CN114524930A - Quaternary copolymer containing phthalic anhydride and ethylene oxide - Google Patents
Quaternary copolymer containing phthalic anhydride and ethylene oxide Download PDFInfo
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- CN114524930A CN114524930A CN202111125717.5A CN202111125717A CN114524930A CN 114524930 A CN114524930 A CN 114524930A CN 202111125717 A CN202111125717 A CN 202111125717A CN 114524930 A CN114524930 A CN 114524930A
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- 229920001577 copolymer Polymers 0.000 title claims abstract description 56
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 title claims abstract description 51
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 title claims abstract description 21
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 title claims abstract description 21
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 36
- 150000008064 anhydrides Chemical class 0.000 claims abstract description 30
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000003054 catalyst Substances 0.000 claims abstract description 20
- 238000002360 preparation method Methods 0.000 claims abstract description 20
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 18
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 18
- 239000000178 monomer Substances 0.000 claims abstract description 18
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 150000004292 cyclic ethers Chemical class 0.000 claims abstract description 5
- LALRXNPLTWZJIJ-UHFFFAOYSA-N triethylborane Chemical compound CCB(CC)CC LALRXNPLTWZJIJ-UHFFFAOYSA-N 0.000 claims description 26
- 150000001875 compounds Chemical class 0.000 claims description 20
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 16
- 229910052796 boron Inorganic materials 0.000 claims description 16
- -1 alkylammonium halide Chemical class 0.000 claims description 15
- 229920006029 tetra-polymer Polymers 0.000 claims description 13
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 11
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 claims description 4
- FPGGTKZVZWFYPV-UHFFFAOYSA-M tetrabutylammonium fluoride Chemical compound [F-].CCCC[N+](CCCC)(CCCC)CCCC FPGGTKZVZWFYPV-UHFFFAOYSA-M 0.000 claims description 4
- 150000008065 acid anhydrides Chemical class 0.000 claims description 3
- CCSBNBKMACZDGN-UHFFFAOYSA-N (2-phenoxyacetyl) 2-phenoxyacetate Chemical compound C=1C=CC=CC=1OCC(=O)OC(=O)COC1=CC=CC=C1 CCSBNBKMACZDGN-UHFFFAOYSA-N 0.000 claims description 2
- BJMLLSSSTGHJJE-UHFFFAOYSA-N (4-methylbenzoyl) 4-methylbenzoate Chemical compound C1=CC(C)=CC=C1C(=O)OC(=O)C1=CC=C(C)C=C1 BJMLLSSSTGHJJE-UHFFFAOYSA-N 0.000 claims description 2
- NMVCQWBTTHDUQD-UHFFFAOYSA-N 2-phenylbutanoyl 2-phenylbutanoate Chemical compound C=1C=CC=CC=1C(CC)C(=O)OC(=O)C(CC)C1=CC=CC=C1 NMVCQWBTTHDUQD-UHFFFAOYSA-N 0.000 claims description 2
- HDFKMLFDDYWABF-UHFFFAOYSA-N 3-phenyloxolane-2,5-dione Chemical compound O=C1OC(=O)CC1C1=CC=CC=C1 HDFKMLFDDYWABF-UHFFFAOYSA-N 0.000 claims description 2
- MWSKJDNQKGCKPA-UHFFFAOYSA-N 6-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1CC(C)=CC2C(=O)OC(=O)C12 MWSKJDNQKGCKPA-UHFFFAOYSA-N 0.000 claims description 2
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 claims description 2
- DPKBAXPHAYBPRL-UHFFFAOYSA-M tetrabutylazanium;iodide Chemical compound [I-].CCCC[N+](CCCC)(CCCC)CCCC DPKBAXPHAYBPRL-UHFFFAOYSA-M 0.000 claims description 2
- BGQMOFGZRJUORO-UHFFFAOYSA-M tetrapropylammonium bromide Chemical compound [Br-].CCC[N+](CCC)(CCC)CCC BGQMOFGZRJUORO-UHFFFAOYSA-M 0.000 claims description 2
- FBEVECUEMUUFKM-UHFFFAOYSA-M tetrapropylazanium;chloride Chemical compound [Cl-].CCC[N+](CCC)(CCC)CCC FBEVECUEMUUFKM-UHFFFAOYSA-M 0.000 claims description 2
- GKXDJYKZFZVASJ-UHFFFAOYSA-M tetrapropylazanium;iodide Chemical compound [I-].CCC[N+](CCC)(CCC)CCC GKXDJYKZFZVASJ-UHFFFAOYSA-M 0.000 claims description 2
- CMHHITPYCHHOGT-UHFFFAOYSA-N tributylborane Chemical compound CCCCB(CCCC)CCCC CMHHITPYCHHOGT-UHFFFAOYSA-N 0.000 claims description 2
