CN117304466A - Degradable polycarbonate and preparation method and application thereof - Google Patents
Degradable polycarbonate and preparation method and application thereof Download PDFInfo
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- 229920000515 polycarbonate Polymers 0.000 title claims abstract description 72
- 239000004417 polycarbonate Substances 0.000 title claims abstract description 72
- 238000002360 preparation method Methods 0.000 title claims abstract description 39
- 238000006243 chemical reaction Methods 0.000 claims abstract description 89
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims abstract description 58
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 51
- 239000003054 catalyst Substances 0.000 claims abstract description 51
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 50
- 239000010936 titanium Substances 0.000 claims abstract description 50
- 239000002808 molecular sieve Substances 0.000 claims abstract description 47
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 47
- 238000005809 transesterification reaction Methods 0.000 claims abstract description 30
- 239000002994 raw material Substances 0.000 claims abstract description 27
- 238000009835 boiling Methods 0.000 claims abstract description 25
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 23
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 20
- 239000010703 silicon Substances 0.000 claims abstract description 20
- 150000004650 carbonic acid diesters Chemical class 0.000 claims abstract description 18
- 230000035484 reaction time Effects 0.000 claims abstract description 16
- 150000005690 diesters Chemical class 0.000 claims abstract description 14
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims abstract description 10
- 230000009471 action Effects 0.000 claims abstract description 5
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 42
- 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 17
- 238000000034 method Methods 0.000 claims description 17
- 230000007062 hydrolysis Effects 0.000 claims description 16
- 238000006460 hydrolysis reaction Methods 0.000 claims description 16
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 12
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 10
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 10
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 239000003381 stabilizer Substances 0.000 claims description 9
- 238000001354 calcination Methods 0.000 claims description 8
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 claims description 8
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 claims description 8
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 238000003837 high-temperature calcination Methods 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 239000012686 silicon precursor Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- ASMQGLCHMVWBQR-UHFFFAOYSA-M diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)([O-])OC1=CC=CC=C1 ASMQGLCHMVWBQR-UHFFFAOYSA-M 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 claims description 4
- 229910000348 titanium sulfate Inorganic materials 0.000 claims description 4
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 4
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 claims description 4
- KKUKTXOBAWVSHC-UHFFFAOYSA-N Dimethylphosphate Chemical compound COP(O)(=O)OC KKUKTXOBAWVSHC-UHFFFAOYSA-N 0.000 claims description 3
- 230000032683 aging Effects 0.000 claims description 3
- 210000000988 bone and bone Anatomy 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 claims description 3
- KUMNEOGIHFCNQW-UHFFFAOYSA-N diphenyl phosphite Chemical compound C=1C=CC=CC=1OP([O-])OC1=CC=CC=C1 KUMNEOGIHFCNQW-UHFFFAOYSA-N 0.000 claims description 3
- 239000003814 drug Substances 0.000 claims description 3
- 229940079593 drug Drugs 0.000 claims description 3
- 230000002439 hemostatic effect Effects 0.000 claims description 3
- 239000002362 mulch Substances 0.000 claims description 3
- 239000005022 packaging material Substances 0.000 claims description 3
- 230000008439 repair process Effects 0.000 claims description 3
- 238000004904 shortening Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 46
- -1 polybutylene carbonate Polymers 0.000 description 30
- 239000000243 solution Substances 0.000 description 21
- 238000003860 storage Methods 0.000 description 12
- 238000005303 weighing Methods 0.000 description 8
- 238000002474 experimental method Methods 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- QLVWOKQMDLQXNN-UHFFFAOYSA-N dibutyl carbonate Chemical compound CCCCOC(=O)OCCCC QLVWOKQMDLQXNN-UHFFFAOYSA-N 0.000 description 5
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical group C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 238000005216 hydrothermal crystallization Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 229910000349 titanium oxysulfate Inorganic materials 0.000 description 3
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical group [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
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
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/20—General preparatory processes
- C08G64/30—General preparatory processes using carbonates
- C08G64/305—General preparatory processes using carbonates and alcohols
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention provides a degradable polycarbonate and a preparation method and application thereof, wherein the preparation method of the degradable polycarbonate specifically comprises the following steps: s1, preparing a titanium-silicon molecular sieve catalyst by taking a silicon source, a titanium source and tetrapropylammonium hydroxide as raw materials; s2, under the action of the titanium-silicon molecular sieve catalyst prepared in the step S1, taking gaseous carbonic diester with low boiling point and 1, 4-butanediol as raw materials, and obtaining polycarbonate prepolymer through transesterification; and S3, carrying out polycondensation reaction on the polycarbonate prepolymer prepared in the step S2 to obtain the degradable polycarbonate, wherein compared with the prior art, the invention enables the low-boiling-point carbonic diester to be in contact with the 1, 4-butanediol in a gas form and to carry out transesterification reaction under the conditions of high temperature and normal pressure, thereby obviously shortening the reaction time and improving the reaction efficiency and the product yield. Meanwhile, the feeding amount of the low-boiling-point carbonic acid diester can be obviously reduced, the using amount of raw materials is greatly reduced, high raw material conversion rate is realized, and the cost is saved.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to degradable polycarbonate and a preparation method and application thereof.
