CN107739435A - A kind of high steric-hindrance amino Schiff base zinc composition catalyst for synthesizing polycyclohexene - Google Patents
A kind of high steric-hindrance amino Schiff base zinc composition catalyst for synthesizing polycyclohexene Download PDFInfo
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- CN107739435A CN107739435A CN201711033948.7A CN201711033948A CN107739435A CN 107739435 A CN107739435 A CN 107739435A CN 201711033948 A CN201711033948 A CN 201711033948A CN 107739435 A CN107739435 A CN 107739435A
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- ethane
- bis
- diimine
- polycyclohexene
- hydroxybenzene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/20—General preparatory processes
- C08G64/32—General preparatory processes using carbon dioxide
- C08G64/34—General preparatory processes using carbon dioxide and cyclic ethers
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C249/02—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of compounds containing imino groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/64—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by introduction of functional groups containing oxygen only in singly bound form
Abstract
The invention discloses a kind of high steric-hindrance amino Schiff base zinc composition catalyst for synthesizing polycyclohexene, the catalyst is 1,2 two(Adjacent salicylal diimine p-hydroxybenzene)Ethane Zn complex, the present invention prepare 1,2 two(Adjacent salicylal diimine p-hydroxybenzene)Ethane Zn complex is a kind of schiff bases complex with high steric-hindrance amino, can effectively be catalyzed the copolyreaction of carbon dioxide and cyclohexene oxide, concretely comprise the following steps:Cyclohexene oxide and above-mentioned catalyst are added in autoclave, then pass to 2 ~ 5MPa carbon dioxide, mechanical agitation, 6 ~ 36h is reacted under conditions of 80 ~ 150 DEG C, cooling, pouring into chloroform dissolves polymer, being added dropwise in methanol makes polymer Precipitation, dry polycyclohexene.Present invention catalytic efficiency under above-mentioned reaction condition is up to 204g polycyclohexenes/g catalyst, and makrolon molar content is more than 90% in copolymer.
Description
Technical field
The present invention relates to a kind of new 1,2- bis-(O- salicylal diimine-p-hydroxybenzene)Ethane zinc is as dioxy
Change carbon and cyclohexene oxide copolyreaction prepares the catalyst of polycyclohexene.
Background technology
With the quickening of countries in the world process of industrialization, population increases rapidly, to the need of the resources such as coal, oil, natural gas
Ask increasing, and a large amount of consumption of these non-renewable resources, energy shortage is not only caused, and lead because of burning and exhausting
Cause atmosphere pollution and " greenhouse effects ".The comprehensive utilization of carbon dioxide is imperative, is for polymer by carbon dioxide transitions
A kind of effective solution route.The fatty poly-ester carbonate that carbon dioxide is copolymerized preparation with epoxide contains fat
Fat race carbonic ester chain link, it is a kind of Biodegradable material, a part of conventional plastic can be substituted and used, contribute to reduction can not
White pollution caused by degradative plastics.
In the twentieth century later stage, auspicious equality people has found that aliphatic can be prepared by oxirane and carbon dioxide addition reaction on well
Makrolon, cause the very big research interest of people quickly.Conventional epoxide is oxirane, expoxy propane, oxidation ring
Hexene etc., conventional catalyst have diethyl zinc catalyst system, zinc carboxylate catalyst system, rare-earth catalysis system, Schiff base metal
Complex, double metal cyanide (DMC) catalyst system and catalyzing etc..In polymerization process, due to thermodynamic stability and inertia, only make two
Carbonoxide activates, and is possible to utilize carbon dioxide synthetic polymer, but many catalyst can only urge at present in a mild condition
Change both coupling reaction generation cyclic carbonates, and other catalyst generate polymer and cyclic carbonate simultaneously, exist mostly
While catalysis generation polymer, cyclic carbonate is more or less generated.The cheap practicality of exploitation, high catalytic efficiency, selectivity are good
Catalyst to improve polymerization yield rate and reaction is carried out under conditions of milder, be the main heat of current such research
Point.