- SCXIYMXMSGJRKW-UHFFFAOYSA-N C1(C=2C(C(=O)O1)=CC=CC2)=O.C2CO2 Chemical compound C1(C=2C(C(=O)O1)=CC=CC2)=O.C2CO2 SCXIYMXMSGJRKW-UHFFFAOYSA-N 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 17
- 239000004033 plastic Substances 0.000 abstract description 7
- 229920003023 plastic Polymers 0.000 abstract description 7
- 229920001400 block copolymer Polymers 0.000 abstract description 4
- 230000035484 reaction time Effects 0.000 abstract description 4
- 230000015556 catabolic process Effects 0.000 abstract description 3
- 238000006731 degradation reaction Methods 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 description 16
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 238000001035 drying Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000005469 granulation Methods 0.000 description 5
- 230000003179 granulation Effects 0.000 description 5
- 239000000155 melt Substances 0.000 description 5
- 150000001413 amino acids Chemical class 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000000071 blow moulding Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000010096 film blowing Methods 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 229920001897 terpolymer Polymers 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 238000006701 autoxidation reaction Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- SIXOAUAWLZKQKX-UHFFFAOYSA-N carbonic acid;prop-1-ene Chemical compound CC=C.OC(O)=O SIXOAUAWLZKQKX-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 230000009878 intermolecular interaction Effects 0.000 description 1
- PNUHMQOYKCSNPU-UHFFFAOYSA-N oxolane;triethylborane Chemical compound C1CCOC1.CCB(CC)CC PNUHMQOYKCSNPU-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/18—Block or graft polymers
- C08G64/183—Block or graft polymers containing polyether sequences
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/20—General preparatory processes
- C08G64/32—General preparatory processes using carbon dioxide
- C08G64/34—General preparatory processes using carbon dioxide and cyclic ethers
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyethers (AREA)
Abstract
The invention belongs to the technical field of C08G65/00, and particularly relates to a benzene-anhydride-containing ethylene oxide quadripolymer. A quaternary copolymer containing phthalic anhydride and ethylene oxide is prepared from copolymer monomer and catalyst; the copolymer monomer is selected from at least two of cyclic ether, benzene-containing anhydride and carbon dioxide. Under the control of the preparation raw materials and conditions of the system, the prepared copolymer can be ensured to be a block copolymer, the ethylene oxide is ensured to exist in the middle of the benzene-containing anhydride, the prepared material is further ensured to have higher internal plasticization, and the molecular weight of the prepared material is ensured to reach 1.0 multiplied by 105The reaction time is reduced in g/mol, and the preparation material has better degradation performance and a huge application prospect in the field of plastics is expanded.
Description
Technical Field
The invention belongs to the technical field of C08G65/00, and particularly relates to a benzene-anhydride-containing ethylene oxide quadripolymer.
Background
With the increasingly strict requirements on environmental protection, the traditional plastic materials such as polyethylene and polypropylene are difficult to degrade, and enter the environment after being discarded, so that serious white pollution is caused, the application value of the plastic materials which are independently used as environmental protection materials is gradually reduced, and at the present stage, the development of the plastic materials with better biodegradable performance is very necessary. The excessive emission of carbon dioxide has caused obvious global warming, and the recovery and utilization of carbon dioxide are of great significance to reduce carbon emission and further improve the climate conditions.