Background
The aliphatic polycarbonate is a degradable high polymer material with no toxicity and good biodegradability and biocompatibility, and can be applied to the fields of medical treatment, packaging and the like. Among them, polybutylene carbonate (PBC) synthesized from a carbonic acid diester and 1, 4-butanediol has been paid attention to as having excellent overall properties, and has higher melting point, glass transition temperature, tensile strength and the like than other aliphatic polycarbonates. The raw materials of the carbonic diester can be diphenyl carbonate, dibutyl carbonate, diethyl carbonate, dimethyl carbonate and the like. The synthesis of polycarbonates by successive transesterification and polycondensation reactions is currently the most common and well-established method. In general, transesterification needs to be performed efficiently at a temperature of 150 ℃ or higher, and the boiling points of diethyl carbonate and dimethyl carbonate are 125 ℃ and 90 ℃ respectively, so that the transesterification is difficult to maintain and participate in the reaction in an environment of 150 ℃ or higher. While diphenyl carbonate and dibutyl carbonate have boiling points of 301 c and 207 c, respectively, to ensure that the reaction is maintained and occurs in a high temperature environment, diphenyl carbonate and dibutyl carbonate are relatively significantly more expensive than low boiling point diethyl carbonate and dimethyl carbonate. For example, the prices of dimethyl carbonate, diethyl carbonate, dibutyl carbonate and diphenyl carbonate are respectively 0.39-0.5 ten thousand yuan/ton, 0.5-0.75 ten thousand yuan/ton, 4.2 ten thousand yuan/ton and 2.5 ten thousand yuan/ton, and if diphenyl carbonate or dibutyl carbonate is adopted as raw materials, the production cost of PBC is greatly increased. If the low boiling point diethyl carbonate and dimethyl carbonate are reacted at a temperature lower than the boiling point thereof, the reaction efficiency is low, the reaction time is long, and a large excess of low boiling point raw materials are often required to compensate for the volatilization loss, resulting in serious waste of raw materials. Therefore, effective measures are necessary to solve the problem that the low-boiling point diethyl carbonate and dimethyl carbonate cannot be maintained and participate in the reaction under the high-temperature transesterification reaction condition.
Disclosure of Invention
The invention aims to provide a preparation method of degradable polycarbonate, which realizes the efficient transesterification of low-boiling-point carbonic acid diester under the high-temperature condition, obviously shortens the reaction time, improves the reaction efficiency, the raw material conversion rate and the product yield, and obtains the polycarbonate based on the low-boiling-point carbonic acid diester with high molecular weight.
In order to achieve the above purpose, the invention adopts the following technical scheme: a preparation method of degradable polycarbonate specifically comprises the following steps:
s1, preparing a titanium-silicon molecular sieve catalyst by taking a silicon source, a titanium source and tetrapropylammonium hydroxide as raw materials;
s2, under the action of the titanium-silicon molecular sieve catalyst prepared in the step S1, taking gaseous carbonic diester with low boiling point and 1, 4-butanediol as raw materials, and obtaining polycarbonate prepolymer through transesterification;
and S3, carrying out polycondensation reaction on the polycarbonate prepolymer prepared in the step S2 to obtain the degradable polycarbonate.
The invention makes the carbonic diester with low boiling point contact with 1, 4-butanediol in gas form under high temperature and normal pressure to generate transesterification reaction, which can obviously shorten the reaction time and improve the reaction efficiency and the product yield. Meanwhile, the feeding amount of the low-boiling-point carbonic acid diester can be obviously reduced, the using amount of raw materials is greatly reduced, high raw material conversion rate is realized, and the cost is saved.
Preferably, in the step S1, the silicon source is at least one selected from the group consisting of ethyl orthosilicate and/or silica sol. According to the invention, the tetraethoxysilane or the silica sol is adopted as a silicon source, so that titanium atoms can enter a molecular sieve framework, the titanium content in the framework is high, and the overall crystallinity of the molecular sieve is higher, so that the molecular sieve has higher catalytic activity.
Preferably, the titanium source is selected from at least one of titanium tetrachloride, tetrabutyl titanate, titanium isopropoxide and titanium sulfate. The tetrabutyl titanate is used as a titanium source, the hydrolysis rate is low, anatase can be prevented from being formed due to the fact that the hydrolysis rate is too high, the hydrolysis rate of the titanium source and the hydrolysis rate of the silicon source tend to be balanced, the titanium content and the crystallinity of the molecular sieve are improved, and therefore catalytic activity is improved. The hydrolysis rates of titanium tetrachloride, titanium isopropoxide and titanium sulfate are matched with the hydrolysis rate of a silicon source, so that the titanium content and crystallinity of the molecular sieve are improved, and the catalytic activity is improved. Compared with the prior art that titanyl sulfate is used as a titanium source, the hydrolysis rate of the titanyl sulfate is higher, and the synthesized molecular sieve contains a large amount of non-framework titanium, and the titanium has an inhibiting effect on the catalytic performance of the molecular sieve.
Preferably, the particle size of the titanium silicalite catalyst is 300-500nm.
