CN115160512A - Lignin-based thermoplastic elastomer with rapid repair function and preparation method thereof - Google Patents
Lignin-based thermoplastic elastomer with rapid repair function and preparation method thereof Download PDFInfo
- Publication number
- CN115160512A CN115160512A CN202211000827.3A CN202211000827A CN115160512A CN 115160512 A CN115160512 A CN 115160512A CN 202211000827 A CN202211000827 A CN 202211000827A CN 115160512 A CN115160512 A CN 115160512A
- Authority
- CN
- China
- Prior art keywords
- lignin
- thermoplastic elastomer
- based thermoplastic
- reaction
- acrylate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920005610 lignin Polymers 0.000 title claims abstract description 132
- 229920002725 thermoplastic elastomer Polymers 0.000 title claims abstract description 67
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 230000008439 repair process Effects 0.000 title abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims description 88
- 239000000178 monomer Substances 0.000 claims description 51
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 36
- 239000012986 chain transfer agent Substances 0.000 claims description 29
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 27
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical group N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 22
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 18
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 10
- PVEOYINWKBTPIZ-UHFFFAOYSA-N but-3-enoic acid Chemical compound OC(=O)CC=C PVEOYINWKBTPIZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 8
- 239000003999 initiator Substances 0.000 claims description 7
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- LMDZBCPBFSXMTL-UHFFFAOYSA-N 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide Chemical compound CCN=C=NCCCN(C)C LMDZBCPBFSXMTL-UHFFFAOYSA-N 0.000 claims description 5
- KRMCNXUYEWISGE-ONEGZZNKSA-N 3,5-Hexadienoic acid Chemical compound OC(=O)C\C=C\C=C KRMCNXUYEWISGE-ONEGZZNKSA-N 0.000 claims description 5
- XUDOZULIAWNMIU-UHFFFAOYSA-N delta-hexenoic acid Chemical compound OC(=O)CCCC=C XUDOZULIAWNMIU-UHFFFAOYSA-N 0.000 claims description 5
- 239000005457 ice water Substances 0.000 claims description 5
- 238000010926 purge Methods 0.000 claims description 5
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 claims description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 4
- 239000000284 extract Substances 0.000 claims description 4
- HVAMZGADVCBITI-UHFFFAOYSA-N pent-4-enoic acid Chemical compound OC(=O)CCC=C HVAMZGADVCBITI-UHFFFAOYSA-N 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 239000000725 suspension Substances 0.000 claims description 4
- 229910000404 tripotassium phosphate Inorganic materials 0.000 claims description 4
- 235000019798 tripotassium phosphate Nutrition 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 claims description 3
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-UHFFFAOYSA-N 0.000 claims description 3
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 claims description 3
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 3
- LNMQRPPRQDGUDR-UHFFFAOYSA-N hexyl prop-2-enoate Chemical compound CCCCCCOC(=O)C=C LNMQRPPRQDGUDR-UHFFFAOYSA-N 0.000 claims description 3
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 claims description 3
- ULDDEWDFUNBUCM-UHFFFAOYSA-N pentyl prop-2-enoate Chemical compound CCCCCOC(=O)C=C ULDDEWDFUNBUCM-UHFFFAOYSA-N 0.000 claims description 3
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 3
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 claims description 2
- IQJVBAIESAQUKR-UHFFFAOYSA-N isocyanic acid;prop-2-enoic acid Chemical compound N=C=O.OC(=O)C=C IQJVBAIESAQUKR-UHFFFAOYSA-N 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims description 2
- 239000012716 precipitator Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000002844 melting Methods 0.000 claims 1
- 229920001971 elastomer Polymers 0.000 abstract description 8
- 239000000806 elastomer Substances 0.000 abstract description 7
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 238000006065 biodegradation reaction Methods 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 description 25
- 239000000047 product Substances 0.000 description 25
- 238000003786 synthesis reaction Methods 0.000 description 25
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 24
- 239000000463 material Substances 0.000 description 22
- 229920000642 polymer Polymers 0.000 description 19
- 239000000243 solution Substances 0.000 description 9
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000010586 diagram Methods 0.000 description 5
- 238000010560 atom transfer radical polymerization reaction Methods 0.000 description 4
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 4
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- DSAYAFZWRDYBQY-UHFFFAOYSA-N 2,5-dimethylhexa-1,5-diene Chemical group CC(=C)CCC(C)=C DSAYAFZWRDYBQY-UHFFFAOYSA-N 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- 229920006392 biobased thermoplastic Polymers 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000004584 polyacrylic acid Substances 0.000 description 2
- YOSXAXYCARLZTR-UHFFFAOYSA-N prop-2-enoyl isocyanate Chemical compound C=CC(=O)N=C=O YOSXAXYCARLZTR-UHFFFAOYSA-N 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 description 1
- YOCIJWAHRAJQFT-UHFFFAOYSA-N 2-bromo-2-methylpropanoyl bromide Chemical compound CC(C)(Br)C(Br)=O YOCIJWAHRAJQFT-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 210000002421 cell wall Anatomy 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010559 graft polymerization reaction Methods 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000006210 lotion Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 239000011664 nicotinic acid Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920001485 poly(butyl acrylate) polymer Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 238000010257 thawing Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000001960 triggered effect Effects 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F289/00—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds not provided for in groups C08F251/00 - C08F287/00
Abstract
The invention discloses a lignin-based thermoplastic elastomer, which relates to the technical field of thermoplastic elastomers and has the following structural formula:
the invention also provides a preparation method of the lignin-based thermoplastic elastomer. The invention has the beneficial effects that: the lignin-based thermoplastic elastomer disclosed by the invention is excellent in mechanical property, good in ductility, good in biodegradation and environment-friendly. The lignin-based elastomer can be quickly healed within one minute under the irradiation of near infrared light, and the lignin-based elastomer with quick repair performance can obviously improve the utilization rate and additional value of lignin and broaden the application of lignin.
