Preparation method of polyether modified silicone oil and textile finishing agent

Abstract

The invention provides a synthesis method of polyether modified amino silicone oil. The method comprises the following steps: adding amino silicon oil and a proper amount of a catalyst into a high-pressure reaction kettle under negative pressure, introducing nitrogen to replace air in the reaction kettle, then heating to 160-180 DEG C, introducing ethylene oxide, reacting under the reaction pressure of 0.3-0.5 MPa, and after the reaction pressure is constant and the reaction is complete, cooling to room temperature to obtain the amino silicon oil. And when the temperature in the reaction kettle is reduced to 60-80 DEG C, introducing nitrogen to blow out the polyether modified amino silicon oil. The preparation method provided by the invention is simple, the technological process is environment-friendly and safe, the product purity is relatively high, and the method is suitable for large-scale production.

Description

Technical Field

[0001] The invention relates to a method for synthesizing polyether-modified amino silicone oil, and belongs to the technical field of preparation of novel nonionic surfactants. Background Art

[0002] Amino silicone oil is widely used in the softening and finishing of cotton, linen, wool, silk and various synthetic fibers. After finishing the fabric, it is easy to cross-link and form a film on the surface of the fabric, making the finished fabric soft and smooth. However, after the amino silicone oil softener cross-links with the fabric to form a film, the water solubility of the formed film is poor, resulting in strong hydrophobicity and poor washing resistance of the finished fabric. At the same time, under high temperature and light, the amino group in the amino silicone oil softener is easily oxidized and the fabric turns yellow, affecting the appearance of the finished fabric. In addition, the amino silicone oil molecule does not contain hydrophilic groups. During use, the amino silicone oil emulsion has poor stability, often accompanied by "demulsification" and "roller sticking" phenomena, and is easy to form "silicon spots" on the surface of the fabric, which limits its scope of use.

[0003] For this reason, the hydrophilic modification of amino silicone oil has attracted wide attention. Among them, the hydrophilic modification method that has been studied more is the introduction of polyether segments. For example, in a super soft and smooth block polyether amino silicone oil and a preparation method thereof disclosed in Chinese patent CN 115181274B, firstly, a terminal epoxy silicone oil is prepared by directly extending the chain of epoxy double capping and organic silicon ring body, and then a synthetic epoxy silicone oil and polyether amine are reacted to synthesize a block polyether amino silicone oil prepolymer to improve the low reaction activity between macromolecules; finally, a small molecule diamine is used to extend the chain of the block polyether amino silicone oil prepolymer so that the silicone oil contains more hydroxyl groups, thereby improving the hydrophilicity of the silicone oil. Another example is a preparation method of polyether polyester modified silicone oil disclosed in Chinese patent CN 104098776 B. The preparation process is first to add dimethyl terephthalate, ethylene glycol and zinc acetate into a reaction vessel to start an ester exchange reaction; add ethylene terephthalate, antimony oxide and polyethylene oxide into a reaction vessel to start a polycondensation reaction to obtain a polyether polyester block copolymer. Then add terminal hydrogen silicone oil, allyl glycidyl ether and Pt catalyst into a reaction vessel for heat preservation reaction, and vacuum remove low-boiling substances; add polyether amine and solvent to the terminal epoxy modified silicone oil, reflux reaction, and reduce pressure to remove the solvent to obtain polyether amino modified silicone oil; finally, the polyether polyester block copolymer and the polyether amino modified silicone oil are uniformly mixed, and the heat preservation reaction is performed to obtain the polyether polyester modified silicone oil. It can be seen that the disadvantages of this type of method for preparing polyether amino silicone oil are that there are many reaction steps, the modification process is complicated and cumbersome, and many reagents, a large amount of solvent, and high energy consumption are used.

