CN116751539A - Composition for fixedly connecting fibers and plant pulp products and preparation method thereof - Google Patents

Abstract

This application provides a method for preparing a composition for fixing connecting fibers and plant pulp products; it includes: S1. Add substance A to a solvent and stir and raise the temperature until it is completely dissolved; S2. After cooling, add organic acid and stir for a period of time; S3 , and then add carbonyl-containing substances to it at a certain rate, mix for 0.3-6h and adjust the system pH to 6.7-7.2; continue stirring for 1-4h, and wait for the solution to cool down naturally to obtain the composition; this application is optimized The structure, molecular weight and number of polar groups of Substance A, as well as the amount and type of carbonyl-containing substances, make the composition particularly suitable for fixation between fibers and plant pulp products, with the best fixation effect and the strongest solvent resistance.

Description

Composition and preparation method for fixing connecting fibers and plant pulp products

Technical field

The present invention relates to the technical field of polymer materials, C08K, and in particular to a composition and preparation method for fixedly connecting bulky fibers and paper products.

Background technique

Fiber and paper products have similar origins. The raw materials for preparation include natural or artificial fibers. There are many products in the industry that involve the connection and fixation of fiber and paper products. However, they are limited by many factors. Currently, in the industry, fiber and paper The fixation and connection stability of the two interfaces of the product are still poor. The connection interface is damaged after being pulled by external force (repeatedly) or soaked in chemicals.

Chinese patent CN2595806Y discloses a fiber tear tape. The fibers are oriented and then coated with an adhesive to form a film, which is used to bond cartons. However, the adhesive in this patent needs to be heated during coating, making it inconvenient to use. And it is not very resistant to erosion by water or other organic solvents. Chinese patent CN107556946A discloses a special paper tube glue for paper, which is made by using polyvinyl alcohol, polyvinyl acetate emulsion, cyclodextrin derivatives, cellulase, modified glass fiber, and polystyrene emulsion. The material can only be used to connect the paper surface, and the connection between the fiber and the paper surface is still not strong, and it is not resistant to chemical immersion, and the raw material cost is also high.

Contents of the invention

In order to solve the above technical problems, the present invention first provides a preparation method for a composition for fixedly connecting fibers and plant pulp products.

Further, the preparation method includes:

S1. Add substance A to the solvent and stir until the temperature is completely dissolved;

S2. After cooling down, add organic acid and stir for a period of time;

S3. Add the carbonyl-containing substance to the solution at a certain rate. After mixing for 0.3-6 hours, adjust the pH of the system to 6.7-7.2. Continue stirring for 1-4 hours and wait until the solution is naturally cooled to obtain the composition.

Further, the substance A has the following structure:

Further, the X ₁ and X ₂ are independently selected from H, -OH, -COOH, -NH ₃ , C2-C8 acyl group, C1-C8 acyloxy group, C2-C15 oxyacyl group, C1-C15 Any one or a combination of alkyl groups, C1-C15 alkoxy groups, n is 1000-3000.

Further, the C2-C8 acyl group includes but is not limited to any one of acetyl, propionyl, butyryl, valeryl, tert-butyryl, hexanoyl, heptanoyl, and octanoyl.

Further, the C1-C8 acyloxy group includes but is not limited to formyloxy, acetoxy, propionyloxy, acryloyloxy, methacryloyloxy, butyryloxy, pivaloyl Any one of oxygen group, tert-butyryloxy group, hexanoyloxy group, heptanoyloxy group and octanoyloxy group.

Further, the C1-C15 alkyl group includes but is not limited to methyl, ethyl, propyl, butyl, isobutyl, tert-butyl, pentyl, isopentyl, neopentyl, hexyl, isohexyl , any one of heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, and pentadecyl.

Further, the C1-C15 alkoxy group includes but is not limited to methoxy, ethoxy, propoxy, butoxy, isobutoxy, tert-butoxy, pentyloxy, isopentyloxy , neopentyloxy, hexyloxy, isohexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy, undecyloxy, dodecyloxy, tridecyloxy, tetradecyloxy Any one of alkoxy and pentadecyloxy

Preferably, at least one of X ₁ and X ₂ is any one of -OH, C1-C8 acyloxy group, and C1-C15 alkoxy group.

