A high melting point oxidized polyethylene wax microemulsion and its preparation method

Abstract

The present invention discloses a high melting point oxidized polyethylene wax microemulsion and a preparation method thereof. The oxidized polyethylene wax microemulsion comprises the following components: 25-40% by weight of high melting point oxidized polyethylene wax, 2-3% by weight of rosin-based gemini surfactant, 0.5-1% by weight of high molecular emulsifier, 0.5-1% by weight of isomeric alcohol polyoxyethylene ether, 0.2-0.5% by weight of alkali metal hydroxide, and 54.5-71.8% by weight of water, based on the total weight of the oxidized polyethylene wax microemulsion. The high melting point oxidized polyethylene wax microemulsion provided by the present invention has small particle size and relatively uniform distribution, and good centrifugal stability and dilution stability. When it is finished on cotton fabrics, the number of needle holes generated during the sewing process of knitted fabrics is significantly reduced, good hand feeling can be obtained and the hydrophilic property of the fabric will not be decreased, and the comprehensive performance is excellent.

Description

Technical Field

[0001] The present invention relates to the field of textile printing and dyeing, and particularly to a high-melting-point oxidized polyethylene wax microemulsion and a preparation method thereof. Background Art

[0002] High-melting-point oxidized polyethylene wax has the characteristics of low viscosity, high softening point, non-toxicity, and non-corrosiveness. Making it into a wax microemulsion can improve the smoothness of yarns, reduce the friction between fibers and sewing needles, and its high melting point can absorb the heat generated by friction during the high-speed sewing process of fabrics, avoiding the formation of holes due to yarn fusing. In addition, it can endow the fabric with a soft hand feeling, improve the mechanical strength of the yarn, reduce surface fuzzing and pilling, etc., so it has been increasingly valued by the textile printing and dyeing industry.

[0003] Due to the characteristics of large relative molecular mass and high non-polarity, high-melting-point oxidized polyethylene wax is difficult to emulsify (in the opinion of the inventor, there is no clear definition of high-melting-point wax at present. The high-melting-point wax in the present invention refers to oxidized polyethylene wax with a melting point higher than 125 °C). To obtain a high-melting-point oxidized polyethylene wax emulsion with better stability, a large amount of emulsifier is required, generally more than 20% of the wax. If the amount of emulsifier is reduced, it will lead to poor dispersion and stability of the wax emulsion, easy stratification and demulsification, affecting its application performance. Generally speaking, the higher the melting point of oxidized polyethylene wax, the greater the emulsification difficulty. Therefore, in the pure high-melting-point oxidized polyethylene wax microemulsion on the market at present, the wax content is not high. That is, the current situation of high-melting-point wax emulsion is relatively low wax content and relatively high surfactant content, which in turn reduces or limits its application.

[0004] In the relevant literature on the emulsification of high-melting-point oxidized polyethylene wax, adding cosolvents, adding low-melting-point wax, modifying the wax, etc. to reduce the emulsification difficulty all have certain effects. In the literature "Preparation and Application of Aqueous OPE Wax Emulsion" (Coal and Chemical Industry, Duan Xinfeng, 2020, NO.8, Vol.43: 134-137), a high-temperature and high-pressure closed method is used to prepare a microemulsion of lower-melting-point wax (melting point 115 °C), and an emulsifier accounting for 25% of the wax dosage is also required. If the amount of emulsifier is less than 25%, stratification, insoluble substances, etc. will occur. Another example is Example 4 in the patent "A Preparation Method of Oxidized Polyethylene Wax Emulsion" (Authorization Publication No.: CN103755978B). When emulsifying the high-melting-point oxidized polyethylene Luwax OA3 of BASF, the amount of emulsifier required is 24.1% of OA3. The inventor has continuously studied the emulsification of high-melting-point oxidized polyethylene wax for many years. In the invention patents that have been applied for and authorized (Authorization Publication No.: CN103865186B and Authorization Publication No.: CN109487560B), the proportion of the emulsifier in the high-melting-point wax all needs to be more than 20%. How to prepare a high-melting-point oxidized polyethylene wax microemulsion with high wax content, low emulsifier dosage, and good stability has always attracted the attention of relevant practitioners. Summary of the Invention

[0005] The object of the present invention is to provide a high melting point oxidized polyethylene wax microemulsion with a high wax content, a small amount of emulsifier used, and high stability.

