CN114773307B - Non-isocyanate polyurethane monomer and thermosetting non-isocyanate shape memory polyurethane, and preparation and recycling methods thereof - Google Patents
Non-isocyanate polyurethane monomer and thermosetting non-isocyanate shape memory polyurethane, and preparation and recycling methods thereof Download PDFInfo
- Publication number
- CN114773307B CN114773307B CN202210543304.7A CN202210543304A CN114773307B CN 114773307 B CN114773307 B CN 114773307B CN 202210543304 A CN202210543304 A CN 202210543304A CN 114773307 B CN114773307 B CN 114773307B
- Authority
- CN
- China
- Prior art keywords
- isocyanate
- polyurethane
- shape memory
- monomer
- preparation
- 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.)
- Active
Links
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 152
- 239000004814 polyurethane Substances 0.000 title claims abstract description 152
- 239000012948 isocyanate Substances 0.000 title claims abstract description 123
- 150000002513 isocyanates Chemical class 0.000 title claims abstract description 121
- 239000000178 monomer Substances 0.000 title claims abstract description 71
- 229920001187 thermosetting polymer Polymers 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 title claims abstract description 20
- 238000004064 recycling Methods 0.000 title claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 44
- 150000005676 cyclic carbonates Chemical class 0.000 claims abstract description 34
- 238000004132 cross linking Methods 0.000 claims abstract description 28
- 238000007731 hot pressing Methods 0.000 claims abstract description 13
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000012650 click reaction Methods 0.000 claims abstract description 10
- 230000035484 reaction time Effects 0.000 claims abstract description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 17
- 150000003141 primary amines Chemical class 0.000 claims description 17
- 239000000376 reactant Substances 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 13
- 239000003960 organic solvent Substances 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical group C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 claims description 6
- 229920000768 polyamine Polymers 0.000 claims description 6
- 150000003573 thiols Chemical class 0.000 claims description 6
- 239000007983 Tris buffer Substances 0.000 claims description 5
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- HCZMHWVFVZAHCR-UHFFFAOYSA-N 2-[2-(2-sulfanylethoxy)ethoxy]ethanethiol Chemical compound SCCOCCOCCS HCZMHWVFVZAHCR-UHFFFAOYSA-N 0.000 claims description 3
- 230000003446 memory effect Effects 0.000 abstract description 8
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 125000002924 primary amino group Chemical class [H]N([H])* 0.000 abstract 1
- -1 ethylene carbonate (4-Vinyl-1, 3-dioxan-2-one) Chemical compound 0.000 description 11
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 10
- 239000004810 polytetrafluoroethylene Substances 0.000 description 10
- 239000000243 solution Substances 0.000 description 9
- 238000003756 stirring Methods 0.000 description 8
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical group NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 description 5
- 230000009477 glass transition Effects 0.000 description 5
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 4
- 150000008064 anhydrides Chemical class 0.000 description 4
- 238000005886 esterification reaction Methods 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 230000001681 protective effect Effects 0.000 description 4
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 3
- IYADXFDWVMRNFK-UHFFFAOYSA-N 4-(hydroxymethyl)-1,3-dioxol-2-one Chemical compound OCC1=COC(=O)O1 IYADXFDWVMRNFK-UHFFFAOYSA-N 0.000 description 3
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 3
- QLCFPDLVOCOPON-UHFFFAOYSA-N CCC(CO)(CO)CO.CC(O)COC(C)COC(C)CO Chemical compound CCC(CO)(CO)CO.CC(O)COC(C)COC(C)CO QLCFPDLVOCOPON-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 2
- TZMFOZBNAFPHHG-UHFFFAOYSA-N SC=CC(=O)O.SC=CC(=O)O.SC=CC(=O)O.C(O)C(CC)(CO)CO Chemical compound SC=CC(=O)O.SC=CC(=O)O.SC=CC(=O)O.C(O)C(CC)(CO)CO TZMFOZBNAFPHHG-UHFFFAOYSA-N 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- FXRVAXZWHRONEV-UHFFFAOYSA-N 1-hydroxypropan-2-yl hydrogen carbonate Chemical compound OCC(C)OC(O)=O FXRVAXZWHRONEV-UHFFFAOYSA-N 0.000 description 1
- JJSYPAGPNHFLML-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;3-sulfanylpropanoic acid Chemical compound OC(=O)CCS.OC(=O)CCS.OC(=O)CCS.CCC(CO)(CO)CO JJSYPAGPNHFLML-UHFFFAOYSA-N 0.000 description 1
- YQEIMEGRSTXEMX-UHFFFAOYSA-N 3-methylbut-2-enoyl 3-methylbut-2-enoate Chemical compound CC(C)=CC(=O)OC(=O)C=C(C)C YQEIMEGRSTXEMX-UHFFFAOYSA-N 0.000 description 1
- KNBJQHMNZVLYGH-UHFFFAOYSA-N C(OCCS)COCCS.C(OCCS)COCCS Chemical compound C(OCCS)COCCS.C(OCCS)COCCS KNBJQHMNZVLYGH-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- NHWGPUVJQFTOQX-UHFFFAOYSA-N ethyl-[2-[2-[ethyl(dimethyl)azaniumyl]ethyl-methylamino]ethyl]-dimethylazanium Chemical compound CC[N+](C)(C)CCN(C)CC[N+](C)(C)CC NHWGPUVJQFTOQX-UHFFFAOYSA-N 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- DCUFMVPCXCSVNP-UHFFFAOYSA-N methacrylic anhydride Chemical compound CC(=C)C(=O)OC(=O)C(C)=C DCUFMVPCXCSVNP-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- ARJOQCYCJMAIFR-UHFFFAOYSA-N prop-2-enoyl prop-2-enoate Chemical compound C=CC(=O)OC(=O)C=C ARJOQCYCJMAIFR-UHFFFAOYSA-N 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000012958 reprocessing Methods 0.000 description 1