Further, when at least one of X ₁ and X ₂ is a C1-C15 alkoxy group, step S1 also includes using a strong acid to treat and purify substance A; the strong acid is such as periodic acid.

Further, the R is H or methyl.

In one embodiment, both X ₁ and X ₂ are -OH, and R is H.

In one embodiment, X ₁ is -H, X ₂ is -OH, and R is H.

Further, the n is 1600-2800.

Preferably, n is 1600-2500, more preferably 1650-1800.

In one embodiment, when X ₁ is -H, X ₂ is -OH, and R is H, the alcoholysis degree of substance A is 75-100%.

This application uses the polar groups of substance A to further cross-link and polymerize substance A, increasing the density of the cross-linked network structure between the molecules of substance A, and better matching the connection needs between fibers and plant pulp products. The degree of polymerization represents the substance The molecular weight and alcoholysis degree of A represent the hydroxyl content of A. Increasing the polymerization degree and alcoholysis degree of A can increase the cross-linking reaction sites of substance A and carbonyl-containing substances, and increase the degree of cross-linking in the composition system, thereby making Composition A has high mechanical properties after curing, but when the polymerization of substance A is too high, the cross-linking points are unevenly distributed after the reaction between the carbonyl-containing substance and substance A, resulting in a reduction in the density of the network structure; alcoholysis Too high or too low a degree will also affect the solvent resistance of the cured composition. Only when the degree of polymerization n of substance A is 1650-1800, the bonding performance is the best.

Preferably, the alcoholysis degree of substance A is 87-100%; more preferably, it is 98-100%.

Further, the temperature in S1 is raised to 85-98°C, preferably 92-98°C; the solvent is selected from any one of water, ethyl acetate, dimethyl sulfoxide, propanol, glycerol, and ethanol; preferably water .

Further, the temperature is lowered to 78-85°C in S2; more preferably, it is 80-85°C; further preferably, it is 83°C.

In this application, organic acids are used instead of inorganic acids because most inorganic acids contain halogen ions or heavy metal acid ions, and the presence of these acids in the system will lead to the risk of excessive halogen or heavy metals in the final composition; in addition, these small molecules Anions tend to migrate outward in the composition after the composition is cured, affecting the structural stability and solvent resistance of the composition.

Further, the organic acids include but are not limited to formic acid, acetic acid, propionic acid, butyric acid, succinic acid, glycolic acid, citric acid, gluconic acid, benzenesulfonic acid, tartaric acid, malic acid, ascorbic acid, glutaric acid , lactic acid, succinic acid, any one or a combination of several.

Further, the organic acid is selected from any one or a combination of acetic acid, propionic acid, butyric acid, glutaric acid, and citric acid.

In one embodiment, the organic acid is acetic acid.

Further, the mass of the organic acid is 0.05-0.5 times the mass of substance A, preferably 0.1-0.25 times.

Further, the carbonyl-containing substance is any one or a combination of several of methylpyrrolidone, polyvinylpyrrolidone, aldehydic acid, formylbenzoic acid, and C2-C18 aldehydes.

Further, the aldehyde acid is selected from any one or a combination of several of glyoxylic acid, propionic acid, butylic acid, glutaric acid, and hexanoic acid.

Further, the C2-C18 aldehyde is selected from any one or a combination of acetaldehyde, propionaldehyde, malondialdehyde, butyraldehyde, succinic aldehyde, glutaraldehyde and adipic aldehyde.

In a preferred embodiment, the carbonyl-containing substance is an aldehyde acid or a C2-C18 aldehyde, more preferably a C2-C18 aldehyde.

Substances containing carbonyl groups will react with the hydroxyl functional groups between substance A, creating bridge connections between the molecular chains of substance A, forming dendritic or network-like macromolecules, further increasing the heat resistance and solvent resistance of the composition; Substances containing carbonyl groups have a significant impact on the degree of cross-linking of the molecular chain of the final composition. When the molecular chain of the substance containing carbonyl groups is too long, the degree of cross-linking of the composition is insufficient, and small molecule solvents will still penetrate into the skeleton structure of the composition. And cause damage, resulting in a decrease in the connection strength between the fiber and the plant pulp product. However, when the molecular chain of the substance containing the carbonyl group is too short, the cross-linking effect is too strong, resulting in a weak relative mobility between the molecular chains of the composition and cannot be used well. It can effectively relieve external stress and cause the final viscosity of the composition to be too large, which is not conducive to processing and use.

