CN115703900B - Photocatalytic degradation method of polyolefin - Google Patents
Photocatalytic degradation method of polyolefin Download PDFInfo
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- CN115703900B CN115703900B CN202110909161.2A CN202110909161A CN115703900B CN 115703900 B CN115703900 B CN 115703900B CN 202110909161 A CN202110909161 A CN 202110909161A CN 115703900 B CN115703900 B CN 115703900B
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- 229920000098 polyolefin Polymers 0.000 title claims abstract description 71
- 238000000034 method Methods 0.000 title claims abstract description 49
- 238000013033 photocatalytic degradation reaction Methods 0.000 title claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 43
- 239000002904 solvent Substances 0.000 claims abstract description 27
- 238000006731 degradation reaction Methods 0.000 claims abstract description 26
- 239000003054 catalyst Substances 0.000 claims abstract description 20
- 239000007857 degradation product Substances 0.000 claims abstract description 20
- 238000001816 cooling Methods 0.000 claims abstract description 15
- 150000001875 compounds Chemical class 0.000 claims abstract description 11
- 229910052751 metal Inorganic materials 0.000 claims abstract description 11
- 239000002184 metal Substances 0.000 claims abstract description 11
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 11
- 239000010937 tungsten Substances 0.000 claims abstract description 11
- 238000005286 illumination Methods 0.000 claims abstract description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 72
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 36
- 239000004698 Polyethylene Substances 0.000 claims description 22
- -1 polyethylene Polymers 0.000 claims description 19
- 238000001035 drying Methods 0.000 claims description 18
- 229920000573 polyethylene Polymers 0.000 claims description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 239000004743 Polypropylene Substances 0.000 claims description 9
- 229920001155 polypropylene Polymers 0.000 claims description 9
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 5
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 4
- 229920001748 polybutylene Polymers 0.000 claims description 3
- 238000006116 polymerization reaction Methods 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 3
- 238000000746 purification Methods 0.000 claims description 3
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 claims description 3
- DTIFFPXSSXFQCJ-UHFFFAOYSA-N tetrahexylazanium Chemical compound CCCCCC[N+](CCCCCC)(CCCCCC)CCCCCC DTIFFPXSSXFQCJ-UHFFFAOYSA-N 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 1
- ZDQWESQEGGJUCH-UHFFFAOYSA-N Diisopropyl adipate Chemical compound CC(C)OC(=O)CCCCC(=O)OC(C)C ZDQWESQEGGJUCH-UHFFFAOYSA-N 0.000 claims 1
- MHDVGSVTJDSBDK-UHFFFAOYSA-N dibenzyl ether Chemical compound C=1C=CC=CC=1COCC1=CC=CC=C1 MHDVGSVTJDSBDK-UHFFFAOYSA-N 0.000 claims 1
- 150000002148 esters Chemical class 0.000 claims 1
- OJURWUUOVGOHJZ-UHFFFAOYSA-N methyl 2-[(2-acetyloxyphenyl)methyl-[2-[(2-acetyloxyphenyl)methyl-(2-methoxy-2-oxoethyl)amino]ethyl]amino]acetate Chemical compound C=1C=CC=C(OC(C)=O)C=1CN(CC(=O)OC)CCN(CC(=O)OC)CC1=CC=CC=C1OC(C)=O OJURWUUOVGOHJZ-UHFFFAOYSA-N 0.000 claims 1
- LCZVKKUAUWQDPX-UHFFFAOYSA-N tert-butyl 2-[(2-acetyloxyphenyl)methyl-[2-[(2-acetyloxyphenyl)methyl-[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]amino]ethyl]amino]acetate Chemical compound CC(=O)OC1=CC=CC=C1CN(CC(=O)OC(C)(C)C)CCN(CC(=O)OC(C)(C)C)CC1=CC=CC=C1OC(C)=O LCZVKKUAUWQDPX-UHFFFAOYSA-N 0.000 claims 1
- 230000015556 catabolic process Effects 0.000 abstract description 24
- 150000001336 alkenes Chemical class 0.000 abstract description 16
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 15
- 239000000463 material Substances 0.000 abstract 1
- 230000001376 precipitating effect Effects 0.000 abstract 1
- 238000001291 vacuum drying Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 14
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 12
- 238000005481 NMR spectroscopy Methods 0.000 description 11
- 238000005227 gel permeation chromatography Methods 0.000 description 11
