阅读说明：本技术 一种石墨烯感温纤维及其制备方法 (Graphene temperature-sensing fiber and preparation method thereof ) 是由 沙嫣 沙晓林 马立国 于 2021-08-19 设计创作，主要内容包括：本发明公开了一种石墨烯感温纤维及其制备方法,该方法包含：步骤1,按比例称取各原料；步骤2,制备石墨烯感温材料；步骤3,将步骤2所得的石墨烯感温材料与粘合剂在水溶液中进行混合分散,得到感温储能浆料；步骤4,通过浸渍或者涂覆的方式,将纤维用步骤3所得的感温储能浆料进行包覆处理；步骤5,将步骤4所得的复合纤维烘干,绕纱后得到石墨烯感温纤维。本发明还提供了通过该方法制备的石墨烯感温纤维。本发明制备的石墨烯感温纤维,可以根据温度不同显示不同的颜色,适用性好、调节能力强,持久耐用,并且制备方法简单,可在绝大部分化纤上进行,工艺简单,成本低廉,应用前景广。(The invention discloses a graphene temperature sensing fiber and a preparation method thereof, wherein the method comprises the following steps: step 1, weighing raw materials in proportion; step 2, preparing a graphene temperature sensing material; step 3, mixing and dispersing the graphene temperature sensing material obtained in the step 2 and an adhesive in an aqueous solution to obtain temperature sensing energy storage slurry; step 4, coating the fibers with the temperature-sensitive energy storage slurry obtained in the step 3 in a dipping or coating mode; and 5, drying the composite fiber obtained in the step 4, and winding to obtain the graphene temperature sensing fiber. The invention also provides the graphene temperature-sensitive fiber prepared by the method. The graphene temperature sensing fiber prepared by the invention can display different colors according to different temperatures, has good applicability, strong regulating capability, durability and simple preparation method, can be carried out on most chemical fibers, and has simple process, low cost and wide application prospect.)

1. A preparation method of graphene temperature-sensitive fibers is characterized by comprising the following steps:

step 1, weighing raw materials in proportion;

step 2, preparing a graphene temperature sensing material;

step 3, mixing and dispersing the graphene temperature sensing material obtained in the step 2 and an adhesive in an aqueous solution to obtain temperature sensing energy storage slurry;

step 4, coating the fibers with the temperature-sensitive energy storage slurry obtained in the step 3 in a dipping or coating mode;

and 5, drying the composite fiber obtained in the step 4, and winding to obtain the graphene temperature sensing fiber.

2. The method of preparing a graphene temperature-sensitive fiber according to claim 1, wherein in the step 2, the graphene temperature-sensitive material is prepared by dissolving graphene oxide in water to obtain a graphene turbid solution, adding chitosan and adjusting a pH value, uniformly stirring and dispersing to obtain a chitosan dispersed turbid solution, adding metal oxide powder and an olefin compound, and heating to react to obtain the graphene temperature-sensitive material.

3. The method of preparing graphene temperature sensing fiber according to claim 2, wherein in the step 2, after adding chitosan, the pH value is adjusted to be less than 7, the chitosan is uniformly dispersed by stirring to obtain a chitosan dispersed turbid solution, then the metal oxide powder and the olefin compound are added, and the mixture is heated to 50-70 ℃ to react for 4-8h to obtain the graphene temperature sensing material.

4. The method of preparing graphene temperature-sensitive fibers according to claim 3, wherein in the step 2, 2-7 parts of graphene oxide, 3-8 parts of chitosan, 3-6 parts of olefin compounds and 1-3 parts of metal oxide powder are used in parts by weight.

5. The method of preparing graphene temperature-sensitive fibers according to claim 4, wherein the olefinic compound is any one or more of n-heneicosane, octadecane and cetyltrimethylammonium bromide; the oxidized metal powder is any one or more of cuprous oxide, ferrous oxide, zinc oxide and ferric oxide.

6. The method of preparing graphene temperature-sensitive fibers according to claim 1, wherein in the step 3, the graphene temperature-sensitive material and the binder are mixed and dispersed in an aqueous solution, and the content of the graphene temperature-sensitive material in the slurry is 12 to 25% by mass.

7. The method of preparing graphene temperature-sensitive fibers according to claim 6, wherein the binder is any one or more of PU resin, acrylic resin, AB glue; the amount of the adhesive is 3.5-5.5% of the slurry by mass percent.

8. The method of preparing graphene temperature sensitive fibers according to claim 1, wherein in the step 4, the fibers are coated by dipping or coating using a yarn sizing device.

