CN102909074B - Immobilized type non-toxic catalyst and method for synthesizing N-phenylmaleimide and N-substitutional phenylmaleimide - Google Patents
Immobilized type non-toxic catalyst and method for synthesizing N-phenylmaleimide and N-substitutional phenylmaleimide Download PDFInfo
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Abstract
The invention provides an immobilized type non-toxic catalyst and a method for synthesizing N-phenylmaleimide and N-substitutional phenylmaleimide. The immobilized type non-toxic catalyst is formed by utilizing a porous zeolite molecular sieve as a carrier, impregnating the porous zeolite molecular sieve into water solution of titanium organic phosphonic chelate or zirconium organic phosphonic chelate or hafnium organic phosphonic chelate for 6-10 hours, reacting and bonding, drying and roasting. Pure products of the N-phenylmaleimide and N-substitutional phenylmaleimide are obtained by adding maleic anhydride and aniline or maleic anhydride and aniline derivatives into the immobilized type non-toxic catalyst as raw materials, sequentially acylating, dehydrating and cyclizing and recrystallizing. The immobilized type non-toxic catalyst is non-toxic and environment-friendly, the method of synthesizing the N-phenylmaleimide and N-substitutional phenylmaleimide is environment-friendly, convenient in operation procss and high in product purity and yield, and solvent used is non-toxic, convenient to recover and reusable.
Description
Technical field
The present invention relates to a kind of non-toxic catalyst and application, particularly a kind of solid-carrying type non-toxic catalyst and synthetic N-phenylmaleimide thereof in the meticulous organic compound of preparation and the method in N-phenyl substituted maleimide amine.
Background technology
N-phenylmaleimide compounds (being called for short N-PMI) is a kind of important Organic Chemicals, it is that one has 1, the five-membered cyclic monomer of 2 one disubstituted ethylene based structures, in polymer processing, as embedded, in macromolecular chain, can increase the inward turning of chain resistance, thereby improve the heat resistance of polymer, resistance to impact, hot melt and processability etc.Thereby be used as ABS resin (acrylonitrile-butadiene one styrene), polyvinyl chloride (PVC), the heat-proof modifier of polymethyl methacrylate (MMA); Also can be used as the crosslinking agent of polypropylene, polyvinyl chloride; Can prepare adhesive, improve the adhesive effect of metal and rubber.N-PMI also has certain antibacterial activity, thereby can be used as anti-fouling agent, the infringement of harmful organism to underwater installation in anti-sealing effectively.In addition, N-PMI also can be used as agricultural chemicals, the raw material of medicine.Therefore, it is a kind of extremely important organic compound.
The preparation of N-phenylmaleimide compounds; normally adopt maleic anhydride (maleic anhydride) and aniline (or derivatives thereof) in organic solvent, to carry out acidylate; again under all kinds of catalyst or dehydrating agent exist, carry out closed loop dehydration subsequently, obtain target product.As the method providing in U.S. Pat P2444536 and the clear 53-53648 of Japan Patent, be to adopt a large amount of acetic anhydride as dehydrating agent.But use the method to prepare N-PMI, can produce a large amount of acetic acid wastewaters, use in addition some poisonous organic solvents, so this method is more unfavorable to safety in production and environmental protection.The clear 53-68770 of Japan Patent and China Patent Publication No. be CN101462997A, CN1962634A in, said method is improved, except not using the acetic anhydride putting on short allowance, also in ring-closure reaction, adopt non-protonic solvent and dewater under strong inorganic acid or organic acid (as: phosphoric acid, the concentrated sulfuric acid, p-methyl benzenesulfonic acid and phosphorus pentoxide) catalysis, the method shortcoming has been to use high price and the poisonous such aprotic polar solvent of dimethyl formamide (DMF), both environment was worked the mischief, and made again production cost increase substantially.Secondly owing to also having used strong acid to make catalyst, except causing production facility corrode very soon, make the loss of solvent larger, and because higher boiling makes in product thorough removal very difficult.In addition, using acid (particularly strong acid), after the synthetic reaction of catalyst, reactant liquor is wanted alkali neutralization and washing repeatedly thereof, operates the very complicated and existence problem that disposes waste liquid.The method has the product thing of paying to generate, and prepares a large amount of solvent refinings of highly purified N-PMI or uses way of distillation separation and purification, thereby affecting purity and the yield of product.In the clear 60-11465 of Japan Patent, the flat 2-223552 of Japan Patent, narrated the preparation method take strong-acid ion exchange resin and superpower acidity resin as the N-phenylmaleimide of catalyst, this method advantage is that catalyst can reclaim, repeated multiple times use, and catalytic efficiency is high, but the use amount of catalyst is larger in these methods, and the price of catalyst own is extremely expensive.In addition, a large amount of toluene, dimethylbenzene and N of using also in the method, N dimethyl formamide or N, N mono-dimethylacetylamide etc. has very large toxicity, and the organic solvent of dangerous and contaminated environment, so its industrial prospect is undesirable.
In U.S. Pat P4400521, disclosed the method for preparing N-phenylmaleimide using metal oxide (as cobalt oxide, nickel oxide, cupric oxide, zinc oxide etc.) and salt (as organic acid and inorganic acid salt) thereof as catalyst, the use of high boiling solvent has been avoided in the use of such catalyst, the temperature that has reduced synthetic reaction is selectively higher, but the use amount of catalyst is large, be difficult to reclaim.In addition; in U.S. Pat P4705866 and the flat 4-295462 of Japan Patent, reported the method for preparing N-phenylmaleimide using organic tin complex compound as new catalyst; although this method productive rate is high; reaction temperature and; but this kind of catalyst activity is difficult to lasting and bad recovery and uses; in addition this agent is expensive and toxicity is very large, and source difficulty, is unfavorable for eco-friendly large-scale production.At Japan Patent JP(03) in 11,060, Japanese recent studies on exploitation take toluene as solvent, under catalyst exists, make the acid of N phenyl maleimide and dichloride Asia cobalt (CO
2cl
2) reaction, then by the chlorination butanedioic acid acid imide of gained through de-HCl(hydrogen chloride) effect makes NPMI yield more than 95%.The method yield is high, but solvent toxicity used is large, and complicated operation, and still in the laboratory research stage, industrial application value is little at present.At Japan Patent JP290868(2004) in, introduced by esterification process the method for synthetic N-phenylmaleimide.It is take sulfuric acid as catalyst, the intermediate N phenyl maleimide acid of cis-butenedioic anhydride and aniline reaction generation is carried out to esterification with alcohol (as methyl alcohol, ethanol), generate maleic amide acid monoester, remove the water of generation simultaneously, and then with phosphoric acid does catalyst, add toluene equal solvent, the ester that makes to generate continues to be reacted into ring and makes N-PMI, this method yield is higher, but operating procedure is too many, the higher current also unrealized suitability for industrialized production of cost.