Description
Technical Field
The invention relates to the technical field of thermoplastic elastomers, in particular to a lignin-based thermoplastic elastomer with a quick repair function and a preparation method thereof.
Background
Lignin (Lignin), the second most abundant natural polymer on earth, is widely present in the cell wall of plants and has been considered as a promising resource to replace existing fossil fuels. The low cost, abundant content, environmental friendliness and good ultraviolet radiation resistance of lignin make lignin have many potential applications, such as adhesives, suntan lotions, carbon fibers, fillers, biologically derived synthetic polymers and composites, and the like. Despite the great potential of lignin, the technology for developing this important resource is not yet mature and lignin-based materials are not usually converted into high-value products.
Thermoplastic elastomers are polymeric materials that have the properties of rubber (high elasticity, compression set, etc.) and the processing properties of plastics (simple process). The cable is widely applied to a plurality of industries such as automobiles, buildings, household equipment, wires and cables, electronic products, food package medical appliances and the like. However, most of thermoplastic elastomers are prepared from petroleum resources, and under the background that the petroleum resources are increasingly scarce and the environmental pollution is increasingly serious nowadays, the bio-based thermoplastic elastomer has extremely important commercial value and environmental protection significance.
In recent years, surface graft polymerization is one of the most prominent techniques for preparing well-defined lignin copolymers, and particularly, a reversible addition-fragmentation chain transfer (RAFT) method is used. For example, the RAFT grafting method successfully synthesizes the copolymer of the lignin grafted poly (n-butyl acrylate) and the 1-vinyl imidazole with different contents. The mechanical property test of the copolymer shows that when the lignin content is 6.1wt%, the tensile breaking elongation of the copolymer can reach 900%, but the tensile strength is only 0.22MPa. (Wang W.Wang F.Zhang C.Tang J.Zeng X.Wan X. (2021) Chemical Engineering Journal,404, art.no. 126358).
The material inevitably generates local damage and microcracks during the use process, and thus macroscopic cracks are triggered to break, thereby influencing the normal use of the material and shortening the service life. Rapid repair of cracks at an early stage is therefore a real and important issue. The rapid repairing material has the advantages of reducing the maintenance cost of the material during the operation period, prolonging the service life of the material and the like. At present, the rapid repair material is applied to the fields of biomedicine, bionic materials, electrolytic cell materials, rapid repair polymer glass and the like.
If the soft-segment and hard-segment polymers can be grafted on lignin, the lignin serves as a crosslinking point in a polymer system, the polymer network is endowed with good chain flexibility and ductility, the hard segment provides strength, and the lignin-based elastomer with excellent performance and rapid repair capability can be prepared.
Chinese patent publication No. CN104356318A discloses a lignin-based star-shaped thermoplastic elastomer and a preparation method thereof, comprising the following steps: (1) Reacting lignin with 2-bromo isobutyryl bromide to synthesize a lignin ATRP (atom transfer radical polymerization) macromolecular initiator; (2) Adding a hard monomer, a soft monomer, a lignin ATRP (atom transfer radical polymerization) macroinitiator, a ligand and a reaction good solvent into a reaction bottle, fully stirring and dissolving, removing oxygen in a mixed solution through the cyclic processes of freezing, vacuumizing and filling nitrogen for three times, adding a catalyst, reacting for 4-48 hours at 55-110 ℃, taking a methanol/water mixed solution as a precipitator, filtering the collected precipitate, and drying to obtain the lignin star-like polymer with ultraviolet absorption performance and thermoplastic elastomer properties. The mechanical property of the lignin-based star polymer is superior to that of a linear polymer with the same composition, and the lignin-based star polymer can be used as a membrane material with ultraviolet absorption characteristics. The lignin-based star-shaped thermoplastic elastomer prepared by the method has no quick repair capability.
Disclosure of Invention
The invention aims to provide a lignin-based thermoplastic elastomer with good ductility, mechanical property and quick repair capability and a preparation method thereof.
The invention solves the technical problems through the following technical means:
a lignin thermoplastic elastomer having the formula:
wherein 0<m≤700，30≤n≤700，R 1 Is composed of
Any one of the groups;
R 2 comprises the following steps:
any one or more groups of (a);
R 3 comprises the following steps:
any one or more of the groups in (a).
Description of the drawings:
represents the group attachment, as follows.
Has the advantages that: the lignin-based thermoplastic elastomer disclosed by the invention is excellent in mechanical property, good in ductility and certain in rapid repair capability. The lignin-based thermoplastic elastomer takes lignin which is a natural biomass material as a rigid main chain, a series of monomers are grafted, rigid lignin serves as a cross-linking point in the whole polymer system, and the long carbon chain monomers endow the polymer network with good chain flexibility and ductility.
The invention also provides a method for preparing the lignin-based thermoplastic elastomer, which comprises the following steps:
(1) Adding a lignin macromolecular chain transfer agent, a reaction monomer A, a reaction monomer B and an initiator into a reaction container filled with a solvent; the structural formula of the lignin macromolecular chain transfer agent is as follows:
wherein R is H or
(2) And (3) removing air and water in the reaction container, reacting at 60-80 ℃, collecting and drying a product after the reaction is finished, and obtaining the lignin-based thermoplastic elastomer.