[0006] One aspect of the present invention provides a high melting point oxidized polyethylene wax microemulsion, comprising the following components:

[0007]

[0008] Based on the total weight of the high melting point oxidized polyethylene wax microemulsion.

[0009] Another aspect of the present invention provides a method for preparing a high melting point oxidized polyethylene wax microemulsion:

[0010] Add 2 - 3% by weight of a rosin - based gemini surfactant, 0.5 - 1% by weight of a polymer emulsifier, and 0.5 - 1% by weight of an isomeric alcohol polyoxyethylene ether to 35 - 45% by weight of water, and stir until homogeneous to obtain solution A;

[0011] Dissolve 0.2 - 0.5% by weight of an alkali metal oxide in 9.5 - 36.8% by weight of water, then add it together with 25 - 40% by weight of oxidized polyethylene wax and solution A into a high - temperature and high - pressure reaction kettle, seal it, and raise the temperature to 140 - 170 °C; after heat - preserving and emulsifying for 40 - 60 min, cool it to 50 - 60 °C at a rate of 6 - 8 °C / min, and filter to obtain the high melting point oxidized polyethylene wax microemulsion.

[0012] Compared with the prior art, the originality of a high melting point oxidized polyethylene wax emulsion and its preparation method of the present invention is manifested in the following aspects: 1) The rosin - based gemini surfactant adopted in the present invention combines the rosin - based with a unique tricyclic diterpene rigid structure and the gemini structure, making it have better thermal stability and mechanical stability, higher surface activity, water solubility, and emulsifying performance. At a lower dosage, it can emulsify high melting point oxidized polyethylene wax; 2) The polymer emulsifier polyisobutylene succinate contains strong polar groups, which can adsorb and combine well with melted oxidized polyethylene wax, and at the same time can form relatively stable hydrogen bonds with water molecules, greatly reducing the surface free energy of emulsion particles and significantly improving the stability of the emulsion; 3) The oxidized polyethylene wax microemulsion prepared by the present invention has a wax content of 30 - 40%, the emulsion state is stable. When applied to cotton fabrics, it significantly improves the sewing performance of the fabrics, has good hydrophilicity, soft hand feeling, and the dosage is reduced by 30% compared with conventional market products. Detailed Embodiments

[0013] In a preferred embodiment, a high melting point oxidized polyethylene wax microemulsion provided by the present invention comprises the following components:

[0014]

[0015] Based on the total weight of the high melting point oxidized polyethylene wax microemulsion.

[0016] In a preferred embodiment, the melting point of the high melting point oxidized polyethylene wax microemulsion is 125 - 150 °C, and the acid value is 15 - 35 mgKOH / g.

[0017] In a preferred embodiment, the rosin-based gemini surfactant is one or more of rosin-based phosphate salt gemini surfactants and rosin-based quaternary ammonium salt gemini surfactants.

[0018] In a preferred embodiment, the structural formula of the rosin-based phosphate salt gemini surfactant is as follows formula (I):

[0019]

[0020] In formula (I), n = 2, 3 or 4.

[0021] In a preferred embodiment, the rosin-based quaternary ammonium salt gemini surfactant is characterized in that: the structural formula is one of the following formula (II) or formula (III):

[0022]

[0023] In formula (II), n = 1, 2, 3 or 4;

[0024]

[0025] In formula (III), n = 1, 2, 3 or 4.

[0026] In a preferred embodiment, the polymeric emulsifier is a polyisobutylene succinate polymeric emulsifier, preferably selected from one of pentaerythritol polyisobutylene succinate, polyethylene glycol polyisobutylene succinate, and polyglycerol polyisobutylene succinate.

