CN114276363B - Method for purifying isosorbide by adopting dihydric alcohol recrystallization - Google Patents
Method for purifying isosorbide by adopting dihydric alcohol recrystallization Download PDFInfo
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- KLDXJTOLSGUMSJ-JGWLITMVSA-N Isosorbide Chemical compound O[C@@H]1CO[C@@H]2[C@@H](O)CO[C@@H]21 KLDXJTOLSGUMSJ-JGWLITMVSA-N 0.000 title claims abstract description 90
- 229960002479 isosorbide Drugs 0.000 title claims abstract description 90
- 238000000034 method Methods 0.000 title claims abstract description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title abstract description 22
- 238000001953 recrystallisation Methods 0.000 title abstract description 14
- 239000013078 crystal Substances 0.000 claims abstract description 30
- 238000002425 crystallisation Methods 0.000 claims abstract description 20
- 230000008025 crystallization Effects 0.000 claims abstract description 20
- 238000006068 polycondensation reaction Methods 0.000 claims description 19
- 238000001816 cooling Methods 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 13
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 12
- 239000001384 succinic acid Substances 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 238000002844 melting Methods 0.000 claims description 10
- 230000008018 melting Effects 0.000 claims description 10
- 150000002148 esters Chemical class 0.000 claims description 9
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 6
- 239000002202 Polyethylene glycol Substances 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- 238000011049 filling Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 238000005086 pumping Methods 0.000 claims description 4
- 239000002904 solvent Substances 0.000 abstract description 11
- 229920000728 polyester Polymers 0.000 abstract description 10
- 238000000746 purification Methods 0.000 abstract description 10
- 229920000515 polycarbonate Polymers 0.000 abstract description 9
- 239000004417 polycarbonate Substances 0.000 abstract description 9
- 239000003960 organic solvent Substances 0.000 abstract description 8
- 238000006116 polymerization reaction Methods 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 230000008569 process Effects 0.000 abstract description 6
- 238000009835 boiling Methods 0.000 abstract description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 29
- 239000004033 plastic Substances 0.000 description 10
- 229920003023 plastic Polymers 0.000 description 10
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 7
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 7
- 239000000178 monomer Substances 0.000 description 7
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 6
- 238000005119 centrifugation Methods 0.000 description 6
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 5
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 5
- 229910001873 dinitrogen Inorganic materials 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000000600 sorbitol Substances 0.000 description 5
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 4
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 description 4
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 3
- 239000002028 Biomass Substances 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000012634 fragment Substances 0.000 description 2
- 230000012010 growth Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000012452 mother liquor Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical compound OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- SNGLYCMNDNOLOF-UHFFFAOYSA-N benzyl phenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OCC1=CC=CC=C1 SNGLYCMNDNOLOF-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229920006238 degradable plastic Polymers 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- PIZLBWGMERQCOC-UHFFFAOYSA-N dibenzyl carbonate Chemical compound C=1C=CC=CC=1COC(=O)OCC1=CC=CC=C1 PIZLBWGMERQCOC-UHFFFAOYSA-N 0.000 description 1
- QLVWOKQMDLQXNN-UHFFFAOYSA-N dibutyl carbonate Chemical compound CCCCOC(=O)OCCCC QLVWOKQMDLQXNN-UHFFFAOYSA-N 0.000 description 1
- ZYKOICDLSSOLAN-UHFFFAOYSA-N diheptyl carbonate Chemical compound CCCCCCCOC(=O)OCCCCCCC ZYKOICDLSSOLAN-UHFFFAOYSA-N 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- FXJUUMGKLWHCNZ-UHFFFAOYSA-N dimethyl furan-2,3-dicarboxylate Chemical compound COC(=O)C=1C=COC=1C(=O)OC FXJUUMGKLWHCNZ-UHFFFAOYSA-N 0.000 description 1
- HSNQKJVQUFYBBY-UHFFFAOYSA-N dipentyl carbonate Chemical compound CCCCCOC(=O)OCCCCC HSNQKJVQUFYBBY-UHFFFAOYSA-N 0.000 description 1
