WO2022267271A1

WO2022267271A1 - Hybrid polymer, preparation method therefor and use thereof

Info

Publication number: WO2022267271A1
Application number: PCT/CN2021/124669
Authority: WO
Inventors: 尹家福; 杨俊升; 殷盼超
Original assignee: 华南理工大学
Priority date: 2021-06-24
Filing date: 2021-10-19
Publication date: 2022-12-29
Also published as: CN113372537B; CN113372537A

Abstract

Disclosed in the present invention are a hybrid polymer, a preparation method therefor and the use thereof. The repeating unit structure of the hybrid polymer of the present invention is as shown in formula (I). The preparation method for the hybrid polymer of the present invention comprises the following steps: 1) reacting trisilanol isooctyl-POSS and vinyl trichlorosilane to obtain a compound 1; 2) reacting the compound 1 and mercaptoethylamine hydrochloride to obtain a compound 2; 3) reacting the compound 2 and cis-5-norbornene-exo-2,3-dicarboxylic anhydride to obtain a monomer; and 4) subjecting the monomer to a polymerization reaction to obtain the hybrid polymer. The hybrid polymer of the present invention has the advantages of light weight, high strength, easy processing and molding, low cost, environmental friendliness, etc., and is suitable for large-scale popularization and application.

Description

A kind of hybrid polymer and its preparation method and application

technical field

The invention relates to the technical field of polymer nanocomposite materials, in particular to a hybrid polymer and its preparation method and application.

Background technique

Impact-resistant materials are special materials with high strength and excellent toughness, which can withstand instantaneous severe impacts and quickly dissipate energy, so as to effectively protect internal structures and equipment. At present, the most widely used impact-resistant materials in the industry are polymer materials such as polyethylene (PE), polyurethane (PU), and acrylonitrile-butadiene-styrene copolymer (ABS). The impact effect requires ultra-high molecular weight, and as the molecular weight increases, the toughness of the system will decrease, and the viscosity coefficient of the system will increase accordingly, which will eventually lead to difficulties in molding and processing the material. In addition, the recycling rate of ultra-high molecular weight polymers is low, and the environmental pollution problems caused by them cannot be underestimated.

Therefore, there is an urgent need to develop a lightweight, high-strength, easy-to-process, low-cost, and environmentally friendly impact-resistant material.

Contents of the invention

The object of the present invention is to provide a hybrid polymer and its preparation method and application.

The technical scheme that the present invention takes is:

A hybrid polymer whose repeat unit structure is as follows:

Preferably, the number average molecular weight of the hybrid polymer is 10000g/mol˜100000g/mol.

The preparation method of above-mentioned hybrid polymer comprises the following steps:

1) Carrying out the reaction of trisilanol isooctyl-POSS and vinyltrichlorosilane to obtain compound 1;

2) Carrying out the reaction of compound 1 and mercaptoethylamine hydrochloride to obtain compound 2;

3) Carrying out the reaction of compound 2 and cis-5-norbornene-exo-2,3-dicarboxylic anhydride to obtain a monomer;

4) Carry out the polymerization reaction of the monomer to obtain the hybrid polymer.

Preferably, the preparation method of above-mentioned hybrid polymer comprises the following steps:

1) Dispersing trisilanol isooctyl-POSS, triethylamine and vinyltrichlorosilane in a solvent and reacting to obtain compound 1;

2) Disperse compound 1, photoinitiator and mercaptoethylamine hydrochloride in a solvent, and react to obtain compound 2;

3) Dispersing compound 2 and cis-5-norbornene-exo-2,3-dicarboxylic anhydride in a solvent and reacting to obtain a monomer;

4) Dispersing the monomer and the catalyst in the solvent, removing water and oxygen from the reaction system, and performing a polymerization reaction to obtain a hybrid polymer.

Preferably, the molar ratio of trisilanol isooctyl-POSS to vinyltrichlorosilane in step 1) is 1:1.2˜1:1.4.

Preferably, the reaction in step 1) is carried out at 0°C to 5°C, and the reaction time is 15h to 25h.

Preferably, the molar ratio of compound 1 and mercaptoethylamine hydrochloride in step 2) is 1:1.8˜1:2.2.

Preferably, the photoinitiator of step 2) is photoinitiator Igracure 2959.

Preferably, the reaction in step 2) is carried out under ultraviolet light irradiation, and the reaction time is 10 minutes to 20 minutes.

Preferably, the molar ratio of compound 2 and cis-5-norbornene-exo-2,3-dicarboxylic anhydride in step 3) is 1:1.8˜1:2.2.

Preferably, the reaction in step 3) is carried out at 130°C-140°C, and the reaction time is 30h-40h.

Preferably, the catalyst in step 4) is [1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]bis(2-bromopyridine)(phenylmethylene ) ruthenium dichloride, 1,3-bis(2,4,6-trimethylphenyl)-2-(imidazolidinylidene)(dichlorobenzylidene)(tricyclohexylphosphine)ruthenium at least one.

