CN107286127A - The preparation method of low acid content 1,4- dioxane -2,5- acetyl butyryls - Google Patents
The preparation method of low acid content 1,4- dioxane -2,5- acetyl butyryls Download PDFInfo
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- CN107286127A CN107286127A CN201610227806.3A CN201610227806A CN107286127A CN 107286127 A CN107286127 A CN 107286127A CN 201610227806 A CN201610227806 A CN 201610227806A CN 107286127 A CN107286127 A CN 107286127A
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- isosorbide
- dioxane
- acetyl butyryl
- nitrae
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- 239000002253 acid Substances 0.000 title claims abstract description 74
- 238000002360 preparation method Methods 0.000 title claims description 17
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 title abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 66
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 62
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 31
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 28
- 239000002904 solvent Substances 0.000 claims abstract description 19
- 239000012043 crude product Substances 0.000 claims abstract description 15
- 238000012691 depolymerization reaction Methods 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 230000035484 reaction time Effects 0.000 claims abstract description 4
- 238000005292 vacuum distillation Methods 0.000 claims abstract description 3
- 238000006116 polymerization reaction Methods 0.000 claims description 27
- 239000003054 catalyst Substances 0.000 claims description 18
- 229920000570 polyether Polymers 0.000 claims description 17
- 239000013078 crystal Substances 0.000 claims description 14
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 8
- 229910052725 zinc Inorganic materials 0.000 claims description 8
- 239000011701 zinc Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 229910052787 antimony Inorganic materials 0.000 claims description 6
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 6
- 150000004820 halides Chemical class 0.000 claims description 6
- -1 organic acid compound Chemical class 0.000 claims description 5
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- 238000009835 boiling Methods 0.000 claims description 4
- 150000002148 esters Chemical group 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 3
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 238000006482 condensation reaction Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 150000002894 organic compounds Chemical class 0.000 claims description 2
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 2
- 150000002910 rare earth metals Chemical class 0.000 claims description 2
- MWVFCEVNXHTDNF-UHFFFAOYSA-N hexane-2,3-dione Chemical group CCCC(=O)C(C)=O MWVFCEVNXHTDNF-UHFFFAOYSA-N 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 238000000034 method Methods 0.000 description 23
- 238000010792 warming Methods 0.000 description 22
- 239000010695 polyglycol Substances 0.000 description 15
- 239000007787 solid Substances 0.000 description 12
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 11
- 229950008885 polyglycolic acid Drugs 0.000 description 9
- 239000004633 polyglycolic acid Substances 0.000 description 9
- 125000000623 heterocyclic group Chemical group 0.000 description 7
- RKDVKSZUMVYZHH-UHFFFAOYSA-N 1,4-dioxane-2,5-dione Chemical compound O=C1COC(=O)CO1 RKDVKSZUMVYZHH-UHFFFAOYSA-N 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 4
- 150000000094 1,4-dioxanes Chemical class 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229920000954 Polyglycolide Polymers 0.000 description 2
- 229920001400 block copolymer Polymers 0.000 description 2
- 238000012661 block copolymerization Methods 0.000 description 2
- 125000005594 diketone group Chemical group 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- HLLSOEKIMZEGFV-UHFFFAOYSA-N 4-(dibutylsulfamoyl)benzoic acid Chemical compound CCCCN(CCCC)S(=O)(=O)C1=CC=C(C(O)=O)C=C1 HLLSOEKIMZEGFV-UHFFFAOYSA-N 0.000 description 1
- 238000002479 acid--base titration Methods 0.000 description 1
- 229920003232 aliphatic polyester Polymers 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000002775 capsule Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 239000002552 dosage form Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D319/00—Heterocyclic compounds containing six-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D319/10—1,4-Dioxanes; Hydrogenated 1,4-dioxanes
- C07D319/12—1,4-Dioxanes; Hydrogenated 1,4-dioxanes not condensed with other rings
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The present invention relates to a kind of production method of the acetyl butyryl of low acid content Isosorbide-5-Nitrae dioxane 2,5, mainly solve prior art and prepare Isosorbide-5-Nitrae dioxane 2, acid content more technical problem during 5 acetyl butyryl, the present invention is by using comprising the following steps：(1) polycondensation：Glycolic acid is subjected to polycondensation reaction, glycol acid oligomer is obtained；(2) Solution Depolymerization, after step (1), at least one solvent is added into reaction system, glycol acid oligomer and solvent is set to be formed homogeneously, raising system reaction temperature is to 230 290 DEG C, vacuum is improved simultaneously to 0.1 5KPa, mixing speed is 30 250 revs/min, glycol acid oligomer is set to occur depolymerization reaction, vacuum distillation goes out target crude product, and the reaction time is the technical scheme of 1 12 hours, preferably solve the problem, in industrialized production available for the acetyl butyryl of low acid content Isosorbide-5-Nitrae dioxane 2,5.