[0004] Another type of hydrophilic modification method is to use monomers such as siloxane ring body, end-capping agent, polyether siloxane and aminosilane coupling agent to prepare polyether modified amino silicone oil by emulsion polymerization in an aqueous solution containing emulsifier and catalyst. This modification method obtains non-blocked polyether modified amino silicone oil. For example, Chinese patent CN 101992042 B discloses a method for preparing an environmentally friendly amino silicone oil emulsifier, first dehydrating fatty acid methyl ester under Al-Mg-based double active site inorganic catalysis, reacting with ethylene oxide, then passing cooling water into the reactor, and then discharging to obtain fatty acid polyoxyethylene (n) methyl ether; then, at least two fatty acid polyoxyethylene (n) methyl ethers with different polymerized ethylene oxide numbers are placed in the reactor to compound into an amino silicone oil emulsifier with an HLB value of 10 to 13. The main disadvantage of this method is that amino silicone oils mostly need to be used in the form of emulsions, and the high viscosity and low surface tension of amino silicone oils determine that it is difficult to emulsify. The particle size and distribution of the emulsion have a great influence on the use effect of amino silicone oil emulsions. Therefore, amino silicone oils need to be emulsified into stable microemulsions to achieve the use effect, which puts forward more stringent requirements on emulsifiers. In the past, alkylphenol polyoxyethylene ether emulsifiers were used more frequently because some alkylphenol compounds related to their metabolic intermediates have weak estrogen activity, which will affect the hormones in women's bodies, so they are banned by countries and regions such as the European Union. Although the commonly used isomeric alcohol ether emulsifiers are environmentally friendly, the isomeric alcohol market is basically monopolized by several multinational companies in Europe and the United States, and the price is relatively high and difficult to obtain. In addition, with the increasingly stringent environmental protection requirements today, there are also mandatory regulations for the VOC and ring content requirements in products, especially for exports to the European and American markets, which must comply with the requirements of the EU REACH regulations on the amount of residual siloxane rings, that is, octamethylcyclotetrasiloxane (D 4 ), decamethylcyclopentasiloxane (D 5 ), dodecamethylcyclohexasiloxane (D 6 ) should be less than 1000×10 -6 Therefore, the traditional 60% block silicone oil can no longer meet the requirements for VOC content and residual ring content.

[0005] In addition, although there are other methods for hydrophilic modification of amino silicone oil, most of them are in the research and development stage and have various obvious disadvantages, such as low product selectivity, high by-product content, expensive and difficult to obtain reaction reagents, or reducing the softness of the product while improving the hydrophilicity, or the VOC content and toxic reagent residues in the product exceed the standard, etc. Summary of the invention

[0006] In view of this, the present invention provides a method for preparing polyether-modified aminosilicone oil. The main concept of the present invention is to utilize the active hydrogen on the amino group in the aminosilicone oil to introduce the polyether segment in one step through an ethoxylation reaction, thereby solving the technical problems of the existing polyether-modified aminosilicone oil preparation method, such as complex operation steps and high energy consumption in the process, and having the advantages of high reaction selectivity and high product purity.

[0007] In order to achieve the above object, the present invention adopts the following technical solutions:

[0008] A method for preparing a polyether-modified amino silicone oil of the present invention comprises the following steps:

[0009] Amino silicone oil and homogeneous calcium-based catalyst are added into a high-pressure reactor under negative pressure, nitrogen is introduced to replace the air in the high-pressure reactor, and then the reaction temperature is increased to 160°C-180°C, ethylene oxide is introduced, and the reaction is carried out under the condition of a reaction pressure of 0.3MPa-0.5MPa. After the reaction is completed, nitrogen is introduced into the high-pressure reactor to purge out the polyether-modified amino silicone oil product.

[0010] Preferably, the amino silicone oil is any one of a side chain type diamino silicone oil, a side chain type monoamino silicone oil, and an amino-terminated amino silicone oil.

[0011] More preferably, the amino silicone oil is any one of the compounds represented by structural formula (1) or (2):

[0012]

[0013] In formula (1) and (2), R 1 =NH 2 or NHCH 2 CH 2 NH 2 ,x is a positive integer between 1 and 300, y is a positive integer between 1 and 60, and z is a positive integer between 1 and 270.

[0014] More preferably, the compound represented by the structural formula (1) or (2) is used to prepare the polyether-modified amino silicone oil, and the reaction synthesis route thereof is as follows:

[0015]

[0016] In the above reaction, R 1 =NH 2 or NHCH 2 CH 2 NH 2 ,

[0017] a is a positive integer from 1 to 30, b is a positive integer from 1 to 30, c is a positive integer from 1 to 30, d is a positive integer from 1 to 30, e is a positive integer from 1 to 50, f is a positive integer from 1 to 50, x is a positive integer from 1 to 300, y is a positive integer from 1 to 60, and z is a positive integer from 1 to 270.