Poly (methyl ethylene carbonate) (PPC) formed by copolymerizing propylene oxide and carbon dioxide is a transparent, completely degradable and environmentally friendly plastic with a tensile strain at break of 600-1200%, but with a low glass transition temperature (Tg-30-40 ℃). The Chinese patent publication No. CN 111378101A discloses a terpolymer of propylene oxide, phthalic anhydride and carbon dioxide, which can improve the glass transition temperature (Tg is 40-50 ℃) on the basis of PPC, but because the activity of the carbon dioxide is low, the initiation reaction is slow, the reaction time is long, and the energy consumption is increased. Also, the melt Mass Flow Rate (MFR) of the propylene oxide-phthalic anhydride-carbon dioxide terpolymer is too high to be processed stably at high temperatures. In order to further optimize the properties of the copolymer obtained, and to ensure the operability of the reaction and to reduce the energy consumption, it is still an important task and challenge to develop a new preparation method of the copolymer.
Disclosure of Invention
In order to solve the technical problems, the invention provides a quaternary copolymer containing anhydride and ethylene oxide, which is prepared from raw materials comprising copolymer monomers and a catalyst;
the copolymer monomer is selected from at least one of cyclic ether, benzene-containing acid anhydride and carbon dioxide.
In some preferred embodiments, the cyclic ether comprises ethylene oxide.
In some preferred embodiments, the weight of ethylene oxide is 15 to 40 wt% of the total weight of the copolymer.
During the experimental work, the applicant found that the activity of the copolymer prepared with ethylene oxide could be greatly improved, and in particular that the better toughness of the tetrapolymer could be ensured when the weight of ethylene oxide is between 15 and 40% by weight of the total weight of the copolymer, which the applicant speculated might be due to: in the reaction process, with the addition of ethylene oxide, active-OH is produced in the system, ring-opening polymerization reaction between the substances containing the amino acid anhydride and the ethylene oxide in the system is promoted, meanwhile, the strength of intermolecular interaction is promoted, the intermolecular chain mutual attachment capacity is enhanced, rapid dispersion and transfer are formed between molecular chain segments when the system faces external force, the phenomenon of local stress concentration is avoided, and therefore, the toughness of the prepared material is improved.
In some preferred embodiments, the phthalic anhydride containing group is selected from at least one of phthalic anhydride, phenylsuccinic anhydride, p-toluic anhydride, phenoxyacetic anhydride, 2-phenylbutyric anhydride, methyltetrahydrophthalic anhydride.
Preferably, the said phthalic anhydride is phthalic anhydride.
In some preferred embodiments, the catalyst is a boron-containing compound and/or an alkylammonium halide.
In some preferred embodiments, the catalyst is a boron-containing compound and an alkylammonium halide.
In some preferred embodiments, the molar ratio of boron-containing compound to alkylammonium halide is (1-10): 1.
more preferably, the molar ratio of the boron-containing compound to the alkylammonium halide is (1-6): 1.
further preferably, the molar ratio of the boron-containing compound to the alkylammonium halide is 2.5: 1.
more preferably, the molar ratio of the triethylboron to the tetra-n-butylammonium bromide is 5.35: 1;
more preferably, the molar ratio of the triethylboron to the tetra-n-butylammonium bromide is 1: 1;
during the experimental process, through a large amount of creative experimental researches of the applicant, the boron-containing compound and the alkyl ammonium halide are selected as the catalyst in the system, and particularly, the catalyst is prepared by the following steps that the molar ratio of the boron-containing compound to the alkyl ammonium halide is (1-6): 1, the side reaction among polymers in the system can be avoided, the occurrence of miscellaneous chains is avoided, the melt flow rate of the prepared copolymer can be greatly improved, the easy flow rate of the copolymer at 160 ℃ can be ensured to be below 20 and be as low as 3.7g/10min, and the possibility of preparing the quaternary copolymer containing the phthalic anhydride and the ethylene oxide in blow molding products is ensured.