- 229920000431 shape-memory polymer Polymers 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- MBYLVOKEDDQJDY-UHFFFAOYSA-N tris(2-aminoethyl)amine Chemical compound NCCN(CCN)CCN MBYLVOKEDDQJDY-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
- C07D317/32—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D317/34—Oxygen atoms
- C07D317/36—Alkylene carbonates; Substituted alkylene carbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G71/00—Macromolecular compounds obtained by reactions forming a ureide or urethane link, otherwise, than from isocyanate radicals in the main chain of the macromolecule
- C08G71/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J11/00—Recovery or working-up of waste materials
- C08J11/04—Recovery or working-up of waste materials of polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2280/00—Compositions for creating shape memory
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention provides non-isocyanate polyurethane monomer, thermosetting non-isocyanate shape memory polyurethane and preparation and recycling methods thereof, and relates to the technical field of polyurethane synthesis. The non-isocyanate polyurethane monomer provided by the invention has a structure shown in formulas I-III. The non-isocyanate polyurethane monomer provided by the invention has a plurality of five-membered cyclic carbonates, and polyurethane generated after the crosslinking reaction of the non-isocyanate polyurethane monomer and the poly primary amine has a shape memory effect and a programmable shape; the polyurethane has excellent mechanical properties, namely Gao Jiangfei isocyanate polyurethane; and recycling can be realized through simple hot pressing, so that the device is more durable and environment-friendly. The invention provides a preparation method of the non-isocyanate polyurethane monomer, which prepares the polyurethane monomer with a plurality of five-membered cyclic carbonates by click reaction of the cyclic carbonate with double bonds and mercaptan, and has the advantages of quick and efficient reaction and reaction time of not more than 10min.
Description
Technical Field
The invention relates to the technical field of polyurethane synthesis, in particular to non-isocyanate polyurethane monomer and thermosetting non-isocyanate shape memory polyurethane and preparation and recycling methods thereof.
Background
The shape memory polymer material is an intelligent material which has a certain initial shape and can recover the initial shape by stimulation of external conditions such as heat, light, electricity, magnetism and the like after being deformed under certain conditions. Shape memory polyurethane materials are an important class of materials. The traditional shape memory polyurethane material is usually polymerized by polyol and isocyanate, wherein the isocyanate is usually synthesized by a phosgene method, the phosgene toxicity is great, the environmental pollution is serious, and the isocyanate itself has strong toxicity, so the exploration of the synthesis of non-isocyanate polyurethane is more and more important. In recent years, researchers develop a route for synthesizing non-isocyanate polyurethane by reacting cyclic carbonate with amine, and the reaction route is more efficient, green and safe, thereby opening up a new way for synthesizing non-isocyanate polyurethane. However, the mechanical properties of the non-isocyanate polyurethane synthesized at present are poor, so that the application of the non-isocyanate polyurethane is limited; also, synthetic non-isocyanate polyurethanes are thermoset polyurethanes crosslinked by covalent bonds, whereas currently thermoset polymers crosslinked by covalent bonds generally do not have recyclability.
Disclosure of Invention
In view of this, the present invention aims to provide a non-isocyanate based polyurethane monomer and a thermosetting non-isocyanate based shape memory polyurethane and methods for preparing and recycling the same. The thermosetting non-isocyanate-based shape memory polyurethane obtained by the reaction of the non-isocyanate-based polyurethane monomer and the amine has excellent mechanical strength and can be recycled.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a non-isocyanate polyurethane monomer which has a structure shown in formulas I-III:
in the formulae I to III, R 1 Is thatWherein R is 2 is-CH 2 -CH 2 -、/>
The invention provides a preparation method of the non-isocyanate polyurethane monomer, which comprises the following steps:
mixing cyclic carbonate with double bonds, mercaptan and a photoinitiator, and carrying out click reaction under ultraviolet irradiation to obtain the non-isocyanate polyurethane monomer;
the cyclic carbonate with double bond is ethylene carbonate or has a structure shown in a formula IV, wherein R 3 is-H or-CH 3 The method comprises the steps of carrying out a first treatment on the surface of the The mercaptan is pentaerythritol tetra-3-mercaptopropionate, trimethylolpropane tri (3-mercaptoacrylate) or 3,6-dioxa-1, 8-octanedithiol;
preferably, the molar ratio of the cyclic carbonate with double bonds to the thiol is 1-4: 1, a step of; the photoinitiator is 2, 2-dimethoxy-2-phenylacetophenone; the mass of the photoinitiator is 1-3% of the sum of the mass of the cyclic carbonate with double bonds and the mass of the mercaptan.