The preparation route of the lignin-based thermoplastic elastomer is as follows:
has the beneficial effects that: the invention can realize the regulation and control of the microstructure of the polymer network by designing the type of the reaction monomer, the grafting density, the relative proportion of the rigid main chain and the grafted side chain and the like, thereby obtaining the lignin-based thermoplastic elastomer material with excellent macroscopic mechanical property and quick repair function.
The higher the rigid chain proportion in the product, the better the mechanical strength. The relative proportion of the rigid main chain and the grafted side chain in the reaction product can be controlled by adjusting the proportion of the reaction monomer and the lignin macromolecular chain transfer agent, the larger the proportion of the reaction monomer to the chain transfer agent is, the higher the proportion of the side chain in the material is, and the reaction monomer A and the reaction monomer B are selected to ensure that the product has different physicochemical properties.
Preferably, the method comprises the following steps:
(1) Adding 1-3 parts by weight of lignin macromolecular chain transfer agent, 1-90 parts by weight of reaction monomer A, 10-60 parts by weight of reaction monomer B and 0.0058-0.0164 part by weight of initiator into a reaction vessel with 200-500 parts by weight of solvent;
(2) The reaction vessel was drained of water and air, the reaction was carried out at 70 ℃ and, after completion of the reaction, the product was collected and dried.
Preferably, the reaction vessel is a reaction flask.
Preferably, the reactive monomer a is: methyl acrylate, ethyl acrylate, propyl acrylate, pentyl acrylate, n-butyl acrylate, hexyl acrylate, hydroxypropyl acrylate, 4-hydroxybutyl acrylate, isooctyl acrylate, lauryl acrylate, isobornyl acrylate or isocyanate acrylate.
Preferably, the reactive monomer B is: acrylic acid, 3-butenoic acid, 4-pentenoic acid, 5-hexenoic acid, 3, 5-hexadienoic acid or 2, 5-dienoic acid acrylic acid.
Any one or more of the groups in (a).
Preferably, the initiator in the step (1) is azobisisobutyronitrile.
Preferably, the solvent in the step (1) is N, N-dimethylformamide.
Preferably, in the step (2), the reaction vessel is subjected to a freezing-vacuum-thawing cycle, after the reaction is carried out for 48 to 72 hours at 70 ℃, the reaction vessel is placed in a precipitating agent for precipitation and collection, and then the collected product is placed in a vacuum drying mode at 50 to 80 ℃.
Preferably, the precipitant is a mixed solution of methanol and water.
Preferably, the preparation method of the lignin macromolecular chain transfer agent in the step (1) comprises the following steps:
(a) Adding 10 parts by weight of 1-mercaptopropionic acid into 20 parts by weight of stirred acetone suspension of tripotassium phosphate at room temperature, adding 21.5 parts by weight of carbon disulfide, stirring for 8 hours, removing the solvent under reduced pressure, adding the residue into saturated saline solution, extracting with dichloromethane, washing with saturated saline solution, drying the extract over anhydrous magnesium sulfate, and removing the solvent under reduced pressure to obtain 1- (benzyltrithiocarbonate) propionic acid as a pale yellow solid;
(b) Adding 1 weight part of lignin, 1-1.5 weight parts of 1- (benzyltrithiocarbonate) propionic acid in the step (a) and 0.02-0.06 weight part of 4-dimethylaminopyridine into 50-80 weight parts of anhydrous dichloromethane; purging with nitrogen for half an hour, dropwise adding 0.5-1 part by weight of 1-ethyl- (3-dimethylaminopropyl) carbodiimide under the condition of ice water bath, reacting at 20-30 ℃, washing, centrifuging and drying to obtain the lignin macromolecular chain transfer agent.
The reaction formula of the lignin macromolecular chain transfer agent is as follows:
preferably, in the step (a), 10 parts by weight of 1-mercaptopropionic acid is added into the stirred acetone suspension of 20 parts by weight of tripotassium phosphate, 21.5 parts by weight of carbon disulfide is added, and the mixture is stirred for 8 hours; the solvent was removed under reduced pressure, the residue was taken up in saturated brine, extracted with 2X 100ml of dichloromethane and then 3X 100ml of saturated brine, the extract was dried over anhydrous magnesium sulfate for 24 hours, and the solvent was removed under reduced pressure to give 1- (benzyltrithiocarbonate) propionic acid as a pale yellow solid.
Preferably, the reaction in step (b) is carried out at 20-30 ℃ for 36-48h, washed with pure water, centrifuged, and dried under vacuum at 30-50 ℃.
The invention has the advantages that:
(1) The lignin-based thermoplastic elastomer has excellent mechanical property, and the stress can reach 11MPa when the strain reaches more than 500 percent. The lignin main chain has a large number of ester bonds, all monomers of the side chain have ester bond structures, and the ester bonds can be well broken and degraded under natural conditions, so that the lignin main chain has good biodegradation and environmental friendliness.
(2) The lignin-based thermoplastic elastomer takes lignin which is a natural biomass material as a rigid main chain, a series of monomers are grafted, the lignin serves as a cross-linking point in a polymer system, the short chain endows the polymer network with good chain flexibility and ductility, the hard section provides strength, and finally the lignin-based thermoplastic elastomer has excellent mechanical properties.
