CN114685996B

CN114685996B - Elastomer composite material and preparation method and application thereof

Info

Publication number: CN114685996B
Application number: CN202210434911.XA
Authority: CN
Inventors: 周鑫; 杨俊升; 殷盼超
Original assignee: South China University of Technology SCUT
Current assignee: South China University of Technology SCUT
Priority date: 2022-04-24
Filing date: 2022-04-24
Publication date: 2022-12-16
Anticipated expiration: 2042-04-24
Also published as: CN114685996A

Abstract

The invention discloses an elastomer composite material and a preparation method and application thereof. The elastomer composite material comprises carboxylated or sulfonated cage-shaped polysilsesquioxane and amino-terminated branched polymer; the weight average molecular weight of the amino-terminated branched polymer is 180-15000. The elastomer composite material disclosed by the application has a crosslinked physical network, wherein reversible electrostatic interaction and hydrogen bond interaction exist between carboxylated or sulfonated cage Polysilsesquioxane (POSS) and amino-terminated branched polymer, meanwhile, the low-molecular-weight branched polymer does not have chain entanglement, and the reversible physical interaction and the low-molecular-weight branched polymer system provide excellent processing performance and self-repairing performance for the elastomer composite material, provide good mechanical performance for the material, and realize excellent impact resistance.

Description

Elastomer composite material and preparation method and application thereof

Technical Field

The invention belongs to the field of materials, and particularly relates to an elastomer composite material as well as a preparation method and application thereof.

Background

The elastomer composite material has important and wide application in the fields of bionic skin, flexible wearable equipment, sensing, impact-resistant materials and the like. Conventional elastomer composite materials are generally prepared based on polymers because the chemically/physically cross-linked network of high molecular weight polymers can provide the material with good elastic and mechanical properties. However, the preparation of elastomer materials based on high molecular weight polymers generally requires high synthesis requirements, and the processing of the prepared elastomer materials also requires complex processes, often requires high temperature for processing and molding, and lacks good processability, thereby limiting the further application of elastomer materials based on high molecular weight polymers. Meanwhile, elastomeric materials based on the preparation of high molecular weight polymers are difficult to recycle after use, which increases the use cost of the materials to some extent. In addition, the self-repairing performance of the elastomer material based on high molecular weight is poor due to molecular chain entanglement or chemical crosslinking. Therefore, the development of an elastomer material which has excellent processability, mechanical properties and self-repairing performance, can be repeatedly used and has a simple preparation method is urgently needed.

Disclosure of Invention

In order to overcome the problems of the prior art described above, it is an object of the present invention to provide an elastomer composite; the second object of the present invention is to provide a process for the preparation of such elastomer composites; it is a further object of the present invention to provide the use of such an elastomer composite.

In order to achieve the purpose, the technical scheme adopted by the invention is as follows:

the present invention provides in a first aspect an elastomer composite comprising a cage polysilsesquioxane and a branched polymer;

the polyhedral oligomeric silsesquioxane is carboxylated or sulfonated polyhedral oligomeric silsesquioxane, the branched polymer is an amino-terminated branched polymer, or the polyhedral oligomeric silsesquioxane is aminated polyhedral oligomeric silsesquioxane, and the branched polymer is a carboxyl-terminated or sulfonic-terminated branched polymer;

the weight average molecular weight of the branched polymer is 180-15000.

Preferably, the weight average molecular weight of the branched polymer is 200-10000; further preferably, the weight average molecular weight of the branched polymer is 600 to 10000; still more preferably, the branched polymer has a weight average molecular weight of 1000 to 3000.

Preferably, the molecular formula of the cage-shaped polysilsesquioxane is (R) ¹ SiO _3/2 ) _n (R ² SiO _3/2 ) _m ；

Wherein n is selected from a positive integer, m is selected from 0 or a positive integer, and n + m =6, 8, 10 or 12; r ¹ Is a group containing an amino group, a carboxyl group or a sulfonic group; r ² Selected from the group consisting of substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted aryl, and substituted or unsubstituted heteroaryl.

Preferably, the formula (R) ¹ SiO _3/2 ) _n (R ² SiO _3/2 ) _m In the formula, m is 0; n =6, 8, 10 or 12; r is ¹ Is a carboxyl group-or sulfonic group-containing group; further preferably, the general formula (R) ¹ SiO _3/2 ) _n (R ² SiO _3/2 ) _m In the formula, m is 0; n =8; r is ¹ Is a carboxyl-containing group.

