阅读说明：本技术 一种水刺激响应橡胶复合材料及其制备方法 (Spunlace-induced response rubber composite material and preparation method thereof ) 是由 夏琳 邱桂学 刘广永 于 2019-08-26 设计创作，主要内容包括：本发明公开了一种水刺激响应橡胶复合材料及其制备方法。本发明包括以下重量份的原料：丁腈橡胶30-80份,聚环氧乙烷20-70份,硫化剂0.8-1.6份,加工助剂0-5份；本发明还给出了上述橡胶复合材料的制备方法,上述原料经过混炼和硫化,得到橡胶复合材料。本发明采用传统橡胶高分子材料与功能性高分子材料相复合,经过混炼和硫化,制备出了一种具有水刺激响应的橡胶复合材料,这是一种新型刺激响应的橡胶复合材料,提高了形状记忆高分子材料的利用价值,该橡胶复合材料质地均匀,具有交联网络结构,不存在脱层等问题,转换温度区间一直处于室温与体温之间,具有更好的形状记忆固定和形状恢复性能,广泛应用于生物医疗等领域。(The invention discloses a spunlace response rubber composite material and a preparation method thereof. The invention comprises the following raw materials in parts by weight: 30-80 parts of nitrile rubber, 20-70 parts of polyethylene oxide, 0.8-1.6 parts of vulcanizing agent and 0-5 parts of processing aid; the invention also provides a preparation method of the rubber composite material, and the rubber composite material is obtained by mixing and vulcanizing the raw materials. The rubber composite material with the spunlace response is prepared by compounding the traditional rubber high polymer material with the functional high polymer material and mixing and vulcanizing, is a novel rubber composite material with the stimulus response, improves the utilization value of the shape memory high polymer material, has uniform texture, has a cross-linked network structure, does not have the problems of delamination and the like, has a conversion temperature interval between room temperature and body temperature, has better shape memory fixation and shape recovery performance, and is widely applied to the fields of biological medical treatment and the like.)

1. The spunlace stress response rubber composite material is characterized by comprising the following raw materials in parts by weight:

30-80 parts of nitrile rubber, 20-70 parts of polyethylene oxide, 0.8-1.6 parts of vulcanizing agent and 0-5 parts of processing aid.

2. A hydroentangling responsive rubber composite as set forth in claim 1, characterized by comprising the following raw materials in parts by weight:

50-60 parts of nitrile rubber, 40-60 parts of polyethylene oxide, 1.0-1.6 parts of vulcanizing agent and 0-5 parts of processing aid.

3. A hydroentangling responsive rubber composite as set forth in claim 1 or 2, characterized by comprising the following raw materials in parts by weight:

50-60 parts of nitrile rubber, 40-60 parts of polyethylene oxide, 1.0-1.5 parts of vulcanizing agent and 2-3 parts of processing aid.

4. A hydroentangling responsive rubber composite as set forth in claim 1 or 2, characterized in that:

the polyethylene oxide has a molecular weight of 80 ten thousand and a PDI of 1.1 to 1.4.

5. A hydroentangling responsive rubber composite as set forth in claim 1 or 2, characterized in that:

the vulcanizing agent is any one of dicumyl peroxide, sulfur, dibenzoyl peroxide and di-tert-butyl peroxide.

6. A hydroentangling responsive rubber composite as set forth in claim 1 or 2, characterized in that:

the processing aid comprises any one or more of a surfactant, a coupling agent, an antioxidant, an accelerator and an activator.

7. A method of preparing a hydroentanglement-responsive rubber composite as claimed in any one of claims 1 to 6, wherein: the method comprises the following steps:

mixing process, in a double-roller open mill, adjusting the roller temperature to 60-80 ℃, adding nitrile rubber and polyethylene oxide, and wrapping the rollers; after the roll is completely wrapped uniformly, adding a vulcanizing agent and a processing aid, and performing thin pass for 3-5 times from left to right; adjusting the roller spacing to 1-3mm, and discharging; standing for 18-24h, refining, and thinly passing for 3-5 times; adjusting the roller spacing to 1-3mm, and discharging;

and (3) a vulcanization process, wherein the vulcanization temperature is 150-.

8. A method of preparing a hydroentanglement-responsive rubber composite as claimed in claim 7, wherein:

the vulcanization process is carried out in a high-temperature plate vulcanizing machine.

9. A method of preparing a hydroentanglement-responsive rubber composite as claimed in claim 7, wherein:

in the mixing process, the roll wrapping time is 4-10 min.

10. A method of preparing a hydroentanglement-responsive rubber composite as claimed in claim 7, wherein:

the temperature of the remixing in the mixing process is 60-80 ℃.

Technical Field

The invention belongs to the technical field of high polymer materials, and particularly relates to a spunlace response rubber composite material and a preparation method thereof.

