Low-temperature low-fluorine waterproof agent and preparation method thereof

Abstract

The invention belongs to the technical field of chemical preparation, and discloses a low-temperature low-fluorine-content waterproof agent which comprises the following components: a copolymer formed by initiating polymerization of a structural monomer, a functional monomer and a cross-linking monomer by adopting an initiator, and a system formed by an emulsifier and a coalescing agent adsorbed on the surface of the copolymer. Through room-temperature stable water-inhibiting cross-linking reaction of keto carbonyl and hydrazide, rapid cross-linking is realized within 40 seconds at the temperature of 100-110 DEG C, damage to fibers caused by traditional high-temperature baking is avoided, formaldehyde is not generated, and the environment-friendly requirement is met. The coalescing agent promotes the emulsion to form a film quickly under a low-temperature condition and helps C-F groups to migrate to the surface of the fabric to form a continuous waterproof film, so that the fabric is endowed with excellent waterproof, oil-proof and antifouling properties. The test of the embodiment shows that the hydrostatic pressure resistance of the treated chemical and blended fabric reaches 4-7kPa, the spraying grade is 3-5 grade, the oil-proof grade is 3-5 grade, and the chemical and blended fabric is obviously superior to that of the traditional process.

Description

Technical Field

[0001] The invention belongs to the technical field of polymer materials, and in particular relates to a low-fluorine waterproofing agent for low-temperature chemical fiber fabrics and a preparation method thereof. Background Art

[0002] With the progress of the times, people have put forward higher requirements for textiles. They not only play the conventional functions of covering the body, keeping out the cold and decoration, but also require the environmental protection and sustainability of raw materials, functionality and intelligence. In the new era, from simple clothing and textiles to special fabrics for medical, military, industrial and other uses, the important indicator is the three-proof performance of the fabric, namely waterproof, oil-proof and anti-fouling performance. And the appropriate surface treatment agent can provide the three-proof performance required by the fabric. At present, the fabric surface treatment agents on the market include fluorine-containing and fluorine-free types. Although fluorine-free waterproofing agents are more environmentally friendly, the waterproof performance they give to fabrics cannot be compared with fluorine-containing waterproofing agents, and the oil-proof effect of fluorine-free waterproofing agents is very poor. The fluorinated water repellents on the market are roughly divided into two categories: C8 and C6. The long-chain perfluoroalkyl group has better water and oil resistance than the short-chain alkyl group. The EU recently proposed a new draft to revise the POPs Regulation (EU) 2019 / 1021 on perfluorooctanoic acid (PFOA) and its salts and related substances. C8 compounds will be completely banned. In line with the world's environmental protection policies, the market will give priority to short-chain fluorinated water repellents with a carbon number of 6 or less. The shortcomings of existing fluorinated fabric finishing agents are:

[0003] The treatment of fabrics with traditional fluorine-containing waterproofing agents requires a large amount of heat energy consumption and requires continuous baking for a long time, which is not enough under the dual requirements of national green energy-saving policies and industrial operation efficiency. In addition, continuous high-temperature baking will affect the performance of certain chemical fibers, such as viscose and acrylic fibers. Therefore, how to treat the fabric substrate in a short time at low temperature without generating formaldehyde gas during the treatment process, and how to obtain efficient special three-proof performance of the substrate after treatment under this condition has become a difficult problem. Summary of the invention

[0004] Purpose of the invention: In order to solve the problems existing in the prior art, the present invention provides a low-temperature and high-efficiency low-fluorine waterproofing agent and a preparation method thereof, wherein a perfluoroalkyl water-repellent agent with a carbon number of less than 6 is used to perform hydrophobic and oil-proof modification on chemical fiber fabrics, and the present invention has the characteristics of good finishing effect, low finishing temperature and fast finishing speed, and its low-temperature rapid cross-linking structure does not produce formaldehyde. While the usage amount is low, the treatment can be completed in 40 seconds under baking at a temperature of 100°C-110°C, and the treated substrate can maintain excellent waterproof and oil-resistant capabilities after treatment, which complies with current green environmental protection policies while reducing energy consumption and improving the efficiency of continuous production in industry.

[0005] Technical solution: A low-temperature and low-fluorine waterproofing agent according to the present invention comprises the following components: a system composed of a copolymer formed by polymerizing a structural monomer, a functional monomer, and a crosslinking monomer using an initiator, and an emulsifier and a film-forming aid adsorbed on the surface of the copolymer;

[0006] The structural monomer includes a fluoroacrylate monomer and / or a long-chain alkyl acrylate monomer;

[0007] The functional monomer includes an unsaturated double-bond hard monomer and / or a halogenated olefin;

[0008] The crosslinking monomer includes an unsaturated monomer with a ketone carbonyl group and a hydrazide monomer;

[0009] The emulsifier includes a cationic emulsifier and / or a nonionic emulsifier;

[0010] The film-forming aid includes an alcohol ester solvent and / or a ketone solvent;

[0011] The initiator is an azo-type polymerization initiator, a redox-type initiator, or a peroxide-type polymerization initiator.

