CN114752057B - 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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- 239000004033 plastic Substances 0.000 title claims abstract description 28
- 229920003023 plastic Polymers 0.000 title claims abstract description 28
- 239000003054 catalyst Substances 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title abstract description 17
- 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 38
- 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 16
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 14
- 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 9
- 239000005977 Ethylene Substances 0.000 claims abstract description 9
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 9
- 229920001470 polyketone Polymers 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 9
- 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
- 230000035484 reaction time Effects 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
- 230000000694 effects Effects 0.000 abstract description 5
- 238000003780 insertion Methods 0.000 abstract description 5
- 230000037431 insertion Effects 0.000 abstract description 5
- 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
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 2
- 239000001301 oxygen Substances 0.000 abstract description 2
- 229910052760 oxygen Inorganic materials 0.000 abstract description 2
- 239000002904 solvent 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 12
- 238000010438 heat treatment Methods 0.000 description 10
- 239000000203 mixture Substances 0.000 description 9
- 238000007789 sealing Methods 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 230000001502 supplementing effect Effects 0.000 description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 229910001868 water Inorganic materials 0.000 description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 229920001038 ethylene copolymer Polymers 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
- 235000019270 ammonium chloride Nutrition 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
- 229920001577 copolymer Polymers 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- IOEDDFFKYCBADJ-UHFFFAOYSA-M lithium;4-methylbenzenesulfonate Chemical compound [Li+].CC1=CC=C(S([O-])(=O)=O)C=C1 IOEDDFFKYCBADJ-UHFFFAOYSA-M 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 238000001782 photodegradation Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 241001391944 Commicarpus scandens Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 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
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 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
- 239000013522 chelant Substances 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- VIDXETATLKBUBY-UHFFFAOYSA-M lithium;benzenesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C1=CC=CC=C1 VIDXETATLKBUBY-UHFFFAOYSA-M 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
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 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
- 238000005086 pumping Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000967 suction filtration Methods 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
- 238000012546 transfer Methods 0.000 description 1
- -1 which uses CO 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)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (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 preparation method, wherein the catalyst comprises palladium acetate, CH 3C6H5SO3PPh2 ligand, toluenesulfonic acid and nitrobenzene. Taking CO and ethylene as raw materials, taking absolute ethyl alcohol as a solvent, and carrying out polymerization reaction for 1-3 hours under the conditions of 2-5MPa, 50-80 ℃ and the existence of the catalyst. The palladium catalyst provided by the invention has the characteristics of weak oxygen affinity and high polar monomer tolerance, the elimination effect of CH 3C6H5SO3PPh2 ligand beta-H is reduced, 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, the processability of degradable plastics is improved by adding a third comonomer, and the degradable plastics with high molecular mass, high toughness and high strength are synthesized.
Description
Technical Field
The invention relates to a preparation method of photodegradable plastics, in particular to a preparation method of a synthetic CO/ethylene/propylene ternary CO-condensation degradation material and a catalyst applicable to the preparation method.
Background
At present, mass production and application of plastics bring great convenience to the life of people, but serious white pollution is caused because plastic wastes and residual films in the environment are permanent garbage. In general, plastics have poor photodegradation and biodegradability in natural environment, and the degradation results of plastics buried in soil are examined by using C 14 isotope tracking, which show that the degradation speed of plastics varies with environmental conditions such as precipitation, air permeability and temperature, but is very slow in general, and generally requires one year, so that a large amount of plastic garbage remains in soil layers of public places, oceans or cultivated lands, causing increasingly serious environmental pollution.
In order to find an effective way to solve the problem that plastic wastes and plastic films pollute the environment, foreign countries have been devoted to research on plastic-degradable plastics which have excellent properties and can be rapidly dissolved, self-decomposed or burned so as not to generate harmful gases. Degradable plastics are materials in which groups which are easy to decompose, chemical bonds which are easy to break, atoms or groups which are easy to transfer, or components which are easy to phagocytize by microorganisms are introduced into the chemical structure of the materials through a novel polymer synthesis technology, or components which are connected on molecules or are integrated are mixed. The molecule can break molecular chains under the action of microorganisms under the illumination, the structure is destroyed, and then the molecule is quickly decomposed in the nature, so that the environment is not polluted.
