CN113372537A - Hybrid polymer and preparation method and application thereof - Google Patents
Hybrid polymer and preparation method and application thereof Download PDFInfo
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- CN113372537A CN113372537A CN202110715841.0A CN202110715841A CN113372537A CN 113372537 A CN113372537 A CN 113372537A CN 202110715841 A CN202110715841 A CN 202110715841A CN 113372537 A CN113372537 A CN 113372537A
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- C08G61/124—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one nitrogen atom in the ring
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- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/045—Polysiloxanes containing less than 25 silicon atoms
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- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
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- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
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- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
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- C08G2261/33—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain
- C08G2261/334—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain containing heteroatoms
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- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/40—Polymerisation processes
- C08G2261/41—Organometallic coupling reactions
- C08G2261/418—Ring opening metathesis polymerisation [ROMP]
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Abstract
The invention discloses a hybrid polymer and a preparation method and application thereof. The repeating unit structure of the hybrid polymer of the present invention is as follows:
the preparation method of the hybrid polymer of the invention comprises the following steps: 1) carrying out reaction of trisilanol isooctyl-POSS and vinyl trichlorosilane to obtain a compound 1; 2) carrying out the reaction of the compound 1 and mercaptoethylamine hydrochloride to obtain a compound 2; 3) carrying out a reaction of the compound 2 and cis-5-norbornene-exo-2, 3-dicarboxylic anhydride to obtain a monomer; 4) carrying out polymerization reaction of the monomers to obtain the hybrid polymer. The hybrid polymer has the advantages of light weight, high strength, easy processing and forming, low cost, environmental protection and the like, and is suitable for large-scale pushingHas wide application.
Description
Technical Field
The invention relates to the technical field of polymer nano composite materials, in particular to a hybrid polymer and a preparation method and application thereof.
Background
The impact-resistant material is a special material with high strength and excellent toughness, and can bear instantaneous severe impact and quickly dissipate energy, so that the internal structure and equipment are effectively protected. At present, the most widely used impact-resistant materials in industry are polymer materials such as Polyethylene (PE), Polyurethane (PU), acrylonitrile-butadiene-styrene copolymer (ABS), etc., which need to have ultrahigh molecular weight to achieve impact-resistant effect, and the toughness of the system decreases with the increase of molecular weight, and the viscosity coefficient of the system increases accordingly, which eventually leads to difficult material molding. In addition, the recycling rate of the ultra-high molecular weight polymer is low, and the problem of environmental pollution is not insignificant.
Therefore, the development of an impact-resistant material which is light in weight, high in strength, easy to machine and form, low in cost and environment-friendly is urgently needed.
Disclosure of Invention
The invention aims to provide a hybrid polymer and a preparation method and application thereof.
The technical scheme adopted by the invention is as follows:
a hybrid polymer having the following repeating unit structure:
preferably, the number average molecular weight of the hybrid polymer is 10000g/mol to 100000 g/mol.
The preparation method of the hybrid polymer comprises the following steps:
1) carrying out reaction of trisilanol isooctyl-POSS and vinyl trichlorosilane to obtain a compound 1;
2) carrying out the reaction of the compound 1 and mercaptoethylamine hydrochloride to obtain a compound 2;
3) carrying out a reaction of the compound 2 and cis-5-norbornene-exo-2, 3-dicarboxylic anhydride to obtain a monomer;
4) carrying out polymerization reaction of the monomers to obtain the hybrid polymer.
Preferably, the preparation method of the hybrid polymer comprises the following steps:
1) dispersing trisilanol isooctyl-POSS, triethylamine and vinyl trichlorosilane in a solvent for reaction to obtain a compound 1;
2) dispersing the compound 1, a photoinitiator and mercaptoethylamine hydrochloride in a solvent for reaction to obtain a compound 2;
3) dispersing the compound 2 and cis-5-norbornene-exo-2, 3-dicarboxylic anhydride in a solvent for reaction to obtain a monomer;
4) dispersing a monomer and a catalyst in a solvent, removing water and oxygen from a reaction system, and then carrying out polymerization reaction to obtain the hybrid polymer.
Preferably, the molar ratio of the trisilanol isooctyl-POSS to the vinyl trichlorosilane in the step 1) is 1: 1.2-1: 1.4.
Preferably, the reaction in the step 1) is carried out at 0-5 ℃, and the reaction time is 15-25 h.
Preferably, the molar ratio of the compound 1 and the mercaptoethylamine hydrochloride in the step 2) is 1: 1.8-1: 2.2.
Preferably, the photoinitiator in the step 2) is a photoinitiator Igracure 2959.
