CN115160512B - 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
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- 229920005610 lignin Polymers 0.000 title claims abstract description 124
- 229920002725 thermoplastic elastomer Polymers 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title abstract description 32
- 230000008439 repair process Effects 0.000 title description 27
- 238000006243 chemical reaction Methods 0.000 claims description 79
- 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 27
- 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 24
- 238000000034 method Methods 0.000 claims description 24
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 17
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 16
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- PVEOYINWKBTPIZ-UHFFFAOYSA-N but-3-enoic acid Chemical compound OC(=O)CC=C PVEOYINWKBTPIZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000003999 initiator Substances 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 6
- XUDOZULIAWNMIU-UHFFFAOYSA-N delta-hexenoic acid Chemical compound OC(=O)CCCC=C XUDOZULIAWNMIU-UHFFFAOYSA-N 0.000 claims description 5
- HVAMZGADVCBITI-UHFFFAOYSA-N pent-4-enoic acid Chemical compound OC(=O)CCC=C HVAMZGADVCBITI-UHFFFAOYSA-N 0.000 claims description 4
- 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
- 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
- 238000001556 precipitation Methods 0.000 claims description 2
- 239000012716 precipitator Substances 0.000 claims description 2
- 238000002844 melting Methods 0.000 claims 1
- 229920001971 elastomer Polymers 0.000 abstract description 9
- 239000000806 elastomer Substances 0.000 abstract description 8
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 238000006065 biodegradation reaction Methods 0.000 abstract description 2
- 230000000704 physical effect Effects 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
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 21
- 229920000642 polymer Polymers 0.000 description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 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
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- LMDZBCPBFSXMTL-UHFFFAOYSA-N 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide Chemical compound CCN=C=NCCCN(C)C LMDZBCPBFSXMTL-UHFFFAOYSA-N 0.000 description 4
- KRMCNXUYEWISGE-ONEGZZNKSA-N 3,5-Hexadienoic acid Chemical compound OC(=O)C\C=C\C=C KRMCNXUYEWISGE-ONEGZZNKSA-N 0.000 description 4
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 4
- 239000005457 ice water Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 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 description 3
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 description 3
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 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
- 238000010586 diagram Methods 0.000 description 3
- 239000000284 extract Substances 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- 229910000404 tripotassium phosphate Inorganic materials 0.000 description 3
- 235000019798 tripotassium phosphate Nutrition 0.000 description 3
- 238000001291 vacuum drying 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
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 description 2
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-UHFFFAOYSA-N 0.000 description 2
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 description 2
- 101710141544 Allatotropin-related peptide Proteins 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- 238000010560 atom transfer radical polymerization reaction Methods 0.000 description 2
- 229920006392 biobased thermoplastic Polymers 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 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
- 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
- 239000002253 acid Substances 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
- XTHRTLHUMOKINM-UHFFFAOYSA-N benzylsulfanylmethanedithioic acid Chemical group SC(=S)SCC1=CC=CC=C1 XTHRTLHUMOKINM-UHFFFAOYSA-N 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 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
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000003776 cleavage reaction Methods 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
- 230000001276 controlling effect Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution 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
- IQJVBAIESAQUKR-UHFFFAOYSA-N isocyanic acid;prop-2-enoic acid Chemical compound N=C=O.OC(=O)C=C IQJVBAIESAQUKR-UHFFFAOYSA-N 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
- 238000005259 measurement Methods 0.000 description 1
- 238000000691 measurement method Methods 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
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen 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
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 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
- 230000007017 scission Effects 0.000 description 1
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- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
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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
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Graft Or Block Polymers (AREA)
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 has the advantages of excellent physical property, good ductility, good biodegradation and environmental friendliness. The lignin-based elastomer can heal rapidly within one minute under the irradiation of near infrared light, and the lignin-based elastomer with rapid repairing performance remarkably improves the utilization rate and the additional value of lignin and widens 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 rapid repair function and a preparation method thereof.
Background
Lignin (Lignin) is the second most abundant natural polymer on earth, widely present on the cell wall of plants, and has been considered as a promising resource to replace existing fossil fuels. Lignin is low in cost, abundant in content, environmentally friendly and good in ultraviolet radiation resistance, so that lignin has many potential applications such as adhesives, suntan lotions, carbon fibers, fillers, biologically derived synthetic polymers, composite materials and the like. Despite the great potential of lignin, the technology to develop this important resource is still immature, and lignin-based materials often cannot be converted to 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). It is widely used in the industries of 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 the bio-based thermoplastic elastomers have extremely important commercial value and environmental significance under the background of increasingly deficient petroleum resources and increasingly serious environmental pollution.