Preferably, the wavelength of the ultraviolet light is 365nm, and the irradiation intensity is 30mw/cm -2 The method comprises the steps of carrying out a first treatment on the surface of the The click reaction time is 5-10 min.
The invention provides thermosetting non-isocyanate-based shape memory polyurethane, which is obtained by crosslinking reaction of non-isocyanate-based polyurethane monomer prepared by the technical scheme or non-isocyanate-based polyurethane monomer prepared by the preparation method of the technical scheme and poly-primary amine.
Preferably, the primary polyamine is 1, 6-hexamethylenediamine, tetraethylenepentamine, isophoronediamine, trimethylolpropane tripropyleneglycol ether (amino-terminated) or tris (2-aminoethylamine); the molar ratio of the non-isocyanate polyurethane monomer to the poly primary amine is (2-3): (2-4).
The invention provides a preparation method of thermosetting non-isocyanate-based shape memory polyurethane, which comprises the following steps:
mixing the non-isocyanate polyurethane monomer, the poly-primary amine and the organic solvent for crosslinking reaction to obtain a reactant; the temperature of the crosslinking reaction is 90-100 ℃;
and heating the reactants in sequence to remove the solvent and solidifying the reactants to obtain the thermosetting non-isocyanate-based shape memory polyurethane.
Preferably, the organic solvent comprises one or more of N, N-dimethylformamide, N-methylpyrrolidone and dimethylacetamide; the time of the crosslinking reaction is 10-48 h.
Preferably, the heating temperature of the heating desolventizing agent is 40-80 ℃ for 20-60 h; the curing temperature is 90-110 ℃ and the curing time is 8-16 h.
The invention provides a recycling method of thermosetting non-isocyanate-based shape memory polyurethane, which comprises the following steps:
hot-pressing the thermosetting non-isocyanate-based shape memory polyurethane to be recycled to obtain recycled thermosetting non-isocyanate-based shape memory polyurethane; the hot pressing temperature is 90-150 ℃, the pressure is 0.5-3 MPa, and the time is 0.5-3 h.
The invention provides a non-isocyanate polyurethane monomer which has a structure shown in formulas I-III. The non-isocyanate polyurethane monomer provided by the invention is provided with a plurality of (2-4) five-membered cyclic carbonates, and the crosslinking degree of polyurethane generated after the crosslinking reaction of the non-isocyanate polyurethane monomer and the poly primary amine is high, so that the mechanical strength of the polyurethane can be improved; the polyurethane synthesized by the monomer and the poly-primary amine is in a glass state at room temperature, and a molecular chain is in a frozen state and has very high stress, so that the obtained polyurethane has very high tensile strength and excellent mechanical property; the synthesized polyurethane is in a glass state (glass transition temperature is 40-60 ℃) at room temperature, has good shape fixability, and has good fluidity at the temperature higher than the glass transition temperature, so that the polyurethane has good shape recovery rate, and thus the polyurethane has good shape memory property. In addition, the thermosetting polyurethane with a cross-linked structure generally does not have recycling, but the thermosetting polyurethane obtained by the cross-linking reaction of the non-isocyanate polyurethane monomer provided by the invention and the polybasic primary amine belongs to polyhydroxyurethane, contains a large amount of urethane bonds and also contains as many hydroxyl groups, and weak hydrogen bonds are formed between the hydroxyl groups and the hydroxyl groups, between the hydroxyl groups and the urethane, and between the urethane and the urethane, and the weak hydrogen bonds are strong, so that the thermosetting polyurethane has recycling performance.
The invention provides the preparation method of the non-isocyanate polyurethane monomer, which adopts the double-bond cyclic carbonate and mercaptan to carry out click reaction to prepare the polyurethane monomer with a plurality of five-membered cyclic carbonates, and the reaction is fast and efficient, and the reaction time is not more than 10min.
