CN104387347B - 2-methyl maleic anhydride and the preparation method of double (citraconimidomethyl) benzene of 1,3- - Google Patents
2-methyl maleic anhydride and the preparation method of double (citraconimidomethyl) benzene of 1,3- Download PDFInfo
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- CN104387347B CN104387347B CN201410661305.7A CN201410661305A CN104387347B CN 104387347 B CN104387347 B CN 104387347B CN 201410661305 A CN201410661305 A CN 201410661305A CN 104387347 B CN104387347 B CN 104387347B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/60—Two oxygen atoms, e.g. succinic anhydride
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D207/44—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members
- C07D207/444—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members having two doubly-bound oxygen atoms directly attached in positions 2 and 5
- C07D207/448—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members having two doubly-bound oxygen atoms directly attached in positions 2 and 5 with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms, e.g. maleimide
Abstract
The invention discloses a kind of 2 methyl maleic anhydrides and 1, the preparation method of 3 pairs of (citraconimidomethyl) benzene, step is: itaconic acid, catalyst are mixed with organic solvent, intensification carries out isomery dehydration, course of reaction constantly separates moisture, remove organic solvent after reaction, obtain 2 methyl maleic anhydride crude products；2 methyl maleic anhydride crude product adsorbents are refined, obtains 2 citraconic acid anhydride products；2 methyl maleic anhydrides and m-xylene diamine being reacted in organic acid, reaction carries out post processing to reactant liquor after terminating, and obtains 1,3 pairs of (citraconimidomethyl) benzene.Equipment requirements is reduced by the refined of the present invention 2 methyl maleic anhydride, and energy consumption is low, and refining effect is good, and 2 methyl maleic anhydrides are high with m-xylene diamine processing safety, and post processing is simple, it is easy to industrialized production.
Description
Technical field
The present invention relates to the preparation method of a kind of anti-recovery agent and raw material thereof, be specifically related to a kind of 1, double (citraconimidomethyl) benzene of 3-and the preparation method of 2-methyl maleic anhydride, belong to anti-recovery agent technical field.
Background technology
Anti-recovery agent is a kind of new type functional rubber chemicals, it occurs Diels-Alder to react with diene/triolefin during sizing material reverts, produce the sulfur cross-linking key that C-C cross-bond destroys with replacement or " compensation ", keep vulcanized network stable, make cured properties to decline.Anti-recovery agent has 1,3-double (citraconimidomethyl) benzene, vegolysen, the double polytype such as sodium thiosulfate dihydrate (HTS), the organic zinc heat-resisting vulcanizing activator of soaps of 6-, wherein 1, the effect of double (citraconimidomethyl) benzene of 3-is the most notable, and its effect is the most progressively approved by each giant tyre enterprise.
1,3-double (citraconimidomethyl) benzene, have another name called 1,3-double (citraconimide ylmethyl) benzene, PK900, put goods on the market by Aksu-Nobel company of Holland in nineteen ninety-five, be in the world first with the product of anti-recovery agent sold, its chemical constitution is as follows:
。
2-methyl maleic anhydride is synthesis 1, the important source material of double (citraconimidomethyl) benzene of 3-or intermediate, and it can synthesize 1 in the presence of a catalyst with m-xylene diamine, double (citraconimidomethyl) benzene of 3-.The synthetic method of 2-methyl maleic anhydride is more, such as, with itaconic acid as raw material, prepared by hot evaporation, acetic anhydride evaporation, acyl chlorides evaporation；Or with itaconic acid as raw material, with alkali metal sulfates, alkali metal phosphate, acid, strong acid weak base salt or strong base-weak acid salt as catalyst, carry out isomerization and dehydration prepares.1 reported now, the preparation method of double (citraconimidomethyl) benzene of 3-is less, and having of having appreciated that is following several:
1, anticipatory remark outstanding person has delivered article (the anticipatory remark outstanding person of entitled " synthesis of double (citraconimidomethyl) benzene of anti-recovery agent 1,3-"；The synthesis of double (citraconimidomethyl) benzene of anti-recovery agent 1,3-；Guangdong chemical industry；4th phase in 2006), 1, the synthesis of double (citraconimidomethyl) benzene of 3-comprises the following steps: by itaconic acid and excess acetyl chloride 1h, it is subsequently adding toluene decompression and reactant and by-product are distilled off, again with toluene distillation once obtains clothing health acid anhydride, then clothing health acid anhydride is added thermal rearrangement and obtains 2-methyl butene dianhydride (citraconic anhydride)；2-methyl butene dianhydride, acetone, m-xylene diamine and acetic anhydride being mixed, reaction generates double citraconoyl amino acid, is subsequently adding two kinds of catalyst continuation reactions and obtains 1, double (citraconimidomethyl) benzene of 3-.The method has the disadvantages that 1), chloroacetic chloride consumption big, it is difficult to reclaim；2), high temperature reset preparation 2-methyl maleic anhydride, energy consumption is high, and resets under high temperature and be the most thoroughly easily caused 2-methyl maleic anhydride underpants bran acid anhydride too high levels；3), rearrangement reaction be reversible reaction, the citraconic anhydride obtained not shelf-stable, mutability is clothing health acid anhydride.
