CN107524001B - A kind of nano textile pulp and preparation method thereof - Google Patents

Abstract

The present invention provides a kind of nanometer textile glue sizes and preparation method thereof.Using the mixture of starch or starch and polyvinyl alcohol as main slurry, polyacrylate slurry and nano-cellulose dispersion liquid or modified nanometer cellulose dispersion liquid are sequentially added into main slurry, 2~3h of constant temperature constant speed mashing off, then using high-shear homogenizer activation 30~60min of stirring, the nanometer textile glue size can be obtained.The present invention is wide by raw material sources, the nano-cellulose or modified nanometer cellulose of large specific surface area are additive, form netted complex, main slurry coating performance is improved to reach, improves yarn count tensile strength, the purpose of toughness and wearability, form replacing for polyvinyl alcohol starching, production cost is reduced, sizing quality is improved, reduces environmental pollution.

Description

A kind of nano textile pulp and preparation method thereof

technical field

The invention relates to a nano-textile slurry and a preparation method thereof.

Background technique

Starch, polyacrylate and polyvinyl alcohol (PVA) are the three main materials for sizing of textile yarns. Among them, PVA sizing is widely used due to its good film-forming properties and high strength, but PVA sizing exists in the sizing process. Time-consuming and energy-consuming, easy to crust, difficult to desizing, not easy to decompose, etc. Therefore, people have been trying to find a sizing or sizing method that can use less or no PVA.

With the development of nanotechnology, people propose to use nanotechnology or nanomaterials to achieve the purpose of improving sizing performance. The reported nano-slurry is mainly prepared by using nanoparticles such as titanium dioxide, silicon dioxide and montmorillonite as additives or chemical synthesis. Although the nano-sized slurry prepared by this method has greatly improved the sizing performance of the yarn, some nano-sized slurry also has functionality, which makes the yarn have the functions of high surface activity and UV shielding. However, the main purpose of yarn sizing is to enhance yarn strength, reduce yarn hairiness, improve yarn wear resistance and other properties to improve yarn weaveability. After weaving, desizing treatment is required to remove the size of the fabric surface. Therefore, the functionality brought by various nanoparticles is temporary, and it is easy to cause environmental pollution during the desizing process.

SUMMARY OF THE INVENTION

In order to solve the above technical problems, the present invention provides a nano-textile slurry and a preparation method thereof. The strength of the yarn is improved and the hairiness of the yarn is reduced by adding the nanocellulose dispersion liquid or the modified nanocellulose dispersion liquid to the slurry.

The technical scheme adopted in the present invention is:

A preparation method of nano-textile slurry, the preparation method comprises the following steps: taking starch as the main slurry, adding polyacrylate type slurry and nano-cellulose dispersion liquid to the main slurry in sequence, and cooking the slurry at a constant temperature and a constant speed 2 to 3 hours, and then use a high-speed homogenizer to activate and stir for 30 to 60 minutes to obtain the nano-textile slurry.

The starch can be replaced by a mixture of starch and polyvinyl alcohol; the weight ratio of starch to polyvinyl alcohol is 2-4:8-6; preferably 4:6. In order to reduce the use of polyvinyl alcohol, the weight ratio of starch to polyvinyl alcohol is limited to 2-4:8-6; because if the polyvinyl alcohol content is too high, it is not easy to desizing, which will pollute the environment and also Makes cooking difficult.

The starch is native starch or modified starch.

The nanocellulose dispersion can be replaced with a modified nanocellulose dispersion.

The modified nanocellulose dispersion liquid is a polymethyl acrylate modified nanocellulose dispersion liquid, a polyethyl acrylate group modified nanocellulose dispersion liquid, and a methyl methacrylate group modified nanocellulose dispersion liquid. one or more. It is preferably a polymethyl acrylate-modified nanocellulose dispersion. The principle of sizing is similar and compatible. Pure nanocellulose dispersion contains only hydroxyl groups and other groups, which is not conducive to the sizing treatment of polyester fiber yarns, that is, it has poor adhesion to polyester cotton blended yarns. Therefore, the modification method is adopted. Grafting a certain ester group on the nanocellulose is beneficial to the penetration and coating of the polyester fiber, that is, the polyester fiber yarn, by the slurry.