Preferably, the specific preparation process of the step S1 is as follows:
s11, slowly dropwise adding a silicon source into a template agent by taking tetrapropylammonium hydroxide as the template agent to obtain a silicon source hydrolysis solution;
s12, dropwise adding a titanium source solution into the silicon source hydrolysis solution prepared in the step S11, and obtaining a titanium silicon precursor solution after stirring and aging reaction;
and S13, carrying out hydrothermal reaction on the titanium-silicon precursor solution, and after the reaction is finished, sequentially carrying out centrifugation, washing, drying and high-temperature calcination to obtain the titanium-silicon molecular sieve catalyst.
Preferably, in the step S13, the parameters of the hydrothermal reaction are as follows: the reaction temperature is 150-200 ℃ and the reaction time is 48-96h; the parameters for high temperature calcination are as follows: the calcination temperature is 450-600 ℃, and the calcination time is 5-24h.
Preferably, in the step S2, the parameters of the transesterification reaction are as follows: the reaction temperature is 150-220 ℃, the reaction time is 1-8h, and the reaction pressure is normal pressure.
Preferably, the titanium silicalite catalyst is added in an amount of 0.1 to 0.5% of the theoretical yield of the degradable polycarbonate.
Preferably, in the step S2, the gaseous low-boiling-point carbonic acid diester is gaseous dimethyl carbonate and/or gaseous diethyl carbonate, and the molar ratio of the gaseous low-boiling-point carbonic acid diester to the 1, 4-butanediol is (1.1-1.5): 1.
Preferably, in the step S3, the raw material further includes a stabilizer, where the stabilizer is at least one selected from trimethyl phosphate, dimethyl phosphate, triphenyl phosphate, diphenyl phosphate, triphenyl phosphite and diphenyl phosphite, and the addition amount of the stabilizer is 0.01-0.3% of the theoretical yield of the degradable polycarbonate.
Preferably, in the step S3, the parameters of the polycondensation reaction are as follows: the reaction temperature is 190-240 ℃, the vacuum degree is less than 100Pa, and the reaction time is 2-10h. In the step S3, the titanium silicalite molecular sieve catalyst can be used as a catalyst for transesterification or polycondensation, so that the titanium silicalite molecular sieve catalyst does not need to be repeatedly added in the step S3.
The second object of the present invention is to provide a degradable polycarbonate produced by the above production method, and the weight average molecular weight of the degradable polycarbonate is 50000g/mol or more.
A third object of the present invention is to provide the use of a degradable polycarbonate for the preparation of shopping bags, for the preparation of packaging materials, for the preparation of agricultural mulch films, for the preparation of sinus drug stents, for the preparation of surgical hemostatic members, for the preparation of medical sutures or for the preparation of bone repair materials.
Compared with the prior art, the invention has the following advantages:
1. the invention makes the carbonic diester with low boiling point contact with 1, 4-butanediol in gas form under high temperature and normal pressure to generate transesterification reaction, which can obviously shorten the reaction time and improve the reaction efficiency and the product yield. Meanwhile, the feeding amount of the low-boiling-point carbonic acid diester can be obviously reduced, the using amount of raw materials is greatly reduced, high raw material conversion rate is realized, and the cost is saved;
2. the titanium-silicon molecular sieve catalyst prepared by the invention not only has high catalytic activity for synthesizing the polycarbonate, but also can avoid the problems of yellowing of the product and gradual deepening of the color caused by prolonging the standing time of the product when tetrabutyl titanate is directly used as the catalyst, thereby successfully obtaining the white polycarbonate product with high molecular weight.
Drawings
FIG. 1 is a degradable polycarbonate prepared in example 4 of the present invention 1 H-NMR spectrum;
FIG. 2 is a GPC curve of a degradable polycarbonate prepared in example 4 of the present invention.
Detailed Description
In order that the above objects, features and advantages of the invention will be readily understood, a more particular description of the invention will be rendered by reference to specific embodiments thereof which are illustrated in the appended drawings.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. In addition, for numerical ranges in this disclosure, it is understood that each intermediate value between the upper and lower limits of the ranges is also specifically disclosed. Every smaller range between any stated value or stated range, and any other stated value or intermediate value within the stated range, is also encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the invention described herein without departing from the scope or spirit of the invention. Other embodiments will be apparent to those skilled in the art from consideration of the specification of the present invention. The specification and examples are exemplary only.
The invention provides a preparation method of degradable polycarbonate, which comprises the following steps:
s1, preparing a titanium silicalite molecular sieve catalyst by taking a silicon source, a titanium source and tetrapropylammonium hydroxide as raw materials, wherein the silicon source is at least one of tetraethoxysilane and/or silica sol, the titanium source is at least one of titanium tetrachloride, tetrabutyl titanate, titanium isopropoxide and titanium sulfate, and the particle size of the obtained titanium silicalite molecular sieve catalyst is 300-500nm;
s2, under the action of the titanium-silicon molecular sieve catalyst prepared in the step S1, taking gaseous carbonic diester with low boiling point and 1, 4-butanediol as raw materials, and obtaining polycarbonate prepolymer through transesterification, wherein the parameters of the transesterification are as follows: the reaction temperature is 150-220 ℃, the reaction time is 1-8h, the reaction pressure is normal pressure, and the addition amount of the titanium silicalite molecular sieve catalyst is 0.1-0.5% of the theoretical yield of the degradable polycarbonate;
s3, carrying out polycondensation reaction on the polycarbonate prepolymer prepared in the step S2 to obtain degradable polycarbonate, wherein the parameters of the polycondensation reaction are as follows: the reaction temperature is 190-240 ℃, the vacuum degree is less than 100Pa, and the reaction time is 2-10h.