In recent years, surface graft polymerization has been one of the most prominent techniques for preparing well-defined lignin copolymers, particularly by the reversible addition-fragmentation chain transfer (RAFT) method. For example, the RAFT grafting method successfully synthesizes the copolymer of lignin grafted poly-n-butyl acrylate and 1-vinyl imidazole with different contents. The mechanical property test of the copolymer shows that when the lignin content is 6.1wt%, the tensile elongation at break 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 in the use process, and the macroscopic cracks are initiated to generate fracture, thereby influencing the normal use of the material and shortening the service life. Rapid repair of cracks early is a real and important problem. The rapid repair material has the advantages of reducing maintenance cost during material operation, prolonging 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 soft and hard segment polymers can be grafted on lignin, the lignin acts 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 quick repair capability can be prepared.
The Chinese patent document with publication number of CN104356318A discloses a lignin-based star-shaped thermoplastic elastomer and a preparation method thereof, and the preparation method comprises the following steps: (1) Reacting lignin with 2-bromoisobutyryl bromide to synthesize lignin ATRP macromolecular initiator; (2) Adding a hard monomer, a soft monomer, a lignin ATRP macromolecular initiator, a ligand and a reaction good solvent into a reaction bottle, fully stirring and dissolving, removing oxygen in the mixed solution through the circulation process of freezing, vacuumizing and nitrogen filling for three times, adding a catalyst to react 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-based star polymer with ultraviolet absorption performance and thermoplastic elastomer properties. The lignin-based star polymer has mechanical properties superior to those of linear polymers with the same composition, and can be used as a film material with ultraviolet absorption characteristics. The lignin-based star-shaped thermoplastic elastomer prepared by the method does not have the capability of rapid repair.
Disclosure of Invention
The invention aims to solve the technical problem of providing a lignin-based thermoplastic elastomer with good ductility, mechanical properties and quick repair capability and a preparation method thereof.
The invention solves the technical problems by the following technical means:
a lignin thermoplastic elastomer having the structural formula:
wherein 0 is<m≤700，30≤n≤700，R 1 Is thatAny one of the groups in (a);
R 2 the method comprises the following steps:any one or more of the groups in (a);
R 3 the method comprises the following steps:
any one or more of the groups in (a).
Description:represents the junction of the groups, as follows.
The beneficial effects are that: the lignin-based thermoplastic elastomer disclosed by the invention has excellent physical properties, good ductility and a certain quick repair capability. The lignin-based thermoplastic elastomer takes lignin, namely a natural biomass material, as a rigid main chain, and is grafted with a series of monomers, the rigid lignin plays a role of a crosslinking 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 lignin macromolecular chain transfer agent, reaction monomer A and reaction monomer B, and initiator into a reaction container filled with solvent; the lignin macromolecular chain transfer agent has the following structural formula:
wherein R is H or
(2) Removing air and water in the reaction vessel, reacting at 60-80 ℃, collecting and drying the product after the reaction is finished, and obtaining the lignin-based thermoplastic elastomer.
The route for the preparation of lignin-based thermoplastic elastomers is shown below:
the beneficial effects are 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 grafting side chain and the like, thereby obtaining the lignin-based thermoplastic elastomer material with excellent macroscopic mechanical property and rapid repair function.
The higher the ratio of rigid chains 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 and 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, so that the product has different physical and chemical 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 and 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 water and air in the reaction vessel were removed, reacted at 70℃and after the reaction was completed, the product was collected and dried.
Preferably, the reaction vessel is a reaction bottle.
Preferably, the reaction 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-dienhexanoic 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, the reaction vessel is subjected to a freeze-vacuum-thaw cycle in step (2), reacted at 70 ℃ for 48-72 hours, then placed in a precipitant for precipitation and collection, and then the collected product is placed in a vacuum for drying at 50-80 ℃.