Schiff bases complex is valued by people as carbon dioxide and the catalyst of epoxide copolyreaction
And have compared with in-depth study, such as the metal complex catalyzed systems of Salen, beta-diimine zinc catalyst system and catalyzing etc., most of kind
Class prepares complicated, cost height, or strict to ratio requirement, adds the cost of production application, and have impact on urging for catalyst
Change effect.
The content of the invention
For problems of the prior art, the present invention provides a kind of high steric-hindrance amino Schiff for synthesizing polycyclohexene
Alkali Zn complex catalyst, 1,2- bis- prepared by the present invention(O- salicylal diimine-p-hydroxybenzene)Ethane Zn complex
It is a kind of schiff bases complex with high steric-hindrance amino, can be effectively catalyzed the copolyreaction of carbon dioxide and cyclohexene oxide.
In order to solve the above technical problems, the present invention uses following technical scheme:
A kind of high steric-hindrance amino Schiff base zinc composition catalyst for synthesizing polycyclohexene, the catalyst is 1,2- bis-(O- water
Poplar aldehyde diimine-p-hydroxybenzene)Ethane Zn complex, its structural formula are。
The 1,2- bis-(O- salicylal diimine-p-hydroxybenzene)The preparation method of ethane Zn complex is as follows:
(1)1,2- bis-(O- salicylide)The preparation of ethane:The NaOH aqueous solution is added to the mixing of salicylide and glycol dibromide
In thing, ebuillition of heated 5h, room temperature is cooled to, isolates organic phase, with 10wt%NaOH aqueous cleaning organic phases, afterwards with nothing
Water MgSO4Drying, the cool overnight at 4 DEG C, 1,2- bis- will be obtained after the solid filtering of precipitation, drying(O- salicylide)Ethane;
(2)1,2- bis-(O- salicylal diimine-p-hydroxybenzene)The preparation of ethane part:By 1,2- bis-(O- salicylide)
Ethane and p-aminophenol are dissolved in ethanol, are stirred and are reacted 6h at a reflux temperature, are cooled to room temperature afterwards, filtering precipitation, are done
1,2- bis- is obtained after dry(O- salicylal diimine-p-hydroxybenzene)Ethane part,
(3)1,2- bis-(O- salicylal diimine-p-hydroxybenzene)The preparation of ethane Zn complex:Weigh 1,2- bis-(It is o-
Salicylal diimine-p-hydroxybenzene)Ethane part is put in the there-necked flask under nitrogen protection, and it is molten to add toluene with syringe
Solution, the lower diethyl zinc toluene solution for adding 10wt% of ice salt bath cooling, stirs 1h, removes ice salt bath, continue to stir at room temperature
1h, obtain 1,2- bis-(O- salicylal diimine-p-hydroxybenzene)Ethane Zn complex catalyst.
The step(1)The mol ratio of middle salicylide and glycol dibromide is 2:1.
The step(2)Middle 1,2- bis-(O- salicylide)The mol ratio of ethane and p-aminophenol is 1:2.
The step(3)Middle 1,2- bis-(O- salicylal diimine-p-hydroxybenzene)Ethane part and diethyl zinc
Mol ratio is 1:1.
Carbon dioxide is catalyzed using the high steric-hindrance amino Schiff base zinc composition catalyst of described synthesis polycyclohexene
The method that polycyclohexene is prepared with cyclohexene oxide copolyreaction, step are as follows:
Cyclohexene oxide and 1,2- bis-(O- salicylal diimine-p-hydroxybenzene)Ethane Zn complex catalyst is added to
In advance through in the dried autoclave of high-temperature vacuum, then passing to 2 ~ 5MPa carbon dioxide, mechanical agitation, 80 ~ 150
6 ~ 36h is reacted under conditions of DEG C, after polymerisation terminates, reactor is placed in water cooled down immediately, release remaining dioxy
Change carbon, pouring into chloroform dissolves polymer, then takes out polymer solution, is added dropwise in methanol, while agitated methanol, makes polymerization
Thing Precipitation, vacuum drying, obtains fatty poly-ester carbonate-polycyclohexene.
The 1,2- bis-(O- salicylal diimine-p-hydroxybenzene)Ethane Zn complex catalyst and cyclohexene oxide
Mass ratio be 1:100~500.