For fear of the shortcoming of above-mentioned patent documentation, reach the expectation that meets environmental requirement and suitability for scale production, in the recent period at Chinese patent CN1915496A(2007) in reported using loaded catalyst and prepared N-PMI as new catalyst.This catalyst is with metal oxide, and zeolite molecular sieve or the mixture of the two be as carrier, take the aqueous solution that contains molysite, nickel salt, cobalt salt or mantoquita as compound the supporting of maceration extract compatibility, makes.But in this catalyst as iron, nickel, cobalt, the copper plasma in activated centre; only to be attached on above-mentioned carrier with the form of physical absorption; in NPMI preparation process; these metal ions can be because of the negative effect of variations in temperature and organic solvent; Deng giving the impact of factor of control, desorption runs off, thereby affects catalytic activity and the efficiency of this catalyst, so further have influence on supported catalyst, reclaims; the effect recycling, discarded object can be unfavorable for environmental protection simultaneously.In addition, in this method, and a large amount of use is inflammable and explosive, the organic solvents such as the toluene of poisonous contaminated environment, dimethylbenzene, so be not suitable for the production of environmental requirement and scale.In addition, at Chinese patent CN-101875626A(2010.11.03) in also reported the method for the synthetic N-PMI of a kind of immobilized supported acid catalyst.This catalyst system floods silica gel, molecular sieve, aluminium oxide, modified resin etc. with strong acid and makes with post-drying.With the synthetic N-PMI of this catalyst, its yield is high, and acid-bearing wastewater discharge is few, and technological process is few, and cost is low.But this method is still used the organic solvents such as toxic, inflammable and explosive toluene, dimethylbenzene and reaction temperature higher in a large number, reaches as high as 160 ℃.Therefore, this method is unfavorable for environmental protection, poor stability, and polymer class accessory substance is more, and product purity, yield may not reach the requirement of top grade product.
Recently, in Chinese patent CN-102399180A (2012.04.04), disclosed the method for synthetic N-PMI of presence of acidic ionic liquid catalyst that utilizes current new and high technology a kind of.This method it is said that productive rate is very high, can reach 97%, and purity is more than 97%.This genealogy of law is made catalyst with some strong inorganic acids as the acidic ion liquid that sulfuric acid is prepared from, and makes solvent with toluene, dimethylbenzene.So this method still exists some shortcomings that are unfavorable for environmental protection, as produced some reluctant acid waste waters in producing, there are the organic solvents such as toluene, dimethylbenzene in process of production can be because of the various factor contaminated environment that can not regulate and control.Security is poor, and cost is higher, is unfavorable for large-scale production.
Summary of the invention
The present invention provides a kind of method in solid-carrying type non-toxic catalyst and synthetic N-phenylmaleimide and N-phenyl substituted maleimide amine according to the deficiencies in the prior art.This synthetic method environmental friendliness, operating procedure is easy, is easy to control, and product purity is high, and productive rate is high, and solvent for use is nonhazardous, is convenient to reclaim, reuse, and suitability for scale production and cost are low.
Described a kind of solid-carrying type non-toxic catalyst, is characterized in that making according to following steps:
(1) in 20-50 ℃ of temperature range, selecting porous zeolite molecular sieve is carrier, and immersed and in maceration extract, flooded 6-10 hour, reaction bonding, wherein maceration extract is the aqueous solution of titanium organic phosphine chelate, or the aqueous solution of zirconium organic phosphine chelate, or the one in the aqueous solution of hafnium organic phosphine chelate, the mass ratio of carrier and maceration extract is 1:1-20; In the aqueous solution of described titanium organic phosphine chelate, the mass concentration of titanium organic phosphine chelate is 10-30%, in the aqueous solution of zirconium organic phosphine chelate, the mass concentration of zirconium organic phosphine chelate is 20-50%, and in the aqueous solution of hafnium organic phosphine chelate, the mass concentration of hafnium organic phosphine chelate is 25-50%;
(2) by the dry 3-6 hour at 60-120 ℃ of the porous zeolite molecular sieve carrier after dipping, then at 300-600 ℃ roasting 4-6 hour, be prepared into immobilized non-toxic catalyst;
Wherein, the aqueous solution of titanium organic phosphine chelate described in step (1) be by Wuxi City Yuan Tai Chemical trade Co., Ltd produce mealy alkali formula titanium carbonate respectively with HEDP, or ATMP, or ethylene diamine tetra methylene phosphonic acid mix and blend 2-3h in the hot water of 90-100 ℃, after transparent to solution, add again organic or inorganic alkaloids to make its pH value reach the y-bend phosphine chelate of 8.5-9.5, or trident phosphine chelating, or the wherein one in four fork phosphine chelates;
The aqueous solution of zirconium organic phosphine chelate described in step (1) be by Wuxi City Yuan Tai Chemical trade Co., Ltd produce powdery zirconium oxycarbonate respectively with HEDP, or ATMP, or ethylene diamine tetra methylene phosphonic acid mix and blend 2-3h in the hot water of 90-100 ℃, after transparent to solution, add again organic or inorganic alkaloids to make its pH value reach the y-bend phosphine chelate of 8.5-9.5, or trident phosphine chelating, or the wherein one in four fork phosphine chelates;
The aqueous solution of hafnium organic phosphine chelate described in step (1) be by Wuxi City Yuan Tai Chemical trade Co., Ltd produce mealy alkali formula hafnium carbonate respectively with HEDP, or ATMP, or ethylene diamine tetra methylene phosphonic acid mix and blend 2-3h in the hot water of 90-100 ℃, after transparent to solution, add again organic or inorganic alkaloids to make its pH value reach the y-bend phosphine chelate (1-hydroxyl ethane-1.1-di 2 ethylhexyl phosphonic acid chelate) of 8.5-9.5, or trident phosphine chelating (N-river three methylenephosphonic acid chelates), or four wherein a kind of in fork phosphine chelate (ethylene diamine tetra methylene phosphonic acid chelate),
Porous zeolite molecular sieve is one or more mixing in Na type zeolite, H type zeolite, X-type zeolite, y-type zeolite, zeolite beta and A type zeolite.
