CN114752057A - Preparation method of photodegradable plastic and catalyst applicable to preparation method - Google Patents
Preparation method of photodegradable plastic and catalyst applicable to preparation method Download PDFInfo
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- CN114752057A CN114752057A CN202110032527.2A CN202110032527A CN114752057A CN 114752057 A CN114752057 A CN 114752057A CN 202110032527 A CN202110032527 A CN 202110032527A CN 114752057 A CN114752057 A CN 114752057A
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- 239000004033 plastic Substances 0.000 title claims abstract description 33
- 229920003023 plastic Polymers 0.000 title claims abstract description 33
- 239000003054 catalyst Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 claims abstract description 40
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 39
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000003446 ligand Substances 0.000 claims abstract description 19
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 15
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims abstract description 12
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000005977 Ethylene Substances 0.000 claims abstract description 10
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 8
- 229920001470 polyketone Polymers 0.000 claims abstract description 5
- 239000002904 solvent Substances 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 25
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- IOEDDFFKYCBADJ-UHFFFAOYSA-M lithium;4-methylbenzenesulfonate Chemical compound [Li+].CC1=CC=C(S([O-])(=O)=O)C=C1 IOEDDFFKYCBADJ-UHFFFAOYSA-M 0.000 claims description 7
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 5
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 239000010410 layer Substances 0.000 claims description 4
- 235000019270 ammonium chloride Nutrition 0.000 claims description 3
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 claims description 3
- 229940092714 benzenesulfonic acid Drugs 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- VIDXETATLKBUBY-UHFFFAOYSA-M lithium;benzenesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C1=CC=CC=C1 VIDXETATLKBUBY-UHFFFAOYSA-M 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 238000005086 pumping Methods 0.000 claims description 3
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 2
- 238000010533 azeotropic distillation Methods 0.000 claims description 2
- 239000000706 filtrate Substances 0.000 claims description 2
- 239000012044 organic layer Substances 0.000 claims description 2
- 238000010992 reflux Methods 0.000 claims description 2
- 238000002390 rotary evaporation Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- -1 washing twice Chemical compound 0.000 claims description 2
- 238000000605 extraction Methods 0.000 claims 1
- 230000035484 reaction time Effects 0.000 claims 1
- 239000007858 starting material Substances 0.000 claims 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 12
- 239000000178 monomer Substances 0.000 abstract description 11
- 238000007334 copolymerization reaction Methods 0.000 abstract description 6
- 229920006238 degradable plastic Polymers 0.000 abstract description 6
- 238000003780 insertion Methods 0.000 abstract description 5
- 230000037431 insertion Effects 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- 230000006872 improvement Effects 0.000 abstract description 4
- 230000008030 elimination Effects 0.000 abstract description 3
- 238000003379 elimination reaction Methods 0.000 abstract description 3
- 229920000642 polymer Polymers 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 2
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 16
- 239000007789 gas Substances 0.000 description 14
- 238000004140 cleaning Methods 0.000 description 11
- 238000002474 experimental method Methods 0.000 description 11
- 238000010791 quenching Methods 0.000 description 11
- 230000000171 quenching effect Effects 0.000 description 11
- 239000000243 solution Substances 0.000 description 10
- 238000007789 sealing Methods 0.000 description 9
- 238000000967 suction filtration Methods 0.000 description 9
- 230000001502 supplementing effect Effects 0.000 description 7
- 239000000203 mixture Substances 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 238000003912 environmental pollution Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000012718 coordination polymerization Methods 0.000 description 2
- 229920001038 ethylene copolymer Polymers 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 244000005700 microbiome Species 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
- 230000020477 pH reduction Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000001782 photodegradation Methods 0.000 description 1
- 239000013502 plastic waste Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 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
- C08G67/00—Macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing oxygen or oxygen and carbon, not provided for in groups C08G2/00 - C08G65/00
- C08G67/02—Copolymers of carbon monoxide and aliphatic unsaturated compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/46—Phosphinous acids [R2POH], [R2P(= O)H]: Thiophosphinous acids including[R2PSH]; [R2P(=S)H]; Aminophosphines [R2PNH2]; Derivatives thereof
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a preparation method of photodegradable plastic and a catalyst applicable to the same, wherein the catalyst comprises palladium acetate and CH3C6H5SO3PPh2Ligand, toluenesulfonic acid and nitrobenzene. CO and ethylene are used as raw materials, absolute ethyl alcohol is used as a solvent, and the polymerization reaction is carried out for 1 to 3 hours under the conditions of 2 to 5MPa, 50 to 80 ℃ and the existence of the catalyst. The palladium catalyst provided by the invention has the characteristics of weak oxophilicity and high tolerance of polar monomer, namely CH3C6H5SO3PPh2The elimination effect of the ligand beta-H is reduced, the improvement of copolymerization reaction activity, the adjustment of polar monomer insertion rate and the improvement of polymer molecular weight are realized, the yield of polymerized polyketone is high, the processability of the degradable plastic is improved by adding a third comonomer, and the degradable plastic with high molecular weight, high toughness and high strength is synthesized.