[0012] Further, as a preferred embodiment, the fluoroacrylate monomer is any one or at least two combinations of perfluorobutyl acrylate, perfluorobutylethyl acrylate, perfluorobutylethyl methacrylate, perfluorohexylethyl acrylate, 3-(perfluorohexyl)propyl acrylate, perfluorohexylethyl methacrylate; for example, the combination of perfluorohexylethyl acrylate and 3-(perfluorohexyl)propyl acrylate, the combination of perfluorohexylethyl acrylate and perfluorohexylethyl methacrylate, the combination of 3-(perfluorohexyl)propyl acrylate and perfluorohexylethyl methacrylate, but not limited to the combinations listed above, and other unlisted combinations within the above combination range are equally applicable;

[0013] The long-chain alkyl acrylate monomer is any one or at least two combinations of dodecyl acrylate, tetradecyl acrylate, hexadecyl acrylate, octadecyl acrylate, docosyl acrylate, dodecyl methacrylate, tetradecyl methacrylate, hexadecyl methacrylate, octadecyl methacrylate, docosyl methacrylate; for example, the combination of octadecyl acrylate and octadecyl methacrylate, the combination of octadecyl acrylate and docosyl acrylate, the combination of hexadecyl acrylate and hexadecyl methacrylate, but not limited to the combinations listed above, and other unlisted combinations within the above combination range are equally applicable, and further preferably octadecyl methacrylate, the combination of octadecyl methacrylate and octadecyl acrylate; most preferably the combination of octadecyl methacrylate and octadecyl acrylate.

[0014] Further, as a preferred embodiment, the unsaturated double-bond hard monomer is any one or a combination of at least two of isobornyl methacrylate, tert-butyl methacrylate, tetrahydrofurfuryl methacrylate, cyclohexyl methacrylate, glycidyl methacrylate, methyl methacrylate, benzyl methacrylate; for example, a combination of methyl methacrylate and cyclohexyl methacrylate, a combination of tert-butyl methacrylate and glycidyl methacrylate, a combination of cyclohexyl methacrylate and benzyl methacrylate, and other combinations not listed within the above combination range are also applicable. Most preferably, it is a combination of benzyl methacrylate and isobornyl methacrylate;

[0015] The halogenated olefin is any one or a combination of at least two of vinyl chloride, vinyl fluoride, vinylidene chloride, 3-chloro-1-propene, tetrafluoroethylene, 1,1,2-trichloroethylene, 3-fluoropropene; further preferably vinyl fluoride and vinylidene chloride, and most preferably vinylidene dichloride. The above specific unsaturated double-bond hard monomer is incorporated into the polymer chain by opening the unsaturated C-C double bond, and its rigid group can provide wear resistance and strength for the fabric substrate, improve stain resistance and support, and increase thermal stability.

[0016] Further, as a preferred embodiment, the specific crosslinking monomer is selected as a ketone carbonyl-containing unsaturated monomer and a hydrazide monomer. The unsaturated monomer can open the C-C double bond and be incorporated into the polymer main chain. The hydrazide monomer is added in the later stage of the emulsion reaction. When treating the substrate, the ketone carbonyl and hydrazide group (-CONHNH2-) in the emulsion undergo a hydrazide crosslinking reaction to form a hydrazone group (-C=N-NH-). The room-temperature crosslinking of the ketone carbonyl and hydrazide group is a water-inhibiting crosslinking system, so the emulsion can remain stable in the presence of water. The crosslinked structure can achieve rapid crosslinking under the condition of 100-110 °C, avoiding the damage to the substrate fibers caused by high-temperature baking of conventional fluorinated waterproof agents; and it does not generate formaldehyde, is environmentally friendly, saves energy and reduces emissions, and improves the efficiency of continuous operation of the enterprise at the same time.

[0017] Among them, the ketone carbonyl-containing unsaturated monomer is any one or a combination of at least two of methacrolein, acetylacetoxyethyl methacrylate, diacetone acrylamide; further selected as acetylacetoxyethyl methacrylate and diacetone acrylamide, and most preferably diacetone acrylamide.