- 239000002244 precipitate Substances 0.000 description 11
- 229920000092 linear low density polyethylene Polymers 0.000 description 10
- 229920001684 low density polyethylene Polymers 0.000 description 10
- 239000004702 low-density polyethylene Substances 0.000 description 10
- 239000012295 chemical reaction liquid Substances 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical compound CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 description 9
- 239000011541 reaction mixture Substances 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- 239000004707 linear low-density polyethylene Substances 0.000 description 8
- 229920001903 high density polyethylene Polymers 0.000 description 7
- 239000004700 high-density polyethylene Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 6
- 229920010126 Linear Low Density Polyethylene (LLDPE) Polymers 0.000 description 5
- 229920003023 plastic Polymers 0.000 description 5
- 239000004033 plastic Substances 0.000 description 5
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 4
- FAMRKDQNMBBFBR-BQYQJAHWSA-N diethyl azodicarboxylate Substances CCOC(=O)\N=N\C(=O)OCC FAMRKDQNMBBFBR-BQYQJAHWSA-N 0.000 description 3
- NCBFTYFOPLPRBX-UHFFFAOYSA-N dimethyl azodicarboxylate Substances COC(=O)N=NC(=O)OC NCBFTYFOPLPRBX-UHFFFAOYSA-N 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- FAMRKDQNMBBFBR-UHFFFAOYSA-N ethyl n-ethoxycarbonyliminocarbamate Chemical compound CCOC(=O)N=NC(=O)OCC FAMRKDQNMBBFBR-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- NCBFTYFOPLPRBX-AATRIKPKSA-N methyl (ne)-n-methoxycarbonyliminocarbamate Chemical compound COC(=O)\N=N\C(=O)OC NCBFTYFOPLPRBX-AATRIKPKSA-N 0.000 description 3
- QWUWMCYKGHVNAV-UHFFFAOYSA-N 1,2-dihydrostilbene Chemical group C=1C=CC=CC=1CCC1=CC=CC=C1 QWUWMCYKGHVNAV-UHFFFAOYSA-N 0.000 description 2
- ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 2,3-dimethylbutane Chemical group CC(C)C(C)C ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-N 0.000 description 1
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- 238000005865 alkene metathesis reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 150000004816 dichlorobenzenes Chemical class 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000002503 iridium Chemical class 0.000 description 1
- 238000005649 metathesis reaction Methods 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000013502 plastic waste Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000010993 response surface methodology Methods 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention relates to the technical field of photocatalytic degradation of polyolefin, in particular to a photocatalytic degradation method of polyolefin and application thereof. According to the invention, polyolefin and azodicarbonate compounds are mixed and dissolved in a proper solvent, a tungsten metal catalyst is added, and a reaction system is heated and stirred under the illumination condition for degradation; and then cooling, precipitating by proper solvent step by step and vacuum drying to obtain the degradation product of polyolefin. The resulting degradation products are functionalized short chain olefin oligomers that can be further used as compatibilizers to improve the compatibility of the polyolefin with other polymeric materials. The degradation reaction condition is mild, the conversion rate is high, the environment is friendly, the catalyst is economical and easy to obtain, and the degradation product can be further applied.
Description
Technical Field
The invention relates to the technical field of degradation of polyolefin, in particular to a photocatalytic degradation method of polyolefin.
Background
In the past 70 years, plastics synthesized from petroleum have been rapidly rising, from less than 200 ten thousand tons in 1950 to 3.8 hundred million tons in 2015, and plastics have become an indispensable product for modern life. A large amount of plastic waste is finally landfilled or incinerated, but the disposal process is harmful to the environment. Among them, polyolefin is the plastic type which is the largest in use in the world currently, and is hardly degraded due to its chemical inertness.