In the aqueous solution of described titanium organic phosphine chelate, the mass concentration of titanium organic phosphine chelate is 15-20%, in the aqueous solution of zirconium organic phosphine chelate, the mass concentration of zirconium organic phosphine chelate is 20-30%, and in the aqueous solution of hafnium organic phosphine chelate, the mass concentration of hafnium organic phosphine chelate is 25-40%; The weight ratio of described carrier and maceration extract is 1:5-20.
Described organic alkaloids is MEA or diethanol amine, and inorganic base material is solid-state potash.
When preparing y-bend phosphine chelate, it is that basic carbonate titanium is 190g that the amount of powdery alkali formula titanium carbonate, Powdered zirconium oxycarbonate and powdery alkali formula hafnium carbonate is 1mol(, zirconium oxycarbonate is 308g, alkaline carbonic acid hafnium is 388g), HEDP 3mol(690g), while selecting MEA or diethanol amine, (MEA is 183g-305g, diethanol amine is 315g-525g), its amount is 3-5mol, select solid-state potash, amount is 3mol (414g); When preparing trident phosphine chelate; it is 570g that the amount of mealy alkali formula titanium carbonate, Powdered zirconium oxycarbonate and powdery alkali formula hafnium carbonate is 3mol(basic carbonate titanium; zirconium oxycarbonate is 924g; basic carbonate hafnium is 1164g); ATMP 6mol(1992g); while selecting MEA or diethanol amine, it is 305g-488g that its amount is 5-8mol(MEA; Diethanol amine is 525-848g), select solid-state potash, amount is 3-5mol (414g-690g); When preparation four fork phosphine chelate, it is 380g that the amount of mealy alkali formula titanium carbonate, Powdered zirconium oxycarbonate and powdery alkali formula hafnium carbonate is 2mol(basic carbonate titanium, zirconium oxycarbonate is 616g, basic carbonate hafnium is 776g), ethylene diamine tetra methylene phosphonic acid 3mol (920g), while selecting MEA or diethanol amine, its amount is 3-5mol, and (MEA is 183g-305g, diethanol amine is 315-525g), select solid-state potash, amount is 3mol (414g).
Apply a method for the synthetic N-phenylmaleimide of above-mentioned solid-carrying type non-toxic catalyst, take maleic anhydride and aniline as raw material, it is characterized in that comprising the following steps successively:
(1) acidylate: maleic anhydride and aniline are carried out to acylation reaction in methyl iso-butyl ketone (MIBK) or diacetone alcohol, reaction temperature is 20-60 ℃, reaction time is 1-3h, obtain the acid of N-phenyl maleimide, wherein the mol ratio of maleic anhydride and aniline is 1-1.3:1, and the mass ratio of maleic anhydride and methyl iso-butyl ketone (MIBK) or diacetone alcohol is 1:2-6;
(2) cyclodehydration: adopt the solid-carrying type non-toxic catalyst described in claim 1 to obtain N-phenylmaleimide crude product 100-120 ℃ of temperature through the cyclization of 3-6h the N-phenyl maleimide acid obtaining in step (1), wherein solid-carrying type non-toxic catalyst accounts for the 1-25% of N-phenyl maleimide acid quality; Described solid-carrying type non-toxic catalyst is take big-hole zeolite molecular sieve as carrier, in the aqueous solution of immersion titanium organic phosphine chelate or the aqueous solution of zirconium organic phosphine chelate or the aqueous solution of hafnium organic phosphine chelate, flood 6-10 hour, after reaction bonding, at 60-120 ℃, be dried 3-6 hour, roasting 4-6 hour at 300-600 ℃ again, be prepared from, described porous zeolite molecular sieve is one or more mixing in Na type zeolite, H type zeolite, X-type zeolite, y-type zeolite, zeolite beta and A type zeolite;
(3) recrystallization: the N-phenylmaleimide crude product of gained in step (2) is recrystallized in non-toxic alcohol kind solvent, obtains N-phenylmaleimide sterling.
In step (2), for the consumption of the solid-carried catalyst of cyclization process, account for the 1-16% of N-phenyl maleimide acid quality.
In step (3) recrystallization process, described non-toxic alcohol kind solvent is ethanol or propyl alcohol or isopropyl alcohol, and the mass ratio of non-toxic alcohol kind solvent and N-phenylmaleimide crude product is 5-10:1.
Apply a method for the synthetic N-phenyl substituted maleimide amine of above-mentioned solid-carrying type non-toxic catalyst, take maleic anhydride and anil as raw material, it is characterized in that comprising the following steps successively:
(1) acidylate: maleic anhydride and anil are carried out to acylation reaction in methyl iso-butyl ketone (MIBK) or diacetone alcohol, reaction temperature is 20-60 ℃, reaction time is 1-3h, obtain N-phenyl and replace maleamic acid, wherein the mol ratio of maleic anhydride and anil is 1-1.3:1, and the mass ratio of maleic anhydride and methyl iso-butyl ketone (MIBK) or diacetone alcohol is 1:2-6;
(2) cyclodehydration: the N-phenyl obtaining in step (1) is replaced to maleamic acid and adopt solid-carrying type non-toxic catalyst to obtain N-phenylmaleimide crude product 100-120 ℃ of temperature through the cyclization of 3-6h, wherein solid-carrying type non-toxic catalyst accounts for the 1-25% that N-phenyl replaces maleamic acid quality; Described solid-carrying type non-toxic catalyst is take big-hole zeolite molecular sieve as carrier, in the aqueous solution of immersion titaniferous organic phosphine chelate or zirconium organic phosphine chelate or hafnium organic phosphine chelate, flood 6-10 hour, after reaction bonding, at 60-120 ℃, be dried 3-6 hour, roasting 4-6 hour at 300-600 ℃ again, be prepared from, described porous zeolite molecular sieve is one or more mixing in Na type zeolite, H type zeolite, X-type zeolite, y-type zeolite, zeolite beta and A type zeolite;
(3) recrystallization: the N-phenyl substituted maleimide amine crude product of gained in step (2) is recrystallized in non-toxic alcohol kind solvent, obtains N-phenyl substituted maleimide amine sterling.