[0018] Preferably, the homogeneous calcium-based catalyst is an organic calcium salt, a fatty alcohol and an alcohol ether reacting at 60° C.-150° C. under the protection of an inert gas, and then an organic acid is added to react for 1-3 hours to obtain a milky white liquid with a pH value of less than 7.

[0019] Preferably, the amount of the homogeneous calcium-based catalyst added is 1%-5% of the total mass of the aminosilicone oil and ethylene oxide.

[0020] Preferably, the end of the reaction is judged by the pressure in the reactor dropping to below 0.1 MPa and remaining constant.

[0021] Preferably, in the polyether-modified aminosilicone oil product prepared by the method of the present invention, the content of polyether-modified aminosilicone oil is ≥ 90%.

[0022] Compared with the prior art, the present invention has the following beneficial effects:

[0023] (1) Using amino silicone oil as raw material, the polyether chain segment is introduced in one step through ethoxylation reaction, which simplifies the operation process and reduces the energy consumption of preparation.

[0024] (2) The amino silicone oil ethoxylation reaction does not require the addition of additional organic solvents, and the production environment is green and environmentally friendly.

[0025] (3) The homogeneous calcium-based catalyst used in the aminosilicone oil ethoxylation reaction is cheap, widely available and easy to obtain.

[0026] (4) No volatile organic compounds are produced during the ethoxylation reaction of amino silicone oil. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] Figure 1 This is the infrared spectrum of the polyether-modified amino silicone oil prepared in the embodiment of the present invention. DETAILED DESCRIPTION

[0028] The present invention provides a method for preparing a polyether-modified amino silicone oil, comprising the following steps:

[0029] Amino silicone oil and homogeneous catalyst are introduced into a high-pressure reactor under negative pressure. The amount of homogeneous catalyst added is 1%-5% of the mass of amino silicone oil and ethylene oxide. Nitrogen is introduced to replace the air in the reactor 3 times. Then the reaction temperature is increased to 160°C-180°C, ethylene oxide is introduced, and ethoxylation reaction is carried out at a reaction pressure of 0.3MPa-0.5MPa. When the temperature in the reactor drops to 60°C-80°C, nitrogen is introduced to blow out the polyether-modified amino silicone oil.

[0030] The PEG content of the product was determined by referring to GB / T 5560-2003 "Determination of polyethylene glycol content and nonionic active substance (adduct) content of nonionic surfactants - Weilbull method". During the ethoxylation reaction, ethylene oxide dimerization side reaction will occur. Under different reaction conditions, the polyether-modified aminosilicone oil products synthesized with different EO addition numbers will contain different contents of byproduct PEG. The lower the PEG content, the less the degree of side reaction.

[0031] The water content of the product is determined by referring to GB / T 7380-1995 "Determination of the water content of surfactants and detergents - Karl Fischer method". During the ethoxylation reaction, under different reaction conditions, polyether-modified amino silicone oil products with different EO addition numbers will contain different amounts of water. The lower the water content, the less side reactions will occur.

[0032] The technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0033] Next, Bluesil TM Extrasoft C845 amino silicone oil (Bluestar Silicone Shanghai Co., Ltd.), amino silicone oil 6409 (Shanghai Suoke Industrial Co., Ltd.) and amino-terminated silicone oil 8K (Zhejiang Kefeng Silicone Co., Ltd.) were used as raw materials to synthesize polyether-modified amino silicone oils under different reaction conditions.

[0034] Example 1

[0035] Amino silicone oil is subjected to ethoxylation reaction in a high-pressure reactor. Amino silicone oil C845 and a catalyst are added to the high-pressure reactor. The amount of homogeneous catalyst NAE-03 added is 1.5% of the mass of amino silicone oil and ethylene oxide. Nitrogen is filled into the high-pressure reactor to replace the air three times. Then the temperature is raised to 170°C and ethylene oxide is introduced. The mass of ethylene oxide is 0.13 times the mass of amino silicone oil. The reaction is carried out at a reaction pressure of 0.3MPa. When the pressure drops below 0.1MPa and remains constant, indicating that the reaction is over, the temperature in the reactor is then lowered to 60°C-80°C and nitrogen is introduced to blow out the polyether-modified amino silicone oil product. See the infrared spectrum for details. Figure 1 .

[0036] The product performance indicators were measured according to the methods in GB / T 5560 and GB / T 7380. The results are shown in Table 1.