The preparation method of the nanocellulose dispersion is as follows: mixing nanocellulose and water, and using a high-speed homogenizer to stir uniformly at a rotating speed of 1500-3000 r/min to form a slurry, and the obtained nanocellulose dispersion has a solid content ratio of is 0.6%. The thixotropy of nanocellulose is very strong. When the mass fraction is greater than 0.3%, it will form a gel state from the dispersion state, and it can be turned into a dilute flowing liquid under the action of a high-speed homogenizer. Nanocellulose is made of Adding the dispersion liquid to the main size, on the one hand, is conducive to the uniform mixing of the raw materials, and on the other hand, it can avoid the agglomeration of nanocellulose during the pulp cooking process, which will affect the uniformity of the sizing film after yarn sizing. and yarn properties.

The preparation method of the modified nanocellulose dispersion is the same as the preparation method of the nanocellulose dispersion.

The preparation method of polymethyl acrylate modified nanocellulose is as follows: acrylic acid is activated by carboxydiimidazole to obtain an active intermediate of acrylic acid; the active intermediate of acrylic acid activates nanocellulose to obtain active nanocellulose; The polymethyl acrylate of ~2300 was added to the dimethyl sulfoxide solution of active nanocellulose and reacted under the action of an initiator to obtain a crude product of polymethyl acrylate modified nanocellulose. The crude product was purified by tetrahydrofuran and obtained after centrifugation. Polymethyl acrylate modified nanocellulose.

The polyethyl acrylate-modified nanocellulose and methyl methacrylate-modified nanocellulose can be prepared by the same preparation method as the polymethyl acrylate-modified nanocellulose.

The molar ratio of the active nanocellulose to polymethyl acrylate is 1:2.

The solid content in the main slurry is 8-12%; preferably 10%. The solid content is high, it is not easy to cook pulp, and the production cost is increased.

The solid content of the polyacrylate slurry is 20%.

The weight of the polyacrylate-based slurry is 5-15% of the weight of the main slurry, preferably 10%. Polyacrylic sizing can improve the flexibility of the sizing film and the permeability of the sizing, but the cost of this sizing is high, and it is generally only used as an auxiliary sizing, so the content should not be too high. At the same time, the polyacrylic sizing is hygroscopic and then sticky, and the phenomenon of hygroscopic and sticky after yarn sizing is easy to occur, which affects the quality of yarn sizing. Therefore, in the present invention, the weight of the polyacrylic sizing is limited to 5% of the weight of the main sizing. ~15%.

The weight of the nanocellulose dispersion is less than 3% of the weight of the main slurry, preferably 0.3-1%. This can prevent the phenomenon of agglomeration of nanocellulose or modified nanocellulose during cooking due to too much feed.

The temperature of the pulp cooking is a constant temperature of 100°C; the stirring speed of the high-speed homogenizer is 1500-3000 r/min, which can prevent the nanocellulose or modified nanocellulose from agglomerating after the pulp cooking.

The present invention further provides the nano-textile slurry prepared according to the above-mentioned preparation method.

The term solid content involved in this article refers to the weight percentage of the raw material in the slurry; when the slurry is prepared, the solvent is all water.

The present invention utilizes nanocellulose or modified nanocellulose as a slurry additive, and utilizes the similar compatibility and nanomaterial properties of cellulose and modified nanofiber with the fiber raw materials contained in the yarn, so as to improve the quality of the slurry and the yarn. The purpose of binding and improving slurry properties.

The invention uses nano-cellulose or modified nano-cellulose with a wide source of raw materials and a large specific surface area as an additive to form a network composite, so as to improve the coating performance of the main slurry, improve the tensile strength, toughness and wear resistance of the yarn count The purpose is to replace polyvinyl alcohol sizing, reduce production costs, improve sizing quality, and reduce environmental pollution.

Description of drawings

Fig. 1 is the scanning electron microscope image of the serous film formed by the nano-textile slurry in embodiment 1;

Fig. 2 is the scanning electron microscope image of the serous film formed by the nano-textile slurry in Comparative Example 1;

3 is a scanning electron microscope image of the sizing film formed by the nano-textile slurry in Comparative Example 2.