[0018] Among them, the hydrazide monomer is any one or a combination of at least two of dihydrazide carbonate, dihydrazide oxalate, dihydrazide succinate, dihydrazide adipate, dihydrazide glutarate; most preferably dihydrazide adipate.

[0019] Further, as a preferred embodiment, the cationic emulsifier is any one of cetyltrimethylammonium bromide, octadecyltrimethylammonium chloride, dodecyldimethylbenzylammonium chloride, distearyldimethylammonium chloride, dimethyldiallylammonium chloride, dipalmitoyloxyethyldimethylammonium chloride, behenyltrimethylammonium chloride, and palmitamidopropyltrimethylammonium chloride, or a combination of at least two thereof; for example, a combination of octadecyltrimethylammonium chloride and dimethyldiallylammonium chloride, a combination of cetyltrimethylammonium bromide and distearyldimethylammonium chloride, a combination of distearyldimethylammonium chloride and palmitamidopropyltrimethylammonium chloride, a combination of distearyldimethylammonium chloride and palmitamidopropyltrimethylammonium chloride, a combination of distearyldimethylammonium chloride and palmitamidopropyltrimethylammonium chloride, a combination of octadecyltrimethylammonium chloride and dimethyldiallylammonium chloride, and a combination of distearyldimethylammonium chloride and palmitamidopropyltrimethylammonium chloride is further preferred.

[0020] The nonionic emulsifier is any one of sorbitan monostearate (Span series), polyoxyethylene sorbitan fatty acid ester (Tween series), fatty alcohol polyoxyethylene ether, alkylphenol polyoxyethylene ether, polyethylene glycol fatty alcohol ether, or a combination of at least two thereof; further preferred are polyoxyethylene sorbitan fatty acid ester and fatty alcohol polyoxyethylene ether series, and the most preferred is a combination of Tween 80 and AEO-9.

[0021] Furthermore, in order to achieve better low-temperature treatment efficiency, a film-forming agent needs to be added to the emulsion, and the film-forming agent is at least one of propylene glycol butyl ether PNB, ethylene glycol butyl ether BCS, propylene glycol methyl ether PGME, isophorone, and cyclohexanone; these additives can help the emulsion to quickly form a continuous film when treating the substrate at a lower temperature, help the CF group to quickly migrate to the surface of the substrate during the substrate treatment process, and enhance the three-proof effect; the film-forming agent is preferably a combination of propylene glycol methyl ether acetate and propylene glycol methyl ether.

[0022] Furthermore, as a preferred embodiment, the mass ratio of the structural monomer, the functional monomer and the cross-linking monomer is (30-80):(20-60):(1-10); the mass ratio of the formed copolymer to the emulsifier, the film-forming agent and the initiator is (60-120):(1-10):(1-20):(0.1-1.2); preferably, the raw materials for preparing the fluorine-containing waterproofing agent include, by weight, 30-80 parts of structural monomers, 30-50 parts of functional monomers, 1-10 parts of cross-linking monomers, 1-10 parts of emulsifiers, 5-20 parts of film-forming agents, 0.1-1.2 parts of initiators and water, and the solid content is controlled between 25% and 35%.

[0023] Among them, the amount of the structural monomer can be 30 parts, 35 parts, 40 parts, 45 parts, 50 parts, 55 parts, 60 parts, 65 parts, 70 parts, 75 parts or 80 parts, etc.; the amount of the functional monomer can be 30 parts, 35 parts, 40 parts, 45 parts or 50 parts, etc.; the amount of the crosslinking monomer can be 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts or 10 parts, etc.; the amount of the emulsifier can be 1 part, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts, 5.5 parts, 6 parts, 6.5 parts, 7 parts, 7.5 parts, 8 parts, 8.5 parts, 9 parts or 10 parts, etc.; the amount of the film-forming agent can be 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts or 20 parts, etc.; the amount of the initiator can be 0.1 part, 0.2 part, 0.3 part, 0.4 part, 0.5 part, 0.6 part, 0.7 part, 0.8 part, 0.9 part, 1.0 part, 1.1 part or 1.2 part, etc., but not limited to the values listed above. Other unlisted values within the above numerical range are equally applicable.

[0024] The present invention also provides a preparation method of the above-mentioned low-temperature and low-fluorine water repellent, comprising the following steps:

[0025] Step (1): Add the structural monomer, functional monomer, keto-carbonyl unsaturated monomer, emulsifier and film-forming agent into a four-necked flask, stir and disperse fully and heat up. After keeping warm at 50 - 60 °C for 1 h, perform homogenization treatment with a high-pressure homogenizer at 30 - 50 MPa to obtain an emulsion;

[0026] Step (2): Continuously perform nitrogen gas phase replacement in the four-necked flask, reheat with an oil bath to 60 - 70 °C, add the initiator at this time, and keep warm at 65 - 70 °C for 4 - 5 h after the temperature rise ends to obtain a second-stage emulsion;

[0027] Step (3): Stop keeping warm, continue stirring. When the emulsion cools down to below 50 °C, add adipic dihydrazide monomer, and stir for 1 - 2 h to obtain the finished emulsion of the low-temperature and low-fluorine water repellent.