Description
Technical field
The present invention relates to a kind of preparation method of the low 1,4- dioxane -2,5- acetyl butyryls of acid content.
Background technology
Poly- Glycolic acid, is a kind of biodegradable linear aliphatic polyesters, because it has good biocompatibility and machine
Tool performance and it is of great interest.The material is also earliest commercialized artificial synthesized operation suture thread.Except that can make
Outside for operation suture thread, it is also applied to as drug release capsules material, gas barrier membrane material, packaging material etc..
The preparation of poly- Glycolic acid typically passes through two kinds of routes：One kind is directly prepared by raw materials melt polycondensation one-step method of Glycolic acid
Poly- Glycolic acid, but molecular weight prepared by this method is not high.Although molecular weight, material can be improved by solid-phase tack producing
Expect hue difference.Another method is that poly- glycol acid oligomer is prepared by raw material of Glycolic acid, then depolymerized oligomer prepare Isosorbide-5-Nitrae-
Dioxane -2,5- acetyl butyryl, Isosorbide-5-Nitrae-dioxane -2,5- acetyl butyryl prepares poly- Glycolic acid by being coordinated ring-opening polymerisation.This is system
The common method of standby high-molecular-weight poly Glycolic acid, and by adding molecular weight regulator, different products can be prepared, meet
Different applications need.
It can be seen that 1,4- dioxane -2,5- acetyl butyryls are the important monomers for preparing poly- Glycolic acid.Such monomer is a kind of cyclic esters
Compound, meets the easy open loop of the water capacity and resolves into linear glycol acid dimer, and further hydrolysis can form Glycolic acid (Fig. 1).Generation
Acid can turn into the catalyst of ring-opening reaction, accelerate the hydrolysis of Isosorbide-5-Nitrae-dioxane -2,5- acetyl butyryl.Thus to make as far as possible during polycondensation
Water is removed from oligomeric objects system.Although strengthening polycondensation reduces the influence of water, oligomer molecules amount can be caused to increase,
Making the viscosity of system during depolymerization increases, and have impact on glycolide from steaming in system.In order to ensure yield, than needing higher
Temperature and vacuum degree condition under react, this can also increase side reaction, while Isosorbide-5-Nitrae-dioxane -2,5- acetyl butyryl is steamed
Take more acid out of, can equally cause deleterious effect.
U.S. patent 2668162 discloses a kind of method, and it is low by melt polycondensation to prepare polyglycolic acid at 170-185 DEG C first
Polymers, is then broken into powder by glycolic acid oligomer, and 1.6-2.0kPa, in 270-285 DEG C of heating, is received under a high vacuum
Steam of the collection gained containing glycolide.The yield highest of thick glycolide can reach 93%, and the thick glycolide of gained further leads to
Cross solvent washing and multiple solvent recrystallization is purified.Experimental study has been carried out according to the method for the patent, has as a result been shown to the greatest extent
Pipe yield is higher, but acid content is higher in the Isosorbide-5-Nitrae of gained-dioxane -2,5- acetyl butyryl, and impurity content is higher.