2, patent 201310719564.4 discloses a kind of anti-recovery agent 1, the preparation method of double (the lemon acid imide methyl) benzene of 3-, it comprises the following steps: itaconic acid, dimethyl sulfoxide and sodium dihydrogen phosphate is mixed, 175-195 DEG C of insulation reaction 1-2h, obtains 2-methyl maleic anhydride；2-methyl maleic anhydride, m-xylene diamine, dimethylbenzene and pyridine being mixed, back flow reaction 3-4h at 120 DEG C, after reaction terminates, crude product is distilled to obtain in decompression, and crude product obtains product through post processings such as recrystallization.This patent has the disadvantage that: 1), use that dimethyl sulfoxide is highly polar, high boiling solvent, the high-leveled and difficult recovery of cost, and big to equipment corrosion；2), using the way of distillation to purify 2-methyl maleic anhydride, energy consumption is high, and yield is low, has the residual generation of solid waste still；3), 1,3-double (citraconimidomethyl) benzene synthesis post-processing step is loaded down with trivial details, and crude product recrystallization uses other organic solvents, and yield is low, and cost is high.
Summary of the invention
The present invention is directed to now 1, the deficiency that double (citraconimidomethyl) the benzene preparation method of 3-exists, it is provided that the preparation method of a kind of 2-methyl maleic anhydride, the method have simple to operate, energy consumption is low, system toxicity is little, corrosivity is little, practical advantage.
Present invention also offers a kind of 1, the preparation method of double (citraconimidomethyl) benzene of 3-, the method is simple and easy to do, and post processing is simple, and safety is high.
The present invention is achieved by the following measures:
The preparation method of a kind of 2-methyl maleic anhydride, comprises the following steps:
(1) itaconic acid, catalyst being mixed with organic solvent, heat up and carry out being dehydrated isomerization reaction, constantly separate moisture in course of reaction, remove organic solvent after reaction, residue is 2-methyl maleic anhydride crude product；
(2) in 2-methyl maleic anhydride crude product, add adsorbent to refine, obtain 2-citraconic acid anhydride product.
Above-mentioned itaconic acid synthesizes the reaction equation of 2-methyl maleic anhydride under catalyst:
Preferably, inventor is found that the catalyst do not pointed out in a kind of prior art, i.e. pyridine.Pyridine is as alkaline matter, and finding in research process can also be as the catalyst in catalysis itaconic acid, and effect is preferable.
When catalyst is pyridine, the consumption of pyridine is the 4.0～6.0 ‰ of itaconic acid quality, preferably 5 ‰.
In above-mentioned steps (1), organic solvent used can be the organic solvent that may be used for this reaction disclosed in prior art, it is contemplated that problems such as the toxicity of solvent, safety in utilization and costs, the preferred dimethylbenzene of the present invention is as organic solvent.
In above-mentioned steps (1), itaconic acid is 20～22:24～26 with the mass ratio of organic solvent.
In above-mentioned steps (1), reaction temperature is 135～145 DEG C.
In above-mentioned steps (1), the response time is generally 1～4h.
