CN114524930B - Tetrapolymer containing phenyl anhydride-ethylene oxide - Google Patents
Tetrapolymer containing phenyl anhydride-ethylene oxide Download PDFInfo
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- CN114524930B CN114524930B CN202111125717.5A CN202111125717A CN114524930B CN 114524930 B CN114524930 B CN 114524930B CN 202111125717 A CN202111125717 A CN 202111125717A CN 114524930 B CN114524930 B CN 114524930B
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 title claims abstract description 32
- 229920006029 tetra-polymer Polymers 0.000 title claims abstract description 24
- 229920001577 copolymer Polymers 0.000 claims abstract description 44
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000002360 preparation method Methods 0.000 claims abstract description 28
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000003054 catalyst Substances 0.000 claims abstract description 19
- 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
- CHIHQLCVLOXUJW-UHFFFAOYSA-N benzoic anhydride Chemical compound C=1C=CC=CC=1C(=O)OC(=O)C1=CC=CC=C1 CHIHQLCVLOXUJW-UHFFFAOYSA-N 0.000 claims abstract description 15
- 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 20
- 150000001875 compounds Chemical class 0.000 claims description 17
- 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 alkyl ammonium halide Chemical class 0.000 claims description 15
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 11
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical group CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 11
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical group [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 11
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 8
- 150000008064 anhydrides Chemical class 0.000 claims description 8
- 230000001788 irregular Effects 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 19
- 239000004033 plastic Substances 0.000 abstract description 8
- 229920003023 plastic Polymers 0.000 abstract description 8
- 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
- 238000001035 drying Methods 0.000 description 5
- 238000005469 granulation Methods 0.000 description 5
- 230000003179 granulation Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000000155 melt Substances 0.000 description 4
- PNUHMQOYKCSNPU-UHFFFAOYSA-N oxolane;triethylborane Chemical compound C1CCOC1.CCB(CC)CC PNUHMQOYKCSNPU-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 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 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 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
- 238000011056 performance test Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229920001897 terpolymer Polymers 0.000 description 2
- FPGGTKZVZWFYPV-UHFFFAOYSA-M tetrabutylammonium fluoride Chemical compound [F-].CCCC[N+](CCCC)(CCCC)CCCC FPGGTKZVZWFYPV-UHFFFAOYSA-M 0.000 description 2
- 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 description 1
- 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 description 1
- 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 description 1
- HDFKMLFDDYWABF-UHFFFAOYSA-N 3-phenyloxolane-2,5-dione Chemical compound O=C1OC(=O)CC1C1=CC=CC=C1 HDFKMLFDDYWABF-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 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
- 238000007259 addition reaction Methods 0.000 description 1
- 238000006701 autoxidation reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 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
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 230000009878 intermolecular interaction Effects 0.000 description 1
- 238000011835 investigation 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
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 description 1
- DPKBAXPHAYBPRL-UHFFFAOYSA-M tetrabutylazanium;iodide Chemical compound [I-].CCCC[N+](CCCC)(CCCC)CCCC DPKBAXPHAYBPRL-UHFFFAOYSA-M 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- BGQMOFGZRJUORO-UHFFFAOYSA-M tetrapropylammonium bromide Chemical compound [Br-].CCC[N+](CCC)(CCC)CCC BGQMOFGZRJUORO-UHFFFAOYSA-M 0.000 description 1
- FBEVECUEMUUFKM-UHFFFAOYSA-M tetrapropylazanium;chloride Chemical compound [Cl-].CCC[N+](CCC)(CCC)CCC FBEVECUEMUUFKM-UHFFFAOYSA-M 0.000 description 1
- GKXDJYKZFZVASJ-UHFFFAOYSA-M tetrapropylazanium;iodide Chemical compound [I-].CCC[N+](CCC)(CCC)CCC GKXDJYKZFZVASJ-UHFFFAOYSA-M 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- CMHHITPYCHHOGT-UHFFFAOYSA-N tributylborane Chemical compound CCCCB(CCCC)CCCC CMHHITPYCHHOGT-UHFFFAOYSA-N 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- 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 tetrapolymer containing phenyl anhydride-ethylene oxide. A tetrapolymer containing phenyl anhydride-ethylene oxide is prepared from copolymer monomer and catalyst; the copolymer monomer is selected from at least two of cyclic ether, phenyl anhydride and carbon dioxide. Under the control of the preparation raw materials and the 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 phenyl anhydride, the preparation material is ensured to have higher internal plasticization, the reaction time is reduced when the molecular weight of the preparation material reaches 1.0X10 5 g/mol, the preparation material is ensured to have better degradation performance, and the huge application prospect in the plastic field is also expanded.
