CN114752045A - Post-treatment process and application of carbon dioxide-based biodegradable multipolymer - Google Patents
Post-treatment process and application of carbon dioxide-based biodegradable multipolymer Download PDFInfo
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- CN114752045A CN114752045A CN202210305111.8A CN202210305111A CN114752045A CN 114752045 A CN114752045 A CN 114752045A CN 202210305111 A CN202210305111 A CN 202210305111A CN 114752045 A CN114752045 A CN 114752045A
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 116
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 58
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 58
- 238000000034 method Methods 0.000 title claims abstract description 34
- 230000008569 process Effects 0.000 title claims abstract description 32
- 239000003292 glue Substances 0.000 claims abstract description 49
- 239000003960 organic solvent Substances 0.000 claims abstract description 34
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 26
- 230000001376 precipitating effect Effects 0.000 claims abstract description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000012535 impurity Substances 0.000 claims abstract description 17
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000000243 solution Substances 0.000 claims description 50
- 238000003756 stirring Methods 0.000 claims description 25
- -1 anhydride compounds Chemical class 0.000 claims description 11
- 239000011259 mixed solution Substances 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 9
- 239000012716 precipitator Substances 0.000 claims description 8
- 239000004593 Epoxy Chemical class 0.000 claims description 7
- 229920001577 copolymer Polymers 0.000 claims description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- 238000007599 discharging Methods 0.000 claims description 6
- 238000011084 recovery Methods 0.000 claims description 6
- 239000006228 supernatant Substances 0.000 claims description 6
- KNKRKFALVUDBJE-UHFFFAOYSA-N 1,2-dichloropropane Chemical compound CC(Cl)CCl KNKRKFALVUDBJE-UHFFFAOYSA-N 0.000 claims description 5
- 238000005086 pumping Methods 0.000 claims description 5
- 239000007790 solid phase Substances 0.000 claims description 5
- 125000002947 alkylene group Chemical group 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 239000012467 final product Substances 0.000 claims description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 3
- 238000007670 refining Methods 0.000 claims description 3
- UOORRWUZONOOLO-OWOJBTEDSA-N (E)-1,3-dichloropropene Chemical compound ClC\C=C\Cl UOORRWUZONOOLO-OWOJBTEDSA-N 0.000 claims description 2
- GJEZBVHHZQAEDB-UHFFFAOYSA-N 6-oxabicyclo[3.1.0]hexane Chemical compound C1CCC2OC21 GJEZBVHHZQAEDB-UHFFFAOYSA-N 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 2
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 2
- ZQKKGHXDMUVUFH-UHFFFAOYSA-N cyclohexanone;propan-2-one Chemical compound CC(C)=O.O=C1CCCCC1 ZQKKGHXDMUVUFH-UHFFFAOYSA-N 0.000 claims description 2
- ZWAJLVLEBYIOTI-UHFFFAOYSA-N cyclohexene oxide Chemical compound C1CCCC2OC21 ZWAJLVLEBYIOTI-UHFFFAOYSA-N 0.000 claims description 2
- FWFSEYBSWVRWGL-UHFFFAOYSA-N cyclohexene oxide Natural products O=C1CCCC=C1 FWFSEYBSWVRWGL-UHFFFAOYSA-N 0.000 claims description 2
- 239000000178 monomer Substances 0.000 claims description 2
- UOORRWUZONOOLO-UHFFFAOYSA-N telone II Natural products ClCC=CCl UOORRWUZONOOLO-UHFFFAOYSA-N 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 abstract description 25
- 239000000047 product Substances 0.000 abstract description 21
- 239000007787 solid Substances 0.000 abstract description 10
- 239000003054 catalyst Substances 0.000 abstract description 8
- 239000006227 byproduct Substances 0.000 abstract description 7
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 abstract description 5
- 238000000926 separation method Methods 0.000 abstract description 4
- 229920005989 resin Polymers 0.000 abstract description 2
- 239000011347 resin Substances 0.000 abstract description 2
- 239000007788 liquid Substances 0.000 abstract 1
- 230000007613 environmental effect Effects 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000009826 distribution Methods 0.000 description 6
- 235000019441 ethanol Nutrition 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 229920001897 terpolymer Polymers 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- SZNYYWIUQFZLLT-UHFFFAOYSA-N 2-methyl-1-(2-methylpropoxy)propane Chemical compound CC(C)COCC(C)C SZNYYWIUQFZLLT-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000004383 yellowing Methods 0.000 description 2
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- QQQCWVDPMPFUGF-ZDUSSCGKSA-N alpinetin Chemical compound C1([C@H]2OC=3C=C(O)C=C(C=3C(=O)C2)OC)=CC=CC=C1 QQQCWVDPMPFUGF-ZDUSSCGKSA-N 0.000 description 1