[0028] Beneficial effects: (1) The scheme of the present invention realizes rapid crosslinking within 40 seconds at 100-110°C through the room temperature stable water-inhibited crosslinking reaction of ketone carbonyl and hydrazide, avoiding the damage to the fiber caused by traditional high temperature baking, avoiding the use of N-hydroxymethyl acrylamide, and not producing formaldehyde. The fluorine content is lower than that of traditional textile waterproofing agents. The overall formula is a low-VOC formula, which is environmentally friendly, conforms to the national call for energy conservation and emission reduction, and effectively improves the efficiency of continuous operation of enterprises. Since the present invention contains a specific low-temperature film-forming aid, the film-forming aid component can quickly penetrate the effective ingredients in the emulsion into the interior of the substrate fiber during the pretreatment process, and quickly migrate the CF group to the fabric surface during the treatment process, forming a three-dimensional grid structure under the crosslinking action, and forming a layer of flexible and waterproof continuous film on the fabric surface, giving the fabric excellent three-proof properties. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] Figure 1 This is the infrared spectrum of the low-temperature, low-fluorine waterproofing agent prepared in Example 1. DETAILED DESCRIPTION

[0030] In order to better illustrate the purpose, technical solutions and advantages of the present invention, the present invention will be further described below in conjunction with embodiments, the purpose of which is to understand the contents of the present invention in detail rather than to limit the present invention.

[0031] Unless otherwise specified, the reagents and raw materials used in the examples and comparative examples of the present invention are conventionally commercially available.

[0032] Embodiment 1:

[0033] The present embodiment provides a preparation process of a low-temperature low-fluorine waterproofing agent emulsion. The raw materials for preparation are as follows (in parts by weight): 40 parts of structural monomers (perfluorohexylethyl methacrylate, octadecyl methacrylate, and octadecyl acrylate in a mass ratio of 2:1.5:1.5), 15 parts of functional monomers (benzyl methacrylate), 3 parts of cross-linking monomers (diacetone acrylamide and adipic acid dihydrazide in a ratio of 1.2:1), 3 parts of emulsifiers (hexadecyltrimethylammonium bromide, Tween 80, and AEO-9 in a mass ratio of 1:1:1), 10 parts of film-forming agents (propylene glycol methyl ether acetate and propylene glycol methyl ether in a mass ratio of 1:1), 0.5 parts of initiators (2,2'-azo(2-methylpropylamidine) dihydrochloride), and 110 parts of water.

[0034] Specific reaction process:

[0035] Step (1): adding the structural monomer, functional monomer, diacetone acrylamide in the cross-linking monomer, the emulsifier, and the functional auxiliary agent into a four-necked flask, stirring and dispersing them fully with a tetrafluoroethylene stirring paddle and heating them, keeping the temperature at 55° C. for 1 hour, and homogenizing them with a high-pressure homogenizer at 40 MPa to obtain an emulsion;

[0036] Step (2): Continuously conduct nitrogen gas phase replacement in a four-necked flask, reheat with an oil bath to 65 °C, add initiator V-50 at this time, and keep it at 65 °C for 4 h after the temperature rise ends to obtain the second-stage emulsion;

[0037] Step (3): Stop heat preservation, continue stirring, add adipic dihydrazide in the above proportion when the emulsion cools below 50 °C, and then stir for 1 h to obtain the finished product of the low-temperature type highly efficient low-fluorine waterproofing agent emulsion.

[0038] As Figure 1 shown, the infrared spectrum of the finished product of the low-temperature type highly efficient low-fluorine waterproofing agent emulsion obtained in this example. It can be seen from the spectrum that multiple sharp absorption peaks are observed in the range of 1000 - 1300 cm -1 , corresponding to the stretching vibration of the C-F bond in the fluorinated acrylate monomer (such as perfluorohexylethyl methacrylate). The strong absorption peak in this region indicates that the fluorocarbon chain is successfully introduced into the copolymer main chain, which is consistent with the chemical structure of the target product. The ester group C=O bond of the acrylate monomer (such as octadecyl methacrylate) shows a significant absorption peak at 1725 cm -1 , with a sharp peak shape and no splitting, indicating that the ester group does not undergo hydrolysis or destruction during the polymerization process, confirming the integrity of the ester group structure in the copolymer.