[0027] In a preferred embodiment, the isomeric alcohol polyoxyethylene ether is isomeric tridecanol polyoxyethylene ether, and the number of polyethylene oxide units is one or more of 7, 8, 10, and 12.

[0028] In a preferred embodiment, the alkali metal hydroxide is one of potassium hydroxide and sodium hydroxide.

[0029] In a preferred embodiment, the preparation method of the high melting point oxidized polyethylene wax microemulsion of the present invention includes:

[0030] Add 2-3% by weight of rosin-based gemini surfactant, 0.5-1% by weight of polymer emulsifier, and 0.5-1% by weight of isomeric alcohol polyoxyethylene ether to 35-45% by weight of water, and stir until homogeneous to obtain Solution A.

[0031] Dissolve 0.2-0.5% by weight of alkali metal oxide in 9.5-36.8% by weight of water, and then add it together with 25-40% by weight of polyethylene oxide wax and Solution A into a high-temperature and high-pressure reaction kettle. After sealing, heat up to 140-170 °C; keep warm and emulsify for 40-60 min, then cool down to 50-60 °C at a rate of 6-8 °C / min, and filter to obtain the high-melting-point polyethylene oxide wax microemulsion.

[0032] The high-melting-point polyethylene oxide wax microemulsion provided by the present invention has small particle size and relatively uniform distribution, and good centrifugal stability and dilution stability. When it is finished on cotton fabrics, it significantly reduces the number of needle holes generated during the sewing process of knitted fabrics, can obtain good hand feeling and will not cause the decline of the hydrophilic performance of the fabrics, and the overall performance is excellent.

[0033] Examples

[0034] The present invention will be further described below in conjunction with specific examples. It should be understood that these examples are only used to illustrate the present invention and not to limit the scope of the present invention. For those not specified in the examples, the techniques or conditions described in the literature in the field are followed, or the product instructions are referred to. In addition, it should be understood that after reading the content taught by the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms also fall within the scope defined by the appended claims of this application.

[0035] The sources of each material are as follows: the high-melting-point polyethylene oxide wax OA3, AC-316A, and RL925 are from BASF, Honeywell (China) Co., Ltd., and Shanghai Ruile New Materials Co., Ltd. respectively; the rosin-based gemini surfactant is from the Chinese Academy of Forestry Sciences, the polyisobutylene succinate is from Nanjing University of Science and Technology, and the isomeric tridecyl alcohol polyoxyethylene ether is from BASF Chemistry. Ordinary chemicals and fabrics are obtained through commercial channels.

[0036] The application performance of the high-melting-point polyethylene oxide wax provided by the present invention is measured by the following method.

[0037] 1. Basic performance test

[0038] 1.1 Microemulsion particle size test

[0039] Prepare a 0.2 wt% polyethylene oxide wax microemulsion, and measure its average particle size with a Zetasizer Nano S90 (Malvern) nanometer particle size analyzer.

[0040] 1.2 Centrifugal stability of microemulsion

[0041] Centrifuge the polyethylene wax oxide microemulsion at 3000 rmp for 30 min (centrifuge model TDZS-WS), and observe whether it separates into layers or precipitates.

[0042] 1.3 Dilution stability

[0043] Dilute the polyethylene wax oxide microemulsion with deionized water to prepare a 5% solution, and observe whether it separates into layers or small particles precipitate after standing naturally for 24 h.

[0044] 2. Performance test on fabric application:

[0045] 2.1 Fabric: Red pure cotton double-sided knitted fabric (specification: 32S, weight: 180 g / m 2 )

[0046] 2.2 Working fluid formula

[0047] Polyethylene wax oxide emulsion: X g / L, penetrant: 2 g / L, citric acid: 0.3 g / L

[0048] 2.3 Finishing process

[0049] One dip and one nip (liquor pickup rate 85%) → drying at 170 °C for 90 s

[0050] 2.4 Sewing performance test:

[0051] Adopt the method imitating M&S, and conduct the test with a 14# sewing needle (testing instrument: L+M SEWABILITY TESTER). Count the number of holes on the fabric. The more the number of holes, the worse the effect.