- VUPKGFBOKBGHFZ-UHFFFAOYSA-N dipropyl carbonate Chemical compound CCCOC(=O)OCCC VUPKGFBOKBGHFZ-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- DNXDYHALMANNEJ-UHFFFAOYSA-N furan-2,3-dicarboxylic acid Chemical compound OC(=O)C=1C=COC=1C(O)=O DNXDYHALMANNEJ-UHFFFAOYSA-N 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 239000003864 humus Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N p-toluenesulfonic acid Substances CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 125000005489 p-toluenesulfonic acid group Chemical group 0.000 description 1
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 description 1
- 230000008635 plant growth Effects 0.000 description 1
- -1 polyethylene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 150000005846 sugar alcohols Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention discloses a method for purifying isosorbide by adopting dihydric alcohol recrystallization. According to the method for purifying the isosorbide by adopting the dihydric alcohol recrystallization, the dihydric alcohol is adopted to replace the common non-reactive organic solvent, the purified isosorbide crystal can be directly used for the polymerization of polyester or polycarbonate, the dihydric alcohol solvent is not required to be removed, the purification method is simple, the solvent removal treatment process is reduced, the post-treatment problem caused by the low-boiling point organic solvent in the subsequent polymerization is avoided, and the crystallization and polymerization production efficiency is improved. In addition, compared with the common non-reactive organic solvent, the dihydric alcohol solvent has the advantages of safety and nonflammability.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a method for purifying isosorbide by adopting dihydric alcohol recrystallization.
Background
The invention and the manufacture of the plastic bring great convenience to the production and the life of people. From the 50 s of the 20 th century, the global plastic annual growth rate remained at 8.5% on average; by 2016, the global plastic production reaches 3.35 hundred million tons. China is the first major country of plastic production and consumption; in 2017, the annual output of Chinese plastic products exceeds 1.0 hundred million tons, and the potential for future growth is still very great. The raw materials of the plastic products are derived from petroleum and belong to non-renewable resources; petroleum exploitation and consumption result in a large amount of greenhouse gas emissions; further, the global temperature rises and extreme weather increases. In addition, the plastic has good stability in the environment, and is difficult to decompose in the natural environment after being abandoned. The waste plastics accumulate in a large amount in the environment, and the polluted soil influences the plant growth; in addition, the waste plastic fragments are finally gathered on the ocean through the river, and the waste plastic fragments enter the dining tables of people after being ingested by fishes and the like, so that potential harm is caused to human health.
Therefore, the development of biomass monomer and (degradable) plastic based on the biomass monomer is one of effective means for relieving resource shortage and solving the problem of white pollution, is beneficial to realizing carbon neutralization and has important economic and social significance.
Isosorbide (IS) IS a glycol prepared from the bio-based polyol sorbitol (DS, D-sorbol) by dehydration. Isosorbide can be used in place of glycol to make polyesters; the rigid structure of the isosorbide chemical structure and the characteristic of chiral hydroxyl make it suitable for constructing various polymer materials with high glass transition temperature and special functions. Sorbitol is listed by the U.S. department of energy as one of twelve important platform compounds; the sugar alcohol monomer which is the most successful in industrialization at present is a model of combining biomass products and enzyme chemical technology.
Isosorbide is prepared by dehydrating and polycondensing sorbitol, and various dehydrated products, humus and other byproducts are simultaneously produced in the process, so that the crude isosorbide is difficult to prepare high molecular weight polyester or polycarbonate as a reaction monomer; purification of the crude isosorbide is required (CN 1207257C). The method for purifying the isosorbide mainly comprises distillation, recrystallization, melt crystallization or distillation-melt crystallization coupling technology refining. A process for purifying isosorbide by distillation, which process gives isosorbide having a low purity (CN 10665497A). The method for refining the isosorbide by melt crystallization or distillation-melt crystallization coupling process has high purity of the obtained isosorbide, but the equipment is complex, and the operation process is complicated (CN 10665497A).
