阅读说明：本技术 一种具有剪切变硬特征的玻璃高分子 (Glass polymer with shearing hardening characteristic ) 是由 周斌 刘林 于 2021-09-09 设计创作，主要内容包括：本发明公开了一种具有剪切变硬特征的玻璃高分子,高分子是含有乙烯基双端基小分子和含有硫醇双端基的小分子为构筑单元,通过硫醇-烯点击加成反应合成具有较高密度的动态交联结构的聚合物,涉及高分子材料领域。本发明利用小分子构筑具有高密度动态硼酸酯键的高分子,且所使用的硼酸酯能快速交换,从而构筑了兼具剪切变硬胶和玻璃高分子两者特性的高分子材料。这种高分子材料无需外加溶剂,模具或高温,只需在外力作用下轻松获得各种3D形状的振动器,所以具有潜在的商用价值和广阔使用前景。(The invention discloses a glass macromolecule with shear hardening characteristics, which is a polymer with a dynamic cross-linked structure with higher density synthesized by mercaptan-alkene click addition reaction by taking a micromolecule containing vinyl double end groups and a micromolecule containing mercaptan double end groups as construction units, and relates to the field of macromolecule materials. The invention constructs the polymer with high-density dynamic borate bond by utilizing micromolecules, and the used borate can be quickly exchanged, thereby constructing the polymer material with the characteristics of both shear hardening glue and glass polymer. The high polymer material can easily obtain vibrators in various 3D shapes without adding solvents, molds or high temperature under the action of external force, so that the high polymer material has potential commercial value and wide application prospect.)

1. A glass polymer having shear hardening characteristics, characterized in that: the polymer is a dynamic cross-linked structure with higher density synthesized by using micromolecules containing vinyl double end groups and thiol double end groups as building units through thiol-ene click addition reaction, so that the material can show high modulus, the used dynamic cross-linked structure is boric acid ester, and the used boric acid ester can be quickly exchanged, so that the shear hardening characteristic and the deformability of the polymer material are endowed.

2. A glass polymer having shear hardening characteristics as defined in claim 1, wherein: the dynamic cross-linked structure is a borate ester.

3. A glass polymer having shear hardening characteristics as defined in claim 1, wherein: the mol ratio of the vinyl functional group in the vinyl double-end micromolecule to the thiol functional group in the micromolecule containing the thiol double-end is 1: 1.

4. a glass polymer having shear hardening characteristics as defined in claim 1, wherein: the vinyl double-end-group-containing compound comprises vinyl borate, diethylene glycol divinyl ether and tetra (ethylene glycol) divinyl ether, wherein the molar content of the vinyl borate is 10-100%.

5. A glass polymer having shear hardening characteristics as defined in claim 1, wherein: the compound containing a thiol double terminal group comprises pentaerythritol tetrakis-3-mercaptopropionate 3, 6-dioxo-1, 8-octanedithiol.

6. A glass polymer having shear hardening characteristics as defined in claim 1, wherein: the content of boric acid ester bonds and the degree of crosslinking can be adjusted, so that the stress relaxation degree and the processability of the polymer can be adjusted.

7. A glass polymer having shear hardening characteristics as defined in claim 1, wherein: the small molecule is a unit construction polymer.

Technical Field

The invention relates to the field of high polymer materials, in particular to a glass polymer with shear hardening characteristics.

Background

Shear hardening materials are a new class of materials that flow as high viscosity liquids at very slow strain rates and exhibit the properties of a normally elastic solid under high strain rates. The material has great application prospect in human body protection, sensing, shock absorption, artificial skin, flexible electronic devices and the like. The most common shear hardening material currently is a low cross-linking degree of polyborosiloxane, commonly known as shear hardening gel (STG), which is obtained by mixing polyboric acid and silicone oil and then cross-linking. In the material, reversible boron-oxygen weak interaction exists, so that the material is in a viscous flow state in a natural state. However, the materials having shear hardening properties are currently relatively few in kind and tend to exhibit relatively weak mechanical strength. In addition, glass polymer (Vitrimer) is a new material that has been developed in recent years, and has a dynamically crosslinked polymer network structure, and the material can change its topology structure without reducing the degree of crosslinking through chain exchange. Such materials not only exhibit good self-repairability and reworkability, but often have relatively high mechanical strength and modulus.