Background

The shape memory polymer material is a polymer material which can restore the initial shape of a product with the initial shape by the stimulation of external conditions (such as heat, electricity, light, chemical induction and the like) after the initial condition of the product is changed and fixed under certain conditions. The shape memory polymer material has large deformation, easy endowment, light weight and structural diversity; and the composite material has excellent insulating property, heat preservation property and easy coloring property, so that the composite material is widely concerned in the fields of biological medical treatment, intelligent textile, high-performance sensors and the like. The shape memory polymer material has great application prospect in the fields of clinical medicine and implanted medical equipment. With the rapid development of the fields of biomedical science, self-repairing materials, high-performance sensors and the like, people put forward higher requirements on shape memory polymer materials, such as requirements on biocompatibility, safety, easy processability, environmental protection, response range and the like, and the requirements all put forward new challenges on the shape memory polymer materials.

At the beginning of research, people mainly study and apply the shape memory behavior of the high polymer material by using the thermal response shape memory. However, shape memory materials have a temperature limit to withstand heat in the field of biomedical and the like. Therefore, the development of more stimulus response modes becomes one of the research hotspots in the field. With the progress of research, researchers begin to deeply research the stimulation mode of the shape memory behavior of the polymer material on the basis of the work of predecessors, and hopefully, the shape memory polymer material which is not limited to thermal stimulation response can be prepared, the utilization value of the shape memory polymer material is improved, the application field of the shape memory polymer material is expanded, and the market potential of the shape memory polymer material is further stimulated.

Disclosure of Invention

The invention aims to provide a spunlace stress response rubber composite material and a preparation method thereof, and aims to solve the problem of human body tolerance temperature limitation of shape memory materials in the fields of biological medicine and the like and develop a water stress response composite material.

In order to solve the technical problems, the invention is mainly realized by the following technical scheme:

in one aspect, the spunlace responsive rubber composite material comprises the following raw materials in parts by weight: 30-80 parts of nitrile rubber, 20-70 parts of polyethylene oxide, 0.8-1.6 parts of vulcanizing agent and 0-5 parts of processing aid.

The invention prepares the macromolecule based shape memory rubber composite material with the water jet shock response by taking the traditional rubber and plastic macromolecule material-nitrile-butadiene rubber (NBR) as a matrix material and compounding the traditional rubber and plastic macromolecule material-polyethylene oxide (PEO) with the composite function as a supplement. The traditional rubber-plastic high polymer material nitrile rubber (NBR) has the characteristics of high elasticity and cross-linked network of rubber materials, and has a polar functional group which has polarity; the functional polymer material polyethylene oxide (PEO) has water absorption capacity, the traditional rubber polymer material is compounded with the functional polymer material to prepare the shape memory polymer composite material responding under the water condition, the utilization value of the shape memory polymer material is improved, the rubber composite material has uniform texture, a cross-linked network structure and the like, the problems of delamination and the like do not exist, the conversion temperature range is always between room temperature and body temperature, the shape memory fixing and shape recovery performance is better, and the rubber composite material is widely applied to the fields of biological medical treatment and the like.

As a preferred embodiment, the feed comprises the following raw materials in parts by weight: 50-60 parts of nitrile rubber, 40-60 parts of polyethylene oxide, 1.0-1.6 parts of vulcanizing agent and 0-5 parts of processing aid. The rubber composite material contains a functional polymer component with water absorption, under the condition of water jet, the functional polymer component can absorb water to increase the distance between molecular chains, the shape of the rubber composite material can be changed under the action of external force, and the shape is fixed after freeze drying; immersing in water again, and enabling the shape of the material to be recovered due to sufficient restoring force provided by the cross-linked network structure existing in the material; the traditional rubber-plastic high polymer material nitrile-butadiene rubber (NBR) and the functional high polymer material polyethylene oxide (PEO) are compounded through a vulcanizing agent to form a cross-linked network structure, so that better shape memory fixation and shape recovery performance can be realized.

As a preferred embodiment, the feed comprises the following raw materials in parts by weight: 50-60 parts of nitrile rubber, 40-60 parts of polyethylene oxide, 1.0-1.5 parts of vulcanizing agent and 2-3 parts of processing aid. The nitrile rubber of the invention can be selected at will, has wide source, low price, convenient acquisition, good performance and easy vulcanization and crosslinking.

As a preferred embodiment, the polyethylene oxide has a molecular weight of 80 ten thousand and a PDI of 1.1 to 1.4. The polyethylene oxide has good water absorption performance, is cheap and easy to obtain, reduces the cost of the rubber composite material, and has good service performance.

As a preferred embodiment, the vulcanizing agent is any one of dicumyl peroxide, sulfur, dibenzoyl peroxide and di-tert-butyl peroxide. The present invention preferably uses a peroxide curing agent that can crosslink the NBR and PEO phases of the composite well, thereby creating a common crosslinked network for better shape memory retention and shape recovery.

As a preferred embodiment, the processing aid comprises any one or more of a surfactant, a coupling agent, an antioxidant, an accelerator and an activator. The invention can also add some processing aids, which is beneficial to improving the comprehensive performance of the rubber composite material and further improving the performance of the rubber composite material.