(3) The invention can realize the adjustment of the microstructure of the polymer network by designing the type of the reaction monomer, the grafting density, the relative proportion of the rigid main chain and the grafted side chain, and the like, thereby obtaining the environment-friendly lignin-based thermoplastic elastomer material with excellent macroscopic mechanical property and natural degradation.
(4) The lignin-based elastomer prepared by the invention can be quickly healed within 2 seconds under the irradiation of near infrared light, and the lignin-based elastomer with quick repair performance can obviously improve the utilization rate and additional value of lignin and broaden the application of lignin.
Drawings
FIG. 1 is a nuclear magnetic hydrogen spectrum of 1- (benzyltrithiocarbonate) propionic acid in example 1 of the present invention;
FIG. 2 is a nuclear magnetic hydrogen spectrum of a lignin-based thermoplastic elastomer 2 in example 4 of the present invention;
FIG. 3 is a nuclear magnetic hydrogen spectrum of lignin-based polymer 9 in comparative example 1 of the present invention;
FIG. 4 is a differential scanning calorimetry plot of the products of examples 3-8 of the present invention and comparative example 1;
FIG. 5 is a graph of the mechanical tensile properties of the products of examples 3-8 of the present invention;
FIG. 6 is a mechanical tensile diagram of the self-healing under near infrared lamp irradiation after the fracture of the product of example 4 according to the present invention;
FIG. 7 is a mechanical tensile diagram of the self-healing under near infrared lamp irradiation after the fracture of the product of example 5 of the present invention;
FIG. 8 is a mechanical tension diagram of the near infrared lamp irradiation self-healing after the fracture of the product of example 6 according to the present invention;
FIG. 9 is a mechanical tension diagram of the self-healing under near infrared lamp irradiation after the product of example 7 of the present invention breaks.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The test materials and reagents used in the following examples, etc., are commercially available unless otherwise specified.
The specific techniques or conditions not specified in the examples can be performed according to the techniques or conditions described in the literature in the field or according to the product specification.
Example 1
The synthesis of the 1- (benzyltrithiocarbonate) propionic acid specifically comprises the following steps:
10.0g of 1-mercaptopropionic acid was added to a stirred acetone suspension of 20g of tripotassium phosphate, 21.5g of carbon disulfide was added thereto, stirring was carried out for 8 hours, the solvent was removed under reduced pressure, the residue was added to saturated brine, extraction was carried out with 2X 100ml of dichloromethane, washing was carried out with 3X 100ml of saturated brine, the extract was dried over anhydrous magnesium sulfate, and the solvent was removed under reduced pressure to obtain 1- (benzyltrithiocarbonate) propionic acid as a pale yellow solid.
Example 2
The synthesis of the Lignin macromolecular chain transfer agent (Lignin-CTA) specifically comprises the following steps:
adding 3g of lignin, 3.96g of 1- (benzyl trithiocarbonate) propionic acid and 60mg of 4-dimethylaminopyridine into a round-bottom flask, adding 150g of anhydrous dichloromethane, purging with nitrogen for half an hour, dropwise adding 1.52g of 1-ethyl- (3-dimethylaminopropyl) carbodiimide under the condition of ice-water bath, reacting for 48 hours at 25 ℃, washing with pure water, centrifuging, and drying under vacuum at 40 ℃ to obtain the lignin macromolecular chain transfer agent.
Example 3
Synthesis of Lignin-based thermoplastic elastomer 1
To a solution of 20g of N, N-dimethylformamide, 0.3g of the macromolecular chain transfer agent for lignin of example 2, 9.00g of n-butyl acrylate, 2.16g of acrylic acid and 1.64mg of azobisisobutyronitrile were added, and after repeating three freeze-vacuum-thaw cycles, a Schlenk reaction flask was vacuum-sealed and placed in an oil bath. After 48 hours of reaction at 70 ℃, the reaction was stopped, precipitated in a large amount of methanol, and the product was dried under reduced pressure at 50 ℃ in a vacuum oven to obtain 2.85g of lignin-based thermoplastic elastomer 1 (m =169, n = 54).
Example 4
Synthesis of Lignin-based thermoplastic elastomer 2
0.3g of a lignin macromolecular chain transfer agent, 7.69g of n-butyl acrylate, 2.88g of acrylic acid and 1.64mg of azobisisobutyronitrile were added to 20g of N, N-dimethylformamide, and after three freeze-vacuum-thaw cycles, the Schlenk reaction flask was sealed in an oil bath under vacuum. After reaction at 60 ℃ for 72h, the reaction was stopped, precipitated in a large amount of methanol, and the product was dried in a vacuum oven at 80 ℃ under reduced pressure to give 2.80g of lignin-based thermoplastic elastomer 2 (m =150, n = 71).
Example 5
Synthesis of Lignin-based thermoplastic elastomer 3
To a solution of 20g of N, N-dimethylformamide, 0.3g of a lignin macromolecular chain transfer agent, 7.05g of n-butyl acrylate, 3.24g of acrylic acid and 1.64mg of azobisisobutyronitrile were added, and after three freeze-vacuum-thaw cycles were repeated, a Schlenk reaction flask was placed in an oil bath in a vacuum-sealed manner. After 50 hours of reaction at 80 ℃, the reaction was stopped, precipitated in a large amount of methanol, and the product was dried under reduced pressure in a vacuum oven at 60 ℃ to obtain 2.79g of lignin-based thermoplastic elastomer 3 (m =173, n = 80).