The invention provides thermosetting non-isocyanate-based shape memory polyurethane, which is obtained by crosslinking reaction of non-isocyanate-based polyurethane monomer prepared by the technical scheme or non-isocyanate-based polyurethane monomer prepared by the preparation method of the technical scheme and poly-primary amine. The non-isocyanate polyurethane provided by the invention has a shape memory effect and a programmable shape; the polyurethane has excellent mechanical properties, namely Gao Jiangfei isocyanate polyurethane; and recycling can be realized through simple hot pressing, so that the device is more durable and environment-friendly. The results of the examples show that the tensile stress of the thermosetting non-isocyanate-based shape memory polyurethane provided by the invention is 50-60 MPa, and the Young modulus is 2.9-3.0 GPa.
The invention provides the preparation method of the thermosetting non-isocyanate-based shape memory polyurethane, which is free of a catalyst, simple in process, easy to control in conditions and convenient for large-scale production.
Drawings
FIG. 1 is a graph showing the shape memory effect of the non-isocyanate based shape memory polyurethane prepared in example 1;
FIG. 2 is a graph showing the effect of recyclability test on non-isocyanate based shape memory polyurethanes prepared in example 3.
Detailed Description
The invention provides a non-isocyanate polyurethane monomer which has a structure shown in formulas I-III:
in the formulae I to III, R 1 Is thatWherein R is 2 is-CH 2 -CH 2 -、/>The "×" in the structural formula indicates the attachment site.
The non-isocyanate polyurethane monomer provided by the invention has a plurality of five-membered cyclic carbonates, and the crosslinking degree of polyurethane generated after the crosslinking reaction of the non-isocyanate polyurethane monomer and the poly primary amine is high, so that the mechanical strength of the polyurethane can be improved.
The invention provides a preparation method of the non-isocyanate polyurethane monomer, which comprises the following steps:
and mixing the cyclic carbonate with double bonds, mercaptan and a photoinitiator, and carrying out click reaction under ultraviolet irradiation to obtain the non-isocyanate polyurethane monomer.
In the invention, the cyclic carbonate with double bonds is ethylene carbonate (4-Vinyl-1, 3-dioxan-2-one) or has a structure shown in a formula IV, wherein R 3 is-H or-CH 3 ：
The present invention is not particularly limited to the source of the cyclic carbonate having a double bond, and can be prepared by commercially available products known to those skilled in the art or by a preparation method known to those skilled in the art; in the present invention, when the double bond-containing cyclic carbonate has a structure represented by formula iv, the preparation method of the double bond-containing cyclic carbonate preferably comprises the steps of: in an organic solvent, carrying out esterification reaction on hydroxymethyl dioxolone and anhydride with double bonds under the catalysis of toluenesulfonic acid to obtain the cyclic carbonate with double bonds; the acid anhydride with double bond is acrylic anhydride or dimethyl acrylic anhydride. In the present invention, the molar ratio of the hydroxymethyl dioxolone to the double bond-bearing anhydride is preferably 2:1, a step of; the mass of the toluenesulfonic acid is preferably 1 to 3% of the sum of the mass of the methyloldioxapentanone (4- (hydroxyymethyl) -1, 3-dioxan-2-one) and the mass of the double bond-bearing anhydride, more preferably 1%; the organic solvent is preferably N, N-Dimethylformamide (DMF); the temperature of the esterification reaction is preferably 100-135 ℃ and the time is preferably 8-10 h; the esterification reaction is preferably carried out under a protective atmosphere, preferably nitrogen. In the invention, taking anhydride with double bond as methacrylic anhydride as an example, the reaction formula of the esterification reaction is shown as formula A:
in the present invention, the thiol is pentaerythritol tetra-3-mercaptopropionate (Pentaerythritol tetrakis), trimethylolpropane tri (3-mercaptoacrylate) (Trimethylolpropane Tris), or 3,6-Dioxa-1,8-octanedithiol (3, 6-Dioxa-1, 8-octanedithiol). In the present invention, the molar ratio of the cyclic carbonate having a double bond to the thiol is preferably 1 to 4:1. in the present invention, the photoinitiator is preferably 2, 2-dimethoxy-2-phenylacetophenone; the mass of the photoinitiator is preferably 1 to 3% of the sum of the mass of the cyclic carbonate having a double bond and the mass of the thiol. In the present invention, the wavelength of the ultraviolet light is preferably 365nm, and the irradiation intensity is preferably 30mw/cm -2 The method comprises the steps of carrying out a first treatment on the surface of the The click reaction time is preferably 5 to 10 minutes. In the invention, taking the cyclic carbonate with double bonds as ethylene carbonate and the thiol as pentaerythritol tetra-3-mercaptopropionate as an example, the reaction formula of the click reaction is shown as a formula B:
the invention prepares the polyurethane monomer with a plurality of five-membered cyclic carbonates by click reaction of the cyclic carbonate with double bonds and mercaptan, and the reaction is fast and efficient.