Detailed ways

The present invention will be described in detail below with reference to Examples 1 to 3, Comparative Examples 1 to 2 and accompanying drawings 1 to 3 of the specification.

The manufacturer, specification and model of each raw material involved in the present invention are respectively:

Starch: raw corn starch, industrial grade, provided by Shandong Zhucheng Xingmao Corn Development Co., Ltd.;

Polyvinyl alcohol: PVA1799, provided by Anhui Wanwei High-tech Materials Co., Ltd.;

Polymethyl acrylate slurry: solid content of 20%, Jinan Shanbo Trading Co., Ltd.;

Nanocellulose: The average length is 1342nm, and the fiber diameter is 12.3nm, provided by Guilin Qihong Technology Co., Ltd.; in the preparation process of nano-textile pulp, nano-cellulose is added in the form of dispersion, and the The preparation method is as follows: mixing nanocellulose and water, and using a high-speed homogenizer at a rotating speed of 1500-3000 r/min to uniformly stir to form a slurry, and the obtained nanocellulose dispersion has a solid content of 0.6%.

Example 1

A preparation method of nano-textile slurry, comprising the following steps:

A mixed slurry made of starch and polyvinyl alcohol in a weight ratio of 4:6 is the main slurry, and the solid content of the main slurry is 10%; polymethyl acrylate slurry and nanofibers are added to the main slurry in turn The weight of the polymethyl acrylate slurry is 10% of the weight of the main slurry, and the solid content of the polymethyl acrylate slurry is 20%; the weight of the nanocellulose dispersion is the main slurry 0.3% of the weight; 100°C constant temperature and constant speed for 2 hours, and then activated and stirred by a high-speed homogenizer for 30 minutes at a stirring speed of 2000 r/min to obtain the nano-textile slurry.

The polyester/cotton 65/35 blended yarn and pure cotton yarn are sizing with the nano-textile slurry prepared in this example. The yarn properties before and after sizing are shown in Table 1 and Table 2 respectively. The SEM image of the serosa formed by the nano-textile slurry is shown in Figure 1. It can be seen from Figure 1 that the serosa is smooth and has no cracking phenomenon.

Table 1 Yarn performance index before sizing

Table 2 Yarn performance index after sizing

From Table 1, Table 2 and Table 5, it can be seen that the breaking strength of the yarn after adding nanocellulose to the slurry increases significantly, and the strength of polyester-cotton blended yarn is increased by 12.9% compared with that before nanocellulose additive is added. , the strength of pure cotton yarn is increased by 4.4%, although the reduction rate of yarn hairiness is not as good as when nanocellulose is not added, but the number of hairiness of yarn above 3mm is similar, and it meets the weaving requirements.

Example 2

A preparation method of nano-textile slurry, comprising the following steps:

Starch is the main slurry, and the solid content of the main slurry is 10%; polymethyl acrylate slurry and nanocellulose dispersion liquid are added to the main slurry in turn, and the weight of the polymethyl acrylate slurry is the main weight. 10% of the weight of the slurry, the solid content of the polymethyl acrylate slurry is 20%; the weight of the nanocellulose dispersion is mainly 1% of the weight of the slurry; the slurry is boiled at a constant temperature and speed of 100 ° C for 2 hours, and then used The high-speed homogenizer is activated and stirred for 30 minutes, and the stirring speed is 2000 r/min, and the nano-textile slurry can be obtained.

The polyester/cotton 65/35 blended yarn and pure cotton yarn were sizing with the nano-textile slurry prepared in this example, and the yarn properties before and after sizing are shown in Table 1 and Table 3, respectively.

Table 3 Yarn performance index after sizing

As can be seen from Table 1, Table 3 and Table 5, when the pure starch after adding nanocellulose is used as the main size, the performance index of the yarn after sizing is different from the performance of the sizing yarn using the mixed size of starch and polyvinyl alcohol. The breaking strength of polyester/cotton yarn increased by 17.6% compared with that before sizing, and the breaking strength of pure cotton yarn increased by 37.3% compared with that before sizing, and the elongation at break also decreased to a certain extent. The hairiness was significantly reduced, indicating that the use of polyvinyl alcohol slurry could be replaced by adding nanocellulose.