The degradation of polyolefin has been developed for many years, and there are many reports at home and abroad that the effective degradation is achieved by various methods. Audisio et al report that polyethylene is degraded by using different types of molecular sieves, and under the condition of a heat-resistant glass reactor at 400 ℃, 90% degradation rate of polyethylene can be realized by using the molecular sieves as catalysts, the liquid conversion rate reaches 90%(Audisio G,Bertini F,Beltrame P L,et al.Catalytic degradation of polyolefins[J].Macromolecular Symposia,1992,57(1):191-209.);, however, the temperature requirement of the reaction system is high, the selectivity of the product is poor, a large amount of energy consumption is wasted, and the product cannot be reused. Wong et al report that the liquid yield can reach 13.6% and the gas yield can reach 2.6% under proper conditions by optimizing the reaction (S.L.Wong,N.Ngadi,N.A.S.Amin,T.A.T.Abdullah,I.M.Inuwa.Pyrolysis of low density polyethylene waste in subcritical water optimized by response surface methodology Environ Technol,37(2016),p.245,10.1080/09593330.2015.1068376). for degrading polyethylene in subcritical water by using a response surface method. Although the method reduces the reaction temperature and reduces the energy consumption, the content of alkene and alkane in the product is higher, the conversion rate is lower, the requirement on reaction equipment is higher, and ideal degradation cannot be realized.
CN105348557 a discloses a process for obtaining degradation products by multiple metathesis reactions of light paraffins with polyethylene. The reaction employs a dehydrogenated iridium catalyst and an olefin metathesis rhenium catalyst to effect degradation of the polyolefin. Although the reaction conditions are mild, the product is liquid fuel or polyethylene paraffin, the catalyst is expensive and consumes a certain amount of alkane, and there are still many limitations in large-scale application.
Therefore, the search for a polyolefin degradation method with mild conditions, high reaction conversion rate, environmental friendliness and economic and easily available catalyst is still the focus of research in the field of polyolefin degradation at present.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a photocatalytic degradation method of polyolefin. The method of the invention not only can effectively reduce the molecular weight of polyolefin, but also can graft azodicarbonate compounds on the main chain of the degraded olefin oligomer, and can be further used as a compatibilizer. The reaction condition is mild, the conversion rate is high, the environment is friendly, the catalyst is economical and easy to obtain, and the product has higher application value.
The aim of the invention can be achieved by the following technical scheme:
The invention provides a photocatalytic degradation method of polyolefin, which comprises the following steps: mixing polyolefin and azodicarbonate compound in a solvent according to a certain proportion, adding tungsten metal catalyst, heating, reacting under illumination condition, standing, cooling, separating precipitate in the solvent, filtering and drying to obtain final polyolefin degradation product.
In one embodiment of the present invention, the polyolefin has the structural formula (I):
Wherein R1 is a hydrogen atom or an unbranched or branched alkyl group having 1 to 5 carbon atoms, and R2 is a hydrogen atom or an unbranched or branched alkyl group having 1 to 5 carbon atoms. n is the degree of polymerization and n is an integer.
In one embodiment of the present invention, the polyolefin may be a single polyolefin of polyethylene, polypropylene, poly (1-butene), poly (1-pentene), etc., preferably polyethylene.
In one embodiment of the present invention, the polyethylene may be one or more of High Density Polyethylene (HDPE), low Density Polyethylene (LDPE), linear Low Density Polyethylene (LLDPE) or polyethylene products used in life such as cling film, PE gloves, PE plastic bags, preferably Linear Low Density Polyethylene (LLDPE).
In one embodiment of the present invention, the azodicarbonate compound is one or more of dimethyl azodicarbonate, diethyl azodicarbonate, diisopropyl azodicarbonate, di-tert-butyl azodicarbonate, dibenzyl azodicarbonate, and bis (2, 2-trichloroethyl) azodicarbonate, preferably dimethyl azodicarbonate and diethyl azodicarbonate.
In one embodiment of the present invention, the mixing ratio of the polyolefin as a reaction raw material to the azodicarbonic acid ester compound is 1 (0.1-10), preferably 1 (1-5), in terms of molar amount.
In one embodiment of the present invention, the solvent is selected from one or more of 1, 2-dichloroethane, 1, 2-tetrachloroethane, dichloromethane, chloroform, preferably 1, 2-dichloroethane.