U.S. patent 4727163 discloses a kind of method, and copolymerization is made using the polyethers with good thermal stability, in polycondensation rank
Section is added in reaction system, and Glycolic acid carries out block copolymerization with polyethers while homopolymerization, also and obtains block copolymer, most
Heating block copolymer carries out depolymerization afterwards, and yield is 67%.Method according to the patent carried out 1,4- dioxanes -2,5- oneself
The preparation of diketone.But the yield of the 1,4- dioxane -2,5- acetyl butyryls obtained by this method is relatively low.Tracing it to its cause to be
The generation of glycolide is due to that the poly- Glycolic acid oligomer end of the chain time is stung to be formed, and block copolymerization, which have impact on back, stings reaction, so as to influence
Yield.
Patent CN 101054371 discloses a kind of method, uses the glycol acid crystal of high-purity for raw material, is contracted by being dehydrated
Poly-, melt polycondensation prepares poly- glycol acid oligomer, and the oligomer of the gained high temperature melting under the catalysis of two kinds of catalyst melts
Poly-, the highest yield of thick Isosorbide-5-Nitrae-dioxane -2,5- acetyl butyryl can reach 86%.This method is extended when mentioning melt polycondensation
Reaction time and improve reaction temperature to make unreacted raw material and water try one's best removals, although water is eliminated as far as possible, solve
It is poly- that above-mentioned yield result need to can be just obtained at higher temperature and vacuum.
The patent CN1496359A of Wu Yu companies mention can using addition high boiling point polar organic solvent and solubilizer to gather
In glycol acid oligomer the problem of being easily drained with coking material is blocked up to solve reaction system.But 1,4- dioxanes -2,5- during depolymerization
Acetyl butyryl can together be steamed with high boiling organic solvent, be result in Isosorbide-5-Nitrae-dioxane -2,5- acetyl butyryl crude product and be mixed with this
Kind of solvent, the solvent in polymerization can be reaction with Isosorbide-5-Nitrae-dioxane -2,5- acetyl butyryl, if do not removed, can directly affect poly-
Glycolic acid performance.The removal of solvent adds the difficulty and production cost of refined purification.
The content of the invention
The technical problems to be solved by the invention are acid contents when prior art prepares 1,4- dioxane -2,5- acetyl butyryls
More the problem of there is provided a kind of production method of low acid content Isosorbide-5-Nitrae-dioxane -2,5- acetyl butyryl, by controlling polycondensation to conciliate
Gather to obtain reaction condition, Isosorbide-5-Nitrae-dioxane -2,5- acetyl butyryl of preparation has the advantages that acid content is low.
In order to solve the above technical problems, the present invention uses following technical scheme：A kind of low acid content 1,4- dioxanes -2,5- oneself
The preparation method of diketone, comprises the following steps：
(1) polycondensation：Glycolic acid is subjected to polycondensation reaction, glycol acid oligomer is obtained；
(2) Solution Depolymerization, after step (1), at least one solvent is added into reaction system, makes glycol acid oligomer and molten
Dosage form improves system reaction temperature to 230-290 DEG C into homogeneous, while improving vacuum to 0.1-5KPa, mixing speed is
30-250 revs/min, glycol acid oligomer is set to occur depolymerization reaction, vacuum distillation obtains low acid content Isosorbide-5-Nitrae-dioxane -2,5-
Acetyl butyryl crude product, the reaction time is 1-12 hours.
In above-mentioned technical proposal, described step (1) polycondensation preferably specifically includes following steps：A) normal pressure polycondensation, is being urged
In the presence of agent, glycol acid crystal is segmented reaction in atmospheric conditions：First stage normal pressure pre-polymerization, keeps reaction temperature to exist
Reacted 0.5~10 hour between the fusing point of Glycolic acid and the boiling point of Glycolic acid；Second stage normal pressure polycondensation, in reaction temperature
112~220 DEG C, condensation reaction or ester exchange reaction are carried out, untill anhydrous steam；B) polycondensation is depressurized, after step a,
System temperature is kept, while improving system vacuum to 0.1-5KPa, proceeds polycondensation reaction or ester exchange reaction, directly
Steamed to no water；C) strengthen polycondensation, after the stepb, keep system temperature and vacuum to continue to react 0.5-10 hours,
Obtain glycol acid oligomer.