Preferably, the structure of the cage-shaped polysilsesquioxane is shown as the formula (I);

preferably, the amino-terminated branched polymer comprises at least one of branched polyethyleneimine, branched polypropyleneimine, branched polybutyleneimine and branched polyamideimine; further preferably, the branched polymer comprises at least one of branched Polyethyleneimine (PEI), branched polypropyleneimine, and branched polybutyleneimine; still further preferably, the branched polymer is a branched polyethyleneimine.

Preferably, the structure of the branched polyethyleneimine is shown as a formula (II);

in the formula (II), a is selected from positive integers of 1-30.

Preferably, in formula (II), a is selected from positive integers of 1 to 20.

Preferably, the molar ratio of the cage polysilsesquioxane to the branched polymer is (0.8-4): 1; further preferably, the molar ratio of the cage polysilsesquioxane to the branched polymer is (1-3): 1; still further preferably, the molar ratio of the cage polysilsesquioxane to the branched polymer is (1.5-2.5): 1; still further preferably, the molar ratio of the cage polysilsesquioxane to the branched polymer is (1.8-2.3): 1.

the second object of the present invention is to provide a process for the preparation of such an elastomer composite, comprising the steps of:

mixing the cage polysilsesquioxane with a branched polymer to obtain the elastomer composite.

Preferably, the cage polysilsesquioxane is a cage polysilsesquioxane solution.

Preferably, the branched polymer is a branched polymer solution.

Preferably, the concentration of the cage-shaped polysilsesquioxane solution is 0.05mol/L to 0.3mol/L; further preferably, the concentration of the cage-shaped polysilsesquioxane solution is 0.08-0.2 mol/L; still more preferably, the concentration of the cage-like polysilsesquioxane solution is 0.08mol/L to 0.15mol/L.

Preferably, the concentration of the branched polymer solution is 0.05mol/L to 0.3mol/L; further preferably, the concentration of the branched polymer solution is 0.08mol/L to 0.2mol/L; still more preferably, the concentration of the branched polymer solution is 0.08 to 0.15mol/L.

Preferably, the solvent of the cage-shaped polysilsesquioxane solution comprises at least one of furan solvents, ester solvents, halogenated alkanes and alcohol solvents; further preferably, the solvent of the cage-shaped polysilsesquioxane solution comprises at least one of tetrahydrofuran, ethyl acetate and dichloromethane.

Preferably, the solvent of the branched polymer solution comprises at least one of an alcohol solvent, an amine solvent and water; further preferably, the solvent of the branched polymer solution comprises at least one of methanol, ethanol, and water.

Preferably, the temperature of the mixing is 10-40 ℃; further preferably, the temperature of the mixing is 20 ℃ to 30 ℃.

Preferably, the method further comprises the step of evaporating the solvent under reduced pressure and/or drying the elastomer composite after the mixing.

Preferably, the carboxylated or sulfonated cage polysilsesquioxane is obtained by a thiol-ene click reaction between alkenyl cage polysilsesquioxane and mercapto carboxylic acid or mercapto sulfonic acid.

Preferably, the alkenyl cage polysilsesquioxane comprises vinyl cage polysilsesquioxane, propenyl cage polysilsesquioxane, butenyl cage polysilsesquioxane.

Preferably, the mercaptocarboxylic acid comprises at least one of thioglycolic acid, mercaptopropionic acid, and mercaptobutyric acid.

The invention also aims to provide application of the elastomer composite material in flexible wearable equipment and impact-resistant materials.

The term "alkyl" as used herein refers to a branched or straight chain saturated aliphatic alkane having the specified number of carbon atoms, minus a hydrogen-derived group. For example, "C1-C10 alkyl" is meant to include C1, C2, C3, C4, C5, C6, C7, C8, C9, C10 alkyl, including "C1-C6 alkyl", "C1-C4 alkyl", "C1-C3 alkyl", specific examples include, but are not limited to: methyl, ethyl, n-propyl, isopropyl, sec-butyl, 2-methylbutyl, 1-dimethylbutyl, and the like.

The "alkenyl group" as referred to herein means a group in which at least two carbon atoms in an alkyl group having the specified number of carbon atoms are replaced with a carbon-carbon double bond. Such as allyl, alkenyl butyl, and the like.