In one embodiment of the present invention, the tungsten metal catalyst is one or more of tetrabutylammonium decatungstate, tetraethylammonium decatungstate and tetrahexylammonium decatungstate, preferably tetrabutylammonium decatungstate.
In one embodiment of the invention, the tungsten metal catalyst is added in an amount of 0.1% to 10%, preferably 1% to 5%, based on the molar amount of polyolefin in the feedstock.
In one embodiment of the present invention, the reaction temperature of the reaction system is required to be 80 to 160 ℃, preferably 100 to 120 ℃.
In one embodiment of the invention, the illumination condition required by the reaction is one or more of sunlight and ultraviolet light, preferably ultraviolet light.
In one embodiment of the invention, the reaction time required for the reaction system is from 12 to 72 hours, preferably from 24 to 48 hours.
In one embodiment of the invention, the separation step of the degradation products is: and (3) standing the reaction system, cooling, adding the reaction system into a solvent for precipitation, and then filtering, separating and drying to obtain polyolefin degradation products.
In one embodiment of the present invention, the solvent for the standing treatment is one or more of methanol, ethanol, acetonitrile, tetrahydrofuran and acetone, preferably methanol.
In one embodiment of the invention, the polyolefin degradation products can be further degraded after purification and drying, and the reaction can be repeated for a plurality of times.
Compared with the prior art, the technical scheme provided by the invention has the following beneficial effects:
(1) The process of the invention realizes the effective degradation of polyolefin under milder conditions, the method can successfully degrade polyolefin into olefin oligomer, and simultaneously realizes the grafting of azodicarbonate compounds onto the degraded olefin oligomer, and the grafting rate of the olefin oligomer can reach more than 40 percent.
(2) The method has mild operation condition, low energy consumption, low catalyst consumption and low price, has wide universality, and can be suitable for different types of polyolefin, including common polyolefin products; such as preservative film, white garbage bag, PE glove, etc.
(3) The method can be repeated for a plurality of times, and multistage degradation is realized. The olefin grafted oligomer obtained by degradation through the method can be used as a potential compatibilizer of polyolefin and other polymer materials, and has great commercial value and industrial application potential.
Drawings
FIG. 1 is a chart of Fourier transform infrared spectroscopy analysis of degradation products.
FIG. 2 is a chart of Fourier transform nuclear magnetic resonance spectroscopy of degradation products.
Detailed Description
The aim of the invention can be achieved by the following technical scheme:
The invention provides a photocatalytic degradation method of polyolefin, which comprises the following steps: mixing polyolefin and azodicarbonate compound in a solvent according to a certain proportion, adding tungsten metal catalyst, heating, reacting under illumination condition, standing, cooling, separating precipitate in the solvent, filtering and drying to obtain final polyolefin degradation product.
In one embodiment of the present invention, the polyolefin has the structural formula (I):
Wherein R1 is a hydrogen atom or an unbranched or branched alkyl group having 1 to 5 carbon atoms, and R2 is a hydrogen atom or an unbranched or branched alkyl group having 1 to 5 carbon atoms. n is the degree of polymerization and n is an integer.
In one embodiment of the present invention, the polyolefin may be polyethylene, polypropylene, poly (1-butene), poly (1-pentene), etc., preferably polyethylene.
In one embodiment of the present invention, the polyethylene may be one or more of High Density Polyethylene (HDPE), low Density Polyethylene (LDPE), linear Low Density Polyethylene (LLDPE) or polyethylene products used in life such as cling film, PE gloves, PE plastic bags, preferably Linear Low Density Polyethylene (LLDPE).
In one embodiment of the present invention, the azodicarbonate compound is one or more of dimethyl azodicarbonate, diethyl azodicarbonate, diisopropyl azodicarbonate, di-tert-butyl azodicarbonate, dibenzyl azodicarbonate, and bis (2, 2-trichloroethyl) azodicarbonate, preferably dimethyl azodicarbonate and diethyl azodicarbonate.
In one embodiment of the present invention, the mixing ratio of the polyolefin as a reaction raw material to the azodicarbonic acid ester compound is 1 (0.1-10), preferably 1 (1-5), in terms of molar amount.
In one embodiment of the present invention, the solvent is selected from one or more of 1, 2-dichloroethane, 1, 2-tetrachloroethane, dichloromethane, chloroform, preferably 1, 2-dichloroethane.
