阅读说明：本技术 一种活化海泡石纤维及其制备方法、以及包含该活化海泡石纤维的尼龙材料及其制备方法 (Activated sepiolite fiber and preparation method thereof, and nylon material containing activated sepiolite fiber and preparation method thereof ) 是由 杨桂生 方永炜 姚晨光 邹冲 朱敏 项灵芝 于 2020-07-06 设计创作，主要内容包括：本发明公开了一种活化海泡石纤维及其制备方法,活化海泡石纤维的制备方法包括以下步骤：向反应釜中加入己内酰胺、海泡石纤维、抗氧剂1010,反应釜内温度为100-120℃,搅拌速度为50-100转/min,反应得到活化海泡石纤维。本发明采用特殊的碱己内酰胺处理海泡石纤维,在高温环境以及低速搅拌的条件下,海泡石纤维解离成细长纤维,分离性能较好,制得的活化海泡石纤维具有良好的活性。本发明还公开了包含上述活化海泡石纤维的尼龙材料及其制备方法。本发明通过将活化海泡石纤维加入至尼龙材料中,能够明显增加尼龙的拉伸强度、弯曲强度及抗冲击强度,提高尼龙材料的机械性能。(The invention discloses an activated sepiolite fiber and a preparation method thereof, wherein the preparation method of the activated sepiolite fiber comprises the following steps: adding caprolactam, sepiolite fibers and an antioxidant 1010 into a reaction kettle, wherein the temperature in the reaction kettle is 100-120 ℃, and the stirring speed is 50-100 r/min, and reacting to obtain the activated sepiolite fibers. The invention adopts special alkali caprolactam to treat the sepiolite fibers, under the conditions of high temperature environment and low-speed stirring, the sepiolite fibers are dissociated into long and thin fibers, the separation performance is better, and the prepared activated sepiolite fibers have good activity. The invention also discloses a nylon material containing the activated sepiolite fiber and a preparation method thereof. According to the invention, the activated sepiolite fibers are added into the nylon material, so that the tensile strength, the bending strength and the impact strength of the nylon can be obviously increased, and the mechanical property of the nylon material is improved.)

1. A preparation method of activated sepiolite fibers is characterized by comprising the following steps: the method comprises the following steps: adding 100 parts of caprolactam, 3-10 parts of sepiolite fibers and 1-2 parts of antioxidant 1010 into a reaction kettle, and sealing the reaction kettle; the temperature in the reaction kettle is 100-.

2. The method of claim 1, wherein: the length of the sepiolite fiber is 10-15mm, and the water content is 10-15%.

3. Activated sepiolite fibers obtained by the process of claim 1.

4. A nylon material is characterized in that: the composition is prepared from the following components in parts by weight:

5. the nylon material of claim 4, wherein: the nylon is one of nylon 6 and nylon 66.

6. The nylon material of claim 5, wherein: the melt index of the nylon 6 under the condition of 230 ℃/2.16kg is 40-50g/10 min; the melt index of the nylon 66 is 8-12g/10min under the condition of 230 ℃/2.16 kg.

7. The nylon material of claim 4, wherein: the antioxidant is a mixture of the antioxidant 1010 and the antioxidant 168 according to the mass ratio of 1: 1.

8. The nylon material of claim 4, wherein: the lubricant is oleamide.

9. The method for preparing a nylon material according to any one of claims 4 to 8, wherein: the method comprises the following steps: adding 100 parts of nylon, 0.5-1 part of antioxidant and 1-2 parts of lubricant into a mixer, and uniformly mixing at normal temperature to obtain a mixture; and adding the mixture from a feed inlet of a double-screw extruder, adding the activated sepiolite fibers from a side feed inlet of the double-screw extruder, and extruding and granulating to obtain the nylon material.

10. The method of claim 9, wherein: the extrusion temperature of the double-screw extruder is 180-280 ℃.

Technical Field

The invention belongs to the technical field of high polymer materials, and particularly relates to an activated sepiolite fiber and a preparation method thereof, as well as a nylon material containing the activated sepiolite fiber and a preparation method thereof.

