preparation method of Phthalic acid, diallyl ester, with phthalic anhydride, vinyl carbinol and stopper under the catalysis of lewis acid catalyst, reacting by heating, after isolating lower floor's inorganic phase, in organic phase, add vinyl carbinol and lewis acid catalyst again, reacting by heating is isolated lower floor's inorganic phase, and organic phase namely gets Phthalic acid, diallyl ester through washing, distillation.
The method preferably includes following steps:
A) under the nitrogen protection, phthalic anhydride, stopper and vinyl carbinol are added reactor;
B) start stirring, add lewis acid catalyst, control temperature＜20 ℃, insulation 10min;
C) rising temperature to 40～80 ℃, insulation 1.5～3.5h;
D) stop to stir, tell lower floor's inorganic phase;
E) in organic phase, add vinyl carbinol;
F) add lewis acid catalyst, rising temperature to 70～80 ℃, insulation 1～2h;
G) stop to stir, tell lower floor's inorganic phase;
H) organic phase with deionized water wash, saturated sodium bicarbonate aqueous solution washing, dry, distillation, collect product.
Wherein, described lewis acid catalyst is selected from any one in hydrogen fluoride, hydrogenchloride, hydrogen bromide, hydrogen iodide, sulphur trioxide, sulfur oxychloride, dichloro sulphonyl, phosphorus trichloride, phosphorus tribromide, phosphorus oxychloride, phosphorus pentachloride, the Vanadium Pentoxide in FLAKES.
The catalyzer total mass of described twice adding is 0.1～10% of phthalic anhydride and vinyl carbinol total mass, is preferably 2～5% of phthalic anhydride and vinyl carbinol total mass; The catalyst quality that adds for the first time be 1～2 times of catalyst quality of for the second time adding.
Described stopper is the phenol stopper, preferably any one in Resorcinol, toluhydroquinone, MEHQ, 2-Tert. Butyl Hydroquinone, 2,5 di tert butyl hydroquinone, cuprous chloride.
Described stopper consumption is 0.1～5.0%, preferred 0.3～0.7% of phthalic anhydride and vinyl carbinol total mass.
The mol ratio of total vinyl carbinol of described phthalic anhydride and twice adding is 1: 10～10: 1, adds for the first time to such an extent that the amount of substance of vinyl carbinol is 1～3 times of phthalic anhydride amount of substance.
The mol ratio of total vinyl carbinol of described phthalic anhydride and twice adding is preferably 1: 3～and 3: 1, add to such an extent that the amount of substance of vinyl carbinol is preferably 2 times of phthalic anhydride amount of substance for the first time.
The present invention has following beneficial effect:
1) esterification temperature is low, reacting balance, and production energy consumption is low;
2) by product that produces in the reaction process is few, and yield is high;
The time of 3) reacting is relatively short, and efficient is high;
4) low temperature reaction reduces or avoids the generation of side reaction, and the products obtained therefrom quality is good, lighter color;
5) because temperature of reaction is lower, and the time is shorter, acid gas is to the equipment corrosion less;
6) the favourable serialization of present method or semi-continuous production, thus can satisfy the scale operation needs.
Prepare the method for Phthalic acid, diallyl ester according to acid catalysis phthalic anhydride of the present invention and vinyl carbinol, can make the product of high-clarity and refractive index, method is simple, and quality better is safe.Can be widely used in aircraft, boats and ships according to the prepared product of the inventive method through the DAP of polymerization gained resin; Wiring board, switch, the transmodulator of electric and electronic products; The electrical equipment such as automobile, railway part, electron device etc.; Strengthen the DAP plastics as glass fibre, be used for Large Radar cover, airplane self-control device, switch element, decorative plate coversheeting material, electric elements, military machinery, communication instrument etc.
Embodiment
The invention will be further described by the following examples.Protection scope of the present invention is not subjected to the restriction of described embodiment.
Embodiment 1 sulphur trioxide catalytic esterification prepares Phthalic acid, diallyl ester
Under the nitrogen protection; to thermometer is housed; reflux condensing tube; in the 1L four neck flasks of airway; add 148.0g phthalic anhydride (1.0mol); 116.0g vinyl carbinol (2.0mol) and 0.5g Resorcinol; open and stir; then pass into the 4.0g sulfur trioxide gas; control reacting liquid temperature＜20 ℃; be incubated 10min after having led to sulphur trioxide; be heated to about 70 ℃; insulation 2h stops to stir, and leaves standstill 20min; isolate lower floor's acid phase (being inorganic phase); in upper organic phase, add 11.6g (0.2mol) vinyl carbinol, open and stir, pass into again the 2.0g sulfur trioxide gas; continue to be warming up to 80 ℃; insulation 1h stops to stir, and tells sour phase after leaving standstill; organic phase is through washing; the saturated sodium bicarbonate washing; anhydrous sodium sulfate drying; (120～130 ℃/8mmHg), get colourless liquid 245.5g ([M+H] of cuts are collected in distillation
+(ESI-MS)=247.3), refractive index is 1.517, yield 99.8%.