In one embodiment of the present invention, the tungsten metal catalyst is one or more of tetrabutylammonium decatungstate, tetraethylammonium decatungstate and tetrahexylammonium decatungstate, preferably tetrabutylammonium decatungstate.
In one embodiment of the invention, the tungsten metal catalyst is added in an amount of 0.1% to 10%, preferably 1% to 5%, based on the molar amount of polyolefin in the feedstock.
In one embodiment of the present invention, the reaction temperature of the reaction system is required to be 80 to 160 ℃, preferably 100 to 120 ℃.
In one embodiment of the invention, the illumination condition required by the reaction is one or more of sunlight and ultraviolet light, preferably ultraviolet light.
In one embodiment of the invention, the reaction time required for the reaction system is from 12 to 72 hours, preferably from 24 to 48 hours.
In one embodiment of the invention, the separation step of the degradation products is: and (3) standing the reaction system, cooling, adding the reaction system into a solvent for precipitation, and then filtering, separating and drying to obtain polyolefin degradation products.
In one embodiment of the present invention, the solvent for the standing treatment is one or more of methanol, ethanol, acetonitrile, tetrahydrofuran and acetone, preferably methanol.
In one embodiment of the invention, the polyolefin degradation products can be further degraded after purification and drying, and the reaction can be repeated for a plurality of times.
The invention will now be described in detail with reference to the drawings and specific examples.
Analytical instrument:
400MHz Fourier transform nuclear magnetic resonance spectrometer, bruker, switzerland;
high temperature gel permeation chromatograph, agilent, usa;
Fourier transform infrared spectrometer (Nicolet 6700), usa Thermofisher.
Raw materials and reagents:
Linear Low Density Polyethylene (LLDPE), beijing Yanshan division of China petrochemical Co., ltd;
low Density Polyethylene (LDPE), chinese petrochemical company limited, beijing yanshan division;
high Density Polyethylene (HDPE), beijing yanshan division, a chinese petrochemical company, inc;
polypropylene (PP), beijing yanshan division, a chinese petrochemical company, limited;
Diisopropyl azodicarboxylate (DIAD), shanghai taitan technologies inc;
diethyl azodicarboxylate (DEAD), shanghai Taitan technologies Co., ltd;
dimethyl azodicarboxylate (DMAD), shanghai Taitan technologies Co., ltd;
Catalyst TBADT, TEADT, THADT was prepared according to the method described in reference chem.
In the following examples:
High temperature gel permeation chromatography test method: 5mg of the dried product obtained in example was weighed, 1mL of trichlorobenzene was added to dissolve, and the dissolved solution was injected through a filter head having a pore size of 0.22 μm using a 2mL syringe, and a sample bottle having a capacity of 2mL was added. And (3) placing the sample bottle into an automatic sample injector of high-temperature GPC, setting a program, testing, presenting a test result in a mode of an outflow curve, and processing by using an Agilent matched program to obtain the molecular weight of the product.
Nuclear magnetic resonance spectroscopy test method: weighing 5mg of the dried product obtained in the example, adding 0.5mL of deuterated dichlorobenzene for dissolution, adding the dissolved solution into a standard nuclear magnetic resonance tube, testing by using a 400MHz nuclear magnetic resonance spectrometer, wherein the test result shows that different groups correspond to characteristic peaks of corresponding chemical displacement, determining the number of polymer monomer units by comparing the peak areas of the characteristic peaks, and further obtaining the overall molecular weight of the polymer by calculation.
The Fourier transform infrared spectrometer testing method comprises the following steps: and uniformly smearing 5mg of powder sample on an infrared spectrometer sample table, screwing a cover plate knob, and testing, wherein in a test result, the grafting rate of the polymer is obtained by comparing the characteristic peak intensity ratio of the grafting functional group and the main chain monomer unit functional group.
Example 1
The embodiment provides a degradation method of LLDPE under sunlight.