[0052] 2.5 Hydrophilicity of fabric:

[0053] According to the test method of water droplet diffusion time described in GB / T 21655.1-2008, record the time required for the water droplet to completely diffuse after contacting the fabric surface. The shorter the diffusion time, the better the hydrophilicity.

[0054] 2.6 Fabric handle:

[0055] Five people respectively conduct touch ratings on the fabric, and take the average value of the results of the five people. The 5-level handle is the best, and the 1-level handle is the worst.

[0056] Example 1

[0057]

[0058] Based on the total weight of the high melting point polyethylene wax oxide microemulsion described above.

[0059] The full name of 1,2-ethylenediammonium dibromide dehydroabietate is: N,N,N,N-tetramethyl-N,N-didehydroabietyl-1,2-ethylenediammonium dibromide.

[0060] Add 2.3% by weight of 1,2-ethylenediammonium dibromide dehydroabietate, 0.8% by weight of polyethylene glycol polyisobutylene succinate, and 0.8% by weight of isomeric tridecanol polyoxyethylene ether (EO = 10) to 40.4% by weight of water, and stir until homogeneous to obtain Solution A;

[0061] Dissolve 0.3% by weight of potassium hydroxide in 23.4% by weight of water, and then add it together with 32% by weight of high melting point oxidized polyethylene wax OA3 and Solution A into a high temperature and high pressure reactor, seal it, and raise the temperature to 150 °C;

[0062] Keep warm and emulsify for 50 min, cool down to 50 °C at a rate of 6 - 8 °C / min, and filter to obtain a high melting point oxidized polyethylene wax microemulsion.

[0063] Example 2

[0064]

[0065] Based on the total weight of the high melting point oxidized polyethylene wax microemulsion.

[0066] The full name of 1,6-hexanediammonium dibromide diethanolamine dehydroabietate is: N,N,N,N-tetramethyl-N,N-diethanolamine-didehydroabietyl-1,6-hexanediammonium dibromide.

[0067] Add 2.5% by weight of 1,6-hexanediammonium dibromide diethanolamine dehydroabietate, 0.9% by weight of pentaerythritol polyisobutylene succinate, and 1% by weight of isomeric tridecanol polyoxyethylene ether (EO = 7) to 40% by weight of water, and stir until homogeneous to obtain Solution A;

[0068] Dissolve 0.5% by weight of sodium hydroxide in 24.1% by weight of water, and then add it together with 31% by weight of high melting point oxidized polyethylene wax A-C 316A and Solution A into a high temperature and high pressure reactor, seal it, and raise the temperature to 160 °C;

[0069] Keep warm and emulsify for 60 min, cool down to 60 °C at a rate of 6 - 8 °C / min, and filter to obtain a high melting point oxidized polyethylene wax microemulsion.

[0070] Example 3

[0071]

[0072]

[0073] Based on the total weight of the high melting point oxidized polyethylene wax microemulsion.

[0074] Add 2.7 wt% of sodium 1,4-butanediol phosphate of dehydroabietyl alcohol, 0.6 wt% of polyglycerol polyisobutenyl succinate, and 0.9 wt% of isomeric tridecyl alcohol polyoxyethylene ether (EO = 8) to 41 wt% of water, and stir until homogeneous to obtain Solution A;

[0075] Dissolve 0.4 wt% of potassium hydroxide in 22.4 wt% of water, then add it together with 32 wt% of high melting point oxidized polyethylene wax RL925 and Solution A into a high-temperature and high-pressure reactor, seal it, and heat up to 150 °C;

[0076] Keep warm and emulsify for 45 min, cool down to 60 °C at a rate of 6 - 8 °C / min, and filter to obtain the high melting point oxidized polyethylene wax microemulsion.

[0077] The performance test results of each example are shown in Table 1 and Table 2.

