Composition for fixedly connecting fibers and plant pulp products and preparation method thereof

Abstract

The present application provides a preparation method of a composition for fixedly connecting fibers and plant pulp products; comprising: S1, adding substance A into a solvent, stirring and heating to completely dissolve; S2, adding an organic acid after cooling and stirring for a period of time; S3, adding a substance containing a carbonyl group thereto at a certain rate, mixing for 0.3 - 6 h, and adjusting the pH of the system to 6.7 - 7.2; continuing to stir for 1 - 4 h, and waiting for the solution to cool naturally to obtain the composition; by optimizing the structure, molecular weight and number of polar groups of substance A, and the dosage and type of the substance containing a carbonyl group, the composition is particularly used for fixing between fibers and plant pulp products, and has the most excellent fixing effect and the strongest solvent resistance.

Description

Technical Field

[0001] The present invention relates to the technical field of polymer materials, C08K, and particularly relates to a composition for fixedly connecting fluffy fibers and paper products and a preparation method thereof. Background Art

[0002] Both fibers and paper products have similar sources, and their preparation raw materials include fibers from natural or artificial sources. There are many products in the industry that involve the connection and fixation of fibers and paper products. However, due to various factors, at present in the industry, the fixation and connection stability of the two interfaces of fibers and paper products are still not good, and the connection interface is damaged after being pulled (repeatedly) by external forces or soaked in chemicals.

[0003] Chinese Patent CN2595806Y discloses a fiber tearing tape. After arranging the fibers in an oriented manner, an adhesive is coated to form a film, which is used for bonding cardboard boxes. However, the adhesive in this patent needs to be heat-treated during coating, which is inconvenient to use, and it cannot well resist the erosion of water or other organic solvents. Chinese Patent CN107556946A discloses a special paper tube glue for paper surface, which is made by using polyvinyl alcohol, polyvinyl acetate emulsion, cyclodextrin derivative, cellulase, modified glass fiber, and polystyrene emulsion. This substance can only be used for the connection of paper surfaces, and the connection between fibers and paper surfaces is still not strong, and it is not resistant to chemical soaking, and the raw material cost is also high. Summary of the Invention

[0004] In order to solve the above technical problems, the present invention first provides a preparation method of a composition for fixedly connecting fibers and plant pulp products.

[0005] Further, the preparation method includes:

[0006] S1. Add substance A to a solvent, stir and heat up to completely dissolve it;

[0007] S2. After cooling, add an organic acid and stir for a period of time;

[0008] S3. Then add a carbonyl-containing substance thereto at a certain rate, mix for 0.3 - 6 h, and adjust the pH of the system to 6.7 - 7.2; continue to stir for 1 - 4 h, and wait for the solution to cool naturally to obtain the composition.

[0009] Further, substance A has the following structure:

[0010]

[0011] Further, X1 and X2 are independently selected from any one or a combination of several of H, -OH, -COOH, -NH3, acyl groups with 2 to 8 carbon atoms, acyloxy groups with 1 to 8 carbon atoms, oxyacyl groups with 2 to 15 carbon atoms, alkyl groups with 1 to 15 carbon atoms, and alkoxy groups with 1 to 15 carbon atoms, and n is 1000 - 3000.

[0012] Further, the acyl groups with 2 to 8 carbon atoms include, but are not limited to, any one of acetyl, propionyl, butyryl, valeryl, tert - butyryl, hexanoyl, heptanoyl, and octanoyl.

[0013] Further, the acyloxy groups with 1 to 8 carbon atoms include, but are not limited to, any one of formyloxy, acetyloxy, propionyloxy, acryloyloxy, methacryloyloxy, butyryloxy, pivaloyloxy, tert - butyryloxy, hexanoyloxy, heptanoyloxy, and octanoyloxy.

[0014] Further, the alkyl groups with 1 to 15 carbon atoms include, but are not limited to, any one of methyl, ethyl, propyl, butyl, isobutyl, tert - butyl, pentyl, isopentyl, neopentyl, hexyl, isohexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, and pentadecyl.