In addition, the applicant has found that in the present system, when the molar ratio of the boron-containing compound to the alkylammonium halide is greater than 6, autoxidation itself occurs, which leads to a decrease in the catalytic effect thereof, and thus affects the preparation of the copolymer.
In some preferred embodiments, the boron-containing compound is selected from one of triethylboron and tributylboron.
In some preferred embodiments, the boron-containing compound is triethylboron.
In the present application, the triethylboron is added in the form of a solution, which is a triethylboron tetrahydrofuran solution, and the molar concentration of the solution is 1 mol/L.
In some preferred embodiments, the alkyl ammonium halide is selected from at least one of tetra-n-butyl ammonium fluoride, tetra-n-butyl ammonium chloride, tetra-n-butyl ammonium bromide, tetra-n-butyl ammonium iodide, tetra-n-propyl ammonium fluoride, tetra-n-propyl ammonium chloride, tetra-n-propyl ammonium bromide, and tetra-n-propyl ammonium iodide.
In some preferred embodiments, the molar ratio of boron-containing compound to anhydride-containing compound is 1: (10-500).
More preferably, the molar ratio of the boron-containing compound to the anhydride-containing compound is 1: (10-500).
More preferably, the molar ratio of the boron-containing compound to the anhydride-containing compound is 1: (80-200).
In some preferred embodiments, the molar ratio of ethylene oxide to anhydride-containing species is 1: (2-20).
More preferably, the molar ratio of the ethylene oxide to the benzene-containing anhydrides is (2-20): 1.
more preferably, the molar ratio of the ethylene oxide to the benzene-containing anhydrides is (3-12): 1.
during the experimental process, the applicant has found through a large number of creative experiments that in the system, the ethylene oxide is selectively added and the molar ratio of the ethylene oxide to the substances containing the phthalic anhydride is ensured to be (3-12): 1, the copolymer obtained by preparation can be greatly improved to be a block copolymer, the reaction activity can be greatly improved, the energy consumption in the reaction process is reduced, the prepared material is ensured to have better mechanical property and biodegradability, and the economic benefit and the application value can be improved, and the reason why the phenomenon appears is presumably that: in the system, the molar ratio of the ethylene oxide to the benzene-containing acid anhydride is controlled to be (3-12): 1, ethylene oxide in the system is adsorbed on the surfaces of triethylboron and alkyl ammonium halide, so that the electron cloud density of a carbon-carbon single bond is deviated to the outer side, addition reaction of substances containing amino acid anhydride is facilitated under the action of the electron cloud density, the chain length of the copolymer is promoted, and meanwhile, under the compounding of the ethylene oxide and the substances containing the amino acid anhydride, the contents of a soft segment and a hard segment in a copolymer molecule can be balanced, so that the better mechanical property of the prepared material is ensured.
In some preferred embodiments, the copolymer is a random structure or a block structure;
the random structure comprises one of formula (1), formula (2), formula (3), formula (4), formula (5), formula (6), formula (7) and formula (8):
formula (1):
wherein a is more than or equal to 1 and less than or equal to 3500, b is more than or equal to 1 and less than or equal to 4000, c is more than or equal to 1 and less than or equal to 6000, d is more than or equal to 1 and less than or equal to 7000, and a, b, c and d are integers;
formula (2):
formula (3):
wherein a is more than or equal to 1 and less than or equal to 4000, b is more than or equal to 1 and less than or equal to 3500, c is more than or equal to 1 and less than or equal to 6000, d is more than or equal to 1 and less than or equal to 7000, and a, b, c and d are integers;
formula (4):
wherein a is more than or equal to 1 and less than or equal to 3500, b is more than or equal to 1 and less than or equal to 4000, c is more than or equal to 1 and less than or equal to 7000, d is more than or equal to 1 and less than or equal to 6000, and a, b, c and d are integers;
formula (5):
wherein a is more than or equal to 1 and less than or equal to 3500, b is more than or equal to 1 and less than or equal to 4000, c is more than or equal to 1 and less than or equal to 6000, d is more than or equal to 1 and less than or equal to 7000, and a, b, c and d are integers;