However, the copolymerization of olefins with polar monomers is not easy at present, and the main reasons for the copolymerization are 3 points: (1) The metal center of the coordination polymerization catalyst generally has strong Lewis acidity, is easy to generate sigma-coordination chelation with polar monomers, and prevents pi-coordination of double bonds so as to inhibit the insertion of the monomers; (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 polar group poisoning metal effects cause coordination polymerization to catalyze the copolymerization of olefins and polar monomers to become the accepted problems and challenges in the olefin polymerization field, and the following reaction formula is the insertion mechanism of ethylene and polar monomers:
And the CO/ethylene copolymer has a high melting point (about 257 ℃) and poor toughness, and is difficult to process, so that the CO/ethylene copolymer is limited to enter certain important application fields. How to prepare a controllable degradable synthetic thermoplastic engineering polymer material which has high toughness and high strength and is endowed with excellent photodegradation by a large number of carbonyl groups on a main chain is 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 applicable to the preparation method, and the plastic prepared by the method has the characteristics of excellent photodegradability, high molecular mass, high toughness, high strength and the like.
To achieve the above object, the present invention provides a self-made palladium catalyst, which can be used for preparing a photodegradable plastic, comprising palladium acetate and CH 3C6H5SO3PPh2 ligand, wherein the molar ratio of palladium acetate to CH 3C6H5SO3PPh2 ligand is 1:0.5 to 40, preferably 1:0.5 to 20, most preferably 1:0.5 to 10.
The invention relates to a preparation method of a self-made palladium catalyst, which is characterized in that the catalyst also comprises toluene sulfonic acid and nitrobenzene; the molar ratio of palladium acetate, CH 3C6H5SO3PPh2 ligand, toluene sulfonic acid and nitrobenzene is 1:0.5 to 50:0.1 to 50:0.1 to 50, preferably 1:0.5 to 20:0.1 to 20:0.1 to 20, most preferably 1:0.5 to 10:0.1 to 10:0.1 to 10.
The preparation method of the CH 3C6H5SO3PPh2 ligand comprises the following steps:
Step (1): preparation of lithium Paralyenesulfonate A round-bottomed flask was charged with 2-3g benzenesulfonic acid, 05-1 gLiOH.H2O 2 O and 3-4mL deionized water and reacted with stirring to about 2-3g. Putting the obtained lithium benzenesulfonate into a small round bottom flask, adding a certain amount of toluene, heating to 120-125 ℃ in an azeotropic way, refluxing and removing water by using a water separator for about 7-9 hours until a clear solution is obtained in the water separator, stopping azeotropic, and vacuumizing toluene to obtain the lithium p-toluenesulfonate;
step (2): 1-2g of lithium p-toluenesulfonate is added into a 100mL Schlenk bottle which is baked by hydrogen, tetrahydrofuran is added, then the mixture is completely dissolved to become white solution, 5-10mL of n-butyllithium is slowly dripped at the temperature of 0-20 ℃, the dripping solution of the butyllithium becomes bright yellow, the dripping is completed in about 1-2 hours, the reaction is stirred for 5-8 hours at normal temperature, then 1-2mL of tetrahydrofuran solution is slowly dripped at room temperature, the solution gradually becomes white solution, and the dripping is completed in about half an hour. Stirring at room temperature for reaction for 10-20 hours to obtain pale yellow clear solution;
Step (3): ammonium chloride was dissolved in 10-20mL of freshly prepared degassed water and a degassed aqueous solution of ammonium chloride was added to the resulting yellow clear solution. After the solution was separated, the organic layer was removed in vacuo, washed twice with 10-20mL of freshly distilled diethyl ether, and acidified by adding 1M degassed HCl under hydrogen atmosphere to leave an inorganic layer. After adding 10-20mL of freshly distilled dichloromethane and extracting twice, anhydrous magnesium sulfate was added and dried overnight. Filtering with double needles, vacuum-pumping the filtrate to remove solvent, adding 10-20mL of newly distilled dichloromethane for redissolution, dripping a small amount of anhydrous methanol, and then placing in a refrigerator for recrystallization to obtain white crystals.