[0039] Symmetric and asymmetric C-H stretching vibration peaks are detected at 2850 cm -1 and 2925 cm -1 respectively, corresponding to the hydrophobic chain segment of the long-chain alkyl (such as octadecyl methacrylate). The relatively high intensity of this absorption peak indicates that the alkyl chain segment is successfully incorporated into the polymer backbone, endowing the product with hydrophobic properties.

[0040] The free ketone carbonyl (C=O) in the DAAM monomer should show a strong absorption peak near 1715 cm -1 in the uncrosslinked state (refer to the standard spectrum). However, in the infrared spectrum of the synthesized product, the intensity of this peak is significantly weakened (residual peak intensity < 10%), indicating that the ketone carbonyl of DAAM is consumed in the crosslinking reaction and converted into a hydrazone bond (-C=N-NH-). A new absorption peak with medium intensity is observed at 1620 cm -1 , which is attributed to the stretching vibration of the C=N bond in the hydrazone bond. The first appearance of this peak directly proves that the ketone carbonyl undergoes a condensation reaction with the acylhydrazide group of ADH to form a stable crosslinked network structure.

[0041] The free acylhydrazide group (-NH-NH 2 ) in the ADH monomer is at 3200 - 3400 cm -1It shows a broad peak (N-H stretching vibration) within a certain range. After crosslinking, the intensity of this broad peak decreases significantly, indicating that the hydrazide group participates in the reaction to form hydrazone bonds, further corroborating the completion of the crosslinking reaction.

[0042] No characteristic peaks of free acid or amide (such as carboxylic acid C=O or secondary amide C=O) at 1680 - 1700 cm -1 were detected in the spectrum, indicating that no side reactions (such as hydrolysis or oxidation) occurred during the crosslinking process, and the reaction path conforms to the design expectation.

[0043] Through infrared spectroscopy analysis, the following conclusions can be drawn:

[0044] (1) The target polymer was successfully synthesized: The characteristic peaks of C-F bond (1000 - 1300 cm -1 ), ester carbonyl C=O (1725 cm -1 ), and long-chain alkyl C-H (2850 - 2925 cm -1 ) are all clearly visible, which are completely consistent with the chemical structure described in the patent.

[0045] (2) Efficient crosslinking of DAAM and ADH: The significant weakening of the ketone carbonyl peak (1715 cm -1 ), the appearance of the hydrazone bond C=N peak (1620 cm -1 ), and the decrease of the broad peak of hydrazide group (3200 - 3400 cm -1 ) together prove that the ketone carbonyl - hydrazide crosslinking reaction is completely completed.

[0046] (3) Stability of the crosslinking system: There is no interference from side reaction peaks, indicating that the crosslinking process is controllable and the product has high chemical stability.

[0047] In summary, the infrared spectroscopy data fully verify the successful synthesis of the polymer in the low-temperature and low-fluorine waterproofing agent.

[0048] Example 2:

[0049] This example is basically the same as Example 1, except that the combination of octadecyl acrylate and octadecyl methacrylate is changed to the combination of docosyl acrylate and octadecyl methacrylate, and the same operations as in Example 1 are carried out to obtain the finished product of the low-temperature and highly efficient low-fluorine waterproofing agent emulsion.

[0050] Example 3:

[0051] This example is basically the same as Example 1, except that the functional monomer is changed to cyclohexyl methacrylate, and the same operations as in Example 1 are carried out to obtain the finished product of the low-temperature and highly efficient low-fluorine waterproofing agent emulsion.

[0052] Example 4:

[0053] This example is basically the same as Example 1, except that the functional monomer is changed to cyclohexyl methacrylate, and the same operations as in Example 1 are carried out to obtain a finished product of a low-temperature type highly efficient low-fluorine waterproofing agent emulsion.

[0054] Example 5:

[0055] This example is basically the same as Example 1, except that the emulsifier is changed to AEO-9 and 1306, and the same operations as in Example 1 are carried out to obtain a finished product of a low-temperature type highly efficient low-fluorine waterproofing agent emulsion.

[0056] Example 6:

[0057] This example is basically the same as Example 1, except that all of the octadecyl methacrylate is replaced with octadecyl acrylate, and the same operations as in Example 1 are carried out to obtain a finished product of a low-temperature type highly efficient low-fluorine waterproofing agent emulsion.