In a specific embodiment, the specific preparation process of step S1 is as follows:
s11, slowly dropwise adding a silicon source into a template agent by taking tetrapropylammonium hydroxide as the template agent to obtain a silicon source hydrolysis solution;
s12, dropwise adding a titanium source solution into the silicon source hydrolysis solution prepared in the step S11, and obtaining a titanium silicon precursor solution after stirring and aging reaction;
s13, carrying out hydrothermal reaction on the titanium-silicon precursor solution, and after the reaction is finished, sequentially carrying out centrifugation, washing, drying and high-temperature calcination to obtain the titanium-silicon molecular sieve catalyst, wherein the parameters of the hydrothermal reaction are as follows: the reaction temperature is 150-200 ℃, the reaction time is 48-96h, and the parameters of high-temperature calcination are as follows: the calcination temperature is 450-600 ℃, and the calcination time is 5-24h.
In a specific embodiment, the gaseous low-boiling carbonic acid diester is gaseous dimethyl carbonate and/or gaseous diethyl carbonate, and the molar ratio of the gaseous low-boiling carbonic acid diester to 1, 4-butanediol is (1.1-1.5): 1.
More preferably, the gaseous low boiling point carbonic acid diester is gaseous dimethyl carbonate. The dimethyl carbonate can be prepared by taking carbon dioxide as a raw material, so that the effective fixation of the carbon dioxide in the degradable polycarbonate can be well completed, and the development of carbon neutralization technology is facilitated.
In a specific embodiment, in the step S3, the raw materials further comprise a stabilizer, wherein the stabilizer is at least one selected from trimethyl phosphate, dimethyl phosphate, triphenyl phosphate, diphenyl phosphate, triphenyl phosphite and diphenyl phosphite, and the addition amount of the stabilizer is 0.01-0.3% of the theoretical yield of the degradable polycarbonate.
In the step S3, the titanium silicalite molecular sieve catalyst can be used as a catalyst for transesterification or polycondensation, so that the titanium silicalite molecular sieve catalyst does not need to be repeatedly added in the step S3.
A second object of embodiments of the present invention is to provide a degradable polycarbonate produced by the above production method, wherein the weight average molecular weight of the degradable polycarbonate is 50000g/mol or more.
A third object of particular embodiments of the present invention is to provide the use of a degradable polycarbonate for the preparation of shopping bags, for the preparation of packaging materials, for the preparation of agricultural mulch films, for the preparation of sinus drug stents, for the preparation of surgical hemostatic members, for the preparation of medical sutures or for the preparation of bone repair materials.
The technical effects of the present invention will be described below with reference to specific examples.
Example 1
The embodiment provides a titanium silicalite molecular sieve catalyst, which is prepared by the following method: and (3) weighing 20g of tetrapropylammonium hydroxide solution, slowly dropwise adding 10g of tetraethoxysilane, continuously stirring for 12 hours after the dripping is finished to obtain tetraethoxysilane hydrolysis solution, weighing 0.6g of tetrabutyl titanate, dissolving the tetrabutyl titanate in 20g of isopropanol, slowly dropwise adding the tetrabutyl titanate into the tetraethoxysilane water solution, raising the temperature to 80 ℃ after the tetrabutyl titanate is hydrolyzed, discharging alcohol, cooling to room temperature after the alcohol is discharged, then filling the reaction kettle, carrying out a hydrothermal reaction at 180 ℃ for 72 hours, centrifuging, washing and drying in sequence after the hydrothermal crystallization is finished, and calcining at 550 ℃ for 16 hours to obtain white titanium-silicon molecular sieve catalyst particles with the titanium-silicon molar ratio of 1:27.
Example 2
The embodiment provides a titanium silicalite molecular sieve catalyst, which is prepared by the following method: and (3) weighing 37g of tetrapropylammonium hydroxide solution, slowly dropwise adding 20g of silica sol AS-40, continuously stirring for 12 hours after the dropwise adding is finished to obtain a silica sol hydrolysis solution, weighing 0.4g of tetrabutyl titanate, dissolving the tetrabutyl titanate in 30g of isopropanol, slowly dropwise adding the tetrabutyl titanate into the silica sol water solution, raising the temperature to 80 ℃ after the tetrabutyl titanate is hydrolyzed, discharging alcohol, cooling to room temperature after the alcohol is discharged, then filling the reaction kettle, carrying out a 55-hour hydrothermal reaction at 200 ℃, centrifuging, washing, drying in sequence after the hydrothermal crystallization is finished, and calcining at 450 ℃ for 24 hours to obtain white titanium-silicon molecular sieve catalyst particles with titanium-silicon molar ratio of 1:113.
