CN110483755A - A method of preparing polyethylene glycol succinate - Google Patents
A method of preparing polyethylene glycol succinate Download PDFInfo
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- CN110483755A CN110483755A CN201910757020.6A CN201910757020A CN110483755A CN 110483755 A CN110483755 A CN 110483755A CN 201910757020 A CN201910757020 A CN 201910757020A CN 110483755 A CN110483755 A CN 110483755A
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- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
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- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
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Abstract
The present invention discloses a kind of method for preparing polyethylene glycol succinate, belongs to polymeric material field.This method is, using the double-component catalyst system being made of schiff base metal complex and quaternary ammonium salt, to synthesize poly glycol ester through polymerisation in solution using maleic anhydride and ethylene oxide as raw material；Then by the method for catalytic hydrogenation, polyethylene glycol succinate is converted by poly glycol ester.Preparation method proposed by the present invention has reaction condition mild, and product polyethylene glycol succinate molecular weight is controllable, and the advantages that narrowly distributing.
Description
Technical field
The invention belongs to polymeric material fields, and in particular to a method of prepare polyethylene glycol succinate.
Background technique
Polyolefin is widely used since it has excellent performance cheap with price.But the type synthetic material is difficult to degrade,
Have become the contemporary primary raw material for causing white pollution.Therefore, the macromolecule of biological degradability is developed by countries in the world weight
Depending on.Polyethylene glycol succinate is a kind of macromolecule with biological degradability, mechanical property and low density polyethylene (LDPE) and isotactic
Polypropylene is close, and its crystal property is good, facilitates processing.The polyethylene glycol succinate being commercialized at present is mainly by fourth two
Acid or dimethyl succinate are synthesized with the method that ethylene glycol carries out melt polycondensation or transesterification.Both methods is directed to high temperature height
The harshness reaction condition such as vacuum, the molecular weight distribution of the larger and synthesized polyethylene glycol succinate of energy consumption are wide.
Summary of the invention
To solve the above problems, the present invention provides a kind of new method for preparing polyethylene glycol succinate, Malaysia is first passed through
Acid anhydrides and ethylene oxide alternating copolymerization prepare poly glycol ester, then synthesize poly-succinic ethylene glycol to its catalytic hydrogenation
Ester is realized and prepares molecular weight in a mild condition controllably and the polyethylene glycol succinate of narrow molecular weight distribution.
To achieve the goals above, The technical solution adopted by the invention is as follows:
A method of polyethylene glycol succinate being prepared, using maleic anhydride and ethylene oxide as raw material, using by Schiff
The double-component catalyst system of alkali metal complex and quaternary ammonium salt composition synthesizes poly glycol ester through polymerisation in solution；Then
By the method for catalytic hydrogenation, polyethylene glycol succinate is converted by poly glycol ester.
The molecular weight of poly glycol ester is 3000~500000g/mol, and molecular weight distribution is 1.1~2.5.
In used double-component catalyst system, the structure of schiff base metal complex is as follows:
In formula:
M is Co3+、Cr3+Or Al3+；
X is Cl-1、NO3 -1、CH3COO-1、ClO4 -1、BF4 -1、BPh4 -1、N3 -1；
R1And R2For H, C1~C6Alkyl, C1~C6Alkoxy, F, Cl, Br or NO2Group, R1With R2It is identical or different.
Quaternary ammonium salt is selected from tetramethyl ammonium chloride, etamon chloride, tetraethylammonium bromide, tetraethyl ammonium iodide, four positive third
Ammonium chloride, tetra-n-butyl ammonium fluoride, benzyltriethylammoinium chloride, benzyl tripropyl ammonium chloride, three n-butylmagnesium chloride ammonium of benzyl,
Three normal-butyl ammonium bromide of benzyl, hexadecyltrimethylammonium chloride, dodecyl trimethyl ammonium chloride, bis- (dihalotriphenylphosphoranes bases)
Ammonium nitrate, bis- (dihalotriphenylphosphoranes base) ammonium acetates or bis- (dihalotriphenylphosphoranes base) ammonium chlorides.