The invention also provides a preparation method of the photodegradable plastic, which uses CO, ethylene and propylene as raw materials, and uses the catalyst to carry out polymerization reaction to obtain the photodegradable plastic with polyketone as a component.
The polymerization pressure of the invention 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.
According to the preparation method of the photodegradable plastic, the palladium acetate is used in an amount of 109-103g atom palladium per mole of ethylene, the nitrobenzene is used in an amount of 1-1000 times mole of palladium, the toluenesulfonic acid is used in an amount of 0.1-50 times mole of palladium, and the CH 3C6H5SO3PPh2 ligand is used in an amount of 0.5-50 times mole of palladium, preferably 0.5-20 times mole.
The preparation method of the photodegradable plastic comprises the following steps:
A self-made palladium catalyst is adopted, and a controllable degradable synthetic photodegradable material is synthesized by CO/ethylene/propylene copolymerization. The method comprises the following specific steps: palladium acetate, CH 3C6H5SO3PPh2 ligand, toluenesulfonic acid and nitrobenzene are dissolved in absolute ethyl alcohol and are sealed in a 250mL high-pressure reaction kettle, the air in the kettle is replaced by CO/ethylene/propylene mixed gas, the mixture is pressurized to 2-5MPa, the mixture is rapidly heated to 50-80 ℃, and finally the mixture is supplemented to a preset pressure, so that the pressure drop of the system is maintained to be less than 0.5-0.2MPa in the reaction process. And after the experiment is finished, quenching to normal temperature, releasing pressure, carrying out suction filtration, 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 oxygen affinity, weak polar heteroatom tolerance and high polar monomer tolerance, also has unique tolerance, and the elimination effect of CH 3C6H5SO3PPh2 ligand beta-H is reduced, so that the elimination rate of beta-H is far smaller than the ethylene insertion rate, the improvement of copolymerization activity, the adjustability of the polar monomer insertion rate and the improvement of polymer molecular weight are realized, therefore, the yield of polymerized polyketone is high, and the third monomer propylene is added into the synthesized polyketone, so that the synthesized polyketone has better mechanical property, is easy to process, widens the application field, improves the processability of degradable plastics, and synthesizes the synthesized CO/ethylene/propylene ternary polymerization degradable plastics with high molecular mass, high toughness and high strength.
Detailed Description
The application will be further illustrated with reference to specific examples. It is to be understood that these examples are illustrative of the present application and are not intended to limit the scope of the present application. Furthermore, it should be understood that various changes and modifications can be made by one skilled in the art after reading the teachings of the present application, and such equivalents are intended to fall within the scope of the application as defined in the appended claims.
Example 1
N (CH 3C6H5SO3PPh2)/n{Pd(Ac0)2 } = 0.5, toluene sulfonic acid and nitrobenzene are dissolved in absolute ethyl alcohol, and are sealed in a 250mL high-pressure reaction kettle, air in the kettle is replaced by CO/ethylene/propylene mixed gas, the mixture is pressurized to 5MPa, the mixture is quickly heated to 70 ℃, and finally the mixture is supplemented with air to a preset pressure, the pressure drop of the system is kept to be less than 0.2MPa in the reaction process, and after the experiment is finished, the mixture is quenched to normal temperature, and the mixture is depressurized, filtered, cleaned and dried.
Example 2
Dissolving n (CH 3C6H5SO3PPh2)/n{Pd(Ac0)2 } = 1, toluene sulfonic 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 to be less than 0.2MPa in the reaction process.
Example 3
Dissolving n (CH 3C6H5SO3PPh2)/n{Pd(Ac0)2 } = 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 to be less than 0.2MPa in the reaction process.
Example 4
Dissolving n (CH 3C6H5SO3PPh2)/n{Pd(Ac0)2 } = 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 to be less than 0.2MPa in the reaction process.