Description
Technical Field
The invention relates to a preparation method of photodegradable plastic, in particular to a preparation method of a synthetic CO/ethylene/propylene ternary CO-condensation degradable material and a catalyst applicable to the preparation method.
Background
At present, the mass production and application of plastics bring great convenience to the life of people, but the plastic waste and residual films in the environment are permanent garbage, which causes serious white pollution. In general, plastics are poor in both photodegradability and biodegradability in natural environment in addition to their biodegradability, and C is used 14Isotope tracking investigation on the decomposition results of plastics buried in soil shows that the degradation speed of plastics varies with environmental conditions such as precipitation, air permeability, temperature and the like, but is generally very slow and generally requires one year, so that a large amount of plastic wastes remain in soil layers of public places, oceans or cultivated lands, and increasingly serious environmental pollution is caused.
In order to find an effective way to solve the environmental pollution caused by plastic wastes and residual films, research on degradable plastics which have the excellent performance of plastics and can be rapidly dissolved, automatically decomposed or combusted so as not to generate harmful gases has been conducted abroad. The degradable plastic is a component which is introduced with easily decomposed groups, easily broken chemical bonds, easily transferred atoms or groups on the chemical structure of the material through a novel polymer synthesis technology, or is connected on molecules or blended with a whole component which can be phagocytized by some microorganisms. Thus, the molecule can break molecular chain under the action of light and microbe to destroy the structure, and the molecule is decomposed fast in natural environment without environmental pollution.
However, the copolymerization of olefin and polar monomer is still considered, and the reason is mainly 3 points: (1) the metal center of the coordination polymerization catalyst generally has strong Lewis acidity, and is easy to generate sigma-coordination chelation with a polar monomer to block pi-coordination of double bonds so as to inhibit the insertion of the monomer; (2) after the polar monomer is inserted, the polar group is easy to coordinate with the metal center to form a stable chelate; (3) the poisoning of the metal by the polar group described above renders the copolymerization of coordination polymerization catalyzed olefins and polar monomers a recognized problem and challenge in the olefin polymerization art, and the following reaction scheme is the mechanism of insertion of ethylene into a polar monomer:
And the CO/ethylene copolymer has a high melting point (about 257 ℃), is difficult to process and has poor toughness, so that the CO/ethylene copolymer is limited to enter some important application fields. How to prepare a controllable degradable synthetic thermoplastic engineering polymer material which has high toughness and high strength and has excellent photodegradability given by a large amount of carbonyl groups on a main chain becomes a technical problem to be solved in the field.
Disclosure of Invention
In order to solve the technical problems, the invention provides a preparation method of photodegradable plastic and a catalyst suitable for the preparation method.
In order to achieve the purpose, the invention provides a self-made palladium catalyst which can be used for preparing photodegradable plastics and comprises palladium acetate and CH3C6H5SO3PPh2Ligand, vinegarAcid palladium and CH3C6H5SO3PPh2The molar ratio of the ligands is 1: 0.5 to 40, preferably 1: 0.5 to 20, most preferably 1: 0.5 to 10.
The preparation method of the self-made palladium catalyst is characterized in that the catalyst also comprises toluenesulfonic acid and nitrobenzene; palladium acetate, CH3C6H5SO3PPh2The molar ratio of the ligand to the toluenesulfonic acid to the nitrobenzene is 1: 0.5-50: 0.1-50: 0.1 to 50, preferably 1: 0.5-20: 0.1-20: 0.1 to 20, most preferably 1: 0.5-10: 0.1-10: 0.1 to 10.