In step (3) recrystallization process, described non-toxic alcohol kind solvent is ethanol or propyl alcohol or isopropyl alcohol, and the mass ratio of non-toxic alcohol kind solvent and N-phenyl substituted maleimide amine crude product is 5-10:1.
In above synthetic reaction, reaction equation is as follows:
(R in formula
1-R
6for hydrogen atom, halogen atom, C
1-C
6alkyl, C
1-C
6alkane ether, hydroxyl, carboxyl, nitro, phenyl etc.).
Solid-carrying type non-toxic catalyst of the present invention is concentrated the advantage that relates to method for preparing catalyst in existing background technology, learn from other's strong points to offset one's weaknesses, promote catalytic activity class, and utilize the solid support method of organic phosphine chemical bonding, by immobilized on big-hole zeolite molecular sieve the organic phosphine chelates such as titanium, zirconium, hafnium, and introduce activated centre titanium, zirconium, hafnium ion, stablized catalytic active center, and the catalysis characteristics of these chelates is transferred on heterogeneous solid catalyst body.Heterogeneous catalysis is easy to separate immobilized organic phosphine chelating catalyst and the advantage of chelate homogeneous catalysis combines, thereby improved the catalytic activity of catalyst and greatly reduced the loss scene of activated centre titanium, zirconium, hafnium ion, reduce equipment corrosion, avoid simple use liquid organic phosphine chelate consumption large, be difficult for the disadvantages such as separating-purifying.
The synthetic method of N-phenylmaleimide of the present invention and N-phenyl substituted maleimide amine, compared with current traditional handicraft, has following beneficial effect:
1. avoided toxic solvent DMF(N, N dimethyl formamide) etc. and inflammable and explosive and have the use of the benzene,toluene,xylene etc. of very large toxicity, can reduce environmental pollution, simplify production technology, reduce production costs;
In synthetic method of the present invention owing to not using strong inorganic acid and organic acid, greatly reduce the unexpected polycondensation of raw materials used and intermediate, the color depth that alleviates product greatly reduces impurity content, so can improve the purity of product, yield;
3. in synthetic method of the present invention, adopt solid-carried catalyst safety non-toxic, be easy to recycle, not only reduce environmental pollution, and reduce production costs.
4. synthetic method of the present invention is easy and simple to handle, and the reaction time is short, and it is high that product is easy to separation and purification yield, is applicable to suitability for industrialized production, has a extensive future.
The specific embodiment
Below in conjunction with specific embodiment, the invention will be further described.
Embodiment 1: a kind of preparation method of solid-carrying type non-toxic catalyst, take 4A type zeolite molecular sieve carrier and the zirconium organic phosphine chelate aqueous solution as initiation material, prepares through following steps successively:
(1) under 20 ℃ of environment, by weight the zirconium organic phosphine chelate aqueous solution that is 50% by 40 parts of zirconium organic phosphine chelate concentration, by 60 parts of clean running water, be diluted to the maceration extract that zirconium organic phosphine chelate concentration is 20%, 6g4A type zeolite molecular sieve carrier is joined in the maceration extract that 36g prepares and flooded 7 hours, and reaction bonding, wherein the mass ratio of 4A type zeolite molecular sieve carrier and the zirconium organic phosphine chelate aqueous solution is 1:6;
(2), by the 4A type zeolite molecular sieve carrier filtering means dehydration after dipping, in 120 ℃ of constant temperature ovens, by the carrier drying after filtering 3 hours, then place in Muffle furnace, with 5 ℃/sec of speed, be warmed up to 400 ℃, roasting 5 hours, obtains solid-carrying type non-toxic catalyst, is designated as 1# solid-carrying type non-toxic catalyst;
Embodiment 2: a kind of preparation method of solid-carrying type non-toxic catalyst, take 4A type zeolite molecular sieve carrier and the hafnium organic phosphine chelate aqueous solution as initiation material, prepares through following steps successively:
(1) under 30 ℃ of environment, by weight the hafnium organic phosphine chelate aqueous solution that is 50% by 45 parts of hafnium organic phosphine chelate concentration, by 55 parts of clean tap water, be diluted to the maceration extract that hafnium organic phosphine chelate concentration is 25%, subsequently, again load weighted 10g4A type molecular sieve carrier is joined in the maceration extract that 50g prepares and flood 5 hours, reaction bonding, wherein the mass ratio of 4A type molecular sieve carrier and maceration extract is 1:5;
(2) by the 4A type molecular sieve carrier filtering means dehydration after dipping, under in 110 ℃ of constant temperature ovens, filtrate has been dried to 4 hours, then has placed in Muffle furnace, with the speed of 5 ℃/sec, be warmed up to 450 ℃ of roastings 4 hours, obtain solid-carrying type non-toxic catalyst, be designated as 2# solid-carrying type non-toxic catalyst.