Background

Sepiolite fiber is a natural mineral fiber that is a fibrous variant of sepiolite mineral, known as α -sepiolite. Sepiolite is described by experts as a layered chain silicate mineral with a layer of magnesiooctahedra sandwiched between two silicon-oxygen tetrahedra in the structure to form a 2: 1 type layered structure unit. The tetrahedral layer is continuous, and the orientation of the active oxygen in the layer is periodically inverted. The octahedral layers form channels arranged alternately in the upper and lower layers. The orientation of the channels is aligned with the fiber axis, allowing water molecules, metal cations, small organic molecules, etc. to enter therein. The sepiolite has good heat resistance, good ion exchange and catalytic properties, excellent corrosion resistance, radiation resistance, insulation, heat insulation and the like, and particularly, Si-OH in the structure of the sepiolite can directly react with organic matters to generate organic mineral derivatives.

In the structural unit, silicon-oxygen tetrahedrons and magnesium-oxygen octahedrons are mutually alternated, and have the transition characteristics of layers and chains. The sepiolite has unique physical and chemical properties, high specific surface area (up to 800-900m/g), large porosity and strong adsorption and catalysis capabilities.

The sepiolite has wide application field, and the sepiolite after a series of treatments such as purification, ultrafine processing, modification and the like can be used as an adsorbent, a purifying agent, a deodorant, a reinforcing agent, a suspending agent, a thixotropic agent, a filler and the like to be applied to the industrial aspects such as water treatment, catalysis, rubber, coating, chemical fertilizer, feed and the like. In addition, the sepiolite has better salt resistance and high temperature resistance, so that the sepiolite can be used as a high-quality drilling mud raw material for petroleum drilling, geothermal drilling and the like.

However, in order to achieve good filling effect of sepiolite fibers, activation treatment is required. After activation treatment, the activity of functional groups on the surface of the sepiolite fiber can be improved, the specific surface area of the sepiolite fiber is increased, and the adsorption and ion exchange capacities are enhanced. The sepiolite is generally activated by acid treatment, surface modification treatment, and the like. Some people activate sepiolite by using alkali, add 20%, 10% and 5% NaOH solution into the sample, soak for 1 hour, filter and dry for use. The alkali treated sample is analyzed, and the result shows that no matter which concentration of alkali has little influence on the structure of the sepiolite.

Polyamide (PA, colloquially referred to as nylon) was the first resin developed for fibers by DuPont in the united states and was commercialized in 1939. In the 50 th of the 20 th century, injection molded products are developed and produced to replace metals to meet the requirements of light weight and cost reduction of downstream industrial products. Polyamides, which contain a number of repeating amide groups in the main chain, are called nylons when used as plastics and as nylon when used as synthetic fibers, are prepared from diamines and diacids, and can also be synthesized from omega-amino acids or cyclic lactams. According to the difference of carbon atom number in diamine and diacid or amino acid, a plurality of different polyamides can be prepared, the variety of the polyamide is dozens, and the polyamide-6 (nylon 6), the polyamide-66 (nylon 66) and the polyamide-610 are most widely applied.

Disclosure of Invention

Aiming at the defects of the prior art, the invention aims to provide a preparation method of activated sepiolite fibers.

The purpose of the invention is realized by the following technical scheme:

a preparation method of activated sepiolite fibers comprises the following steps: adding 100 parts of caprolactam, 3-10 parts of sepiolite fibers and 1-2 parts of antioxidant 1010 into a reaction kettle, and sealing the reaction kettle; the temperature in the reaction kettle is 100-. Preferably, the length of the sepiolite fiber is 10-15mm, the pH value is 9, and the water content is 10-15%.

A second object of the present invention is to provide activated sepiolite fibers obtained by the above-described preparation method.

The third purpose of the invention is to provide a nylon material, which is prepared from the following components in parts by weight:

preferably, the nylon is one of nylon 6 and nylon 66. Further preferably, the melt index of the nylon 6 at 230 ℃/2.16kg is 40-50g/10 min; the melt index of the nylon 66 is 8-12g/10min under the condition of 230 ℃/2.16 kg.

As a preferred technical scheme, the antioxidant is a mixture of antioxidant 1010 and antioxidant 168 according to a mass ratio of 1: 1.

As a preferred embodiment, the lubricant is oleamide.

The fourth purpose of the invention is to provide a preparation method of the nylon material, which comprises the following steps: adding 100 parts of nylon, 0.5-1 part of antioxidant and 1-2 parts of lubricant into a mixer, and uniformly mixing at normal temperature to obtain a mixture; and adding the mixture from a feed inlet of a double-screw extruder, adding the activated sepiolite fibers from a side feed inlet of the double-screw extruder, and extruding and granulating to obtain the nylon material. Preferably, the extrusion temperature of the twin-screw extruder is 180-280 ℃.

