CN116023566A - Narrow-distribution bio-based polyitaconate homopolymer and preparation method thereof - Google Patents
Narrow-distribution bio-based polyitaconate homopolymer and preparation method thereof Download PDFInfo
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- CN116023566A CN116023566A CN202111255953.9A CN202111255953A CN116023566A CN 116023566 A CN116023566 A CN 116023566A CN 202111255953 A CN202111255953 A CN 202111255953A CN 116023566 A CN116023566 A CN 116023566A
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- 229920001519 homopolymer Polymers 0.000 title claims abstract description 40
- 238000009826 distribution Methods 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000000178 monomer Substances 0.000 claims abstract description 41
- LVHBHZANLOWSRM-UHFFFAOYSA-N itaconic acid Chemical compound OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000010560 atom transfer radical polymerization reaction Methods 0.000 claims abstract description 18
- 239000002253 acid Substances 0.000 claims abstract description 10
- 150000002148 esters Chemical class 0.000 claims abstract description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 44
- 238000006243 chemical reaction Methods 0.000 claims description 23
- 229910052757 nitrogen Inorganic materials 0.000 claims description 22
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 18
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 18
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 16
- 239000003999 initiator Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 15
- VHJFWJXYEWHCGD-UHFFFAOYSA-N 4-nonyl-2-(4-nonylpyridin-2-yl)pyridine Chemical compound CCCCCCCCCC1=CC=NC(C=2N=CC=C(CCCCCCCCC)C=2)=C1 VHJFWJXYEWHCGD-UHFFFAOYSA-N 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 10
- ODWXUNBKCRECNW-UHFFFAOYSA-M bromocopper(1+) Chemical compound Br[Cu+] ODWXUNBKCRECNW-UHFFFAOYSA-M 0.000 claims description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 9
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 9
- -1 itaconic acid ester Chemical class 0.000 claims description 7
- 239000003446 ligand Substances 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 claims description 6
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 2
- ZQMHJBXHRFJKOT-UHFFFAOYSA-N methyl 2-[(1-methoxy-2-methyl-1-oxopropan-2-yl)diazenyl]-2-methylpropanoate Chemical compound COC(=O)C(C)(C)N=NC(C)(C)C(=O)OC ZQMHJBXHRFJKOT-UHFFFAOYSA-N 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 5
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims 1
- 238000006116 polymerization reaction Methods 0.000 abstract description 10
- 238000011161 development Methods 0.000 abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 24
- 238000005227 gel permeation chromatography Methods 0.000 description 15
- 239000007788 liquid Substances 0.000 description 12
- ZWWQRMFIZFPUAA-UHFFFAOYSA-N dimethyl 2-methylidenebutanedioate Chemical compound COC(=O)CC(=C)C(=O)OC ZWWQRMFIZFPUAA-UHFFFAOYSA-N 0.000 description 9
- 239000000203 mixture Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- 238000001291 vacuum drying Methods 0.000 description 7
- 239000007795 chemical reaction product Substances 0.000 description 6
- 238000010526 radical polymerization reaction Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- DFQSWFGKYUFIFW-UHFFFAOYSA-N dipropyl 2-methylidenebutanedioate Chemical compound CCCOC(=O)CC(=C)C(=O)OCCC DFQSWFGKYUFIFW-UHFFFAOYSA-N 0.000 description 4
- 238000005189 flocculation Methods 0.000 description 4
- 230000016615 flocculation Effects 0.000 description 4
- NKNDPYCGAZPOFS-UHFFFAOYSA-M copper(i) bromide Chemical compound Br[Cu] NKNDPYCGAZPOFS-UHFFFAOYSA-M 0.000 description 3
- 238000010550 living polymerization reaction Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000012265 solid product Substances 0.000 description 3
- 229910021589 Copper(I) bromide Inorganic materials 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- OGVXYCDTRMDYOG-UHFFFAOYSA-N dibutyl 2-methylidenebutanedioate Chemical compound CCCCOC(=O)CC(=C)C(=O)OCCCC OGVXYCDTRMDYOG-UHFFFAOYSA-N 0.000 description 2
- ZEFVHSWKYCYFFL-UHFFFAOYSA-N diethyl 2-methylidenebutanedioate Chemical compound CCOC(=O)CC(=C)C(=O)OCC ZEFVHSWKYCYFFL-UHFFFAOYSA-N 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 239000008204 material by function Substances 0.000 description 2
- 229920002725 thermoplastic elastomer Polymers 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
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- 238000007865 diluting Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- OJURWUUOVGOHJZ-UHFFFAOYSA-N methyl 2-[(2-acetyloxyphenyl)methyl-[2-[(2-acetyloxyphenyl)methyl-(2-methoxy-2-oxoethyl)amino]ethyl]amino]acetate Chemical compound C=1C=CC=C(OC(C)=O)C=1CN(CC(=O)OC)CCN(CC(=O)OC)CC1=CC=CC=C1OC(C)=O OJURWUUOVGOHJZ-UHFFFAOYSA-N 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000007342 radical addition reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
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- 238000012360 testing method Methods 0.000 description 1
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- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
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Abstract
The invention discloses a narrow-distribution bio-based polyitaconate homopolymer and a preparation method thereof. The structural unit of the polyitaconic acid ester homopolymer is as follows:
the preparation method comprises the following steps: and (3) performing reverse atom transfer radical polymerization on components comprising the itaconate monomer to prepare the polyitaconate homopolymer. The invention applies the reverse atom transfer radical polymerization with active polymerization characteristics to the bio-based itaconate monomer, expands the application range of the monomer, synthesizes a narrow-distribution polyitaconate homopolymer, and has important significance for sustainable development.
