CN116854847A - Preparation process of modified degradable PE material - Google Patents
Preparation process of modified degradable PE material Download PDFInfo
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- CN116854847A CN116854847A CN202310829603.1A CN202310829603A CN116854847A CN 116854847 A CN116854847 A CN 116854847A CN 202310829603 A CN202310829603 A CN 202310829603A CN 116854847 A CN116854847 A CN 116854847A
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- 239000000463 material Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000000178 monomer Substances 0.000 claims abstract description 29
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000005977 Ethylene Substances 0.000 claims abstract description 26
- FUSFWUFSEJXMRQ-UHFFFAOYSA-N 2-bromo-1,1-dimethoxyethane Chemical compound COC(CBr)OC FUSFWUFSEJXMRQ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 9
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 7
- 229910000042 hydrogen bromide Inorganic materials 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 63
- 238000003756 stirring Methods 0.000 claims description 31
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 24
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 22
- 239000007789 gas Substances 0.000 claims description 19
- 238000002156 mixing Methods 0.000 claims description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 14
- 239000001257 hydrogen Substances 0.000 claims description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims description 13
- 238000001914 filtration Methods 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 10
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000011954 Ziegler–Natta catalyst Substances 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000007789 sealing Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- XKBGEWXEAPTVCK-UHFFFAOYSA-M methyltrioctylammonium chloride Chemical compound [Cl-].CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC XKBGEWXEAPTVCK-UHFFFAOYSA-M 0.000 claims description 5
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 4
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 4
- 239000000706 filtrate Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 5
- 238000009776 industrial production Methods 0.000 abstract description 2
- 239000002861 polymer material Substances 0.000 abstract description 2
- 239000004698 Polyethylene Substances 0.000 description 32
- -1 Polyethylene Polymers 0.000 description 13
- 229920000573 polyethylene Polymers 0.000 description 12
- 230000015556 catabolic process Effects 0.000 description 10
- 238000006731 degradation reaction Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- 238000005457 optimization Methods 0.000 description 5
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 3
- 238000003780 insertion Methods 0.000 description 3
- 230000037431 insertion Effects 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 230000008707 rearrangement Effects 0.000 description 2
- 238000007142 ring opening reaction Methods 0.000 description 2
- 238000005730 ring rearrangement reaction Methods 0.000 description 2
- 241000222120 Candida <Saccharomycetales> Species 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 238000010535 acyclic diene metathesis reaction Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229940117927 ethylene oxide Drugs 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- UCUUFSAXZMGPGH-UHFFFAOYSA-N penta-1,4-dien-3-one Chemical class C=CC(=O)C=C UCUUFSAXZMGPGH-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000006552 photochemical reaction Methods 0.000 description 1
- 239000002504 physiological saline solution Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/02—Ethene
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D323/00—Heterocyclic compounds containing more than two oxygen atoms as the only ring hetero atoms
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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)
- Polyethers (AREA)
Abstract
The invention discloses a preparation process of a modified degradable PE material, and relates to the technical field of high polymer materials. In the preparation of the modified degradable PE material, diethylene glycol and 2-bromo-1, 1-dimethoxyethane are reacted, hydrogen bromide is eliminated to prepare a degradable monomer, and the degradable monomer is embedded in the ethylene polymerization process to prepare the modified degradable PE material. The modified degradable PE material prepared by the invention has good degradability, simple process and easy industrial production.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a preparation process of a modified degradable PE material.
Background
Polyethylene is a very important material and has many advantages such as high strength, corrosion resistance, good durability, etc. The good durability is one of the most important advantages of polyethylene materials, but it is also a major disadvantage of polyethylene in the present day. The main chain of polyethylene is composed of continuous methylene groups, and is difficult to degrade without external stimulus. Most polyethylene products, such as bags, containers, etc., are typically disposed of after a single use, and such discarded polyethylene remains in nature for many years without degradation, which can have a serious impact on the terrestrial and marine environments.
At present, plastic contamination has become a global issue, so the design of synthetic environmentally friendly degradable polyethylene materials is the goal of many scientists. From a chemical synthesis point of view, some degradable groups such as ester bonds, carbonyl groups, etc. are theoretically introduced to the polyethylene backbone, and degradation of the polyethylene can be caused by destruction of these groups. In the last century, copolymers of ethylene and carbon monoxide, vinyl ketones were developed, with carbonyl groups introduced into the main chain or side groups of the polyethylene, which can undergo Norrish I and Norrish I photochemical reactions leading to degradation of the polymer, but the insertion rate of carbonyl groups is generally very low. It has recently been reported that degradable polyethylene copolymers having bonds in the main chain are synthesized by a stepwise polycondensation method using long chain diacids and diols, and an acyclic diene metathesis polymerization method, but monomers in these methods are not directly derived from ethylene and require special design, so that development of a simple process and degradable PE material is necessary.