In above-mentioned technical proposal, the catalyst be preferably the halide or the organic acid compound of tin of tin, the oxide of antimony,
The halide of antimony, the organic acid compound of antimony, the oxide of zinc, the halide of zinc, the cooperation of the organic compound of zinc or zinc
Mixture more than thing, the complex of organo-aluminum compound or aluminium, rare earth metal complex are at least one or two, catalyst
Consumption be Glycolic acid consumption 0.001-10wt%.；
In above-mentioned technical proposal, preferred mixing speed is 30-250 revs/min during the reinforcement polycondensation reaction.
In above-mentioned technical proposal, the solvent added during step (2) Solution Depolymerization is preferably polyethers quasi-oligomer, such
It can be liquid or solid during oligomer normal temperature, solvent can be used as liquid under de-polymerization temperature；The solvent added during depolymerization
Amount be glycol acid oligomer amount 10-80wt%, preferably 20-60%；The molecular structure of the polyether oligomers is preferred
For R6O(-R5 h-O-)qR7, wherein R5For-CH2-、-CH2CH2At least one of-；R6For-H ,-CH3、-CH2CH3
At least one of；R7For-H ,-CH3、-CH2CH3At least one of；0<h<4；0<q<200；Depolymerization reaction temperature
Degree is preferably 230-270 DEG C；The vacuum of depolymerization reaction is preferably 1-5KPa；The time of depolymerization reaction is preferably 1-10 hours.
The test of acid content is determined by the way of acid base titration in Isosorbide-5-Nitrae-dioxane -2,5- acetyl butyryl in the present invention, specific step
It is rapid as follows：Take two conical flasks, add the solvent and indicator of equivalent, weigh a certain amount of Isosorbide-5-Nitrae-dioxane -2,5- oneself two
Ketone is added in a conical flask, until completely dissolved, is titrated with the titrating solution of the concentration known prepared, another taper product
Solution be used as blank.
The advantage of the invention is that：When preparing Isosorbide-5-Nitrae-dioxane -2,5- acetyl butyryl, by controlling polycondensation reaction condition to conciliate
Poly- reaction condition, can prepare Isosorbide-5-Nitrae-dioxane -2,5- acetyl butyryl of low acid content.
Using technical scheme, a kind of polyethers is added as solvent in depolymerization, while low whipping speed is
Stirred under 30-250 revs/min, Isosorbide-5-Nitrae-dioxane -2,5- acetyl butyryl of low acid content can be prepared, acid content is reachable
1.51×10-4mol·g-1, achieve preferable technique effect.
Embodiment
Embodiments and advantages of the present invention are further illustrated with following non-limiting example.
[embodiment 1]
Added into reactor after 600g glycol acid crystal and 3g stannous octoate catalysts, temperature rises to 90 DEG C from room temperature,
After solid is completely dissolved, 112 DEG C of beginning pre-polymerizations are warming up to, 210 DEG C are warming up to after pre-polymerization 1h, after after anhydrous steam,
System keeping temperature simultaneously starts to vacuumize.This process vacuum degree control is in 3KPa.After after anhydrous steam, system keeps the shape
State continues to react 1.5h, obtains poly- glycol acid oligomer 451g.