Embodiment 2 hydrogenchloride catalysis prepare Phthalic acid, diallyl ester
Under the nitrogen protection; to thermometer is housed; reflux condensing tube; in the 1L four neck flasks of airway; add 148.0g phthalic anhydride (1.0mol); 78.0g vinyl carbinol (1.34mol) and 0.5g cuprous chloride; open and stir; then pass into the 4g hydrogen chloride gas; control reacting liquid temperature＜20 ℃ have led to rear insulation 10min, are heated to 70 ℃; insulation 3h; leave standstill, isolate lower floor's acid phase, in upper organic phase, add 51.0g vinyl carbinol (0.88mol); open and stir; pass into again the 4.0g hydrogen chloride gas, continue to be warming up to 80 ℃, insulation 1h; stop to stir; tell sour phase after leaving standstill, organic phase is through washing; the sodium bicarbonate washing; anhydrous sodium sulfate drying; (120～130 ℃/8mmHg), get colourless liquid 239.5g ([M+H] of cuts are collected in distillation
+(ESI-MS)=247.3), refractive index is 1.516, yield 97.2%.
Embodiment 3 hydrogen fluoride catalyzed prepare Phthalic acid, diallyl ester
Under the nitrogen protection; to thermometer is housed; reflux condensing tube; in the 1L four neck flasks of airway; add 148.0g phthalic anhydride (1.0mol); 100.0g vinyl carbinol (1.72mol) and 0.5g toluhydroquinone; open and stir; then pass into the 4.0g hydrogen fluoride gas; control reacting liquid temperature＜20 ℃ have led to rear insulation 10min, are heated to 45 ℃; insulation 2.5h; leave standstill, isolate lower floor's acid phase, in upper organic phase, add 29.0g vinyl carbinol (0.5mol); open and stir; pass into again the 4.0g hydrogen fluoride gas, continue to be warming up to 80 ℃, insulation 1.5h; stop to stir; tell sour phase after leaving standstill, organic phase is through washing; the sodium bicarbonate washing; anhydrous sodium sulfate drying; (120～130 ℃/8mmHg), get colourless liquid 243.5g ([M+H] of cuts are collected in distillation
+(ESI)=247.3), refractive index is 1.517, yield 99.0%.
Embodiment 4 phosphorus trichloride catalysis prepare Phthalic acid, diallyl ester
Under the nitrogen protection; to thermometer is housed; reflux condensing tube; in the 1L four neck flasks of airway; add 148.0g phthalic anhydride (1.0mol); 116.0g vinyl carbinol (2.0mol) and 0.6g MEHQ; open and stir; then splash into the 4.0g phosphorus trichloride; control reacting liquid temperature＜20 ℃ have led to rear insulation 10min, are heated to 60 ℃; insulation 1.5h; leave standstill, isolate lower floor's acid phase, in upper organic phase, add 11.6g vinyl carbinol (0.2mol); open and stir; splash into again the 2.0g phosphorus trichloride, continue to be warming up to 80 ℃, insulation 1h; stop to stir; tell sour phase after leaving standstill, organic phase is through washing; the sodium bicarbonate washing; anhydrous sodium sulfate drying; (120～130 ℃/8mmHg), get colourless liquid 245.8g ([M+H] of cuts are collected in distillation
+(ESI)=247.3), refractive index is 1.517, yield 99.6%.
Embodiment 5 thionyl chloride catalysis prepare Phthalic acid, diallyl ester
Under the nitrogen protection; to thermometer is housed; reflux condensing tube; in the 1L four neck flasks of airway; add 148.0g phthalic anhydride (1.0mol); 116.0g vinyl carbinol (2.0mol) and 0.5g 2-Tert. Butyl Hydroquinone; open and stir; then drip the 4g sulfur oxychloride; control reacting liquid temperature＜20 ℃ have led to rear insulation 10min, are heated to 60 ℃; insulation 1h; leave standstill, isolate lower floor's acid phase, in upper organic phase, add 11.5g vinyl carbinol (0.2mol); open and stir; drip again the 2.0g sulfur oxychloride, continue to be warming up to 80 ℃, insulation 1h; stop to stir; tell sour phase after leaving standstill, organic phase is through washing; the sodium bicarbonate washing; anhydrous sodium sulfate drying; (120～130 ℃/8mmHg), get colourless liquid 244.2g ([M+H] of cuts are collected in distillation
+(ESI)=247.3), refractive index is 1.517, yield 99.3%.
Embodiment 6 hydrogen bromide catalysis prepare Phthalic acid, diallyl ester
Under the nitrogen protection; to thermometer is housed; reflux condensing tube; in the 1L four neck flasks of airway; add 148.0g phthalic anhydride (1.0mol); 100.0g vinyl carbinol (1.72mol) and 0.5g 2; the 5-di-tert-butyl hydroquinone; open to stir, then pass into the 4g bromize hydrogen gas, control reacting liquid temperature＜20 ℃; led to rear insulation 10min; be heated to 65 ℃, insulation 1.5h leaves standstill; isolate lower floor's acid phase; in upper organic phase, add 25.0g vinyl carbinol (0.43mol), open and stir, pass into again the 3.0g bromize hydrogen gas; continue to be warming up to 80 ℃; insulation 1h stops to stir, and tells sour phase after leaving standstill; organic phase is through washing; the sodium bicarbonate washing; anhydrous sodium sulfate drying; (120～130 ℃/8mmHg), get colourless liquid 243.0g ([M+H] of cuts are collected in distillation
+(ESI)=247.3), refractive index is 1.517, yield 98.8%.