The isosorbide is purified by recrystallization, so that a high-purity product can be obtained, the equipment is simple, and the defects are that the organic solvent is used and remains and cannot be directly used as a polymerization monomer, and the solvent needs to be removed by means of vacuum and the like (CN 106279197A); in addition, the solvent is inflammable, and the requirement on equipment safety is high (CN 1207257C). Therefore, a recrystallization method for simply preparing the polymer grade isosorbide monomer needs to be developed, and the solvent is safe and efficient; the monomer after recrystallization can be directly used for preparing polyester or polycarbonate. How to implement this approach is still a challenge.
Disclosure of Invention
The invention aims at solving the problems of the purification of isosorbide for synthesizing polyester and polycarbonate at present and aims at providing a method for purifying isosorbide by adopting glycol recrystallization.
In order to solve the problems, the invention adopts the following technical scheme:
a method for purifying isosorbide by adopting glycol recrystallization, comprising the following steps:
mixing the crude isosorbide with a glycol, and heating the mixture to a complete melt;
cooling and crystallizing the completely melted mixture solution to separate out isosorbide crystals;
and separating the isosorbide crystals from the mother liquor to obtain purified isosorbide crystals.
The isosorbide crystal obtained by the purification method can be directly used for preparing polyester or polycarbonate, and the dihydric alcohol contained in the purified isosorbide crystal is not required to be removed, so that the isosorbide crystal can directly participate in the synthesis reaction of the polyester or polycarbonate, and the performance of the prepared polyester or polycarbonate is not influenced. Compared with the traditional organic solvent used for recrystallization and purification, the dihydric alcohol used in the invention has higher boiling point, is not easy to volatilize, is safer to use and has higher purification efficiency.
By adopting the purification method, dihydric alcohol with the solidifying point of minus 20 ℃ to 50 ℃ is preferably used, and the dihydric alcohol can reach a complete melting state at a lower heating temperature after being mixed with the crude isosorbide. The dihydric alcohol includes hydroxyl-terminated dihydric alcohol and dihydric alcohol oligomer, for example, optional dihydric alcohol is at least one of ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, hydroxyl-terminated polyethylene glycol, polyethylene glycol monomethyl ether, hydroxyl-terminated polypropylene glycol, polypropylene glycol monomethyl ether and polyethylene glycol-propylene glycol monomethyl ether. Preferably, 1, 4-butanediol is used.
Depending on the type of glycol used, the appropriate crystallization temperature is chosen such that isosorbide can crystallize out at this crystallization temperature while the glycol is still present in the mother liquor in a liquid state. The temperature of the cooling crystallization can be selected to be 0-50 ℃. Preferably, the temperature of the cooling crystallization is 10 ℃ to 30 ℃. More preferably, the temperature of the cooling crystallization is 20 ℃. The temperature range is close to room temperature, so that the energy consumption for cooling and crystallizing can be reduced, and the cooling and crystallizing operation is facilitated.
By adopting the purification method, the mass ratio of the dihydric alcohol to the crude isosorbide can be selected to be (3-6): 10. Preferably, the mass ratio of the dihydric alcohol to the crude isosorbide is 3:10, so that purified isosorbide crystals can be obtained in higher yields. And the purity of the obtained isosorbide crystal is also higher.
The isosorbide crystal purified by the method can be directly polymerized with dicarboxylic acid to prepare polyester polymer compounds, and the optional dicarboxylic acid comprises terephthalic acid, dimethyl terephthalate, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, furandicarboxylic acid, dimethyl furandicarboxylate and terephthaloyl chloride.
The isosorbide crystal purified by the method can be directly polymerized with carbonic ester to prepare polycarbonate high molecular compounds, and the optional carbonic ester comprises dimethyl carbonate, diethyl carbonate, dipropyl carbonate, dibutyl carbonate, dipentyl carbonate, diheptyl carbonate, diphenyl carbonate, dibenzyl carbonate and benzyl phenyl carbonate.