CH of the present invention3C6H5SO3PPh2The preparation method of the ligand comprises the following steps:
step (1): firstly, preparing lithium p-toluenesulfonate, adding 2-3g of benzenesulfonic acid and 05-1g of LiOH & H into a round-bottomed flask2And stirring O and 3-4mL of deionized water to react for about 2-3g, and performing rotary evaporation to remove water to obtain a white solid. Placing the obtained lithium benzenesulfonate in a small round-bottom flask, adding a certain amount of toluene, carrying out azeotropic heating to 120-125 ℃, refluxing and dewatering by a water separator for about 7-9 hours until a clear solution is obtained in the water separator, stopping azeotropic distillation, and removing toluene in vacuum to obtain the lithium p-toluenesulfonate;
step (2): adding 1-2g of lithium p-toluenesulfonate into a 100mL Schlenk bottle which is roasted by hydrogen in a pumping way, adding tetrahydrofuran, then completely dissolving to obtain a white solution, slowly dropwise adding 5-10mL of n-butyllithium at the temperature of 0-20 ℃, reacting at normal temperature for 5-8 hours after dropwise adding the solution along with the dropwise adding of the butyl lithium to obtain a bright yellow solution, and gradually adding 1-2mL of tetrahydrofuran solution at the room temperature to obtain a white solution after dropwise adding for about half an hour. Stirring and reacting for 10-20 hours at room temperature to obtain a light yellow clear solution;
and (3): ammonium chloride was dissolved in 10-20mL of freshly prepared degassed water and the resulting yellow clear solution was added to a degassed aqueous solution of ammonium chloride. The solution is layered and the organic layer is removed in vacuum, 10-20mL of newly distilled ether is added for washing twice, the solution is separated in hydrogen atmosphere to leave an inorganic layer, and 1M degassed HCL is added for acidification. The mixture was extracted twice with freshly distilled 10-20mL of dichloromethane, dried overnight with anhydrous magnesium sulfate. And (3) after double-needle filtration, removing the solvent from the filtrate in vacuum, adding newly steamed 10-20mL of dichloromethane for re-dissolution, dropwise adding a small amount of anhydrous methanol, and putting the mixture into a refrigerator for recrystallization to obtain white crystals.
The invention also provides a preparation method of the photodegradable plastic, which takes CO, ethylene and propylene as raw materials, and uses the catalyst to carry out polymerization reaction to obtain the photodegradable plastic with the component of polyketone.
The polymerization pressure is 2-10MPa, the polymerization temperature is 50-80 ℃, and the polymerization time is 1-3 hours; the volume ratio of CO/ethylene/propylene is 1-20: 1-20: 1-10, preferably 1-10: 1-10: 1-5.
The preparation method of the photodegradable plastic comprises the steps of using the palladium acetate to ensure that each mole of ethylene contains 103g atom of 109-palladium, using the nitrobenzene to be 1-1000 times mole of the palladium, using the toluenesulfonic acid to be 0.1-50 times mole of the palladium, and using CH3C6H5SO3PPh2The amount of the ligand to be used is 0.5 to 50-fold mol based on the palladium, preferably 0.5 to 20-fold mol.
The preparation method of the photodegradable plastic comprises the following steps:
the controllable degradable synthetic photodegradation material is synthesized by CO/ethylene/propylene copolymerization by adopting a self-made palladium catalyst. The method comprises the following specific steps: mixing palladium acetate and CH3C6H5SO3PPh2Dissolving ligand, toluenesulfonic acid and nitrobenzene in absolute ethyl alcohol, sealing in a 250mL high-pressure reaction kettle, replacing air in the kettle with CO/ethylene/propylene mixed gas, pressurizing to 2-5MPa, rapidly heating to 50-80 ℃, and finally supplying gas to a predetermined pressure, wherein the pressure drop of the system is maintained to be less than 0.5-0.2MPa in the reaction process. After the experiment is finished, quenching to normal temperature, releasing pressure, filtering, cleaning and drying to obtain the photodegradable plastic.
Compared with the prior art, the invention has the following advantages:
the palladium catalyst provided by the invention has the characteristics of high oxophilicity, weak tolerance to polar heteroatoms and polar monomers, and unique tolerance,CH3C6H5SO3PPh2the elimination effect of the ligand beta-H is reduced, so that the elimination rate of the beta-H is far less than the insertion rate of ethylene, the improvement of copolymerization activity, the adjustment of polar monomer insertion rate and the improvement of polymer molecular weight are realized, the yield of polymerized polyketone is high, and the synthesized polyketone added with the third monomer propylene has better mechanical property, is easy to process, widens the application field, improves the processability of degradable plastics, and synthesizes high-molecular-quality, high-toughness and high-strength synthetic CO/ethylene/propylene ternary copolymerization degradable plastics.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention can be made by those skilled in the art after reading the teaching of the present invention, and these equivalents also fall within the scope of the claims appended to the present application.