- 229920005603 alternating copolymer Polymers 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- XCIXKGXIYUWCLL-UHFFFAOYSA-N cyclopentanol Chemical compound OC1CCCC1 XCIXKGXIYUWCLL-UHFFFAOYSA-N 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/64—Polyesters containing both carboxylic ester groups and carbonate groups
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention discloses a post-treatment process of a carbon dioxide-based biodegradable multipolymer, which comprises the following steps: the invention adopts 1, 2-dichloroethane organic solvent and absolute ethyl alcohol as the precipitating agent to act synergistically, can improve the removal rate of impurities such as catalyst, by-products and the like, improve the quality of polymer products, obtain transparent resin polymers, and adopt the following steps of dissolving the prepared polymer glue solution by using an organic solvent, then adding the precipitating agent to precipitate solids, and carrying out solid-liquid separation to obtain pure multipolymer, wherein the weight ratio of the glue solution to the organic solvent is 1: (0.4-1) and the weight ratio of the glue solution to the precipitating agent 1: the weight ratio of (0.4-1.5) can improve the impurity removal rate, avoid the loss of small molecular polymers in polymer products, improve the product yield and increase the weight ratio of the propylene carbonate in the polymers.
Description
Technical Field
The invention relates to a post-treatment process of a carbon dioxide-based biodegradable multipolymer, which relates to C08G, in particular to a macromolecular compound obtained by reactions other than carbon-carbon unsaturated bonds.
Background
The traditional plastic polymer has poor biodegradability, causes serious white pollution along with the increase of the using amount, and has greatly limited use of polymer materials with poor degradation performance along with the gradual improvement of environmental awareness of people. However, the post-treatment process of the carbon dioxide-based biodegradable multipolymer in the current market is not good, the catalyst and the by-product in the production process can not be effectively separated from the product polymer, so that the generated polymer has high impurity content and the product is yellow in color, and therefore, the post-treatment of the polymer is of great importance for improving the product quality of the polymer resin.
The Chinese invention patent CN200910100817.5 discloses a preparation method of alternating copolymer of maleic anhydride and vinyl acetate, which can improve the polymerization efficiency of the polymer by using supercritical carbon dioxide as a polymerization medium, reduce the generation of by-products and obtain a pure polymerization product, but the requirement standard of the supercritical carbon dioxide for process production on equipment is high and the cost is high. Chinese patent CN98125655.4 discloses a method for preparing high molecular weight aliphatic polycarbonate, which adopts rare earth complex combination to form a catalyst, improves the polymerization efficiency of the polymer, increases the molecular weight of the polymer, but the post-treatment step of the polymer needs to use a large amount of organic solvent for purification and refining, and has higher energy consumption.
Disclosure of Invention
In order to improve the impurity removal rate of the carbon dioxide-based biodegradable multi-component copolymer and reduce the use volatilization of organic solvents in the post-treatment step, the invention provides a post-treatment process of the carbon dioxide-based biodegradable multi-component copolymer, which comprises the following steps:
(1) placing the glue solution in a common dissolving tank, stirring to rotate at 60-100r/min, slowly adding organic solvent for dissolving, and stirring at a certain temperature for dissolving for 1-10min to obtain a mixed solution;
(2) transferring the mixed solution into a precipitator, stirring until the rotation speed is 60-100r/min, slowly adding a precipitator, stirring for 3-10min after the addition is finished, stopping stirring, and standing for 5-30 min;
(3) pumping the layered supernatant into a rectifying tower of a recovery system by using a pipeline, extruding the lower solid phase by using a screw rod, entering a devolatilization machine for devolatilization, devolatilizing for 0.1-2h at a certain temperature and under a vacuum degree, and discharging to obtain the final product.
In a preferred embodiment, the dope is a carbon dioxide-based multipolymer and impurities thereof, and the carbon dioxide-based multipolymer contains carbonate monomers on a main chain.
In a preferred embodiment, the comonomer in the carbon dioxide-based multipolymer is selected from one or a combination of more of carbon dioxide, epoxy compounds, anhydride compounds and ester compounds.