formula (6):
wherein a is more than or equal to 1 and less than or equal to 4000, b is more than or equal to 1 and less than or equal to 3500, c is more than or equal to 1 and less than or equal to 7000, d is more than or equal to 1 and less than or equal to 6000, and a, b, c and d are integers;
formula (7):
wherein a is more than or equal to 1 and less than or equal to 3500, b is more than or equal to 1 and less than or equal to 4000, c is more than or equal to 1 and less than or equal to 7000, d is more than or equal to 1 and less than or equal to 6000, and a, b, c and d are integers;
formula (8):
wherein a is more than or equal to 1 and less than or equal to 4000, b is more than or equal to 1 and less than or equal to 3500, c is more than or equal to 1 and less than or equal to 6000, d is more than or equal to 1 and less than or equal to 7000, and a, b, c and d are integers;
the block structure comprises one of a formula (9) and a formula (10);
formula (9):
wherein a is more than or equal to 1 and less than or equal to 3500, b is more than or equal to 1 and less than or equal to 6000, c is more than or equal to 1 and less than or equal to 7000, d is more than or equal to 1 and less than or equal to 3500, and a, b, c and d are integers;
formula (10):
wherein a is more than or equal to 1 and less than or equal to 4000, b is more than or equal to 1 and less than or equal to 7000, c is more than or equal to 1 and less than or equal to 6000, d is more than or equal to 1 and less than or equal to 4000, and a, b, c and d are integers.
Further preferably, the structure of the copolymer is a block structure.
In the experimental process, the applicant finds that the addition of ethylene oxide in the system can ensure that the prepared copolymer is a block copolymer, ensure that the ethylene oxide exists in the middle of the benzene-containing anhydrides, further ensure that the prepared material has higher internal plasticization effect and ensure that the molecular weight of the prepared material reaches 1.0 multiplied by 105The reaction time is reduced in g/mol, and the preparation material has better degradation performance and a huge application prospect in the field of plastics is expanded.
In some preferred embodiments, the starting materials for the preparation of the tetrapolymer further comprise propylene oxide and carbon dioxide.
In the present application, the preparation method of the quaternary copolymer containing the anhydride group and the ethylene oxide comprises the following steps:
adding the preparation raw materials into a reaction kettle, then adding a catalyst, adding carbon dioxide, heating for reaction, and after the reaction is finished, sequentially performing devolatilization, drying and granulation to obtain the quaternary copolymer containing the phthalic anhydride and the ethylene oxide.
Has the advantages that: the quaternary copolymer containing the anhydride-ethylene oxide provided by the invention has the following advantages:
1. the quaternary copolymer containing the anhydride and the ethylene oxide can ensure that the prepared material has better mechanical property under the control of the proportion of the ethylene oxide and the anhydride, avoids local stress concentration when external force is applied, and improves the application value;
2. the copolymer obtained by preparation can be ensured to be a block copolymer under the control of the preparation raw materials and conditions of the system, the ethylene oxide is ensured to exist in the middle of the benzene-containing anhydride, and the prepared material is further ensured to have higher internal plasticization effect, and the molecular weight of the prepared material is ensured to reach 1.0 multiplied by 105The reaction time is reduced in g/mol, and the preparation material has better degradation performance and a huge application prospect in the field of plastics is expanded;
3. the quaternary copolymer containing the anhydride and the ethylene oxide obviously reduces the melt Mass Flow Rate (MFR), is convenient for stable processing at high temperature, and is more suitable for processing such as film blowing and the like.
Detailed Description
Examples
Example 1
A quadripolymer containing anhydride-ethylene oxide is prepared from copolymer monomer and catalyst;
the copolymer monomer comprises the following components in parts by weight: 8.81 parts of ethylene oxide, 2.96 parts of phthalic anhydride and 11.62 parts of propylene oxide.
The copolymer monomer also includes carbon dioxide.