Example 3
The embodiment provides a titanium silicalite molecular sieve catalyst, which is prepared by the following method: 14g of tetrapropylammonium hydroxide solution is weighed, 25g of tetraethoxysilane is slowly added dropwise, stirring is continued for 12 hours after the dripping is finished to obtain tetraethoxysilane hydrolysis solution, then 0.5g of titanium isopropoxide is weighed, dissolved in 40g of isopropanol, slowly added dropwise into tetraethoxysilane aqueous solution, after the titanium isopropoxide is hydrolyzed, the temperature is raised to 80 ℃ for alcohol discharging, after the alcohol discharging is finished, the solution is cooled to room temperature, then the solution is filled into a reaction kettle, the reaction kettle is subjected to a 96-hour hydrothermal reaction at 150 ℃, and after the hydrothermal crystallization is finished, the solution is sequentially centrifuged, washed and dried, and calcined at 600 ℃ for 5 hours to obtain white titanium-silicon molecular sieve catalyst particles with titanium-silicon molar ratio of 1:61.
Example 4
The embodiment provides a degradable polycarbonate which is prepared by the following method: 90.12g of 1, 4-butanediol, 135.12g of dimethyl carbonate and 0.2324g of the titanium silicalite molecular sieve catalyst prepared in the example 1 are weighed for later use; putting 1, 4-butanediol and titanium silicalite molecular sieve catalyst into a 2L reaction kettle, raising the temperature of the reaction kettle to 180 ℃, gradually adding a set amount of dimethyl carbonate into the reaction kettle in a gas form for 1.0h, after the dimethyl carbonate is added, finishing the transesterification reaction to obtain about 107.9g of prepolymer, and calculating the conversion rate of the dimethyl carbonate to be 62.0%; then adding 0.1162g of triphenyl phosphate into the reaction kettle, raising the temperature to 220 ℃, vacuumizing the reaction system to make the vacuum degree smaller than 100Pa, starting polycondensation reaction, and ending after 5.0 h.
The mass of the resulting degradable polycarbonate based on low-boiling carbonic acid diester (i.e., polybutylene carbonate) was 92.9g, and the theoretical product mass was 116.1g, so that the yield of the degradable polycarbonate in this example was 80%.
The polybutylene carbonate obtained in this example was observed to be white, and further experiments revealed that the polybutylene carbonate was still white after 6 months of storage at room temperature.
The polybutylene carbonate obtained in this example was obtained by detection 1 H-NMR is shown in FIG. 1. From fig. 1, it can be derived that: 7.27ppm of the solvent peak for deuterated chloroform and 4.17ppm of CH near carbonate bond in 1, 4-butanediol 2 H peak (4H) of 1.77ppm at 1,4-butanediol intermediate CH 2 H peak (4H).
GPC curves of the polybutylene carbonate obtained in this example are shown in FIG. 2. As is clear from the integral calculation of FIG. 2, the molecular weight of the polybutylene carbonate obtained in this example was 56300g/mol.
Example 5
The embodiment provides a degradable polycarbonate which is prepared by the following method: 180.24g of 1, 4-butanediol, 198.18g of dimethyl carbonate and 1.161g of the titanium silicalite molecular sieve catalyst prepared in example 1 are weighed for later use; putting 1, 4-butanediol and titanium silicalite molecular sieve catalyst into a 2L reaction kettle, raising the temperature of the reaction kettle to 170 ℃, gradually adding a set amount of dimethyl carbonate into the reaction kettle in a gas form for 2.0h, after the addition of the dimethyl carbonate is finished, finishing the transesterification reaction to obtain about 220.6g of prepolymer, and calculating the conversion rate of the dimethyl carbonate to be 86.4%; then adding 0.2789g of trimethyl phosphate into a reaction kettle, raising the temperature to 220 ℃, vacuumizing the reaction system to make the vacuum degree smaller than 50Pa, starting polycondensation reaction, and ending after 4.0h to obtain 197.4g of degradable polycarbonate (namely polybutylene carbonate) based on low-boiling-point carbonic diester, wherein the theoretical product has the mass of 232.2g and the yield of 85%.
The polybutylene carbonate obtained in this example was white and had a molecular weight of 52600g/mol, and further experiments revealed that it was still white when taken out after storage at room temperature for 6 months.
Example 6
The embodiment provides a degradable polycarbonate which is prepared by the following method: 540.72g of 1, 4-butanediol, 1134.06g of diethyl carbonate and 2.7864g of the titanium silicalite molecular sieve catalyst prepared in example 2 are weighed for later use; putting 1, 4-butanediol and titanium silicalite molecular sieve catalyst into a 5L reaction kettle, raising the temperature of the reaction kettle to 200 ℃, gradually adding a set amount of dimethyl carbonate into the reaction kettle in a gas form within 3.0h, after the addition of the dimethyl carbonate is finished, finishing the transesterification reaction to obtain about 626.9g of prepolymer, and calculating the conversion rate of the dimethyl carbonate to be 69.2%; then adding 2.0916g of diphenyl phosphate into a reaction kettle, raising the temperature to 240 ℃, vacuumizing the reaction system to make the vacuum degree smaller than 80Pa, starting polycondensation reaction, and ending after 2.0h to obtain 536.4g of degradable polycarbonate (namely polybutylene carbonate) based on low-boiling-point carbonic diester, wherein the theoretical product has the mass of 696.6g and the yield of 77%.