Oligomer (the R of 90g polyethers is added into oligomer5For-CH2-；R6For-CH3；R7For-CH3；H=2；Q=20.),
Depolymerization system is stirred under 200 revs/min of speed in 270 DEG C of reaction temperature, vacuum 1KPa, is carried out reaction and is prepared Isosorbide-5-Nitrae-dioxa
Ring -2,5- acetyl butyryl, reaction stops reaction after 2 hours, obtains Isosorbide-5-Nitrae-dioxane -2,5- acetyl butyryl crude product 401g, acid content
2.99×10-4mol·g-1。
[embodiment 2]
Added into reactor after 600g glycol acid crystal and 3g stannous octoate catalysts, temperature rises to 90 DEG C from room temperature,
After solid is completely dissolved, 112 DEG C of beginning pre-polymerizations are warming up to, 210 DEG C are warming up to after pre-polymerization 1h, after after anhydrous steam,
System keeping temperature simultaneously starts to vacuumize.This process vacuum degree control is in 3KPa.After after anhydrous steam, system keeps the shape
State continues to react 1.5h, obtains poly- glycol acid oligomer 454g.
Oligomer (the R of 90g polyethers is added into oligomer5For-CH2-；R6For-CH3；R7For-CH3；H=2；Q=20.),
Depolymerization system is stirred under 200 revs/min of speed in 270 DEG C of reaction temperature, vacuum 1.5KPa, is carried out reaction and is prepared Isosorbide-5-Nitrae-dioxy
Heterocycle -2,5- acetyl butyryl, reaction stops reaction after 2 hours, obtains Isosorbide-5-Nitrae-dioxane -2,5- acetyl butyryl crude product 396g, acid contains
Amount 2.59 × 10-4mol·g-1。
[embodiment 3]
Added into reactor after 600g glycol acid crystal and 3g stannous octoate catalysts, temperature rises to 90 DEG C from room temperature,
After solid is completely dissolved, 112 DEG C of beginning pre-polymerizations are warming up to, 210 DEG C are warming up to after pre-polymerization 1h, after after anhydrous steam,
System keeping temperature simultaneously starts to vacuumize.This process vacuum degree control is in 3KPa.After after anhydrous steam, system keeps the shape
State continues to react 1.5h, obtains poly- glycol acid oligomer 451g.
Oligomer (the R of 90g polyethers is added into oligomer5For-CH2-；R6For-CH3；R7For-CH3；H=2；Q=20.),
Depolymerization system is stirred under 200 revs/min of speed in 260 DEG C of reaction temperature, vacuum 2KPa, is carried out reaction and is prepared Isosorbide-5-Nitrae-dioxa
Ring -2,5- acetyl butyryl, reaction stops reaction after 2 hours, obtains Isosorbide-5-Nitrae-dioxane -2,5- acetyl butyryl crude product 387g, acid content
2.49×10-4mol·g-1。
[embodiment 4]
Added into reactor after 600g glycol acid crystal and 3g stannous octoate catalysts, temperature rises to 90 DEG C from room temperature,
After solid is completely dissolved, 112 DEG C of beginning pre-polymerizations are warming up to, 210 DEG C are warming up to after pre-polymerization 1h, after after anhydrous steam,
System keeping temperature simultaneously starts to vacuumize.This process vacuum degree control is in 3KPa.After after anhydrous steam, system keeps the shape
State continues to react 1.5h, obtains poly- glycol acid oligomer 451g.
Oligomer (the R of 90g polyethers is added into oligomer5For-CH2-；R6For-CH3；R7For-CH3；H=2；Q=20.),
Depolymerization system is stirred under 200 revs/min of speed in 270 DEG C of reaction temperature, vacuum 2.5KPa, is carried out reaction and is prepared Isosorbide-5-Nitrae-dioxy
Heterocycle -2,5- acetyl butyryl, reaction stops reaction after 2 hours, obtains Isosorbide-5-Nitrae-dioxane -2,5- acetyl butyryl crude product 378g, acid contains
Amount 1.51 × 10-4mol·g-1。
[embodiment 5]
Added into reactor after 600g glycol acid crystal and 3g stannous octoate catalysts, temperature rises to 90 DEG C from room temperature,
After solid is completely dissolved, 112 DEG C of beginning pre-polymerizations are warming up to, 210 DEG C are warming up to after pre-polymerization 1h, after after anhydrous steam,
System keeping temperature simultaneously starts to vacuumize.This process vacuum degree control is in 3KPa.After after anhydrous steam, system keeps the shape
State continues to react 1.5h, obtains poly- glycol acid oligomer 451g.