The invention provides thermosetting non-isocyanate-based shape memory polyurethane, which is obtained by crosslinking reaction of non-isocyanate-based polyurethane monomer prepared by the technical scheme or non-isocyanate-based polyurethane monomer prepared by the preparation method of the technical scheme and poly-primary amine. In the present invention, the primary polyamine is preferably 1, 6-hexamethylenediamine (1, 6-Diaminohexane), tetraethylenepentamine (etraethylene pentamine), isophoronediamine (Isophorone diamine), trimethylolpropane tripropyleneglycol ether (amino-terminated) (trimethylolpropane Tris [ poly (propylene glycol), amine-terminated ] ether) or Tris (2-aminoethylamine) (Tris (2-aminoethyl) amine); the molar ratio of the non-isocyanate polyurethane monomer to the poly primary amine is preferably (2-3): (2-4), specifically based on a molar ratio of cyclic carbonate functional groups in the non-isocyanate polyurethane monomer to amine functional groups in the primary polyamine of 1:1. The non-isocyanate polyurethane provided by the invention has a shape memory effect and a programmable shape; and has excellent mechanical properties, namely Gao Jiangfei isocyanate polyurethane.
The invention provides a preparation method of thermosetting non-isocyanate-based shape memory polyurethane, which comprises the following steps:
mixing the non-isocyanate polyurethane monomer, the poly-primary amine and the organic solvent for crosslinking reaction to obtain a reactant; the temperature of the crosslinking reaction is 90-100 ℃;
and heating the reactants in sequence to remove the solvent and solidifying the reactants to obtain the thermosetting non-isocyanate-based shape memory polyurethane.
The invention mixes the non-isocyanate polyurethane monomer, the poly primary amine and the organic solvent to carry out crosslinking reaction under protective atmosphere to obtain a reactant. In the present invention, the amount of the primary polyamine is the same as that of the above technical scheme, and will not be described herein. In the present invention, the organic solvent preferably includes one or more of N, N-Dimethylformamide (DMF), N-methylpyrrolidone (NMP) and dimethylacetamide (DMAc), and the amount of the organic solvent is not particularly required in the present invention, so that the reaction can be smoothly performed. In the present invention, the time of the crosslinking reaction is preferably 10 to 48 hours, more preferably 12 to 48 hours; the crosslinking reaction is preferably carried out under a protective atmosphere, which is not particularly required in the present invention, and a protective atmosphere known to those skilled in the art, such as nitrogen, may be used. In the present invention, the specific operation of the crosslinking reaction is preferably: mixing the non-isocyanate polyurethane monomer with an organic solvent under the stirring condition to obtain a non-isocyanate polyurethane monomer solution; and adding the poly-primary amine into the non-isocyanate polyurethane monomer solution to carry out crosslinking reaction at 90-100 ℃ under the stirring condition. In the invention, taking the non-isocyanate polyurethane monomer with a structure shown in a formula V as an example, the primary polyamine is isophorone diamine, and the reaction formula of the crosslinking reaction is shown in a formula C:
after the reactant is obtained, the reactant is sequentially heated to remove the solvent and cured to obtain the thermosetting non-isocyanate-based shape memory polyurethane. The reactant is poured into a mould, preferably a polytetrafluoroethylene mould, for heating, solvent removal and solidification; the heating temperature for heating and removing the solvent is preferably 40-80 ℃, more preferably 60 ℃, and the time is preferably 20-60 h, more preferably 24-48 h; the curing temperature is preferably 90 to 110 ℃, more preferably 100 ℃, and the curing time is preferably 8 to 16 hours, more preferably 10 to 14 hours.
The preparation method of the thermosetting non-isocyanate-based shape memory polyurethane provided by the invention does not need a catalyst, and is simple in process, easy in condition control and convenient for large-scale production.
The invention also provides a recycling method of the thermosetting non-isocyanate-based shape memory polyurethane, which comprises the following steps:
and hot-pressing the thermosetting non-isocyanate-based shape memory polyurethane to be recovered to obtain the thermosetting non-isocyanate-based shape memory polyurethane to be recovered.
In the invention, the temperature of the hot pressing is 90-150 ℃, preferably 95-100 ℃; the pressure of the hot pressing is 0.5-3 MPa, preferably 1-2 MPa; the hot pressing time is 0.5-3 h, preferably 2.5-3 h.
The thermosetting non-isocyanate-based shape memory polyurethane provided by the invention can be recycled through simple hot pressing, so that the polyurethane is more durable and environment-friendly.