Disclosure of Invention
The invention aims to provide a preparation process of a modified degradable PE material, which solves the problems in the prior art.
The preparation technology of the modified degradable PE material is that the modified degradable PE material is prepared by embedding a degradable monomer in the ethylene polymerization process.
Preferably, the degradable monomer is prepared by reacting diethylene glycol and 2-bromo-1, 1-dimethoxyethane and then eliminating hydrogen bromide.
The preparation process of the modified degradable PE material mainly comprises the following preparation steps:
(1) Uniformly mixing 2-bromo-1, 3, 6-trioxycyclobutane, methyl trioctyl ammonium chloride and tetrahydrofuran according to the mass ratio of 1:0.01-0.02:6-8 in a nitrogen atmosphere, adding potassium tert-butoxide with the mass of 1.4-1.6 times that of the 2-bromo-1, 3, 6-trioxycyclobutane at a constant speed within 40-50 min under the stirring condition of 0-2 ℃ and 300-500 r/min, continuously stirring and reacting for 70-80 min after the addition is finished, continuously stirring and reacting for 10-14 h at the temperature of 15-25 ℃, adding diethyl ether with the mass of 6-8 times that of the 2-bromo-1, 3, 6-trioxycyclobutane, continuously stirring for 6-8 min, filtering to remove filter residues, and standing filtrate at the temperature of 60-70 ℃ for 10-12 h to obtain degradable monomers;
(2) Uniformly mixing a degradable monomer and n-heptane according to the mass ratio of 1:10-12, adding the mixture into a reaction kettle, adding a catalyst with the mass of 0.03-0.05 times of the degradable monomer into the reaction kettle, sealing the reaction kettle, heating to 50-60 ℃, introducing hydrogen/ethylene mixed gas with the mass of 3-5 times of the reaction kettle at the temperature from the bottom of the reaction kettle for exhausting, closing an air outlet of the reaction kettle, continuously introducing the hydrogen/ethylene mixed gas until the pressure of the reaction kettle reaches 0.6-0.8 MPa, introducing pure ethylene gas in the reaction process, keeping the pressure in the reaction kettle unchanged, stirring the mixture for 20-24 h at 100-200 r/min, cooling to 10-20 ℃, filtering, washing the mixture with pure water and absolute ethyl alcohol for 3-5 times, and drying the mixture at 60-70 ℃ for 4-6 h at 50-100 Pa to obtain the modified degradable PE material.
As optimization, the preparation method of the 2-bromo-1, 3, 6-trioxycyclobutane in the step (1) comprises the following steps: evenly mixing diethylene glycol and 2-bromo-1, 1-dimethoxyethane according to a molar ratio of 1:1, adding p-toluenesulfonic acid with the mass of 0.01-0.02 times of that of the diethylene glycol, stirring and reacting for 20-24 h at 110-120 ℃ and 300-500 r/min, and standing for 10-12 h at 60-70 ℃ and 1-2 kPa.
As an optimization, the reaction formula of the 2-bromo-1, 3, 6-trioxycyclobutane in the step (1) is as follows:
as an optimization, the reaction formula of the degradable monomer in the step (1) is as follows:
preferably, the catalyst in the step (2) is a Ziegler-Natta catalyst.
As optimization, the volume fraction of hydrogen in the hydrogen/ethylene mixed gas in the step (2) is 5-10%.
As an optimization, the reaction formula of the modified degradable PE material in the step (2) is as follows:
compared with the prior art, the invention has the following beneficial effects:
when the modified degradable PE material is prepared, a degradable monomer is embedded in the ethylene polymerization process to prepare the modified degradable PE material.
Firstly, diethylene glycol and 2-bromo-1, 1-dimethoxyethane react, then hydrogen bromide is eliminated to prepare a degradable monomer, double bonds of the degradable monomer are connected with a ring, ring opening and rearrangement can occur during polymerization, ester bonds and ether bonds are inserted into a main chain of a polyethylene molecule, and compared with a long carbon chain, the ester bonds and the ether bonds are easily degraded by acid and alkali and microorganisms, so that degradation performance is improved.