Embodiment 3: a kind of preparation method of solid-carrying type non-toxic catalyst, take 10X zeolite molecular sieve carrier and the zirconium organic phosphine chelate aqueous solution as initiation material, prepares through following steps successively:
(1) under 25 ℃ of environment, selecting the zirconium organic phosphine chelate aqueous solution 50g that zirconium organic phosphine chelate concentration is 50% is maceration extract, again load weighted 5g10X zeolite molecular sieve carrier is joined in the maceration extract preparing and flooded 6 hours, reaction bonding, wherein the mass ratio of 10X zeolite molecular sieve carrier and maceration extract is 1:10;
(2), by the 10X zeolite molecular sieve carrier filtering means dehydration after dipping, in 60 ℃ of constant temperature ovens, by the carrier drying after filtering 6 hours, then place in Muffle furnace, with 5 ℃/sec of speed, be warmed up to 300 ℃, roasting 6 hours, obtains solid-carrying type non-toxic catalyst, is designated as 3# solid-carrying type non-toxic catalyst
Embodiment 4: a kind of preparation method of solid-carrying type non-toxic catalyst, take 10X zeolite molecular sieve carrier and the titanium organic phosphine chelate aqueous solution as initiation material, prepares through following steps successively:
(1) under 40 ℃ of environment, select the titanium organic phosphine chelate aqueous solution that titanium organic phosphine chelate concentration is 30% as maceration extract, and the 5g10X zeolite molecular sieve carrier taking is joined in the maceration extract preparing and flooded 7 hours, reaction bonding, wherein the mass ratio 1:10 of 10X zeolite molecular sieve carrier and maceration extract;
(2), by the 10X zeolite molecular sieve carrier filtering means dehydration after dipping, in 110 ℃ of constant temperature ovens, by the carrier drying after filtering 3 hours, then place in Muffle furnace, with 5 ℃/sec of speed, be warmed up to 500 ℃, roasting 4 hours, obtains solid-carrying type non-toxic catalyst, is designated as 4# solid-carrying type non-toxic catalyst.
In hafnium organic phosphine chelate in above four embodiment, zirconium organic phosphine chelate, titanium organic phosphine chelate, have y-bend phosphine chelate to have again trident phosphine chelating and four fork phosphine chelates:
Wherein titanium, zirconium, hafnium y-bend phosphine chelate aqueous solution preparation process is: first by 3mol(690g) HEDP (solid-state HEDP) be dissolved in 90-100 ℃ etc. in quality hot water, then under agitation, point 5-10 batch adds the mealy alkali formula titanium carbonate (190g) of producing from Wuxi City Yuan Tai Chemical trade Co., Ltd of 1mol or powdery zirconium oxycarbonate (308g) or mealy alkali formula hafnium carbonate (388g) the solution of HEDP to, and 2-3h is stirred in continuation in 90-100 ℃ of temperature range, after liquid is transparent, add again the MEA (183g-305g) of 3-5mol or 50% aqueous solution of diethanol amine (315g-525g), as required, the aqueous solution that also can add the potash (414g) 50% of 3mol continues to stir in 90-100 ℃ of temperature range makes solution all-transparent, pH value reaches 8.5-9.5, thereby make titanium, zirconium, the y-bend phosphine chelate aqueous solution of hafnium,
Titanium, zirconium, hafnium trident phosphine chelate aqueous solution preparation process is: first by 6mol(1992g) ATMP (be called for short ATMP) be dissolved in the hot water of the quality such as 90-100 ℃, then under agitation divide the 5-10 batch of mealy alkali formula titanium carbonate (570g) of producing from Wuxi City Yuan Tai Chemical trade Co., Ltd or powdery zirconium oxycarbonate (924g) or the mealy alkali formula hafnium carbonate (1164g) by 3mol to add to the solution of ATMP, and 2-3h is stirred in continuation at 90-100 ℃ of temperature, after liquid is transparent, again 50% aqueous solution (solid-state) of the potash (414g-690g) of the aqueous solution of the MEA of 5-8mol (305g-488g) or diethanol amine (525g-848g) 50% or 3-5mol is added in above-mentioned solution, at 90-100 ℃ of temperature, continue to stir, make solution all-transparent, final pH value reaches 8.5-9.5, thereby make titanium, zirconium, the hafnium trident phosphine chelate aqueous solution,
Titanium, zirconium, hafnium four is pitched phosphine chelate preparation process: first the ethylene diamine tetra methylene phosphonic acid of 3mol (920g) (solid-state) is dissolved in the hot water of the quality such as 90-100 ℃, then under agitation, point 5-10 batch adds the mealy alkali formula titanium carbonate (380g) of producing from Wuxi City Yuan Tai Chemical trade Co., Ltd of 2mol or powdery zirconium oxycarbonate (616g) or mealy alkali formula hafnium carbonate (776g) four fork phosphine solution to, and at 90-100 ℃ of temperature, continue to stir 2-3h, after liquid is transparent, add again monoethanol (183g-305g) or diethanol amine (315g-525g) 50% aqueous solution of 3-5mol, the potash (solid-state) that also can add 3mol according to need of production 50% aqueous solution (414g), and at 90-100 ℃ of temperature, continue to stir, cause liquid all-transparent.PH value is controlled at 8.5-9.5, thereby make titanium, zirconium, hafnium four, pitches the phosphine chelate aqueous solution.
Embodiment 5: a kind of synthetic method of N-phenylmaleimide, take maleic anhydride and aniline as main initiation material, through following step, make successively:
(1) acidylate, the preparation of N-phenyl maleimide acid: electric mixer is being housed, thermometer, in the reactor of rotation flow point water condenser and dropping funel, add successively respectively the about 200g of methyl iso-butyl ketone (MIBK) 250ml(), maleic anhydride 50g (about 0.5mol), in the lower turn on agitator of room temperature (25 ℃ of left and right), stir, after treating that maleic anhydride dissolves, again the aniline being pre-mixed and methyl isobutyl ketone solution (it is 42g aniline and 46g methyl iso-butyl ketone (MIBK) that 42ml aniline and 58ml methyl iso-butyl ketone (MIBK) are converted into weight) are passed through to dropping funel, splash into lentamente in reactor, remain on 25-35 ℃ (scope) lower reaction, approximately within 0.5-1 hour, drip off.After dropwising, then slaking reaction 1h.Wherein, the mol ratio of maleic anhydride and aniline is 1:1.1, and the mass ratio of maleic anhydride and methyl iso-butyl ketone (MIBK) is 1:4.92.
(2) cyclodehydration, the preparation of N-phenylmaleimide crude product:
Continuing under the state stirring, add the about 8g of 1# solid-carrying type non-toxic catalyst of preparation in embodiment 1, heating reactant liquor, to boiling (approximately 110 ℃ of left and right), carries out cyclodehydration reaction, until the water surface in water knockout drum no longer rises, reaction time is about 3h, cooling stops reaction, filters and separates solid-carrying type catalyst, and solvent is removed in decompression distillation, obtain the N-phenylmaleimide crude product 95g of yellow crystal, for lower step recrystallization.