[0015] Further, the alkoxy groups with 1 to 15 carbon atoms include, but are not limited to, any one of methoxy, ethoxy, propoxy, butoxy, isobutoxy, tert - butoxy, pentyloxy, isopentyloxy, neopentyloxy, hexyloxy, isohexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy, undecyloxy, dodecyloxy, tridecyloxy, tetradecyloxy, and pentadecyloxy.

[0016] Preferably, at least one of X1 and X2 is any one of -OH, acyloxy groups with 1 to 8 carbon atoms, and alkoxy groups with 1 to 15 carbon atoms.

[0017] Further, when at least one of X1 and X2 is an alkoxy group with 1 to 15 carbon atoms, step S1 further includes treating substance A with a strong acid and then purifying; the strong acid such as periodic acid.

[0018] Further, R is H or methyl.

[0019] In one embodiment, both X1 and X2 are -OH and R is H.

[0020] In one embodiment, X1 is -H, X2 is -OH, and R is H.

[0021] Further, n is 1600 - 2800.

[0022] Preferably, n is 1600 - 2500, more preferably 1650 - 1800.

[0023] In one embodiment, when X1 is -H, X2 is -OH, and R is H, the alcoholysis degree of substance A is 75 - 100%.

[0024] In this application, the polar groups of substance A are used to further crosslink and polymerize substance A, increasing the compactness of the crosslinking network structure between substance A molecules, better matching the connection requirements between fibers and plant pulp products. The degree of polymerization represents the molecular weight of substance A, and the alcoholysis degree represents the hydroxyl content of A. Increasing the degree of polymerization and alcoholysis degree of A can increase the crosslinking reaction sites between substance A and carbonyl-containing substances, improve the crosslinking degree within the composition system, and thus enable composition A to have high mechanical properties after curing. However, when the degree of polymerization of substance A is too high, the crosslinking points are unevenly distributed after the reaction between the carbonyl-containing substance and substance A, resulting in a decrease in the compactness of the network structure; too high or too low alcoholysis 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 adhesion performance is the most excellent.

[0025] Preferably, the alcoholysis degree of substance A is 87 - 100%; more preferably 98 - 100%.

[0026] Further, in S1, the temperature 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, ethanol; preferably water.

[0027] Further, in S2, the temperature is lowered to 78 - 85 °C; more preferably 80 - 85 °C; further preferably 83 °C.

[0028] In this application, organic acids are used instead of inorganic acids because most inorganic acids contain halide ions or heavy metal acid radicals, and the presence of these acids in the system will lead to the risk of exceeding the standards of halogens or heavy metals in the final composition; in addition, these small molecule anions are prone to migrate outward in the composition after curing, affecting the structural stability and solvent resistance of the composition.

[0029] Further, the organic acid includes but is not limited to any one or a combination of 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.

[0030] Further, the organic acid is selected from any one or a combination of acetic acid, propionic acid, butyric acid, glutaric acid, citric acid.

[0031] In one embodiment, the organic acid is acetic acid.

[0032] Furthermore, the mass of the organic acid is 0.05 - 0.5 times the mass of Substance A, preferably 0.1 - 0.25 times.

[0033] Furthermore, the substance containing a carbonyl group is any one or a combination of N-methylpyrrolidone, polyvinylpyrrolidone, aldehyde acid, formylbenzoic acid, and aldehydes with C2 - C18 carbon atoms.

[0034] Furthermore, the aldehyde acid is selected from any one or a combination of glyoxylic acid, pyruvic aldehyde acid, butyric aldehyde acid, glutaric aldehyde acid, and hexaldehyde acid.

[0035] Furthermore, the aldehydes with C2 - C18 carbon atoms are selected from any one or a combination of acetaldehyde, propionaldehyde, malonaldehyde, butyraldehyde, succinaldehyde, glutaraldehyde, and adipic dialdehyde.

[0036] In a preferred embodiment, the substance containing a carbonyl group is aldehyde acid or aldehydes with C2 - C18 carbon atoms, more preferably aldehydes with C2 - C18 carbon atoms.

[0037] The substance containing a carbonyl group reacts with the hydroxyl functional group in Substance A, forming a cross - link between the molecular chains of Substance A to generate dendritic or network - like macromolecules, further increasing the heat resistance and solvent resistance of the composition; the substance containing a carbonyl group has a significant impact on the cross - linking degree of the final composition's molecular chains. When the molecular chain of the substance containing a carbonyl group is too long, the cross - linking degree of the composition is insufficient, and small - molecule solvents can still penetrate into the framework 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 a carbonyl group is too short, the cross - linking effect is too strong, resulting in insufficient relative mobility between the molecular chains of the composition, being unable to relieve external stress well, and causing the final viscosity of the composition to be too large, which is not conducive to processing and use.