Description
Technical Field
The invention belongs to the technical field of C08G65/00, and particularly relates to a tetrapolymer containing phenyl anhydride-ethylene oxide.
Background
With the increasing strictness of environmental protection requirements, the traditional plastic materials such as polyethylene, polypropylene and the like are difficult to degrade, and the waste plastic materials enter the environment to cause serious white pollution, so that the application value of the plastic materials which are independently used as environmental protection materials is gradually reduced, and at the present stage, the plastic materials with better biodegradability are very necessary to be developed. The excessive emission of carbon dioxide has caused obvious global warming, and the recovery and utilization of carbon dioxide are of great significance in reducing carbon emission and further improving climate conditions.
The polymethyl ethylene carbonate (PPC) formed by copolymerizing propylene oxide and carbon dioxide is transparent and completely degradable environment-friendly plastic, the tensile strain at break is 600-1200%, but the glass transition temperature is low (Tg=30-40 ℃). The Chinese patent publication No. CN 111378101A discloses a terpolymer of propylene oxide, phthalic anhydride and carbon dioxide, which can raise the glass transition temperature (Tg=40-50 ℃) on the basis of PPC, but the carbon dioxide has low activity, slow initiation reaction, long reaction time and increased energy consumption. And, the melt Mass Flow Rate (MFR) of the propylene oxide-phthalic anhydride-carbon dioxide terpolymer is too high for stable processing at high temperatures. In order to further optimize the properties of the copolymers produced 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 process for the preparation of copolymers.
Disclosure of Invention
In order to solve the technical problems, a first aspect of the invention provides a tetrapolymer containing phenyl anhydride-ethylene oxide, wherein the preparation raw materials comprise a copolymer monomer and a catalyst;
The copolymer monomer is selected from at least one of cyclic ether, phenyl 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 weight percent of the total weight of the copolymer.
During the course of the experiment, the applicant found that the activity of the preparation of the copolymer can be greatly improved by adding ethylene oxide, and in particular, when the weight of ethylene oxide is 15-40% of the total weight of the copolymer, the preparation of the tetrapolymer can be ensured to have better toughness, and the reason for this phenomenon is presumed to be due to the fact that the applicant: in the reaction process, along with the addition of ethylene oxide, active-OH is produced in a system, ring-opening polymerization reaction between phenyl anhydride substances and ethylene oxide in the system is promoted, meanwhile, the strength of intermolecular interaction is promoted, the mutual attaching capacity between molecular chains is enhanced, rapid dispersion and transfer are formed between the molecular chain segments when the surface external force acts on the molecular chain segments, and local stress concentration phenomenon is avoided, so that the toughness of the prepared material is improved.
In some preferred embodiments, the phenyl-containing anhydride is selected from at least one of phthalic anhydride, phenylsuccinic anhydride, p-toluic anhydride, phenoxyacetic anhydride, 2-phenylbutyric anhydride, methyltetrahydrophthalic anhydride.
Preferably, the phenyl-containing anhydride is phthalic anhydride.
In some preferred embodiments, the catalyst is a boron-containing compound and/or an alkyl ammonium halide.
In some preferred embodiments, the catalyst is a boron-containing compound and an alkyl ammonium halide.
In some preferred embodiments, the molar ratio of boron-containing compound to alkyl ammonium halide is (1-10): 1.
Further preferably, the molar ratio of the boron-containing compound to the alkyl ammonium halide is (1-6): 1.
Further preferably, the molar ratio of the boron-containing compound to the alkyl ammonium halide is 2.5:1.
Further preferably, the mole ratio of triethylboron and tetra-n-butyl ammonium bromide is 5.35:1, a step of;
Further preferably, the mole ratio of triethylboron to tetra-n-butyl ammonium bromide is 1:1, a step of;
During the experimental process, through a great deal of creative experimental investigation by the applicant, it was found that boron-containing compounds and alkylammonium halides were selected as catalysts in the system, in particular in the molar ratio (1-6): under the condition of 1, the side reaction between polymers in the system can be avoided, the occurrence of hybrid 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 as low as 3.7g/10min, and the possibility of preparing the phenyl anhydride-ethylene oxide-containing tetrapolymer in a blow molding product is ensured.