The non-isocyanate-based polyurethane monomer and the thermosetting non-isocyanate-based shape memory polyurethane provided by the present invention and the preparation and recycling methods thereof are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
A non-isocyanate polyurethane monomer is prepared by the following steps:
uniformly mixing 2.7g of ethylene carbonate, 2.9g of pentaerythritol tetra-3-mercaptopropionate and 60mg of photoinitiator (2, 2-dimethoxy-2-phenylacetophenone), and placing the mixed liquid under an ultraviolet lamp (the wavelength of ultraviolet light is 365nm, and the irradiation intensity is 30 mw/cm) -2 ) Reacting for 10min to obtain a monomer with four five-membered cyclic carbonates, namely a non-isocyanate polyurethane monomer, wherein the reaction formula is as follows:
a thermosetting non-isocyanate-based shape memory polyurethane is prepared by the following steps:
adding 15mL of DMF solvent into the non-isocyanate polyurethane monomer (with four five-membered cyclic carbonates), and mechanically stirring until the mixture is uniform to obtain a non-isocyanate polyurethane monomer solution; adding 2.043g of isophorone diamine into the non-isocyanate polyurethane monomer solution, and stirring for 48 hours at 90 ℃ to perform crosslinking reaction; pouring the reactant obtained by the reaction into a polytetrafluoroethylene mould, drying the polytetrafluoroethylene mould in an oven at 60 ℃ for 24 hours to remove the solvent, and then drying and curing the polytetrafluoroethylene mould at 100 ℃ for 12 hours to obtain the non-isocyanate-based shape memory polyurethane with the glass transition temperature of 68.1 ℃. The reaction formula is as follows:
example 2
A non-isocyanate polyurethane monomer is prepared by the following steps:
2.8g of hydroxymethyl dioxolone, 1.9g of dimethacrylate and 47mg of toluene sulfonic acid in N 2 Reacting at 135 ℃ for 6 hours to synthesize the cyclic carbonate with double bonds; uniformly mixing the obtained cyclic carbonate with double bond, 2.1g of 3,6-dioxa-1,8-octanedithiol and 60mg of photoinitiator (2, 2-dimethoxy-2-phenylacetophenone), and placing the mixed liquid under an ultraviolet lamp (wavelength of ultraviolet light is 365nm, irradiation intensity is 30 mw/cm) -2 ) Reacting for 5min to synthesize a monomer with double-ring carbonate, namely a non-isocyanate polyurethane monomer, wherein the reaction formula is as follows:
a thermosetting non-isocyanate-based shape memory polyurethane is prepared by the following steps:
adding 15mL of DMF solvent into the non-isocyanate polyurethane monomer (with double-ring carbonate) and mechanically stirring until the mixture is uniform to obtain a non-isocyanate polyurethane monomer solution; adding 1.2g of tri (2-amino ethylamine) into the non-isocyanate polyurethane monomer solution, and stirring for 36 hours at 90 ℃ to carry out crosslinking reaction; pouring the reactant obtained by the reaction into a polytetrafluoroethylene mould, drying the polytetrafluoroethylene mould in an oven at 60 ℃ for 24 hours to remove the solvent, and then drying and curing the polytetrafluoroethylene mould at 100 ℃ for 12 hours to obtain the non-isocyanate-based shape memory polyurethane with the glass transition temperature of 41.8 ℃. The reaction formula is as follows:
example 3
A non-isocyanate polyurethane monomer is prepared by the following steps:
uniformly mixing 2.7g ethylene carbonate, 3.2g trimethylolpropane tri (3-mercaptopropionate) and 60mg photoinitiator (2, 2-dimethoxy-2-phenylacetophenone), placing the mixed liquid under an ultraviolet lamp (the wavelength of ultraviolet light is 365nm, and the irradiation intensity is 30 mw/cm) -2 ) And (3) reacting for 10min to synthesize a monomer with three five-membered cyclic carbonates, namely a non-isocyanate polyurethane monomer, wherein the reaction formula is as follows:
a thermosetting non-isocyanate-based shape memory polyurethane is prepared by the following steps:
adding 15mL of DMF solvent into the non-isocyanate polyurethane monomer (with three five-membered cyclic carbonates), and mechanically stirring until the mixture is uniform to obtain a non-isocyanate polyurethane monomer solution; adding 1.4g of 1, 6-hexamethylenediamine into a non-isocyanate polyurethane monomer solution, stirring for 48 hours at 100 ℃ and carrying out crosslinking reaction; pouring the reactant obtained by the reaction into a polytetrafluoroethylene mould, drying the polytetrafluoroethylene mould in an oven at 60 ℃ for 24 hours to remove the solvent, and then drying and curing the polytetrafluoroethylene mould at 100 ℃ for 12 hours to obtain the non-isocyanate-based shape memory polyurethane with the glass transition temperature of 56.6 ℃. The reaction formula is as follows:
performance testing was performed on the non-isocyanate based shape memory polyurethanes prepared in examples 1-3:
shape memory effect test: FIG. 1 is a graph showing the shape memory effect of the polyurethane prepared in example 1. As shown in fig. 1, the initial polyurethane sample is horizontal, and can be given an arbitrary shape (e.g., curved) when placed in an environment of 90 ℃, and then can be fixed when placed at room temperature, and the shape remains unchanged after a period of time, which means that the polyurethane sample has a good shape fixing rate and shape retention property, and then can be restored when placed in an environment of 90 ℃, and the restoring time varies according to the difficulty of the shape given thereto, but generally does not exceed 20s. The polyurethanes prepared in examples 2 to 3 also have a similar good shape memory effect as tested.