[0038] In a more preferred embodiment, the aldehydes with C2 - C18 carbon atoms are glutaraldehyde or adipic dialdehyde.

[0039] Furthermore, the mass of the substance containing a carbonyl group is 0.01 - 0.1 times the mass of Substance A; preferably 0.01 - 0.05 times.

[0040] Preferably, the certain rate in S3 means: based on the total mass parts of the substance containing a carbonyl group, the substance containing a carbonyl group is added at an addition rate of 0.1 - 0.5 parts per minute.

[0041] In the preparation method of this application, it is necessary to strictly control the dropping rate of the substance containing a carbonyl group. When the dropping rate is too fast, the randomness of the reaction sites between Substance A with a large number of cross - linkable sites and the substance containing a carbonyl group increases, which will seriously affect the uniformity of the functional groups of the composition, ultimately leading to a decrease in the connection strength between the fiber and the plant pulp product.

[0042] Further, S3 is specifically as follows: Based on the total mass parts of the carbonyl-containing substance, the carbonyl-containing substance is added at an addition rate of 0.1 - 0.5 parts per minute. Heating is stopped 2 - 4 hours after starting to drip the carbonyl-containing substance, and after stirring for 0.3 - 2 hours, the pH of the system is adjusted to 6.7 - 7.2; stirring is continued for 1 - 4 hours, and the solution is allowed to cool naturally to obtain the composition.

[0043] More preferably, in S3, based on the total mass parts of the carbonyl-containing substance, the carbonyl-containing substance is added at an addition rate of 0.15 - 0.3 parts per minute.

[0044] Further, in the preparation method, the rotation speed of the solution must be maintained at 100 - 150 revolutions per minute.

[0045] Secondly, the present application also provides a composition of the fixed connection fiber and the plant pulp product obtained by the preparation method.

[0046] Further, the fiber includes but is not limited to at least one of natural fiber, artificial fiber, and synthetic fiber.

[0047] Further, the natural fiber includes but is not limited to at least one of cotton fiber, hemp fiber, silk fiber, and wool fiber.

[0048] Further, the artificial fiber includes but is not limited to at least one of viscose fiber and acetate fiber.

[0049] Further, the synthetic fiber includes but is not limited to at least one of polypropylene fiber, polyacrylonitrile fiber, polyvinyl formal fiber, and polyamide fiber.

[0050] Preferably, the fiber is a natural fiber, and more preferably cotton fiber.

[0051] Further, the present application does not make specific requirements on the shapes of the fiber and the plant pulp product, which can be adjusted according to needs. The shapes of the plant pulp product can be, for example, rod-shaped, flat-plate-shaped, irregular-shaped, etc. The plant pulp product refers to a product made from plants after pulping and then processed, such as felt paper.

[0052] Further, after being pressed, the fiber is in any one of an oval shape, a water droplet shape, and a wavy shape.

[0053] Further, after being fixed by the composition, the fiber and the plant pulp product are used in the manufacturing and processing processes of sensitive industries such as electronic devices, optical instruments, and optical fibers.

[0054] Beneficial effects

[0055] 1. By optimizing the structure, molecular weight, and number of polar groups of Substance A, this application uses a carbonyl-containing substance as a connecting bridge to increase the crosslinking degree between Substance A and the finally formed composition. Further optimizing the dosage and type of the carbonyl-containing substance enables the composition to have a specific crosslinked network structure and crosslinking degree, enhancing the fixing effect on fiber and plant pulp products.

[0056] 2. By optimizing the dropping rate of the carbonyl-containing substance, this application improves the uniformity of the distribution of Substance A and its reaction sites, thereby enhancing the distribution uniformity of functional groups within the composition. While improving the fixing effect of the composition on fiber and plant pulp products, it also increases the structural stability and solvent resistance of the composition.