The molar ratio of schiff base metal complex and quaternary ammonium salt is 1:0.5~10, preferably 1:1.
Maleic anhydride and molar ratio are 1:1~1:10, preferably 1:3；Ethylene oxide and schiff base metal cooperate
The molar ratio of object is 100:1~10000:1, preferably 900:1.
The temperature of solution polymerization be 0~120 DEG C, preferably 25 DEG C, the reaction time be 0.1~for 24 hours, by maleic anhydride
Depending on conversion ratio；Used solvent is selected from toluene, dimethylbenzene, trichloro-benzenes, tetrahydrofuran, methylene chloride or chloroform, epoxy second
The molar ratio of alkane and solvent is 1:0.5~1:10.
The catalytic hydrogenation reaction of poly glycol ester is carried out under solution, solvent is selected from toluene, dimethylbenzene, chlorine
The mass ratio of benzene, tetrahydrofuran, methylene chloride or chloroform, poly glycol ester and solvent is 1:10~1:400, and hydrogen is added to urge
Agent is the catalyst based on Pd or Ni；Hydrogen Vapor Pressure is 0.1~10MPa, preferably 4MPa；The temperature of catalytic hydrogenation is 0
~120 DEG C, preferably 25 DEG C；Reaction time is 0.1~36h.
Compared with the prior art, the present invention it is significant the utility model has the advantages that
1, the method that the present invention prepares polyethylene glycol succinate does not need the operating condition of high temperature high vacuum, can be in room temperature
Deng carrying out under the conditions of mild.
2, polyethylene glycol succinate molecular weight prepared by the present invention is controllable, and narrow molecular weight distribution.
Detailed description of the invention
Fig. 1 is poly glycol ester in embodiment 11H NMR figure.
Fig. 2 is polyethylene glycol succinate in embodiment 11H NMR figure.
Specific embodiment
In order to be specifically described the present invention, with reference to the accompanying drawing and specific embodiment carries out technical solution of the present invention
It is described in detail.
In the present invention, the serial number such as following formula of major catalyst (schiff base metal complex) in used dual-component catalyst
Shown in, co-catalyst is quaternary ammonium salt.
Embodiment 1
25mL stainless steel cauldron equipped with magneton is vacuumized and is cooled to room temperature to it in 130 DEG C of dry 12h or more, punching
Enter nitrogen to prepare to use.It is added into reaction kettle and contains maleic anhydride, major catalyst 1a and the bis- (dihalotriphenylphosphoranes of co-catalyst
Base) ammonium acetate, methylene chloride dissolution is added, ethylene oxide, major catalyst 1a, co-catalyst, maleic anhydride, epoxy is then added
The molar ratio of ethane and methylene chloride is 1/0.5/300/600/300.Reaction kettle is put into 0 DEG C of ice bath and is reacted, after 24 hours,
The complete ethylene oxide of unreacted in reaction system is drained with solvent.Resulting crude product is dissolved in methylene chloride, then dropwise
Methanol, which is added, is precipitated polymer.It is vacuum dried to obtain pure poly ethylene glycol after repeating this process 3~5 times
Ester, GPC test display molecular weight is 5200g/mol, molecular weight distribution 1.23.Take the resulting poly glycol ester of 0.4g
It is added in autoclave, the dissolution of 4g methylene chloride is added, Pd/C catalyst is then added, and be filled with 10MPa hydrogen, react 5 in 0 DEG C
Hour.Kettle is opened, Pd/C is filtered out with filter paper, then drains filtrate decompression,1H NMR shows that double bond is all hydrogenated,
Poly glycol ester is hydrogenated to polyethylene glycol succinate, specific as depicted in figs. 1 and 2.