9. The method of preparing graphene temperature sensitive fibers according to claim 1, wherein in the step 5, the drying is performed at a temperature of 90 to 150 ° and a pressure of 0.4 to 2Mpa under normal pressure, and a winding speed is 50 to 100 m/min.

10. A graphene temperature sensitive fiber prepared by the method of any one of claims 1 to 9.

Technical Field

The invention relates to a thermochromic graphene composite fiber and a preparation method thereof, and particularly relates to a graphene thermochromic fiber and a preparation method thereof.

Background

Along with the improvement of living standard of people, the requirements on the fiber products worn by people are higher and higher, especially some sports clothes have higher requirements on temperature and need to have a bidirectional temperature regulation function, and the traditional phase change fiber has the defects of no lasting heat storage performance, less cycle times and low practicability.

Graphene oxide (graphene oxide) is an oxide of graphene, generally indicated by GO, and is brown-yellow in color, and commercially available products are in the form of powder, flakes, and solution. After oxidation, the oxygen-containing functional groups on the graphene are increased, so that the graphene is more active than graphene in property, and the properties of the graphene can be improved through various reactions with the oxygen-containing functional groups. The graphene has a huge specific surface area, can be used as a high-quality adsorbent, and can play a role in an electron transfer channel when being used as a semiconductor nanoparticle supporting material, so that the performances of electricity, optics, photoelectric conversion and the like of a semiconductor are effectively improved.

Chitosan is a product of chitin after partial acetyl groups are removed, is a common natural polymer, and is also a copolymer of glucosamine and N-acetylglucosamine. The chitosan molecule contains a large amount of amino and hydroxyl, so the chitosan molecule is active in chemical property and has excellent performances such as good biocompatibility and functionality, blood compatibility, safety, microbial biodegradability and the like. Chitosan has poor heat resistance and cannot be applied to chemical fiber spinning.

Disclosure of Invention

The invention aims to provide a thermochromic graphene composite fiber and a preparation method thereof.

In order to achieve the above object, the present invention provides a method for preparing a graphene temperature sensitive fiber, wherein the method comprises: step 1, weighing raw materials in proportion; step 2, preparing a graphene temperature sensing material; step 3, mixing and dispersing the graphene temperature sensing material obtained in the step 2 and an adhesive in an aqueous solution to obtain temperature sensing energy storage slurry; step 4, coating the fibers with the temperature-sensitive energy storage slurry obtained in the step 3 in a dipping or coating mode; and 5, drying the composite fiber obtained in the step 4, and winding to obtain the graphene temperature sensing fiber.

In the step 2, the graphene temperature sensing material is prepared by dissolving graphene oxide in water to obtain a graphene turbid liquid, adding chitosan and adjusting the pH value, stirring and dispersing uniformly to obtain a chitosan dispersed turbid liquid, adding metal oxide powder and an olefin compound, and heating to react to obtain the graphene temperature sensing material.

In the step 2, after adding chitosan, adjusting the pH value to be less than 7, stirring and dispersing uniformly to obtain a chitosan dispersed turbid solution, adding metal oxide powder and an olefin compound, and heating to 50-70 ℃ to react for 4-8 hours to obtain the graphene temperature sensing material.

In the step 2, 2-7 parts of graphene oxide, 3-8 parts of chitosan, 3-6 parts of an olefin compound and 1-3 parts of metal oxide powder are adopted according to parts by weight.

In the preparation method of the graphene temperature-sensitive fiber, the olefin compound is any one or more of n-heneicosane, octadecane and hexadecyl trimethyl ammonium bromide; the oxidized metal powder is any one or more of cuprous oxide, ferrous oxide, zinc oxide and ferric oxide.

In the step 3, the graphene temperature sensing material and the binder are mixed and dispersed in the aqueous solution, and the content of the graphene temperature sensing material in the slurry is 12 to 25% by mass.

In the preparation method of the graphene temperature sensing fiber, the adhesive is any one or more of PU resin, acrylic resin and AB glue; the amount of the adhesive is 3.5-5.5% of the slurry by mass percent.

In the preparation method of the graphene temperature sensing fiber, in the step 4, the fiber is coated by dipping or coating by using yarn sizing equipment.

In the step 5, the graphene temperature sensing fiber is dried at a temperature of 90-150 ℃ and a pressure of 0.4-2Mpa under normal pressure, and the yarn winding speed is 50-100 m/min.

The invention also provides the graphene temperature-sensitive fiber prepared by the method.