The present invention uses adsorbent mode to refine obtained 2-methyl maleic anhydride crude product, refined method is simple, adsorbent is added stirring and adsorbing in 2-methyl maleic anhydride crude product, some in crude product can be affected the material of 2-methyl maleic anhydride quality and remove by adsorbent, such as by-product (mainly 2-citraconic acid anhydride polymer) etc..Before absorption, 2-methyl maleic anhydride crude product color is deep, polymer content is high, 2-methyl maleic anhydride content is only capable of reaching about 94%, it is not used to prepare 1, double (citraconimidomethyl) benzene of 3-, after adsorption refining, gained 2-methyl maleic anhydride product colour shoals, clarifies, and for liquid, 2-methyl maleic anhydride purity can reach more than 98%.This process for purification is more simple to operate than the distillation method for refining that commonly uses now, and energy consumption is low, it is to avoid the generation of residue (being called for short still residual) in still in still-process, reduces the loss in subtractive process of the 2-methyl maleic anhydride, improves its yield.
Adsorbent used by the present invention can be the adsorbent that activated carbon, kieselguhr etc. have absorbability.
The consumption of adsorbent of the present invention is generally the 8～10 ‰ of itaconic acid quality, and preferably 8.5 ‰, consumption is few.
In above-mentioned subtractive process, after 2-methyl maleic anhydride crude product is cooled to 60～70 DEG C, add adsorbent, after being preferably dropped to 61-62 DEG C, add adsorbent.
In above-mentioned subtractive process, after adding adsorbent, refiltering after stirring a period of time, so that impurity can sufficiently be removed, mixing time can be passed through product colour, purity situation etc. and judge, generally 1～4h.
In the preparation method of above-mentioned 2-methyl maleic anhydride, in 2-citraconic acid anhydride product, 2-methyl maleic anhydride purity is high, pyridine as catalyst has residual in final 2-citraconic acid anhydride product, the existence of pyridine does not affect follow-up preparation 1, double (citraconimidomethyl) benzene of 3-, the step that therefore pyridine removes further is not essential.
The 2-citraconic acid anhydride product that said method obtains may be used for preparing 1, double (citraconimidomethyl) benzene of 3-, and method includes:
(1) itaconic acid, catalyst being mixed with organic solvent, heat up and carry out isomery dehydration, constantly separate moisture in course of reaction, remove organic solvent after reaction, residue is 2-methyl maleic anhydride crude product；
(2) in 2-methyl maleic anhydride crude product, add adsorbent to refine, obtain 2-citraconic acid anhydride product；
(3) 2-methyl maleic anhydride and m-xylene diamine being reacted in a solvent, reaction carries out post processing to reactant liquor after terminating, and obtains 1, and double (citraconimidomethyl) benzene of 3-, described solvent is organic acid.
The equation of 2-methyl maleic anhydride and m-xylene diamine reaction is as follows:
In above-mentioned steps (3), 2-methyl maleic anhydride and m-xylene diamine react in organic acid, and organic acid is reaction medium, can play again the effect of catalyst, need not additionally add catalyst.The content of acid is relatively large, promotes to react and quickly carries out, and makes the water of abjection in reaction have little time to destroy 2-methyl maleic anhydride, is therefore not required in course of reaction add dehydrant.Additionally, replace anhydride with organic acid, also overcome anhydride use big to equipment corrosion, cannot the high defect of cost recovery.Organic acid in this step can be selected from the organic acid such as formic acid, acetic acid, propanoic acid, butanoic acid, valeric acid, caproic acid, is preferably acetic acid from cost consideration.
In above-mentioned steps (3), 2-methyl maleic anhydride: solvent: the mass ratio of m-xylene diamine is 1:1:0.55～0.65, preferably 1:1:0.60.
In above-mentioned steps (3), reaction temperature is 50～70 DEG C, preferably 55 DEG C～60 DEG C.
In above-mentioned steps (3), the response time is 1～2h.
In above-mentioned steps (3), the post processing of reactant liquor include cooling, crystallize, filter, be dried step.
In above-mentioned steps (3), it is typically reduced to 5～10 DEG C and carries out crystallize.
Instant invention overcomes existing preparation method long flow path, defect that energy consumption is high, have the advantage that
1, the present invention can not use the solvents that toxicity is big, corrosivity is big such as chlorobenzene, dimethyl sulfoxide, acetic anhydride, and toxicity is little, substantially improves operating environment, greatly reduces the corrosion to equipment, more environmentally friendly safety.