As a preferred embodiment, the epoxy compound is an alkylene oxide, and preferably, the alkylene oxide is one or a combination of several selected from ethylene oxide, propylene oxide, butylene oxide, cyclohexene oxide, epichlorohydrin and cyclopentane oxide.
As a preferred embodiment, the acid anhydride compound is one or a combination of more of maleic anhydride, phthalic anhydride and acetic anhydride.
As a preferred embodiment, the carbon dioxide-based multipolymer is a propylene oxide-phthalic anhydride-carbon dioxide terpolymer.
As a preferred embodiment, the carbon dioxide-based multipolymer has a number average molecular weight of 0.1 to 5.0X 105g/mol, molecular weight distribution of 1-15.
As a preferred embodiment, the carbon dioxide-based multipolymer has a solid content of 50 to 65%, and preferably the viscosity of the carbon dioxide-based multipolymer at 25 ℃ is 2 to 15X 104mPa.s。
In a preferred embodiment, the carbon dioxide-based multipolymer has a number average molecular weight of 9.76X 104g/mol, molecular weight distribution of 1.85, solid content of 56.54%, viscosity at 25 ℃ of 40860 mPa.s.
As a preferred embodiment, the dipole moment of the organic solvent is 3-5D, and preferably, the organic solvent is selected from one or a combination of several of dichloromethane, 1, 2-dichloroethane, 1, 2-dichloropropane, 1, 3-dichloropropene, ethyl acetate, methyl acetate and acetone cyclohexanone.
As a preferred embodiment, the organic solvent is 1, 2-dichloroethane.
In a preferred embodiment, the precipitating agent is selected from one or a combination of several of alcohols, alkanes and ethers.
In a preferred embodiment, the alcohol is selected from one or more of methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, n-pentanol, n-hexanol, methyl propanol, cyclopentanol, and cyclohexanol.
In a preferred embodiment, the alkane is selected from one or a combination of several of n-octane, n-decane and n-nonane.
As a preferred embodiment, the ether substance is selected from one or a combination of several of ethyl ether, n-butyl ether, isobutyl ether, n-propyl ether and isopropyl ether.
In a preferred embodiment, the precipitating agent is ethanol, and more preferably, the ethanol is absolute ethanol.
In the experimental process, the applicant finds that the organic solvent of 1, 2-dichloropropane and the precipitating agent of absolute ethyl alcohol act synergistically to improve the performance of the product and reduce the yellowing effect of the polymer, and guesses that the possible reasons are as follows: the 1, 2-dichloropropane can dissolve the carbon dioxide-based multipolymer to form a solution state, and a catalyst and a byproduct in the production process can also be dissolved in a glue solution, the carbon dioxide-based multipolymer can become solid to be separated out after absolute ethyl alcohol is added and the carbon dioxide-based multipolymer is kept in the solution, but the catalyst and the byproduct still remain in the solution, and the separation of the carbon dioxide-based multipolymer glue solution from the catalyst and the byproduct is realized through layering, so that the product quality of the polymer is improved, and the yellowing is avoided. The synergistic effect of the organic solvent and the precipitating agent can realize the complete separation of the carbon dioxide-based multipolymer and impurities, simplify the complex procedures of the subsequent devolatilization treatment process and greatly improve the removal rate of the impurities. And the synergistic action of the 1, 2-dichloropropane and the absolute ethyl alcohol can realize the dissolution of impurities without causing the loss of small molecular weight products, can completely separate out all polymerization products in a separation stage, and avoids the reduction of the yield of the products caused by the fact that small-weight products are not separated out.
As a preferred embodiment, the weight ratio of the glue solution to the organic solvent is 1: (0.2-2), preferably, the weight ratio of the glue solution to the precipitating agent is 1: (0.2-3).
As a preferred embodiment, the weight ratio of the glue solution to the organic solvent is 1: (0.4-1), preferably, the weight ratio of the glue solution to the precipitating agent is 1: (0.4-2.2).
As a preferred embodiment, the weight ratio of the glue solution to the organic solvent is 1: 0.9, preferably, the weight ratio of the glue solution to the precipitating agent is 1: 1.3.
in the experimental process, the applicant finds that the glue solution and the organic solvent adopt the following formula (1: (0.4-1), and adopting a glue solution and a precipitating agent in a weight ratio of 1: the weight ratio of (0.4-1.5) can make the polymer product be completely separated out, and the impurity can be remained in the solution, so that the impurity removal rate can be greatly raised, at the same time the polymer with small molecular weight also can be separated out, and the reduction of product yield can be reduced.