Polymerizate is characterized using infrared spectrum and nucleus magnetic hydrogen spectrum.Polymer each characteristic peak in infrared spectrum
Ownership it is as follows:1459,1375,3001 cm-1(CH3);786,1488,2893 cm-1(CH2);2869 cm-1, 1338 cm-1
(CH);1750cm-1(C=O);1249 cm-1(C-O)。1748cm-1With 1256 cm-1The two characteristic absorption peaks demonstrate gained
The presence of carbonate unit on main polymer chain.Nucleus magnetic hydrogen spectrum (400MHz, CDCl3):[m, the CH (CO of δ 4.623)], 4.1 [m,
CH2(CO3)], 3.42 [CH2(O) and CH (O)], 1.39 (d, CH3)。
The present invention is catalyzed carbon dioxide and cyclohexene oxide copolyreaction, catalytic efficiency highest under above-mentioned reaction condition
Reach 204g polycyclohexenes/g catalyst, makrolon molar content is more than 90% in copolymer.
The present invention is prepared for a kind of novel high-level resistance Schiff base zinc composition catalyst, for being catalyzed carbon dioxide and oxidation
Cyclohexene copolyreaction can obtain high catalytic efficiency.
Embodiment
With reference to specific embodiment, the present invention will be further described.It should be understood that following examples are merely to illustrate this
Invention can make one not for limitation the scope of the present invention, the person skilled in the art in the field according to the content of foregoing invention
A little nonessential modifications and adaptations.
Embodiment 1
The 1,2- bis- of the present embodiment(O- salicylal diimine-p-hydroxybenzene)The preparation method of ethane Zn complex:
(1)1,2- bis-(O- salicylide)The preparation of ethane
By NaOH(11.25g)It is dissolved in water(78mL)Solution be slowly added into the salicylide of boiling(2.44g 0.02mol)With 1,
2- Bromofumes(1.88g 0.01mol)Mixture in, ebuillition of heated 5h, be cooled to room temperature, isolate organic phase, use
10wt%NaOH(20mL)Aqueous cleaning organic phase, afterwards with anhydrous MgSO4Dry, the cool overnight at 4 DEG C, by precipitation
Solid filters out, and is dried in vacuo in vacuum drying chamber, obtains 1,2- bis-(O- salicylide)Ethane;
(2)1,2- bis-(O- salicylal diimine-p-hydroxybenzene)The preparation of ethane part
Weigh 1,2- bis-(O- salicylide)Ethane(2.7g, 0.01mol)And p-aminophenol(2.18g, 0.02mol), it is dissolved in second
In alcohol, stir and react 6h at a reflux temperature, be cooled to room temperature afterwards, filtering precipitation, dry.Obtain 1,2- bis-(O- bigcatkin willow
Aldehyde diimine-p-hydroxybenzene)Ethane part;Structural formula is as follows:
Structural characterization is carried out to part:1H NMR (400 MHz, CDCl3): δ 4.3(s, 4H, -CH2), 6.6~7.9(m,
16H, aromatic H), 8.3(s, 2H, -CH), 9.4(s, 2H, -OH);
(3)1,2- bis-(O- salicylal diimine-p-hydroxybenzene)The preparation of ethane Zn complex
Weigh 1,2- bis-(O- salicylal diimine-p-hydroxybenzene)Ethane part(4.52g, 0.01mol)It is put in nitrogen guarantor
In there-necked flask under shield, toluene is added with syringe(10mL)Dissolving, the lower diethyl zinc toluene for adding 10wt% of ice salt bath cooling
Solution(1.235g containing diethyl zinc, 0.01mol), 1h is stirred, removes ice salt bath, continues to stir 1h at room temperature, obtains 1,2- bis-
(O- salicylal diimine-p-hydroxybenzene)Ethane Zn complex.