Example 1
N (CH)3C6H5SO3PPh2)/n{Pd(Ac0)20.5, dissolving toluenesulfonic acid and nitrobenzene in absolute ethyl alcohol, sealing in a 250mL high-pressure reaction kettle, replacing air in the kettle with CO/ethylene/propylene mixed gas, pressurizing to 5MPa, rapidly heating to 70 ℃, and finally supplying air to a preset pressure, wherein the pressure drop of the system is kept less than 0.2MPa in the reaction process. After the experiment is finished, quenching to normal temperature, relieving pressure, performing suction filtration, cleaning and drying.
Example 2
N (CH)3C6H5SO3PPh2)/n{Pd(Ac0)2Dissolving 1, toluenesulfonic acid and nitrobenzene in absolute ethyl alcohol, sealing in a 250mL high-pressure reaction kettle, replacing air in the kettle with CO/ethylene/propylene mixed gas, pressurizing to 5MPa, rapidly heating to 70 ℃, and finally supplementing air to a preset pressure, wherein the pressure drop of the system is kept less than 0.2MPa in the reaction process. After the experiment is finished, quenching to normal temperature, releasing pressure, filtering, cleaning and dryingAnd (4) finishing.
Example 3
N (CH)3C6H5SO3PPh2)/n{Pd(Ac0)2Dissolving 2, toluenesulfonic acid and nitrobenzene in absolute ethyl alcohol, sealing in a 250mL high-pressure reaction kettle, replacing air in the kettle with CO/ethylene/propylene mixed gas, pressurizing to 5MPa, rapidly heating to 70 ℃, and finally supplementing air to a preset pressure, wherein the pressure drop of the system is kept less than 0.2MPa in the reaction process. After the experiment is finished, quenching to normal temperature, releasing pressure, performing suction filtration, cleaning and drying.
Example 4
N (CH)3C6H5SO3PPh2)/n{Pd(Ac0)2Dissolving 3, toluenesulfonic acid and nitrobenzene in absolute ethyl alcohol, sealing in a 250mL high-pressure reaction kettle, replacing air in the kettle with CO/ethylene/propylene mixed gas, pressurizing to 5MPa, rapidly heating to 70 ℃, and finally supplementing air to a preset pressure, wherein the pressure drop of the system is kept less than 0.2MPa in the reaction process. After the experiment is finished, quenching to normal temperature, releasing pressure, performing suction filtration, cleaning and drying.
Example 5
N (CH)3C6H5SO3PPh2)/n{Pd(Ac0)2Dissolving 4, toluenesulfonic acid and nitrobenzene in absolute ethyl alcohol, sealing in a 250mL high-pressure reaction kettle, replacing air in the kettle with CO/ethylene/propylene mixed gas, pressurizing to 5MPa, rapidly heating to 70 ℃, and finally supplementing air to a preset pressure, wherein the pressure drop of the system is kept less than 0.2MPa in the reaction process. After the experiment is finished, quenching to normal temperature, releasing pressure, performing suction filtration, cleaning and drying.
Example 6
N (CH)3C6H5SO3PPh2)/n{Pd(Ac0)2Dissolving 5, toluenesulfonic acid and nitrobenzene in absolute ethyl alcohol, sealing in a 250mL high-pressure reaction kettle, replacing air in the kettle with CO/ethylene/propylene mixed gas, pressurizing to 5MPa, rapidly heating to 70 ℃, and finally supplementing air to a predetermined pressure, and maintaining the system in the reaction process The pressure drop is less than 0.2 MPa. After the experiment is finished, quenching to normal temperature, relieving pressure, performing suction filtration, cleaning and drying.
Example 7
N (CH)3C6H5SO3PPh2)/n{Pd(Ac0)26, toluene sulfonic acid and nitrobenzene are dissolved in absolute ethyl alcohol, the mixture is sealed in a 250mL high-pressure reaction kettle, air in the kettle is replaced by CO/ethylene/propylene mixed gas, the pressure is increased to 5MPa, the temperature is rapidly increased to 70 ℃, finally, the gas is supplied to the preset pressure, and the pressure drop of the system is maintained to be less than 0.2MPa in the reaction process. After the experiment is finished, quenching to normal temperature, relieving pressure, performing suction filtration, cleaning and drying.