Compared with the prior art, the invention has the beneficial effects that:

(1) the invention adopts special alkali caprolactam to treat the sepiolite fibers, under the conditions of high temperature environment and low-speed stirring, the sepiolite fibers are dissociated into long and thin fibers, the separation performance is better, and the prepared activated sepiolite fibers have good activity. Caprolactam is weak base, the reaction conditions are closely related to the structure of the product in the preparation process, and when the temperature is too high, the sepiolite fibers are easily decomposed into fine fibers, so that the viscosity of the sepiolite fibers is increased, and the separation difficulty is increased; too fast stirring speed easily causes fiber damage and fiber breakage, and further destroys the mechanical property of the fiber.

(2) According to the invention, the activated sepiolite fibers are added into the nylon material, so that the tensile strength, the bending strength and the impact strength of the nylon can be obviously increased, and the mechanical property of the nylon material is improved.

Detailed Description

The present invention will be further described with reference to the following examples. It is to be understood that the embodiments described are only a few embodiments of the present invention, and not all 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 types and suppliers of reagents used in this example were as follows: caprolactam purity higher than 99%, manufacturer basf, germany; the melt index of nylon 6 is 45g/10min, the manufacturer basf, germany, brand PA 68202L; the nylon 66 resin manufacturer, Toshima Marx, is entitled EPR27, and has a melt index of 10.8g/10 min; the length of sepiolite fiber is 10mm, the pH value is 9, the water content is 12%, and a manufacturer is Shijiazhui Ruiyuan product Limited; the oleamide is purchased from a Heimenghualong oil and fat auxiliary agent factory, is white powder, has a melting point of 72-82 ℃, and has an amide content of more than 99.9 percent. The antioxidant is a mixture of the antioxidant 1010 and the antioxidant 168 according to the mass ratio of 1: 1. The reagents are provided only for illustrating the sources and components of the reagents used in the experiments of the present invention, so as to be fully disclosed, and do not indicate that the present invention cannot be realized by using other reagents of the same type or other reagents supplied by other suppliers.

Example 1

Preparation of activated sepiolite fibers:

and (3) adding 100 parts of caprolactam, 10 parts of sepiolite fibers and 1 part of antioxidant 1010 into the reaction kettle, and sealing the reaction kettle. Adjusting the temperature to 120 ℃, stirring for 1 hour at 100 r/min, decompressing, filtering and drying at normal temperature to obtain the activated sepiolite fiber for later use.

Example 2

Adding 6100 parts of nylon, 0.5 part of antioxidant and 1 part of oleamide into a mixer, uniformly mixing at normal temperature, adding the mixture from a feed inlet of a double-screw extruder, adding 10 parts of the activated sepiolite fiber prepared in the example 1 from a side feed inlet of the double-screw extruder, extruding and granulating. The temperatures of the zones of the double-screw extruder are respectively 1 zone 180 ℃, 2 zone 190 ℃, 3 zone 200 ℃, 4 zone 210 ℃, 5 zone 220 ℃, 6 zone 230 ℃, 7 zone 240 ℃, 8 zone 250 ℃ and die head zone 260 ℃.

Example 3

Nylon 66100 parts, antioxidant 1 part, and oleamide 2 parts are added into a mixer, mixed evenly at normal temperature, added from the feed inlet of a double screw extruder, and 40 parts of the activated sepiolite fiber prepared in example 1 is added from the side feed inlet of the double screw extruder, extruded and granulated. The temperatures of the zones of the twin-screw extruder are respectively 1 zone 200 ℃, 2 zone 220 ℃, 3 zone 230 ℃, 4 zone 240 ℃, 5 zone 260 ℃, 6 zone 260 ℃, 7 zone 270 ℃, 8 zone 280 ℃ and die zone 280 ℃.

Example 4

Nylon 66100 parts, antioxidant 0.5 parts, and oleamide 1 part are added into a mixer, mixed evenly at normal temperature, added from the feed inlet of a double screw extruder, and 20 parts of the activated sepiolite fiber prepared in example 1 is added from the side feed inlet of the double screw extruder, extruded and granulated. The temperatures of the zones of the twin-screw extruder are respectively 1 zone 200 ℃, 2 zone 220 ℃, 3 zone 230 ℃, 4 zone 240 ℃, 5 zone 260 ℃, 6 zone 260 ℃, 7 zone 270 ℃, 8 zone 280 ℃ and die zone 280 ℃.