Preferably, the reaction in the step 2) is carried out under the irradiation of ultraviolet light, and the reaction time is 10min to 20 min.
Preferably, the molar ratio of the compound 2 in the step 3) to cis-5-norbornene-exo-2, 3-dicarboxylic anhydride is 1:1.8 to 1: 2.2.
Preferably, the reaction in the step 3) is carried out at 130-140 ℃, and the reaction time is 30-40 h.
Preferably, the catalyst in the step 4) is at least one of [1, 3-bis (2,4, 6-trimethylphenyl) -2-imidazolidinylidene ] bis (2-bromopyridine) (phenylmethylene) ruthenium dichloride and 1, 3-bis (2,4, 6-trimethylphenyl) -2- (imidazolidinylidene) (dichlorobenzylidene) (tricyclohexylphosphine) ruthenium.
Further preferably, the catalyst in step 4) is Grubbs' three-generation catalyst ([1, 3-bis (2,4, 6-trimethylphenyl) -2-imidazolidinylidene ] bis (2-bromopyridine) (phenylmethylene) ruthenium dichloride).
Preferably, the water and oxygen removal in the step 4) adopts a circulation freezing and thawing method.
Preferably, the polymerization reaction in the step 4) is carried out at room temperature, and the reaction time is 0.5 h-2 h.
The invention has the beneficial effects that: the hybrid polymer has the advantages of light weight, high strength, easy processing and forming, low cost, environmental friendliness and the like, and is suitable for large-scale popularization and application.
Specifically, the method comprises the following steps:
1) the mechanical strength of the hybrid polymer can be greatly improved by the aid of a multilevel structure and a synergistic topological effect of POSS (polyhedral oligomeric silsesquioxane), so that the hybrid polymer has high modulus and excellent toughness and has a wide application prospect in the field of impact-resistant materials;
2) the impact resistance of the hybrid polymer does not depend on high molecular weight, has good processability, is convenient for processing and forming, and is beneficial to large-scale production and processing;
3) the hybrid polymer can be remolded through simple reprocessing operation under the condition that the hybrid polymer fails due to impact, has high recycling rate, and is a resource-saving and environment-friendly high polymer material.
Drawings
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of Compound 1 in the example.
FIG. 2 is a NMR spectrum of Compound 2 in example.
FIG. 3 is a NMR spectrum of a monomer in example.
FIG. 4 is a comparison of the NMR spectra of the monomers and hybrid polymers in the examples.
FIG. 5 is a comparison graph of gel permeation chromatography of monomers and hybrid polymers in the examples.
Fig. 6 is a real photograph of the split hopkinson pressure bar experimental apparatus.
FIG. 7 is a stress-strain curve of the hybrid polymer in the examples after being impacted at different rates.
FIG. 8 is a photograph of an embodiment of a hybrid polymer after being subjected to different rates of impact.
FIG. 9 is a stress-strain curve of the hybrid polymer of the example after multiple reworking.
Detailed Description
The invention will be further explained and illustrated with reference to specific examples.
Example (b):
a hybrid polymer, the method of making comprising the steps of:
1) adding 15.0g (12.67mmol) of trisilanol isooctyl-POSS (American Hybrid Plastics), 1.66g (16.47mmol) of triethylamine and 150mL of anhydrous tetrahydrofuran into a reaction bottle with the volume of 500mL, stirring until the solid is completely dissolved, placing the reaction bottle in an ice bath at 0 ℃, dispersing 2.65g (16.46mmol) of vinyl trichlorosilane with 50mL of anhydrous tetrahydrofuran, transferring the mixture into a dropping funnel, slowly dropwise adding the mixture into the reaction bottle, continuing stirring for 20 hours after the dropwise adding is finished, filtering, taking the filtrate, spin-drying to obtain a crude product, purifying the crude product by using a silica gel chromatographic column, and obtaining 9.0g of compound 1 (colorless and transparent viscous liquid, the yield of 57 percent and a nuclear magnetic resonance hydrogen spectrum chart shown in figure 1) by using a pure Petroleum Ether (PE) as an eluent;
2) 9.0g (7.28mmol) of Compound 1 and 34mg (0.15mmol) of the photoinitiator Igracure 2959 are added to 80mL of tetrahydrofuran, stirred until the solid is completely dissolved, and 1.66g (14.59mmol) of mercaptoethylamine hydrochloride is dispersed in 25mL of CH3In OH, uniformly mixing the two solutions, performing illumination in an ultraviolet reactor for 15min, performing reduced pressure distillation to remove the solvent, washing with a NaOH solution with the concentration of 1mol/L for 2 times, adding anhydrous sodium sulfate for drying, filtering, taking the filtrate for spin-drying, and performing vacuum drying at room temperature for 24h to obtain 7.6g of compound 2 (a light yellow viscous liquid, the yield is 80%, and a nuclear magnetic resonance hydrogen spectrogram is shown in figure 2);