In a more preferred embodiment, the C2-C18 aldehyde is glutaraldehyde or adipic aldehyde.

Further, the mass of the carbonyl-containing substance is 0.01-0.1 times the mass of substance A; preferably 0.01-0.05 times.

Preferably, a certain rate in S3 means: adding the carbonyl-containing substance at an addition speed of 0.1-0.5 parts/minute based on the total mass parts of the carbonyl-containing substance.

In the preparation method of the present application, the dropping speed of the carbonyl-containing substance needs to be strictly controlled. If the dropping speed is too fast, the randomness of the reaction sites of Substance A, which contains a large number of cross-linkable sites, and the carbonyl-containing substance will increase, which will seriously affect the composition. The uniformity of functional groups ultimately leads to a decrease in the strength of the connection between fiber and plant pulp products.

Further, the S3 is specifically: based on the total mass parts of the carbonyl-containing material, add the carbonyl-containing material at an addition rate of 0.1-0.5 parts/minute, and stop heating after 2-4 hours from the dropwise addition of the carbonyl-containing material. , after stirring for 0.3-2h, adjust the pH of the system to 6.7-7.2; continue stirring for 1-4h, and wait for the solution to cool down naturally to obtain the composition.

More preferably, the carbonyl group-containing substance is added to S3 at an addition rate of 0.15-0.3 parts/minute based on the total mass parts of the carbonyl group-containing substance.

Further, in the preparation method, the solution rotation speed must be maintained at 100-150 rpm.

Secondly, this application also provides a composition for fixedly connecting fibers and plant pulp products obtained by the preparation method.

Further, the fibers include but are not limited to at least one of natural fibers, man-made fibers, and synthetic fibers.

Further, the natural fiber includes but is not limited to at least one of cotton fiber, hemp fiber, silk fiber and wool fiber.

Further, the man-made fiber includes but is not limited to at least one of viscose fiber and acetate fiber.

Further, the synthetic fibers include but are not limited to at least one of polypropylene fibers, polyacrylonitrile fibers, polyvinyl formal fibers, and polyamide fibers.

Preferably, the fibers are natural fibers, more preferably cotton fibers.

Furthermore, this application does not impose specific requirements on the shape of the fiber and plant pulp products, which can be adjusted as needed. The shapes of the plant pulp products can be optional, such as rod-shaped, flat-shaped, special-shaped, etc. The plant pulp products refer to products that are processed using plants as pulp, such as felt paper.

Further, the fiber may be in any one of an oval shape, a drop shape, and a wavy shape after being pressed.

Further, the fiber and plant pulp products are used in the manufacturing and processing of sensitive industries such as electronic devices, optical instruments, and optical fibers after being fixed by the composition.

beneficial effects

1. In this application, by optimizing the structure, molecular weight and number of polar groups of substance A, the substance containing carbonyl groups serves as a connecting bridge to increase the degree of cross-linking between substance A and the final composition, and further optimizes the amount and type of substances containing carbonyl groups. Make the composition have a specific cross-linked network structure and degree of cross-linking, and improve the fixation effect on fibers and plant pulp products;

2. This application improves the uniformity of the distribution of substance A and its reaction sites by optimizing the dripping speed of carbonyl-containing substances, thereby improving the distribution uniformity of functional groups in the composition, and improving the composition's effect on fiber and plant pulp products. While fixing, it also increases the structural stability and solvent resistance of the composition;

3. The composition prepared in this application is especially used for fixing fiber and plant pulp products, with the best fixing effect; and the composition prepared in this application complies with national standards for restricted substances, and the product has good strength and high reliability.

Detailed ways

Example

Example 1

This embodiment provides a method for preparing a composition for fixedly connecting fibers and plant pulp products; the fibers are cotton fibers, and the plant pulp products are paper sticks.

