CN117164817B - Autocatalysis type cardanol-based self-repairing and recyclable polymer and preparation method thereof - Google Patents
Autocatalysis type cardanol-based self-repairing and recyclable polymer and preparation method thereof Download PDFInfo
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- JOLVYUIAMRUBRK-UHFFFAOYSA-N 11',12',14',15'-Tetradehydro(Z,Z-)-3-(8-Pentadecenyl)phenol Natural products OC1=CC=CC(CCCCCCCC=CCC=CCC=C)=C1 JOLVYUIAMRUBRK-UHFFFAOYSA-N 0.000 title claims abstract description 115
- YLKVIMNNMLKUGJ-UHFFFAOYSA-N 3-Delta8-pentadecenylphenol Natural products CCCCCCC=CCCCCCCCC1=CC=CC(O)=C1 YLKVIMNNMLKUGJ-UHFFFAOYSA-N 0.000 title claims abstract description 115
- FAYVLNWNMNHXGA-UHFFFAOYSA-N Cardanoldiene Natural products CCCC=CCC=CCCCCCCCC1=CC=CC(O)=C1 FAYVLNWNMNHXGA-UHFFFAOYSA-N 0.000 title claims abstract description 115
- PTFIPECGHSYQNR-UHFFFAOYSA-N cardanol Natural products CCCCCCCCCCCCCCCC1=CC=CC(O)=C1 PTFIPECGHSYQNR-UHFFFAOYSA-N 0.000 title claims abstract description 115
- JOLVYUIAMRUBRK-UTOQUPLUSA-N Cardanol Chemical compound OC1=CC=CC(CCCCCCC\C=C/C\C=C/CC=C)=C1 JOLVYUIAMRUBRK-UTOQUPLUSA-N 0.000 title claims abstract description 68
- 229920000642 polymer Polymers 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 238000005844 autocatalytic reaction Methods 0.000 title description 2
- 238000000034 method Methods 0.000 claims abstract description 26
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000002994 raw material Substances 0.000 claims abstract description 13
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims abstract description 11
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000007259 addition reaction Methods 0.000 claims abstract description 8
- 239000003054 catalyst Substances 0.000 claims description 34
- -1 cardanol amino polyol Chemical class 0.000 claims description 29
- 150000007519 polyprotic acids Polymers 0.000 claims description 24
- 229920005862 polyol Polymers 0.000 claims description 21
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 20
- 239000004593 Epoxy Substances 0.000 claims description 14
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 claims description 12
- 239000000178 monomer Substances 0.000 claims description 10
- 230000009471 action Effects 0.000 claims description 8
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 8
- 238000003786 synthesis reaction Methods 0.000 claims description 8
- 125000003700 epoxy group Chemical group 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 7
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 claims description 6
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 5
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 claims description 4
- 230000002194 synthesizing effect Effects 0.000 claims description 4
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 claims description 3
- 150000003077 polyols Chemical class 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000001308 synthesis method Methods 0.000 claims description 3
- CEYYIKYYFSTQRU-UHFFFAOYSA-M trimethyl(tetradecyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCC[N+](C)(C)C CEYYIKYYFSTQRU-UHFFFAOYSA-M 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 12
- 239000003822 epoxy resin Substances 0.000 abstract description 10
- 229920000647 polyepoxide Polymers 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 3
- 238000006116 polymerization reaction Methods 0.000 abstract description 3
- 238000011161 development Methods 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 abstract description 2
- 238000001311 chemical methods and process Methods 0.000 abstract 1
- 238000005265 energy consumption Methods 0.000 abstract 1
- 238000006735 epoxidation reaction Methods 0.000 abstract 1
- 239000003208 petroleum Substances 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 14
- 239000000047 product Substances 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 4
- 230000008439 repair process Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- 238000003556 assay Methods 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
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- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
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- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 239000002250 absorbent Substances 0.000 description 2
- 230000002745 absorbent Effects 0.000 description 2
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- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
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- 238000002390 rotary evaporation Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
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- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
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Classifications
-
- 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
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- Epoxy Resins (AREA)
Abstract
The invention provides an autocatalytic cardanol-based self-repairing and recyclable polymer and a preparation method thereof, and belongs to the technical field of development and preparation of bio-based self-repairing materials. The invention takes cardanol, epichlorohydrin, diethanolamine and mercaptopropionic acid as main raw materials, and adopts epoxidation, addition reaction, click chemistry method and melt polymerization method to synthesize the self-catalyzed cardanol-based self-repairing polymer. The main raw materials of the invention are renewable and do not depend on petroleum; the preparation process is simple and reasonable, and the energy consumption is low; the product has good thermal stability, can be recycled and is easy to degrade and recycle. Test results show that the self-repairable epoxy resin prepared by the invention has excellent self-repairing effect and recoverability.
Description
Technical Field
The invention relates to the technical field of development and preparation of bio-based self-repairing materials, in particular to an autocatalytic cardanol-based self-repairing and recyclable polymer and a preparation method thereof.
Background
The preparation of polymeric materials using renewable resources instead of traditional non-renewable petrochemical resources as raw materials is becoming a growing research hotspot. Thermosetting epoxy resins are important polymer materials, and are widely used in the fields of adhesives, paints, molded plastics, composite materials, and the like because of their excellent adhesive properties, heat/chemical resistance, insulation, mechanical strength, and the like. However, epoxy resin can hardly undergo secondary processing due to its unique three-dimensional network structure during molding and use, cannot be recovered after the end of service life, and the inside of the material inevitably has microcracks, so that only waste treatment can be performed. Research shows that the dynamic covalent bond is introduced into the polymer material, so that the self-repairing can be performed after the internal damage of the material, and the structure and functional material with longer service life, more reliable performance and higher economic value can be obtained. Therefore, it is very necessary to study how to be compatible with the excellent mechanical properties, self-repairing, recycling and reprocessing of epoxy resin, and is also an ideal treatment method for solving various environmental problems such as fossil energy crisis, prolonging the service life of materials and the like.
The relatively widely studied bio-based recyclable polymers today mostly require the introduction of external catalysts during the curing process. The external catalyst has two important problems, namely, the toxicity is high, and the external catalyst can threaten the health of human bodies; secondly, the catalyst is difficult to dissolve in epoxy resin, even has the problems of phase separation and the like after solidification, and if the catalyst is applied to a coating and a binder, the catalyst may corrode a substrate. In addition, the stability of external catalysts is poor, and the problems of catalyst leaching, hydrolysis and the like have long plagued people. Therefore, the method for searching the bio-based epoxy monomer precursor for replacing the external catalyst and synthesizing the self-catalytic cardanol-based self-repairing and recyclable polymer has important significance.
Disclosure of Invention
In view of the above, the invention aims to provide an autocatalytic cardanol-based self-repairing and recyclable polymer and a preparation method thereof, and aims to overcome the defects that the traditional epoxy resin is easy to generate microcracks, difficult to carry out secondary processing and the like, and a catalyst-free bio-based self-repairing and recyclable material of a homogeneous system is synthesized by introducing dynamic ester bonds in a polymerization process, so that a product obtained by the method has a higher repairing effect.
In order to achieve the above object, the present invention provides the following technical solutions: the preparation method of the autocatalytic cardanol-based self-repairing and recyclable polymer comprises the following steps:
(1) Under the inert gas atmosphere, using cardanol and epichlorohydrin as raw materials, and under the action of a catalyst, synthesizing cardanol glycidyl ether by epoxy synthesis of cardanol;
(2) Carrying out addition reaction on the obtained cardanol glycidyl ether and diethanolamine to obtain cardanol amino polyol;
(3) Under the condition of ultraviolet light, taking the obtained cardanol amino polyol and mercaptopropionic acid as raw materials, and adopting a click chemical synthesis method under the action of a catalyst to obtain cardanol amino polybasic acid;
(4) And mixing and uniformly stirring the synthesized cardanol amino polybasic acid and an epoxy monomer, and curing to obtain the self-catalytic cardanol self-repairing and recyclable polymer.
Preferably, in the step (1), the molar ratio of cardanol to epichlorohydrin is 1 (6-10); the dosage of the catalyst is 2% of the mass of cardanol.
Preferably, the catalyst in the step (1) is at least one of benzyltriethylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium chloride, dodecyltrimethylammonium chloride, tetradecyltrimethylammonium chloride and triphenylphosphine.
Preferably, in the step (2), the molar ratio of cardanol glycidyl ether to diethanolamine is 1: (0.8-1.2).
Preferably, in the step (2), the addition reaction temperature is 70±5 ℃ and the reaction time is 4 hours.
Preferably, in the step (3), the molar ratio of the mercaptopropionic acid to the cardanol amine-based polyol is (2-3): 1; the dosage of the catalyst is 2% of the total mass of the cardanol amino polyol and the mercaptopropionic acid.
Preferably, the catalyst of step (3) is photoinitiator-184 or photoinitiator-1173.
Preferably, in the step (3), the reaction time in the click chemistry synthesis method is 12-15h.
Preferably, in the step (4), when the cardanol amine-based polybasic acid is mixed with the epoxy monomer for curing, the molar ratio of epoxy groups to carboxyl groups is 1 (0.25-1).
The invention also provides the autocatalytic cardanol-based self-repairing and recyclable polymer prepared by the preparation method.
The beneficial technical effects are as follows:
1. the invention uses the bio-based cardanol as the main raw material, has low production cost, avoids the dependence on petrochemical raw materials, reduces the pollution of chemical synthesis technology to the environment, and greatly improves the bio-based content and the environmental protection of the target epoxy resin.
2. The invention synthesizes cardanol amino polybasic acid by adopting click reaction, has simple reaction process, no side reaction and byproduct generation, mild reaction condition, high product purity and stable quality.
3. The invention solves the defects of easy generation of microcracks, difficult secondary processing and the like of the traditional epoxy resin, and synthesizes the catalyst-free bio-based self-repairing recyclable material of a homogeneous system by introducing dynamic ester bonds in the polymerization process.
Drawings
FIG. 1 is an infrared spectrum of cardanol amine-based polybasic acid and its process products prepared in example 1;
FIG. 2 is a nuclear magnetic resonance hydrogen spectrum of cardanol amine-based polybasic acid and its process product prepared in example 1;
FIG. 3 is a chemical structural formula of cardanol amine-based polybasic acid and its process products prepared in example 1.
Detailed Description
The invention provides a preparation method of an autocatalytic cardanol-based self-repairing and recyclable polymer, which comprises the following steps:
(1) Under the inert gas atmosphere, using cardanol and epichlorohydrin as raw materials, and under the action of a catalyst, synthesizing cardanol glycidyl ether by epoxy synthesis of cardanol;
(2) Carrying out addition reaction on the obtained cardanol glycidyl ether and diethanolamine to obtain cardanol amino polyol;
(3) Under the condition of ultraviolet light, taking the obtained cardanol amino polyol and mercaptopropionic acid as raw materials, and adopting a click chemical synthesis method under the action of a catalyst to obtain cardanol amino polybasic acid;
(4) And mixing and uniformly stirring the synthesized cardanol amino polybasic acid and an epoxy monomer, and curing to obtain the self-catalytic cardanol self-repairing and recyclable polymer.
In the invention, cardanol and epichlorohydrin are used as raw materials in an inert gas atmosphere, and cardanol is epoxy-synthesized into cardanol glycidyl ether under the action of a catalyst.
In the present invention, the inert atmosphere is preferably one or two or more of nitrogen, helium or argon; the molar ratio of cardanol to epichlorohydrin is preferably 1 (6-10), more preferably 1:7, preparing a base material; the dosage of the catalyst is preferably 2% of the mass of cardanol; the catalyst is preferably at least one of benzyltriethylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium chloride, dodecyltrimethylammonium chloride, tetradecyltrimethylammonium chloride and triphenylphosphine, more preferably benzyltriethylammonium chloride.
Specifically, the cardanol glycidyl ether synthesized by the cardanol epoxy compound comprises the following steps:
uniformly mixing cardanol and epichlorohydrin under an inert gas atmosphere, heating to a first temperature, adding a catalyst to react for 2 hours, cooling to a second temperature, adding sodium hydroxide, and continuing to react for 3 hours to obtain cardanol glycidyl ether.
In the present invention, the first reaction temperature is preferably 120 ℃, and the second reaction temperature is preferably 60 ℃; in the invention, the molar ratio of the sodium hydroxide to the cardanol is preferably 1:1; in the invention, after the reaction is finished, the cardanol glycidyl ether can be prepared by filtering the reaction product.
After the cardanol glycidyl ether is obtained, the cardanol glycidyl ether and diethanolamine are subjected to addition reaction to obtain the cardanol amino polyol.
In the present invention, the molar ratio of cardanol glycidyl ether to diethanolamine is preferably 1: (0.8-1.2), more preferably 1:1, the addition reaction temperature is preferably 70.+ -. 5 ℃ and the reaction time is 4 hours.
In the invention, after the reaction is finished, the method further comprises the steps of dissolving an organic phase, extracting with ethyl acetate, washing to be neutral, adding a water absorbent, drying, filtering, and removing a solvent to obtain the cardanol amino polyol.
After cardanol amino polyol is obtained, under the ultraviolet light condition, the cardanol amino polyol and mercaptopropionic acid are taken as raw materials, and a click chemical synthesis method is adopted under the action of a catalyst to obtain the cardanol amino acid.
In the invention, the wavelength of the ultraviolet light is 300-350 nanometers; the molar ratio of the mercaptopropionic acid to the cardanol amine-based polyol is preferably (2-3): 1, more preferably 3:1; the dosage of the catalyst is 2% of the total mass of the cardanol amino polyol and the mercaptopropionic acid; the catalyst is photoinitiator-184 or photoinitiator-1173; the reaction time in the click chemistry synthesis method is preferably 12-15h.
In the invention, after the reaction is finished, the method also comprises impurity removal of the product, wherein the impurity removal is to remove redundant mercaptopropionic acid from the reaction solution through rotary evaporation at 80 ℃ to obtain cardanol amino poly-acid.
After the cardanol amino polybasic acid is obtained, the synthesized cardanol amino polybasic acid and the epoxy monomer are mixed and stirred uniformly, and the self-catalytic cardanol based self-repairing and recyclable polymer is obtained after curing.
In the invention, when the cardanol amino polybasic acid is mixed with an epoxy monomer for curing, the molar ratio of epoxy groups to carboxyl groups is preferably 1 (0.25-1), more preferably 1 (0.5-1).
In the present invention, the epoxy monomer is any epoxy monomer, more preferably bisphenol a diglycidyl ether.
In the present invention, the curing is sequentially 100℃for 2 hours, 120℃for 2 hours, 140℃for 2 hours and 160℃for 4 hours.
The invention also provides the autocatalytic cardanol-based self-repairing and recyclable polymer prepared by the preparation method.
The invention also includes subjecting the resulting polymer to self-healing assays and recovery assays. Specifically, the self-repair assay was performed as follows: scratch experiments are carried out by using a surgical blade, and repair is carried out at 180 ℃ for 5-15min.
The recovery measurement was performed as follows: pulverizing the epoxy resin cured product, and molding at 180-200deg.C and 15MPa for 2-3 hr.
For a better understanding of the present invention, the following examples are further illustrated, but are not limited to the following examples.
Example 1
Preparation of autocatalytic cardanol-based self-repairing and recyclable polymer
1) Uniformly mixing cardanol and epichlorohydrin in a molar ratio of 1:7 under nitrogen, heating to 120 ℃, adding benzyl triethyl ammonium chloride in an amount of 2% of the cardanol mass, and reacting for 2 hours. And then cooling to 60 ℃, adding sodium hydroxide with the same molar weight as cardanol, continuing to react for 3 hours, and filtering a reaction product after the reaction is finished to obtain the cardanol glycidyl ether.
2) Uniformly mixing cardanol glycidyl ether and diethanolamine in a molar ratio of 1:1, heating to 70 ℃ and reacting for 4 hours. After the reaction is finished, the organic phase is dissolved and extracted by ethyl acetate, then washed to be neutral, added with water absorbent for drying, filtered, and the solvent is removed to obtain the cardanol amino polyol.
3) Uniformly mixing cardanol amino polyol and mercaptopropionic acid in a molar ratio of 1:3, adding a catalyst which is a photoinitiator 1173, wherein the dosage of the catalyst is 2% of the total mass of the cardanol amino polyol and the mercaptopropionic acid. The reaction was carried out for 12h under ultraviolet light having a wavelength of 320 nm. And removing excessive mercaptopropionic acid by rotary evaporation at 80 ℃ to obtain cardanol amino polybasic acid.
4) Bisphenol A diglycidyl ether and synthetic cardanol amino polybasic acid are prepared by the following steps of: carboxyl=1:1, and is uniformly mixed and stirred, and is sequentially solidified at 100 ℃/2 hours, 120 ℃/2 hours, 140 ℃/2 hours and 160 ℃/4 hours to obtain the autocatalytic cardanol-based self-repairing and recyclable polymer.
The structure of the intermediate product prepared by the method is determined, and the determination method adopted by the method is infrared spectrum (FTIR) and nuclear magnetic resonance hydrogen spectrum @ 1 H-NMR)。
FIGS. 1 and 2 show the infrared spectrum (FTIR) and nuclear magnetic resonance hydrogen spectrum of cardanol amine-based polybasic acid and its process product obtained in example 1 1 H-NMR), fig. 3 shows the chemical structural formula of the cardanol amino polyacid obtained in example 1 and its process products. Can be used in infrared spectrum of cardanolTo observe the distribution of the phenolic hydroxyl groups (3337 cm -1 ) And c=c (3008, 911,873cm -1 ) Is not shown in the figure). In the reaction from cardanol to cardanol glycidyl ether, the phenolic hydroxyl group (3337 cm -1 ) The absorption peak disappeared and epoxy groups (910 cm) -1 ) Is not shown in the figure). In the reaction from cardanol glycidyl ether to cardanol amino polyol, hydroxyl group (3345 cm -1 ) The absorption peak reappears. Furthermore, at 3008cm -1 And 878cm -1 The c=c peak at the position disappeared, and a broader carboxyl peak (1729 cm -1 ) Indicating that the cardanol amino polybasic acid is successfully prepared. In addition, NMR spectra of cardanol glycidyl ether, cardanol amino polyol, cardanol amino polybasic acid showed that characteristic chemical shifts at 5.2-5.4ppm, 5.7-5.8ppm and 4.9-5.0ppm correspond to carbon-carbon double bonds (c=c), respectively. After the final reaction, the peaks of the double bonds of the product to be obtained completely disappear. Therefore, the method can successfully prepare the cardanol amino polybasic acid.
Example 2
The difference from example 1 is that the molar ratio of epoxy groups to carboxyl groups in the bisphenol A diglycidyl ether of step (4) to the synthesized cardanol amine-based polybasic acid is replaced with 1:0.75.
Example 3
The difference from example 1 is that the molar ratio of epoxy groups to carboxyl groups in the bisphenol A diglycidyl ether and the synthesized cardanol amine-based polybasic acid in step (4) is replaced with 1:0.5.
Example 4
The difference from example 1 is that the molar ratio of epoxy groups to carboxyl groups in the bisphenol A diglycidyl ether and the synthesized cardanol amine-based polybasic acid in step (4) is replaced with 1:0.25.
Example 5
The difference from example 2 is that the catalyst in step (3) is replaced with photoinitiator 1173 and photoinitiator 184.
Example 6
The difference from example 5 is that the reaction time of step (3) is replaced by 15h with 12h.
Example 7
The difference from example 2 is that the catalyst in step (1) is benzyl triethyl ammonium chloride instead of tetrabutyl ammonium bromide, the amount is unchanged.
Example 8
The difference from example 2 is that the molar ratio of cardanol to epichlorohydrin in step (1) was changed to 1:10.
Characterization of physical Properties of the products obtained according to the invention
1. The autocatalytic cardanol-based self-repairing and recyclable polymers prepared in examples 1-8 were tested for self-repairing properties by the following method: scratch experiments are carried out by using a surgical blade, and repair is carried out at 180 ℃ for 5-15min.
TABLE 1 characterization of the self-healing properties of the self-catalyzed cardanol-based and recyclable polymers prepared in examples 1-8
| Numbering device | Tensile Strength | Elongation at break | Initial scratch depth | Depth of scratch after repair | Self-repair rate | Repair time |
| Example 1 | 1.5MPa | 96％ | 52.8μm | 2.3μm | 96％ | 15min |
| Example 2 | 1.9MPa | 161％ | 32.5μm | 2.4μm | 93％ | 15min |
| Example 3 | 10.8MPa | 172％ | 42.6μm | 6.1μm | 86％ | 15min |
| Example 4 | 57.8MPa | 4％ | 35.4μm | 20.2μm | 43％ | 15min |
| Example 5 | 1.8MPa | 152％ | 40.8μm | 2.4μm | 100％ | 15min |
| Example 6 | 2.0MPa | 165％ | 45.2μm | 2.5μm | 95％ | 15min |
| Example 7 | 1.9MPa | 172％ | 36.7μm | 2.2μm | 94％ | 15min |
| Example 8 | 2.0MPa | 156％ | 38.4μm | 2.2μm | 95％ | 15min |
As can be seen from Table 1, the bio-based self-repairing materials obtained by different proportions in examples 1 to 8 have higher self-repairing rate at 180 ℃ and a self-repairing time of 15min.
2. The autocatalytic cardanol-based self-repairing and recyclable polymer prepared in examples 1-8 was subjected to a recyclable property test, which was carried out as follows: pulverizing the epoxy resin cured product, and molding at 180-200deg.C and 15MPa for 2-3 hr.
TABLE 2 characterization of the recoverable Properties of the self-catalyzed cardanol-based self-repair and recoverable polymers prepared in examples 1-8
As can be seen from Table 2, the bio-based self-healing materials obtained by different proportions in examples 1 to 8 were higher in recovery efficiency at 180℃except for example 4.
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 (9)
1. The preparation method of the autocatalytic cardanol-based self-repairing and recyclable polymer is characterized by comprising the following steps of:
(1) Under the inert gas atmosphere, using cardanol and epichlorohydrin as raw materials, and under the action of a catalyst, synthesizing cardanol glycidyl ether by epoxy synthesis of cardanol;
(2) Carrying out addition reaction on the obtained cardanol glycidyl ether and diethanolamine to obtain cardanol amino polyol;
(3) Under the condition of ultraviolet light, taking the obtained cardanol amino polyol and mercaptopropionic acid as raw materials, and adopting a click chemical synthesis method under the action of a catalyst to obtain cardanol amino polybasic acid;
(4) Mixing and uniformly stirring the synthesized cardanol amino polybasic acid and an epoxy monomer, and curing to obtain an autocatalytic cardanol-based self-repairing and recyclable polymer;
in the step (3), the molar ratio of the mercaptopropionic acid to the cardanol amino polyol is (2-3) 1;
in the step (4), when the cardanol amino polybasic acid is mixed with an epoxy monomer for curing, the molar ratio of epoxy groups to carboxyl groups is 1 (0.5-1).
2. The preparation method according to claim 1, wherein in the step (1), the molar ratio of cardanol to epichlorohydrin is 1 (6-10); the dosage of the catalyst is 2% of the mass of cardanol.
3. The preparation method according to claim 1 or 2, wherein the catalyst in the step (1) is at least one of benzyltriethylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium chloride, dodecyltrimethylammonium chloride, tetradecyltrimethylammonium chloride and triphenylphosphine.
4. The method according to claim 1, wherein in the step (2), the molar ratio of cardanol glycidyl ether to diethanolamine is 1: (0.8-1.2).
5. The method according to claim 1, wherein in the step (2), the addition reaction temperature is 70.+ -. 5 ℃ and the reaction time is 4 hours.
6. The method according to claim 1, wherein in the step (3), the catalyst is used in an amount of 2% of the total mass of the cardanol-based polyol and mercaptopropionic acid.
7. The method of claim 1 or 6, wherein the catalyst in step (3) is photoinitiator-184 or photoinitiator-1173.
8. The method according to claim 1, wherein the reaction time in the click chemistry synthesis method in the step (3) is 12 to 15 hours.
9. The autocatalytic cardanol-based self-repairing and recyclable polymer prepared by the preparation method of any one of claims 1-8.
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