Oligomer (the R of 90g polyethers is added into oligomer5For-CH2-；R6For-CH3；R7For-CH3；H=2；Q=20.),
Depolymerization system is stirred under 200 revs/min of speed in 260 DEG C of reaction temperature, vacuum 1.5KPa, is carried out reaction and is prepared Isosorbide-5-Nitrae-dioxy
Heterocycle -2,5- acetyl butyryl, reaction stops reaction after 2 hours, obtains Isosorbide-5-Nitrae-dioxane -2,5- acetyl butyryl crude product 399g, acid contains
Amount 2.81 × 10-4mol·g-1。
[embodiment 6]
Added into reactor after 600g glycol acid crystal and 3g stannous octoate catalysts, temperature rises to 90 DEG C from room temperature,
After solid is completely dissolved, 112 DEG C of beginning pre-polymerizations are warming up to, 210 DEG C are warming up to after pre-polymerization 1h, after after anhydrous steam,
System keeping temperature simultaneously starts to vacuumize.This process vacuum degree control is in 3KPa.After after anhydrous steam, system keeps the shape
State continues to react 1.5h, obtains poly- glycol acid oligomer 451g.
Oligomer (the R of 90g polyethers is added into oligomer5For-CH2-；R6For-CH3；R7For-CH3；H=2；Q=20.),
Depolymerization system is stirred under 200 revs/min of speed in 250 DEG C of reaction temperature, vacuum 1.5KPa, is carried out reaction and is prepared Isosorbide-5-Nitrae-dioxy
Heterocycle -2,5- acetyl butyryl, reaction stops reaction after 2 hours, obtains Isosorbide-5-Nitrae-dioxane -2,5- acetyl butyryl crude product 276g, acid contains
Amount 5.07 × 10-4mol·g-1。
[embodiment 7]
Added into reactor after 600g glycol acid crystal and 3g stannous octoate catalysts, temperature rises to 90 DEG C from room temperature,
After solid is completely dissolved, 112 DEG C of beginning pre-polymerizations are warming up to, 210 DEG C are warming up to after pre-polymerization 1h, after after anhydrous steam,
System keeping temperature simultaneously starts to vacuumize.This process vacuum degree control is in 3KPa.After after anhydrous steam, system keeps the shape
State continues to react 1.5h, obtains poly- glycol acid oligomer 451g.
Oligomer (the R of 90g polyethers is added into oligomer5For-CH2-；R6For-CH3；R7For-CH3；H=2；Q=20.),
Depolymerization system is stirred under 100 revs/min of speed in 270 DEG C of reaction temperature, vacuum 1.5KPa, is carried out reaction and is prepared Isosorbide-5-Nitrae-dioxy
Heterocycle -2,5- acetyl butyryl, reaction stops reaction after 2 hours, obtains Isosorbide-5-Nitrae-dioxane -2,5- acetyl butyryl crude product 276g, acid contains
Amount 5.41 × 10-4mol·g-1。
[embodiment 8]
Added into reactor after 600g glycol acid crystal and 3g stannous octoate catalysts, temperature rises to 90 DEG C from room temperature,
After solid is completely dissolved, 112 DEG C of beginning pre-polymerizations are warming up to, 210 DEG C are warming up to after pre-polymerization 1h, after after anhydrous steam,
System keeping temperature simultaneously starts to vacuumize.This process vacuum degree control is in 3KPa.After after anhydrous steam, system keeps the shape
State continues to react 0.5h, obtains poly- glycol acid oligomer 453g.