Currently, there is no material that combines the properties of both shear-hardening glue and glass polymer.

Disclosure of Invention

Based on the above, the present invention aims to provide a glass polymer with shear hardening characteristics, so as to solve the technical problems.

In order to achieve the purpose, the invention provides the following technical scheme: a glass macromolecule with shear hardening characteristics is a macromolecule containing vinyl double-end groups, a micromolecule containing thiol double-end groups, a polymer with a reversible cross-linked network structure, which is synthesized by mixing the micromolecule containing vinyl double-end groups, the micromolecule containing thiol double-end groups and an initiator through thiol-ene click addition reaction, wherein the initiator is an ultraviolet initiator.

By adopting the technical scheme, the core technology is to construct glass macromolecules by taking micromolecules as units, specifically, firstly, the micromolecules containing vinyl double-end-group borate are synthesized, then, the micromolecules containing thiol double-end-group borate are mixed with an initiator, and the polymer with a reversible crosslinking network structure is synthesized through thiol-ene click addition reaction, the polymer obtained by the scheme has higher crosslinking degree and boric acid ester bonds are quickly exchanged, so that the polymer has deformability, when external force (low strain rate) is slowly applied, the exchange reaction between the boric acid ester bonds can be sufficiently carried out, so that the internal stress is relaxed, the lower modulus is caused, under the condition, the polymer presents plasticity and presents like liquid, but when the external force (high strain rate) is quickly applied, the time scale can be sufficiently short, so that the boric acid ester bond correlation can be practically ignored, the internal stresses cannot relax in time, resulting in a high modulus, polymer like elastomer, so that in this way glass macromolecules with shear-hardening properties can be obtained.

The invention is further configured such that the dynamic cross-linking structure is a borate ester.

Further, the molar ratio of the vinyl functional group in the vinyl double-end small molecule to the thiol functional group in the thiol double-end containing small molecule is 1: 1.

further, the compound containing vinyl double end groups comprises vinyl borate ester, diethylene glycol divinyl ether and tetra (ethylene glycol) divinyl ether, wherein the molar content of the vinyl borate ester is 10-100%.

Further to the present invention, the compound containing a thiol double terminal group comprises pentaerythritol tetrakis-3-mercaptopropionate 3, 6-dioxo-1, 8-octanedithiol.

Further, the borate bond content and the degree of crosslinking can be adjusted, thereby adjusting the stress relaxation degree and the processability of the polymer.

Furthermore, the stress relaxation degree and the processing performance of the polymer can be effectively adjusted by adjusting the content of the boric acid ester bond.

In summary, the invention mainly has the following beneficial effects:

the invention utilizes boric acid ester bonds to carry out association exchange reaction without a catalyst, and rearranges a polymer network structure, thereby constructing a high polymer material with the characteristics of both shear hardening glue and glass high polymer. The high polymer material can easily obtain vibrators in various 3D shapes without adding solvents, molds or high temperature under the action of external force, so that the high polymer material has potential commercial value and wide application prospect.

Drawings

FIG. 1 is a graph of the rheological properties of glass polymers of the present invention;

FIG. 2 is a table showing the influence of viscoelasticity of glass polymers according to various embodiments of the present invention;

FIG. 3 is a table of values of the effect of different borate bond contents on the mechanical properties of glass polymers according to the present invention;

FIG. 4 is a 3D deformation diagram of the glass polymer material of the present invention;

FIG. 5 is a graph showing the effect of the draw rate on samples obtained in some examples of the invention.

Detailed Description

The technical solution in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention. The embodiments described below with reference to the accompanying drawings are illustrative only for the purpose of explaining the present invention, and are not to be construed as limiting the present invention.

Example 1

6g of benzene-1, 4-diboronic acid and 9.82g of 3-allyloxy-1, 2-propanediol were dissolved in an aqueous tetrahydrofuran solution (120 ml of tetrahydrofuran with 0.15ml of water), 10g of magnesium sulfate was added thereto, and after stirring at room temperature for 24 hours, the mixture was concentrated by filtration to obtain a divinylboronic acid ester-containing liquid as a colorless oil. Mixing 11.2mmol divinyl borate, 75mg photoinitiator 651 photoinitiator and 5.59mmol pentaerythritol tetra-3-mercaptopropionate (abbreviated as PTMP), adding 1 wt% of alpha-dimethyl acetal, performing ultrasonic treatment in dark for two minutes to form a uniform solution, rapidly pouring the uniform mixed solution into a polytetrafluoroethylene mold for photocuring, and performing photocuring by using a mold with the wavelength of 365nm and the intensity of 15mW/cm²The UV lamp (2) was irradiated for 30 minutes under the same conditions as the conditions for 30 minutes, and the obtained sample was named BE 100-100.