Description
Technical Field
The invention relates to the technical field of living radical polymerization, in particular to a narrow-distribution bio-based polyitaconic acid ester homopolymer and a preparation method thereof.
Background
Living polymerization is an important technology of high molecular chemistry, and is an important means for realizing molecular design and synthesizing a series of polymer materials with different structures and specific properties, such as polymers with special structures of blocks, grafts, stars, hyperbranched and the like. Since the 1956 Schwarz et al reported an anionic polymerization technique without chain transfer and chain termination, the study of living polymerization has been greatly developed. In 1995, professor Wang Jinshan, U.S. university of Carcinyl Mercury and Matyjaszewski et al successfully introduced transition metal catalyzed atom transfer radical addition polymerization (ATRP) into polymer chemistry, suggesting a novel controlled/living radical polymerization process, ATRP. Atom Transfer Radical Polymerization (ATRP) is used as a novel precise polymerization reaction, can realize controllable living polymerization, can reach expected molecular weight of a product, has narrow molecular weight distribution, is successfully applied to prepare various advanced materials with controlled structures, can synthesize well-defined gradients, blocks, comb-shaped copolymers and the like, and has the advantages of controllable molecular weight, narrow molecular weight distribution and the like. Specific examples of applications for functional materials include thermoplastic elastomers, functionalized surfaces and bio-related materials. ATRP has been commercialized in the united states, europe and japan. Some of the current and upcoming applications include specialty materials for liquid glues, coatings, dispersants, sealants, health and cosmetic products, and materials for the photovoltaic and biomedical fields.
RATRP (reverse atom transfer radical polymerization) was developed based on the conventional ATRP method. The polymerization system is initiated by copper bromide and azo catalysts, such as 2,2' -azo bis (2-methylpropanenitrile) (AIBN), and the metal catalyst and initiator are more convenient to store and are more beneficial to industrialization. In one aspect, AIBN reduces copper bromide to form lower cuprous bromide. On the other hand, azo initiators can initiate a great number of monomers to form free radical initiators, which also expands the application range of the monomers. The catalyst cuprous bromide starts to mediate a forward ATRP polymerization system, dynamic balance is established between regenerated species and dormant species, and controllable polymerization is realized in ATRP.
However, most of the vinyl monomers (e.g., styrene, methyl methacrylate, acrylic acid) polymerized using RATRP are currently derived from petrochemical products and are non-renewable resources.
Therefore, the application of living radical polymerization to the polymerization of renewable bio-based monomers and the excellent properties of the resulting polymers are currently a problem to be solved.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a narrow-distribution bio-based polyitaconate homopolymer and a preparation method thereof. The preparation method comprises the following steps: and (3) performing reverse atom transfer radical polymerization on components comprising the itaconate monomer to prepare the polyitaconate homopolymer. The invention applies the reverse atom transfer radical polymerization with active polymerization characteristics to the bio-based itaconate monomer, expands the application range of the monomer, synthesizes a narrow-distribution polyitaconate homopolymer, and has important significance for sustainable development.
It is an object of the present invention to provide a narrow distribution biobased polyitaconate homopolymer.