The "amino group" as referred to herein means a group in which at least one carbon atom in an alkyl group having the specified number of carbon atoms is replaced with a nitrogen atom, and the amino group is a primary amino group or a secondary amino group. Such as methylamino, ethylamino, and the like.

The "substituted or unsubstituted aryl group" as referred to herein means a group in which at least one hydrogen atom in an alkyl group having the specified number of carbon atoms is replaced with an aromatic group. Such as phenyl, benzyl, 4-chlorophenyl, and the like.

The "substituted or unsubstituted heteroaryl group" as used herein refers to a group in which at least one hydrogen atom in an alkyl group having the specified number of carbon atoms is replaced with a heteroaryl group. Such as 2-pyridyl, 4-chloro-2-pyridyl, and the like.

The beneficial effects of the invention are:

the elastomer composite material disclosed by the application has a cross-linked physical network, wherein reversible electrostatic interaction and hydrogen bond interaction exist between carboxyl or sulfonic acid groups and amino groups, and meanwhile, the branched polymer with low molecular weight does not have chain entanglement and reversible physical interaction, so that the branched polymer system with low molecular weight provides excellent processing performance and self-repairing performance for the elastomer composite material, provides good mechanical properties for the material, and realizes excellent impact resistance.

Specifically, the invention has the following advantages:

1. cage Polysilsesquioxane (POSS) as a relatively rigid nanoparticle mixed with a polymer substrate can improve the mechanical strength of the composite. The cage-shaped polysilsesquioxane has definite and easily-modified sites, can be selectively modified with negative charge groups (carboxyl, sulfonic acid or amino) with controllable quantity by a simple chemical method, and forms a physical crosslinking network with a polymer through hydrogen bond/electrostatic interaction. Meanwhile, the dynamic hydrogen bond/electrostatic interaction can endow the material with good processing performance and self-repairing capability. The polyhedral oligomeric silsesquioxane has certain universality, and surface sites which are easy to modify can be provided with various surface functional groups, so that the polyhedral oligomeric silsesquioxane is compounded with other suitable polymers to prepare a composite material with good performance. The specific modifiable sites of the cage-shaped polysilsesquioxane can also accurately control the number of the modifiable sites, so that the mechanical property of the composite material can be accurately regulated and controlled.

2. The preparation method of the elastomer composite material disclosed by the application has simple steps, can finish the preparation process by only one-step mixing, is easy to control the process quality and is beneficial to industrial production.

3. The elastomer composite material disclosed by the application forms a physical network through electrostatic interaction and hydrogen bond interaction of carboxyl and amino, meanwhile, polyethyleneimine with low molecular weight does not have chain entanglement, the physical network of a system has faster dynamics and reversible physical interaction, the material is endowed with excellent processing performance, reusability and self-repairing performance, the polyethyleneimine can be processed by simple kneading at room temperature, the problem of complex processing of the traditional elastomer composite material is overcome, and a new feasible method is provided for preparing the elastomer composite material based on small molecules. The carboxylated POSS and the polyethyleneimine in the elastomer composite material disclosed by the application have strong mechanical strength, and the material is endowed with good tensile property and impact resistance, and the elastomer composite material can be applied to flexible wearable equipment and impact resistant materials.

Drawings

FIG. 1 is a schematic synthesis scheme of an elastomer composite of the examples.

FIG. 2 is a graph of a sample of example 2 after mixing of polyethyleneimine and carboxylated POSS.

FIG. 3 is a graph of a sample of the elastomer composite prepared in example 2.

FIG. 4 is a stretch diagram of a sample of the elastomer composite prepared in example 2.

FIG. 5 is a nuclear magnetic resonance hydrogen spectrum of the carboxylated POSS prepared in the example.

FIG. 6 is a WAXS spectrum of an elastomer composite prepared according to examples 1-3.

FIG. 7 is a differential scanning calorimetry thermogram of the elastomer composite prepared in example 2.

FIG. 8 is a schematic of the self-healing properties of the elastomer composite prepared in example 2.

FIG. 9 is a graph of the tensile profiles of the elastomer composites prepared in examples 1-3.

FIG. 10 is a diagram of a sample object and an experimental sample of the split Hopkinson pressure bar experimental device.