(3) recrystallization:
Above-mentioned gained solid is added in 950ml ethanol and is recrystallized, decompress filter obtains yellow crystalline product N-phenylmaleimide sterling 85g subsequently, the m of yield 90% prepared N-phenylmaleimide, and p is 88-91 ℃, through GPC purity analysis, its result is more than 99%.
Embodiment 6:
The synthetic method of N-o-methyl-phenyl-maleimide, take Malaysia acyl acid anhydride and o-toluidine as main initiation material, through following steps, make successively:
(1) acidylate, the preparation of N-o-methyl-phenyl-maleamic acid: electric mixer is being housed, thermometer, reflux water-dividing condenser, in the reaction of dropping funel, add successively methyl iso-butyl ketone (MIBK) 300ml(240g) maleic anhydride 60g(0.61mol), open and stir, be heated to 30 ℃, after maleic anhydride dissolves completely again by the o-toluidine being pre-mixed and methyl isobutyl ketone solution (it is about 50g o-toluidine and 40g methyl iso-butyl ketone (MIBK) that 50mol o-toluidine and 50ml methyl iso-butyl ketone (MIBK) are converted into weight), by dropping funel, slowly add in reactor, in about 0.5 hour, drip off.After dropwising, then slaking reaction 1 hour.Wherein, the mol ratio of Malaysia acyl acid anhydride and methylaniline is 1:1.3, and the mass ratio of maleic anhydride and methyl iso-butyl ketone (MIBK) is 1:4.3.
(2) cyclodehydration, the preparation of N-o-methyl-phenyl-maleimide: continuing under the situation stirring, the 2# solid-carrying type non-toxic catalyst that 8g is prepared by embodiment bis-adds in reactor, be heated to approximately 110 ℃ and carry out back flow reaction, until the water surface in water knockout drum no longer rises, the reaction time is about 2.5 hours.Stop subsequently reaction, cooling, filters to isolate 2# solid-carried catalyst, and solvent is removed in decompression distillation, obtains the N-(aminomethyl phenyl of faint yellow crystallization) the about 100g of maleic amide crude product, for lower step recrystallization.
(3) recrystallization: above-mentioned gained solids is added in 1000ml propyl alcohol and is recrystallized, decompress filter obtains faint yellow crystalline solid N-(aminomethyl phenyl subsequently) maleimide sterling 92g, yield is 92%, prepared N-(o-methyl-phenyl-) m of maleimide, p is 75-77 ℃, through GPC purity analysis, its result is more than 99%.
Embodiment 7
N-(p-hydroxybenzene) synthetic method of maleimide, take maleic anhydride and para hydroxybenzene amine as main initiation material, through following step, make successively:
(1) acidylate, N-(p-hydroxybenzene) preparation of maleamic acid: electric mixer is being housed, thermometer, reflux water-dividing condenser, in the reactor of dropping funel, adds diacetone alcohol 300ml successively, the about 60g of maleic anhydride 0.6mol(); Open and stir, be heated to 40 ℃, after maleic anhydride dissolves completely, again by para hydroxybenzene amine good pre-coordination and diacetone mixed liquor (para hydroxybenzene amine 0.5mol, it is about 54g para hydroxybenzene amine that diacetone alcohol 60mol is converted into weight, 56g diacetone alcohol), by dropping funel, slowly add in reactor, in about 0.5 hour, drip off.And then slaking reaction 1.5 hours.Wherein, the mol ratio of maleic anhydride and para hydroxybenzene amine is 1:1.1, the mass ratio 1:5.6 of maleic anhydride and diacetone alcohol.
(2) cyclodehydration, N-(p-hydroxybenzene) preparation of maleimide: in the situation that continuing to stir, the 3# solid-carrying type non-toxic catalyst that 8g is prepared through embodiment tri-adds in reactor, heat temperature raising carries out cyclodehydration reaction, until the water surface in water knockout drum no longer rises to terminal, approximately 2 hours reaction time.Stop subsequently reaction, cooling, filters to isolate 3# solid-carried catalyst, and solvent is removed in decompression distillation, obtains the N-(p-hydroxybenzene of yellowish orange crystallization) the about 102g of maleimide crude product, for lower step recrystallization.
(3) recrystallization: above-mentioned prepared solids is added in 800ml isopropyl alcohol and is recrystallized, and decompress filter makes light yellow orange crystalline solid N-(p-hydroxybenzene subsequently) maleimide sterling, its quality is 95g, yield is 93%.Prepared sterling N-(p-hydroxybenzene) m of maleimide, P is 183-185 ℃, through GPC purity analysis, its result is more than 99%.
Embodiment 8:
N-(is to carboxyl phenyl) synthetic method of maleimide, take Malaysia acyl acid anhydride and to carboxyl aniline as main initiation material, through following step, make successively:
(1) acidylate, N-(is to carboxyl phenyl) preparation of maleamic acid: electric mixer is being housed, thermometer, reflux water-dividing condenser, in dropping funel reactor, adds diacetone alcohol 300ml(280g successively), the about 60g of maleic anhydride 0.6mol(); Open and stir, be heated to 50 ℃, after maleic anhydride dissolves completely, again by good pre-coordination to carboxyl aniline and diacetone alcohol mixed liquor (to carboxyl aniline 0.5mol, diacetone alcohol 70ml, is converted into weight and is about 68.5g to carboxyl aniline, 66g diacetone alcohol) by dropping funel, slowly add in reactor, in 0.5 hour, drip off, and then slaking reaction 1 hour.Wherein, maleic anhydride with to the mol ratio of carboxyl aniline, be 1:1.14, the mass ratio of maleic anhydride and diacetone alcohol is 1:5.7.