The graphene temperature sensing fiber and the preparation method thereof provided by the invention have the following advantages:

according to the invention, the graphene is combined with the microcapsule to prepare the graphene temperature sensing material, so that the temperature sensing capability and the temperature regulating capability of the microcapsule are improved, and the obtained fiber can display different colors according to different temperatures.

The invention is combined on the fiber through the coating process, improves the application of the microcapsule and can coat on most of the fiber.

The graphene temperature-sensing fiber prepared by the method has the advantages of simple and easy operation process, low cost and high economic benefit, and is suitable for large-scale industrial production.

Detailed Description

The following further describes embodiments of the present invention.

The invention provides a preparation method of graphene temperature-sensitive fibers, which comprises the following steps:

step 1, weighing raw materials in proportion; step 2, preparing a graphene temperature sensing material; step 3, mixing and dispersing the graphene temperature sensing material obtained in the step 2 and an adhesive in an aqueous solution to obtain temperature sensing energy storage slurry; step 4, coating the fibers with the temperature-sensitive energy storage slurry obtained in the step 3 in a dipping or coating mode; and 5, drying the composite fiber obtained in the step 4, and winding to obtain the graphene temperature sensing fiber.

In the step 2, the graphene temperature sensing material is prepared by dissolving graphene oxide in water to obtain a graphene turbid liquid (graphene microcapsule turbid liquid), adding chitosan and adjusting the pH value, stirring and dispersing uniformly to obtain a chitosan dispersed turbid liquid, adding metal oxide powder and an olefin compound, and heating and reacting to obtain the graphene temperature sensing material.

In the step 2, after adding chitosan, adjusting the pH value to be less than 7, stirring and dispersing uniformly to obtain a chitosan dispersed turbid solution, adding oxidized metal powder and an olefin compound, and heating to 50-70 ℃ for reaction for 4-8h to obtain the graphene temperature sensing material.

In the step 2, 2-7 parts of graphene oxide, 3-8 parts of chitosan, 3-6 parts of olefin compounds and 1-3 parts of metal oxide powder are adopted according to parts by weight.

The olefin compound is one or more of n-heneicosane, octadecane, hexadecyl trimethyl ammonium bromide and the like; the metal oxide powder is any one or more of cuprous oxide, ferrous oxide, zinc oxide, ferric oxide, etc.

In the step 3, the temperature sensing slurry is prepared by mixing and dispersing the graphene temperature sensing material and the adhesive in an aqueous solution, wherein the content of the graphene temperature sensing material in the slurry is 12-25% by mass percent.

The adhesive is any one or more of PU resin (polyurethane), acrylic resin, AB glue and the like; the amount of the adhesive is 3.5-5.5% of the slurry by mass percent.

The AB glue is a two-component adhesive, the AB glue is a difference name of two-liquid mixed hardening glue, one liquid is the original glue, the other liquid is the hardening agent, the two liquids can be hardened after being mixed, and the AB glue is one of normal-temperature hardening glue which is not required to be hardened and cured by temperature. Commercially available AB adhesives are available in the form of acrylic, epoxy, polyurethane, and the like.

And 4, adopting yarn sizing equipment to coat the fibers in a dipping or coating mode. That is, the prepared temperature sensitive paste is coated on the fiber. The fiber can be any of the existing common fibers.

In step 5, drying is carried out at the temperature of 90-150 ℃ and under the pressure of 0.4-2Mpa under normal pressure, and the yarn winding speed is 50-100 m/min.

The equipment used in the present invention is known to those skilled in the art.

The invention also provides the graphene temperature-sensitive fiber prepared by the method.

The graphene temperature sensing fiber and the preparation method thereof provided by the present invention will be further described with reference to the following embodiments.

Example 1

A preparation method of a graphene temperature-sensitive fiber comprises the following steps:

step 1, weighing the raw materials in proportion.

And 2, preparing the graphene temperature sensing material.

The graphene temperature sensing material is prepared by dissolving graphene oxide in water to obtain a graphene turbid liquid, adding chitosan, adjusting the pH value to be less than 7, uniformly stirring and dispersing to obtain a chitosan dispersed turbid liquid, adding metal oxide powder and an olefin compound, heating to 50-70 ℃, and reacting for 4-8 hours to obtain the graphene temperature sensing material.

Preferably, 2 parts of graphene oxide, 3 parts of chitosan, 3 parts of olefin compound and 1 part of metal oxide powder are adopted in parts by weight.

The olefin compound is cetyl trimethyl ammonium bromide; the oxidized metal powder is cuprous oxide.