Mechanical property test: the non-isocyanate based shape memory polyurethanes prepared in examples 1-3 were tested for mechanical properties including Tensile stress (Tensile strain), tensile strain (Tensile strain) and Young's modulus (Young's modulus), using a universal stretcher, and the test results are shown in table 1:
TABLE 1 mechanical Properties of non-isocyanate based shape memory polyurethanes prepared in examples 1-3
Recyclability test: the non-isocyanate-based shape memory polyurethane of example 1 was mashed and put into a mold for hot pressing at 100℃under a pressure of 2MPa for 3 hours, and the results are shown in FIG. 2. As can be seen from fig. 2, the polyurethane produced has very good recycling and reprocessing properties. The polyurethanes prepared in examples 2 to 3 have the same properties.
From the above examples, it can be seen that the polyurethane produced by the crosslinking reaction of the non-isocyanate polyurethane monomer and the poly-primary amine has a shape memory effect; the polyurethane has excellent mechanical properties, namely Gao Jiangfei isocyanate polyurethane; and recycling can be realized through simple hot pressing.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (10)
1. A non-isocyanate-based polyurethane monomer characterized by having the structure of formula iii:
formula III.
2. The method for preparing the non-isocyanate-based polyurethane monomer according to claim 1, comprising the steps of:
mixing cyclic carbonate with double bonds, mercaptan and a photoinitiator, and carrying out click reaction under ultraviolet irradiation to obtain the non-isocyanate polyurethane monomer;
the cyclic carbonate with double bonds has a structure shown in a formula IV, wherein R 3 is-CH 3 The method comprises the steps of carrying out a first treatment on the surface of the The mercaptan is 3,6-dioxa-1, 8-octanedithiol;
formula IV.
3. The preparation method according to claim 2, wherein the molar ratio of the cyclic carbonate having a double bond to the thiol is 1 to 4:1, a step of; the photoinitiator is 2, 2-dimethoxy-2-phenylacetophenone; the mass of the photoinitiator is 1-3% of the sum of the mass of the cyclic carbonate with double bonds and the mass of the mercaptan.
4. A method according to claim 2 or 3, wherein the ultraviolet light has a wavelength of 365nm and an irradiation intensity of 30mw/cm -2 The method comprises the steps of carrying out a first treatment on the surface of the The click reaction time is 5-10 min.
5. The thermosetting non-isocyanate-based shape memory polyurethane is characterized in that the non-isocyanate-based polyurethane monomer prepared by the non-isocyanate-based polyurethane monomer according to claim 1 or the non-isocyanate-based polyurethane monomer prepared by the preparation method according to any one of claims 2-4 is obtained through crosslinking reaction with a poly-primary amine, and the poly-primary amine is tris (2-aminoethylamine).
6. The thermoset non-isocyanate based shape memory polyurethane of claim 5, wherein the molar ratio of non-isocyanate based polyurethane monomer to primary polyamine is (2-3): (2-4).
7. A process for the preparation of a thermoset non-isocyanate based shape memory polyurethane as claimed in claim 5 or 6 comprising the steps of:
mixing the non-isocyanate polyurethane monomer, the poly-primary amine and the organic solvent for crosslinking reaction to obtain a reactant; the temperature of the crosslinking reaction is 90-100 ℃;
and heating the reactants in sequence to remove the solvent and solidifying the reactants to obtain the thermosetting non-isocyanate-based shape memory polyurethane.
8. The preparation method according to claim 7, wherein the organic solvent comprises one or more of N, N-dimethylformamide, N-methylpyrrolidone and dimethylacetamide; the time of the crosslinking reaction is 10-48 h.
9. The preparation method according to claim 7, wherein the heating temperature for heating the solvent is 40-80 ℃ for 20-60 hours; the curing temperature is 90-110 ℃ and the curing time is 8-16 h.