Compared with the prior art, the invention has the technical effects that:
according to the method for purifying the isosorbide by adopting the dihydric alcohol recrystallization, the dihydric alcohol is adopted to replace the common non-reactive organic solvent, the purified isosorbide crystal can be directly used for the polymerization of polyester or polycarbonate, the dihydric alcohol solvent is not required to be removed, the purification method is simple, the solvent removal treatment process is reduced, the post-treatment problem caused by the low-boiling point organic solvent in the subsequent polymerization is avoided, and the crystallization and polymerization production efficiency is improved. In addition, compared with the common non-reactive organic solvent, the dihydric alcohol solvent has the advantages of safety and nonflammability.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention.
It will be appreciated by those skilled in the art that the objects and advantages that can be achieved with the present invention are not limited to the above-described specific ones, and that the above and other objects that can be achieved with the present invention will be more clearly understood from the following detailed description.
Drawings
The accompanying drawings are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate the invention and together with the description serve to explain, without limitation, the invention.
FIG. 1 is a nuclear magnetic resonance spectrum of isosorbide obtained by recrystallization and purification using 1, 4-butanediol as a solvent in example 3 of the present invention.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
Before describing the present invention in detail, it is to be understood that the terminology used herein is for the purpose of describing particular embodiments only, and is not intended to limit the scope of the present invention, which will be limited only by the appended claims. For a more complete understanding of the invention described herein, the following terms are used and their definitions are shown below. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
All the starting materials mentioned in the examples below are commercially available, unless otherwise specified.
The crude isosorbide of the present invention is derived from the sorbitan polycondensation preparation. The crude isosorbide can be obtained by the following method: the sorbitol is 100g, the catalyst is p-toluenesulfonic acid (1.0 wt%) and the catalyst is heated under the protection of nitrogen for 2-4 hours at the normal pressure and the temperature is 120-140 ℃. And then reacting at the vacuum degree of 80-100 Pa, heating at the temperature of 160-180 ℃, and separating out the crude isosorbide through reduced pressure distillation. The composition of crude sorbitol was determined using nuclear magnetism using deuterated dimethyl sulfoxide as solvent.
Example 1
100g (purity 98.0%) of crude isosorbide and 30 g of ethylene glycol were added to the three-necked flask, followed by three replacements by vacuum pumping and nitrogen filling. Heating to 80 ℃ for melting, cooling to 20 ℃ per minute at 15 ℃ for constant temperature crystallization, and separating out isosorbide crystals after 2 hours. After centrifugation of the crystals, the isosorbide yield was 84% (wherein the isosorbide content was 93.0%, and the ethylene glycol content was 7.0%). 50 g of separated isosorbide and 48 g of succinic acid are directly added with 0.098 g (1.0 per mill) of tetrabutyl titanate, heated to 175 ℃ and subjected to polycondensation for 6 hours; then vacuum polycondensation is adopted, the temperature is raised to 240 ℃, and the reaction is carried out for 2 hours, so as to obtain the poly (isosorbide-succinic acid) ester with the molecular weight of 25kg/mol.
Example 2
100g (purity 98.0%) of crude isosorbide and 30 g of polyethylene glycol (molecular weight 400 g/mol) were added to the three-necked flask, followed by three replacements by vacuum-pumping and nitrogen-filling. Heating to 80 ℃ for melting, cooling to 20 ℃ per minute at 15 ℃ for constant temperature crystallization, and separating out isosorbide crystals after 3 hours. After the crystals were centrifuged, the isosorbide yield was 45% (wherein the isosorbide content was 91.0% and the polyethylene glycol content was 9.0%). 50 g of separated isosorbide and 48 g of succinic acid are directly added with 0.098 g (1.0 per mill) of tetrabutyl titanate, heated to 175 ℃ and subjected to polycondensation for 6 hours; then vacuum polycondensation is adopted, the temperature is raised to 240 ℃, and the reaction is carried out for 2 hours, thus obtaining the poly (isosorbide-succinic acid) ester with the molecular weight of 18kg/mol.