And secondly, the method has simple process steps and is easy for industrial production.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The method provided by the present invention is described in detail by the following examples for more clarity of illustration.
Example 1
The preparation process of the modified degradable PE material mainly comprises the following preparation steps:
(1) Uniformly mixing diethylene glycol and 2-bromo-1, 1-dimethoxyethane according to a molar ratio of 1:1, adding p-toluenesulfonic acid with the mass of 0.01 times of diethylene glycol, stirring and reacting for 24 hours at 110 ℃,300r/min, standing for 12 hours at 60 ℃ under 1kPa to prepare 2-bromo-1, 3, 6-trioxycyclobutane, adding diethyl ether with the mass of 6 times of 2-bromo-1, 3, 6-trioxycyclobutane, methyl trioctyl ammonium chloride and tetrahydrofuran according to a mass ratio of 1:0.01:8, uniformly mixing at 0 ℃, stirring at 300r/min, adding potassium tert-butoxide with the mass of 1.4-1.6 times of 2-bromo-1, 3, 6-trioxycyclobutane at a uniform speed within 40min, continuously stirring and reacting for 70 minutes after the addition, continuously stirring and reacting for 14 hours at 15 ℃, adding diethyl ether with the mass of 6 times of 2-bromo-1, 3, 6-trioxycyclobutane, continuously stirring for 8 minutes, filtering and removing filter residues, and standing for 12 hours at 60 ℃ under 1kPa to prepare degradable monomers;
(2) Uniformly mixing a degradable monomer and n-heptane according to the mass ratio of 1:10, adding the mixture into a reaction kettle, adding a Ziegler-Natta catalyst which is 0.03 times of the mass of the degradable monomer into the reaction kettle, sealing the reaction kettle, heating to 50 ℃, introducing hydrogen/ethylene mixed gas which is 3 times of the mass of the reaction kettle at the temperature from the bottom of the reaction kettle for exhausting, closing an air outlet of the reaction kettle, continuously introducing the hydrogen/ethylene mixed gas until the pressure of the reaction kettle reaches 0.6MPa, introducing pure ethylene gas in the reaction process, keeping the pressure in the reaction kettle unchanged, stirring for 24 hours at 100r/min, cooling to 10 ℃, filtering, washing 3 times by pure water and absolute ethyl alcohol respectively, and drying at 60 ℃ for 6 hours under 50Pa to obtain the modified degradable PE material.
Example 2
The preparation process of the modified degradable PE material mainly comprises the following preparation steps:
(1) Uniformly mixing diethylene glycol, 2-bromo-1, 1-dimethoxyethane according to a molar ratio of 1:1, adding p-toluenesulfonic acid with the mass of 0.015 times of diethylene glycol, stirring and reacting at 115 ℃ for 22 hours at 400r/min, standing at 65 ℃ for 11 hours at 1.5kPa to prepare 2-bromo-1, 3, 6-trioxycyclobutane, in a nitrogen atmosphere, uniformly mixing 2-bromo-1, 3, 6-trioxycyclobutane, methyltrioctylammonium chloride and tetrahydrofuran according to a mass ratio of 1:0.015:7, adding potassium tert-butoxide with the mass of 1.5 times of 2-bromo-1, 3, 6-trioxycyclobutane at a constant speed within 45min under the stirring condition at 1 ℃ at 400r/min, continuously stirring and reacting for 75 minutes after the addition, continuously stirring and reacting at 20 ℃ for 12 hours, adding diethyl ether with the mass of 7 times of 2-bromo-1, 3, 6-trioxycyclobutane, continuously stirring for 7 minutes, filtering and removing filter residues, standing at 65 ℃ for 11 hours to prepare degradable monomers;
(2) Uniformly mixing a degradable monomer and n-heptane according to a mass ratio of 1:11, adding the mixture into a reaction kettle, adding a Ziegler-Natta catalyst which is 0.04 times of the mass of the degradable monomer into the reaction kettle, sealing the reaction kettle, heating to 55 ℃, introducing hydrogen/ethylene mixed gas which is 4 times of the mass of the reaction kettle at the temperature from the bottom of the reaction kettle for exhausting, closing an air outlet of the reaction kettle, continuously introducing the hydrogen/ethylene mixed gas until the pressure of the reaction kettle reaches 0.7MPa, introducing pure ethylene gas in the reaction process, keeping the pressure in the reaction kettle unchanged, stirring for reacting for 22h at 150r/min, cooling to 15 ℃, filtering, washing 4 times by pure water and absolute ethyl alcohol respectively, and drying for 5h at 65 ℃ and 70Pa to obtain the modified degradable PE material.