In a preferred embodiment, the temperature in the step 1 is 1 to 100 ℃, preferably, the devolatilization temperature in the step 3 is 60 to 200 ℃, and the devolatilization vacuum degree is-0.1 to-1 MPa.
As a preferred embodiment, the temperature of the step 1 is 20-60 ℃, preferably, the devolatilization temperature of the step 3 is 140-180 ℃, and the devolatilization vacuum degree is-0.1-0.5 MPa.
In a preferred embodiment, the temperature in the step 1 is 40 ℃, and the devolatilization temperature in the step 3 is preferably 150 ℃, and the devolatilization vacuum degree is-0.1 MPa.
The second aspect of the invention provides an application of a post-treatment process of a carbon dioxide-based biodegradable multipolymer, which is applied to the refining of carbon dioxide-based biodegradable binary and above multipolymers.
Compared with the prior art, the invention has the following beneficial effects:
(1) according to the post-treatment process of the carbon dioxide-based biodegradable multipolymer, the 1, 2-dichloroethane organic solvent and the absolute ethyl alcohol are adopted as the precipitating agents to act synergistically, so that the removal rate of impurities such as catalysts and byproducts can be improved, the quality of polymer products is improved, and the transparent resin polymer is obtained.
(2) The invention relates to a post-treatment process of a carbon dioxide-based biodegradable multipolymer, which adopts a glue solution and an organic solvent 1: (0.4-1) and the weight ratio of the glue solution to the precipitating agent 1: the weight ratio of (0.4-1.5) can improve the impurity removal rate, avoid the loss of small molecular polymers in polymer products, improve the product yield and increase the weight ratio of the propylene carbonate in the polymers.
(3) According to the post-treatment process of the carbon dioxide-based biodegradable multipolymer, the dissolving temperature of 10-60 ℃ is adopted in the step 1, so that the dissolving effect of the glue solution and the impurities can be improved, the impurities can be completely dissolved, and the impurities are prevented from being incompletely separated to be impure.
(4) The post-treatment process of the carbon dioxide-based biodegradable multipolymer adopts the devolatilization temperature of 140-180 ℃, improves the devolatilization efficiency, adopts single organic solvent and precipitating agent, has simple devolatilization process, and is suitable for large-scale industrial production.
(5) According to the post-treatment process of the carbon dioxide-based biodegradable multipolymer, the layered supernatant is pumped out by a pipeline and enters a recovery system, so that the organic solvent and the precipitating agent can be recovered and reused, the utilization rate of the organic solvent is increased, and the environmental protection problem caused by the use of the organic solvent is reduced.
Drawings
FIG. 1 is a schematic view of the post-treatment process of the carbon dioxide-based biodegradable multipolymer of the present invention.
In the figure: 1. a reaction kettle; 2. a dissolving tank; 3. a precipitator; 4. a rectifying tower; 5. a devolatilization machine.
Detailed Description
The present invention will be specifically described below by way of examples. It should be noted that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention, and that the insubstantial modifications and adaptations of the present invention by those skilled in the art based on the above disclosure are still within the scope of the present invention.
In addition, the starting materials used are all commercially available, unless otherwise specified.
Example 1
A post-treatment process of a carbon dioxide-based biodegradable multipolymer comprises the following steps:
(1) taking 20kg of glue solution from the reaction kettle 1, placing the glue solution in a common dissolving tank 2, opening and stirring the glue solution until the rotating speed is 80r/min, slowly adding an organic solvent for dissolving, and stirring the glue solution for dissolving for 5min at a certain temperature after the adding is finished to obtain a mixed solution;
(2) transferring the mixed solution into a precipitator 3, starting stirring until the rotating speed is 80r/min, slowly adding a precipitating agent, stirring for 5min after the adding is finished, stopping stirring, and standing for 30 min;
(3) pumping the layered supernatant into a rectifying tower 4 of a recovery system by using a pipeline, extruding the lower solid phase by using a screw rod, entering a devolatilization machine 5 for devolatilization, devolatilizing for 2 hours at a certain temperature and under a vacuum degree, and discharging to obtain the final product.