2, Methanamide is not used when the present invention prepares 2-methyl maleic anhydride, using adsorbent mode impurity removal and purification, replace the purification step of tradition rectification and purification 2-methyl maleic anhydride, thick anhydride is refined to be reduced equipment requirements, energy consumption is low, do not produce still residual, the more environmentally friendly cleaning of technique, more simple and easy to do, reduce complex process degree, gained anhydride purity is high, and yield is high, and refining effect is good.
3, during 2-methyl maleic anhydride of the present invention reacts with m-xylene diamine, replace solvent and the combination (especially aroma type solvent and the combination of anhydride catalyst) of catalyst with acid, decrease the kind of raw material, reduce production cost, improve processing safety, it is easy to industrialized production.Reacted reactant liquor post processing is simple, and directly cooling crystallize just can be met the product of requirement, it is not necessary to carries out recrystallization again.
4, the present invention 1, double (citraconimidomethyl) the benzene purity of 3-is high, and yield is high, it is not necessary to increases equipment, has preferable practicality.
Accompanying drawing explanation
Fig. 1 is gained 2-methyl maleic anhydride of the present invention1HNMR(CDCl3) collection of illustrative plates.
Fig. 2 is the mass-spectrogram of gained 2-methyl maleic anhydride of the present invention.
Fig. 3 is the DSC spectrogram of double (citraconimidomethyl) benzene of gained 1,3-of the present invention.
Fig. 4 is the HPLC spectrogram of double (citraconimidomethyl) the benzene standard substance of 1,3-.
Fig. 5 is the HPLC spectrogram of double (citraconimidomethyl) benzene of gained 1,3-of the present invention.
Detailed description of the invention
Being further detailed the present invention below by specific embodiment, the description below is only exemplary, is not defined its content.
Embodiment
1
1) in being connected to water knockout drum, condensing tube and churned mechanically 1000ml there-necked flask, 400g itaconic acid, 460g dimethylbenzene, 2g pyridine are added, after stirring mixing, it is rapidly heated to 140 DEG C, backflow insulation reaction 1.5h, the period moisture of reaction abjection is constantly taken out of by dimethylbenzene, reach theoretical point water yield 55.4g, close heating stopped reaction, obtain the mixed liquor of thick 2-methyl maleic anhydride.
2) process removing solvent is: mixed liquor is warming up to 165～170 DEG C, and under normal pressure, distillation abjection dimethylbenzene 454g, obtains 2-methyl maleic anhydride crude product.
3) 2-methyl maleic anhydride crude product is cooled to 61～62 DEG C, is slowly added to 3.4g activated carbon, stirring, adsorb 2h.After absorption terminates, sucking filtration, obtain refined citraconic anhydride 340g.Fig. 1 and Fig. 2 is products obtained therefrom1HNMR(CDCl3) collection of illustrative plates and mass-spectrogram, as can be seen from the figure products obtained therefrom is citraconic anhydride.Being as the criterion with itaconic acid and calculate the yield of citraconic anhydride, computing formula is: yield=(mProduct×MItaconic acid)/(mItaconic acid×MProduct), it being computed, product yield is 98.7%.Using gas chromatographic detection product purity, recording its purity is 99.2%.
4) in being connected to condensing tube and churned mechanically 1000ml flask, add the 340g of preparation in step 3) refine citraconic anhydride and 340g glacial acetic acid, stirring, weigh 204g m-xylene diamine to be added dropwise in flask, in 5min, dropping is complete, open heating, being rapidly heated to 55～60 DEG C, reflux insulation reaction 1.5h.
5) after reaction terminates, it is cooled to 5～10 DEG C, crystallizes 1.5h.
6) filter, be dried to obtain white powder 477.5g.
Products obtained therefrom differential scanning calorimetry being analyzed, gained DSC figure is as it is shown on figure 3, it can be seen that this product peak shape and commercially available 1, double (citraconimidomethyl) benzene standard substance peak shape of 3-is basically identical.Fig. 4 and Fig. 5 is 1, double (citraconimidomethyl) the benzene commercial standard of 3-and the HPLC figure of the present embodiment products obtained therefrom, and as can be seen from the figure their retention time is consistent, thus proves that products obtained therefrom of the present invention is 1, double (citraconimidomethyl) benzene of 3-.