Oligomer (the R of 90g polyethers is added into oligomer5For-CH2-；R6For-CH3；R7For-CH3；H=2；Q=20.),
Depolymerization system is stirred under 100 revs/min of speed in 270 DEG C of reaction temperature, vacuum 1.5KPa, is carried out reaction and is prepared Isosorbide-5-Nitrae-dioxy
Heterocycle -2,5- acetyl butyryl, reaction stops reaction after 2 hours, obtains Isosorbide-5-Nitrae-dioxane -2,5- acetyl butyryl crude product 408g, acid contains
Amount 6.67 × 10-4mol·g-1。
[comparative example 1]
Added into reactor after 600g glycol acid crystal and 3g stannous octoate catalysts, temperature rises to 90 DEG C from room temperature,
After solid is completely dissolved, 112 DEG C of beginning pre-polymerizations are warming up to, 210 DEG C are warming up to after pre-polymerization 1h, after after anhydrous steam,
System keeping temperature simultaneously starts to vacuumize.This process vacuum degree control is in 3KPa.After after anhydrous steam, system keeps the shape
State continues to react 1.5h, obtains poly- glycol acid oligomer 454g.
By the poly- glycol acid oligomer in 270 DEG C of reaction temperature, vacuum 1.5KPa is stirred under 200 revs/min of speed, carried out
Reaction prepares Isosorbide-5-Nitrae-dioxane -2,5- acetyl butyryl, and reaction stops reaction after 2 hours, obtains Isosorbide-5-Nitrae-dioxane -2,5- acetyl butyryl
Crude product 331g, acid content 9.13 × 10-4mol·g-1。
[comparative example 2]
Added into reactor after 600g glycol acid crystal and 3g stannous octoate catalysts, temperature rises to 90 DEG C from room temperature,
After solid is completely dissolved, 112 DEG C of beginning pre-polymerizations are warming up to, 210 DEG C are warming up to after pre-polymerization 1h, after after anhydrous steam,
System keeping temperature simultaneously starts to vacuumize.This process vacuum degree control is in 3KPa.After after anhydrous steam, system keeps the shape
State continues to react 1.5h, obtains poly- glycol acid oligomer 451g.
By the poly- glycol acid oligomer in 270 DEG C of reaction temperature, vacuum 1.5KPa carries out reaction and prepares Isosorbide-5-Nitrae-dioxy
Heterocycle -2,5- acetyl butyryl, reaction stops reaction after 2 hours, obtains Isosorbide-5-Nitrae-dioxane -2,5- acetyl butyryl crude product 230g, acid contains
Amount 1.12 × 10-3mol·g-1。
[comparative example 3]
Added into reactor after 600g glycol acid crystal and 3g stannous octoate catalysts, temperature rises to 90 DEG C from room temperature,
After solid is completely dissolved, 112 DEG C of beginning pre-polymerizations are warming up to, 210 DEG C are warming up to after pre-polymerization 1h, after after anhydrous steam,
System keeping temperature simultaneously starts to vacuumize.This process vacuum degree control is in 3KPa.After after anhydrous steam, system keeps the shape
State continues to react 1.5h, obtains poly- glycol acid oligomer 453g.
Oligomer (the R of 90g polyethers is added into oligomer5For-CH2-；R6For-CH3；R7For-CH3；H=2；Q=20.),
Depolymerization system carries out reaction and prepares Isosorbide-5-Nitrae-dioxane -2,5- acetyl butyryl, instead in 270 DEG C of reaction temperature, vacuum 1KPa
Answer and stop reaction after 2 hours, obtain Isosorbide-5-Nitrae-dioxane -2,5- acetyl butyryl crude product 401g, acid content 8.79 × 10-4mol·g-1。
Claims (10)
1. a kind of preparation method of Isosorbide-5-Nitrae-dioxane -2,5- acetyl butyryl, comprises the following steps：
(1) polycondensation：Glycolic acid is subjected to polycondensation reaction, glycol acid oligomer is obtained；
(2) Solution Depolymerization, after step (1), at least one solvent is added into reaction system, glycol acid oligomer and solvent is formed homogeneously, improve system reaction temperature to 230-290 DEG C, while improving vacuum to 0.1-5KPa, mixing speed is 30-250 revs/min, glycol acid oligomer is set to occur depolymerization reaction, vacuum distillation goes out target crude product, and the reaction time is 1-12 hours.