The glue solution is a carbon dioxide-based multipolymer and impurities thereof, the carbon dioxide-based multipolymer is an epoxy propane-phthalic anhydride-carbon dioxide terpolymer, and the number average molecular weight is 9.76 multiplied by 104g/mol, molecular weight distribution of 1.85, solid content of 56.54%, viscosity at 25 ℃ of 40860mPa.s, available from Shandong Lianxin environmental protection science and technology Co.
The organic solvent is 1, 2-dichloroethane, industrial grade, purity 99.9%, and is purchased from Shanghai chlor-alkali chemical industry Co., Ltd.
The precipitating agent is absolute ethyl alcohol, has industrial grade and purity of 99.9 percent, and is purchased from catalpo Danyang chemical industry Co.
The weight ratio of the glue solution to the organic solvent is 1: 0.5, wherein the weight ratio of the glue solution to the precipitating agent is 1: 1.3.
the temperature of the step 1 is 40 ℃, the devolatilization temperature of the step 3 is 150 ℃, and the vacuum degree is-0.1 MPa.
Example 2
A post-treatment process of a carbon dioxide-based biodegradable multipolymer comprises the following steps:
(1) taking 20kg of glue solution from the reaction kettle 1, placing the glue solution in a common dissolving tank 2, opening and stirring the glue solution until the rotating speed is 80r/min, slowly adding an organic solvent for dissolving, and after the adding is finished, stirring the glue solution for dissolving for 10min at a certain temperature to obtain a mixed solution;
(2) transferring the mixed solution into a precipitator 3, starting stirring until the rotating speed is 80r/min, slowly adding a precipitator, stirring for 5min after the addition is finished, stopping stirring, and standing for 30 min;
(3) pumping the layered supernatant into a rectifying tower 4 of a recovery system by using a pipeline, extruding the lower solid phase by using a screw rod, entering a devolatilization machine 5 for devolatilization, devolatilizing for 1h at a certain temperature and under a vacuum degree, and discharging to obtain the final product.
The glue solution is a product mainly comprising a carbon dioxide-based multipolymer, the carbon dioxide-based multipolymer is an epoxy propane-phthalic anhydride-carbon dioxide terpolymer, and the number average molecular weight is 1.13 multiplied by 105g/mol, molecular weight distribution of 2.03, solid content of 57.83%, and viscosity of 21080mPa.s at 25 ℃ were purchased from Shandong Lianxin environmental protection science and technology Co., Ltd.
The organic solvent is 1, 2-dichloroethane, industrial grade, purity 99.9%, and is purchased from Shanghai chlor-alkali chemical industry Co., Ltd.
The precipitating agent is absolute ethyl alcohol, has industrial grade and purity of 99.9 percent, and is purchased from catalpo Danyang chemical industry Co.
The weight ratio of the glue solution to the organic solvent is 1: 0.9, wherein the weight ratio of the glue solution to the precipitating agent is 1: 2.
the temperature of the step 1 is 40 ℃, the devolatilization temperature of the step 3 is 160 ℃, and the devolatilization vacuum degree is-0.1 MPa.
Example 3
A post-treatment process of a carbon dioxide-based biodegradable multipolymer comprises the following steps:
(1) taking 15kg of glue solution from the reaction kettle 1, placing the glue solution in a common dissolving tank 2, opening and stirring the glue solution until the rotating speed is 80r/min, slowly adding an organic solvent for dissolving, and stirring and dissolving the glue solution for 5min at a certain temperature after the adding is finished to obtain a mixed solution;
(2) Transferring the mixed solution into a precipitator 3, starting stirring until the rotating speed is 80r/min, slowly adding a precipitating agent, stirring for 5min after the adding is finished, stopping stirring, and standing for 30 min;
(3) pumping the layered supernatant into a rectifying tower 4 of a recovery system by using a pipeline, extruding the lower solid phase by using a screw rod, entering a devolatilization machine 5 for devolatilization, devolatilizing for 0.5h at a certain temperature and under a vacuum degree, and discharging to obtain the catalyst.
The glue solution is a product mainly comprising a carbon dioxide-based multipolymer, the carbon dioxide-based multipolymer is a propylene oxide-phthalic anhydride-carbon dioxide terpolymer, and the number average molecular weight is 1.5 multiplied by 105g/mol, molecular weight distribution of 3.15, solid content of 61.23%, viscosity at 25 ℃ of 148560mPa.s, which is available from Shandong Lianxin environmental protection science and technology Co.
The organic solvent is 1, 2-dichloroethane, industrial grade, purity 99.9%, and is purchased from Shanghai chlor-alkali chemical industry Co., Ltd.