Embodiment 2
25mL stainless steel cauldron equipped with magneton is vacuumized and is cooled to room temperature to it in 130 DEG C of dry 12h or more, punching
Enter nitrogen to prepare to use.It is added into reaction kettle and contains maleic anhydride, major catalyst 1a and the bis- (dihalotriphenylphosphoranes of co-catalyst
Base) ammonium acetate, chloroform dissolution is added, ethylene oxide, major catalyst 1a, co-catalyst, maleic anhydride, ethylene oxide is then added
Molar ratio with chloroform is 1/1/300/900/900.Reaction kettle is put into 25 DEG C of oil baths and is reacted, after 2 hours, by reaction system
The complete ethylene oxide of middle unreacted is drained with solvent.Resulting crude product is dissolved in methylene chloride, ethyl alcohol, which is then added dropwise, to be made
Polymer is precipitated.It is vacuum dried to obtain pure poly glycol ester, GPC test after repeating this process 3~5 times
Display molecular weight is 10200g/mol, molecular weight distribution 1.25.Take the resulting poly glycol ester of 0.3g that high pressure is added
In kettle, the dissolution of 10g chloroform is added, Pd/C catalyst is then added, and be filled with 5MPa hydrogen, is reacted 8 hours at 25 DEG C.It opens
Pd/C is filtered out with filter paper, is then drained filtrate decompression by kettle,1H NMR shows that double bond is all hydrogenated, poly- Malaysia
Sour glycol ester is hydrogenated to polyethylene glycol succinate.
Embodiment 3
25mL stainless steel cauldron equipped with magneton is vacuumized and is cooled to room temperature to it in 130 DEG C of dry 12h or more, punching
Enter nitrogen to prepare to use.It is added into reaction kettle and contains maleic anhydride, major catalyst 1b and the bis- (dihalotriphenylphosphoranes of co-catalyst
Base) ammonium nitrate, chloroform dissolution is added, ethylene oxide, major catalyst 1b, co-catalyst, maleic anhydride, ethylene oxide is then added
Molar ratio with chloroform is 1/2/200/600/1800.Reaction kettle is put into 50 DEG C of oil baths and is reacted, after 2 hours, by reactant
The complete ethylene oxide of unreacted is drained with solvent in system.Resulting crude product is dissolved in methylene chloride, ether is then added dropwise
Polymer is precipitated.Vacuum dried to obtain pure poly glycol ester after repeating this process 3~5 times, GPC is surveyed
Examination display molecular weight is 8300g/mol, molecular weight distribution 1.22.High pressure is added in the resulting poly glycol ester of 0.4g
In kettle, the dissolution of 160g chloroform is added, Raney's nickel catalyst is then added, and be filled with 4MPa hydrogen, is reacted 36 hours in 50 DEG C.It opens
Raney's nickel is filtered out with filter paper, then drains filtrate decompression by kettle,1H NMR shows that double bond is all hydrogenated, poly- horse
Carry out sour glycol ester and is hydrogenated to polyethylene glycol succinate.
Embodiment 4
25mL stainless steel cauldron equipped with magneton is vacuumized and is cooled to room temperature to it in 130 DEG C of dry 12h or more, punching
Enter nitrogen to prepare to use.It is added into reaction kettle and contains maleic anhydride, major catalyst 1b and the bis- (dihalotriphenylphosphoranes of co-catalyst
Base) ammonium nitrate, chloroform dissolution is added, ethylene oxide, major catalyst 1b, co-catalyst, maleic anhydride, ethylene oxide is then added
Molar ratio with chloroform is 1/3/300/900/1800.Reaction kettle is put into 70 DEG C of oil baths and is reacted, after 5 hours, by reactant
The complete ethylene oxide of unreacted is drained with solvent in system.Resulting crude product is dissolved in methylene chloride, ether is then added dropwise
Polymer is precipitated.Vacuum dried to obtain pure poly glycol ester after repeating this process 3~5 times, GPC is surveyed
Examination display molecular weight is 5600g/mol, molecular weight distribution 1.24.High pressure is added in the resulting poly glycol ester of 0.4g
In kettle, the dissolution of 16g chloroform is added, Pd/C catalyst is then added, and be filled with 2MPa hydrogen, is reacted 3 hours in 80 DEG C.Kettle is opened,
Pd/C is filtered out with filter paper, then drains filtrate decompression,1H NMR shows that double bond is all hydrogenated, poly second
Diol ester is hydrogenated to polyethylene glycol succinate.