Embodiment 2
The present embodiment utilizes 1,2- bis-(O- salicylal diimine-p-hydroxybenzene)Ethane Zn complex be catalyzed carbon dioxide with
The step of cyclohexene oxide copolyreaction, is as follows:
10g cyclohexene oxides and 0.1g 1,2- bis-(O- salicylal diimine-p-hydroxybenzene)Ethane Zn complex adds
To in advance through in the dried autoclave of high-temperature vacuum, then passing to 2MPa carbon dioxide, mechanical agitation, at 130 DEG C
At a temperature of, 6h is reacted, after polymerisation terminates, reactor is placed in water cooled down immediately, slowly released from gas feed mouth
Remaining carbon dioxide, pouring into chloroform dissolves polymer, takes out polymer solution, is added dropwise in methanol, while agitated methanol,
Make polymer Precipitation, be dried in vacuo.Polycyclohexene 7.4g is obtained, makrolon molar content is 92%.
Embodiment 3
The present embodiment utilizes 1,2- bis-(O- salicylal diimine-p-hydroxybenzene)Ethane Zn complex be catalyzed carbon dioxide with
The step of cyclohexene oxide copolyreaction, is as follows:
50g cyclohexene oxides and 0.1g 1,2- bis-(O- salicylal diimine-p-hydroxybenzene)Ethane Zn complex adds
To in advance through in the dried autoclave of high-temperature vacuum, then passing to 4MPa carbon dioxide, mechanical agitation, at 120 DEG C
At a temperature of, 20h is reacted, after polymerisation terminates, reactor is placed in water cooled down immediately, slowly released from gas feed mouth
Remaining carbon dioxide, pouring into chloroform dissolves polymer, takes out polymer solution, is added dropwise in methanol, while agitated methanol,
Make polymer Precipitation, be dried in vacuo to obtain polycyclohexene 20.4g, makrolon molar content is 95%.
Embodiment 4
The present embodiment utilizes 1,2- bis-(O- salicylal diimine-p-hydroxybenzene)Ethane Zn complex be catalyzed carbon dioxide with
The step of cyclohexene oxide copolyreaction, is as follows:
30g cyclohexene oxides and 0.1g 1,2- bis-(O- salicylal diimine-p-hydroxybenzene)Ethane Zn complex adds
To in advance through in the dried autoclave of high-temperature vacuum, then passing to 5MPa carbon dioxide, mechanical agitation, at 150 DEG C
At a temperature of, 6h is reacted, after polymerisation terminates, reactor is placed in water cooled down immediately, slowly released from gas feed mouth
Remaining carbon dioxide, pouring into chloroform dissolves polymer, takes out polymer solution, is added dropwise in methanol, while agitated methanol,
Make polymer Precipitation, be dried in vacuo to obtain polycyclohexene 15.82g, makrolon molar content is 97%.
Embodiment 5
The present embodiment utilizes 1,2- bis-(O- salicylal diimine-p-hydroxybenzene)Ethane Zn complex be catalyzed carbon dioxide with
The step of cyclohexene oxide copolyreaction, is as follows:
20g cyclohexene oxides and 0.1g 1,2- bis-(O- salicylal diimine-p-hydroxybenzene)Ethane Zn complex adds
To in advance through in the dried autoclave of high-temperature vacuum, then passing to 3MPa carbon dioxide, mechanical agitation, in 80 DEG C of bars
Under part, 36h is reacted, after polymerisation terminates, reactor is placed in water cooled down immediately, slowly released from gas feed mouth surplus
Remaining carbon dioxide, pouring into chloroform dissolves polymer, takes out polymer solution, is added dropwise in methanol, while agitated methanol, makes
Polymer Precipitation, is dried in vacuo to obtain polycyclohexene 11.8g, and makrolon molar content is 91%.
The general principle and principal character and advantages of the present invention of the present invention has been shown and described above.The skill of the industry
For art personnel it should be appreciated that the present invention is not limited to the above embodiments, described in above-described embodiment and specification is explanation
The principle of the present invention, without departing from the spirit and scope of the present invention, various changes and modifications of the present invention are possible, these
Changes and improvements all fall within the protetion scope of the claimed invention.The claimed scope of the invention by appended claims and
Its equivalent thereof.