In addition, the applicant found that when the molar ratio of the boron-containing compound and the alkylammonium halide added is greater than 6 in the system, autoxidation itself occurs, resulting in a decrease in the catalytic effect thereof and thus affecting 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 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 1mol/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, tetra-n-propyl ammonium iodide.
In some preferred embodiments, the molar ratio of boron-containing compound to phenyl-containing anhydride is 1: (10-500).
Further preferably, the molar ratio of the boron-containing compound to the phenyl-containing anhydride is 1: (10-500).
Further preferably, the molar ratio of the boron-containing compound to the phenyl-containing anhydride is 1: (80-200).
In some preferred embodiments, the molar ratio of ethylene oxide to the phenyl-containing anhydride is 1: (2-20).
Further preferably, the molar ratio of the ethylene oxide to the phenyl anhydride is (2-20): 1.
Further preferably, the molar ratio of the ethylene oxide to the phenyl anhydride-containing compound is (3-12): 1.
The applicant has found through a number of inventive experiments during the course of the experiments that in the system ethylene oxide was selectively added and the molar ratio to the substances containing the phenylanhydrides was ensured to be (3-12): 1, the prepared copolymer is a block copolymer, the reaction activity can be greatly improved, the energy consumption in the reaction process is reduced, the preparation material has better mechanical property and biodegradability, the economic benefit and the application value can be improved, and the reason for the phenomenon is presumed to be probably because of the following reasons: in the system, the molar ratio of the ethylene oxide to the phenyl anhydride is controlled to be (3-12): in the process 1, ethylene oxide in the system can be adsorbed on the surfaces of triethylboron and alkyl ammonium halide, so that the electron cloud density of carbon-carbon single bonds is biased to the outside, the addition reaction of substances containing phenyl anhydride under the action of the electron cloud density is facilitated, the chain length of the copolymer is promoted to be increased, and meanwhile, the content of a soft chain segment and a hard chain segment in the copolymer molecule can be balanced under the compounding of the ethylene oxide and the substances containing phenyl anhydride, so that the better mechanical property of the prepared material is ensured.
In some preferred embodiments, the copolymer is of random or block structure;
the irregular structure comprises one of a formula (1), a formula (2), a formula (3), a formula (4), a formula (5), a formula (6), a formula (7) and a formula (8):
Formula (1):
Wherein a is more than or equal to 1 and less than or equal to 3500,1 and less than or equal to b is more than or equal to 4000, c is more than or equal to 1 and less than or equal to 6000,1 and d is more than or equal to 7000, and a, b, c and d are integers;
formula (2):
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 3500,1 and less than or equal to c and less than or equal to 7000,1 and d is more than or equal to 6000, and a, b, c and d are integers;
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 3500,1 and less than or equal to c and less than or equal to 6000,1 and d is more 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 3500,1 and less than or equal to b is more than or equal to 4000, c is more than or equal to 1 and less than or equal to 7000,1 and d is more 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 3500,1 and less than or equal to b is more than or equal to 4000, c is more than or equal to 1 and less than or equal to 6000,1 and d is more 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 3500,1 and less than or equal to c and less than or equal to 7000,1 and d is more 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 3500,1 and less than or equal to b is more than or equal to 4000, c is more than or equal to 1 and less than or equal to 7000,1 and d is more 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 3500,1 and less than or equal to c is more than or equal to 6000,1 and d is more than or equal to 7000, and a, b, c and d are integers;
the block structure comprises one of the formula (9) and the formula (10);
formula (9):
Wherein a is more than or equal to 1 and less than or equal to 3500,1 and less than or equal to b is more than or equal to 6000,1 and less than or equal to c and less than or equal to 7000,1 and less than or equal to d 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 7000,1 and less than or equal to c and less than or equal to 6000,1 and d is more than or equal to 4000, and a, b, c and d are integers.
Further preferably, the copolymer has a block structure.
In the experimental process, the applicant finds that the addition of the ethylene oxide into the system can ensure that the prepared copolymer is a block copolymer, and that the ethylene oxide exists in the middle of the phenyl anhydride, so that the preparation material has a higher internal plasticization effect, the reaction time is reduced when the molecular weight of the preparation material reaches 1.0X10 5 g/mol, the preparation material has better degradation performance, and the huge application prospect in the plastic field is expanded.
In some preferred embodiments, the tetrapolymer is prepared from a feedstock that also includes propylene oxide and carbon dioxide.