The catalyst is tetra-n-butylammonium bromide and triethylboron;
the triethylboron is added in the form of a solution, the triethylboron is a tetrahydrofuran solution of triethylboron, and the molar concentration of the solution is 1 mol/L.
The molar ratio of the triethylboron to the tetra-n-butylammonium bromide is 2.5: 1;
the molar ratio of the triethylboron to the phthalic anhydride is 1: 200 of a carrier;
the preparation method of the quaternary copolymer containing the anhydride and the ethylene oxide comprises the following steps:
adding the preparation raw materials into a reaction kettle, adding a catalyst under the anhydrous and anaerobic conditions, charging carbon dioxide until the pressure is 1.2MPa, heating and reacting at 65 ℃, ending the reaction for 7 hours, and sequentially performing devolatilization, drying and granulation to obtain the quaternary copolymer containing the phthalic anhydride and the ethylene oxide.
Molecular weight measurement by GPC method gave, number average molecular weight (Mn): 1.21X 105g/mol, molecular weight distribution coefficient (PDI): 2.16.
example 2
A quadripolymer containing anhydride-ethylene oxide is prepared from copolymer monomer and catalyst;
the copolymer monomer comprises the following components in parts by weight: 6.19 parts of ethylene oxide, 4.16 parts of phthalic anhydride and 24.47 parts of propylene oxide.
The copolymer monomer also includes carbon dioxide.
The catalyst is tetra-n-butylammonium bromide and triethylboron;
the triethylboron is added in the form of a solution, the triethylboron is a tetrahydrofuran solution of triethylboron, and the molar concentration of the solution is 1 mol/L.
The molar ratio of the triethylboron to the tetra-n-butylammonium bromide is 5.35: 1;
the molar ratio of the triethylboron to the phthalic anhydride is 1: 187;
the preparation method of the quaternary copolymer containing the anhydride and the ethylene oxide comprises the following steps:
adding the preparation raw materials into a reaction kettle, adding a catalyst under the anhydrous and anaerobic conditions, charging carbon dioxide until the pressure is 1.2MPa, heating and reacting at 65 ℃, ending the reaction for 8.9 hours, and sequentially performing devolatilization, drying and granulation to obtain the quaternary copolymer containing the amino acid anhydride and the ethylene oxide.
Molecular weight measurement by GPC method gave, number average molecular weight (Mn): 1.11X 105g/mol, molecular weight distribution coefficient (PDI): 2.77.
example 3
A quadripolymer containing anhydride-ethylene oxide is prepared from copolymer monomer and catalyst;
the copolymer monomer comprises the following components in parts by weight: 2.05 parts of ethylene oxide, 3.45 parts of phthalic anhydride and 5.41 parts of propylene oxide.
The copolymer monomer also includes carbon dioxide.
The catalyst is tetra-n-butylammonium bromide and triethylboron;
the triethylboron is added in the form of a solution, the triethylboron is a tetrahydrofuran solution of triethylboron, and the molar concentration of the solution is 1 mol/L.
The molar ratio of the triethylboron to the tetra-n-butylammonium bromide is 1: 1;
the molar ratio of the triethylboron to the phthalic anhydride is 1: 100, respectively;
the preparation method of the quaternary copolymer containing the anhydride and the ethylene oxide comprises the following steps:
adding the preparation raw materials into a reaction kettle, adding a catalyst under the anhydrous and anaerobic conditions, charging carbon dioxide until the pressure is 1.2MPa, heating and reacting at 65 ℃, and after the reaction is finished for 9 hours, sequentially performing devolatilization, drying and granulation to obtain the quaternary copolymer containing the phthalic anhydride and the ethylene oxide.
Molecular weight measurement by GPC method gave, number average molecular weight (Mn): 1.30X 105g/mol, molecular weight distribution coefficient (PDI): 2.36.
comparative example 1
A copolymer is prepared by raw materials including copolymer monomers and a catalyst;
the copolymer monomer comprises the following components in parts by weight: 2.85 parts of phthalic anhydride and 5.75 parts of propylene oxide.
The copolymer monomer also includes carbon dioxide.