Claims (7)
- A kind of 1. high steric-hindrance amino Schiff base zinc composition catalyst for synthesizing polycyclohexene, it is characterised in that:The catalyst is 1, 2- bis-(O- salicylal diimine-p-hydroxybenzene)Ethane Zn complex, its structural formula are。
- 2. the high steric-hindrance amino Schiff base zinc composition catalyst of synthesis polycyclohexene according to claim 1, it is special Sign is:The 1,2- bis-(O- salicylal diimine-p-hydroxybenzene)The preparation method of ethane Zn complex is as follows:(1)1,2- bis-(O- salicylide)The preparation of ethane:The NaOH aqueous solution is added to the mixing of salicylide and glycol dibromide In thing, ebuillition of heated 5h, room temperature is cooled to, isolates organic phase, with 10wt%NaOH aqueous cleaning organic phases, afterwards with nothing Water MgSO4Drying, the cool overnight at 4 DEG C, 1,2- bis- will be obtained after the solid filtering of precipitation, drying(O- salicylide)Ethane;(2)1,2- bis-(O- salicylal diimine-p-hydroxybenzene)The preparation of ethane part:By 1,2- bis-(O- salicylide) Ethane and p-aminophenol are dissolved in ethanol, are stirred and are reacted 6h at a reflux temperature, are cooled to room temperature afterwards, filtering precipitation, are done 1,2- bis- is obtained after dry(O- salicylal diimine-p-hydroxybenzene)Ethane part;(3)1,2- bis-(O- salicylal diimine-p-hydroxybenzene)The preparation of ethane Zn complex:Weigh 1,2- bis-(It is o- Salicylal diimine-p-hydroxybenzene)Ethane part is put in the there-necked flask under nitrogen protection, and it is molten to add toluene with syringe Solution, the lower diethyl zinc toluene solution for adding 10wt% of ice salt bath cooling, stirs 1h, removes ice salt bath, continue to stir at room temperature 1h, obtain 1,2- bis-(O- salicylal diimine-p-hydroxybenzene)Ethane Zn complex catalyst.
- 3. the high steric-hindrance amino Schiff base zinc composition catalyst of synthesis polycyclohexene according to claim 1, it is special Sign is:The step(1)The mol ratio of middle salicylide and glycol dibromide is 1:1.
- 4. the high steric-hindrance amino Schiff base zinc composition catalyst of synthesis polycyclohexene according to claim 1, it is special Sign is:The step(2)Middle 1,2- bis-(O- salicylide)The mol ratio of ethane and p-aminophenol is 1:2.
- 5. the high steric-hindrance amino Schiff base zinc composition catalyst of synthesis polycyclohexene according to claim 1, it is special Sign is:The step(3)Middle 1,2- bis-(O- salicylal diimine-p-hydroxybenzene)Ethane part and diethyl zinc rub Your ratio is 1:1.
- 6. utilize the high steric-hindrance amino Schiff base zinc composition catalyst catalysis two of the synthesis polycyclohexene described in claim 1 The method that carbonoxide prepares polycyclohexene with cyclohexene oxide copolyreaction, it is characterised in that step is as follows:Cyclohexene oxide and 1,2- bis-(O- salicylal diimine-p-hydroxybenzene)Ethane Zn complex is added to prior warp In the dried autoclave of high-temperature vacuum, 2 ~ 5MPa carbon dioxide, mechanical agitation, in 80 ~ 150 DEG C of bar are then passed to 6 ~ 36h is reacted under part, after polymerisation terminates, reactor is placed in water cooled down immediately, slowly release remaining titanium dioxide Carbon, pouring into chloroform dissolves polymer, then takes out polymer solution, is added dropwise in methanol, while agitated methanol, makes polymer Precipitation, vacuum drying, obtains polycyclohexene.
- 7. according to claim 6 urged using the high steric-hindrance amino Schiff base zinc composition catalyst for synthesizing polycyclohexene Change the method that carbon dioxide prepares polycyclohexene with cyclohexene oxide copolyreaction, it is characterised in that:The 1,2- bis- (O- salicylal diimine-p-hydroxybenzene)The mass ratio of ethane Zn complex catalyst and cyclohexene oxide is 1:100~ 500。
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