Example 2

6g of benzene-1, 4-diboronic acid and 9.82g of 3-allyloxy-1, 2-propanediol were dissolved in an aqueous tetrahydrofuran solution (120 ml of tetrahydrofuran with 0.15ml of water), 10g of magnesium sulfate was added thereto, and after stirring at room temperature for 24 hours, the mixture was concentrated by filtration to obtain a divinylboronic acid ester-containing liquid as a colorless oil.

Mixing 8.4mmol of divinyl borate, 2.8mmol of diethylene glycol divinyl ether, 75mg of photoinitiator 651 photoinitiator and 5.59mmol of pentaerythritol tetra-3-mercaptopropionate, adding 1 wt% of alpha-dimethyl acetal, carrying out dark ultrasonic treatment for two minutes to form a uniform solution, then quickly pouring the mixed solution into a polytetrafluoroethylene mold for photocuring, and carrying out photocuring by using a polytetrafluoroethylene mold with the wavelength of 365nm and the intensity of 15mW/cm²The UV lamp (2) was irradiated for 30 minutes under the same conditions as the conditions for 30 minutes, and the obtained sample was named BE 75-100.

Example 3

6g of benzene-1, 4-diboronic acid and 9.82g of 3-allyloxy-1, 2-propanediol were dissolved in an aqueous tetrahydrofuran solution (120 ml of tetrahydrofuran with 0.15ml of water), 10g of magnesium sulfate was added thereto, and after stirring at room temperature for 24 hours, the mixture was concentrated by filtration to obtain a divinylboronic acid ester-containing liquid as a colorless oil.

Mixing 5.6mmol divinyl borate containing divinyl, 5.6mmol diethylene glycol divinyl ether, 75mg photoinitiator 651 photoinitiator and 5.59mmol pentaerythritol tetra-3-mercaptopropionate, adding 1 wt% of alpha-dimethyl acetal, performing dark ultrasound for two minutes to form a uniform solution, rapidly pouring the mixed solution into a polytetrafluoroethylene mold for photocuring, and performing photocuring by using a mold with the wavelength of 365nm and the intensity of 15mW/cm²The UV lamp (2) was irradiated for 30 minutes under the same conditions as the conditions for 30 minutes, and the obtained sample was named BE 50-100.

Example 4

6g of benzene-1, 4-diboronic acid and 9.82g of 3-allyloxy-1, 2-propanediol were dissolved in an aqueous tetrahydrofuran solution (120 ml of tetrahydrofuran with 0.15ml of water), 10g of magnesium sulfate was added thereto, and after stirring at room temperature for 24 hours, the mixture was concentrated by filtration to obtain a divinylboronic acid ester-containing liquid as a colorless oil.

2.8mmol of divinyl borate, 8.4mmol of diethylene glycol divinyl ether, 75mg of photoinitiator 651 photoinitiator and 5.59mmol of pentaerythritol tetra-3-mercaptopropionate are blended, 1 wt% of alpha-dimethyl acetal is added, and after being protected from light and subjected to ultrasonic treatment for two minutes, a uniform solution is formed, then the mixed solution is quickly poured into a polytetrafluoroethylene mold for photocuring, the wavelength is 365nm, and the intensity is 15mW/cm²The UV lamp (2) was irradiated for 30 minutes under the same conditions as the conditions for 30 minutes, and the obtained sample was named BE 25-100.

Example 5

6g of benzene-1, 4-diboronic acid and 9.82g of 3-allyloxy-1, 2-propanediol were dissolved in an aqueous tetrahydrofuran solution (120 ml of tetrahydrofuran with 0.15ml of water), 10g of magnesium sulfate was added thereto, and after stirring at room temperature for 24 hours, the mixture was concentrated by filtration to obtain a divinylboronic acid ester-containing liquid as a colorless oil.