The preparation method includes:

S1. Add substance A to water and stir for 20 minutes at a speed of 120 rpm, then raise the temperature to 95°C and continue stirring until substance A is completely dissolved; the mass fraction of substance A in water is 5.3%;

S2. After cooling to 83°C, add organic acid and stir for 5 minutes; the mass of organic acid is 0.16 times the mass of substance A;

S3. Based on the total mass parts of the carbonyl-containing substance, add the carbonyl-containing substance at an addition rate of 0.2 parts/minute. Stop heating 2 hours after the dropwise addition of the carbonyl-containing substance. Stir for 0.5 hours and then use sodium hydroxide to remove the system. Adjust the pH to 7.0; continue stirring for 1 hour and then close the reaction kettle to drain the water. After stirring for another 2 hours, stop stirring and wait until the solution is naturally cooled to obtain the composition. The mass of the substance containing the carbonyl group is 0.014 times the mass of substance A.

The substance A has the following structure:

The degree of alcoholysis _of substance _A is 99%, where aldehyde;

This embodiment also provides a composition for fixedly connecting fibers and plant pulp products obtained according to the preparation method.

Example 2

This embodiment provides a method for preparing a composition for fixedly connecting fibers and plant pulp products; the fibers are cotton fibers, and the plant pulp products are paper sticks.

The preparation method includes:

S1. Add substance A to water and stir for 40 minutes at a speed of 100 rpm, then raise the temperature to 92°C and continue stirring until substance A is completely dissolved; the mass fraction of substance A in water is 4%;

S2. After cooling to 80°C, add organic acid and stir for 10 minutes; the mass of organic acid is 0.1 times the mass of substance A;

S3. Based on the total mass parts of the carbonyl-containing substance, add the carbonyl-containing substance at an addition rate of 0.5 parts/minute. Stop heating 3 hours after the dropwise addition of the carbonyl-containing substance. Stir for 0.3 hours and then use sodium hydroxide to remove the system. Adjust the pH to 7.0; continue stirring for 1 hour and then close the reaction kettle to drain the water. After stirring for another 2 hours, stop stirring and wait until the solution is naturally cooled to obtain the composition. The mass of the carbonyl-containing substance is 0.01 times the mass of substance A.

The substance A has the following structure:

The degree of alcoholysis of substance _{A is} 99%; wherein ;

This embodiment also provides a composition for fixedly connecting fibers and plant pulp products obtained according to the preparation method.

Example 3

This embodiment provides a method for preparing a composition for fixedly connecting fibers and plant pulp products; the fibers are cotton fibers, and the plant pulp products are paper sticks.

The preparation method includes:

S1. Add substance A to water and stir for 5 minutes at a speed of 150 rpm, then raise the temperature to 98°C and continue stirring until substance A is completely dissolved; the mass fraction of substance A in water is 6%;

S2. After cooling to 85°C, add organic acid and stir for 3 minutes; the mass of organic acid is 0.25 times the mass of substance A;

S3. Based on the total mass parts of the carbonyl-containing substance, add the carbonyl-containing substance at an addition rate of 0.3 parts/minute. Stop heating 4 hours after the dropwise addition of the carbonyl-containing substance. After stirring for 2 hours, use sodium hydroxide to adjust the system pH. Adjust to 7.2; continue stirring for 3 hours and then close the reaction kettle to drain the water. After stirring for another 1 hour, stop stirring and wait until the solution is naturally cooled to obtain the composition. The mass of the carbonyl-containing substance is 0.05 times the mass of substance A.

The substance A has the following structure:

The degree of alcoholysis of substance _{A is} 99%; wherein ;

This embodiment also provides a composition for fixedly connecting fibers and plant pulp products obtained according to the preparation method.

Example 4

Basically consistent with Example 1, the difference is that: in the preparation method, S3 is specifically: based on the total mass parts of the carbonyl-containing material, add the carbonyl-containing material at an addition speed of 0.5 parts/minute.

Example 5

Basically consistent with Example 1, the difference is that: in the preparation method, S3 is specifically: based on the total mass parts of the carbonyl-containing material, add the carbonyl-containing material at an addition rate of 0.7 parts/minute.

Example 6

It is basically the same as Example 1, except that the organic acid is replaced with hydrochloric acid.

Example 7

It is basically the same as Example 1, except that the organic acid is replaced by ascorbic acid.

Example 8

Basically consistent with Example 1, the difference is that: the alcoholysis degree of substance A is 88%; wherein X ₁ is -H, the X ₂ is -OH, R is H; n is 1700.