[0057] 3. The composition prepared in this application is particularly used for fixing between fiber and plant pulp products, with the most excellent fixing effect. Moreover, the composition of this application complies with the national standards regarding restricted substances, and the product has good strength and high reliability. Detailed implementation methods

[0058] Examples

[0059] Example 1

[0060] This example provides a preparation method for a composition used to fixedly connect fiber and plant pulp products; the fiber is cotton fiber, and the plant pulp product is a paper stick.

[0061] The preparation method includes:

[0062] S1. Add Substance A to water and stir at a speed of 120 revolutions per minute for 20 minutes, 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%.

[0063] S2. After cooling to 83°C, add organic acid and stir for 5 minutes; the mass of the organic acid is 0.16 times the mass of Substance A.

[0064] S3. Based on the total mass portion of the carbonyl-containing substance, add the carbonyl-containing substance at an addition rate of 0.2 parts per minute. Stop heating 2 hours after starting to add the carbonyl-containing substance. After stirring for 0.5 hours, use sodium hydroxide to adjust the pH of the system to 7.0. Continue stirring for 1 hour, then close the reaction kettle to drain water. After stirring for another 2 hours, stop stirring and wait for the solution to cool naturally to obtain the composition; the mass of the carbonyl-containing substance is 0.014 times the mass of Substance A.

[0065] Substance A has the following structure:

[0066] The alcoholysis degree of Substance A is 99%, where X1 is -H, X2 is -OH, R is H; n is approximately 1700; the organic acid is acetic acid, and the carbonyl-containing substance is glutaraldehyde;

[0067] This example also provides a composition for fixedly connecting fibers and plant pulp products obtained according to the above preparation method.

[0068] Example 2

[0069] This example provides a preparation method for a composition for fixedly connecting fibers and plant pulp products; the fiber is cotton fiber, and the plant pulp product is a paper stick.

[0070] The preparation method includes:

[0071] S1. Add Substance A to water and stir at a speed of 100 revolutions per minute for 40 minutes, 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%.

[0072] S2. After cooling to 80 °C, add the organic acid and stir for 10 minutes; the mass of the organic acid is 0.1 times the mass of Substance A.

[0073] S3. Based on the total mass of the carbonyl-containing substance, add the carbonyl-containing substance at an addition rate of 0.5 parts per minute. Stop heating 3 hours after starting to drip the carbonyl-containing substance. After stirring for 0.3 hours, use sodium hydroxide to adjust the pH of the system to 7.0; continue stirring for 1 hour, then close the drain of the reaction kettle, and then stop stirring after stirring for 2 hours and wait for the solution to cool naturally to obtain the composition; the mass of the carbonyl-containing substance is 0.01 times the mass of Substance A.

[0074] Substance A has the following structure:

[0075] The alcoholysis degree of Substance A is 99%; where X1 is -H, X2 is -OH, R is H; n is 1700; the organic acid is acetic acid, and the carbonyl-containing substance is glutaraldehyde;

[0076] This example also provides a composition for fixedly connecting fibers and plant pulp products obtained according to the above preparation method.

[0077] Example 3

[0078] This example provides a preparation method for a composition for fixedly connecting fibers and plant pulp products; the fiber is cotton fiber, and the plant pulp product is a paper stick.

[0079] The preparation method includes:

[0080] S1. Add Substance A to water and stir at a speed of 150 revolutions per minute for 5 minutes, then heat up to 98 °C and continue stirring until Substance A is completely dissolved; the mass fraction of Substance A in water is 6%;

[0081] S2. After cooling to 85 °C, add organic acid and stir for 3 minutes; the mass of the organic acid is 0.25 times the mass of Substance A;

[0082] S3. Based on the total mass portion of the substance containing a carbonyl group, add the substance containing a carbonyl group at an addition rate of 0.3 parts per minute. Stop heating 4 hours after starting to drip the substance containing a carbonyl group, stir for 2 hours, and then adjust the pH of the system to 7.2 using sodium hydroxide; continue stirring for 3 hours, then close the drain of the reaction kettle, and stop stirring after another 1 hour. Wait for the solution to cool naturally to obtain the composition; the mass of the substance containing a carbonyl group is 0.05 times the mass of Substance A.