[0058] Example 7:

[0059] This example is basically the same as Example 1, except that all of the octadecyl methacrylate is replaced with perfluorohexylethyl methacrylate, and the same operations as in Example 1 are carried out to obtain a finished product emulsion of a low-temperature highly efficient low-fluorine waterproofing agent.

[0060] Example 8:

[0061] This example is basically the same as Example 1, except that all of the octadecyl acrylate is replaced with octadecyl methacrylate, and the same operations as in Example 1 are carried out to obtain a finished product of a low-temperature type highly efficient low-fluorine waterproofing agent emulsion.

[0062] Example 9:

[0063] This example is basically the same as Example 1, except that the cationic emulsifier is changed to octadecyl trimethyl ammonium chloride, and the same operations as in Example 1 are carried out to obtain a finished product of a low-temperature type highly efficient low-fluorine waterproofing agent emulsion.

[0064] Example 10:

[0065] The preparation process of the low-temperature and low-fluorine waterproofing agent emulsion provided in this example is as follows. The preparation raw materials are as follows (by weight): 32 parts of structural monomers (the mass ratio of perfluorohexylethyl methacrylate, stearyl methacrylate, and octadecyl acrylate is 2:1:1), 15 parts of functional monomer (benzyl methacrylate), 3 parts of cross-linking monomer (the ratio of diacetone acrylamide to adipic dihydrazide is 1.2:1), 3 parts of emulsifier (the mass ratio of octadecyl dimethyl ammonium chloride, palmamido propyl trimethyl ammonium chloride, Tween 80, and AEO-9 is 1:1:1:1), 10 parts of film-forming agent (the mass ratio of propylene glycol methyl ether acetate to propylene glycol methyl ether is 1:1), 0.5 part of initiator (2,2'-azobis(2-methylpropionamidine) dihydrochloride), and 110 parts of water.

[0066] The preparation method refers to Example 1.

[0067] Example 11:

[0068] The preparation process of the low-temperature and low-fluorine waterproofing agent emulsion provided in this example is as follows. The preparation raw materials are as follows (by weight): 20 parts of structural monomers (the mass ratio of perfluorohexylethyl methacrylate to octadecyl acrylate is 3:1), 18 parts of functional monomer (benzyl methacrylate), 3 parts of cross-linking monomer (the ratio of diacetone acrylamide to adipic dihydrazide is 1.2:1), 3 parts of emulsifier (the mass ratio of octadecyl dimethyl ammonium chloride, palmamido propyl trimethyl ammonium chloride, Tween 80, and AEO-9 is 1:1:1:1), 10 parts of film-forming agent (the mass ratio of propylene glycol methyl ether acetate to propylene glycol methyl ether is 1:1), 0.5 part of initiator (2,2'-azobis(2-methylpropionamidine) dihydrochloride), and 110 parts of water.

[0069] The preparation method refers to Example 1.

[0070] Comparative Example 1:

[0071] The fluorine-containing waterproofing agent emulsion provided in this example has the following preparation raw materials (by weight): 40 parts of structural monomers (the mass ratio of perfluorohexylethyl methacrylate, stearyl methacrylate, and octadecyl acrylate is 2:1.5:1.5), 15 parts of functional monomer (benzyl methacrylate), 3 parts of cross-linking monomer (diacetone acrylamide), 3 parts of emulsifier (the mass ratio of cetyl trimethyl ammonium bromide, Tween 80, and AEO-9 is 1:1:1), 10 parts of film-forming agent (the mass ratio of propylene glycol methyl ether acetate to propylene glycol methyl ether is 1:1), 0.5 part of initiator (2,2'-azobis(2-methylpropionamidine) dihydrochloride), and 110 parts of water

[0072] The preparation method refers to Example 1.

[0073] Comparative Example 2:

[0074] This example provides a fluorine-containing waterproofing agent emulsion, and the preparation raw materials are as follows (by weight): 40 parts of structural monomers (the mass ratio of perfluorohexylethyl methacrylate, octadecyl methacrylate, and octadecyl acrylate is 2:1.5:1.5), 15 parts of functional monomers (benzyl methacrylate), 3 parts of crosslinking monomers (2-hydroxyethyl methacrylate HEMA), 3 parts of emulsifiers (the mass ratio of cetyltrimethylammonium bromide, Tween 80, and AEO-9 is 1:1:1), 10 parts of functional additives (the mass ratio of propylene glycol methyl ether acetate and propylene glycol methyl ether is 1:1), 0.5 part of initiator (2,2'-azobis(2-methylpropionamidine) dihydrochloride), and 110 parts of water.

[0075] The preparation method refers to Example 1.