Example 6
Synthesis of Lignin-based thermoplastic elastomer 4
0.3g of a lignin macromolecular chain transfer agent, 6.41g of n-butyl acrylate, 3.60g of acrylic acid and 1.64mg of azobisisobutyronitrile were added to 20g of N, N-dimethylformamide, and after three freeze-vacuum-thaw cycles, a Schlenk reaction flask was placed in an oil bath in a vacuum-sealed manner. After 48 hours of reaction at 70 ℃, the reaction was stopped, precipitated in a large amount of methanol, and the product was dried under reduced pressure in a vacuum oven at 50 ℃ to obtain 1.17g of lignin-based thermoplastic elastomer 4 (m =68, n = 42).
Example 7
Synthesis of Lignin-based thermoplastic elastomer 5
To a solution of 20g of N, N-dimethylformamide, 0.3g of a lignin macromolecular chain transfer agent, 5.12g of n-butyl acrylate, 3.84g of acrylic acid and 1.64mg of azobisisobutyronitrile were added, and after three freeze-vacuum-thaw cycles were repeated, a Schlenk reaction flask was placed in an oil bath in a vacuum-sealed manner. After 48 hours at 70 ℃, the reaction was stopped, precipitated in a large amount of methanol, and the product was dried under reduced pressure in a vacuum oven at 50 ℃ to obtain 1.0g of all-bio-based thermoplastic elastomer 5 (m =44, n = 61).
Example 8
Synthesis of Lignin-based thermoplastic elastomer 6
To a solution of 20g of N, N-dimethylformamide, 0.3g of a lignin macromolecular chain transfer agent, 3.84g of n-butyl acrylate, 5.04g of acrylic acid and 1.64mg of azobisisobutyronitrile were added, and after three freeze-vacuum-thaw cycles were repeated, a Schlenk reaction flask was placed in an oil bath in a vacuum-sealed manner. After 48 hours of reaction at 70 ℃, the reaction was stopped, precipitated in a large amount of methanol, and the product was dried under reduced pressure at 50 ℃ in a vacuum oven to obtain 0.85g of lignin-based thermoplastic elastomer 6 (m =57, n = 35).
Example 9
Synthesis of Lignin-based thermoplastic elastomer 7
The preparation method is the same as in example 5, except that: the reaction monomer A is isobornyl acrylate, and the reaction monomer B is 4-pentenoic acid.
Example 10
Synthesis of Lignin-based thermoplastic elastomer 8
The preparation method is the same as that of example 5, except that: the reaction monomer A is acrylic acid isocyanate, and the reaction monomer B is 4-pentenoic acid.
Example 11
Synthesis of Lignin-based thermoplastic elastomer 9
The preparation method is the same as that of example 5, except that: the reaction monomer A is isobornyl acrylate, and the reaction monomer B is 2, 5-diene caproic acid acrylic acid.
Example 12
Synthesis of Lignin-based thermoplastic elastomer 10
The preparation method is the same as in example 5, except that: the reaction monomer A is acrylic acid isocyanate, and the reaction monomer B is 2, 5-diene caproic acid acrylic acid.
Example 13
Synthesis of Lignin-based thermoplastic elastomer 11
The preparation method is the same as in example 5, except that: the reaction monomer A is methyl acrylate, and the reaction monomer B is 3-butenoic acid.
Example 14
Synthesis of Lignin-based thermoplastic elastomer 12
The preparation method is the same as in example 5, except that: the reaction monomer A is ethyl acrylate, and the reaction monomer B is 5-hexenoic acid.
Example 15
Synthesis of Lignin-based thermoplastic elastomer 13
The preparation method is the same as that of example 5, except that: the reaction monomer A is propyl acrylate, and the reaction monomer B is 3, 5-hexadienoic acid.
Example 16
Synthesis of Lignin-based thermoplastic elastomer 14
The preparation method is the same as in example 5, except that: the reaction monomer A is amyl acrylate, and the reaction monomer B is 3-butenoic acid.
Example 17
Synthesis of Lignin-based thermoplastic elastomer 15
The preparation method is the same as that of example 5, except that: the reaction monomer A is hexyl acrylate, and the reaction monomer B is 5-hexenoic acid.
Example 18
Synthesis of Lignin-based thermoplastic elastomer 16
The preparation method is the same as that of example 5, except that: the reaction monomer A is hydroxypropyl acrylate, and the reaction monomer B is 3, 5-hexadienoic acid.
Example 19
Synthesis of Lignin-based thermoplastic elastomer 17
The preparation method is the same as that of example 5, except that: the reaction monomer A is 4-hydroxy butyl acrylate, and the reaction monomer B is 3-butenoic acid.
Example 20
Synthesis of Lignin-based thermoplastic elastomer 18
The preparation method is the same as that of example 5, except that: the reaction monomer A is isooctyl acrylate, and the reaction monomer B is 5-hexenoic acid.
Example 21
Synthesis of Lignin-based thermoplastic elastomer 19
The preparation method is the same as that of example 5, except that: the reaction monomer A is lauryl acrylate, and the reaction monomer B is 3, 5-hexadienoic acid.
Example 22
The synthesis of the Lignin macromolecular chain transfer agent (Lignin-CTA) specifically comprises the following steps:
adding 3g of lignin, 3g of 1- (benzyltrithiocarbonate) propionic acid and 150mg of 4-dimethylaminopyridine into a round-bottom flask, adding 180g of anhydrous dichloromethane, purging with nitrogen for half an hour, dropwise adding 1.5g of 1-ethyl- (3-dimethylaminopropyl) carbodiimide under the condition of ice-water bath, reacting for 40 hours at the temperature of 20 ℃, washing with pure water, performing centrifugal separation, and performing vacuum drying at the temperature of 30 ℃ to obtain the lignin macromolecular chain transfer agent.