11.2mmol of diethylene glycol divinyl ether75mg of photoinitiator 651 photoinitiator, 5.59mmol of pentaerythritol tetra-3-mercaptopropionate, 1 wt% of alpha-dimethyl acetal, and then carrying out dark ultrasonic treatment for two minutes to form a uniform solution, and then quickly pouring the mixed solution into a polytetrafluoroethylene mold for photocuring, wherein the wavelength is 365nm, and the intensity is 15mW/cm²The UV lamp (2) was irradiated for 30 minutes under the same conditions as the conditions for 30 minutes, and the obtained sample was named BE 0-100.

Example 6

6g of benzene-1, 4-diboronic acid and 9.82g of 3-allyloxy-1, 2-propanediol were dissolved in an aqueous tetrahydrofuran solution (120 ml of tetrahydrofuran with 0.15ml of water), 10g of magnesium sulfate was added thereto, and after stirring at room temperature for 24 hours, the mixture was concentrated by filtration to obtain a divinylboronic acid ester-containing liquid as a colorless oil.

Mixing 11.2mmol divinyl borate, 75mg photoinitiator 651 photoinitiator, 2.24mmol pentaerythritol tetra-3-mercaptopropionate (abbreviated as PTMP) and 6.72mmol alpha-dimethyl acetal, adding 1 wt% alpha-dimethyl acetal, performing ultrasonic treatment in dark place for two minutes to obtain a uniform solution, rapidly pouring the mixed solution into a polytetrafluoroethylene mold for photocuring, and performing photocuring with the wavelength of 365nm and the intensity of 15mW/cm²The UV lamp (2) was irradiated for 30 minutes under the same conditions as the conditions for 30 minutes, and the obtained sample was named BE 100-25.

Example 7

6g of benzene-1, 4-diboronic acid and 9.82g of 3-allyloxy-1, 2-propanediol were dissolved in an aqueous tetrahydrofuran solution (120 ml of tetrahydrofuran with 0.15ml of water), 10g of magnesium sulfate was added thereto, and after stirring at room temperature for 24 hours, the mixture was concentrated by filtration to obtain a divinylboronic acid ester-containing liquid as a colorless oil.

Mixing 11.2mmol divinyl borate containing 75mg photoinitiator 651 photoinitiator, 1.02mmol pentaerythritol tetra-3-mercaptopropionate and 9.16mmol alpha-dimethyl acetal, adding 1 wt% alpha-dimethyl acetal, performing dark ultrasound for two minutes to form a uniform solution, rapidly pouring the mixed solution into a polytetrafluoroethylene mold for photocuring, and performing photocuring by using a mold with a wavelength of 365nm and a strength of 15mW/cm²The UV lamp (2) was irradiated for 30 minutes under the same conditions as the conditions for the reverse side for 30 minutes, and the obtainedThe resulting sample was named BE 100-10.

Example 8

6g of benzene-1, 4-diboronic acid and 9.82g of 3-allyloxy-1, 2-propanediol were dissolved in an aqueous tetrahydrofuran solution (120 ml of tetrahydrofuran with 0.15ml of water), 10g of magnesium sulfate was added thereto, and after stirring at room temperature for 24 hours, the mixture was concentrated by filtration to obtain a divinylboronic acid ester-containing liquid as a colorless oil.

Mixing 11.2mmol divinyl borate containing ester, 75mg photoinitiator 651 photoinitiator, 1.06mmol pentaerythritol tetra-3-mercaptopropionate and 10.14mmol alpha-dimethyl acetal, adding 1 wt% alpha-dimethyl acetal, performing dark ultrasound for two minutes to form a uniform solution, rapidly pouring the mixed solution into a polytetrafluoroethylene mold for photocuring, and performing photocuring by using a mold with the wavelength of 365nm and the intensity of 15mW/cm²The UV lamp (2) was irradiated for 30 minutes under the same conditions as the conditions for 30 minutes, and the obtained sample was named BE 100-5.

Although embodiments of the present invention have been shown and described, it is intended that the present invention should not be limited thereto, that the particular features, structures, materials or characteristics described may be combined in any suitable manner in any one or more embodiments or examples, and that modifications, substitutions, variations or the like, which are not inventive and may be made by those skilled in the art without departing from the principle and spirit of the present invention and without departing from the scope of the claims.