Example 3

A preparation method of nano-textile slurry, comprising the following steps:

Starch is used as the main slurry, and the solid content of the main slurry is 10%; polymethyl acrylate slurry and polymethyl acrylate modified nanocellulose dispersion are added to the main slurry in sequence, and the polymethyl acrylate slurry is added to the main slurry. The weight of the slurry is mainly 10% of the weight of the slurry, and the solid content of the polymethyl acrylate slurry is 20%; the weight of the polymethyl acrylate modified nanocellulose dispersion is mainly 1% of the weight of the slurry ; 100 ℃ constant temperature and constant speed to cook pulp for 2h, and then use a high-speed homogenizer to activate and stir for 30min, and the stirring speed is 2000r/min, and the nano-textile pulp can be obtained.

The preparation method of polymethyl acrylate modified nanocellulose is:

Using dichloromethane as a solvent, acrylic acid was dissolved in dichloromethane, placed in a three-necked flask and fully stirred, and then a quantitative amount of carboxydiimidazole was weighed and added to the three-necked flask in batches, and reacted at room temperature for 4 hours to prepare the active intermediate of acrylic acid. body (AA-CDI).

Weigh 0.5 g of nanocellulose into a test tube, add 10 ml of dimethyl sulfoxide and mix until the nanocellulose is fully dispersed in dimethyl sulfoxide, then replace the solvent dimethyl sulfoxide with dichloromethane, and then add The dichloromethane solution containing nanocellulose is added to the active intermediate of acrylic acid, and the reaction is carried out at room temperature for 20 hours to prepare the activated nanocellulose.

The polymethyl acrylate with a relative molecular mass of 2000 is added to the dimethyl sulfoxide solution of activated nanocellulose, and the crude product of polymethyl acrylate modified nanocellulose is obtained by reacting under the action of an initiator, wherein the active nanofibers are reacted. The molar ratio of tetrahydrofuran to polymethyl acrylate was 1:2, and the reaction was carried out for 8 hours at room temperature. Then, an appropriate amount of tetrahydrofuran was added to the crude product, and the pure polymethyl acrylate modified nanocellulose was obtained by centrifugal washing.

The polyester/cotton 65/35 blended yarn and pure cotton yarn were sizing with the nano-textile slurry prepared in this example. The yarn properties before and after sizing are shown in Table 1 and Table 4, respectively.

Table 4 Yarn performance index after sizing

It can be seen from Table 1 and Table 4 that after sizing the polyester/cotton yarn and pure cotton yarn with the nano-textile slurry in this example, the breaking strength of the polyester/cotton yarn increased by 36.0% compared with that before the sizing. The breaking strength of pure cotton yarn was increased by 47.7% compared with that before sizing, and the yarn hairiness was significantly lower than that before sizing.

Under the condition that other raw materials and dosages remain unchanged, in this example, nano-textile slurry was obtained by adding polymethyl acrylate modified nanocellulose. In Example 2, nano-textile slurry was obtained by adding nanocellulose. 1. It can be seen from Table 3 that after sizing the polyester/cotton yarn and pure cotton yarn, the breaking strength of the polyester/cotton yarn in this example is increased by 15.6% compared with the polyester/cotton yarn in Example 2, and the elongation at break also has a certain degree of , the breaking strength of pure cotton yarn increased by 7.6%, and the elongation at break remained the same. It shows that the addition of modified nanocellulose can significantly improve the performance of the yarn.

Comparative Example 1

A preparation method of textile pulp, comprising the following steps:

The mixed slurry made of starch and polyvinyl alcohol in a weight ratio of 4:6 is the main slurry, and the solid content of the main slurry is 10%; The weight of the methyl acrylate pulp is 10% of the weight of the main pulp, and the solid content of the polymethyl acrylate pulp is 20%.