In a 10mL flask, 56mg of LLDPE (2 mmol) having a molecular weight of 28000, 808mg of DIAD (4 mmol), and 166mg TBADT (0.05 mmol) were dissolved in 5mL of tetrachloroethane, and the reaction system was purged with nitrogen for 1 hour and then sealed. The reaction mixture was then heated to 110℃and stirred for 48h under solar irradiation. Then cooling, pouring the reaction liquid into methanol to separate out precipitate. The obtained solid was washed three times with a mixture of methanol and acetonitrile, and then the solvent was removed under reduced pressure, followed by drying. The molecular weight of the product measured by high-temperature gel permeation chromatography and nuclear magnetic resonance spectrometer is 4000, and the grafting rate of azodicarbonate groups on the olefin oligomer measured by a Fourier transform infrared spectrometer is 51.6%.
Example 2
The embodiment provides a degradation method of LDPE under sunlight.
In a 10mL flask, 36mg of LDPE (2 mmol) having a molecular weight of 18000, 404mg of DIAD (2 mmol), and 65mg TBADT (0.02 mmol) were dissolved in 5mL of tetrachloroethane, and the reaction system was purged with nitrogen for 1 hour and then sealed. Subsequently, the reaction mixture was heated to 100℃and stirred for 60 hours under irradiation of sunlight. Then cooling, pouring the reaction liquid into methanol to separate out precipitate. The obtained solid was washed three times with a mixture of methanol and acetonitrile, and then the solvent was removed under reduced pressure, followed by drying. The molecular weight of the product measured by high temperature gel permeation chromatography and nuclear magnetic resonance spectrometer is 3000, and the grafting rate of azodicarbonate group on olefin oligomer measured by Fourier transform infrared spectrometer is 85.0%.
Example 3
The embodiment provides a degradation method of HDPE under sunlight.
In a 10mL flask, 40mg of LDPE (2 mmol) having a molecular weight of 20000, 1010mg of DIAD (5 mmol), 133mg TBADT (0.04 mmol) were dissolved in 5mL of 1, 2-dichloroethane, and the reaction system was purged with nitrogen for 1 hour and then sealed. The reaction mixture was then heated to 120℃and stirred under sunlight for 36h. Then cooling, pouring the reaction liquid into methanol to separate out precipitate. The obtained solid was washed three times with a mixture of methanol and acetonitrile, and then the solvent was removed under reduced pressure, followed by drying. The product was analyzed by high temperature gel permeation chromatography with a molecular weight of 1500 and a grafting ratio of azodicarbonate groups on the olefin oligomer of 80.2% by fourier transform infrared spectrometer.
Example 4
The embodiment provides a degradation method of PE gloves under an ultraviolet lamp.
In a 10mL flask, 56mg of the chopped PE glove (1 mmol), 808mg of DIAD (4 mmol), and 166mg TBADT (0.05 mmol) were dissolved in 5mL of tetrachloroethane, and the reaction system was purged with nitrogen for 1 hour and then sealed. The reaction mixture was then heated to 120℃and stirred under UV light for 60h. Then cooling, pouring the reaction liquid into methanol to separate out precipitate. The obtained solid was washed three times with a mixture of methanol and acetonitrile, and then the solvent was removed under reduced pressure, followed by drying. The molecular weight of the product is 3400 measured by high-temperature gel permeation chromatography and the grafting rate of azodicarbonate groups on the olefin oligomer is 42.9 percent measured by a Fourier transform infrared spectrometer.
Example 5
The embodiment provides a degradation method of PP under sunlight.
In a 10mL flask, 60mg of PP (2 mmol) having a molecular weight of 30000, 696mg of DEAD (4 mmol) and 163mg TEADT (0.05 mmol) were dissolved in 5mL of tetrachloroethane, and the reaction system was purged with nitrogen for 1 hour and then sealed. The reaction mixture was then heated to 110℃and stirred for 48h under solar irradiation. Then cooling, pouring the reaction liquid into methanol to separate out precipitate. The obtained solid was washed three times with a mixture of methanol and acetonitrile, and then the solvent was removed under reduced pressure, followed by drying. The molecular weight of the product measured by high-temperature gel permeation chromatography and nuclear magnetic resonance spectrometer is 3500, and the grafting rate of azodicarbonate group on olefin oligomer measured by Fourier transform infrared spectrometer is 50.9%.
Example 6
The embodiment provides a degradation method of PP under an ultraviolet lamp.