Embodiment 5
25mL stainless steel cauldron equipped with magneton is vacuumized and is cooled to room temperature to it in 130 DEG C of dry 12h or more, punching
Enter nitrogen to prepare to use.It is added into reaction kettle and contains maleic anhydride, major catalyst 1c and the bis- (dihalotriphenylphosphoranes of co-catalyst
Base) ammonium acetate, chloroform dissolution is added, ethylene oxide, major catalyst 1c, co-catalyst, maleic anhydride, ethylene oxide is then added
Molar ratio with chloroform is 1/5/300/900/900.Reaction kettle is put into 50 DEG C of oil baths and is reacted, after 2 hours, by reaction system
The complete ethylene oxide of middle unreacted is drained with solvent.Resulting crude product is dissolved in methylene chloride, ether, which is then added dropwise, to be made
Polymer is precipitated.It is vacuum dried to obtain pure poly glycol ester, GPC test after repeating this process 3~5 times
Display molecular weight is 6520g/mol, molecular weight distribution 1.18.Autoclave is added in the resulting poly glycol ester of 0.4g
In, the dissolution of 16g chloroform is added, Raney's nickel catalyst is then added, holding reaction system Hydrogen Vapor Pressure is 0.1MPa, anti-in 50 DEG C
It answers 24 hours.Kettle is opened, Raney's nickel is filtered out with filter paper, then drains filtrate decompression,1H NMR shows double bond all
It is hydrogenated, poly glycol ester is hydrogenated to polyethylene glycol succinate.
Embodiment 6
25mL stainless steel cauldron equipped with magneton is vacuumized and is cooled to room temperature to it in 130 DEG C of dry 12h or more, punching
Enter nitrogen to prepare to use.It is added into reaction kettle and contains maleic anhydride, major catalyst 1c and the bis- (dihalotriphenylphosphoranes of co-catalyst
Base) ammonium acetate, chloroform dissolution is added, ethylene oxide, major catalyst 1c, co-catalyst, maleic anhydride, ethylene oxide is then added
Molar ratio with chloroform is 1/10/600/1200/1200.Reaction kettle is put into 25 DEG C of oil baths and is reacted, after 3 hours, will be reacted
The complete ethylene oxide of unreacted is drained with solvent in system.Resulting crude product is dissolved in methylene chloride, first is then added dropwise
Polymer is precipitated in alcohol.It is vacuum dried to obtain pure poly glycol ester, GPC after repeating this process 3~5 times
Test display molecular weight is 5310g/mol, molecular weight distribution 1.24.The resulting poly glycol ester of 0.4g is added high
It presses in kettle, the dissolution of 20g chlorobenzene is added, Pd/C catalyst is then added, and be filled with 4MPa hydrogen, is reacted 0.1 hour in 120 DEG C.
Kettle is opened, Pd/C is filtered out with filter paper, then drains filtrate decompression,1H NMR shows that double bond is all hydrogenated, poly- horse
Carry out sour glycol ester and is hydrogenated to polyethylene glycol succinate.
Embodiment 7
25mL stainless steel cauldron equipped with magneton is vacuumized and is cooled to room temperature to it in 130 DEG C of dry 12h or more, punching
Enter nitrogen to prepare to use.It is added into reaction kettle and contains maleic anhydride, major catalyst 1d and the bis- (dihalotriphenylphosphoranes of co-catalyst
Base) ammonium nitrate, toluene dissolution is added, is then added ethylene oxide, catalyst 1d, co-catalyst, maleic anhydride, ethylene oxide with
The molar ratio of toluene is 1/1/100/100/1000.Reaction kettle is put into 120 DEG C of oil baths and is reacted, after 0.1 hour, by reactant
The complete ethylene oxide of unreacted is drained with solvent in system.Resulting crude product is dissolved in methylene chloride, ethyl alcohol is then added dropwise
Polymer is precipitated.Vacuum dried to obtain pure poly glycol ester after repeating this process 3~5 times, GPC is surveyed
Examination display molecular weight is 7700g/mol, molecular weight distribution 1.20.High pressure is added in the resulting poly glycol ester of 0.4g
In kettle, the dissolution of 16g chloroform is added, Raney's nickel catalyst is then added, and be filled with 4MPa hydrogen, is reacted 2 hours in 40 DEG C.It opens
Raney's nickel is filtered out with filter paper, then drains filtrate decompression by kettle,1H NMR shows that double bond is all hydrogenated, poly- horse
Carry out sour glycol ester and is hydrogenated to polyethylene glycol succinate.