The solvent is tetrahydrofuran, and the weight part is 2.16 parts;
the molar ratio of the triethylboron to the tetra-n-butylammonium bromide is 3.24: 1;
adding the preparation raw materials into a reaction kettle, adding a catalyst in an anhydrous and oxygen-free environment, charging carbon dioxide until the pressure is 1.2MPa, reacting for 7 hours at 65 ℃, and sequentially performing devolatilization, drying and granulation to obtain the copolymer.
Molecular weight measurement by GPC method gave, number average molecular weight (Mn): 1.53X 105g/mol, molecular weight distribution coefficient (PDI): 2.30.
and (3) performance testing:
the melt Mass Flow Rate (MFR) at various temperatures, 2.16kg load, was tested and the results are reported in the table below.
Comparative example 1 was tested and no data on mass flow rate was obtained at 190 ℃.
The performance test results show that the melt flow indexes of the quaternary copolymer containing the anhydride and the ethylene oxide are different at the temperature of 160-190 ℃, which shows that the quaternary copolymer has stable processability at high temperature and can be conveniently used in the fields of film blowing, blow molding and the like.
Claims (10)
1. A quadripolymer containing phthalic anhydride-ethylene oxide is characterized in that the preparation raw materials comprise a copolymer monomer and a catalyst;
the copolymer monomer is selected from at least one of cyclic ether, benzene-containing acid anhydride and carbon dioxide.
2. The anhydride-containing ethylene oxide tetrapolymer of claim 1, wherein said cyclic ether comprises ethylene oxide.
3. The anhydride-containing ethylene oxide tetrapolymer of claim 2, wherein the weight of ethylene oxide is 15 to 40% by weight based on the total weight of the copolymer.
4. The anhydride-containing ethylene oxide tetrapolymer according to claim 1, wherein the anhydride-containing tetrapolymer is at least one selected from the group consisting of phthalic anhydride, phenylsuccinic anhydride, p-toluic anhydride, phenoxyacetic anhydride, 2-phenylbutyric anhydride, and methyltetrahydrophthalic anhydride.
5. The anhydride-containing ethylene oxide tetrapolymer of claim 1, wherein said catalyst is a boron-containing compound and/or an alkylammonium halide.
6. The anhydride-containing ethylene oxide tetrapolymer of claim 5, wherein said boron-containing compound is one selected from the group consisting of triethylboron and tributylboron.
7. The anhydride-containing ethylene oxide tetrapolymer according to claim 5, wherein the alkyl ammonium halide is at least one selected from the group consisting of tetra-n-butylammonium fluoride, tetra-n-butylammonium chloride, tetra-n-butylammonium bromide, tetra-n-butylammonium iodide, tetra-n-propylammonium fluoride, tetra-n-propylammonium chloride, tetra-n-propylammonium bromide and tetra-n-propylammonium iodide.
8. The anhydride-containing ethylene oxide tetrapolymer of claim 4, wherein the molar ratio of the boron-containing compound to the anhydride-containing compound is 1: (10-500).