Preferably, the precipitating agent 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 3-mercaptopropionic acid into 20 parts by weight of an acetone suspension of tripotassium phosphate after stirring 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, extracting with dichloromethane, washing with saturated saline, drying the extract on anhydrous magnesium sulfate, and removing the solvent under reduced pressure to obtain light yellow solid 3- (benzyltrithiocarbonate) propionic acid;
(b) Adding 1 part by weight of lignin, 1 to 1.5 parts by weight of 3- (benzyltrithiocarbonate) propionic acid in step (a), and 0.02 to 0.06 part by weight of 4-dimethylaminopyridine to 50 to 80 parts by weight of anhydrous dichloromethane; and (3) dropwise adding 0.5-1 part by weight of 1-ethyl- (3-dimethylaminopropyl) carbodiimide into the mixture under the condition of nitrogen purging for half an hour in an ice water bath, reacting the mixture at 20-30 ℃, and washing, centrifuging and drying the mixture to obtain the lignin macromolecular chain transfer agent.
The lignin macromolecular chain transfer agent has the following reaction formula:
preferably, 10 parts by weight of 3-mercaptopropionic acid is added to the stirred acetone suspension of 20 parts by weight of tripotassium phosphate in step (a), 21.5 parts by weight of carbon disulfide is added, and stirring is carried out for 8 hours; the solvent was removed under reduced pressure, and the residue was extracted with 2X 100ml of methylene chloride, then washed with 3X 100ml of saturated brine, and the extract was dried over anhydrous magnesium sulfate for 24 hours, and the solvent was removed under reduced pressure to give 3- (benzyltrithiocarbonate) propionic acid as a pale yellow solid.
Preferably, in the step (b), the reaction is carried out at 20-30 ℃ for 36-48 hours, and the reaction product is centrifugally separated after being washed by pure water and is dried at 30-50 ℃ in vacuum.
The invention has the advantages that:
(1) The lignin-based thermoplastic elastomer has excellent mechanical properties, and the stress can reach 11MPa while the strain reaches more than 500%. The lignin main chain has a large amount of ester bonds, the monomers of the side chains have ester bond structures, and the ester bonds can be well broken and degraded under natural conditions, so that the lignin has good biodegradation and environmental friendliness.
(2) According to the lignin-based thermoplastic elastomer, lignin, which is a natural biomass material, is taken as a rigid main chain, a series of monomers are grafted, the lignin serves as a crosslinking point in a polymer system, a short chain endows a polymer network with good chain flexibility and ductility, a hard segment provides strength, and the final lignin-based elastomer has excellent mechanical properties.
(3) The invention can realize the adjustment of the microstructure of the polymer network by designing the types of the reaction monomers, the grafting density, the relative proportion of the rigid main chain and the grafting side chain and the like, thereby obtaining the environment-friendly lignin-based thermoplastic elastomer material with excellent macroscopic mechanical properties and natural degradation.
(4) The lignin-based elastomer prepared by the method can heal rapidly within 2 seconds under the irradiation of near infrared light, and the lignin-based elastomer with rapid repairing performance can obviously improve the utilization rate and the additional value of lignin and widen the application of lignin.
Drawings
FIG. 1 is a nuclear magnetic resonance spectrum of 3- (benzyltrithiocarbonate) propionic acid in example 1 of the present invention;
FIG. 2 is a nuclear magnetic resonance spectrum of lignin-based thermoplastic elastomer 2 in example 4 of the present invention;
FIG. 3 is a nuclear magnetic resonance spectrum of lignin-based polymer 13 according to comparative example 1 of the present invention;
FIG. 4 is a differential scanning calorimeter plot of the products of examples 3-8 and comparative example 1 of the present invention;
FIG. 5 is a mechanical drawing of the product of examples 3-8 of the present invention;
FIG. 6 is a mechanical stretching chart of autonomous repair after product breakage in example 4 of the present invention under irradiation of near infrared light;
FIG. 7 is a mechanical stretching chart of autonomous repair after product breakage in example 5 of the present invention under irradiation of near infrared light;
FIG. 8 is a mechanical stretching chart of autonomous repair after product breakage in example 6 of the present invention under irradiation of near infrared light;
FIG. 9 is a mechanical tensile diagram of autonomous repair upon near infrared light irradiation after cleavage of the product of example 7 of the present invention.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions in the embodiments of the present invention will be clearly and completely described in the following in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The test materials, reagents and the like used in the examples described below are commercially available unless otherwise specified.