Embodiment 8
25mL stainless steel cauldron equipped with magneton is vacuumized and is cooled to room temperature to it in 130 DEG C of dry 12h or more, punching
Enter nitrogen to prepare to use.It is added into reaction kettle and contains maleic anhydride, major catalyst 1d and the bis- (dihalotriphenylphosphoranes of co-catalyst
Base) ammonium nitrate, methylene chloride dissolution is added, ethylene oxide, major catalyst 1d, co-catalyst, maleic anhydride, epoxy is then added
The molar ratio of ethane and methylene chloride is 1/1/1000/10000/5000.Reaction kettle is put into 25 DEG C of oil baths and is reacted, 14 hours
Afterwards, the complete ethylene oxide of unreacted in reaction system is drained with solvent.Resulting crude product is dissolved in methylene chloride, then by
Being added dropwise to methanol is precipitated polymer.It is vacuum dried to obtain pure poly second two after repeating this process 3~5 times
Alcohol ester, GPC test display molecular weight is 24100g/mol, molecular weight distribution 1.24.By the resulting poly second two of 0.4g
Alcohol ester is added in autoclave, and the dissolution of 30g chloroform is added, Pd/C catalyst is then added, and be filled with 6MPa hydrogen, reacts in 25 DEG C
12 hours.Kettle is opened, Pd/C is filtered out with filter paper, then drains filtrate decompression,1H NMR shows that double bond is all added
Hydrogen, poly glycol ester are hydrogenated to polyethylene glycol succinate.
Embodiment 9
25mL stainless steel cauldron equipped with magneton is vacuumized and is cooled to room temperature to it in 130 DEG C of dry 12h or more, punching
Enter nitrogen to prepare to use.It is added into reaction kettle and contains maleic anhydride, major catalyst 1e and the bis- (dihalotriphenylphosphoranes of co-catalyst
Base) ammonium nitrate, methylene chloride dissolution is added, ethylene oxide, major catalyst 1e, co-catalyst, maleic anhydride, epoxy is then added
The molar ratio of ethane and methylene chloride is 1/1/200/600/300.Reaction kettle is put into 25 DEG C of oil baths and is reacted, it, will after 2 hours
The complete ethylene oxide of unreacted is drained with solvent in reaction system.Resulting crude product is dissolved in methylene chloride, is then added dropwise
Entering poor solvent ether is precipitated polymer.It is vacuum dried to obtain pure poly after repeating this process 3~5 times
Glycol ester, GPC test display molecular weight is 8900g/mol, molecular weight distribution 1.19.By the resulting poly second of 0.4g
Diol ester is added in autoclave, and the dissolution of 40g chloroform is added, Pd/C catalyst is then added, and be filled with 1MPa hydrogen, in 100 DEG C
Reaction 6 hours.Kettle is opened, Pd/C is filtered out with filter paper, then drains filtrate decompression,1H NMR shows double bond whole quilts
Add hydrogen, poly glycol ester is hydrogenated to polyethylene glycol succinate.