Being as the criterion calculating 1 with m-xylene diamine, the yield of double (citraconimidomethyl) benzene of 3-, computing formula is: yield=(mProduct×MIsophthalic two Methylamine)/(mIsophthalic two Methylamine×MProduct), being computed yield is 98.3%.HPLC is used to record its purity 99.5%.
Embodiment
2
1) in being connected to water knockout drum, condensing tube and churned mechanically 500ml there-necked flask, 200g itaconic acid, 230g dimethylbenzene, pyridine 0.8g are added, after stirring mixing, it is rapidly heated to 141 DEG C, backflow insulation reaction 4h, the period moisture of reaction abjection is constantly taken out of by dimethylbenzene, reach theoretical point water yield 27.6g, close heating stopped reaction, obtain the mixed liquor of thick 2-methyl maleic anhydride.
2) process removing solvent is: mixed liquor is warming up to 165～170 DEG C, and under normal pressure, distillation abjection dimethylbenzene 228g, obtains 2-methyl maleic anhydride crude product.
3) 2-methyl maleic anhydride crude product is cooled to 61～62 DEG C, is slowly added to 1.7g activated carbon, stirring, adsorb 2h.After absorption terminates, sucking filtration, obtain refined citraconic anhydride 165.4g.In terms of itaconic acid, its yield is 96.0%, and it is 98.7% that gas chromatogram (GC) records its purity.
Embodiment
3
1) in being connected to water knockout drum, condensing tube and churned mechanically 500ml there-necked flask, 200g itaconic acid, 230g dimethylbenzene, pyridine 1.2g are added, after stirring mixing, it is rapidly heated to 140 DEG C, backflow insulation reaction 1.5h, the period moisture of reaction abjection is constantly taken out of by dimethylbenzene, reach theoretical point water yield 27.8g, close heating stopped reaction, obtain the mixed liquor of thick 2-methyl maleic anhydride.
2) process removing solvent is: mixed liquor is warming up to 165～170 DEG C, and under normal pressure, distillation abjection dimethylbenzene 227g, obtains 2-methyl maleic anhydride crude product.
3) 2-methyl maleic anhydride crude product is cooled to 61～62 DEG C, is slowly added to 1.7g activated carbon, stirring, adsorb 2h.After absorption terminates, sucking filtration, obtain refined citraconic anhydride 170g.In terms of itaconic acid, its yield is 98.7%, and it is 99.1% that GC records its purity.
Embodiment
4
1) in being connected to water knockout drum, condensing tube and churned mechanically 500ml there-necked flask, 200g itaconic acid, 230g dimethylbenzene, pyridine 1.0g are added, after stirring mixing, it is rapidly heated to 140 DEG C, backflow insulation reaction 1.5h, the period moisture of reaction abjection is constantly taken out of by dimethylbenzene, reach theoretical point water yield 27.6g, close heating stopped reaction, obtain the mixed liquor of thick 2-methyl maleic anhydride.
2) process removing solvent is: mixed liquor is warming up to 165～170 DEG C, and under normal pressure, distillation abjection dimethylbenzene 229g, obtains 2-methyl maleic anhydride crude product.
3) 2-methyl maleic anhydride crude product is cooled to 61～62 DEG C, is slowly added to 1.7g kieselguhr, stirring, adsorb 4h.After absorption terminates, sucking filtration, obtain refined citraconic anhydride 163.7g.In terms of itaconic acid, its yield is 95%, and it is 98.2% that GC records its purity.
Embodiment
5
1) in being connected to water knockout drum, condensing tube and churned mechanically 500ml there-necked flask, 200g itaconic acid, 230g dimethylbenzene, pyridine 1.0g are added, after stirring mixing, it is rapidly heated to 140 DEG C, backflow insulation reaction 2h, the period moisture of reaction abjection is constantly taken out of by dimethylbenzene, reach theoretical point water yield 27.8g, close heating stopped reaction, obtain the mixed liquor of thick 2-methyl maleic anhydride.
2) process removing solvent is: mixed liquor is warming up to 165～170 DEG C, and under normal pressure, distillation abjection dimethylbenzene 227g, obtains 2-methyl maleic anhydride crude product.