2. Isosorbide-5-Nitrae according to claim 1-dioxane-2,5- acetyl butyryl preparation method, it is characterised in that step (1) polycondensation specifically includes following steps：A) normal pressure polycondensation, in the presence of a catalyst, reaction is segmented by glycol acid crystal in atmospheric conditions：First stage normal pressure pre-polymerization, keeps reaction temperature to be reacted 0.5~10 hour between the fusing point of Glycolic acid and the boiling point of Glycolic acid；Second stage normal pressure polycondensation, in 112~220 DEG C of reaction temperature, carries out condensation reaction or ester exchange reaction, untill anhydrous steam；B) polycondensation is depressurized, after step a, system temperature is kept, while improving system vacuum to 0.1-5KPa, proceeds polycondensation reaction or ester exchange reaction, until no water is steamed；C) strengthen polycondensation, after the stepb, keep system temperature and vacuum to continue to react 0.5-10 hours, obtain glycol acid oligomer.
3. according to claim 21,4- dioxanes -2,5- acetyl butyryl preparation methods, it is characterized in that the mixture of catalyst used at least one or two above of organic acid compound, the oxide of antimony, the halide of antimony, the organic acid compound of antimony, the oxide of zinc, the halide of zinc, complex, the complex of organo-aluminum compound or aluminium, the rare earth metal complex of the organic compound of zinc or zinc of halide or tin of tin, the consumption of catalyst is the 0.001-10wt% of Glycolic acid consumption.
4. Isosorbide-5-Nitrae according to claim 1 or 2-dioxane-2,5- acetyl butyryl preparation method, it is characterised in that the solvent added during step (2) Solution Depolymerization is polyethers quasi-oligomer, and the polyethers quasi-oligomer is liquid under de-polymerization temperature.
5. Isosorbide-5-Nitrae according to claim 1 or 2-dioxane-2,5- acetyl butyryl preparation method, it is characterised in that the amount of the solvent added during step (2) Solution Depolymerization is the 10-80wt% of glycol acid oligomer amount.
6. Isosorbide-5-Nitrae according to claim 1 or 2-dioxane-2,5- acetyl butyryl preparation method, it is characterised in that the amount of the solvent added during step (2) Solution Depolymerization is the 20-60% for glycol acid oligomer amount of glycol acid oligomer amount.
7. Isosorbide-5-Nitrae according to claim 4-dioxane-2,5- acetyl butyryl preparation method, it is characterised in that the molecular structure of the polyether oligomers is R6O(-R5 h-O-)qR7, wherein R5For-CH2-、-CH2CH2At least one of-；R6For-H ,-CH3、-CH2CH3At least one of；R7For-H ,-CH3、-CH2CH3At least one of；0<h<4；0<q<200.
8. Isosorbide-5-Nitrae according to claim 1 or 2-dioxane-2,5- acetyl butyryl preparation method, it is characterised in that 230-270 DEG C of hour of depolymerization reaction temperature.
9. Isosorbide-5-Nitrae according to claim 1 or 2-dioxane-2,5- acetyl butyryl preparation method, it is characterised in that the vacuum 1-5KPa of depolymerization reaction.
10. Isosorbide-5-Nitrae according to claim 1 or 2-dioxane-2,5- acetyl butyryl preparation method, it is characterised in that the time of depolymerization reaction is 1-10 hours.
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| CN114805283A (en) * | 2022-04-29 | 2022-07-29 | 内蒙古久泰新材料有限公司 | A kind of method for continuous and stable preparation of high-quality glycolide |
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