Example 23
The synthesis of the Lignin macromolecular chain transfer agent (Lignin-CTA) specifically comprises the following steps:
adding 3g of lignin, 4.5g of 1- (benzyltrithiocarbonate) propionic acid and 180mg of 4-dimethylaminopyridine into a round-bottom flask, adding 240g of anhydrous dichloromethane, purging with nitrogen for half an hour, dropwise adding 3g of 1-ethyl- (3-dimethylaminopropyl) carbodiimide under the condition of ice-water bath, reacting for 36 hours at 30 ℃, washing with pure water, performing centrifugal separation, and performing vacuum drying at 50 ℃ to obtain the lignin macromolecular chain transfer agent.
Example 24
The preparation method of this example is the same as example 3, except that: the amount of N, N-dimethylformamide added was changed to 35g.
Example 25
The preparation method of this example is the same as example 3, except that: the amount of N, N-dimethylformamide added was changed to 50g.
Example 26
The preparation method of this example is the same as example 3, except that: the amount of the lignin macromolecular chain transfer agent added was changed to 0.1g.
Example 27
The preparation method of this example is the same as example 3, except that: the amount of the lignin macromolecular chain transfer agent added was changed to 0.2g.
Example 28
The preparation method of this example is the same as example 3, except that: the amount of n-butyl acrylate added was changed to 0.1g.
Example 29
The preparation method of this example is the same as example 3, except that: the amount of n-butyl acrylate added was changed to 0.2g.
Example 30
The preparation method of this example is the same as example 3, except that: the amount of acrylic acid added was changed to 1g.
Example 31
The preparation method of this example is the same as example 3, except that: the amount of acrylic acid added was changed to 6g.
Example 32
The preparation method of this example is the same as example 3, except that: the amount of azobisisobutyronitrile added was changed to 0.58g.
Example 33
The preparation method of this example is the same as example 3, except that: the amount of azobisisobutyronitrile added was changed to 1.2g.
Comparative example 1
Synthesis of Lignin-based Polymer 13
To 10ml of N, N-dimethylformamide was added 0.1g of a lignin macromolecular chain transfer agent, 1.08g of acrylic acid and 0.58mg of azobisisobutyronitrile, and after repeating three freeze-vacuum-thaw cycles, a Schlenk reaction flask was placed in an oil bath under vacuum and sealed conditions. After 48 hours of reaction at 70 ℃, the reaction was stopped, precipitated in a large amount of ethyl acetate, and the product was dried in a vacuum oven at 50 ℃ under reduced pressure to obtain 0.21g of lignin-based polymer 7 (m =0, n = 47).
Comparative example 2
Synthesis of Lignin-based Polymer 14
To 10ml of N, N-dimethylformamide was added 0.1g of a lignin macromolecular chain transfer agent, 1.92g of butyl acrylate and 0.58mg of azobisisobutyronitrile, and after repeating three freeze-vacuum-thaw cycles, a Schlenk reaction flask was placed in an oil bath under vacuum and sealed conditions. After 48h at 70 ℃, the reaction was stopped, precipitated in a large amount of ethyl acetate, and the product was dried in a vacuum oven at 50 ℃ under reduced pressure to give 0.53g of lignin-based polymer 7 (m =54, n = 0).
The products of comparative examples 1-2 could not be hot-pressed into tablets and their properties could not be measured.
The properties of the lignin-based thermoplastic elastomers obtained in examples 3 to 8 were measured by the following methods:
(1) Performing nuclear magnetic analysis on the structure;
(2) Measuring a stress-strain curve;
(3) Determining Young modulus, tensile strength, elongation at break and toughness;
(4) And (4) measuring the rapid repair performance.
FIG. 4 is a scanning differential thermal map of the products of example 3-example 8 and comparative example 1. It can be seen that the glass transition temperature of polyacrylic acid is higher, that of the copolymerization product of acrylic acid and n-butyl acrylate is lower, and that the glass transition temperature increases with increasing acrylic acid content.
Table 1 shows the results of the performance tests of the thermoplastic elastomers containing lignin in examples 3 to 8:
as can be seen from Table 1, the strain of the lignin-based thermoplastic elastomer material can reach more than 1400% at most, and the stress reaches about 0.5MPa at the same time. In example 5, the stress reached about 11MPa and the strain also reached 450% or more. It shows that a series of materials with good ductility and certain mechanical strength can be obtained by regulating the proportion of the grafting monomers. Overall, it can be seen that the strain of the obtained lignin-based thermoplastic elastomer material decreases with the increase of the acrylic acid content, and the stress tends to increase and then decrease. This is because the water absorption of the lignin-based thermoplastic elastomer material increases with the increase of the polyacrylic acid content, thereby affecting the mechanical properties of the material.
The dumbbell samples of examples 5 and 6 were cut into two pieces, and then the cut portions were recombined into one piece, and left at room temperature without application of external force and irradiated with a near infrared lamp. The mechanical properties were measured in different time periods, respectively.
Fig. 6 and 7 are quick repair tensile diagrams of example 5 and example 6, respectively, and it can be seen that the obtained lignin-based thermoplastic elastomer has quick repair capability under irradiation of a near infrared lamp.