In another aspect, a method of preparing a hydroentanglement-responsive rubber composite of the present invention comprises the steps of: mixing process, in a double-roller open mill, adjusting the roller temperature to 60-80 ℃, adding nitrile rubber and polyethylene oxide, and wrapping the rollers; after the roll is completely wrapped uniformly, adding a vulcanizing agent and a processing aid, and performing thin pass for 3-5 times from left to right; adjusting the roller spacing to 1-3mm, and discharging; standing for 18-24h, refining, and thinly passing for 3-5 times; adjusting the roller spacing to 1-3mm, and discharging; and (3) a vulcanization process, wherein the vulcanization temperature is 150-.

The preparation method of the spunlace shock response rubber composite material takes the traditional rubber-plastic high polymer material, namely nitrile-butadiene rubber (NBR), as a base material, and compounds the functional high polymer material, namely polyethylene oxide (PEO), and the preparation method is obtained by mixing and vulcanizing.

As a preferred embodiment, the vulcanization process is carried out in a high temperature press. The existing high-temperature flat vulcanizing machine is adopted to carry out vulcanization treatment on the rubber material after mixing, the equipment is common, the operation is convenient, the additional investment cannot be increased, and the production cost is reduced.

As a preferred embodiment, in the mixing process, the roll-coating time is 4-10 min. Whether the complete roll wrapping uniformity of the nitrile rubber and the polyethylene oxide is realized or not can be intuitively controlled through the roll wrapping time, the control is convenient, the operation is convenient, and the production simplification is improved.

As a preferred embodiment, the temperature of the remilling in the mixing process is 60-80 ℃. After the nitrile rubber and the polyethylene oxide are mixed for the first time, the mixture returns to the open mill again for remixing, so that the mixing uniformity between the nitrile rubber and the polyethylene oxide is further improved, and the processing performance of the nitrile rubber and the polyethylene oxide is improved.

Compared with the prior art, the invention has the beneficial effects that: the invention takes the traditional rubber-plastic high polymer material-nitrile-butadiene rubber (NBR) as a base material, compounds the functional high polymer material with water absorption-polyethylene oxide (PEO), the two materials supplement each other, under the action of a vulcanizing agent, a cross-linked network structure is formed, and the high polymer-based shape memory rubber composite material with spunlace shock response is prepared; under the condition of water stimulation, the functional polymer component of the rubber composite material can absorb water, so that the distance between molecular chains is increased, the shape of the rubber composite material can be changed under the action of external force, and the shape of the rubber composite material can be fixed by freeze drying; the rubber composite material is immersed in water again, and due to the fact that the cross-linked network exists in the material to provide sufficient restoring force, the shape of the material is restored, better shape memory fixing and shape restoring performance can be achieved, the utilization value of the shape memory polymer material is improved, the rubber composite material is uniform in texture, tight in interlayer combination, free of the problems of delamination and the like, has better shape memory fixing and shape restoring performance, and is widely applied to the fields of biological medicine and the like. The method has the advantages of short process flow, simple operation, no special requirements on equipment, high production efficiency and low cost.

Detailed Description

The technical solutions of the present invention will be described clearly and completely with reference to specific embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

The invention relates to a spunlace response rubber composite material which comprises the following raw materials in parts by weight: 30-80 parts of nitrile rubber, 20-70 parts of polyethylene oxide, 0.8-1.6 parts of vulcanizing agent and 0-5 parts of processing aid.

Preferably, the feed comprises the following raw materials in parts by weight: 50-60 parts of nitrile rubber, 40-60 parts of polyethylene oxide, 1.0-1.6 parts of vulcanizing agent and 0-5 parts of processing aid.

Further, the feed comprises the following raw materials in parts by weight: 50-60 parts of nitrile rubber, 40-60 parts of polyethylene oxide, 1.0-1.5 parts of vulcanizing agent and 2-3 parts of processing aid.

Specifically, the polyethylene oxide has a molecular weight of 80 ten thousand and a PDI of 1.1 to 1.4.

Again preferably, the vulcanizing agent is any one of dicumyl peroxide, sulfur, dibenzoyl peroxide and di-tert-butyl peroxide.

Still further, the processing aid comprises any one or more of a surfactant, a coupling agent, an antioxidant, an accelerator and an activator.

The preparation method of the spunlace response rubber composite material comprises the following steps:

mixing process, in a double-roller open mill, adjusting the roller temperature to 60-80 ℃, adding nitrile rubber and polyethylene oxide, and wrapping the rollers; after the roll is completely wrapped uniformly, adding a vulcanizing agent and a processing aid, and performing thin pass for 3-5 times from left to right; adjusting the roller spacing to 1-3mm, and discharging; standing for 18-24h, refining, and thinly passing for 3-5 times; adjusting the roller spacing to 1-3mm, and discharging;

and (3) a vulcanization process, wherein the vulcanization temperature is 150-.

Specifically, the vulcanization process is carried out in a high-temperature press vulcanizer.

Further, in the mixing process, the roll wrapping time is 4-10 min.

Preferably, the temperature of the remixing in the mixing process is 60-80 ℃.