FIG. 11 is a stress-strain plot of elastomer composites prepared in example 2 at different impact strain rates.

FIG. 12 is a graph of samples of the elastomer composite prepared in example 2 after impact at different strain rates.

FIG. 13 is a test plot of the stress-strain curve of the crushed elastomer composite of example 2 after plastic working.

Detailed Description

The following examples are presented to further illustrate the practice of the invention, but the practice and protection of the invention is not limited thereto. It is noted that the processes described below, if not specifically described in detail, are all realizable or understandable by those skilled in the art with reference to the prior art. The reagents or apparatus used are not indicated to the manufacturer, and are considered to be conventional products available for commercial purchase.

FIG. 1 is a schematic representation of the synthesis scheme of the elastomer composite of the examples of the present application, and the present disclosure is further illustrated with reference to FIG. 1 in conjunction with the specific examples.

Examples carboxylated POSS was prepared from Vinyl POSS (VPOSS) and thioglycolic acid by thiol-ene click reaction under uv irradiation. The preparation method comprises the following specific preparation steps and conditions:

in a 200mL beaker was added 5g of octavinyl POSS (7.9 mmol), 100mL of tetrahydrofuran was added and stirred for ten minutes to dissolve VPOSS, 159mg of photoinitiator was added and stirred for 10 minutes, then 4.9mL (69 mmol) of thioglycolic acid was added and stirred for 10 minutes with the beaker covered with tinfoil. And placing the solution in an ultraviolet reactor, stirring and irradiating for 15 minutes, evaporating under reduced pressure to remove tetrahydrofuran, dissolving the obtained mucus in 50mL of dichloromethane, adding 50mL of water for washing, repeating the washing step for three times, evaporating under reduced pressure to remove dichloromethane, and drying under vacuum for 12 hours to obtain light yellow mucus, thus obtaining octa-carboxylated POSS.

The polyethyleneimine selected in the examples is branched polyethyleneimine, has no entanglement in molecular weight, and has the following chemical structural formula:

example 1

The elastomer composite of this example was prepared as follows:

2.7g of carboxylated POSS were dissolved in tetrahydrofuran to give a solution with a concentration of 0.1mmol/mL, and 0.6g of polyethyleneimine (Mw = 600) was dissolved in water to give a solution with a concentration of 0.1 mmol/mL. 10mL of the polyethyleneimine solution was added to a 100mL round bottom flask and 20mL of the carboxylated POSS solution was slowly added dropwise while stirring. And (3) evaporating the obtained light yellow turbid liquid under reduced pressure to remove the solvent, and drying the obtained yellow viscous liquid in a vacuum oven for 12 hours to obtain the POSS/PEI elastomer composite material.

Example 2

The elastomer composite of this example was prepared as follows:

2.7g of carboxylated POSS was dissolved in tetrahydrofuran to make a solution with a concentration of 0.1mmol/mL and 1.8g of polyethyleneimine (Mw = 1800) was dissolved in water to make a solution with a concentration of 0.1 mmol/mL. 10mL of the polyethyleneimine solution was added to a 100mL round bottom flask and 20mL of the carboxylated POSS solution was slowly added dropwise while stirring. And (3) evaporating the obtained light yellow turbid liquid under reduced pressure to remove the solvent, and drying the obtained yellow viscous liquid in a vacuum oven for 12 hours to obtain the POSS/PEI elastomer composite material.

FIG. 2 is a graph of a sample of example 2 after mixing of polyethyleneimine and carboxylated POSS; FIG. 3 is a graph of a sample of the elastomer composite prepared in example 2; FIG. 4 is a stretch diagram of a sample of the elastomer composite prepared in example 2.

Example 3

The elastomer composite of this example was prepared as follows:

2.7g of carboxylated POSS was dissolved in tetrahydrofuran to make a solution with a concentration of 0.1mmol/mL and 10.0g of polyethyleneimine (Mw = 10000) was dissolved in water to make a solution with a concentration of 0.1 mmol/mL. 10mL of the polyethyleneimine solution was added to a 100mL round bottom flask and 20mL of the carboxylated POSS solution was slowly added dropwise while stirring. And (3) evaporating the obtained light yellow turbid liquid under reduced pressure to remove the solvent, and drying the obtained yellow viscous liquid in a vacuum oven for 12 hours to obtain the POSS/PEI elastomer composite material.