3) 2-methyl maleic anhydride crude product is cooled to 61～62 DEG C, is slowly added to 3.4g activated carbon, stirring, adsorb 2h.After absorption terminates, sucking filtration, obtain refined citraconic anhydride 158.3g.In terms of itaconic acid, its yield is 91.8%, and it is 99.5% that GC records its purity.
Embodiment
6
1) in being connected to water knockout drum, condensing tube and churned mechanically 500ml there-necked flask, 200g itaconic acid, 255g dimethylbenzene, pyridine 1.0g are added, after stirring mixing, it is rapidly heated to 135 DEG C, backflow insulation reaction 3h, the period moisture of reaction abjection is constantly taken out of by dimethylbenzene, reach theoretical point water yield 27.6g, close heating stopped reaction, obtain the mixed liquor of thick 2-methyl maleic anhydride.
2) process removing solvent is: mixed liquor is warming up to 165～170 DEG C, and under normal pressure, distillation abjection dimethylbenzene 251g, obtains 2-methyl maleic anhydride crude product.
3) 2-methyl maleic anhydride crude product is cooled to 61～62 DEG C, is slowly added to 1.7g activated carbon, stirring, adsorb 2h.After absorption terminates, sucking filtration, obtain refined citraconic anhydride 166.3g.In terms of itaconic acid, its yield is 96.5%, and it is 98.5% that GC records its purity.
Embodiment
7
1) in being connected to water knockout drum, condensing tube and churned mechanically 500ml there-necked flask, 200g itaconic acid, 230g dimethylbenzene, pyridine 1.0g are added, after stirring mixing, it is rapidly heated to 145 DEG C, backflow insulation reaction 1.5h, the period moisture of reaction abjection is constantly taken out of by dimethylbenzene, reach theoretical point water yield 27.6g, close heating stopped reaction, obtain the mixed liquor of thick 2-methyl maleic anhydride.
2) process removing solvent is: heated up 165～170 DEG C by mixed liquor, and under normal pressure, distillation abjection dimethylbenzene 228g, obtains 2-methyl maleic anhydride crude product.
3) 2-methyl maleic anhydride crude product is cooled to 61～62 DEG C, is slowly added to 1.7g activated carbon, stirring, adsorb 2h.After absorption terminates, sucking filtration, obtain refined citraconic anhydride 170.0g.In terms of itaconic acid, its yield is 98.6%, and it is 99.5% that GC records its purity.
Embodiment
8
1) in being connected to water knockout drum, condensing tube and churned mechanically 500ml there-necked flask, 200g itaconic acid, 230g dimethylbenzene, pyridine 1.0g are added, after stirring mixing, it is rapidly heated to 140 DEG C, backflow insulation reaction 4h, the period moisture of reaction abjection is constantly taken out of by dimethylbenzene, reach theoretical point water yield 27.6g, close heating stopped reaction, obtain the mixed liquor of thick 2-methyl maleic anhydride.
2) process removing solvent is: mixed liquor is warming up to 165～170 DEG C, and under normal pressure, distillation abjection dimethylbenzene 228g, obtains 2-methyl maleic anhydride crude product.
3) 2-methyl maleic anhydride crude product is cooled to 70 DEG C, is slowly added to 2g activated carbon, stirring, adsorb 2h.After absorption terminates, sucking filtration, obtain refined citraconic anhydride 166.4g.In terms of itaconic acid, its yield is 96.6%, and it is 98.5% that GC records its purity.
Embodiment
9
1) in being connected to condensing tube and churned mechanically 250ml flask, add 85g embodiment 1 and refine citraconic anhydride and 85g glacial acetic acid, stirring, weigh 47g m-xylene diamine and be added dropwise in flask, in 5min, dropping is complete, opening heating, be rapidly heated to 55～60 DEG C, reflux insulation reaction 1.5h.
2) after reaction terminates, it is cooled to 5～10 DEG C, crystallizes 2.5h.
3) filter, be dried to obtain white powder 110.2g.
In terms of m-xylene diamine, the yield of 1,3-double (citraconimidomethyl) benzene is 98.5%, and HPLC records its purity 97.5%.