The polybutylene carbonate obtained in this example was white and had a molecular weight of 63000g/mol, and further experiments revealed that it remained white after 6 months of storage at room temperature.
Example 7
The embodiment provides a degradable polycarbonate which is prepared by the following method: weighing 9012g of 1, 4-butanediol, 10809.6g of dimethyl carbonate and 11.61g of the titanium silicalite molecular sieve catalyst prepared in example 2 for later use; putting 1, 4-butanediol and titanium silicalite molecular sieve catalyst into a 50L reaction kettle, raising the temperature of the reaction kettle to 150 ℃, gradually adding a set amount of dimethyl carbonate into the reaction kettle in a gas form for 8.0h, after the dimethyl carbonate is added, finishing the transesterification reaction to obtain about 10216.8g of prepolymer, and calculating the conversion rate of the dimethyl carbonate to 73.3%; then adding 11.61g of triphenyl phosphite into a reaction kettle, raising the temperature to 190 ℃, vacuumizing the reaction system to make the vacuum degree smaller than 100Pa, starting polycondensation reaction, and ending after 10.0h to obtain 9868.5g of degradable polycarbonate (namely polybutylene carbonate) based on low-boiling point carbonic diester, wherein the theoretical product has the mass of 11610g and the yield of 85%.
The polybutylene carbonate obtained in this example was white and had a molecular weight of 116500g/mol, and further experiments revealed that it was still white when taken out and observed after storage at room temperature for 6 months.
Example 8
The embodiment provides a degradable polycarbonate which is prepared by the following method: weighing 18024g of 1, 4-butanediol, 25222.4g of dimethyl carbonate and 69.66g of the titanium silicalite molecular sieve catalyst prepared in example 3 for later use; putting 1, 4-butanediol and titanium silicalite molecular sieve catalyst into a 50L reaction kettle, raising the temperature of the reaction kettle to 190 ℃, gradually adding a set amount of dimethyl carbonate into the reaction kettle in a gas form within 3.0h, after the addition of the dimethyl carbonate is finished, finishing the transesterification reaction to obtain about 22523g of prepolymer, and calculating the conversion rate of the dimethyl carbonate to be 69.3%; then adding 2.322g of triphenyl phosphate into a reaction kettle, raising the temperature to 220 ℃, vacuumizing the reaction system to make the vacuum degree smaller than 30Pa, starting polycondensation reaction, and ending 7.0h to obtain 19040g of degradable polycarbonate (namely polybutylene carbonate) based on low-boiling point carbonic diester, wherein the theoretical product has the mass of 23220g and the yield of 82%.
The polybutylene carbonate obtained in this example was white and had a molecular weight of 98100g/mol, and further experiments revealed that it was still white when taken out after storage at room temperature for 6 months.
Comparative example 1
The comparative example provides a polybutylene carbonate prepared by the following method: weighing 90.12g of 1, 4-butanediol, 450.4g of dimethyl carbonate and 0.2324g of tetrabutyl titanate, simultaneously putting the materials into a 2L reaction kettle, raising the temperature of the reaction kettle to 85 ℃, and carrying out transesterification reaction for 96 hours to obtain 64.2g of prepolymer, wherein the conversion rate of the dimethyl carbonate is 36.9%; then adding 0.1162g of triphenyl phosphate into a reaction kettle, raising the temperature to 220 ℃, vacuumizing the reaction system to make the vacuum degree smaller than 100Pa, starting polycondensation reaction, and ending after 5.0h to obtain 41.7g of polybutylene carbonate, wherein the theoretical product has the mass of 116.1g and the yield of 35.9%.
The polybutylene carbonate obtained in this comparative example was pale yellow and had a molecular weight of 32300g/mol, and further experiments revealed that it was observed to be yellow when it was taken out after storage at room temperature for 6 months.
Comparative example 2
The comparative example provides a polybutylene carbonate prepared by the following method: 90.12g of 1, 4-butanediol, 450.4g of dimethyl carbonate and 0.2324g of the titanium silicalite molecular sieve catalyst prepared in the example 1 are weighed, and simultaneously put into a 2L reaction kettle, the temperature of the reaction kettle is increased to 85 ℃ for transesterification, and 73.2g of prepolymer is obtained after 50 hours, and the conversion rate of the dimethyl carbonate is 42%. Then adding 0.1162g of triphenyl phosphate into a reaction kettle, raising the temperature to 220 ℃, vacuumizing the reaction system to make the vacuum degree smaller than 100Pa, starting polycondensation reaction, and ending after 5.0h to obtain 58.6g of polybutylene carbonate, wherein the theoretical product has the mass of 116.1g and the yield of 50.5%.
The polybutylene carbonate obtained in this comparative example was white and had a molecular weight of 46600g/mol, and further experiments revealed that it remained white after 6 months of storage at room temperature.