Example 3
The preparation process of the modified degradable PE material mainly comprises the following preparation steps:
(1) Uniformly mixing diethylene glycol, 2-bromo-1, 1-dimethoxyethane according to a molar ratio of 1:1, adding p-toluenesulfonic acid with the mass of 0.02 times of diethylene glycol, stirring at 120 ℃ for reaction for 20h at 500r/min, standing at 70 ℃ for 10h at 2kPa to prepare 2-bromo-1, 3, 6-trioxycyclobutane, mixing 2-bromo-1, 3, 6-trioxycyclobutane, methyltrioctylammonium chloride and tetrahydrofuran according to a mass ratio of 1:0.02:8 uniformly in a nitrogen atmosphere, adding potassium tert-butoxide with the mass of 1.6 times of 2-bromo-1, 3, 6-trioxycyclobutane at a uniform speed within 50min under the stirring condition of 500r/min at 2 ℃, continuing stirring for reaction for 80min after the addition is finished, rising the temperature to 25 ℃, continuing stirring for reaction for 10h at 25 ℃, adding diethyl ether with the mass of 6-8 times of 2-bromo-1, 3, 6-trioxycyclobutane, continuing stirring for 8min, filtering to remove filter residues, and standing at 70 ℃ for 10h at 2kPa to prepare degradable monomers;
(2) Uniformly mixing a degradable monomer and n-heptane according to the mass ratio of 1:10, adding the mixture into a reaction kettle, adding a Ziegler-Natta catalyst which is 0.05 times of the mass of the degradable monomer into the reaction kettle, sealing the reaction kettle, heating to 60 ℃, introducing hydrogen/ethylene mixed gas which is 5 times of the mass of the reaction kettle at the temperature from the bottom of the reaction kettle for exhausting, closing an air outlet of the reaction kettle, continuously introducing the hydrogen/ethylene mixed gas until the pressure of the reaction kettle reaches 0.8MPa, introducing pure ethylene gas in the reaction process, keeping the pressure in the reaction kettle unchanged, stirring for reacting for 20h at 200r/min, cooling to 20 ℃, filtering, washing 5 times by pure water and absolute ethyl alcohol respectively, and drying for 4h at 70 ℃ and 100Pa to obtain the modified degradable PE material.
Comparative example 1
Adding n-heptane into a reaction kettle until the n-heptane reaches 50% of the capacity of the reaction kettle, adding a Ziegler-Natta catalyst with the mass of 0.004 times of that of the n-heptane, sealing the reaction kettle, heating to 55 ℃, introducing hydrogen/ethylene mixed gas with the volume of 4 times of that of the reaction kettle at the temperature from the bottom of the reaction kettle for exhausting, closing an air outlet of the reaction kettle until the pressure of the reaction kettle reaches 0.7MPa, introducing pure ethylene gas in the reaction process, keeping the pressure in the reaction kettle unchanged, stirring and reacting for 22h at 150r/min, cooling to 15 ℃, filtering, washing with pure water and absolute ethyl alcohol for 4 times respectively, and drying at 65 ℃ and 70Pa for 5h to obtain the PE material.
Experimental example
Degradation performance test:
10g of the materials obtained in examples 1 to 3 and comparative example 1 were immersed in 100mL of physiological saline, 20mL of PBS buffer LA1812 was added, 1g of the biological enzyme derived from Candida langasiensis was further added, and the materials were stirred at 37℃and 100r/min for 20 days, centrifugally separated, filtered, washed and dried, and the degradation rate was calculated as the mass difference before and after enzymolysis of the materials obtained in examples 1 to 3 and comparative example 1.
The following table 1 gives the results of performance analysis of degradability of modified degradable PE materials using examples 1 to 3 of the present invention and comparative example 1.
TABLE 1
| Degradation rate | Degradability of | ||
| Example 1 | 8.7％ | Comparative example 1 | 0.4％ |
| Example 2 | 8.9％ | ||
| Example 3 | 8.9％ |
From comparison of experimental data of examples 1 to 3 and comparative example 1 in Table 2, it can be found that the modified degradable PE material prepared by the invention has good degradation performance.