Example 8
N (CH)3C6H5SO3PPh2)/n{Pd(Ac0)2Dissolving 7, toluenesulfonic acid and nitrobenzene in absolute ethyl alcohol, sealing in a 250mL high-pressure reaction kettle, replacing air in the kettle with CO/ethylene/propylene mixed gas, pressurizing to 5MPa, rapidly heating to 70 ℃, and finally supplying air to a predetermined pressure, wherein the pressure drop of the system is kept less than 0.2MPa in the reaction process. After the experiment is finished, quenching to normal temperature, relieving pressure, performing suction filtration, cleaning and drying.
Example 9
N (CH)3C6H5SO3PPh2)/n{Pd(Ac0)2Dissolving 8, toluenesulfonic acid and nitrobenzene in absolute ethyl alcohol, sealing in a 250mL high-pressure reaction kettle, replacing air in the kettle with CO/ethylene/propylene mixed gas, pressurizing to 5MPa, rapidly heating to 70 ℃, and finally supplementing air to a preset pressure, wherein the pressure drop of the system is kept less than 0.2MPa in the reaction process. After the experiment is finished, quenching to normal temperature, releasing pressure, performing suction filtration, cleaning and drying.
Example 10
N (CH)3C6H5SO3PPh2)/n{Pd(Ac0)29, toluene sulfonic acid and nitrobenzene were dissolved in absolute ethanol, the mixture was sealed in a 250mL autoclave, the air in the autoclave was replaced with a CO/ethylene/propylene mixed gas, and the pressure was increased to 5MPa, rapidly heating to 70 ℃, and finally supplementing air to a preset pressure, wherein the pressure drop of a system is maintained to be less than 0.2MPa in the reaction process. After the experiment is finished, quenching to normal temperature, relieving pressure, performing suction filtration, cleaning and drying.
Comparative example 1
A copolymer of carbon monoxide and ethylene was prepared under the same conditions as in the preparation of the copolymer of example 2.
Table 1 shows the results of the performance analysis of examples 1 to 10 and comparative example 1
TABLE 1
As shown in Table 1, palladium acetate and CH were used3C6H5SO3PPh2The catalyst prepared by the ligand is used for preparing the carbon monoxide and ethylene/propylene terpolymer, and the obtained copolymer has the advantages of high yield, wider molecular weight distribution, high toughness, high strength and the like.
Claims (14)
1. A catalyst for preparing photodegradable plastics, which comprises palladium acetate and CH3C6H5SO3PPh2Ligand, said palladium acetate and CH3C6H5SO3PPh2The molar ratio of the ligands is 1: 0.5 to 40.
2. The catalyst for preparing photodegradable plastic according to claim 1, wherein the catalyst further comprises toluene sulfonic acid and nitrobenzene, and the palladium acetate, CH 3C6H5SO3PPh2The mol ratio of the ligand, the toluenesulfonic acid and the nitrobenzene is 1: 0.5-40: 0.1 to 50: 0.1 to 50.
3. The catalyst for preparing photodegradable plastics according to claim 2, wherein the catalyst further comprises toluene sulfonic acid and nitrobenzene, and the palladium acetate, CH3C6H5SO3PPh2The mol ratio of the ligand, the toluenesulfonic acid and the nitrobenzene is 1: 0.5-20: 0.1-20: 0.1 to 20.
4. The catalyst for preparing photodegradable plastic of claim 3, wherein the palladium acetate and CH3C6H5SO3PPh2The molar ratio of the ligands is 1: 0.5-10: 0.1-10: 0.1 to 10.