Example 5
Dissolving n (CH 3C6H5SO3PPh2)/n{Pd(Ac0)2 } = 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 to be less than 0.2MPa in the reaction process.
Example 6
Dissolving n (CH 3C6H5SO3PPh2)/n{Pd(Ac0)2 } = 5, toluene sulfonic 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 to be less than 0.2MPa in the reaction process.
Example 7
Dissolving n (CH 3C6H5SO3PPh2)/n{Pd(Ac0)2 } = 6, toluene sulfonic 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 to be less than 0.2MPa in the reaction process.
Example 8
Dissolving n (CH 3C6H5SO3PPh2)/n{Pd(Ac0)2 } = 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 supplementing air to a preset pressure, wherein the pressure drop of the system is kept to be less than 0.2MPa in the reaction process.
Example 9
Dissolving n (CH 3C6H5SO3PPh2)/n{Pd(Ac0)2 } = 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 to be less than 0.2MPa in the reaction process.
Example 10
Dissolving n (CH 3C6H5SO3PPh2)/n{Pd(Ac0)2 } = 9, 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 to be less than 0.2MPa in the reaction process.
Comparative example 1
Under the same conditions as in example 2, a carbon monoxide and ethylene copolymer was produced. Table 1 shows the results of the performance analysis of examples 1 to 10 and comparative example 1
TABLE 1
As can be seen from Table 1, the catalyst prepared from palladium acetate and CH 3C6H5SO3PPh2 ligand is used for preparing the copolymer of carbon monoxide and ethylene/propylene terpolymer, and the obtained copolymer has the advantages of high yield, wide molecular weight distribution, high toughness, high strength and the like.
Claims (8)
1. A catalyst for preparing photodegradable plastic, which is characterized by comprising palladium acetate, CH 3C6H5SO3PPh2 ligand, toluene sulfonic acid and nitrobenzene, wherein the molar ratio of the palladium acetate to the CH 3C6H5SO3PPh2 ligand to the toluene sulfonic acid to the nitrobenzene is 1:0.5 to 40:0.1 to 50:0.1 to 50.
2. The catalyst for preparing photodegradable plastic according to claim 1, wherein the molar ratio of palladium acetate, CH 3C6H5SO3PPh2 ligand, toluene sulfonic acid and nitrobenzene is 1:0.5 to 20: 0.1-20: 0.1 to 20.
3. The catalyst for preparing photodegradable plastic according to claim 2, wherein the molar ratio of palladium acetate, CH 3C6H5SO3PPh2 ligand, toluene sulfonic acid and nitrobenzene is 1:0.5 to 10: 0.1-10: 0.1 to 10.
4. A method for preparing photodegradable plastic, which is characterized in that the photodegradable plastic with components of polyketone is obtained by taking CO, ethylene and propylene as raw materials and carrying out polymerization reaction by using the catalyst as set forth in any one of claims 1-3.
5. The method for preparing a photodegradable plastic according to claim 4, wherein the reaction pressure of the polymerization reaction is 2 to 10MPa, the reaction temperature is 50 to 80 ℃, and the reaction time is 1 to 3 hours; the volume ratio of CO to ethylene to propylene is 1-20:1-20:1-10.
6. The method for preparing a photodegradable plastic according to claim 5, wherein the volume ratio of CO, ethylene and propylene is 1 to 10:1-10:1-5.
7. The method of producing a photodegradable plastic according to claim 4, wherein the palladium acetate is used in an amount of 109 to 103g of atomic palladium per mol of ethylene, the nitrobenzene is used in an amount of 1 to 1000 times the molar amount of palladium, the toluene sulfonic acid is used in an amount of 0.1 to 50 times the molar amount of palladium, and the CH 3C6H5SO3PPh2 ligand is used in an amount of 0.5 to 50 times the molar amount of palladium.
8. The method for preparing a photodegradable plastic according to claim 4, wherein the amount of the CH 3C6H5SO3PPh2 ligand is 0.5 to 20 times the molar amount of 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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