In a 10mL flask, 40mg of PP (2 mmol) having a molecular weight of 20000, 1010mg of DMAD (5 mmol) and 135mg THADT (0.04 mmol) were dissolved in 5mL of 1, 2-dichloroethane, and the reaction system was purged with nitrogen for 1 hour and then sealed. The reaction mixture was then heated to 120℃and stirred under UV light for 36h. Then cooling, pouring the reaction liquid into methanol to separate out precipitate. The obtained solid was washed three times with a mixture of methanol and acetonitrile, and then the solvent was removed under reduced pressure, followed by drying. The molecular weight of the product measured by high temperature gel permeation chromatography and nuclear magnetic resonance spectrometer is 2900, and the grafting rate of azodicarbonate group on the olefin oligomer measured by Fourier transform infrared spectrometer is 56.8%.
Example 7
The embodiment provides a degradation method of LLDPE under sunlight.
In a 10mL flask, 56mg of LLDPE (2 mmol) having a molecular weight of 28000, 808mg of DIAD (4 mmol) and 66.5mg TBADT (0.02 mmol) were dissolved in 5mL of tetrachloroethane, and the reaction system was purged with nitrogen for 1 hour and then sealed. Subsequently, the reaction mixture was heated to 80℃and stirred for 48 hours under irradiation of sunlight. Then cooling, pouring the reaction liquid into methanol to separate out precipitate. The obtained solid was washed three times with a mixture of methanol and acetonitrile, and then the solvent was removed under reduced pressure, followed by drying. The molecular weight of the product is 5100 measured by high-temperature gel permeation chromatography and the grafting rate of the azodicarbonate group on the olefin oligomer is 47.6 percent measured by a Fourier transform infrared spectrometer.
Example 8
The embodiment provides a degradation method of LLDPE under sunlight.
In a 10mL flask, 56mg of LLDPE (2 mmol) having a molecular weight of 28000, 2020mg of DIAD (10 mmol) and 332mg TBADT (0.1 mmol) were dissolved in 5mL of tetrachloroethane, and the reaction system was purged with nitrogen for 1 hour and then sealed. The reaction mixture was then heated to 160℃and stirred for 48h under solar irradiation. Then cooling, pouring the reaction liquid into methanol to separate out precipitate. The obtained solid was washed three times with a mixture of methanol and acetonitrile, and then the solvent was removed under reduced pressure, followed by drying. The molecular weight of the product measured by high temperature gel permeation chromatography and nuclear magnetic resonance spectrometer is 2100, and the grafting rate of azodicarbonate group on olefin oligomer measured by Fourier transform infrared spectrometer is 69.4%.
Example 9
The embodiment provides a degradation method of LLDPE under sunlight.
In a 10mL flask, 56mg of LLDPE (2 mmol) having a molecular weight of 28000, 1616mg of DIAD (8 mmol) and 133mg TBADT (0.04 mmol) were dissolved in 5mL of tetrachloroethane, and the reaction system was purged with nitrogen for 1 hour and then sealed. The reaction mixture was then heated to 140℃and stirred for 48h under solar irradiation. Then cooling, pouring the reaction liquid into methanol to separate out precipitate. The obtained solid was washed three times with a mixture of methanol and acetonitrile, and then the solvent was removed under reduced pressure, followed by drying. The molecular weight of the product is 3300 measured by high temperature gel permeation chromatography and the grafting rate of azodicarbonate groups on the olefin oligomer is 55.3 percent measured by a Fourier transform infrared spectrometer.
Wherein fig. 1 shows fourier transform infrared spectrum analysis charts of degradation products in examples 1 and 2, in fig. 1, a is an undegraded polymer, B is a polymer corresponding to degradation degree of example 2, and C is a polymer corresponding to degradation degree of example 1.
Fig. 2 is a chart of fourier transform nuclear magnetic resonance spectroscopy adapted to the degradation products of all examples, and fig. 2a, b, c, d correspond to the corresponding characteristic hydrogen atoms in the formulae in the chart in sequence.
The previous description of the embodiments is provided to facilitate a person of ordinary skill in the art in order to make and use the present invention. It will be apparent to those skilled in the art that various modifications can be readily made to these embodiments and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above-described embodiments, and those skilled in the art, based on the present disclosure, should make improvements and modifications without departing from the scope of the present invention.