From comparison of experimental data of examples 1, 2, 3 and comparative example 1, it was found that examples 1, 2, 3 have a high degradation rate compared to comparative example 1, indicating that insertion of a degradable monomer during ethylene polymerization, the double bond of the degradable monomer being linked to a ring, ring opening and rearrangement during polymerization, insertion of an ester bond and an ether bond into the main chain of a polyethylene molecule, and the ester bond and the ether bond being easily degraded by an acid base and microorganisms as compared to a long carbon chain, thereby improving degradation performance.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are, therefore, to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.
Claims (9)
1. The modified degradable PE material is characterized in that the modified degradable PE material is prepared by embedding a degradable monomer in an ethylene polymerization process.
2. The modified degradable PE material of claim 1, characterized in that the degradable monomer is prepared by reacting diethylene glycol, 2-bromo-1, 1-dimethoxyethane and then eliminating hydrogen bromide.
3. The preparation process of the modified degradable PE material is characterized by mainly comprising the following preparation steps:
(1) Uniformly mixing 2-bromo-1, 3, 6-trioxycyclobutane, methyl trioctyl ammonium chloride and tetrahydrofuran according to the mass ratio of 1:0.01-0.02:6-8 in a nitrogen atmosphere, adding potassium tert-butoxide with the mass of 1.4-1.6 times that of the 2-bromo-1, 3, 6-trioxycyclobutane at a constant speed within 40-50 min under the stirring condition of 0-2 ℃ and 300-500 r/min, continuously stirring and reacting for 70-80 min after the addition is finished, continuously stirring and reacting for 10-14 h at the temperature of 15-25 ℃, adding diethyl ether with the mass of 6-8 times that of the 2-bromo-1, 3, 6-trioxycyclobutane, continuously stirring for 6-8 min, filtering to remove filter residues, and standing filtrate at the temperature of 60-70 ℃ for 10-12 h to obtain degradable monomers;
(2) Uniformly mixing a degradable monomer and n-heptane according to the mass ratio of 1:10-12, adding the mixture into a reaction kettle, adding a catalyst with the mass of 0.03-0.05 times of the degradable monomer into the reaction kettle, sealing the reaction kettle, heating to 50-60 ℃, introducing hydrogen/ethylene mixed gas with the mass of 3-5 times of the reaction kettle at the temperature from the bottom of the reaction kettle for exhausting, closing an air outlet of the reaction kettle, continuously introducing the hydrogen/ethylene mixed gas until the pressure of the reaction kettle reaches 0.6-0.8 MPa, introducing pure ethylene gas in the reaction process, keeping the pressure in the reaction kettle unchanged, stirring the mixture for 20-24 h at 100-200 r/min, cooling to 10-20 ℃, filtering, washing the mixture with pure water and absolute ethyl alcohol for 3-5 times, and drying the mixture at 60-70 ℃ for 4-6 h at 50-100 Pa to obtain the modified degradable PE material.
4. The process for preparing a modified degradable PE material according to claim 3, wherein the preparation method of the 2-bromo-1, 3, 6-trioxycyclobutane in the step (1) comprises the following steps: evenly mixing diethylene glycol and 2-bromo-1, 1-dimethoxyethane according to a molar ratio of 1:1, adding p-toluenesulfonic acid with the mass of 0.01-0.02 times of that of the diethylene glycol, stirring and reacting for 20-24 h at 110-120 ℃ and 300-500 r/min, and standing for 10-12 h at 60-70 ℃ and 1-2 kPa.
5. A process for preparing a modified degradable PE material according to claim 3, characterized in that the reaction formula of 2-bromo-1, 3, 6-trioxycyclobutane of step (1) is as follows:
6. a process for preparing a modified degradable PE material according to claim 3, characterized in that the degradable monomer of step (1) has the following reaction formula:
7. a process for the preparation of a modified degradable PE material according to claim 3, characterized in that the catalyst of step (2) is a Ziegler-Natta catalyst.
8. The process for preparing a modified degradable PE material according to claim 3, wherein the hydrogen gas/ethylene mixed gas in the step (2) has a volume fraction of 5-10%.
9. A process for preparing a modified degradable PE material according to claim 3, characterized in that the modified degradable PE material of step (2) has the following reaction formula:
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| Application Number | Priority Date | Filing Date | Title |
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| CN202310829603.1A CN116854847A (en) | 2023-07-07 | 2023-07-07 | Preparation process of modified degradable PE material |
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| CN202310829603.1A CN116854847A (en) | 2023-07-07 | 2023-07-07 | Preparation process of modified degradable PE material |
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