Performance test

1. Nuclear magnetic resonance hydrogen spectroscopy test

FIG. 5 is a nuclear magnetic resonance hydrogen spectrum of the carboxylated POSS prepared in the example. The nuclear magnetic resonance hydrogen spectrogram is used for representing the chemical structure of the prepared carboxylated POSS and determining the condition that the surface of the POSS carries carboxyl. From figure 5 it can be determined that the compound prepared in the example is an octacarboxylated POSS.

2. Wide angle X-ray Scattering test (WAXS)

The wide-angle X-ray scattering can be used for phase analysis and identification of the POSS/PEI elastomer composite material to obtain the dispersion of the carboxylated POSS in the material and further evaluate the homogeneity of the material, and fig. 6 is a wide-angle X-ray scattering spectrogram of the elastomer composite materials prepared in examples 1-3. As can be seen in FIG. 6, the carboxylated POSS is uniformly dispersed and does not significantly aggregate in the elastomer composite prepared in example 2.

3. Differential scanning calorimetry test (DSC)

Differential scanning calorimetry is often used to test the glass transition temperature (Tg) of a material to characterize how fast the material segments move, and thus to show the processability of the material at room temperature. FIG. 7 is a differential scanning calorimetry thermogram of the elastomer composite prepared in example 2. FIG. 7 shows that the glass transition temperature of the POSS/PEI elastomer composite material prepared in example 2 is-15.6 ℃ and is far lower than room temperature, so that the segment of the material can move rapidly at room temperature, and the POSS/PEI elastomer composite material shows excellent processability and self-repairing performance.

4. Self-repair performance test

FIG. 8 is a schematic of the self-healing properties of the elastomer composite prepared in example 2. Wherein, the first sheet on the left of the upper part of fig. 8 is an original real image of the elastomer composite, the second sheet in the middle of the upper part of fig. 8 is a real image of the elastomer composite after being cut, the third sheet on the right of the upper part of fig. 8 is a real image of the elastomer composite after being cut, two pieces of the elastomer composite after being cut are placed for 2 hours at room temperature, and the fourth sheet on the lower part of fig. 8 is a real image of the elastomer composite after being contacted. As can be seen from fig. 8, after the elastomer composite prepared in example 2 was cut, it was possible to achieve good self-repair in only 2 hours at room temperature without any other auxiliary means.

5. Tensile Property test

One of the important methods for testing the mechanical properties of the material in a tensile test can obtain the elastic modulus and the elongation at break of the material, and further evaluate the mechanical properties and the toughness of the material. The tensile rate during this test was 50mm/min. FIG. 9 is a graph of the tensile profiles of the elastomer composites prepared in examples 1-3. As can be seen from FIG. 9, the elastic modulus of the elastomer materials prepared in examples 1 to 3 reached 15.9MPa, and the elongation at break reached 550%, indicating excellent tensile properties.

6. Impact resistance test

Hopkinson Pressure Bars (SHPBs) are commonly used for researching the stress-strain relationship and failure mechanism of a material under impact load, and further characterizing the impact resistance of the material. FIG. 10 is a diagram of a sample object and an experimental sample of the split Hopkinson pressure bar experimental device. Wherein, fig. 10 (a) is a real object diagram of the split hopkinson pressure bar experimental device; FIG. 10 (b) is a diagram showing the sample being held by the striking rod; FIG. 10 (c) is an enlarged representation of the sample held by the striking rod; FIG. 10 (d) is a 10mm sample object of the experiment; FIG. 10 (e) is a drawing showing a sample of a 5mm test. When the striking rod (bullet) in the gun chamber is shot into the input rod at a certain speed, an incident pulse is generated in the input rod, the stress wave reaches the test piece through the elastic input rod, and the test piece is deformed at a high speed under the action of the stress pulse. The stress wave passes through the test piece to simultaneously generate a reflected pulse, and the reflected pulse enters the elastic input rod and a projected pulse enters the output rod. The velometer can obtain the striking speed of the bullet, the strain gauge is pasted on the elastic rod, and the dynamic stress and the strain parameters of the strain pulse calculation material are recorded. The sample sizes for the impact test were: cylindrical samples having a diameter of 10mm and a thickness of 5 mm.