10. A method for recycling a thermosetting non-isocyanate based shape memory polyurethane according to claim 5 or 6, comprising the steps of:
hot-pressing the thermosetting non-isocyanate-based shape memory polyurethane to be recycled to obtain recycled thermosetting non-isocyanate-based shape memory polyurethane; the hot pressing temperature is 90-150 ℃, the pressure is 0.5-3 MPa, and the time is 0.5-3 h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210543304.7A CN114773307B (en) | 2022-05-18 | 2022-05-18 | Non-isocyanate polyurethane monomer and thermosetting non-isocyanate shape memory polyurethane, and preparation and recycling methods thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210543304.7A CN114773307B (en) | 2022-05-18 | 2022-05-18 | Non-isocyanate polyurethane monomer and thermosetting non-isocyanate shape memory polyurethane, and preparation and recycling methods thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114773307A CN114773307A (en) | 2022-07-22 |
| CN114773307B true CN114773307B (en) | 2024-01-26 |
Family
ID=82409491
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210543304.7A Active CN114773307B (en) | 2022-05-18 | 2022-05-18 | Non-isocyanate polyurethane monomer and thermosetting non-isocyanate shape memory polyurethane, and preparation and recycling methods thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114773307B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000319504A (en) * | 1999-05-11 | 2000-11-21 | Japan Chemical Innovation Institute | New polyhydroxyurethane and its production |
| JP2016050303A (en) * | 2014-08-29 | 2016-04-11 | 日本合成化学工業株式会社 | Active energy ray-curable composition and production method for cured coating film thereof |
| CN106832266A (en) * | 2017-02-24 | 2017-06-13 | 广东工业大学 | A kind of aqueous polyurethane and UV-curable waterborne polyurethane coating and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8912303B1 (en) * | 2011-11-03 | 2014-12-16 | U.S. Department Of Energy | Poly(hydroxyl urethane) compositions and methods of making and using the same |
-
2022
- 2022-05-18 CN CN202210543304.7A patent/CN114773307B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000319504A (en) * | 1999-05-11 | 2000-11-21 | Japan Chemical Innovation Institute | New polyhydroxyurethane and its production |
| JP2016050303A (en) * | 2014-08-29 | 2016-04-11 | 日本合成化学工業株式会社 | Active energy ray-curable composition and production method for cured coating film thereof |
| CN106832266A (en) * | 2017-02-24 | 2017-06-13 | 广东工业大学 | A kind of aqueous polyurethane and UV-curable waterborne polyurethane coating and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| Access to nonisocyanate poly(thio)urethanes: A comparative study;Vincent Besse et al;Journal of Polymer Science Part A Polymer Chemistry;第51卷(第15期);3284-3296 * |
| Tunable poly(hydroxyl urethane) from CO2-Based intermediates using thiol-ene chemistry;Tang, C. N. et al;Journal of Polymer Science, Part A: Polymer Chemistry;第49卷(第8期);2024-2032 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114773307A (en) | 2022-07-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Fang et al. | Light-and heat-triggered polyurethane based on dihydroxyl anthracene derivatives for self-healing applications | |
| Rossegger et al. | Digital light processing 3D printing with thiol–acrylate vitrimers | |
| Zhang et al. | Intrinsic self-healing of covalent polymers through bond reconnection towards strength restoration | |
| Ni et al. | Morphology and thermal properties of inorganic–organic hybrids involving epoxy resin and polyhedral oligomeric silsesquioxanes | |
| Tian et al. | A thermally remendable epoxy resin | |
| Fang et al. | Thermal-and mechanical-responsive polyurethane elastomers with self-healing, mechanical-reinforced, and thermal-stable capabilities | |
| CN109370131B (en) | Dynamic topological interlocking dual network and preparation method and application thereof | |
| Zhang et al. | Room temperature self-healable epoxy elastomer with reversible alkoxyamines as crosslinkages | |
| TWI305785B (en) | Acrylated semi-crystalline hyperbranched polyurethane oligomer and preparation method thereof | |
| WO2015119688A2 (en) | Shape-memory-self-healing polymers (smshps) | |
| CN111253572B (en) | Preparation method of bismaleimide-based thermosetting shape memory resin | |
| CN109679103B (en) | Dynamic thermoreversible and remodelable polysiloxane elastomer material and preparation method thereof | |
| CN111349257B (en) | Method for constructing 3D shape memory material through optical programming, obtained product and application | |
| CN103709114B (en) | A kind of double bond containing benzoxazine compound, preparation method and application thereof | |
| Li et al. | Design of well-defined shape memory networks with high homogeneity: towards advanced shape memory polymeric materials | |
| CN109232838B (en) | Preparation method of novel biodegradable rapid photocuring molding material | |
| CN107428896A (en) | For polymerizeing the ring-type dynamic polyureas of urea production | |
| CN115403764B (en) | Polyaryletherketone compound containing epoxy group and preparation method thereof | |
| Wei et al. | Fabrication of castor oil-based hyperbranched urethane acrylate UV-curable coatings via thiol-ene click reactions | |
| CN112442158A (en) | Bio-based degradable benzoxazine resin, preparation method thereof, cured resin thereof, compound thereof and degradation method | |
| Liu et al. | Synthesis and characterization of interpenetrating polymer networks (IPNs) based on UV curable resin and blocked isocyanate/polyols | |
| CN112341349A (en) | Functional group-containing benzoxazine oligomer, low-temperature crosslinked benzoxazine resin and preparation method thereof | |
| CN114773307B (en) | Non-isocyanate polyurethane monomer and thermosetting non-isocyanate shape memory polyurethane, and preparation and recycling methods thereof | |
| Gong et al. | A novel bio-based degradable, reinforced vitrimer regulated by intramolecular hydrogen bonding | |
| CN108299623B (en) | Method for preparing recyclable epoxy resin by using body click chemical reaction |
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 |