Embodiment 10
25mL stainless steel cauldron equipped with magneton is vacuumized and is cooled to room temperature to it in 130 DEG C of dry 12h or more, punching
Enter nitrogen to prepare to use.It is added into reaction kettle and contains maleic anhydride, major catalyst 1e and the bis- (dihalotriphenylphosphoranes of co-catalyst
Base) ammonium nitrate, methylene chloride dissolution is added, ethylene oxide, major catalyst 1e, co-catalyst, maleic anhydride, epoxy is then added
The molar ratio of ethane and methylene chloride is 1/1/400/1200/1200.Reaction kettle is put into 25 DEG C of oil baths and is reacted.10 hours
Afterwards, the complete ethylene oxide of unreacted in reaction system is drained with solvent.Resulting crude product is dissolved in methylene chloride, then by
Being added dropwise to methanol is precipitated polymer.It is vacuum dried to obtain pure poly second two after repeating this process 3~5 times
Alcohol ester, GPC test display molecular weight is 14100g/mol, molecular weight distribution 1.27.By the resulting poly second two of 0.4g
Alcohol ester is added in autoclave, and the dissolution of 25g chloroform is added, Pd/C catalyst is then added, and be filled with 6MPa hydrogen, reacts in 25 DEG C
6 hours.Kettle is opened, Pd/C is filtered out with filter paper, then drains filtrate decompression,1H NMR shows that double bond is all added
Hydrogen, poly glycol ester are hydrogenated to polyethylene glycol succinate.
Embodiment 11
25mL stainless steel cauldron equipped with magneton is vacuumized and is cooled to room temperature to it in 130 DEG C of dry 12h or more, punching
Enter nitrogen to prepare to use.It is added into reaction kettle and contains maleic anhydride, major catalyst 1f and the bis- (dihalotriphenylphosphoranes of co-catalyst
Base) ammonium acetate, tetrahydrofuran dissolution is added, ethylene oxide, major catalyst 1f, co-catalyst, maleic anhydride, epoxy is then added
The molar ratio of ethane and tetrahydrofuran is 1/1/200/600/900.It will be put into 25 DEG C of oil baths and react, after 6 hours, by reactant
The complete ethylene oxide of unreacted is drained with solvent in system.Resulting crude product is dissolved in methylene chloride, methanol is then added dropwise
Polymer is precipitated.Vacuum dried to obtain pure poly glycol ester after repeating this process 3~5 times, GPC is surveyed
Examination display molecular weight is 7500g/mol, molecular weight distribution 1.20.High pressure is added in the resulting poly glycol ester of 0.4g
In kettle, the dissolution of 20g chloroform is added, Pd/C catalyst is then added, and be filled with 5MPa hydrogen, is reacted 3 hours in 80 DEG C.Kettle is opened,
Pd/C is filtered out with filter paper, then drains filtrate decompression,1H NMR shows that double bond is all hydrogenated, poly second
Diol ester is hydrogenated to polyethylene glycol succinate.
Embodiment 12
25mL stainless steel cauldron equipped with magneton is vacuumized and is cooled to room temperature to it in 130 DEG C of dry 12h or more, punching
Enter nitrogen to prepare to use.It is added into reaction kettle and contains maleic anhydride, major catalyst 1f and the bis- (dihalotriphenylphosphoranes of co-catalyst
Base) ammonium acetate, trichloro-benzenes dissolution is added, ethylene oxide, major catalyst 1f, co-catalyst, maleic anhydride, epoxy second is then added
The molar ratio of alkane and trichloro-benzenes is 1/3/300/900/900.Reaction kettle is put into 50 DEG C of oil baths and is reacted, after 2 hours, will be reacted
The complete ethylene oxide of unreacted is drained in system.Resulting crude product is dissolved in methylene chloride, methanol, which is then added dropwise, to be made to gather
Object is closed to be precipitated.Vacuum dried to obtain pure poly glycol ester after repeating this process 3~5 times, GPC test is aobvious
Show that molecular weight is 13100g/mol, molecular weight distribution 1.25.Autoclave is added in the resulting poly glycol ester of 0.4g
In, the dissolution of 10g chloroform is added, Pd/C catalyst is then added, and be filled with 4MPa hydrogen, is reacted 4 hours in 60 DEG C.Kettle is opened, is used
Filter paper filters out Pd/C, filtrate and then decompressing and extracting,1H NMR shows that double bond is all hydrogenated, poly ethylene glycol
Ester is hydrogenated to polyethylene glycol succinate.