Comparative example 3
The comparative example provides a polybutylene carbonate prepared by the following method: weighing 90.12g of 1, 4-butanediol, 135.12g of dimethyl carbonate and 0.2324g of tetrabutyl titanate for later use; 1, 4-butanediol and tetrabutyl titanate are put into a 2L reaction kettle, the temperature of the reaction kettle is increased to 180 ℃, a set amount of dimethyl carbonate is gradually added into the reaction kettle in a gas form within 1.0h, the transesterification reaction is finished after the addition of the dimethyl carbonate is finished, about 94.0g of prepolymer is obtained, and the conversion rate of the dimethyl carbonate is calculated to be 54.0%. Then, 0.1162g of triphenyl phosphate is added into a reaction kettle, the temperature is increased to 220 ℃, the reaction system is vacuumized to make the vacuum degree smaller than 100Pa, the polycondensation reaction is started, and after 5.0h, 70.8g of degradable polycarbonate (namely polybutylene carbonate) based on low-boiling-point carbonic diester is obtained, the theoretical product quality is 116.1g, and the yield is 61%.
The polybutylene carbonate obtained in this comparative example was pale yellow in molecular weight of 52200g/mol, and further tested, and after 6 months of storage at room temperature, it was taken out and observed to be yellow.
Comparative example 4
The comparative example provides a preparation method of a titanium silicalite molecular sieve catalyst, which is different from example 1 only in that the silicon source in the comparative example is sodium silicate, and the other is the same as example 1, and the description thereof is omitted.
Comparative example 5
This comparative example provides a degradable polycarbonate, the preparation method of which differs from that of example 8 only in that the titanium silicalite catalyst of this comparative example is prepared in comparative example 4, and the other is the same as that of example 8, and the details are not repeated here. The conversion of dimethyl carbonate was calculated to be 51.0%, the theoretical product mass was 23220g, and the yield was 60.2%.
The polybutylene carbonate obtained in this comparative example was white and had a molecular weight of 41000g/mol. After storage at room temperature for 6 months, the product was taken out and observed to remain white.
Comparative example 6
The comparative example provides a preparation method of a titanium silicalite molecular sieve catalyst, which is different from example 1 only in that the titanium source in the comparative example is titanyl sulfate, and the other is the same as example 1, and the details are not repeated here.
Comparative example 7
This comparative example provides a degradable polycarbonate, the preparation method of which differs from that of example 8 only in that the titanium silicalite catalyst of this comparative example is prepared in comparative example 6, and the other is the same as that of example 8, and the details are not repeated here. The conversion of dimethyl carbonate was found to be 43.3%, the theoretical product mass was 23220g and the yield was 52.4%.
The polybutylene carbonate obtained in this comparative example was white and had a molecular weight of 26400g/mol. After storage at room temperature for 6 months, the product was taken out and observed to remain white.
Comparative example 8
This comparative example provides a degradable polycarbonate which is produced by a process differing from example 8 only in that in this comparative example the 50L reactor temperature is first raised to 140℃and transesterification is allowed to occur at 140 ℃ o C is performed in the same manner as in example 8, and the details thereof are not repeated here. The conversion of dimethyl carbonate was calculated to be 51.7%, the theoretical product mass was 23220g and the yield was 55.9%.
The polybutylene carbonate obtained in this comparative example was white and had a molecular weight of 30600g/mol. After storage at room temperature for 6 months, the product was taken out and observed to remain white.
Comparative example 9
This comparative example provides a degradable polycarbonate which is produced by a process differing from example 8 only in that in this comparative example the 50L reactor temperature is first raised to 235℃and transesterification is allowed to occur at 230 ° o C is performed in the same manner as in example 8, and the details thereof are not repeated here. The conversion of dimethyl carbonate was calculated to be 53.7%, the theoretical product mass was 23220g and the yield was 64.6%.
The polybutylene carbonate obtained in this comparative example was white and had a molecular weight of 47300g/mol. After storage at room temperature for 6 months, the product was taken out and observed to remain white.
Comparative example 10
The comparative example provides a degradable polycarbonate, and the preparation method thereof is different from example 8 only in that the polycondensation reaction temperature of the comparative example is 180 ℃, and the other steps are the same as in example 8, and are not repeated here.
Since the polycondensation reaction temperature is 180 ℃, the polycondensation reaction is finished after 24 hours. The polybutylene carbonate obtained in this comparative example was white and had a molecular weight of 24400g/mol.
Comparative example 11
The comparative example provides a degradable polycarbonate, and the preparation method thereof is different from example 8 only in that the polycondensation reaction temperature of the comparative example is 250 ℃, and the other steps are the same as in example 8, and are not repeated here.
Since the polycondensation reaction temperature is 250℃and the temperature is too high, thermal degradation of the polycarbonate occurs at the same time as the polymerization, and the molecular weight of the obtained polybutylene carbonate is 16800g/mol.
The results of the comparative example and comparative example are combined to show that:
(1) Comparing comparative example 1 with comparative example 2, example 4 with comparative example 3, it is found that the titanium silicalite molecular sieve catalyst has higher catalytic activity than the traditional tetrabutyl titanate catalyst in terms of polycarbonate synthesis, can obviously shorten the reaction time, and improves the conversion rate of raw materials and the yield of products. In addition, white products can be obtained instead of yellow using titanium silicalite catalysts.