Example 5

Adding 6100 parts of nylon, 1 part of antioxidant and 2 parts of oleamide into a mixer, uniformly mixing at normal temperature, adding the mixture from a feed inlet of a double-screw extruder, adding 30 parts of the activated sepiolite fiber prepared in the example 1 from a side feed inlet of the double-screw extruder, extruding and granulating. The temperatures of the zones of the double-screw extruder are respectively 1 zone 180 ℃, 2 zone 190 ℃, 3 zone 200 ℃, 4 zone 210 ℃, 5 zone 220 ℃, 6 zone 230 ℃, 7 zone 240 ℃, 8 zone 250 ℃ and die head zone 260 ℃.

Comparative example 1

Adding 6100 parts of nylon, 1 part of antioxidant and 2 parts of oleamide into a mixer, uniformly mixing at normal temperature, adding the mixture from a feed inlet of a double-screw extruder, adding 30 parts of sepiolite fiber (not activated) from a side feed inlet of the double-screw extruder, extruding and granulating. The temperatures of the zones of the double-screw extruder are respectively 1 zone 180 ℃, 2 zone 190 ℃, 3 zone 200 ℃, 4 zone 210 ℃, 5 zone 220 ℃, 6 zone 230 ℃, 7 zone 240 ℃, 8 zone 250 ℃ and die head zone 260 ℃.

Comparative example 2

(1) Adding sepiolite fibers into a NaOH solution with the mass fraction of 15%, soaking for 1 hour, filtering, and drying for later use.

(2) Adding 6100 parts of nylon, 1 part of antioxidant and 2 parts of oleamide into a mixer, uniformly mixing at normal temperature, adding the mixture from a feed inlet of a double-screw extruder, adding 30 parts of the activated sepiolite fiber obtained in the step (1) from a side feed inlet of the double-screw extruder, extruding and granulating. The temperatures of the zones of the double-screw extruder are respectively 1 zone 180 ℃, 2 zone 190 ℃, 3 zone 200 ℃, 4 zone 210 ℃, 5 zone 220 ℃, 6 zone 230 ℃, 7 zone 240 ℃, 8 zone 250 ℃ and die head zone 260 ℃.

Comparative example 3

(1) Adding sepiolite fibers into a hydrochloric acid solution with the mass fraction of 10%, soaking for 1 hour, filtering, and drying for later use.

(2) Adding 6100 parts of nylon, 1 part of antioxidant and 2 parts of oleamide into a mixer, uniformly mixing at normal temperature, adding the mixture from a feed inlet of a double-screw extruder, adding 30 parts of the activated sepiolite fiber obtained in the step (1) from a side feed inlet of the double-screw extruder, extruding and granulating. The temperatures of the zones of the double-screw extruder are respectively 1 zone 180 ℃, 2 zone 190 ℃, 3 zone 200 ℃, 4 zone 210 ℃, 5 zone 220 ℃, 6 zone 230 ℃, 7 zone 240 ℃, 8 zone 250 ℃ and die head zone 260 ℃.

The physical properties of the products obtained in the above examples and comparative examples were measured as follows:

tensile properties were measured according to ASTM D638 (tensile speed 5 mm/min); flexural Properties were measured according to ASTM D790 (bending speed 1.25 mm/min); notched izod impact performance was tested according to ASTM D256;

the compositions of the invention were injection molded using ASTM standards, with bar dimensions (length. times. width. times. thickness) being: tensile bars (dumbbell type) 170mm by 13mm by 3.2 mm; bending a sample bar, 127mm × 13mm × 3.2 mm; notched impact bars, 127mm x 13mm x 3.2mm, V-shaped notches, with a notch depth of 1/5;

the performance of the products made in the examples and comparative examples was tested as follows:

TABLE 1 data of the performance tests of the products obtained in the examples and comparative examples

As can be seen from the above table, the sepiolite fiber treated by the special alkali (caprolactam) is added into the nylon matrix, so that the tensile strength, the bending strength and the impact strength of the nylon can be obviously improved.

The embodiments described above are intended to facilitate one of ordinary skill in the art in understanding and using the present invention. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the embodiments described herein, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.