In the application, the preparation method of the phenyl anhydride-ethylene oxide-containing tetrapolymer comprises the following steps:
Adding the preparation raw materials into a reaction kettle, adding a catalyst, adding carbon dioxide, heating for reaction, and sequentially performing devolatilization, drying and granulation after the reaction is finished to obtain the phenyl anhydride-ethylene oxide tetrapolymer.
The beneficial effects are that: the phenyl anhydride-ethylene oxide-containing tetrapolymer provided by the invention has the following advantages:
1. the phenyl anhydride-ethylene oxide-containing quaternary copolymer provided by the invention can ensure that the prepared material has better mechanical properties under the control of the proportion of ethylene oxide to phenyl anhydride, avoids local concentration of stress when receiving the action of external force, and improves the application value of the material;
2. Under the control of the preparation raw materials and the 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 phenyl anhydride, the preparation material is ensured to have higher internal plasticization, the reaction time is reduced when the molecular weight of the preparation material reaches 1.0X10 5 g/mol, the preparation material is ensured to have better degradation performance, and the huge application prospect in the plastic field is also expanded;
3. the quaternary copolymer containing the phenyl anhydride and the ethylene oxide provided by the invention obviously reduces the Mass Flow Rate (MFR) of a melt, 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 tetrapolymer containing phenyl 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 comprises carbon dioxide.
The catalyst is tetra-n-butyl ammonium bromide and triethylboron;
The triethylboron is added in the form of a solution, which is triethylboron tetrahydrofuran solution, and the molar concentration of the solution is 1mol/L.
The mole ratio of the triethylboron to the tetra-n-butyl ammonium bromide is 2.5:1, a step of;
the mole ratio of the triethylboron to the phthalic anhydride is 1:200;
the preparation method of the phenyl anhydride-ethylene oxide-containing tetrapolymer comprises the following steps:
Adding the preparation raw materials into a reaction kettle, adding a catalyst under the anhydrous and anaerobic condition, charging carbon dioxide to the pressure of 1.2MPa, heating and reacting at 65 ℃ for 7 hours, and then finishing the reaction, and sequentially performing devolatilization, drying and granulation to obtain the phenyl anhydride-ethylene oxide tetrapolymer.
Molecular weight was measured by GPC to obtain a number average molecular weight (Mn): 1.21X10 5 g/mol, molecular weight distribution coefficient (PDI): 2.16.
Example 2
A tetrapolymer containing phenyl 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 comprises carbon dioxide.
The catalyst is tetra-n-butyl ammonium bromide and triethylboron;
The triethylboron is added in the form of a solution, which is triethylboron tetrahydrofuran solution, and the molar concentration of the solution is 1mol/L.
The mole ratio of the triethylboron to the tetra-n-butyl ammonium bromide is 5.35:1, a step of;
the mole ratio of the triethylboron to the phthalic anhydride is 1:187;
the preparation method of the phenyl anhydride-ethylene oxide-containing tetrapolymer comprises the following steps:
Adding the preparation raw materials into a reaction kettle, adding a catalyst under the anhydrous and anaerobic condition, charging carbon dioxide to the pressure of 1.2MPa, heating at 65 ℃ for reaction, finishing the reaction after 8.9 hours, and sequentially performing devolatilization, drying and granulation to obtain the phenyl anhydride-ethylene oxide quaternary copolymer.
Molecular weight was measured by GPC to obtain a number average molecular weight (Mn): 1.11X10 5 g/mol, molecular weight distribution coefficient (PDI): 2.77.
Example 3
A tetrapolymer containing phenyl 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 comprises carbon dioxide.
The catalyst is tetra-n-butyl ammonium bromide and triethylboron;
The triethylboron is added in the form of a solution, which is triethylboron tetrahydrofuran solution, and the molar concentration of the solution is 1mol/L.
The mol ratio of the triethylboron to the tetra-n-butyl ammonium bromide is 1:1, a step of;
the mole ratio of the triethylboron to the phthalic anhydride is 1:100;
the preparation method of the phenyl anhydride-ethylene oxide-containing tetrapolymer comprises the following steps:
Adding the preparation raw materials into a reaction kettle, adding a catalyst under the anhydrous and anaerobic condition, charging carbon dioxide to the pressure of 1.2MPa, heating and reacting at 65 ℃ for 9 hours, and sequentially performing devolatilization, drying and granulation to obtain the phenyl anhydride-ethylene oxide tetrapolymer.
Molecular weight was measured by GPC to obtain a number average molecular weight (Mn): 1.30X10 5 g/mol, molecular weight distribution coefficient (PDI): 2.36.