Claims (8)
1. a kind of method for preparing polyethylene glycol succinate, which is characterized in that using maleic anhydride and ethylene oxide as raw material, adopt
With the double-component catalyst system being made of schiff base metal complex and quaternary ammonium salt, poly ethylene glycol is synthesized through polymerisation in solution
Ester；Then by the method for catalytic hydrogenation, polyethylene glycol succinate is converted by poly glycol ester；
Wherein:
The molar ratio of schiff base metal complex and quaternary ammonium salt is 1:0.5~10；
Maleic anhydride and molar ratio are 1:1~1:10；
The molar ratio of epoxy second hydrocarbon and schiff base metal complex is 100:1~10000:1；
The temperature of solution polymerization be 0~120 DEG C, the reaction time be 0.1~for 24 hours；Used solvent is selected from toluene, diformazan
The molar ratio of benzene, trichloro-benzenes, tetrahydrofuran, methylene chloride or chloroform, ethylene oxide and solvent is 1:0.5~1:10；
The catalytic hydrogenation reaction of poly glycol ester is carried out under solution, solvent be selected from toluene, dimethylbenzene, trichloro-benzenes,
The mass ratio of tetrahydrofuran, methylene chloride or chloroform, poly glycol ester and solvent is 1:10~1:400, hydrogenation catalyst
Agent is the catalyst based on Pd or Ni；Hydrogen Vapor Pressure is 0.1~10MPa；The temperature of catalytic hydrogenation is 0~120 DEG C；Reaction
Time is 0.1~36h.
2. a kind of method for preparing polyethylene glycol succinate according to claim 1, which is characterized in that used double
In component catalyst system, the structure of schiff base metal complex is as follows:
In formula:
Indicate link position；
M is Co3+、Cr3+Or Al3+；
X is Cl-1、NO3 -1、CH3COO-1、ClO4 -1、BF4 -1、BPh4 -1、N3 -1；
R1And R2For H, C1~C6Alkyl, C1~C6Alkoxy, F, Cl, Br or NO2Group, R1With R2It is identical or different；
Quaternary ammonium salt is selected from tetramethyl ammonium chloride, etamon chloride, tetraethylammonium bromide, tetraethyl ammonium iodide, four normal propyl chlorides
Change ammonium, tetra-n-butyl ammonium fluoride, benzyltriethylammoinium chloride, benzyl tripropyl ammonium chloride, three n-butylmagnesium chloride ammonium of benzyl, benzyl
Three normal-butyl ammonium bromides, hexadecyltrimethylammonium chloride, dodecyl trimethyl ammonium chloride, bis- (dihalotriphenylphosphoranes base) nitric acid
Ammonium, bis- (dihalotriphenylphosphoranes base) ammonium acetates or bis- (dihalotriphenylphosphoranes base) ammonium chlorides.
3. a kind of method for preparing polyethylene glycol succinate according to claim 1 or 2, it is characterised in that: schiff bases
The molar ratio of metal complex and quaternary ammonium salt is 1:1；
Maleic anhydride and molar ratio are 1:3；
The molar ratio of epoxy second hydrocarbon and schiff base metal complex is 900:1.
4. a kind of method for preparing polyethylene glycol succinate according to claim 1 or 2, it is characterised in that:
The temperature of solution polymerization is 25 DEG C；
The temperature of catalytic hydrogenation is 25 DEG C.
5. a kind of method for preparing polyethylene glycol succinate according to claim 3, it is characterised in that:
The temperature of solution polymerization is 25 DEG C；
The temperature of catalytic hydrogenation is 25 DEG C.
6. a kind of according to claim 1, method for preparing polyethylene glycol succinate described in 2 or 5, which is characterized in that poly- horse
The molecular weight for carrying out sour glycol ester is 3000~500000g/mol, and molecular weight distribution is 1.1~2.5.
7. a kind of method for preparing polyethylene glycol succinate according to claim 3, which is characterized in that poly second
The molecular weight of diol ester is 3000~500000g/mol, and molecular weight distribution is 1.1~2.5.
8. a kind of method for preparing polyethylene glycol succinate according to claim 4, which is characterized in that poly second
The molecular weight of diol ester is 3000~500000g/mol, and molecular weight distribution is 1.1~2.5.
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