[0083] The above-mentioned Substance A has the following structure:

[0084] The alcoholysis degree of Substance A is 99%; where X1 is -H, X2 is -OH, R is H; n is 1700; the organic acid is acetic acid, and the substance containing a carbonyl group is glutaraldehyde;

[0085] This example also provides a composition for fixedly connecting fibers and plant pulp products obtained according to the above preparation method.

[0086] Example 4

[0087] It is basically the same as Example 1, except that in the above preparation method, S3 is specifically: based on the total mass portion of the substance containing a carbonyl group, add the substance containing a carbonyl group at an addition rate of 0.5 parts per minute.

[0088] Example 5

[0089] It is basically the same as Example 1, except that in the above preparation method, S3 is specifically: based on the total mass portion of the substance containing a carbonyl group, add the substance containing a carbonyl group at an addition rate of 0.7 parts per minute.

[0090] Example 6

[0091] It is basically the same as Example 1, except that the organic acid is replaced with hydrochloric acid.

[0092] Example 7

[0093] It is basically the same as Example 1, except that the organic acid is replaced with ascorbic acid.

[0094] Example 8

[0095] Basically the same as Example 1, with the differences being that the alcoholysis degree of Substance A is 88%; X1 is -H, X2 is -OH, R is H; and n is 1700.

[0096] Example 9

[0097] Basically the same as Example 1, with the differences being that the alcoholysis degree of Substance A is 78%; X1 is -H, X2 is -OH, R is H; and n is 1700.

[0098] Example 10

[0099] Basically the same as Example 1, with the differences being that the alcoholysis degree of Substance A is 88%; X1 is -H, X2 is -OH, R is H; and n is 2000.

[0100] Example 11

[0101] Basically the same as Example 1, with the difference being that the rotation speed in the preparation method is 300 revolutions per minute.

[0102] Example 12

[0103] Basically the same as Example 1, with the difference being that the substance containing a carbonyl group is butyraldehyde.

[0104] Example 13

[0105] Basically the same as Example 1, with the difference being that the substance containing a carbonyl group is adipaldehyde. Performance test method:

[0106] Wind the cotton fiber around a paper rod and then put it into a forming tool for pressing. Then, inject the composition of the example into the die hole to soak and shape the cotton fiber. After that, dry it at a temperature of 80 °C for 1 h to obtain the fixed product. Conduct a tensile strength test on the cotton fiber fabric of the product, and the test result takes the average value of 5 products. Immerse the product in an ethanol solution with a volume fraction of 70% and let it stand for 3 h. Then take it out and observe whether there is cotton fiber shedding, swelling, or deformation.

[0107] Performance test results:

[0108] The test results are shown in Table 1.

[0109] Table 1

[0110]

[0111]

[0112] Analysis results: From the above results, it can be seen that only the polymer of substance A, the degree of alcoholysis, the types of carbonyl-containing substances, and the addition rate will affect the progress of the crosslinking reaction, and thus affect the network structure strength and compactness of the final composition. Only when the polymer of substance A is 1700, the degree of alcoholysis is 99%, crosslinking with glutaraldehyde and strictly controlling the dropping rate can the bonding performance of the composition to fiber and plant pulp products reach the best, and the fiber strength is also more reliable. Using organic acids can avoid the influence of the later migration of inorganic acid anions on the composition structure, but when the molecular chain of the organic acid is too long, its intermolecular interaction with the composition will still affect the latter.

Claims

1. A method for preparing a composition for fixedly connecting fibers and plant pulp products, characterized in that, The preparation method includes the following steps: S1. Add substance A into a solvent, stir and heat up to complete dissolution; S2. After cooling, add an organic acid and stir for a period of time; S3. Then add the carbonyl-containing substance thereto at an addition rate of 0.1 - 0.5 parts per minute, mix for 0.3 - 6 h, and adjust the pH of the system to 6.7 - 7.2; continue to stir for 1 - 4 h, and wait for the solution to cool naturally to obtain the composition; Substance A has the following structure: X1 is H, X2 is -OH, and R is H; n is 1650 - 1800; The carbonyl-containing substance is glutaraldehyde; The mass of the carbonyl-containing substance is 0.01 - 0.1 times the mass of substance A; The alcoholysis degree of substance A is 87 - 100%; The fiber is cotton fiber; The organic acid is acetic acid.

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