Comparative example 1
A copolymer, the preparation raw materials comprise a copolymer monomer 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 comprises carbon dioxide.
The solvent is tetrahydrofuran, and the weight part of the solvent is 2.16 parts;
the mole ratio of the triethylboron to the tetra-n-butyl ammonium bromide is 3.24:1, a step of;
Adding the preparation raw materials into a reaction kettle, adding a catalyst in an anhydrous and anaerobic environment, flushing carbon dioxide to a pressure of 1.2MPa, reacting for 7 hours at 65 ℃, and sequentially performing devolatilization, drying and granulation to obtain the copolymer.
Molecular weight was measured by GPC to obtain a number average molecular weight (Mn): 1.53X10 5 g/mol, molecular weight distribution coefficient (PDI): 2.30.
Performance test:
Melt Mass Flow Rates (MFR) under a load of 2.16kg at different temperatures were tested and the results are recorded in the following table.
Comparative example 1 was tested to fail to obtain data on mass flow rate at 190 ℃.
The performance test results show that in the application, the melt flow indexes of the prepared quaternary copolymer containing the phenyl anhydride and the ethylene oxide all have different results at 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 (4)
1. A tetrapolymer containing phenyl anhydride-ethylene oxide is characterized in that the preparation raw materials comprise a copolymer monomer and a catalyst;
The copolymer monomer is cyclic ether, phenyl-containing anhydride and carbon dioxide;
The cyclic ether is ethylene oxide and propylene oxide;
The catalyst is a boron-containing compound and alkyl ammonium halide;
the boron-containing compound is triethylboron;
the alkyl ammonium halide is tetra-n-butyl ammonium bromide;
the molar ratio of the boron-containing compound to the alkyl ammonium halide is (1-6): 1, a step of;
The weight of the ethylene oxide is 15-40wt% of the total weight of the copolymer;
The phenyl-containing anhydride is phthalic anhydride.
2. The phenyl anhydride-ethylene oxide-containing tetrapolymer according to claim 1, wherein the molar ratio of the boron-containing compound to the phenyl anhydride is 1: (10-500).
3. The phenyl anhydride-ethylene oxide-containing tetrapolymer according to any one of claims 1 to 2, wherein the copolymer has a random structure or a block structure;
the irregular structure comprises one of the formula (1), the formula (2), the formula (3), the formula (4), the formula (5) and the formula (6):
formula (1):
，
Wherein a is more than or equal to 1 and less than or equal to 3500,1 and less than or equal to b is more than or equal to 4000, c is more than or equal to 1 and less than or equal to 6000,1 and d is more than or equal to 7000, and a, b, c and d are integers;
Formula (2):
，
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 3500,1 and less than or equal to c and less than or equal to 7000,1 and d is more than or equal to 6000, and a, b, c and d are integers;
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 3500,1 and less than or equal to c and less than or equal to 6000,1 and d is more 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 4000, b is more than or equal to 1 and less than or equal to 3500,1 and less than or equal to c is more than or equal to 6000,1 and d is more than or equal to 7000, and a, b, c and d are integers;
The block structure comprises one of the formula (5) and the formula (6);
formula (5):
，
Wherein a is more than or equal to 1 and less than or equal to 3500,1 and less than or equal to b is more than or equal to 6000,1 and less than or equal to c and less than or equal to 7000,1 and less than or equal to d and less than or equal to 3500, 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 7000,1 and less than or equal to c and less than or equal to 6000,1 and d is more than or equal to 4000, and a, b, c and d are integers.
4. The phenyl anhydride-ethylene oxide-containing tetrapolymer according to claim 3, wherein the copolymer has 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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| Alternating Copolymerization of Carbon Dioxide and Epoxide Catalyzed by the Aluminum Porphyrin-Quaternary Organic Salt or -Triphenylphosphine System. Synthesis of Polycarbonate with Well-Controlled Molecular Weight;Takuzo Aida et al.;《Macromolecules》;第19卷;第9页左栏第3段、第11页表Ⅱ、图7 * |
| Takuzo Aida et al..Alternating Copolymerization of Carbon Dioxide and Epoxide Catalyzed by the Aluminum Porphyrin-Quaternary Organic Salt or -Triphenylphosphine System. Synthesis of Polycarbonate with Well-Controlled Molecular Weight.《Macromolecules》.1986,第19卷第9页左栏第3段、第11页表Ⅱ、图7. * |
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