As shown in fig. 6, the mechanical properties of the sample of example 4 before fracture were: tensile strength of 3.21MPa and breaking elongation of 1270 percent. The paint is quickly repaired after being irradiated by a near infrared lamp for 50s, and the mechanical property after quick repair is as follows: tensile strength 2.85MPa, elongation at break 1240%.
As shown in fig. 7, the mechanical properties of the sample of example 5 before fracture were: the tensile strength is 13.9MPa, and the breaking elongation is 510%. The quick repair is complete after the irradiation of a near infrared lamp for 60s, and the mechanical properties after the quick repair are as follows: the tensile strength is 13.5MPa, and the breaking elongation is 490 percent.
As shown in fig. 8, the mechanical properties of the sample of example 6 before fracture were: tensile strength of 5.3MPa and breaking elongation of 450%. The quick repairing is complete after the near infrared lamp irradiates for 40s, and the mechanical property after the quick repairing is as follows: tensile strength 4.5MPa, elongation at break 470%.
As shown in fig. 9, the mechanical properties of the sample of example 7 before fracture were: tensile strength of 2.95MPa and elongation at break of 365%. The quick repairing is complete after the near infrared lamp irradiates for 50s, and the mechanical property after the quick repairing is as follows: tensile strength of 2.53MPa and elongation at break of 355%.
The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (10)
1. A lignin-based thermoplastic elastomer characterized by: the structural formula is as follows:
wherein m is more than 0 and less than or equal to 700, n is more than or equal to 30 and less than or equal to 700 1 Is composed of
Any one of the groups;
R 2 comprises the following steps:
any one or more groups of (a);
R 3 comprises the following steps:
any one or more groups of (a).
2. Method for preparing a lignin-based thermoplastic elastomer according to claim 1, characterized in that: the method comprises the following steps:
(1) Adding a lignin macromolecular chain transfer agent, a reaction monomer A, a reaction monomer B and an initiator into a reaction container filled with a solvent; the structural formula of the lignin macromolecular chain transfer agent is as follows:
(2) And (3) removing air and water in the reaction container, reacting at 60-80 ℃, collecting and drying a product after the reaction is finished, and obtaining the lignin-based thermoplastic elastomer.
3. The method of lignin-based thermoplastic elastomer according to claim 2, characterized in that: the method comprises the following steps:
(1) Adding 1-3 parts by weight of lignin macromolecular chain transfer agent, 1-90 parts by weight of reaction monomer A, 10-60 parts by weight of reaction monomer B and 0.0058-0.0164 part by weight of initiator into a reaction vessel with 200-500 parts by weight of solvent;
(2) The reaction vessel was drained of water and air, the reaction was carried out at 70 ℃ and, after completion of the reaction, the product was collected and dried.
4. The method for producing a lignin-based thermoplastic elastomer according to claim 2, characterized in that: the reaction monomer A is as follows: methyl acrylate, ethyl acrylate, propyl acrylate, pentyl acrylate, n-butyl acrylate, hexyl acrylate, hydroxypropyl acrylate, 4-hydroxybutyl acrylate, isooctyl acrylate, lauryl acrylate, isobornyl acrylate or isocyanate acrylate.
5. The method of lignin-based thermoplastic elastomer according to claim 2, characterized in that: the reaction monomer B is as follows: acrylic acid, 3-butenoic acid, 4-pentenoic acid, 5-hexenoic acid, 3, 5-hexadienoic acid or 2, 5-dienoic acid acrylic acid.
6. The method of lignin-based thermoplastic elastomer according to claim 2, characterized in that: the solvent in the step (1) is N, N-dimethylformamide.
7. The method of lignin-based thermoplastic elastomer according to claim 2, characterized in that: in the step (1), the initiator is azobisisobutyronitrile.
8. The method of lignin thermoplastic elastomer according to claim 2, characterized in that: and (3) performing freezing-vacuum-melting circulation on the reaction container in the step (2), reacting at 70 ℃ for 36-48h, precipitating in a precipitator, collecting, and vacuum-drying the collected product at 50-80 ℃.
9. The method of lignin-based thermoplastic elastomer according to claim 2, characterized in that: the preparation method of the lignin macromolecular chain transfer agent in the step (1) comprises the following steps:
(a) Adding 10 parts by weight of 1-mercaptopropionic acid into a stirred acetone suspension of 20 parts by weight of tripotassium phosphate, adding 21.5 parts by weight of carbon disulfide, stirring for 8 hours, removing the solvent under reduced pressure, adding the residue into saturated saline solution, extracting with dichloromethane, washing with saturated saline solution, drying the extract with anhydrous magnesium sulfate, and removing the solvent under reduced pressure to obtain a light yellow solid 1- (benzyltrithiocarbonate) propionic acid;
(b) Adding 1 weight part of lignin, 1-1.5 weight parts of 1- (benzyltrithiocarbonate) propionic acid in the step (a) and 0.02-0.06 weight part of 4-dimethylaminopyridine into 50-80 weight parts of anhydrous dichloromethane, purging with nitrogen for half an hour, dropwise adding 0.5-1 weight part of 1-ethyl- (3-dimethylaminopropyl) carbodiimide under the condition of ice-water bath, reacting at 20-30 ℃, washing, centrifuging and drying to obtain the lignin macromolecular chain transfer agent.