The polyester/cotton 65/35 blended yarn and pure cotton yarn are sizing with the nano-textile slurry prepared in this example. The yarn properties before and after sizing are shown in Table 1 and Table 5, respectively. This comparative example obtains The SEM image of the serosa formed by the textile slurry is shown in Figure 2. It can be seen from Figure 2 that there are certain cracks on the surface of the serosa. It can be seen from the comparison of Figure 1 and Figure 2 that the addition of nanocellulose to the slurry is beneficial to the formation of a smooth surface film.

Table 5 Yarn performance index after sizing

Comparative Example 2

A preparation method of nano-textile slurry, comprising the following steps:

A mixed slurry made of starch and polyvinyl alcohol in a weight ratio of 4:6 is the main slurry, and the solid content of the main slurry is 10%; polymethyl acrylate slurry and nanofibers are added to the main slurry in turn The weight of the polymethyl acrylate slurry is 10% of the weight of the main slurry, and the solid content of the polymethyl acrylate slurry is 20%; the weight of the nanocellulose dispersion is the main slurry 3% of the weight; 100°C constant temperature and constant speed for 2 hours, and then activated and stirred by a high-speed homogenizer for 30 minutes, the stirring speed of which is 2000 r/min, the nano-textile slurry can be obtained.

The polyester/cotton 65/35 blended yarn and pure cotton yarn are sizing with the nano-textile slurry prepared in this example. The yarn properties before and after sizing are shown in Table 1 and Table 6, respectively. This comparative example obtains The SEM image of the serosa formed by the nano-textile slurry is shown in Figure 3. It can be seen from Figure 3 that there are certain particles in the serosa, indicating that when the nanocellulose content is relatively high, the Cellulose is prone to agglomeration.

It can be seen from Table 1, Table 3 and Table 6 that when the nanocellulose content in the slurry is too high, the improvement of the hairiness index of the yarn after sizing becomes significantly worse, indicating that the nanocellulose content in the slurry is too high. Agglomeration and increased surface energy of the sizing occur to reduce the covering properties of the yarn.

Table 6 Yarn performance index after sizing

The above-mentioned detailed description of a nano-textile slurry and its preparation method with reference to the examples is illustrative rather than restrictive, and several examples can be listed according to the limited scope, so it is not departing from the general concept of the present invention. The following changes and modifications shall fall within the protection scope of the present invention.

Claims (10)

1. a preparation method of nano-textile slurry, is characterized in that, described preparation method comprises the following steps: take starch as main slurry, in main slurry, add polyacrylate type slurry and nano-cellulose dispersion successively , cook pulp at constant temperature and constant speed for 2~3h, and then use high-speed homogenizer to activate and stir for 30~60min to obtain the nano-textile pulp; The weight of the nanocellulose dispersion is less than 3% of the weight of the main pulp. 2. preparation method according to claim 1 is characterized in that, described starch can be replaced with the mixture of starch and polyvinyl alcohol; The ratio of the weight of starch and polyvinyl alcohol is 2～4:8～6. 3. The preparation method according to claim 1, wherein the nanocellulose dispersion can be replaced by a modified nanocellulose dispersion. 4. preparation method according to claim 3, is characterized in that, described modified nanocellulose dispersion liquid is polymethyl acrylate modified nanocellulose dispersion liquid, polyethyl acrylate modified nanocellulose dispersion liquid , one or more of methyl methacrylate-based modified nanocellulose dispersions. 5 . The preparation method according to claim 1 , wherein the solid content in the main slurry is 8-12%. 6 . 6 . The preparation method according to claim 1 , wherein the solid content of the nanocellulose dispersion is 0.6%. 7 . 7 . The preparation method according to claim 1 , wherein the weight of the polyacrylate-based slurry is 5-15% of the weight of the main slurry. 8 . 8. The preparation method according to any one of claims 1-3, wherein the weight of the nanocellulose dispersion is 0.3-1% of the weight of the main slurry. 9. The preparation method according to any one of claims 1-3, characterized in that, the temperature of the boiled pulp is a constant temperature of 100°C; the stirring speed of the high-speed homogenizer is 1500-3000 r/min. 10. The nano-textile slurry prepared by the preparation method according to any one of claims 1-9.