[0076] To verify the effects of the waterproof emulsions in Examples 1-11 and Comparative Examples 1-2 above, effect tests were carried out on them:

[0077] Immerse the polyester fabric (gram weight: 100 g / m 2 ) in the waterproofing agent emulsions of Examples 1-11 and Comparative Examples 1-2, and remove the excess liquid with a cloth rolling machine. The standard acquisition value of the liquor pickup rate is set to 140. Fix the polyester fabric on a qualitative dryer and perform a setting treatment at 110 °C for 40 s to obtain a sample for evaluation. Evaluate the water repellency (hydrostatic pressure resistance) and oil repellency of the sample.

[0078] The evaluation criteria for the performance of hydrophobic substrates in this field are specifically as follows:

[0079] 1. Hydrostatic pressure resistance

[0080] According to the requirements of GB / T 4744-2013, apply a continuously increasing water pressure to the specimen at a water pressure rising rate of 6.0 kPa / min, and observe the water seepage phenomenon. Record the hydrostatic pressure value when the third water droplet just appears on the specimen. If the fabric ruptures and water jets out or the composite fabric shows a water-filled bulge phenomenon during the test, record the hydrostatic pressure value at this time. The hydrostatic pressure resistance performance level is shown in Table 1.

[0081] Table 1: Hydrostatic pressure resistance performance grade table of GB / T 4744-2013

[0082]

[0083] 2. Spray waterproofness test

[0084] Carry out a spray water test according to AATCC-22. The spray waterproofness is represented by a waterproof grade. The suffix "+" attached to the data means that the performance is slightly better than the grade performance characterized by the value, and the suffix "-" attached to the data means that the performance is slightly inferior to the grade performance characterized by the value. The evaluation criteria are shown in Table 2;

[0085] Table 2: Spraying Waterproofness Test Standard Table

[0086] Level Evaluation criteria 1 The entire wetted surface is wetted 2 Half of the wetted surface is wetted 3 The wetted surface is not wetted but has continuous water droplets 4 The wetted surface is not wetted and has a small amount of water droplets 5 The wetted surface is not wetted and has no water droplets attached

[0087] 3. Oil Resistance Performance Test Method

[0088] The oil resistance performance test is carried out according to AATCC-TM188. Drop the oil of the corresponding grade on the fabric and observe the penetration situation within 30 seconds. The highest grade of oil that does not penetrate is the oil resistance grade of this waterproof agent. The standard evaluation is shown in Table 3.

[0089] Table 3: Oil Resistance Grade Standard Table

[0090] Level Evaluation criteria 1 Medical lubricating oil 2 A mixed solution of 35 parts of hexadecane and 65 parts of medical lubricating oil 3 Hexadecane 4 Tetradecane 5 Dodecane 6 n-Decane 7 n-Octane 8 n-Heptane

[0091] The detection and evaluation results of the samples in 11 examples and 2 comparative examples are shown in Table 4.

[0092] Table 4: Performance Test Results of Examples 1-11 and Comparative Examples 1-2

[0093]

[0094]

[0095] As can be seen from the data in Table 4, due to its unique low-temperature rapid cross-linking system, the surface treatment agent of the present invention enables the chemical fiber fabric substrate to be rapidly processed in an industrial low-temperature (100-110 °C) environment, avoiding the damage to the substrate fibers caused by the high-temperature long-time baking of conventional fluorine-containing waterproof agents, avoiding the use of N-methylolacrylamide, not generating formaldehyde, being environmentally friendly, conforming to the national call for energy conservation and emission reduction, and at the same time effectively improving the efficiency of the enterprise's continuous operation. It has excellent use effects under low-temperature treatment and is a highly efficient fluorine-containing water repellent.

[0096] As described above, although the present invention has been shown and described with reference to specific preferred embodiments, it should not be construed as a limitation of the present invention itself. Various changes in form and detail may be made without departing from the spirit and scope of the present invention as defined by the appended claims.

Claims

1. A low-temperature low-fluorine waterproofing agent, characterized in that The invention comprises the following components: a copolymer formed by polymerization of structural monomers, functional monomers and cross-linking monomers by using an initiator, and a system consisting of an emulsifier and a film-forming aid adsorbed on the surface of the copolymer; The structural monomers include fluorine-containing acrylate monomers and / or long-chain alkyl acrylate monomers; The functional monomers include unsaturated double bond hard monomers and / or halogenated olefins; The cross-linking monomers include unsaturated monomers with ketocarbonyl groups and hydrazide monomers; The emulsifier includes a cationic emulsifier and / or a nonionic emulsifier; The film-forming aid comprises an alcohol ester solvent and / or a ketone solvent; The initiator is an azo type polymerization initiator, a redox type initiator or a peroxide type polymerization initiator.