FIG. 11 is a stress-strain plot of elastomer composites prepared in example 2 at different impact strain rates. Table 1 shows the calculated elastic modulus for the stress-strain curves of the elastomer composites prepared in example 2 at different impact strain rates. As can be seen from FIG. 11 and Table 1, the strain rate with impact is from 900s ^-1 Increase to 2600s ^-1 The elastomer composite prepared in example 2 exhibited an increased modulus of elasticity, up to 5045MPa, and excellent mechanical strength.

TABLE 1 elastic modulus of stress-strain curve of elastomer composite prepared in example 2

Strain rate/s ^-1	900	1600	2000	2600
					Modulus of elasticity/MPa	1848	2393	3546	5045

FIG. 12 is a graph of samples of the elastomer composite prepared in example 2 after impact at different strain rates. Wherein, FIG. 12 (a) is at 1000s ^-1 Graph of the sample after strain rate impact; FIG. 12 (b) is at 1600s ^-1 Graph of the sample after strain rate impact; . FIG. 12 (c) is a graph at 2000s ^-1 Graph of sample after strain rate impact; FIG. 12 (d) is a graph at 2600s ^-1 Graph of sample after strain rate impact. As can be seen in FIG. 12, the elastomer composite prepared in example 2 was at 900s ^-1 And 1600s ^-1 Is kept intact at a strain rate of 2000s without being damaged ^-1 And 2600s ^-1 At strain rate, only the sample boundaries were broken, indicating that the elastomer composite of example 2 has excellent impact resistance.

After the elastomer composite prepared in example 2 was impact-crushed, the partially crushed elastomer composite was subjected to simple kneading plastic working, and then subjected to stress-strain curve test of repeated impact for a plurality of times. FIG. 13 is a test plot of the stress-strain curve of the crushed elastomer composite of example 2 after plastic working. As can be seen from fig. 13, the elastomer composite material prepared in example 2 can be simply and rapidly processed and molded at room temperature, and the mechanical properties of the recovered and reprocessed material are not significantly reduced, and can withstand repeated impacts many times, which indicates that the elastomer composite material has excellent processability and excellent reusability, and can be widely applied to biomimetic materials, flexible wearable devices, sensing materials, and impact-resistant materials.

The synthetic process of the elastomer composite material disclosed in the embodiment is simple and easy to implement, the carboxylated POSS is obtained by only carrying out one-step click reaction on the vinyl POSS and the thioglycollic acid, then the carboxylated POSS tetrahydrofuran solution and the polyethyleneimine aqueous solution are simply mixed, the solvent is removed, and the elastomer composite material can be prepared by drying, so that the process quality of the product is easy to control, and the industrial production is facilitated.

The above examples are preferred embodiments of the present invention, but the present invention is not limited to the above examples, 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 they are included in the scope of the present invention.

Claims

1. An elastomer composite characterized by: the elastomer composite comprises a cage polysilsesquioxane and a branched polymer;

the structure of the cage-shaped polysilsesquioxane is shown as the formula (I):

the branched polymer is an amino-terminated branched polymer;

the weight average molecular weight of the branched polymer is 180-15000.

2. The elastomer composite of claim 1, wherein: the amino-terminated branched polymer comprises at least one of branched polyethyleneimine, branched polypropyleneimine, branched polybutyleneimine and branched polyamideimine.

3. The elastomer composite of claim 1 or 2, wherein: the molar ratio of the cage polysilsesquioxane to the branched polymer is (0.8-4): 1.

4. a process for preparing an elastomer composite as claimed in any one of claims 1 to 3, characterized in that: the method comprises the following steps:

5. The method of claim 4, wherein: the cage-shaped polysilsesquioxane is a cage-shaped polysilsesquioxane solution; the branched polymer is a branched polymer solution.

6. The production method according to claim 5, characterized in that: the concentration of the cage-shaped polysilsesquioxane solution is 0.05mol/L to 0.3mol/L; the concentration of the branched polymer solution is 0.05 mol/L-0.3 mol/L.

7. The method of claim 6, wherein: the solvent of the cage-shaped polysilsesquioxane solution comprises at least one of furan solvents, ester solvents, halogenated alkanes and alcohol solvents; the solvent of the branched polymer solution comprises at least one of an alcohol solvent, an amine solvent and water.

8. Use of the elastomer composite of any of claims 1-3 in flexible wearable devices, impact resistant materials.