The precipitating agent is absolute ethyl alcohol, has industrial grade and purity of 99.9 percent, and is purchased from catalpo Danyang chemical industry Co.
The weight ratio of the glue solution to the organic solvent is 1: 1, wherein the weight ratio of the glue solution to the precipitating agent is 1: 2.2.
the temperature of the step 1 is 40 ℃, the devolatilization temperature of the step 3 is 180 ℃, and the devolatilization vacuum degree is-0.1 MPa.
Example 4
A post-treatment process of a carbon dioxide-based biodegradable multipolymer comprises the following steps:
taking 10kg of glue solution from the reaction kettle 1, placing the glue solution in a double-screw self-cleaning mixing extruder, adding pure water, heating to 80 ℃, washing for 30min, tabletting, slicing, drying and discharging to obtain the glue solution.
The glue solution is a product mainly comprising a carbon dioxide-based multipolymer, the carbon dioxide-based multipolymer is an epoxy propane-phthalic anhydride-carbon dioxide terpolymer, and the number average molecular weight is 1.5 multiplied by 105g/mol, molecular weight distribution of 3.15, solid content of 61.23%, and viscosity of 148560mPa.s at 25 ℃ were purchased from Shandong Lianxin environmental protection science and technology Co., Ltd.
The conductivity of the pure water is 18.26M omega cm, and the pure water is purchased from Shandong Lianxin environmental protection science and technology Limited.
The mass ratio of the glue solution to the pure water is 1: 5.
performance test
1. Appearance color: the color appearance of the prepared polymer was visually observed.
2. Yield: weighing the mass m of the resulting solid sample1(ii) a Yield m (glue solution) x glue solution solid content/m1×100％。
3. The mass ratio of the propylene carbonate is as follows: the mass fraction of propylene carbonate in the polymer was determined by NMR spectroscopy.
The test results are shown in Table 1.
TABLE 1
| Apparent color | Yield/% | Propylene carbonate ratio by mass/%) | |
| Example 1 | Transparent colorless | 98.05 | 0.9 |
| Example 2 | Transparent and colorless | 99.67 | 0.3 |
| Example 3 | Transparent and colorless | 99.83 | 0.0 |
| Example 4 | Opaque, amber | 105 | 2.5 |
Claims (10)
1. A post-treatment process of a carbon dioxide-based biodegradable multipolymer is characterized by comprising the following steps:
(1) placing the glue solution in a common dissolving tank, opening and stirring to the rotating speed of 60-100r/min, slowly adding an organic solvent for dissolving, and after the adding is finished, stirring and dissolving at a certain temperature for 1-10min to obtain a mixed solution;
(2) transferring the mixed solution into a precipitator, stirring until the rotating speed is 60-100r/min, slowly adding a precipitating agent, stirring for 3-10min after the adding is finished, stopping stirring, and standing for 5-30 min;
(3) pumping the layered supernatant into a recovery system by a pipeline, extruding the lower solid phase by a screw rod, devolatilizing in a devolatilization machine at a certain temperature and vacuum degree for 0.1-2h, and discharging to obtain the final product.
2. The post-treatment process of the carbon dioxide-based biodegradable multipolymer as claimed in claim 1, wherein the glue solution is a carbon dioxide-based multipolymer and impurities thereof, and the main chain of the carbon dioxide-based multipolymer contains carbonate monomers.
3. The post-treatment process of the carbon dioxide-based biodegradable multipolymer according to claim 2, wherein the comonomer in the carbon dioxide-based multipolymer is one or a combination of several selected from carbon dioxide, epoxy compounds, anhydride compounds and ester compounds.
4. The post-treatment process of the carbon dioxide-based biodegradable multipolymer according to claim 3, characterized in that the epoxy compound is alkylene oxide.
5. The post-treatment process of the carbon dioxide-based biodegradable multi-component copolymer as claimed in claim 4, wherein the alkylene oxide is selected from one or more of ethylene oxide, propylene oxide, butylene oxide, cyclohexene oxide, epichlorohydrin and cyclopentane oxide.
6. The post-treatment process of the carbon dioxide-based biodegradable multi-component copolymer as claimed in claim 1 or 2, wherein the dipole moment of the organic solvent is 3-5D, preferably, the organic solvent is selected from one or more of dichloromethane, 1, 2-dichloroethane, 1, 2-dichloropropane, 1, 3-dichloropropene, ethyl acetate, methyl acetate, acetone cyclohexanone.