Claims (19)
1. A method of photocatalytic degradation of a polyolefin, the method comprising the steps of: mixing polyolefin and azodicarbonate compound in solvent, adding tungsten metal catalyst, then carrying out degradation reaction under illumination condition, standing, separating and drying to obtain polyolefin degradation product;
The structural general formula of the polyolefin is shown as the following formula (I):
Wherein R 1 is a hydrogen atom or an unbranched or branched alkyl group having 1 to 5 carbon atoms, and R 2 is a hydrogen atom or an unbranched or branched alkyl group having 1 to 5 carbon atoms; n is the degree of polymerization and n is an integer;
The azodicarbonate compound is one or more of azodicarbonate dimethyl ester, azodicarbonate diethyl ester, azodicarbonate diisopropyl ester, azodicarbonate di-tert-butyl ester, azodicarbonate dibenzyl ester and azodicarbonate bis (2, 2-trichloroethyl) ester;
The solvent is one or more selected from 1, 2-dichloroethane, 1, 2-tetrachloroethane, dichloromethane and chloroform.
2. The method of photocatalytic degradation of a polyolefin according to claim 1, wherein the polyolefin is polyethylene, polypropylene, poly (1-butene) or poly (1-pentene).
3. The method of photocatalytic degradation of a polyolefin according to claim 2, wherein the polyolefin is polyethylene.
4. The method for photocatalytic degradation of polyolefin according to claim 1, wherein the mixing ratio of polyolefin to azodicarbonate compound in the reaction raw material is 1 (0.1-10) in terms of molar amount.
5. The method for photocatalytic degradation of polyolefin according to claim 4, wherein the mixing ratio of polyolefin to azodicarbonate compound in the reaction raw material is 1 (1-5) in terms of molar amount.
6. A method of photocatalytic degradation of a polyolefin according to claim 1, characterized in that said solvent is selected from 1, 2-dichloroethane.
7. The method for photocatalytic degradation of polyolefin according to claim 1, wherein the tungsten metal catalyst is one or more of tetrabutylammonium decatungstate, tetraethylammonium decatungstate, and tetrahexylammonium decatungstate.
8. The method for photocatalytic degradation of polyolefin according to claim 1, wherein the tungsten metal catalyst is added in an amount of 0.1% to 10% based on the molar amount of polyolefin in the raw material.
9. The method for photocatalytic degradation of polyolefin according to claim 8, wherein the tungsten metal catalyst is added in an amount of 1% to 5% based on the molar amount of polyolefin in the raw material.
10. The method for photocatalytic degradation of a polyolefin according to claim 1, wherein the reaction temperature is 80-160 ℃.
11. The method for photocatalytic degradation of a polyolefin according to claim 10, wherein the reaction temperature is 100-120 ℃.
12. The method for photocatalytic degradation of polyolefin according to claim 1, wherein the illumination condition is one or more of sunlight and ultraviolet light.
13. The method of photocatalytic degradation of a polyolefin as set forth in claim 12, wherein the illumination condition is ultraviolet light.
14. The method for photocatalytic degradation of polyolefin according to claim 1, wherein the reaction time is 12 to 72 hours.
15. The method for photocatalytic degradation of polyolefin according to claim 14, wherein the reaction time is 24 to 48 hours.
16. The method for photocatalytic degradation of polyolefin according to claim 1, wherein the step of separating and drying after the standing treatment of the degradation product is: and (3) standing, cooling and adding the reaction system into a solvent for precipitation, and then filtering and separating to obtain polyolefin degradation products.
17. The method for photocatalytic degradation of polyolefin according to claim 16, wherein the solvent for the stationary treatment is one or more of methanol, ethanol, acetonitrile, tetrahydrofuran and acetone.
18. A method for photocatalytic degradation of a polyolefin according to claim 17, wherein the solvent for the stationary treatment is methanol.
19. The method for photocatalytic degradation of a polyolefin according to any one of claims 1 to 18, wherein the polyolefin degradation product is further degraded after purification and drying, and the reaction is repeated a plurality of times.
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