3) 9.8g (7.46mmol) of compound 2 and 2.45g (14.91mmol) of cis-5-norbornene-exo-2, 3-dicarboxylic anhydride are added to 350mL of toluene, the temperature is raised to 135 ℃, the mixture is reacted for 36h under nitrogen atmosphere, the mixture is cooled to room temperature and the solvent is distilled off under reduced pressure to obtain a crude product, and the crude product is purified by a silica gel chromatographic column, wherein the eluent is PE: EA (95:5, v/v), 7.1g of monomer (colorless transparent viscous liquid, the yield is 65%, the nuclear magnetic resonance hydrogen spectrum is shown in figure 3) is obtained, and the whole synthetic route of the monomer is as follows:
4) 1g of the monomer from step 3) and 1.5mL of anhydrous tetrahydrofuran were charged into a Schlenk flask (Schlenk flask), stirred for 15min, deoxygenated by removing water by cyclic freeze-thawing, and 12mg of Grubbs's tertiary catalyst ([1, 3-bis (2,4, 6-trimethylphenyl) -2-imidazolidinylidene subunit, ([1, 3-bis (2,4, 6-trimethylphenyl) -2-imidazolidinylidene ] was added under nitrogen]Bis (2-bromopyridine) (phenylmethylene) ruthenium dichloride), continuously removing water and oxygen by circularly freezing and thawing, stirring for 2h at 25 ℃ after a reaction system is thawed, adding 0.2mL of vinyl ether after the reaction is finished, continuously stirring for 0.5h to quench the reaction, adding 2.5mL of tetrahydrofuran diluted reaction solution, slowly dripping the diluted reaction solution into 75mL of methanol to precipitate a product, centrifuging for 5min at the rotating speed of 11000r/min, and vacuum drying the solid obtained by centrifuging for 24h at room temperature to obtain the hybrid polymer, wherein the structure of a repeating unit of the hybrid polymer is that
The number average molecular weight was 10000 g/mol.
And (3) performance testing:
1) the NMR spectra of the monomers and the hybrid polymers in this example are shown in FIG. 4, and the GPC spectra are shown in FIG. 5.
As can be seen from fig. 4: the nuclear magnetic peak at 6.3ppm disappeared after the polymerization reaction was completed, and instead a new cluster of nuclear magnetic signals appeared at 5.5ppm, and the change in the nuclear magnetic resonance hydrogen spectrum corresponded to the cleavage of the double bond of the monomer molecule and the formation of the double bond on the main chain of the hybrid polymer.
As can be seen from fig. 5: the retention time of the hybrid polymer is significantly reduced compared to the monomer, further confirming the successful performance of the polymerization reaction.
2) A Split Hopkinson pressure bar experiment device (Split-Hopkinson pressure bar experiment device, a physical photograph is shown in figure 6, a is a complete machine, b is a sample table, c is a partial enlarged view of the sample table, and d and e are test samples) is adopted to test the mechanical behavior of the hybrid polymer under the condition of dynamic impact, the stress-strain curves of the hybrid polymer obtained through testing after being impacted by different rates are shown in figure 7, the physical photograph of the hybrid polymer after being impacted by different rates is shown in figure 8, and the stress-strain curves of the hybrid polymer after being reprocessed for multiple times are shown in figure 9.
As can be seen from FIGS. 7 to 9: the hybrid polymer shows excellent impact resistance under different strain rates, and can resist the strain rate of 1000s-1The dynamic impact of (2) can only cause the edge part to be damaged, the sample of the middle part can still be kept intact, and when the strain rate reaches 1800s-1In the mean time, the test piece is no longer able to withstand such high strain rate stress waves that the hybrid polymer fails completely after impact, the sample is 1000s-1After impact is carried out at the strain rate, quantitative recovery of the sample can be realized through simple reprocessing, and the impact resistance of the recovered sample is not obviously changed compared with that of the initial sample, even if the sample is recovered after multiple impacts.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A hybrid polymer characterized by the following repeating unit structure:
2. the hybrid polymer according to claim 1, characterized in that: the number average molecular weight of the hybrid polymer is 10000 g/mol-100000 g/mol.