Example 3
100g (purity 98.0%) of crude isosorbide and 30 g of butanediol were added to the three-necked flask, and the flask was then evacuated and replaced with nitrogen gas three times. Heating to 80 ℃ for melting, cooling to 20 ℃ per minute at 15 ℃ for constant temperature crystallization, and separating out isosorbide crystals after 1 hour. After centrifugation of the crystals, the yield of isosorbide was 94% (wherein the isosorbide content was 96.0% and the butylene glycol content was 4.0%). 50 g of separated isosorbide and 48 g of succinic acid are directly added with 0.098 g (1.0 per mill) of tetrabutyl titanate, heated to 175 ℃ and subjected to polycondensation for 6 hours; then vacuum polycondensation is adopted, the temperature is raised to 240 ℃, and the reaction is carried out for 2 hours, so as to obtain the poly (isosorbide-succinic acid) ester with the molecular weight of 35kg/mol.
Example 4
100g (purity 98.0%) of crude isosorbide and 60 g of butanediol were added to the three-necked flask, and the flask was then evacuated and replaced with nitrogen gas three times. Heating to 80 ℃ for melting, cooling to 20 ℃ per minute at 15 ℃ for constant temperature crystallization, and separating out isosorbide crystals after 1.5 hours. After the crystals were centrifuged, the isosorbide yield was 64% (wherein the isosorbide content was 94.0% and the butylene glycol content was 6.0%). 50 g of separated isosorbide and 48 g of succinic acid are directly added with 0.098 g (1.0 per mill) of tetrabutyl titanate, heated to 175 ℃ and subjected to polycondensation for 6 hours; then vacuum polycondensation is adopted, the temperature is raised to 240 ℃, and the reaction is carried out for 2 hours, so as to obtain the poly (isosorbide-succinic acid) ester with the molecular weight of 35kg/mol.
Example 5
100g (purity 98.0%) of crude isosorbide and 30 g of butanediol were added to the three-necked flask, and the flask was then evacuated and replaced with nitrogen gas three times. Heating to 80 ℃ for melting, cooling to 20 ℃ per minute at 15 ℃ for constant temperature crystallization, and separating out isosorbide crystals after 1 hour. After centrifugation of the crystals, the yield of isosorbide was 94% (wherein the isosorbide content was 96.0% and the butylene glycol content was 4.0%). 30 g of separated isosorbide, 30 g of butanediol and 65 g of succinic acid are directly added with 0.186 g (1.5 per mill) of tetrabutyl titanate, heated to 175 ℃ and subjected to polycondensation for 6 hours; then vacuum polycondensation is adopted, the temperature is raised to 240 ℃, and the reaction is carried out for 2 hours, thus obtaining the poly (isosorbide-butanediol-succinic acid) ester with the molecular weight of 51kg/mol.
Example 6
100g (purity 98.0%) of crude isosorbide and 30 g of ethylene glycol were added to the three-necked flask, followed by three replacements by vacuum pumping and nitrogen filling. Heating to 80 ℃ for melting, cooling to 20 ℃ per minute at 15 ℃ for constant temperature crystallization, and separating out isosorbide crystals after 2 hours. After centrifugation of the crystals, the isosorbide yield was 84% (wherein the isosorbide content was 93.0%, and the ethylene glycol content was 7.0%). 50 g of isosorbide and 73.3 g of diphenyl carbonate after separation, 0.037 g (0.3 per mill) of lithium acetylacetonate is directly added, heated to 175 ℃ and subjected to polycondensation for 5 hours; then vacuum polycondensation is adopted, the temperature is raised to 250 ℃, and the reaction is carried out for 2 hours, thus obtaining the poly isosorbide carbonate with the molecular weight of 34kg/mol.
Example 7
100g (purity 98.0%) of crude isosorbide and 30 g of butanediol were added to the three-necked flask, and the flask was then evacuated and replaced with nitrogen gas three times. Heating to 80 ℃ for melting, cooling to 20 ℃ per minute at 15 ℃ for constant temperature crystallization, and separating out isosorbide crystals after 1 hour. After centrifugation of the crystals, the yield of isosorbide was 94% (wherein the isosorbide content was 96.0% and the butylene glycol content was 4.0%). 50 g of isosorbide and 73.3 g of diphenyl carbonate after separation, 0.037 g (0.3 per mill) of lithium acetylacetonate is directly added, heated to 175 ℃ and subjected to polycondensation for 5 hours; then vacuum polycondensation is adopted, the temperature is raised to 250 ℃, and the reaction is carried out for 2 hours, thus obtaining the poly isosorbide carbonate with the molecular weight of 38kg/mol.