(2) cyclodehydration, N-(is to carboxyl phenyl) preparation of maleimide: continuing under the state stirring, 1# solid-carrying type non-toxic catalyst prepared by embodiment mono-is that 1:1 mixes with the 2# solid-carrying type non-toxic catalyst of preparation in embodiment bis-according to weight ratio, and mixed 10g solid-carrying type non-toxic catalyst is added in reactor, heat temperature raising carries out cyclodehydration reaction, until the water surface in water knockout drum no longer rises.Reaction time is about 3 hours.Subsequently, cooling, stops reaction, filters to isolate composite solid carried catalyst, and solvent is removed in decompression distillation, obtains the N-(of white crystals to carboxyl phenyl) maleimide crude product, be about 104g, for lower step recrystallization.
(3) recrystallization:
Above-mentioned prepared solids is placed in to 1000ml isopropyl alcohol and is recrystallized, decompress filter obtains white crystals body N-(to carboxyl phenyl) maleimide sterling, its quality is 94g, yield is 94%.Prepared sterling N-(is to carboxyl phenyl) m of maleimide, p is 231-233 ℃, through GPC purity analysis, its result is more than 99%.
Embodiment 9:
The synthetic method of N-phenylmaleimide, take maleic anhydride and aniline as main initiation material, through following step, make successively:
(1) acidylate, the preparation of N-phenyl maleimide acid: electric mixer is being housed, thermometer, reflux water-dividing condenser, in dropping funel reactor, add successively methyl iso-butyl ketone (MIBK) 400ml (320g), the about 60g of Malaysia acyl acid anhydride 0.6mol(), open and stir, be heated to 35 ℃, after maleic anhydride is entirely molten, again by aniline good pre-coordination and methyl iso-butyl ketone (MIBK) mixed liquor (the about 50g of aniline 50ml(), methyl iso-butyl ketone (MIBK) 60ml(48g)) by dropping funel, slowly add in reactor, in 1 hour, drip off, and then slaking reaction 30-40 minute.Wherein, the mol ratio of maleic anhydride and aniline is 1:1.2, and the mass ratio of maleic anhydride and methyl iso-butyl ketone (MIBK) is 1:6.
(2) cyclodehydration, the preparation of N-phenylmaleimide: continuing under the situation stirring, the 4# solid-carrying type non-toxic catalyst that 10g is prepared by embodiment tetra-adds in reactor, and heat temperature raising carries out cyclodehydration reaction, until the water surface in water knockout drum no longer rises.Reaction time was controlled at about 3 hours.Subsequently, cooling, stops reaction, filters to isolate solid-carried catalyst 4#, and solvent is removed in decompression distillation, obtains green-yellow crystallization N-phenylmaleimide crude product and (is about 100g, for lower step recrystallization.
(3) recrystallization:
The above-mentioned crude product making is placed in to 950ml isopropyl alcohol and is recrystallized, suction filtration obtains green-yellow acicular crystals, N-phenylmaleimide sterling, its quality is 90g, and yield is about 90%, and the mp of prepared sterling is 88-91 ℃, through GPC purity analysis, its result is on 99%.
The embodiment more than enumerating is only several representational specific embodiment of the present invention.Obviously, the present invention is not limited to above embodiment, can also have many distortion.All distortion that those of ordinary skill in the art can directly derive or associate from content disclosed by the invention, all should think protection scope of the present invention.
Claims (9)
1. a solid-carrying type non-toxic catalyst, is characterized in that making according to following steps:
(1) in 20-50 ℃ of temperature range, selecting porous zeolite molecular sieve is carrier, and immersed and in maceration extract, flooded 6-10 hour, reaction bonding, wherein maceration extract is the aqueous solution of titanium organic phosphine chelate, or the aqueous solution of zirconium organic phosphine chelate, or the one of the aqueous solution of hafnium organic phosphine chelate, the mass ratio of carrier and maceration extract is 1:1-20; In the aqueous solution of described titanium organic phosphine chelate, the mass concentration of titanium organic phosphine chelate is 10-30%, in the aqueous solution of zirconium organic phosphine chelate, the mass concentration of zirconium organic phosphine chelate is 20-50%, and in the aqueous solution of hafnium organic phosphine chelate, the mass concentration of hafnium organic phosphine chelate is 25-50%;
(2) by the dry 3-6 hour at 60-120 ℃ of the porous zeolite molecular sieve carrier after dipping, then at 300-600 ℃ roasting 4-6 hour, be prepared into immobilized non-toxic catalyst;
Wherein, the aqueous solution of titanium organic phosphine chelate described in step (1) be by mealy alkali formula titanium carbonate respectively with HEDP, or ATMP, or ethylene diamine tetra methylene phosphonic acid mix and blend 2-3h in the hot water of 90-100 ℃, after transparent to solution, add again organic or inorganic alkaloids to make its pH value reach the y-bend phosphine chelate of 8.5-9.5, or trident phosphine chelating, or the one in four fork phosphine chelates;
The aqueous solution of zirconium organic phosphine chelate described in step (1) be by powdery zirconium oxycarbonate respectively with HEDP, or ATMP, or ethylene diamine tetra methylene phosphonic acid mix and blend 2-3h in the hot water of 90-100 ℃, after transparent to solution, add again organic or inorganic alkaloids to make its pH value reach the y-bend phosphine chelate of 8.5-9.5, or trident phosphine chelating, or the one in four fork phosphine chelates;
The aqueous solution of hafnium organic phosphine chelate described in step (1) be by mealy alkali formula hafnium carbonate respectively with HEDP, or ATMP, or ethylene diamine tetra methylene phosphonic acid mix and blend 2-3h in the hot water of 90-100 ℃, after transparent to solution, add again organic or inorganic alkaloids to make its pH value reach the y-bend phosphine chelate of 8.5-9.5, or trident phosphine chelating, or the one in four fork phosphine chelates;
Porous zeolite molecular sieve is one or more mixing in Na type zeolite, H type zeolite, X-type zeolite, y-type zeolite, zeolite beta and A type zeolite.
2. a kind of solid-carrying type non-toxic catalyst according to claim 1, it is characterized in that: in the aqueous solution of described titanium organic phosphine chelate, the mass concentration of titanium organic phosphine chelate is 15-20%, in the aqueous solution of zirconium organic phosphine chelate, the mass concentration of zirconium organic phosphine chelate is 20-30%, and in the aqueous solution of hafnium organic phosphine chelate, the mass concentration of hafnium organic phosphine chelate is 25-40%; The weight ratio of described carrier and maceration extract is 1:5-20.