Those of skill in the art, without any particular mention of the techniques or conditions, may follow the techniques or conditions described in the literature in this field or follow the product specifications.
Example 1
The synthesis of 3- (benzyl trithiocarbonate group) propionic acid specifically comprises the following steps:
10.0g of 3-mercaptopropionic acid was added to a stirred acetone suspension of 20g of tripotassium phosphate, 21.5g of carbon disulfide was further added thereto, stirring was carried out for 8 hours, the solvent was removed under reduced pressure, the residue was added to saturated brine, extracted with 2X 100ml of methylene chloride, washed with 3X 100ml of saturated brine, and the extract was dried over anhydrous magnesium sulfate, and the solvent was removed under reduced pressure to give 3- (benzyltrithiocarbonate) propionic acid as a pale yellow solid.
Example 2
The synthesis of Lignin macromolecular chain transfer agent (Lignin-CTA) specifically comprises the following steps:
3g of lignin, 3.96g of 3- (benzyltrithiocarbonate) propionic acid and 60mg of 4-dimethylaminopyridine are added into a round-bottomed flask, 150g of anhydrous dichloromethane is added, nitrogen is purged for half an hour, 1.52g of 1-ethyl- (3-dimethylaminopropyl) carbodiimide is dropwise added under the ice water bath condition, the reaction is carried out for 48 hours at 25 ℃, the reaction is carried out, pure water is used for washing, centrifugal separation is carried out, and vacuum drying is carried out at 40 ℃ to prepare the lignin macromolecular chain transfer agent.
Example 3
Synthesis of lignin-based thermoplastic elastomer 1
To 20g of N, N-dimethylformamide was added 0.3g of the lignin macromolecular chain transfer agent of example 2, 9.00g of n-butyl acrylate, 2.16g of acrylic acid and 1.64mg of azobisisobutyronitrile, and after repeating three freeze-vacuum-thaw cycles, the Schlenk flask was vacuum-sealed in an oil bath. After 48h 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 give 2.85g of lignin-based thermoplastic elastomer 1 (m=169, n=54).
Example 4
Synthesis of lignin-based thermoplastic elastomer 2
To 20g of N, N-dimethylformamide was added 0.3g of lignin macromolecular chain transfer agent, 7.69g of n-butyl acrylate, 2.88g of acrylic acid and 1.64mg of azobisisobutyronitrile, and after repeating three freeze-vacuum-thaw cycles, the Schlenk flask was vacuum-sealed in an oil bath. After 72h at 60 ℃, the reaction was stopped, precipitated in a large amount of methanol, and the product was dried under reduced pressure at 80 ℃ in a vacuum oven to give 2.80g of lignin-based thermoplastic elastomer 2 (m=150, n=71).
Example 5
Synthesis of lignin-based thermoplastic elastomer 3
To 20g of N, N-dimethylformamide was added 0.3g of lignin macromolecular chain transfer agent, 7.05g of n-butyl acrylate, 3.24g of acrylic acid and 1.64mg of azobisisobutyronitrile, and after repeating three freeze-vacuum-thaw cycles, the Schlenk flask was vacuum-sealed in an oil bath. After 50h at 80 ℃, the reaction was stopped, precipitated in a large amount of methanol, and the product was dried under reduced pressure at 60 ℃ in a vacuum oven to give 2.79g of lignin-based thermoplastic elastomer 3 (m=173, n=80).
Example 6
Synthesis of lignin-based thermoplastic elastomer 4
To 20g of N, N-dimethylformamide was added 0.3g of lignin macromolecular chain transfer agent, 6.41g of n-butyl acrylate, 3.60g of acrylic acid and 1.64mg of azobisisobutyronitrile, and after repeating three freeze-vacuum-thaw cycles, the Schlenk flask was vacuum-sealed in an oil bath. After 48h 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 give 1.17g of lignin-based thermoplastic elastomer 4 (m=68, n=42).
Example 7
Synthesis of lignin-based thermoplastic elastomer 5
To 20g of N, N-dimethylformamide was added 0.3g of lignin macromolecular chain transfer agent, 5.12g of n-butyl acrylate, 3.84g of acrylic acid and 1.64mg of azobisisobutyronitrile, and after repeating three freeze-vacuum-thaw cycles, the Schlenk flask was vacuum-sealed in an oil bath. After 48h 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 give 1.0g of the whole bio-based thermoplastic elastomer 5 (m=44, n=61).