Example 8
100g (purity 98.0%) of crude isosorbide and 30 g of butanediol were added to the three-necked flask, and the flask was then evacuated and replaced with nitrogen gas three times. Heating to 80 ℃ for melting, cooling to 20 ℃ per minute at 15 ℃ for constant temperature crystallization, and separating out isosorbide crystals after 1 hour. After centrifugation of the crystals, the yield of isosorbide was 94% (wherein the isosorbide content was 96.0% and the butylene glycol content was 4.0%). 60 g of isosorbide, 40 g of 1, 6-hexanediol and 160.4 g of diphenyl carbonate after separation, 0.078 g (0.3%o) of lithium acetylacetonate is directly added, heated to 175 ℃ and subjected to polycondensation for 5 hours; then vacuum polycondensation is adopted, the temperature is raised to 250 ℃, and the reaction is carried out for 2 hours, thus obtaining the poly (isosorbide-hexanediol) carbonic ester with the molecular weight of 56kg/mol.
Moreover, any combination of the various embodiments of the invention can be made without departing from the spirit of the invention, which should also be considered as disclosed herein.
The present invention is not limited to the above-described specific embodiments, and various modifications and variations are possible. Any modification, equivalent replacement, improvement, etc. of the above embodiments according to the technical substance of the present invention should be included in the protection scope of the present invention.
Claims (1)
1. A method for preparing poly (isosorbide-succinate), comprising the steps of:
100g of crude isosorbide with the purity of 98.0% is added into a three-neck flask, 30 g of polyethylene glycol with the molecular weight of 400g/mol is added, and then the three times of vacuum pumping and nitrogen filling replacement are carried out;
heating to 80 ℃ for melting, cooling to 20 ℃ per minute at 15 ℃ for constant temperature crystallization, and separating out isosorbide crystals after 3 hours;
centrifugal separation of crystals;
50 g of isosorbide and 48 g of succinic acid after separation, 0.098 g of tetrabutyl titanate is directly added, and the mixture is heated to 175 ℃ and subjected to polycondensation for 6 hours; then vacuum polycondensation is adopted, the temperature is raised to 240 ℃, and the poly (isosorbide-succinic acid) ester is obtained after the reaction for 2 hours.
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| CN1298343A (en) * | 1998-04-23 | 2001-06-06 | 纳幕尔杜邦公司 | Isosorbide containing polyesters and methods for making same |
| CN1333775A (en) * | 1999-01-11 | 2002-01-30 | 纳幕尔杜邦公司 | Process and products of purification of anhydrosugar alcohol |
| CN101585909A (en) * | 2009-06-22 | 2009-11-25 | 南京工业大学 | Preparation method of isosorbide-containing polyester |
| CN107955142A (en) * | 2016-10-18 | 2018-04-24 | 中国石油化工股份有限公司 | Preparation method containing isobide polyester |
| CN108727578A (en) * | 2018-03-15 | 2018-11-02 | 中国科学院成都有机化学有限公司 | A kind of preparation method of isobide base makrolon |
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| CN1298343A (en) * | 1998-04-23 | 2001-06-06 | 纳幕尔杜邦公司 | Isosorbide containing polyesters and methods for making same |
| CN1333775A (en) * | 1999-01-11 | 2002-01-30 | 纳幕尔杜邦公司 | Process and products of purification of anhydrosugar alcohol |
| CN101585909A (en) * | 2009-06-22 | 2009-11-25 | 南京工业大学 | Preparation method of isosorbide-containing polyester |
| CN107955142A (en) * | 2016-10-18 | 2018-04-24 | 中国石油化工股份有限公司 | Preparation method containing isobide polyester |
| CN108727578A (en) * | 2018-03-15 | 2018-11-02 | 中国科学院成都有机化学有限公司 | A kind of preparation method of isobide base makrolon |
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