The structural unit of the polyitaconic acid ester homopolymer is as follows:
wherein R is 1 And R is 2 Each independently selected from H or C 1 ～C 10 Alkyl, preferably methyl or butyl, and R 1 And R is 2 Not simultaneously H;
number average molecular weight M of the polyitaconate homopolymer n =4000 to 20000g/mol, preferably M n =4500 to 10000g/mol, more preferably M n =4500 to 7000g/mol; the molecular weight distribution coefficient pdi=1.0 to 1.50, preferably pdi=1.0 to 1.40, and more preferably pdi=1.09 to 1.30.
It is a further object of the present invention to provide a process for the preparation of polyitaconate homopolymers as one of the objects of the present invention.
The method comprises the following steps:
and (3) performing reverse atom transfer radical polymerization on components comprising the itaconate monomer to prepare the polyitaconate homopolymer.
In a preferred embodiment of the present invention,
the method comprises the following steps:
and (3) adding the itaconate monomer, an initiator, a catalyst, a ligand and a solvent into a reaction tube, reacting under the condition of nitrogen or inert gas, and precipitating and drying to obtain the polyitaconate homopolymer.
In a preferred embodiment of the present invention,
the itaconic acid ester monomer has the structure that:
wherein R is 1 And R is 2 Each independently selected from H or C 1 ～C 10 Alkyl, preferably methyl or butyl, and R 1 And R is 2 And not H at the same time.
In a preferred embodiment of the present invention,
the initiator is at least one of Azobisisobutyronitrile (AIBN), dimethyl Azobisisobutyrate (AIBME) and Azobisisoheptonitrile (ABVN); and/or the number of the groups of groups,
the catalyst is copper bromide (CuBr) 2 ) Copper chloride (CuCl) 2 ) At least one of (a) and (b); and/or the number of the groups of groups,
the ligand is at least one of 4,4' -dinonyl-2, 2' -bipyridine (dNbpy) and 2,2' -bipyridine (Bpy); and/or the number of the groups of groups,
the solvent is at least one of diphenyl ether, anisole, cyclohexanone, toluene and tetrahydrofuran, preferably at least one of diphenyl ether, anisole and cyclohexanone.
In a preferred embodiment of the present invention,
the itaconate ester monomer: and (3) an initiator: catalyst: the molar ratio of the ligand is 1: (0.001-0.01): (0.0001-0.01): (0.001 to 0.04), preferably 1: (0.001-0.01): (0.0001-0.01): (0.001-0.01).
In a preferred embodiment of the present invention,
the volume ratio of the solvent to the itaconate monomer is 1:0.5 to 1:4, preferably 1:0.5 to 1:1.
in a preferred embodiment of the present invention,
the reaction temperature is 60-120 ℃, preferably 60-80 ℃ and the reaction time is 4-12 h.
It is a further object of the present invention to provide a polyitaconate homopolymer prepared by the process of the second object of the present invention.
The specific technical scheme of the invention is as follows:
the preparation method of the narrow-distribution bio-based polyitaconate homopolymer comprises the following steps: firstly, adding a solvent, a catalyst, a ligand, a monomer and an initiator into a reaction tube, freezing and vacuumizing by liquid nitrogen, introducing nitrogen for thawing three times through a double-row-tube vacuum gas distributor, then placing the mixture into an oil bath for reaction, diluting the mixture with tetrahydrofuran, introducing the mixture into methanol for precipitation, and vacuum drying to obtain a product (the methanol is easy to volatilize, the vacuum drying temperature is normal temperature, the methanol can volatilize more quickly after the temperature is increased by 50 ℃, the temperature is not too high, and the phenomena of material deterioration and the like are avoided).
The principle and the beneficial effects of the invention are as follows:
the invention adopts Reverse Atom Transfer Radical Polymerization (RATRP), retains the characteristics of controllable molecular weight and narrow molecular weight distribution of Atom Transfer Radical Polymerization (ATRP), successfully synthesizes a narrow-distribution biobased polyitaconic acid ester homopolymer by using itaconic acid ester monomers completely derived from biological raw materials, greatly expands the application range and application range of the RATRP monomers, and has important significance for energy conservation, emission reduction and sustainable development.