(2) Comparing examples 4-8 with comparative examples 1-2, it was found that the time of transesterification reaction can be controlled within 8.0h in cooperation with the operation method of gradually adding 1, 4-butanediol in the form of gas of low boiling point carbonic acid diester under the action of titanium silicalite catalyst, the conversion rate of carbonic acid diester is more than 62%, and the yield is more than 77%, which is quite obvious improvement compared with the conventional catalyst and low temperature transesterification reaction. In addition, the feeding amount of the carbonic acid diester with low boiling point can be obviously reduced, and the raw material cost is greatly saved.
From the above results, it can be seen that the invention makes the carbonic diester with low boiling point contact with 1, 4-butanediol in gas form under high temperature and normal pressure and generate transesterification reaction, which can raise the reaction temperature from lower than boiling point to 150-220 deg.C, obviously shorten the reaction time, and raise the reaction efficiency and product yield. Meanwhile, the feeding amount of the low-boiling-point carbonic acid diester can be obviously reduced, the using amount of raw materials is greatly reduced, high raw material conversion rate is realized, and the cost is saved.
Although the present disclosure is disclosed above, the scope of the present disclosure is not limited thereto. Various changes and modifications may be made by one skilled in the art without departing from the spirit and scope of the disclosure, and these changes and modifications will fall within the scope of the disclosure.
Claims (10)
1. The preparation method of the degradable polycarbonate is characterized by comprising the following steps of:
s1, preparing a titanium-silicon molecular sieve catalyst by taking a silicon source, a titanium source and tetrapropylammonium hydroxide as raw materials;
s2, under the action of the titanium-silicon molecular sieve catalyst prepared in the step S1, taking gaseous carbonic diester with low boiling point and 1, 4-butanediol as raw materials, and obtaining polycarbonate prepolymer through transesterification;
and S3, carrying out polycondensation reaction on the polycarbonate prepolymer prepared in the step S2 to obtain the degradable polycarbonate.
2. The method for producing a degradable polycarbonate according to claim 1, wherein in the step S1, the silicon source is selected from the group consisting of ethyl orthosilicate and/or silica sol; and/or the number of the groups of groups,
the titanium source is at least one of titanium tetrachloride, tetrabutyl titanate, titanium isopropoxide and titanium sulfate; and/or the number of the groups of groups,
the particle size of the titanium-silicon molecular sieve catalyst is 300-500nm.
3. The method for preparing the degradable polycarbonate according to claim 1, wherein the specific preparation process of the step S1 is as follows:
s11, slowly dropwise adding a silicon source into a template agent by taking tetrapropylammonium hydroxide as the template agent to obtain a silicon source hydrolysis solution;
s12, dropwise adding a titanium source solution into the silicon source hydrolysis solution prepared in the step S11, and obtaining a titanium silicon precursor solution after stirring and aging reaction;
and S13, carrying out hydrothermal reaction on the titanium-silicon precursor solution, and after the reaction is finished, sequentially carrying out centrifugation, washing, drying and high-temperature calcination to obtain the titanium-silicon molecular sieve catalyst.
4. The method for producing a degradable polycarbonate as described in claim 3, wherein in the step S13, the parameters of the hydrothermal reaction are as follows: the reaction temperature is 150-200 ℃ and the reaction time is 48-96h;
the parameters for high temperature calcination are as follows: the calcination temperature is 450-600 ℃, and the calcination time is 5-24h.
5. The method for producing a degradable polycarbonate according to claim 1, wherein in the step S2, the parameters of the transesterification reaction are as follows: the reaction temperature is 150-220 ℃, the reaction time is 1-8h, and the reaction pressure is normal pressure; and/or the addition of the titanium silicalite molecular sieve catalyst is 0.1-0.5% of the theoretical yield of the degradable polycarbonate.
6. The method for producing a degradable polycarbonate according to claim 1, wherein in the step S2, the gaseous low boiling point carbonic acid diester is gaseous dimethyl carbonate and/or gaseous diethyl carbonate, and the molar ratio of the gaseous low boiling point carbonic acid diester to 1, 4-butanediol is (1.1 to 1.5): 1.
7. The method for preparing a degradable polycarbonate according to claim 1, wherein in the step S3, a stabilizer is further included in the raw material, the stabilizer is at least one selected from the group consisting of trimethyl phosphate, dimethyl phosphate, triphenyl phosphate, diphenyl phosphate, triphenyl phosphite and diphenyl phosphite, and the addition amount of the stabilizer is 0.01-0.3% of the theoretical yield of the degradable polycarbonate.
8. The method for producing a degradable polycarbonate according to claim 1, wherein in the step S3, the parameters of the polycondensation reaction are as follows: the reaction temperature is 190-240 ℃, the vacuum degree is less than 100Pa, and the reaction time is 2-10h.
9. A degradable polycarbonate produced by the production method according to any one of claims 1 to 8, wherein the weight average molecular weight of the degradable polycarbonate is 50000g/mol or more.
10. Use of the degradable polycarbonate according to claim 9 for the preparation of shopping bags, for the preparation of packaging materials, for the preparation of agricultural mulch films, for the preparation of sinus drug stents, for the preparation of surgical hemostatic members, for the preparation of medical sutures or for the preparation of bone repair materials.
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