And 3, mixing and dispersing the graphene temperature sensing material obtained in the step 2 and an adhesive in an aqueous solution to obtain temperature sensing energy storage slurry. The content of the graphene temperature sensing material in the slurry is 12% by mass.

The adhesive is PU resin; the amount of binder used was 3.5% by mass of the slurry.

And 4, coating the fibers with the temperature-sensitive energy storage slurry obtained in the step 3 in a dipping or coating mode.

Preferably, the fibers are coated by dipping or coating using a yarn sizing apparatus.

And 5, drying the composite fiber obtained in the step 4 at a temperature of 90-150 ℃ and under a pressure of 0.4-2Mpa under normal pressure, and then winding to obtain the graphene temperature sensing fiber. The winding speed is 50-100 m/min.

The embodiment also provides the graphene temperature-sensitive fiber prepared by the method.

Example 2

A preparation method of a graphene temperature-sensitive fiber comprises the following steps:

step 1, weighing the raw materials in proportion.

And 2, preparing the graphene temperature sensing material.

The graphene temperature sensing material is prepared by dissolving graphene oxide in water to obtain a graphene turbid liquid, adding chitosan, adjusting the pH value to be less than 7, uniformly stirring and dispersing to obtain a chitosan dispersed turbid liquid, adding metal oxide powder and an olefin compound, heating to 50-70 ℃, and reacting for 4-8 hours to obtain the graphene temperature sensing material.

Preferably, 4 parts of graphene oxide, 5 parts of chitosan, 4 parts of olefin compound and 1.5 parts of metal oxide powder are adopted in parts by weight.

The olefinic compound is octadecane; the oxidized metal powder is ferrous oxide.

And 3, mixing and dispersing the graphene temperature sensing material obtained in the step 2 and an adhesive in an aqueous solution to obtain temperature sensing energy storage slurry. The content of the graphene temperature sensing material in the slurry is 15% by mass.

The adhesive is acrylic resin; the amount of binder was 4% by mass of the slurry.

And 4, coating the fibers with the temperature-sensitive energy storage slurry obtained in the step 3 in a dipping or coating mode.

Preferably, the fibers are coated by dipping or coating using a yarn sizing apparatus.

And 5, drying the composite fiber obtained in the step 4 at a temperature of 90-150 ℃ and under a pressure of 0.4-2Mpa under normal pressure, and then winding to obtain the graphene temperature sensing fiber. The winding speed is 50-100 m/min.

The embodiment also provides the graphene temperature-sensitive fiber prepared by the method.

Example 3

A preparation method of a graphene temperature-sensitive fiber comprises the following steps:

step 1, weighing the raw materials in proportion.

And 2, preparing the graphene temperature sensing material.

The graphene temperature sensing material is prepared by dissolving graphene oxide in water to obtain a graphene turbid liquid, adding chitosan, adjusting the pH value to be less than 7, uniformly stirring and dispersing to obtain a chitosan dispersed turbid liquid, adding metal oxide powder and an olefin compound, heating to 50-70 ℃, and reacting for 4-8 hours to obtain the graphene temperature sensing material.

Preferably, 5 parts of graphene oxide, 6 parts of chitosan, 4.5 parts of olefin compound and 2 parts of metal oxide powder are adopted in parts by weight.

The olefin compound is n-heneicosane; metal oxide powder zinc oxide.

And 3, mixing and dispersing the graphene temperature sensing material obtained in the step 2 and an adhesive in an aqueous solution to obtain temperature sensing energy storage slurry. The content of the graphene temperature sensing material in the slurry is 18% by mass.

The adhesive is AB adhesive; the amount of binder used was 4.5% by mass of the slurry.

And 4, coating the fibers with the temperature-sensitive energy storage slurry obtained in the step 3 in a dipping or coating mode.

Preferably, the fibers are coated by dipping or coating using a yarn sizing apparatus.

And 5, drying the composite fiber obtained in the step 4 at a temperature of 90-150 ℃ and under a pressure of 0.4-2Mpa under normal pressure, and then winding to obtain the graphene temperature sensing fiber. The winding speed is 50-100 m/min.

The embodiment also provides the graphene temperature-sensitive fiber prepared by the method.

Example 4

A preparation method of a graphene temperature-sensitive fiber comprises the following steps:

step 1, weighing the raw materials in proportion.

And 2, preparing the graphene temperature sensing material.