[0078] Table 1 Basic properties of the high melting point oxidized polyethylene wax microemulsion

[0079] Particle size (nm) Centrifugal stability Dilution stability Example 1 176.30 No stratification, no precipitation No stratification, no precipitation Example 2 192.81 No stratification, no precipitation No stratification, no precipitation Example 3 158.86 No stratification, no precipitation No stratification, no precipitation

[0080] Table 2 Application properties of the high melting point oxidized polyethylene wax microemulsion

[0081]

[0082] It can be seen from Table 1 and Table 2 that: the high melting point oxidized polyethylene wax microemulsion provided by the present invention has small particle size and relatively uniform distribution, good centrifugal stability and dilution stability. When it is finished on cotton fabrics, it significantly reduces the number of needle holes generated during the sewing process of knitted fabrics and improves the sewing performance of the fabrics. It can obtain good hand feeling and will not cause the decline of the hydrophilic property of the fabrics. Especially compared with market samples, the dosage can be reduced by 30%. Overall, the high melting point oxidized polyethylene wax microemulsion provided by the present invention has outstanding application performance and is significantly better than conventional market samples.

[0083] Although the present invention has been disclosed as above with examples, it is not intended to limit the protection scope of the present invention. Any person skilled in the art, without departing from the concept and scope of the present invention, the changes and modifications made shall fall within the protection scope of the present invention.

Claims

1. A high melting point oxidized polyethylene wax microemulsion, which is composed of the following components: Based on the total weight of the high melting point oxidized polyethylene wax microemulsion, The rosin-based gemini surfactant is one or more of rosin-based phosphate salt type gemini surfactants and rosin-based quaternary ammonium salt type gemini surfactants, The structural formula of the rosin-based phosphate salt type gemini surfactant is the following formula (I): In formula (I), n = 2, 3 or 4, The structural formula of the rosin-based quaternary ammonium salt type gemini surfactant is one of the following formula (II) or formula (III): In formula (II), n = 1, 2, 3 or 4, In formula (III), n = 1, 2, 3 or 4, The polymer emulsifier is a polyisobutylene succinate polymer emulsifier.

2. The high melting point oxidized polyethylene wax microemulsion according to claim 1, characterized in that: The melting point of the high melting point oxidized polyethylene wax microemulsion is 125 - 150 °C, and the acid value is 15 - 35 mgKOH / g.

3. The high melting point oxidized polyethylene wax microemulsion according to claim 1, characterized in that: The polyisobutylene succinate polymer emulsifier is one of pentaerythritol polyisobutylene succinate, polyethylene glycol polyisobutylene succinate, and polyglycerol polyisobutylene succinate.

4. The high melting point oxidized polyethylene wax microemulsion according to claim 1, characterized in that: The isomeric alcohol polyoxyethylene ether is isomeric tridecyl alcohol polyoxyethylene ether, and the number of polyoxyethylene units is one or more of 7, 8, 10, and 12.

5. The high melting point oxidized polyethylene wax microemulsion according to claim 1, characterized in that: The alkali metal hydroxide is one of potassium hydroxide and sodium hydroxide.

6. The preparation method of the high melting point oxidized polyethylene wax microemulsion according to any one of claims 1 to 5, which comprises: Adding 2 - 3% by weight of the rosin-based gemini surfactant, 0.5 - 1% by weight of the polymer emulsifier, and 0.5 - 1% by weight of the isomeric alcohol polyoxyethylene ether to 35 - 45% by weight of water, and stirring until homogeneous to obtain solution A; Dissolving 0.2 - 0.5% by weight of the alkali metal oxide in 9.5 - 36.8% by weight of water, and then adding it together with 25 - 40% by weight of the oxidized polyethylene wax and solution A into a high-temperature and high-pressure reaction kettle, sealing and heating to 140 - 170 °C; After heat preservation and emulsification for 40 - 60 min, cooling to 50 - 60 °C at a rate of 6 - 8 °C / min, and filtering to obtain the high melting point oxidized polyethylene wax microemulsion.

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