9. The anhydride-containing ethylene oxide tetrapolymer according to any one of claims 1 to 8, wherein the copolymer has a random structure or a block structure;
the random structure comprises one of formula (1), formula (2), formula (3), formula (4), formula (5), formula (6), formula (7) and formula (8):
formula (1):
wherein a is more than or equal to 1 and less than or equal to 3500, b is more than or equal to 1 and less than or equal to 4000, c is more than or equal to 1 and less than or equal to 6000, d is more than or equal to 1 and less than or equal to 7000, and a, b, c and d are integers;
formula (2):
formula (3):
wherein a is more than or equal to 1 and less than or equal to 4000, b is more than or equal to 1 and less than or equal to 3500, c is more than or equal to 1 and less than or equal to 6000, d is more than or equal to 1 and less than or equal to 7000, and a, b, c and d are integers;
formula (4):
wherein a is more than or equal to 1 and less than or equal to 3500, b is more than or equal to 1 and less than or equal to 4000, c is more than or equal to 1 and less than or equal to 7000, d is more than or equal to 1 and less than or equal to 6000, and a, b, c and d are integers;
formula (5):
wherein a is more than or equal to 1 and less than or equal to 3500, b is more than or equal to 1 and less than or equal to 4000, c is more than or equal to 1 and less than or equal to 6000, d is more than or equal to 1 and less than or equal to 7000, and a, b, c and d are integers;
formula (6):
wherein a is more than or equal to 1 and less than or equal to 4000, b is more than or equal to 1 and less than or equal to 3500, c is more than or equal to 1 and less than or equal to 7000, d is more than or equal to 1 and less than or equal to 6000, and a, b, c and d are integers;
formula (7):
formula (8):
the block structure comprises one of a formula (9) and a formula (10);
formula (9):
wherein a is more than or equal to 1 and less than or equal to 3500, b is more than or equal to 1 and less than or equal to 6000, c is more than or equal to 1 and less than or equal to 7000, d is more than or equal to 1 and less than or equal to 3500, and a, b, c and d are integers;
formula (10):
wherein a is more than or equal to 1 and less than or equal to 4000, b is more than or equal to 1 and less than or equal to 7000, c is more than or equal to 1 and less than or equal to 6000, d is more than or equal to 1 and less than or equal to 4000, and a, b, c and d are integers.
10. The anhydride-containing ethylene oxide tetrapolymer according to claim 9, wherein the structure of said tetrapolymer is a block structure.
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| PCT/CN2022/119766 WO2023045898A1 (en) | 2021-09-24 | 2022-09-20 | Phenyl anhydride-ethylene oxide quaternary copolymer |
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| WO2023045898A1 (en) * | 2021-09-24 | 2023-03-30 | 山东联欣环保科技有限公司 | Phenyl anhydride-ethylene oxide quaternary copolymer |
| CN115991865A (en) * | 2023-03-22 | 2023-04-21 | 山东联欣环保科技有限公司 | Semi-aromatic carbon dioxide-based tetrapolymer and preparation and modification methods thereof |
| CN116021850A (en) * | 2023-03-30 | 2023-04-28 | 山东联欣环保科技有限公司 | Barrier biodegradable cigarette packaging film and preparation process thereof |
| CN116041679A (en) * | 2023-04-03 | 2023-05-02 | 山东联欣环保科技有限公司 | Polycarbonate biodegradable elastomer and preparation method thereof |
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| CN116333279B (en) * | 2023-05-29 | 2024-04-12 | 山东联欣环保科技有限公司 | Polycarbonate toughening resin |
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| CN111378101B (en) * | 2020-04-26 | 2022-02-01 | 中山大学 | Preparation method of biodegradable carbon dioxide-based polyester-polycarbonate terpolymer |
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| CN114524929B (en) * | 2021-09-24 | 2023-07-25 | 山东联欣环保科技有限公司 | Preparation method of carbon dioxide-based tetrapolymer |
| CN114524930A (en) * | 2021-09-24 | 2022-05-24 | 山东联欣环保科技有限公司 | Quaternary copolymer containing phthalic anhydride and ethylene oxide |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2023045898A1 (en) * | 2021-09-24 | 2023-03-30 | 山东联欣环保科技有限公司 | Phenyl anhydride-ethylene oxide quaternary copolymer |
| CN115991865A (en) * | 2023-03-22 | 2023-04-21 | 山东联欣环保科技有限公司 | Semi-aromatic carbon dioxide-based tetrapolymer and preparation and modification methods thereof |
| CN116021850A (en) * | 2023-03-30 | 2023-04-28 | 山东联欣环保科技有限公司 | Barrier biodegradable cigarette packaging film and preparation process thereof |
| CN116041679A (en) * | 2023-04-03 | 2023-05-02 | 山东联欣环保科技有限公司 | Polycarbonate biodegradable elastomer and preparation method thereof |
| CN116041679B (en) * | 2023-04-03 | 2023-07-04 | 山东联欣环保科技有限公司 | Polycarbonate biodegradable elastomer and preparation method thereof |
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