7. The post-treatment process of the carbon dioxide-based biodegradable multipolymer according to claim 1 or 2, characterized in that the precipitating agent is selected from one or a combination of several of alcohol substances, alkane and ether substances.
8. The post-treatment process of the carbon dioxide-based biodegradable multipolymer according to claim 1 or 2, characterized in that the weight ratio of the glue solution to the organic solvent is 1: (0.2-2), preferably, the weight ratio of the glue solution to the precipitating agent is 1: (0.2-3).
9. The post-treatment process of the carbon dioxide-based biodegradable multi-copolymer according to claim 1 or 2, wherein the temperature of step 1 is 1-100 ℃, and preferably the devolatilization temperature of step 3 is 60-200 ℃.
10. Use of the post-treatment process of carbon dioxide-based biodegradable multi-component copolymer according to any of claims 1-9 in the refining of carbon dioxide-based biodegradable di-and copolymers.
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| PCT/CN2023/079431 WO2023179335A1 (en) | 2022-03-25 | 2023-03-03 | Post-treatment process for carbon-dioxide-based biodegradable multipolymer, and use thereof |
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| CN115716911A (en) * | 2022-11-18 | 2023-02-28 | 山东联欣环保科技有限公司 | Devolatilization method and devolatilization system |
| WO2023179335A1 (en) * | 2022-03-25 | 2023-09-28 | 山东联欣环保科技有限公司 | Post-treatment process for carbon-dioxide-based biodegradable multipolymer, and use thereof |
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| US4975525A (en) * | 1988-03-21 | 1990-12-04 | Arco Chemical Technology, Inc. | Formation of discrete polyalkylene carbonate particles by solvent/non-solvent precipitation |
| CN101003620A (en) * | 2006-01-17 | 2007-07-25 | 河南天冠企业集团有限公司 | Devolatilization technique and equipment without auxiliary agent for aliphatic polycarbonate resin |
| CN111635517A (en) * | 2020-05-12 | 2020-09-08 | 中国化学赛鼎宁波工程有限公司 | Method for removing catalyst in carbon dioxide-propylene oxide copolymer |
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| CN1412221A (en) * | 2001-10-09 | 2003-04-23 | 威海威高创新有限公司 | Preparation method of medical carbon dioxide copolymer |
| CN102964584B (en) * | 2012-11-14 | 2014-12-31 | 万华化学集团股份有限公司 | Purification method of crude polycarbonate solution |
| JP6078166B2 (en) * | 2013-05-27 | 2017-02-08 | エルジー・ケム・リミテッド | Process for producing polyalkylene carbonate |
| KR101767310B1 (en) * | 2015-07-10 | 2017-08-10 | 국민대학교산학협력단 | Method for synthesizing terpolymer of epoxide containing electon withdrawing group, CO2 and epoxide non-contaning electon withdrawing group |
| CN111378101B (en) * | 2020-04-26 | 2022-02-01 | 中山大学 | Preparation method of biodegradable carbon dioxide-based polyester-polycarbonate terpolymer |
| CN114752045A (en) * | 2022-03-25 | 2022-07-15 | 山东联欣环保科技有限公司 | Post-treatment process and application of carbon dioxide-based biodegradable multipolymer |
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| US4975525A (en) * | 1988-03-21 | 1990-12-04 | Arco Chemical Technology, Inc. | Formation of discrete polyalkylene carbonate particles by solvent/non-solvent precipitation |
| CN101003620A (en) * | 2006-01-17 | 2007-07-25 | 河南天冠企业集团有限公司 | Devolatilization technique and equipment without auxiliary agent for aliphatic polycarbonate resin |
| CN111635517A (en) * | 2020-05-12 | 2020-09-08 | 中国化学赛鼎宁波工程有限公司 | Method for removing catalyst in carbon dioxide-propylene oxide copolymer |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2023179335A1 (en) * | 2022-03-25 | 2023-09-28 | 山东联欣环保科技有限公司 | Post-treatment process for carbon-dioxide-based biodegradable multipolymer, and use thereof |
| CN115716911A (en) * | 2022-11-18 | 2023-02-28 | 山东联欣环保科技有限公司 | Devolatilization method and devolatilization system |
| WO2024104366A1 (en) * | 2022-11-18 | 2024-05-23 | 山东联欣环保科技有限公司 | Devolatilization method and devolatilization system |
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