Example 8
Synthesis of lignin-based thermoplastic elastomer 6
To 20g of N, N-dimethylformamide was added 0.3g of lignin macromolecular chain transfer agent, 3.84g of n-butyl acrylate, 5.04g of acrylic acid and 1.64mg of azobisisobutyronitrile, and after repeating three freeze-vacuum-thaw cycles, the Schlenk flask was vacuum-sealed in an oil bath. After 48h 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 give 0.85g 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 in example 5, except that: the reaction monomer A is acrylic 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 in 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 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 in 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 in 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 in 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 in 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 in 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 in 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 Lignin macromolecular chain transfer agent (Lignin-CTA) specifically comprises the following steps:
3g of lignin, 3g of 3- (benzyltrithiocarbonate) propionic acid and 150mg of 4-dimethylaminopyridine are added into a round-bottomed flask, 180g of anhydrous dichloromethane is added, nitrogen is purged for half an hour, 1.5g of 1-ethyl- (3-dimethylaminopropyl) carbodiimide is dropwise added under the ice water bath condition, the reaction is carried out for 40 hours at 20 ℃, the reaction is carried out, pure water is used for washing, centrifugal separation is carried out, and vacuum drying is carried out at 30 ℃ to prepare the lignin macromolecular chain transfer agent.
Example 23
The synthesis of Lignin macromolecular chain transfer agent (Lignin-CTA) specifically comprises the following steps:
3g of lignin, 4.5g of 3- (benzyltrithiocarbonate) propionic acid and 180mg of 4-dimethylaminopyridine are added into a round-bottomed flask, 240g of anhydrous dichloromethane is added, nitrogen is purged for half an hour, 3g of 1-ethyl- (3-dimethylaminopropyl) carbodiimide is dropwise added under the ice water bath condition, the reaction is carried out for 36 hours at 30 ℃, the reaction is carried out, pure water is used for washing, centrifugal separation is carried out, and the lignin macromolecular chain transfer agent is prepared by vacuum drying at 50 ℃.
Example 24
The preparation method of this example is the same as that of 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 that of 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 that of example 3, except that: the addition amount of the lignin macromolecular chain transfer agent is changed to 0.1g.
Example 27
The preparation method of this example is the same as that of example 3, except that: the addition amount of the lignin macromolecular chain transfer agent is changed to 0.2g.
Example 28
The preparation method of this example is the same as that of 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 that of 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 that of 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 that of 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 that of example 3, except that: the addition amount of azobisisobutyronitrile was changed to 0.58g.
Example 33
The preparation method of this example is the same as that of example 3, except that: the addition amount of azobisisobutyronitrile 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 lignin macromolecular chain transfer agent, 1.08g of acrylic acid and 0.58mg of azobisisobutyronitrile, and after repeating three freeze-vacuum-thaw cycles, the Schlenk flask was vacuum-sealed in an oil bath. After 48h at 70 ℃, the reaction was stopped, precipitated in a large amount of ethyl acetate, and the product was dried under reduced pressure at 50 ℃ in a vacuum oven to give 0.21g lignin-based polymer 13 (m=0, n=47).
Comparative example 2
Synthesis of lignin-based Polymer 14
To 10ml of N, N-dimethylformamide was added 0.1g of lignin macromolecular chain transfer agent, 1.92g of butyl acrylate and 0.58mg of azobisisobutyronitrile, and after repeating three freeze-vacuum-thaw cycles, the Schlenk flask was vacuum-sealed in an oil bath. After 48h at 70 ℃, the reaction was stopped, precipitated in a large amount of ethyl acetate, and the product was dried under reduced pressure at 50 ℃ in a vacuum oven to give 0.53g lignin-based polymer 14 (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 prepared in examples 3-8 were measured, and the following measurement methods were all known in the art:
(1) Performing nuclear magnetic analysis on the structure;
(2) Determining a stress-strain curve;
(3) Young's modulus, tensile strength, elongation at break and toughness were measured;
(4) And (5) quick repair performance measurement.
FIG. 4 is a scanning differential thermal diagram 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, the glass transition temperature of the copolymerization product of acrylic acid and n-butyl acrylate is lower, and the glass transition temperature increases with the acrylic acid content.