Embodiment
10
1) in being connected to condensing tube and churned mechanically 250ml flask, add 85g embodiment 1 and refine citraconic anhydride and 85g glacial acetic acid, stirring, weigh 55.2g m-xylene diamine and be added dropwise in flask, in 5min, dropping is complete, opening heating, be rapidly heated to 55～60 DEG C, reflux insulation reaction 2h.
2) after reaction terminates, it is cooled to 5～10 DEG C, crystallizes 2.5h.
3) filter, be dried to obtain white powder 125.6g.
In terms of m-xylene diamine, the yield of 1,3-double (citraconimidomethyl) benzene is 95.5%, and HPLC records its purity 96.0 %.
Embodiment
11
1) in being connected to condensing tube and churned mechanically 250ml flask, add 85g embodiment 1 and refine citraconic anhydride and 85g glacial acetic acid, stirring, weigh 51g m-xylene diamine and be added dropwise in flask, in 5min, dropping is complete, opening heating, be rapidly heated to 70 DEG C, reflux insulation reaction 2h.
2) after reaction terminates, it is cooled to 5～10 DEG C, crystallizes 2.5h.
3) filter, be dried to obtain white powder 120.1g.
In terms of m-xylene diamine, the yield of 1,3-double (citraconimidomethyl) benzene is 98.6%, and HPLC records its purity 99.0%.
Embodiment
12
1) in being connected to condensing tube and churned mechanically 250ml flask, add 85g embodiment 1 and refine citraconic anhydride and 85g glacial acetic acid, stirring, weigh 51g m-xylene diamine and be added dropwise in flask, in 5min, dropping is complete, opening heating, be rapidly heated to 50 DEG C, reflux insulation reaction 1h.
2) after reaction terminates, it is cooled to 5～10 DEG C, crystallizes 2.5h.
3) filter, be dried to obtain white powder 117.3g.
In terms of m-xylene diamine, the yield of 1,3-double (citraconimidomethyl) benzene is 96.5%, and HPLC records its purity 97.4%.
Embodiment
13
1) in being connected to condensing tube and churned mechanically 250ml flask, add 85g embodiment 1 and refine citraconic anhydride and 85g propanoic acid, stirring, weigh 51g m-xylene diamine and be added dropwise in flask, in 5min, dropping is complete, opening heating, be rapidly heated to 60 DEG C, reflux insulation reaction 1.5h.
2) after reaction terminates, it is cooled to 5 DEG C～10 DEG C, crystallizes 1.5h.
3) filter, be dried to obtain white powder 114.2g.
In terms of m-xylene diamine, the yield of 1,3-double (citraconimidomethyl) benzene is 94.0%, and HPLC records its purity 99.0%.
Embodiment
14
1) in being connected to condensing tube and churned mechanically 250ml flask, add 85g embodiment 1 and refine citraconic anhydride and 85g caproic acid, stirring, weigh 51g m-xylene diamine and be added dropwise in flask, in 5min, dropping is complete, opening heating, be rapidly heated to 60 DEG C, reflux insulation reaction 1.5h.
2) after reaction terminates, it is cooled to 5 DEG C～10 DEG C, crystallizes 1h.
3) filter, be dried to obtain white powder 112.6g.
In terms of m-xylene diamine, the yield of 1,3-double (citraconimidomethyl) benzene is 92.5%, and HPLC records its purity 99.1%.
Comparative example
1
The 2-methyl maleic anhydride crude product prepared in Example 3, the mode using decompression distillation refines, method is as follows: be connected to condensing tube, still head, in the vacuum decompression distilling apparatus of adapter tube, above-mentioned obtain thick 2-citraconic acid anhydride solution and be heated to 140 DEG C～150 DEG C, it is evacuated to-0.096Mpa, starting to collect effluent, be warming up to 170 DEG C to thick 2-citraconic acid anhydride solution, evaporating head no longer has fraction to flow out, stopped reaction, obtaining faint yellow supernatant liquid 153.2g, with the itaconic acid rate of collecting for 89.1%, it is 99.8% that HPLC records purity.