3. a kind of solid-carrying type non-toxic catalyst according to claim 1, is characterized in that: described organic alkaloids is MEA or diethanol amine, inorganic base material is solid-state potash.
4. a kind of solid-carrying type non-toxic catalyst according to claim 1, it is characterized in that: when preparing y-bend phosphine chelate, the amount of powdery alkali formula titanium carbonate, Powdered zirconium oxycarbonate and powdery alkali formula hafnium carbonate is 1mol, HEDP 3mol, while selecting MEA or diethanol amine, its amount is 3-5mol, selects solid-state potash, and amount is 3mol; When preparing trident phosphine chelate, the amount of mealy alkali formula titanium carbonate, Powdered zirconium oxycarbonate and powdery alkali formula hafnium carbonate is 3mol, ATMP 6mol, while selecting MEA or diethanol amine, its amount is 5-8mol, select solid-state potash, amount is 3-5mol; When preparation four fork phosphine chelate, the amount of mealy alkali formula titanium carbonate, Powdered zirconium oxycarbonate and powdery alkali formula hafnium carbonate is 2mol, ethylene diamine tetra methylene phosphonic acid 3mol, while selecting MEA or diethanol amine, its amount is 3-5mol, select solid-state potash, amount is 3mol.
5. application rights requires a method for the synthetic N-phenylmaleimide of the solid-carrying type non-toxic catalyst described in 1, take maleic anhydride and aniline as raw material, it is characterized in that comprising the following steps successively:
(1) acidylate: maleic anhydride and aniline are carried out to acylation reaction in methyl iso-butyl ketone (MIBK) or diacetone alcohol, reaction temperature is 20-60 ℃, reaction time is 1-3h, obtain the acid of N-phenyl maleimide, wherein the mol ratio of maleic anhydride and aniline is 1-1.3:1, and the mass ratio of maleic anhydride and methyl iso-butyl ketone (MIBK) or diacetone alcohol is 1:2-6;
(2) cyclodehydration: adopt the solid-carrying type non-toxic catalyst described in claim 1 to obtain N-phenylmaleimide crude product 100-120 ℃ of temperature through the cyclization of 3-6h the N-phenyl maleimide acid obtaining in step (1), wherein solid-carrying type non-toxic catalyst accounts for the 1-25% of N-phenyl maleimide acid quality; Described solid-carrying type non-toxic catalyst is take porous zeolite molecular sieve as carrier, in the aqueous solution of immersion titanium organic phosphine chelate or the aqueous solution of zirconium organic phosphine chelate or the aqueous solution of hafnium organic phosphine chelate, flood 6-10 hour, after reaction bonding, at 60-120 ℃, be dried 3-6 hour, roasting 4-6 hour at 300-600 ℃ again, be prepared from, described porous zeolite molecular sieve is one or more mixing in Na type zeolite, H type zeolite, X-type zeolite, y-type zeolite, zeolite beta and A type zeolite;
(3) recrystallization: the N-phenylmaleimide crude product of gained in step (2) is recrystallized in non-toxic alcohol kind solvent, obtains N-phenylmaleimide sterling.
6. a kind of method of applying the synthetic N-phenylmaleimide of solid-carrying type non-toxic catalyst according to claim 5, is characterized in that: the 1-16% that accounts for N-phenyl maleimide acid quality in step (2) for the consumption of the solid-carried catalyst of cyclization process.
7. a kind of method of applying the synthetic N-phenylmaleimide of solid-carrying type non-toxic catalyst according to claim 5, it is characterized in that: in step (3) recrystallization process, described non-toxic alcohol kind solvent is ethanol or propyl alcohol or isopropyl alcohol, and the mass ratio of non-toxic alcohol kind solvent and N-phenylmaleimide crude product is 5-10:1.
8. application rights requires a method for the synthetic N-phenyl substituted maleimide amine of the solid-carrying type non-toxic catalyst described in 1, take maleic anhydride and anil as raw material, it is characterized in that comprising the following steps successively:
(1) acidylate: maleic anhydride and anil are carried out to acylation reaction in methyl iso-butyl ketone (MIBK) or diacetone alcohol; reaction temperature is 20-60 ℃; reaction time is 1-3h; obtain N-phenyl and replace maleamic acid; wherein the mol ratio of maleic anhydride and anil is 1-1.3:1, and the mass ratio of maleic anhydride and methyl iso-butyl ketone (MIBK) or diacetone alcohol is 1:2-6
(2) cyclodehydration: the N-phenyl obtaining in step (1) is replaced to maleamic acid and adopt solid-carrying type non-toxic catalyst to obtain N-phenyl substituted maleimide amine crude product 100-120 ℃ of temperature through the cyclization of 3-6h, wherein solid-carrying type non-toxic catalyst accounts for the 1-25% that N-phenyl replaces maleamic acid quality; Described solid-carrying type non-toxic catalyst is take porous zeolite molecular sieve as carrier, in the aqueous solution of immersion titaniferous organic phosphine chelate or zirconium organic phosphine chelate or hafnium organic phosphine chelate, flood 6-10 hour, after reaction bonding, at 60-120 ℃, be dried 3-6 hour, roasting 4-6 hour at 300-600 ℃ again, be prepared from, described porous zeolite molecular sieve is one or more mixing in Na type zeolite, H type zeolite, X-type zeolite, y-type zeolite, zeolite beta and A type zeolite;
(3) recrystallization: the N-phenyl substituted maleimide amine crude product of gained in step (2) is recrystallized in non-toxic alcohol kind solvent, obtains N-phenyl substituted maleimide amine sterling.
9. a kind of method of applying the synthetic N-phenyl substituted maleimide amine of solid-carrying type non-toxic catalyst according to claim 8, it is characterized in that: in step (3) recrystallization process, described non-toxic alcohol kind solvent is ethanol or propyl alcohol or isopropyl alcohol, and the mass ratio of non-toxic alcohol kind solvent and N-phenyl substituted maleimide amine crude product is 5-10:1.
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