Further preferably, the catalyst in step 4) is Grubbs third-generation catalyst ([1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]bis(2-bromopyridine)( phenylmethylene) ruthenium dichloride).

Preferably, the water and oxygen removal in step 4) adopts a cycle freezing and thawing method.

Preferably, the polymerization reaction in step 4) is carried out at room temperature, and the reaction time is 0.5h-2h.

The beneficial effects of the invention are: the hybrid polymer of the invention has the advantages of light weight, high strength, easy processing and molding, low cost, and environmental friendliness, and is suitable for large-scale popularization and application.

Specifically:

1) The multi-level structure in the hybrid polymer of the present invention and the synergistic topological effect of POSS can greatly improve its mechanical strength, so that it has both high modulus and excellent toughness, and has broad application prospects in the field of impact-resistant materials;

2) The impact resistance of the hybrid polymer of the present invention does not depend on high molecular weight, has good processability, is convenient for processing and molding, and is conducive to large-scale production and processing;

3) The hybrid polymer of the present invention can be reshaped through simple reprocessing operations when it becomes invalid due to impact, and the recycling rate is extremely high. It is a kind of resource-saving and environment-friendly polymer material.

Description of drawings

Fig. 1 is the proton nuclear magnetic resonance spectrum figure of the compound 1 in the embodiment.

Fig. 2 is the proton nuclear magnetic resonance spectrum of compound 2 in the embodiment.

Fig. 3 is the proton nuclear magnetic resonance spectrogram of the monomer in the embodiment.

Fig. 4 is a comparison chart of the H NMR spectrum of the monomer and the hybrid polymer in the embodiment.

Fig. 5 is a comparison chart of gel permeation chromatograms of monomers and hybrid polymers in the examples.

Fig. 6 is a physical photo of the separated Hopkinson compression bar experimental device.

Fig. 7 is the stress-strain curve of the hybrid polymer in the embodiment after being impacted at different speeds.

Fig. 8 is a physical photo of the hybrid polymer in the embodiment after being impacted at different speeds.

Fig. 9 is the stress-strain curve of the hybrid polymer in the embodiment after multiple reprocessing.

detailed description

The present invention will be further explained and illustrated below in conjunction with specific embodiments.

Example:

A kind of hybrid polymer, its preparation method comprises the following steps:

1) Add 15.0g (12.67mmol) of trisilanol isooctyl-POSS (U.S. Hybrid Plastics), 1.66g (16.47mmol) of triethylamine and 150mL of anhydrous tetrahydrofuran into a reaction flask with a volume of 500mL, and stir Until the solid is completely dissolved, put it in an ice bath at 0°C, then disperse 2.65g (16.46mmol) of vinyltrichlorosilane with 50mL of anhydrous tetrahydrofuran, transfer it to the dropping funnel, and slowly drop it into the reaction flask , continue to stir for 20h after the dropwise addition, filter, take the filtrate and spin dry to obtain the crude product, then utilize the silica gel chromatography column to carry out purification to the crude product, the eluent is pure petroleum ether (PE), obtain 9.0g of compound 1 (colorless Transparent viscous liquid, productive rate 57%, proton nuclear magnetic resonance spectrogram is as shown in Figure 1);

2) Add 9.0g (7.28mmol) of compound 1 and 34mg (0.15mmol) of photoinitiator Igracure 2959 into 80mL of tetrahydrofuran, stir until the solid is completely dissolved, and then add 1.66g (14.59mmol) of mercaptoethylamine salt Disperse the acid salt in 25mL of CH ₃ OH, then mix the above two solutions evenly and irradiate in a UV reactor for 15min, distill off the solvent under reduced pressure, wash twice with NaOH solution with a concentration of 1mol/L, add anhydrous sulfuric acid Sodium was dried, filtered, the filtrate was spin-dried, and vacuum-dried at room temperature for 24 hours to obtain 7.6 g of compound 2 (pale yellow viscous liquid, yield 80%, H NMR spectrum as shown in Figure 2);

3) Add 9.8g (7.46mmol) of compound 2 and 2.45g (14.91mmol) of cis-5-norbornene-exo-2,3-dicarboxylic anhydride into 350mL of toluene, heat up to 135°C, and nitrogen atmosphere The reaction was carried out for 36h, cooled to room temperature, and the solvent was distilled off under reduced pressure to obtain a crude product, which was purified by a silica gel chromatographic column, and the eluent was PE:EA (95:5, v/v) to obtain 7.1g of Monomer (colorless and transparent viscous liquid, productive rate 65%, hydrogen nuclear magnetic resonance spectrogram as shown in Figure 3), the whole synthetic route of monomer is as follows:

4) Add 1g of the monomer in step 3) and 1.5mL of anhydrous tetrahydrofuran into a Schlenk bottle (Schlenk bottle), stir for 15min, remove water and oxygen through cyclic freezing and thawing, and add 12mg of Grubbs third-generation catalyst under nitrogen atmosphere ([1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]bis(2-bromopyridine)(phenylmethylene)ruthenium dichloride), continued through Cycle freezing and thawing to remove water and oxygen. After the reaction system is thawed, stir at 25°C for 2h. After the reaction, add 0.2mL of vinyl ether and continue stirring for 0.5h to quench the reaction. Add 2.5mL of tetrahydrofuran to dilute the reaction solution. Dilute the diluted The reaction solution was slowly added dropwise to 75mL of methanol to precipitate the product, centrifuged at 11000r/min for 5min, and the centrifuged solid was vacuum-dried at room temperature for 24h to obtain a hybrid polymer, whose repeating unit structure was

The number average molecular weight is 10000 g/mol.

Performance Testing:

1) The comparison chart of the H NMR spectra of monomers and hybrid polymers in this example is shown in Figure 4, and the comparison chart of Gel Permeation Chromatography (GPC) is shown in Figure 5.

It can be seen from Figure 4 that the NMR peak at 6.3ppm disappeared after the polymerization reaction was completed, and instead, a new cluster of NMR signals appeared at 5.5ppm, and the change in the H-NMR spectrum corresponds to the breakage of the double bond of the monomer molecule and the formation of double bonds on the hybrid polymer backbone.

It can be seen from Figure 5 that compared with the monomer, the retention time of the hybrid polymer is significantly reduced, further confirming the successful progress of the polymerization reaction.

2) A Split-Hopkinson pressure bar instrument is used. The physical photos are shown in Figure 6, a is the whole machine, b is the sample stage, c is the partial enlarged view of the sample stage, d and e For the test sample) to test the mechanical behavior of the hybrid polymer under dynamic impact conditions, the stress-strain curves of the hybrid polymer obtained after the test are subjected to impact at different rates are shown in Figure 7, and the hybrid polymer is subjected to different rates of impact The physical photo after impact is shown in Figure 8, and the stress-strain curve of the hybrid polymer after multiple reprocessing is shown in Figure 9.

From Figures 7 to 9, it can be seen that the hybrid polymer exhibits excellent impact resistance at different strain rates. The hybrid polymer can withstand a dynamic impact with a strain rate of 1000s ^-1 , and only the edge part will be damaged, and the middle part will be damaged. The sample can still remain intact. When the strain rate reaches 1800s ^-1 , the specimen can no longer withstand the stress wave with such a high strain rate, so that the hybrid polymer completely fails after the ^impact . After impacting at a high speed, the quantitative recovery of the sample can be achieved after simple reprocessing. Compared with the original sample, the impact resistance of the recovered sample has no obvious change, even after multiple impacts. The recovery situation is still the same.

The above-mentioned embodiment is a preferred embodiment of the present invention, but the embodiment of the present invention is not limited by the above-mentioned embodiment, and any other changes, modifications, substitutions, combinations, Simplifications should be equivalent replacement methods, and all are included in the protection scope of the present invention.

Claims

A hybrid polymer, characterized in that its repeat unit structure is as follows:
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.
The preparation method of the hybrid polymer described in claim 1 or 2, is characterized in that, comprises the following steps:

1) Carrying out the reaction of trisilanol isooctyl-POSS and vinyltrichlorosilane to obtain compound 1;

2) Carrying out the reaction of compound 1 and mercaptoethylamine hydrochloride to obtain compound 2;

3) Carrying out the reaction of compound 2 and cis-5-norbornene-exo-2,3-dicarboxylic anhydride to obtain a monomer;

4) Carry out the polymerization reaction of the monomer to obtain the hybrid polymer.
The preparation method according to claim 3, characterized in that: in step 1), the molar ratio of trisilanol isooctyl-POSS to vinyltrichlorosilane is 1:1.2˜1:1.4.
The preparation method according to claim 3 or 4, characterized in that: the reaction in step 1) is carried out at 0°C to 5°C, and the reaction time is 15h to 25h.
The preparation method according to claim 3, characterized in that: in step 2), the molar ratio of compound 1 and mercaptoethylamine hydrochloride is 1:1.8-1:2.2.
The preparation method according to claim 3, characterized in that the molar ratio of compound 2 and cis-5-norbornene-exo-2,3-dicarboxylic anhydride in step 3) is 1:1.8 to 1:2.2 .
The preparation method according to claim 3 or 7, characterized in that: the reaction in step 3) is carried out at 130°C-140°C, and the reaction time is 30h-40h.
According to the preparation method described in any one of claims 3, 4, 6 and 7, it is characterized in that: the polymerization reaction described in step 4) is carried out at room temperature, and the reaction time is 0.5h～2h.
An impact-resistant material, characterized in that its composition includes the hybrid polymer described in claim 1 or 2.