Comparative example
2
The 2-methyl maleic anhydride crude product prepared in Example 8, is cooled to 52～55 DEG C by 2-methyl maleic anhydride crude product, is slowly added to 1.7g activated carbon, stirring, adsorbs 2h.After absorption terminates, sucking filtration, obtain refined citraconic anhydride 169.7g.In terms of itaconic acid, its yield is 98.4%, and it is 96.4% that GC records its purity, and color is light brown.This product and m-xylene diamine are carried out reaction and cannot obtain double (citraconimidomethyl) benzene of 1,3-.
Comparative example
3
1) in being connected to condensing tube and churned mechanically 250ml flask, add 85g embodiment 1 and refine citraconic anhydride and 85g glacial acetic acid, stirring, weigh 51g m-xylene diamine and be added dropwise in flask, in 5min, dropping is complete, opening heating, be rapidly heated to 60 DEG C, reflux insulation reaction 1.5h.
2) after reaction terminates, it is cooled to 15 DEG C～20 DEG C, crystallizes 10h.
3) filter, be dried to obtain white powder 85g.
In terms of m-xylene diamine, the yield of 1,3-double (citraconimidomethyl) benzene is 70.0%, and HPLC records its purity 99.4%.
Claims (16)
1. a preparation method for 2-methyl maleic anhydride, is characterized in that comprising the following steps:
(1) itaconic acid, catalyst being mixed with organic solvent, heat up and carry out being dehydrated isomerization reaction, constantly separate moisture in course of reaction, remove organic solvent after reaction, residue is 2-methyl maleic anhydride crude product；
(2) in 2-methyl maleic anhydride crude product, add adsorbent to refine, obtain 2-citraconic acid anhydride product；In step (1), described catalyst is pyridine；In step (2), described adsorbent is activated carbon or kieselguhr.
Preparation method the most according to claim 1, is characterized in that: in step (1), and the consumption of pyridine is the 4.0～6 ‰ of itaconic acid quality；In step (2), the consumption of adsorbent is the 8～10 ‰ of itaconic acid quality.
Preparation method the most according to claim 1 and 2, is characterized in that: in step (1), and the consumption of pyridine is the 5 ‰ of itaconic acid quality.
Preparation method the most according to claim 1 and 2, is characterized in that: in step (2), and the consumption of adsorbent is the 8.5 ‰ of itaconic acid quality.
Preparation method the most according to claim 1 and 2, is characterized in that: in step (1), and reaction temperature is 135～145 DEG C；In step (2), after 2-methyl maleic anhydride crude product is cooled to 60～70 DEG C, add adsorbent.
Preparation method the most according to claim 5, is characterized in that: in step (2), after 2-methyl maleic anhydride crude product is cooled to 61-62 DEG C, adds adsorbent.
Preparation method the most according to claim 5, is characterized in that: in step (1), and the response time is 1～4h；After adding adsorbent, stirring 1～4h refilters.
8. one kind 1, the preparation method of double (citraconimidomethyl) benzene of 3-, it is characterized in that: prepare 2-methyl maleic anhydride according to the preparation method of the 2-methyl maleic anhydride according to any one of claim 1-7,2-methyl maleic anhydride, solvent and m-xylene diamine are mixed, reacting, reaction carries out post processing to reactant liquor after terminating, and obtains 1, double (citraconimidomethyl) benzene of 3-, described solvent is organic acid.
Preparation method the most according to claim 8, is characterized in that: 2-methyl maleic anhydride: solvent: the mass ratio of m-xylene diamine is 1:1:0.55～0.65；Described organic acid includes formic acid, acetic acid, propanoic acid, butanoic acid, valeric acid or caproic acid.
Preparation method the most according to claim 9, is characterized in that: 2-methyl maleic anhydride: solvent: the mass ratio of m-xylene diamine is 1:1:0.60.
11. preparation methoies according to claim 9, is characterized in that: described organic acid is acetic acid.
Preparation method 12. according to Claim 8, described in 9,10 or 11, is characterized in that: reaction temperature is 50～70 DEG C.
13. preparation methoies according to claim 12, is characterized in that: reaction temperature is 55-60 DEG C.
14. preparation methoies according to claim 12, is characterized in that: the response time is 1～2h.
15. preparation methoies according to claim 8, is characterized in that: the post processing of reactant liquor include cooling, crystallize, filter, be dried step.
16. preparation methoies according to claim 15, is characterized in that: during reactant liquor post processing, be down to temperature 5～10 DEG C carry out crystallize.
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