10. The method of lignin-based thermoplastic elastomer according to claim 9, wherein: reacting at 20-30 ℃ for 36-48h in the step (b), washing with pure water, centrifuging, and drying at 30-50 ℃ in vacuum.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211000827.3A CN115160512B (en) | 2022-08-19 | 2022-08-19 | Lignin-based thermoplastic elastomer with rapid repair function and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211000827.3A CN115160512B (en) | 2022-08-19 | 2022-08-19 | Lignin-based thermoplastic elastomer with rapid repair function and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115160512A true CN115160512A (en) | 2022-10-11 |
| CN115160512B CN115160512B (en) | 2024-01-30 |
Family
ID=83480831
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211000827.3A Active CN115160512B (en) | 2022-08-19 | 2022-08-19 | Lignin-based thermoplastic elastomer with rapid repair function and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115160512B (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104356318A (en) * | 2014-11-10 | 2015-02-18 | 中国林业科学研究院林产化学工业研究所 | Lignin-based starlike thermoplastic elastomer and preparation method thereof |
| CN106397688A (en) * | 2016-08-30 | 2017-02-15 | 苏州世名科技股份有限公司 | Polymer-modified lignin dispersant and preparation method thereof |
-
2022
- 2022-08-19 CN CN202211000827.3A patent/CN115160512B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104356318A (en) * | 2014-11-10 | 2015-02-18 | 中国林业科学研究院林产化学工业研究所 | Lignin-based starlike thermoplastic elastomer and preparation method thereof |
| CN106397688A (en) * | 2016-08-30 | 2017-02-15 | 苏州世名科技股份有限公司 | Polymer-modified lignin dispersant and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| HAILING LIU等: "Lignin-Based Polymers via Graft Copolymerization", 《JOURNAL OF POLYMER SCIENCE, PART A: POLYMER CHEMISTRY》, vol. 55, pages 3515 * |
| HAILING LIU等: "Self-Healing Properties of Lignin-Containing Nanocomposite:Synthesis of Lignin- graf t-poly(5-acetylaminopentyl acrylate) via RAFT and Click Chemistry", 《MACROMOLECULES》, vol. 49, pages 7246, XP055968499, DOI: 10.1021/acs.macromol.6b01028 * |
| YINGCHAO WANG等: "Amphiphilic Lignin Nanoparticles Made from Lignin-Acrylic Acid-Methyl Methacrylate Copolymers", 《NANOMATERIALS》, vol. 12, pages 2612 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115160512B (en) | 2024-01-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Ohno et al. | Nitroxide‐controlled free radical polymerization of a sugar‐carrying acryloyl monomer | |
| CN104356318B (en) | A kind of starlike thermoplastic elastomer (TPE) of lignin-base and preparation method thereof | |
| Jiang et al. | Cellulose graft copolymers toward strong thermoplastic elastomers via RAFT polymerization | |
| US6228945B1 (en) | Three arm star compositions of matter having diblock arms based on polyisobutylene and methods of preparation | |
| Shen et al. | Synthesis of graft copolymer of ethyl cellulose through living polymerization and its self-assembly | |
| Cheng et al. | Sustainable elastomers derived from cellulose, rosin and fatty acid by a combination of “graft from” RAFT and isocyanate chemistry | |
| Zhang et al. | The synthesis of bottlebrush cellulose-graft-diblock copolymer elastomers via atom transfer radical polymerization utilizing a halide exchange technique | |
| CN1884319A (en) | Copolymer containing alpha-methyl styrol structural unit, its preparation method and application | |
| CN112279961B (en) | Preparation method of photoresponse adhesive with strong adhesion under water and prepared photoresponse adhesive | |
| Lin et al. | Core–shell particles to toughen epoxy resins. I. Preparation and characterization of core–shell particles | |
| CN115160512B (en) | Lignin-based thermoplastic elastomer with rapid repair function and preparation method thereof | |
| CN111187373A (en) | Epoxy vegetable oil nucleic acid base copolymer, preparation method thereof and application of composite material | |
| Kennedy et al. | Polyisobutylene-toughened poly (methyl methacrylate). 1. Synthesis, characterization, and tensile properties of PMMA-l-PIB networks | |
| CN113461891A (en) | Self-repairing acrylate polyurethane material and synthetic method thereof | |
| CN110330667B (en) | Simple preparation method of water-soluble polyrotaxane crosslinking agent and product thereof | |
| CN110713600A (en) | Preparation method of self-healing silicon elastomer based on metal coordination bond-hydrogen bond double crosslinking and elastomer | |
| CN116284681A (en) | Preparation method and application of high-temperature-resistant polyurethane resin | |
| JP6473348B2 (en) | Method for producing (meth) acrylic lactic acid macromonomer, and method for producing polylactic acid graft polymer and polylactic acid comb polymer using (meth) acrylic lactic acid macromonomer | |
| Wang et al. | Structure and properties of maleated high‐density polyethylene | |
| CN110903430B (en) | Lock type self-repairing polymer and preparation method and application thereof | |
| Avella et al. | Preparation of poly (β‐hydroxybutyrate)/poly (methyl methacrylate) blends by reactive blending and their characterisation | |
| Angelovici et al. | Copolymerization of acrylic esters with ethyl α‐cyanocinnamate | |
| CN1103408A (en) | Synthesis of random styrene-maleic anhydride copolymer | |
| CN110527074A (en) | Maleic anhydride homopolymers/propylene oxide/carbon dioxide copolymerization one kettle way preparation crosslinking poly (propylene carbonate) method | |
| CN110938168A (en) | Hydrophobic hydrogen bond enhanced hydrogel and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |