CN110724380A - Prepolymer for self-repairing wear-resistant material and application thereof - Google Patents
Prepolymer for self-repairing wear-resistant material and application thereof Download PDFInfo
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- CN110724380A CN110724380A CN201910907264.8A CN201910907264A CN110724380A CN 110724380 A CN110724380 A CN 110724380A CN 201910907264 A CN201910907264 A CN 201910907264A CN 110724380 A CN110724380 A CN 110724380A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08L79/085—Unsaturated polyimide precursors
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/24—Preparation of carboxylic acid esters by reacting carboxylic acids or derivatives thereof with a carbon-to-oxygen ether bond, e.g. acetal, tetrahydrofuran
- C07C67/26—Preparation of carboxylic acid esters by reacting carboxylic acids or derivatives thereof with a carbon-to-oxygen ether bond, e.g. acetal, tetrahydrofuran with an oxirane ring
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
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- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
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- C—CHEMISTRY; METALLURGY
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- C—CHEMISTRY; METALLURGY
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/12—Shape memory
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Abstract
The invention discloses a prepolymer for a self-repairing wear-resistant material and application thereof. The preparation method comprises the following steps of blending 2-allyl phenyl glycidyl ether and adipic acid in acetonitrile, and carrying out esterification reaction under the condition that quaternary ammonium salt is used as a catalyst to obtain bis (3- (2-allylphenoxy) -2-hydroxypropyl) adipate containing reversible dynamic groups; then evenly mixing the bis (3- (2-allylphenoxy) -2-hydroxypropyl) adipate, bismaleimide and aluminum oxide to obtain a prepolymer, and curing to obtain the self-repairing wear-resistant material. The self-repairing wear-resistant material prepared from the prepolymer disclosed by the invention not only has good wear resistance, heat resistance and mechanical properties, but also can be remolded under a hot-pressing condition, and has a wide application prospect.
Description
Technical Field
The invention relates to a prepolymer for a self-repairing wear-resistant material and application thereof, belonging to the field of thermosetting shape memory polymers and recyclable polymers.
Background
Recently, remoldable thermosetting SMPs developed cannot combine high heat resistance, high mechanical properties and good shape memory properties, and cannot be applied as wear-resistant materials. Bismaleimide is a thermosetting resin, has excellent mechanical property and heat resistance, is widely applied to the fields of aerospace and the like, and at present, wear-resistant materials based on bismaleimide resin are rarely reported, most of the bismaleimide resin is used as a modifier (the dosage is less than that of main resin) for modifying other substances, and the reasonable process for preparing the bismaleimide resin has good practical significance.
In addition, the thermosetting resin is considered to be formed once and cannot be recycled, once the wear-resistant product has defects such as cracks, the wear-resistant product can only be scrapped, and serious resource waste and environmental pollution are caused.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a remodelable shape memory bismaleimide resin prepolymer with good shape memory performance, high heat resistance and high tensile property and a preparation method thereof.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the preparation method of the prepolymer for the self-repairing wear-resistant material comprises the following steps:
(1) reacting 2-allylphenyl glycidyl ether with adipic acid in the presence of a quaternary ammonium salt to prepare bis (3- (2-allylphenoxy) -2-hydroxypropyl) adipate;
(2) stirring and mixing bis (3- (2-allylphenoxy) -2-hydroxypropyl) adipate, bismaleimide, a zinc compound and a filler system to obtain a prepolymer for the self-repairing wear-resistant material; the filler system includes an epoxy resin and alumina.
The prepolymer for the self-repairing wear-resistant material can be used for preparing the wear-resistant material, and specifically comprises the following steps:
(3) carrying out hot-pressing curing and post-treatment on the self-repairing wear-resistant material by using a prepolymer system to obtain the self-repairing wear-resistant material;
(4) and (3) carrying out hot pressing treatment on the self-repairing wear-resistant material after cracking to obtain the repaired wear-resistant material, thereby realizing self repairing of the self-repairing wear-resistant material.
Adding epoxy resin into ethanol containing aluminum oxide, stirring for 2 hours, and drying to obtain a filler system; the epoxy resin is bisphenol A epoxy resin; the particle size of the alumina is 0.3-0.4 micron. Preferably the mass of the epoxy resin is 10% of the mass of the alumina; the filler system of the invention is composed of epoxy resin and alumina.
In the invention, epoxy chloropropane is added into a mixed solution of 2-allyl phenol, sodium hydroxide, quaternary ammonium salt and tetrahydrofuran to react to prepare 2-allyl phenyl glycidyl ether.
In the technical scheme, in the step (1), the mass ratio of the 2-allyl phenyl glycidyl ether to the adipic acid to the quaternary ammonium salt is 120: 36-44: 5-10, the reaction temperature is 65-80 ℃, and the reaction time is 8-12 hours; in the step (2), the mass ratio of the bismaleimide to the bis (3- (2-allylphenoxy) -2-hydroxypropyl) adipate to the zinc compound to the filler system is 50: 70-75: 6-6.5: 4, the stirring temperature is 130-135 ℃, and the stirring time is 50-60 min.
In the technical scheme, the quaternary ammonium salt is tetramethyl ammonium bromide and/or tetrabutyl ammonium bromide; the zinc compound is zinc acetylacetonate hydrate; the bismaleimide is one or more of N, N '-4,4' -diphenylmethane bismaleimide, N '- (1, 4-phenylene) bismaleimide and N, N' -m-phenylene bismaleimide.
The invention also discloses an application of the prepolymer for the self-repairing wear-resistant material in preparing a wear-resistant object.
In the technical scheme, in the step (3), the hot pressing temperature is 150-220 ℃, the pressure is 1-5 MPa, the time is 3-6 h, the post-treatment temperature is 240 ℃, and the time is 2 h; in the step (4), the temperature of the hot pressing treatment is 260-280 ℃, the pressure is 30-35 MPa, and the time is 4-6 h.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention synthesizes a novel diallyl compound containing reversible dynamic groups, which is used for modifying bismaleimide and preparing a prepolymer containing reversible covalent bonds and used for a novel self-repairing wear-resistant material.
2. Compared with the traditional thermosetting SMPs, the remoldable shape memory bismaleimide prepared by the prepolymer disclosed by the invention has good shape memory performance and remoldability.
3. Compared with the remolding shape memory thermosetting resin reported in the existing literature, the prepolymer for the self-repairing wear-resistant material prepared by the prepolymer has outstanding heat resistance and is expressed by the initial thermal decomposition temperature (T)di) Up to 358 ℃ and glass transition temperature (T)g) Up to 139 ℃. The good heat resistance of the prepolymer for the self-repairing wear-resistant material benefits from the reasonable formula and preparation process of a resin system, and a large number of benzene rings in the resin and six-membered rings formed by curing and other annular structures.
4. Compared with the traditional 2,2' -diallyl bisphenol A, the synthesis of the novel diallyl compound-bis (3- (2-allylphenoxy) -2-hydroxypropyl) adipate provided by the invention does not need high-temperature rearrangement, and has the advantages of simple synthesis process and low energy consumption.
5. Compared with the traditional 2,2' -diallyl bisphenol A, the bis (3- (2-allylphenoxy) -2-hydroxypropyl) adipate synthesized by the method is non-bisphenol A, so that the risks of carcinogenesis, teratogenicity, influence on fertility and the like of the bisphenol A are avoided.
Drawings
FIG. 1 is a reaction scheme for the synthesis of 2-allylphenyl glycidyl ether and bis (3- (2-allylphenoxy) -2-hydroxypropyl) adipate prepared according to the present invention.
FIG. 2 shows the NMR spectrum of 2-allylphenyl glycidyl ether prepared in example 1 of the present invention: (1H-NMR）。
FIG. 3 is a drawing showing bis (3- (2-allylphenoxy) -2-hydroxypropyl) adipate prepared in example 1 of the present invention1H-NMR。
FIG. 4 is a high resolution mass spectrum of bis (3- (2-allylphenoxy) -2-hydroxypropyl) adipate prepared in example 1 of the present invention.
Detailed Description
The technical solution of the present invention is further described with reference to the accompanying drawings and examples.
The preparation method of the prepolymer for the self-repairing wear-resistant material comprises the following steps:
(1) reacting 2-allylphenyl glycidyl ether with adipic acid in the presence of a quaternary ammonium salt to prepare bis (3- (2-allylphenoxy) -2-hydroxypropyl) adipate;
(2) stirring and mixing bis (3- (2-allylphenoxy) -2-hydroxypropyl) adipate, bismaleimide, a zinc compound and a filler system to obtain a prepolymer for the self-repairing wear-resistant material; the filler system includes an epoxy resin and alumina.
Synthesis example
Mixing 120g of 2-allylphenol, 140g of sodium hydroxide, 10g of tetrabutylammonium bromide and 230g of tetrahydrofuran by mass, and carrying out heat preservation reaction for 1.5h at 35 ℃ under the stirring condition to obtain a solution A; slowly dropwise adding 270g of epoxy chloropropane into the solution A, and keeping the temperature at 35 ℃ and stirring for reacting for 6 hours; and after the reaction is finished, removing tetrahydrofuran and epichlorohydrin by vacuum rotary evaporation to obtain a crude product. Washing the crude product with saturated ammonium chloride solution (200 mL × 2) and deionized water (200 mL × 2), and separating and purifying with chromatographic column to obtain yellow transparent liquid, i.e. 2-allyl phenyl glycidyl ether, with yield of about 93%, according to the reaction formula1H-NMR is shown in the attached figures 1 and 2 respectively. Mixing 120g of 2-allyl phenyl glycidyl ether, 40g of adipic acid, 10g of tetrabutylammonium bromide and 230g of acetonitrile by mass, and carrying out heat preservation reaction for 8 hours at 70 ℃ under the stirring condition; after the reaction is finished, removing acetonitrile by vacuum rotary evaporation to obtain a crude product. Washing the crude product with saturated sodium bicarbonate solution (200 mL × 2) and deionized water (200 mL × 2), and purifying with chromatographic column to obtain yellow transparent viscous liquid, i.e. bis (3- (2-allylphenoxy) -2-hydroxypropyl) adipate with yield of 87.2%, according to the reaction formula,1H-NMR and high resolution mass spectra are shown in FIGS. 1, 3 and 4, respectively, and used in the following examples.
10g of epoxy resin (Sanmu SM 6101) was added to 500g of ethanol containing 100g of alumina (particle size 350 nm), stirred at room temperature (800 rpm) for 2 hours and then baked at 80 ℃ for 1 hour to obtain a filler system for use in the following examples and comparative example one.
Example preparation of prepolymer for self-repairing wear-resistant Material
50g of N, N '-4,4' -diphenylmethane bismaleimide, 73.41g of bis (3- (2-allylphenoxy) -2-hydroxypropyl) adipate, 6.29g (22.3 mmol) of zinc acetylacetonate hydrate and 4g of a filler system were mixed and prepolymerized with stirring at 130 ℃ for 60min, obtained from a prepolymer for repair of abrasion-resistant materials, and a sample was taken for DSC test.
Cooling the prepolymer for the self-repairing wear-resistant material to room temperature, adding the cooled prepolymer into a mold preheated at 150 ℃, and carrying out hot pressing and post-treatment according to the following processes: 150 ℃/1h/1MPa +180 ℃/2 h/3MPa +200 ℃/1.5 h/5MPa +220 ℃/1.5 h/5MPa and 240 ℃/2 h; and (5) naturally cooling and demoulding to obtain the self-repairing wear-resistant material, and testing TG, DMA, bending strength and wear resistance.
Embodiment two self-repairing method of self-repairing wear-resistant material and self-repairing wear-resistant material
After cracking (three irregular cracks due to the knocking of a stainless steel hammer) of the self-repairing wear-resistant material in the first embodiment, putting the self-repairing wear-resistant material into a preheated die at 200 ℃ (the crack is in contact with the die), and then carrying out hot pressing for 5 hours under the conditions that the temperature is 270 ℃ and the pressure is 30 MPa; and demolding after natural cooling to obtain the self-repairing wear-resistant material, thereby realizing the self-repairing of the bismaleimide wear-resistant material. The obtained self-repairing wear-resistant material has smooth and crack-free surface, which indicates that the resin particles have dynamic ester exchange reaction to reconnect the particles. This result is a good demonstration of the remodeling that can be achieved by the shape memory bismaleimide resin prepared by the present invention. And testing the TG, the bending strength and the wear resistance of the self-repairing wear-resistant material.
Comparative example 1
1) Preparation of diallyl bisphenol A modified bismaleimide resin
Stirring 50g of N, N ' -4,4' -diphenylmethane bismaleimide, 43.03g of 2,2' -diallyl bisphenol A, 6.29g of zinc acetylacetonate hydrate and 4g of a filler system at 130 ℃ for prepolymerization for 60min to obtain a prepolymer, and sampling to test DSC; cooling the clear prepolymer to room temperature, adding the cooled clear prepolymer into a mold preheated at 150 ℃, and carrying out hot pressing and post-treatment according to the following processes: 150 ℃/1h/1MPa +180 ℃/2 h/3MPa +200 ℃/1.5 h/5MPa +220 ℃/1.5 h/5MPa and 240 ℃/2 h; and (5) naturally cooling and then demoulding to obtain the wear-resistant material, and testing the wear resistance.
The wear-resistant material in the first comparative example is cracked (the stainless steel is hammered and irregularly cracked into five blocks), then is placed into a preheated die at 200 ℃ (the cracks are contacted), and then is hot-pressed for 5 hours under the conditions that the temperature is 270 ℃ and the pressure is 30 MPa; and (3) naturally cooling and demoulding to obtain a plate with obvious cracks, wherein the plate is easy to break and almost has no mechanical strength, and the diallyl bisphenol A modified bismaleimide resin is proved not to be remodelable.
From the DSC results (10 ℃/min) of the prepolymer for the self-repairing wear-resistant material of the embodiment of the present invention and the prepolymer for the diallyl bisphenol a modified bismaleimide resin of the comparative example i under a nitrogen atmosphere, it can be seen that the maximum reaction exothermic peak of the prepolymer for the self-repairing wear-resistant material of the embodiment is 243.2 ℃ which is lower than 250.3 ℃ of the diallyl bisphenol a modified bismaleimide resin, which indicates that the reactivity of the prepolymer for the self-repairing wear-resistant material of the embodiment is higher than that of the diallyl bisphenol a modified bismaleimide resin.
Wherein, TdiTo initiate the thermal decomposition temperature, it was routinely obtained according to the TGA curve (10 ℃/min) of the sample under nitrogen atmosphere; t isgThe glass transition temperature is obtained by DMA test (1 Hz, 3 ℃/min, 20-350 ℃, three-point bending); the flexural strength was tested in a universal tester (80 mm 15mm 4 mm).
Comparative example No. two
Mixing 50g of N, N '-4,4' -diphenylmethane bismaleimide, 73.41g of bis (3- (2-allylphenoxy) -2-hydroxypropyl) adipate and 6.29g of zinc acetylacetonate hydrate, and stirring at 130 ℃ to perform prepolymerization for 60min to obtain a prepolymer; cooling the clear prepolymer to room temperature, adding the cooled clear prepolymer into a mold preheated at 150 ℃, and carrying out hot pressing and post-treatment according to the following processes: 150 ℃/1h/1MPa +180 ℃/2 h/3MPa +200 ℃/1.5 h/5MPa +220 ℃/1.5 h/5MPa and 240 ℃/2 h; and (5) naturally cooling and demoulding to obtain the self-repairing wear-resistant material, and testing TG and wear resistance.
Comparative example No. three
Mixing 50g of N, N '-4,4' -diphenylmethane bismaleimide, 73.41g of bis (3- (2-allylphenoxy) -2-hydroxypropyl) adipate, 6.29g of zinc acetylacetonate hydrate and 4g of a filler system, and stirring at 130 ℃ to perform prepolymerization for 60min to obtain a prepolymer; cooling the clear prepolymer to room temperature, adding the cooled clear prepolymer into a mold preheated at 150 ℃, and carrying out hot pressing and post-treatment according to the following processes: 150 ℃/1h/1MPa +180 ℃/2 h/3MPa +200 ℃/1.5 h/5MPa +220 ℃/1.5 h/5MPa and 240 ℃/2 h; and (5) naturally cooling and demoulding to obtain the self-repairing wear-resistant material, and testing TG and wear resistance. In the comparative example, 0.5gKH-550 was added to 200g of ethanol containing 50g of alumina (particle size 350 nm), stirred at room temperature (800 rpm) for 2 hours, and then baked at 80 ℃ for 1 hour to obtain a filler system.
Table 1 shows the above examples and the comparative related performance tests, and it can be seen that the use of epoxy resin compounded alumina together with bismaleimide can ensure heat resistance while exhibiting excellent wear resistance; meanwhile, the prepolymer prepared by the method can be put on the market as a product.
Claims (10)
1. The prepolymer for the self-repairing wear-resistant material is characterized by comprising the following steps:
(1) reacting 2-allylphenyl glycidyl ether with adipic acid in the presence of a quaternary ammonium salt to prepare bis (3- (2-allylphenoxy) -2-hydroxypropyl) adipate;
(2) stirring and mixing bis (3- (2-allylphenoxy) -2-hydroxypropyl) adipate, bismaleimide, a zinc compound and a filler system to obtain a prepolymer for the self-repairing wear-resistant material; the filler system includes an epoxy resin and alumina.
2. The prepolymer for the self-repairing wear-resistant material of claim 1, wherein epoxy chloropropane is added into a mixed solution of 2-allyl phenol, sodium hydroxide, quaternary ammonium salt and tetrahydrofuran to react to prepare 2-allyl phenyl glycidyl ether.
3. The prepolymer for the self-repairing wear-resistant material as claimed in claim 1, wherein in the step (1), the mass ratio of the 2-allyl phenyl glycidyl ether to the adipic acid to the quaternary ammonium salt is 120: 36-44: 5-10, the reaction temperature is 65-80 ℃, and the reaction time is 8-12 hours.
4. The prepolymer for the self-repairing wear-resistant material as claimed in claim 1, wherein the quaternary ammonium salt is tetramethylammonium bromide and/or tetrabutylammonium bromide; the zinc compound is zinc acetylacetonate hydrate.
5. The prepolymer for the self-repairing wear-resistant material as claimed in claim 1, wherein the filler system is obtained by adding epoxy resin into ethanol containing alumina, stirring for 2 hours, and then drying.
6. The prepolymer for the self-repairing wear-resistant material as claimed in claim 1, wherein in the step (2), the mass ratio of bismaleimide to bis (3- (2-allylphenoxy) -2-hydroxypropyl) adipate to zinc compound to the filler system is 50: 70-75: 6-6.5: 4, the stirring temperature is 130-135 ℃, and the stirring time is 50-60 min.
7. The prepolymer for the self-repairing wear-resistant material as claimed in claim 1, wherein the bismaleimide is one or more of N, N '-4,4' -diphenylmethane bismaleimide, N '- (1, 4-phenylene) bismaleimide, and N, N' -m-phenylene bismaleimide.
8. The prepolymer for the self-repairing wear-resistant material of claim 1, wherein the epoxy resin is bisphenol A epoxy resin.
9. The prepolymer for the self-repairing wear-resistant material as claimed in claim 1, wherein the particle size of the alumina is 0.3-0.4 μm.
10. The use of the prepolymer for the self-healing abrasion resistant material of claim 1 in the preparation of an abrasion resistant article.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113683585A (en) * | 2021-09-26 | 2021-11-23 | 齐鲁工业大学 | Preparation method of epoxy group-containing phthalonitrile monomer |
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| CN106585047A (en) * | 2016-12-04 | 2017-04-26 | 苏州大学 | High-toughness bismaleimide resin material and preparation method thereof |
| CN106700073A (en) * | 2016-12-03 | 2017-05-24 | 苏州大学 | Modified bismaleimide resin and preparation method thereof |
| CN109929109A (en) * | 2019-03-19 | 2019-06-25 | 武汉理工大学 | A kind of high tenacity high-low temperature resistant Bismaleimides resin pre-polymer and preparation method thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106700073A (en) * | 2016-12-03 | 2017-05-24 | 苏州大学 | Modified bismaleimide resin and preparation method thereof |
| CN106585047A (en) * | 2016-12-04 | 2017-04-26 | 苏州大学 | High-toughness bismaleimide resin material and preparation method thereof |
| CN109929109A (en) * | 2019-03-19 | 2019-06-25 | 武汉理工大学 | A kind of high tenacity high-low temperature resistant Bismaleimides resin pre-polymer and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113683585A (en) * | 2021-09-26 | 2021-11-23 | 齐鲁工业大学 | Preparation method of epoxy group-containing phthalonitrile monomer |
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