The graphene temperature sensing material is prepared by dissolving graphene oxide in water to obtain a graphene turbid liquid, adding chitosan, adjusting the pH value to be less than 7, uniformly stirring and dispersing to obtain a chitosan dispersed turbid liquid, adding metal oxide powder and an olefin compound, heating to 50-70 ℃, and reacting for 4-8 hours to obtain the graphene temperature sensing material.

Preferably, the graphene oxide/metal oxide composite material comprises 6 parts by weight of graphene oxide, 7 parts by weight of chitosan, 5 parts by weight of an olefin compound and 2.5 parts by weight of metal oxide powder.

The olefin compound is any one of n-heneicosane, octadecane and hexadecyl trimethyl ammonium bromide; the oxidized metal powder is ferric oxide.

And 3, mixing and dispersing the graphene temperature sensing material obtained in the step 2 and an adhesive in an aqueous solution to obtain temperature sensing energy storage slurry. The content of the graphene temperature-sensitive material in the slurry is 22% by mass.

The adhesive is any one of PU resin, acrylic resin and AB glue; the amount of binder used was 5% by mass of the slurry.

And 4, coating the fibers with the temperature-sensitive energy storage slurry obtained in the step 3 in a dipping or coating mode.

Preferably, the fibers are coated by dipping or coating using a yarn sizing apparatus.

And 5, drying the composite fiber obtained in the step 4 at a temperature of 90-150 ℃ and under a pressure of 0.4-2Mpa under normal pressure, and then winding to obtain the graphene temperature sensing fiber. The winding speed is 50-100 m/min.

The embodiment also provides the graphene temperature-sensitive fiber prepared by the method.

Example 5

A preparation method of a graphene temperature-sensitive fiber comprises the following steps:

step 1, weighing the raw materials in proportion.

And 2, preparing the graphene temperature sensing material.

The graphene temperature sensing material is prepared by dissolving graphene oxide in water to obtain a graphene turbid liquid, adding chitosan, adjusting the pH value to be less than 7, uniformly stirring and dispersing to obtain a chitosan dispersed turbid liquid, adding metal oxide powder and an olefin compound, heating to 50-70 ℃, and reacting for 4-8 hours to obtain the graphene temperature sensing material.

Preferably, 7 parts of graphene oxide, 8 parts of chitosan, 6 parts of olefin compound and 3 parts of metal oxide powder are adopted in parts by weight.

The olefin compound is any of n-heneicosane, octadecane and hexadecyl trimethyl ammonium bromide; the metal oxide powder is any of cuprous oxide, ferrous oxide, zinc oxide and ferric oxide.

And 3, mixing and dispersing the graphene temperature sensing material obtained in the step 2 and an adhesive in an aqueous solution to obtain temperature sensing energy storage slurry. The content of the graphene temperature sensing material in the slurry is 25% by mass.

The adhesive is any of PU resin, acrylic resin and AB glue; the amount of binder used was 5.5% by mass of the slurry.

And 4, coating the fibers with the temperature-sensitive energy storage slurry obtained in the step 3 in a dipping or coating mode.

Preferably, the fibers are coated by dipping or coating using a yarn sizing apparatus.

And 5, drying the composite fiber obtained in the step 4 at a temperature of 90-150 ℃ and under a pressure of 0.4-2Mpa under normal pressure, and then winding to obtain the graphene temperature sensing fiber. The winding speed is 50-100 m/min.

The embodiment also provides the graphene temperature-sensitive fiber prepared by the method.

Experiments and tests were performed on various embodiments of the present invention, and the results are as follows.

The color change temperature is as follows: 32.6-37.1 ℃, the color-changing time is 30-45s, the color-changing temperature is 25.6-30.2 ℃, the time is 40-55s, the surface of the coating is smooth and flat, the color change is obvious, the reversibility is good, compared with other fibers, the color-changing time is longer, the color is obvious, and the temperature sensing temperature is more sensitive.

The graphene temperature sensing fiber and the preparation method thereof provided by the invention provide a preparation method of the graphene temperature sensing fiber which is good in applicability, strong in regulating capability and durable. Firstly, preparing a graphene temperature sensing material, then preparing temperature sensing slurry by using the material, and then coating the prepared temperature sensing slurry on fibers to obtain the temperature sensing fibers. The fiber can display different colors according to different temperatures, has simple preparation method, can be carried out on most chemical fibers, and has simple process, low cost and wide application prospect.

While the present invention has been described in detail with reference to the preferred embodiments, it should be understood that the above description should not be taken as limiting the invention. Various modifications and alterations to this invention will become apparent to those skilled in the art upon reading the foregoing description. Accordingly, the scope of the invention should be determined from the following claims.