5. The catalyst for preparing photodegradable plastic according to claim 1, wherein the CH is3C6H5SO3PPh2The preparation method of the ligand comprises the following steps:
step (1): preparing lithium p-toluenesulfonate, adding benzenesulfonic acid and LiOH & H into a round-bottom flask2Stirring O and mL deionized water for reaction, and performing rotary evaporation to remove water to obtain lithium benzenesulfonate; placing lithium benzenesulfonate in a small round-bottom flask, adding toluene for azeotropic heating, refluxing and dewatering by using a water separator for about 7-9 hours until a clear solution is obtained in the water separator, stopping azeotropic distillation, and removing toluene in vacuum to obtain lithium p-toluenesulfonate;
step (2): adding lithium p-toluenesulfonate and tetrahydrofuran into an mLSchlen bottle which is subjected to hydrogen pumping and roasting, completely dissolving to obtain a white solution, slowly dropwise adding n-butyllithium at the temperature of 0-20 ℃, reacting and stirring at normal temperature for 5-8 hours along with the change of the dropwise added solution of the butyllithium into bright yellow, then slowly dropwise adding a tetrahydrofuran solution at the temperature, gradually changing the solution into a white solution, and stirring and reacting at the room temperature for 10-20 hours to obtain a light yellow clear solution;
And (3): dissolving ammonium chloride in degassed water, adding into the yellowish clear solution of step (2), vacuum-removing organic layer after solution layering, adding newly distilled 10-20mL diethyl ether, washing twice, and hydrogen atmosphereThe lower layer was separated leaving an inorganic layer, acidified by addition of 1M degassed HCl. Adding dichloromethane for extraction, adding anhydrous magnesium sulfate, and drying overnight; filtering with double needle, vacuum-pumping the filtrate to remove solvent, adding dichloromethane for redissolving, dropwise adding small amount of anhydrous methanol, and recrystallizing in refrigerator to obtain CH3C6H5SO3PPh2A ligand.
6. The catalyst for preparing photodegradable plastics according to claim 5, wherein in step (1), the benzene sulfonic acid is added in an amount of 2-3g, and the LiOH. H2The addition amount of O is 05-1g and the addition amount of deionized water is 3-4 mL.
7. The catalyst for preparing photodegradable plastic according to claim 5, wherein in step (1), the azeotropic heating temperature is 120-125 ℃.
8. The catalyst for preparing photodegradable plastics according to claim 5, wherein in step (2), the amount of the lithium p-toluenesulfonate added is 1 to 2 g; the adding amount of the n-butyllithium is 5-10 mL; the addition amount of the tetrahydrofuran solution is 1-2 mL.
9. The catalyst for preparing photodegradable plastics according to claim 5, wherein in step (3), the amount of degassed water added is 10-20 mL; the addition amount of the diethyl ether is 10-20 mL; the addition amount of the dichloromethane is 10-20 mL.
10. A process for the preparation of a photodegradable plastic, characterized in that a polymerization is carried out using CO, ethylene and propylene as starting materials, using a catalyst as claimed in claim 19, to obtain a photodegradable plastic having a polyketone component.
11. The method for preparing photodegradable plastic according to claim 10, wherein the reaction pressure of the polymerization reaction is 2-10MPa, the reaction temperature is 50-80 ℃, and the reaction time is 1-3 hours; the volume ratio of the CO to the ethylene to the propylene is 1-20: 1-20: 1-10.
12. The method for preparing photodegradable plastic according to claim 11, wherein the volume ratio of CO, ethylene and propylene is 1-10: 1-10: 1-5.
13. The method for preparing photodegradable plastic according to claim 10, wherein the amount of palladium acetate is such that each mole of ethylene contains 109-103g atomic palladium, the amount of nitrobenzene is 1-1000 times the mole of palladium, the amount of toluene sulfonic acid is 0.1-50 times the mole of palladium, and CH 3C6H5SO3PPh2The dosage of the ligand is 0.5 to 50 times of the molar weight of the palladium.
14. The method for preparing photodegradable plastic according to claim 10, wherein the CH is3C6H5SO3PPh2The dosage of the ligand is 0.5 to 20 times of the molar weight of the palladium.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US4855399A (en) * | 1987-02-26 | 1989-08-08 | Shell Oil Company | Carbon monoxide/olefin co-polymerization process with phosphino substituted sulfonic acid catalyst |
| CN102584896A (en) * | 2011-12-21 | 2012-07-18 | 华东理工大学 | Catalyzing system formed by (P, O) ligand and palladium acetate and method for catalyzing olefin polymerization through utilizing catalyzing system |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4855399A (en) * | 1987-02-26 | 1989-08-08 | Shell Oil Company | Carbon monoxide/olefin co-polymerization process with phosphino substituted sulfonic acid catalyst |
| CN102584896A (en) * | 2011-12-21 | 2012-07-18 | 华东理工大学 | Catalyzing system formed by (P, O) ligand and palladium acetate and method for catalyzing olefin polymerization through utilizing catalyzing system |
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