Example 9

Basically consistent with Example 1, the difference is that: the alcoholysis degree of substance A is 78%; wherein X ₁ is -H, the X ₂ is -OH, R is H; n is 1700.

Example 10

Basically consistent with Example 1, the difference is that: the alcoholysis degree of substance A is 88%; wherein X ₁ is -H, the X ₂ is -OH, R is H; n is 2000.

Example 11

It is basically the same as Example 1, except that the rotation speed in the preparation method is 300 rpm.

Example 12

It is basically the same as Example 1, except that the carbonyl-containing substance is butyraldehyde.

Example 13

It is basically the same as Example 1, except that the carbonyl-containing substance is adipic dialdehyde. Performance testing method:

Wrap the cotton fiber around the paper stick and put it into the molding tool to press it. Then punch the composition of the example into the mold hole to soak the cotton fiber and shape it. Then dry it at a temperature of 80°C for 1 hour to obtain the fixed product. Fiber fabric strength test, the test results are the average of 5 products. Soak the product in an ethanol solution with a volume fraction of 70% and leave it for 3 hours. Then take it out and observe whether the cotton fiber has delinting, swelling, and deformation.

Performance test results:

The test results are shown in Table 1.

Table 1

Analysis results: From the above results, it can be seen that only the polymer and alcoholysis degree of substance A, the type of carbonyl-containing substance and the rate of acceleration will affect the progress of the cross-linking reaction, which will in turn affect the network structure strength and compactness of the final composition. . Only when the polymer of substance A is 1700 and the alcoholysis degree is 99%, using glutaraldehyde cross-linking and strictly controlling the dripping speed, can the composition have the best bonding performance to fiber and plant pulp products, and the fiber strength will also be improved. More reliable. The use of organic acids can avoid the impact of the later migration of inorganic acid anions on the structure of the composition. However, when the organic acid molecular chain is too long, its intermolecular interaction with the composition will still have an impact on the latter.

Claims (10)

1. A method for preparing a composition for fixing connecting fibers and plant pulp products, characterized in that the preparation method includes: S1. Add substance A to the solvent and stir until the temperature is completely dissolved; S2. After cooling down, add organic acid and stir for a period of time; S3. Add the carbonyl-containing substance to it at a certain rate. After mixing for 0.3-6 hours, adjust the pH of the system to 6.7-7.2. Continue stirring for 1-4 hours and wait until the solution is naturally cooled to obtain the composition; The substance A has the following structure: Further, the X ₁ and X ₂ are independently selected from H, -OH, -COOH, -NH ₃ , C2-C8 acyl group, C1-C8 acyloxy group, C2-C15 oxyacyl group, C1-C15 Any one or a combination of alkyl groups and C1-C15 alkoxy groups. 2. The preparation method according to claim 1, wherein n is 1000-3000. 3. The preparation method according to claim 1, characterized in that at least one of X ₁ and X ₂ is any one of -OH, C1-C8 acyloxy group, and C1-C15 alkoxy group. . 4. The preparation method according to claim 1, wherein n is 1650-1800. 5. The preparation method according to claim 3, characterized in that the alcoholysis degree of the substance A is 87-100%. 6. The preparation method according to claim 1, wherein the organic acid includes formic acid, acetic acid, propionic acid, butyric acid, succinic acid, glycolic acid, citric acid, gluconic acid, benzenesulfonic acid, Any one or a combination of tartaric acid, malic acid, ascorbic acid, glutaric acid, lactic acid, and succinic acid. 7. The preparation method according to claim 1, wherein the carbonyl-containing substance is any one of methylpyrrolidone, polyvinylpyrrolidone, aldehydic acid, formyl benzoic acid, C2-C18 aldehydes, or A combination of several. 8. The preparation method according to claim 1, characterized in that the mass of the carbonyl-containing substance is 0.01-0.1 times the mass of substance A. 9. The preparation method according to claim 1, characterized in that the certain rate in S3 means: adding the carbonyl-containing substance at an addition speed of 0.1-0.5 parts/minute based on the total mass parts of the carbonyl-containing substance. 10. The composition of fixedly connected fibers and plant pulp products prepared according to the preparation method according to any one of claims 1 to 9, characterized in that the fibers are cotton fibers.