Embodiment 7 hydrogen iodide catalysis prepare Phthalic acid, diallyl ester
Under the nitrogen protection; to thermometer is housed; reflux condensing tube; in the 1L four neck flasks of airway; add 148.0g phthalic anhydride (1.0mol); 116.0g vinyl carbinol (2.0mol) and 0.5g Resorcinol; open and stir; then pass into 5.0g hydrogen iodide gas; control reacting liquid temperature＜20 ℃ have led to rear insulation 10min, are heated to 63 ℃; insulation 2h; leave standstill, isolate lower floor's acid phase, in upper organic phase, add 15.0g vinyl carbinol (0.26mol); open and stir; pass into again 2.5g hydrogen iodide gas, continue to be warming up to 85 ℃, insulation 1h; stop to stir; tell sour phase after leaving standstill, organic phase is through washing; the sodium bicarbonate washing; anhydrous sodium sulfate drying; (120～130 ℃/8mmHg), get colourless liquid 243.8g ([M+H] of cuts are collected in distillation
+(ESI)=247.3), refractive index is 1.517, yield 99.1%.
Claims (7)
1. the preparation method of a Phthalic acid, diallyl ester, it is characterized in that phthalic anhydride, vinyl carbinol and stopper under the catalysis of lewis acid catalyst, reacting by heating, after isolating lower floor's inorganic phase, in organic phase, add vinyl carbinol and lewis acid catalyst again, reacting by heating is isolated lower floor's inorganic phase, and organic phase namely gets Phthalic acid, diallyl ester through washing, distillation; The method comprises the steps:
A) under the nitrogen protection, phthalic anhydride, stopper and vinyl carbinol are added reactor;
B) start stirring, add lewis acid catalyst, control temperature＜20 ℃, insulation 10min;
C) rising temperature to 40 ~ 80 ℃, insulation 1.5 ~ 3.5h;
D) stop to stir, tell lower floor's inorganic phase;
E) in organic phase, add vinyl carbinol;
F) add lewis acid catalyst, rising temperature to 70 ~ 80 ℃, insulation 1 ~ 2h;
G) stop to stir, tell lower floor's inorganic phase;
H) organic phase with deionized water wash, saturated sodium bicarbonate aqueous solution washing, dry, distillation, collect product;
Wherein, described lewis acid catalyst is selected from any one in hydrogen fluoride, hydrogenchloride, hydrogen bromide, hydrogen iodide, sulphur trioxide, sulfur oxychloride, dichloro sulphonyl, phosphorus trichloride, phosphorus tribromide, phosphorus oxychloride, phosphorus pentachloride, the Vanadium Pentoxide in FLAKES.
2. the preparation method of Phthalic acid, diallyl ester according to claim 1, the catalyzer total mass that it is characterized in that described twice adding is 0.1～10% of phthalic anhydride and vinyl carbinol total mass; The catalyst quality that adds for the first time be 1 ~ 2 times of catalyst quality of for the second time adding.
3. the preparation method of Phthalic acid, diallyl ester according to claim 2, the catalyzer total mass that it is characterized in that described twice adding is 2～5% of phthalic anhydride and vinyl carbinol total mass; The catalyst quality that adds for the first time be 1 ~ 2 times of catalyst quality of for the second time adding.
4. the preparation method of Phthalic acid, diallyl ester according to claim 1, it is characterized in that described stopper is selected from any one in Resorcinol, toluhydroquinone, MEHQ, 2-Tert. Butyl Hydroquinone, 2,5 di tert butyl hydroquinone, the cuprous chloride.
5. the preparation method of Phthalic acid, diallyl ester according to claim 5 is characterized in that described stopper consumption is 0.1～5.0% of phthalic anhydride and vinyl carbinol total mass.
6. the preparation method of Phthalic acid, diallyl ester according to claim 1, the mol ratio that it is characterized in that total vinyl carbinol of described phthalic anhydride and twice adding is 1:10～10:1, adds for the first time to such an extent that the amount of substance of vinyl carbinol is 1～3 times of phthalic anhydride amount of substance.
7. the preparation method of Phthalic acid, diallyl ester according to claim 6, the mol ratio that it is characterized in that total vinyl carbinol of described phthalic anhydride and twice adding is 1:3～3:1, adds for the first time to such an extent that the amount of substance of vinyl carbinol is 2 times of phthalic anhydride amount of substance.
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Denomination of invention: A kind of preparation method of diallyl phthalate Effective date of registration: 20220815 Granted publication date: 20131023 Pledgee: Postal Savings Bank of China Limited Shouguang sub branch Pledgor: SHOUGUANG NUOMENG CHEMICAL Co.,Ltd. Registration number: Y2022980012623 |