2. The low-temperature low-fluorine waterproofing agent according to claim 1, characterized in that: The fluorine-containing acrylate monomer is any one of perfluorobutyl acrylate, perfluorobutyl ethyl acrylate, perfluorobutyl ethyl methacrylate, perfluorohexyl ethyl acrylate, 3-(perfluorohexyl)propyl acrylate, and perfluorohexyl ethyl methacrylate, or a combination of at least two thereof; The long-chain alkyl acrylate monomer is any one of dodecyl acrylate, tetradecyl acrylate, hexadecyl acrylate, octadecyl acrylate, behenyl acrylate, dodecyl methacrylate, tetradecyl methacrylate, hexadecyl methacrylate, octadecyl methacrylate, and behenyl methacrylate, or a combination of at least two of them.

3. The low-temperature low-fluorine waterproofing agent according to claim 1, characterized in that: The unsaturated double-bond hard monomer is any one of isobornyl methacrylate, tert-butyl methacrylate, tetrahydrofuran methacrylate, cyclohexyl methacrylate, glycidyl methacrylate, methyl methacrylate, and benzyl methacrylate, or a combination of at least two thereof; The halogenated olefin is any one of vinyl chloride, vinyl fluoride, vinylidene chloride, 3-chloro-1-propylene, tetrafluoroethylene, 1,1,2-trichloroethylene, and 3-fluoropropylene, or a combination of at least two thereof.

4. The low-temperature low-fluorine waterproofing agent according to claim 1, characterized in that: The unsaturated monomer with ketocarbonyl group is any one of methacrolein, acetoacetoxyethyl methacrylate, and diacetone acrylamide, or a combination of at least two of them.

5. The low-temperature low-fluorine waterproofing agent according to claim 1, characterized in that: The unsaturated monomer with ketocarbonyl group is acetoacetoxyethyl methacrylate or diacetone acrylamide.

6. The low-temperature low-fluorine waterproofing agent according to claim 1, characterized in that: The hydrazide monomer is any one of carbonate dihydrazide, oxalic acid dihydrazide, succinic acid dihydrazide, adipic acid dihydrazide and glutaric acid dihydrazide, or a combination of at least two of them.

7. The low-temperature low-fluorine waterproofing agent according to claim 1, characterized in that: The cationic emulsifier is any one of cetyltrimethylammonium bromide, octadecyltrimethylammonium chloride, dodecyldimethylbenzylammonium chloride, dioctadecyldimethylammonium chloride, dimethyldiallylammonium chloride, dipalmitoyloxyethyldimethylammonium chloride, behenyltrimethylammonium chloride, and palmitamidopropyltrimethylammonium chloride, or a combination of at least two thereof; the nonionic emulsifier is any one of sorbitan monostearate, polyoxyethylene sorbitan fatty acid ester, fatty alcohol polyoxyethylene ether, alkylphenol polyoxyethylene ether, and polyethylene glycol fatty alcohol ether, or a combination of at least two thereof.

8. The low-temperature low-fluorine waterproofing agent according to claim 1, characterized in that: The film-forming agent is at least one of propylene glycol butyl ether (PNB), ethylene glycol butyl ether (BCS), propylene glycol methyl ether (PGME), isophorone and cyclohexanone.

9. The low-temperature low-fluorine waterproofing agent according to claim 1, characterized in that: The mass ratio of the structural monomer, the functional monomer and the cross-linking monomer is (30-80):(20-60):(1-10); the mass ratio of the formed copolymer to the emulsifier, the film-forming agent and the initiator is (60-120):(1-10):(1-20):(0.1-1.2).

10. A method for preparing the low-temperature low-fluorine waterproofing agent according to any one of claims 1 to 9, characterized in that The steps include: Step (1): adding structural monomers, functional monomers, ketocarbonyl unsaturated monomers, emulsifiers, and film-forming agents into a four-necked flask, stirring and dispersing them fully, and heating them, keeping them at 50-60° C. for 1 hour, and homogenizing them at 30-50 MPa using a high-pressure homogenizer to obtain an emulsion; Step (2): nitrogen gas phase replacement is continuously performed in a four-necked flask, and the temperature is raised to 60-70° C. in an oil pan for a second time. At this time, an initiator is added, and after the temperature surge is completed, the temperature is kept at 65-70° C. for 4-5 hours to obtain a second-stage emulsion; Step (3): stop keeping warm, continue stirring, wait for the emulsion to cool down to below 50°C, then add adipic acid dihydrazide monomer, and stir for another 1-2 hours to obtain a low-temperature low-fluorine waterproofing agent finished emulsion.

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