3. The method for preparing a hybrid polymer according to claim 1 or 2, comprising the steps of:
1) carrying out reaction of trisilanol isooctyl-POSS and vinyl trichlorosilane to obtain a compound 1;
2) carrying out the reaction of the compound 1 and mercaptoethylamine hydrochloride to obtain a compound 2;
3) carrying out a reaction of the compound 2 and cis-5-norbornene-exo-2, 3-dicarboxylic anhydride to obtain a monomer;
4) carrying out polymerization reaction of the monomers to obtain the hybrid polymer.
4. The production method according to claim 3, characterized in that: the molar ratio of the trisilanol isooctyl-POSS to the vinyl trichlorosilane in the step 1) is 1: 1.2-1: 1.4.
5. The production method according to claim 3 or 4, characterized in that: the reaction in the step 1) is carried out at 0-5 ℃, and the reaction time is 15-25 h.
6. The production method according to claim 3, characterized in that: the molar ratio of the compound 1 in the step 2) to the mercaptoethylamine hydrochloride is 1: 1.8-1: 2.2.
7. The production method according to claim 3, characterized in that: the molar ratio of the compound 2 in the step 3) to cis-5-norbornene-exo-2, 3-dicarboxylic anhydride is 1: 1.8-1: 2.2.
8. The production method according to claim 3 or 7, characterized in that: the reaction in the step 3) is carried out at 130-140 ℃, and the reaction time is 30-40 h.
9. The production method according to any one of claims 3, 4,6 and 7, characterized in that: and 4) carrying out the polymerization reaction at room temperature for 0.5-2 h.
10. An impact resistant material, characterized in that its composition comprises the hybrid polymer according to claim 1 or 2.
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| CN202110715841.0A CN113372537B (en) | 2021-06-24 | 2021-06-24 | Hybrid polymer and preparation method and application thereof |
| PCT/CN2021/124669 WO2022267271A1 (en) | 2021-06-24 | 2021-10-19 | Hybrid polymer, preparation method therefor and use thereof |
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| WO2022267271A1 (en) * | 2021-06-24 | 2022-12-29 | 华南理工大学 | Hybrid polymer, preparation method therefor and use thereof |
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| US5138003A (en) * | 1988-06-04 | 1992-08-11 | Nippon Zeon Co., Ltd. | Ring opening method and reaction solution |
| WO2001072870A1 (en) * | 2000-03-31 | 2001-10-04 | Zeon Corporation | Molded norbornene resin and process for producing the same |
| CN104877112A (en) * | 2015-03-03 | 2015-09-02 | 北京理工大学 | Norbornene imide heat-resistant polymer porous material and preparation method thereof |
| CN106633087A (en) * | 2016-10-09 | 2017-05-10 | 苏州大学 | Eight-arm heteroarm star-shaped polymer and preparation method thereof |
| CN107586385A (en) * | 2016-07-08 | 2018-01-16 | 华南农业大学 | A kind of nano zirconium dioxide/sulfur-containing polymer organic inorganic hybridization resin and its preparation and application |
| CN109608624A (en) * | 2018-11-12 | 2019-04-12 | 天津大学 | A kind of ion selfreparing high molecular material that mechanical performance is controllable and preparation method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103923282B (en) * | 2014-01-08 | 2018-04-06 | 南开大学 | The copolymer and preparation method of the silsesquioxane containing polyoxometallate |
| CN108997563A (en) * | 2018-08-09 | 2018-12-14 | 上海应用技术大学 | A kind of method of ROMP polymerization preparation based polyalcohol containing POSS |
| CN113372537B (en) * | 2021-06-24 | 2022-06-14 | 华南理工大学 | Hybrid polymer and preparation method and application thereof |
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5138003A (en) * | 1988-06-04 | 1992-08-11 | Nippon Zeon Co., Ltd. | Ring opening method and reaction solution |
| WO2001072870A1 (en) * | 2000-03-31 | 2001-10-04 | Zeon Corporation | Molded norbornene resin and process for producing the same |
| CN104877112A (en) * | 2015-03-03 | 2015-09-02 | 北京理工大学 | Norbornene imide heat-resistant polymer porous material and preparation method thereof |
| CN107586385A (en) * | 2016-07-08 | 2018-01-16 | 华南农业大学 | A kind of nano zirconium dioxide/sulfur-containing polymer organic inorganic hybridization resin and its preparation and application |
| CN106633087A (en) * | 2016-10-09 | 2017-05-10 | 苏州大学 | Eight-arm heteroarm star-shaped polymer and preparation method thereof |
| CN109608624A (en) * | 2018-11-12 | 2019-04-12 | 天津大学 | A kind of ion selfreparing high molecular material that mechanical performance is controllable and preparation method |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022267271A1 (en) * | 2021-06-24 | 2022-12-29 | 华南理工大学 | Hybrid polymer, preparation method therefor and use thereof |
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