Table 1 shows the results of performance tests for lignin-based thermoplastic elastomers contained in examples 3-8:
as can be seen from Table 1, the lignin-based thermoplastic elastomer material has a maximum strain of 1400% or more, and a stress of about 0.5 MPa. In example 5, the strain was 450% or more while the stress was about 11MPa. The method shows that a series of materials with good ductility and certain mechanical strength can be obtained by regulating and controlling the proportion of grafting monomers. Overall, it can be seen that the resulting lignin-based thermoplastic elastomer material strain decreases with increasing acrylic content, with the stress then tending to increase and decrease. This is because as the polyacrylic acid content increases, the water absorption of the lignin-based thermoplastic elastomer material increases, thereby affecting the mechanical properties of the material.
The dumbbell-shaped samples of example 5 and example 6 were cut into two pieces, and then the cut was recombined into one piece, and the pieces were left at room temperature without applying external force and irradiated with a near infrared lamp. The mechanical properties were measured over different time periods, respectively.
Fig. 6 and 7 are rapid repair stretch diagrams of examples 4 and 5, respectively, showing the ability of the resulting lignin-based thermoplastic elastomer to rapidly repair under near infrared light irradiation.
As shown in fig. 6, the mechanical properties of the sample of example 4 before fracture were: tensile strength 3.21MPa and elongation at break 1270%. The rapid repair is carried out after the irradiation of a near infrared lamp for 50s, and the mechanical properties after the rapid repair are as follows: tensile strength 2.85MPa and elongation at break 1240%.
As shown in fig. 7, the mechanical properties of the sample of example 5 before fracture were: tensile strength 13.9MPa and elongation at break 510%. The rapid repair is complete after the near infrared lamp irradiates for 60 seconds, and the mechanical properties after the rapid repair are as follows: tensile strength 13.5MPa and elongation at break 490%.
As shown in fig. 8, the mechanical properties of the sample of example 6 before fracture were: tensile strength 5.3MPa and elongation at break 450%. After the near infrared lamp irradiates for 40s, the rapid repair is complete, and the mechanical properties after the rapid repair are 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 2.95MPa and elongation at break 365%. After the near infrared lamp irradiates for 50s, the quick repair is complete, and the mechanical properties after the quick repair are as follows: the tensile strength is 2.53MPa, and the elongation at break is 355%.
The above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the 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 scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention.
Claims (6)
1. A lignin-based thermoplastic elastomer characterized by: the structural formula is as follows:
wherein m is more than or equal to 44 and less than or equal to 173, n is more than or equal to 35 and less than or equal to 80, R 1 Is thatAny one of the groups in (a);
R 2 the method comprises the following steps:
any one or more of the groups in (a);
R 3 the method comprises the following steps:
any one or more of the groups in (a).
2. A method of preparing the lignin-based thermoplastic elastomer according to claim 1 wherein: the method comprises the following steps:
(1) Adding lignin macromolecular chain transfer agent, reaction monomer A and reaction monomer B, and initiator into a reaction container filled with solvent; the lignin macromolecular chain transfer agent has the following structural formula:
wherein R is
The reaction monomer A is: methyl acrylate, ethyl acrylate, n-propyl acrylate, n-pentyl acrylate, n-butyl acrylate or n-hexyl acrylate;
the reaction monomer B is: acrylic acid, 3-butenoic acid, 4-pentenoic acid or 5-hexenoic acid;
(2) Removing air and water in the reaction vessel, reacting at 60-80 ℃, collecting and drying the 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 wherein: 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 and 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 water and air in the reaction vessel were removed, reacted at 70℃and after the reaction was completed, the product was collected and dried.
4. The method of lignin-based thermoplastic elastomer according to claim 2 wherein: the solvent in the step (1) is N, N-dimethylformamide.
5. The method of lignin-based thermoplastic elastomer according to claim 2 wherein: the initiator in the step (1) is azobisisobutyronitrile.
6. The method of lignin thermoplastic elastomer according to claim 2 wherein: the reaction vessel is subjected to freeze-vacuum-melting circulation in the step (2), the reaction vessel is reacted for 36-48 hours at 70 ℃, then the reaction vessel is placed in a precipitator for precipitation and collection, and then the collected product is placed in a vacuum for drying at 50-80 ℃.
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| 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 |
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