The polyitaconic acid ester homopolymer can be prepared by a bulk and emulsion non-living radical polymerization method, but the methods have the defects of uncontrollable molecular weight, wide molecular weight distribution and the like, for example, the polyitaconic acid dimethyl ester obtained by bulk polymerization has a number average molecular weight of 1 w-2 w and a molecular weight distribution coefficient PDI of 1.5-2.5, which limits the application range, and the prepared polyitaconic acid ester homopolymer has controllable molecular weight and narrow molecular weight distribution, and the prepared lower molecular weight polyitaconic acid ester homopolymer can be used as a plasticizer, a medicine carrying material and the like. Secondly, the molecular chain of polyitaconic acid ester homopolymer prepared by a non-active free radical polymerization method such as bulk and emulsion is dead chain, and further modification such as modification of block, grafting and the like cannot be performed. The invention adopts active free radical polymerization, so that the generated radical at the molecular chain end of the polyitaconate homopolymer can not be deactivated, and the radical at the end of certain conditions can attack the monomer with double bonds to initiate the polymerization of the monomer, so as to generate a copolymer such as a block or a graft, and the like, and the polymer can be applied as a thermoplastic elastomer, a surfactant, a coating, a biological drug-carrying material and other functional materials.
Drawings
FIG. 1 shows nuclear magnetic patterns of itaconate monomers of examples 1, 4, 5 and 6 and corresponding polyitaconate homopolymers prepared therefrom, wherein a, b, c and d represent itaconate monomer side chains R of examples 6, 5, 4 and 1, respectively 1 The methyl groups of the above are as follows:
in the figures, a ', b', c ', d' represent the side chains R of the polyitaconate homopolymers prepared in example 6, example 5, example 4 and example 1, respectively 1 The methyl groups of the above are as follows:
Detailed Description
The present invention is described in detail below with reference to the specific drawings and examples, and it is necessary to point out that the following examples are given for further illustration of the present invention only and are not to be construed as limiting the scope of the present invention, since numerous insubstantial modifications and adaptations of the invention to those skilled in the art will still fall within the scope of the present invention.
The raw materials used in the examples are all conventional commercially available raw materials except dipropyl itaconate; dipropyl itaconate is a reference: the preparation method is characterized in that the preparation method is prepared from the research on design, preparation and application of different side chain itaconate bio-based elastomers.
The type and manufacturer of the detection instrument used in the invention are as follows:
TABLE 1
| Test method | Model/manufacturer |
| Nuclear magnetism | AVANCEIII/Bruker |
| Gel Permeation Chromatography (GPC) | Waters1515 |
Example 1
Using dimethyl itaconate (DMI) monomer as an example, 2.53ml (18 mmol) of dimethyl itaconate monomer, 14.77mg (0.09 mmol) of initiator AIBN, 20.1mg (0.09 mmol) of copper bromide, 28.1mg (0.18 mmol) of 2,2' -bipyridine, 1.265ml of cyclohexanone were charged into a 25ml reaction tube. The reaction was frozen with liquid nitrogen under nitrogen and then evacuated for 5min before nitrogen was introduced and thawed in a water bath. The mixture is circulated for 3 times and put into an oil bath pot at 80 ℃ for reaction for 12 hours. Adding 10ml tetrahydrofuran, slowly introducing the reaction product into methanol for flocculation, vacuum drying to obtain white solid product polydimethyl itaconate (PDMI), and determining the number average molecular weight M by Gel Permeation Chromatography (GPC) n =6202 g/mol, the molecular weight distribution coefficient pdi=1.13.
Example 2
Using dimethyl itaconate (DMI) monomer as an example, 2.53ml (18 mmol) of dimethyl itaconate monomer, 20.72mg (0.09 mmol) of AIBME initiator, 20.1mg (0.09 mmol) of copper bromide, 36.77mg (0.09 mmol) of 4,4 '-dinonyl-2, 2' -bipyridine (dNbpy) and 1.265ml of cyclohexanone were charged into a 25ml reaction tube. The reaction was frozen with liquid nitrogen under nitrogen and then evacuated for 5min before nitrogen was introduced and thawed in a water bath. The mixture is circulated for 3 times and put into an oil bath pot at 80 ℃ for reaction for 12 hours. Adding 10ml tetrahydrofuran, slowly introducing the reaction product into methanol for flocculation, vacuum drying to obtain white solid product polydimethyl itaconate (PDMI), and determining the number average molecular weight M by Gel Permeation Chromatography (GPC) n =4645 g/mol, molecular weight distribution coefficient pdi=1.09.
Example 3
Using dimethyl itaconate (DMI) monomer as an example, 2.53ml (18 mmol) of dimethyl itaconate monomer, 14.77mg (0.09 mmol) of AIBN initiator, 10.05mg (0.045 mmol) of copper bromide, 36.77mg (0.09 mmol) of 4,4 '-dinonyl-2, 2' -bipyridine (dNbpy) and 1.265ml of cyclohexanone were charged into a 25ml reaction tube. The reaction was frozen with liquid nitrogen under nitrogen and then evacuated for 5min before nitrogen was introduced and thawed in a water bath. The mixture is circulated for 3 times and put into an oil bath pot at 80 ℃ for reaction for 6 hours. Adding 10ml tetrahydrofuran, slowly introducing the reaction product into methanol for flocculation, vacuum drying to obtain white solid product polydimethyl itaconate (PDMI), and determining the number average molecular weight M by Gel Permeation Chromatography (GPC) n 7096g/mol, and the molecular weight distribution coefficient pdi=1.24.
Example 4
Taking diethyl itaconate monomer (DEI) as an example, 2.53ml (14 mmol) of diethyl itaconate monomer, 14.77mg (0.09 mmol) of AIBN as an initiator, 10.05mg (0.045 mmol) of copper bromide, 14.056mg (0.09 mmol) of 2,2' -bipyridine and 1.265ml of cyclohexanone were charged into a 25ml reaction tube. The reaction was frozen with liquid nitrogen under nitrogen and then evacuated for 5min before nitrogen was introduced and thawed in a water bath. The mixture is circulated for 3 times and put into an oil bath pot at 80 ℃ for reaction for 12 hours. 10ml of tetrahydrofuran was added, and the reaction product was slowly introduced into methanolVacuum drying to obtain liquid polyethyl itaconate (PDEI) with certain viscosity, and measuring the number average molecular weight M by Gel Permeation Chromatography (GPC) n Molecular weight distribution coefficient pdi=1.25, =9764 g/mol.
Example 5
Taking dipropyl itaconate monomer (DPrI) as an example, 2.53ml (12 mmol) of dipropyl itaconate monomer, 20.72mg (0.09 mmol) of initiator AIBME, 2.01mg (0.009 mmol) of copper bromide, 7.36mg (0.018 mmol) of 4,4 '-dinonyl-2, 2' -bipyridine (dNbpy) and 1.265ml of cyclohexanone were charged into a 25ml reaction tube. The reaction was frozen with liquid nitrogen under nitrogen and then evacuated for 5min before nitrogen was introduced and thawed in a water bath. The mixture is circulated for 3 times and put into an oil bath pot at 60 ℃ for reaction for 12 hours. Adding 10ml tetrahydrofuran, slowly introducing the reaction product into methanol for flocculation, vacuum drying to obtain liquid polypropylene itaconate (PDPrI) with certain viscosity, and determining the number average molecular weight M by Gel Permeation Chromatography (GPC) n Molecular weight distribution coefficient pdi=1.41, = 14771 g/mol.
Example 6
Taking dibutyl itaconate monomer (DBI) as an example, 2.53ml (10 mmol) of dibutyl itaconate monomer, 20.72mg (0.09 mmol) of initiator AIBME, 2.01mg (0.009 mmol) of copper bromide, 7.36mg (0.018 mmol) of 4,4 '-dinonyl-2, 2' -bipyridine, 2.53ml of cyclohexanone were charged into a 25ml reaction tube. The reaction was frozen with liquid nitrogen under nitrogen and then evacuated for 5min before nitrogen was introduced and thawed in a water bath. Circulating for 3 times, reacting in 60 deg.C oil bath for 12 hr, adding 10ml tetrahydrofuran, slowly introducing the reaction product into methanol, vacuum drying to obtain liquid dibutyl Polyitaconate (PDBI) with certain viscosity, and measuring the number average molecular weight M by Gel Permeation Chromatography (GPC) n Molecular weight distribution coefficient pdi=1.37, = 12449 g/mol.
The resulting polymers were increased in flexibility and exhibited liquid state due to the chain length of the itaconate monomer side groups in examples 4-6 and the large molecular chain spacing.
The nuclear magnetic patterns of different itaconate monomers and their corresponding polyitaconate homopolymers were compared (FIG. 1), and the changes in the methyl groups of the side chains were observed, from which it can be seen that example 6, example 5, example 4 and example 1 were preparedThe nuclear magnetic patterns of the prepared polyitaconate homopolymer all show new peaks (a ', b', c ', d', respectively) which are side chains R 1 The result of the offset of methyl on the polymer shows that the polymerization system is successfully initiated, new substances are generated, and the polymer itaconate homopolymer is successfully synthesized through characterization of the molecular weight and molecular weight distribution of the product. The nuclear magnetic patterns of the polyitaconate homopolymers prepared in example 2 and example 3 are the same as those of example 1, and the side chain R 1 The methyl groups on the two groups are offset, and a new peak appears.
Table 2 shows the data obtained from GPC tests on polyitaconate homopolymers prepared in examples 1-6.
TABLE 2 examples 1-6 molecular weights and molecular weight distribution
Claims (10)
1. A narrow distribution biobased polyitaconate homopolymer characterized by:
the structural unit of the polyitaconic acid ester homopolymer is as follows:
wherein R is 1 And R is 2 Each independently selected from H or C 1 ～C 10 Alkyl, and R 1 And R is 2 Not simultaneously H;
number average molecular weight M of the polyitaconate homopolymer n =4000 to 20000g/mol, and the molecular weight distribution coefficient pdi=1.0 to 1.50.
2. The polyitaconate homopolymer of claim 1, wherein:
R 1 and R is 2 Each independently selected from methyl or butyl;
number average molecular weight M of the polyitaconate homopolymer n ＝4500～10000g/mol，The molecular weight distribution coefficient pdi=1.0 to 1.40.
3. A process for the preparation of a narrow distribution biobased polyitaconate homopolymer as claimed in any one of claims 1 to 2 characterised in that the process comprises:
and (3) performing reverse atom transfer radical polymerization on components comprising the itaconate monomer to prepare the polyitaconate homopolymer.
4. A method of preparation according to claim 3, characterized in that the method comprises:
and (3) adding the itaconate monomer, an initiator, a catalyst, a ligand and a solvent into a reaction tube, reacting under the condition of nitrogen or inert gas, and precipitating and drying to obtain the polyitaconate homopolymer.
5. The method of manufacturing according to claim 4, wherein:
the itaconic acid ester monomer has the structure that:
wherein R is 1 And R is 2 Each independently selected from H or C 1 ～C 10 Alkyl, preferably methyl or butyl, and R 1 And R is 2 And not H at the same time.
6. The method of manufacturing according to claim 4, wherein:
the initiator is at least one of azodiisobutyronitrile, dimethyl azodiisobutyrate and azodiisoheptonitrile; and/or the number of the groups of groups,
the catalyst is at least one of copper bromide and copper chloride; and/or the number of the groups of groups,
the ligand is at least one of 4,4' -dinonyl-2, 2' -bipyridine and 2,2' -bipyridine; and/or the number of the groups of groups,
the solvent is at least one of diphenyl ether, anisole, cyclohexanone, toluene and tetrahydrofuran.
7. The method of manufacturing according to claim 4, wherein:
the itaconate ester monomer: and (3) an initiator: catalyst: the molar ratio of the ligand is 1: (0.001-0.01): (0.0001-0.01): (0.001-0.04).
8. The method of manufacturing according to claim 4, wherein:
the volume ratio of the solvent to the itaconate monomer is 1:0.5 to 1:4.
9. the method of manufacturing according to claim 4, wherein:
the reaction temperature is 60-120 ℃ and the reaction time is 4-12 h.
10. A polyitaconate homopolymer prepared by the process of any one of claims 3-9.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003313252A (en) * | 2002-04-22 | 2003-11-06 | Chisso Corp | Itaconic acid derivative and polymer thereof |
| CN104245762A (en) * | 2012-02-03 | 2014-12-24 | 帝斯曼知识产权资产管理有限公司 | Polymer, process and composition |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003313252A (en) * | 2002-04-22 | 2003-11-06 | Chisso Corp | Itaconic acid derivative and polymer thereof |
| CN104245762A (en) * | 2012-02-03 | 2014-12-24 | 帝斯曼知识产权资产管理有限公司 | Polymer, process and composition |
Non-Patent Citations (2)
| Title |
|---|
| MARTA FERNÁNDEZ-GARCÍA ET AL.: ""Atom-Transfer Radical Polymerization of Dimethyl Itaconate"", 《MACROMOLECULAR CHEMISTRY AND PHYSICS》, vol. 202, no. 7, pages 1213 - 1218 * |
| 周其凤等: "《高分子化学》", 化学工业出版社, pages: 123 * |
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