[0037] Example 2

[0038] Amino silicone oil is subjected to ethoxylation reaction in a high-pressure reactor. Amino silicone oil C845 and a catalyst are added to the high-pressure reactor. The amount of homogeneous catalyst NAE-03 added is 2% of the mass of amino silicone oil and ethylene oxide. Nitrogen is filled into the high-pressure reactor to replace the air three times. Then the temperature is raised to 180°C and ethylene oxide is introduced. The mass of ethylene oxide is 0.26 times the mass of amino silicone oil. The reaction is carried out at a reaction pressure of 0.4MPa. When the pressure drops below 0.1MPa and remains constant, indicating that the reaction is over, the temperature in the reactor is then lowered to 60°C-80°C and nitrogen is introduced to blow out the polyether-modified amino silicone oil product. See the infrared spectrum for details. Figure 1 .

[0039] The product performance indicators were measured according to the methods in GB / T 5560 and GB / T 7380. The results are shown in Table 1.

[0040] Example 3

[0041] Amino silicone oil is subjected to ethoxylation reaction in a high-pressure reactor. Amino silicone oil 6409 and a catalyst are added to the high-pressure reactor. The amount of homogeneous catalyst NAE-03 added is 1.5% of the mass of amino silicone oil and ethylene oxide. Nitrogen is filled into the high-pressure reactor to replace the air three times. Then the temperature is raised to 170°C and ethylene oxide is introduced. The mass of ethylene oxide is 0.15 times the mass of amino silicone oil. The reaction is carried out at a reaction pressure of 0.5MPa. When the pressure drops below 0.1MPa and remains constant, indicating that the reaction is over, the temperature in the reactor is then lowered to 60°C-80°C, nitrogen is introduced, and the polyether-modified amino silicone oil product is blown out. See the infrared spectrum for details. Figure 1 .

[0042] The product performance indicators were measured according to the methods in GB / T 5560 and GB / T 7380. The results are shown in Table 1.

[0043] Example 4

[0044] Amino silicone oil is subjected to ethoxylation reaction in a high-pressure reactor. Amino silicone oil 6409 and a catalyst are added to the high-pressure reactor. The amount of homogeneous catalyst NAE-03 added is 2% of the mass of amino silicone oil and ethylene oxide. Nitrogen is filled into the high-pressure reactor and the air is replaced 3 times. Then the temperature is raised to 170°C and ethylene oxide is introduced. The mass of ethylene oxide is 0.30 times the mass of amino silicone oil. The reaction is carried out at a reaction pressure of 0.5MPa. When the pressure drops below 0.1MPa and remains constant, indicating that the reaction is over, the temperature in the reactor is then lowered to 60°C-80°C and nitrogen is introduced to blow out the polyether-modified amino silicone oil product. See the infrared spectrum for details. Figure 1 .

[0045] The product performance indicators were measured according to the methods in GB / T 5560 and GB / T 7380. The results are shown in Table 1.

[0046] Example 5

[0047] Amino silicone oil is subjected to ethoxylation reaction in a high-pressure reactor. End-amino silicone oil 8K and catalyst are added to the high-pressure reactor. The amount of homogeneous catalyst NAE-03 added is 1.5% of the mass of amino silicone oil and ethylene oxide. Nitrogen is filled into the high-pressure reactor to replace the air 3 times. Then the temperature is raised to 170°C and ethylene oxide is introduced. The mass of ethylene oxide is 0.06 times the mass of amino silicone oil. The pressure rises to 0.1MPa. Then nitrogen is introduced to react at a reaction pressure of 0.3MPa. When the pressure drops below 0.1MPa and remains constant, indicating that the reaction is over, the temperature in the reactor is then lowered to 60°C-80°C and nitrogen is introduced to blow out the polyether-modified amino silicone oil product. See the infrared spectrum. Figure 1 .

[0048] The product performance indicators were measured according to the methods in GB / T 5560 and GB / T 7380. The results are shown in Table 1.

[0049] Figure 1 This is the infrared spectrum of the polyether-modified amino silicone oil prepared in Example 1, Example 2, Example 3, Example 4, and Example 5 of the present invention. -1 is the stretching vibration peak of the hydroxyl hydrogen bond, 2962.55cm -1 and 2904.68cm -1 The stretching vibration peaks of methyl and methylene are 1267.18 cm -1 -Si-CH 3 The CH bending vibration peak and 800.42cm -1 is the stretching vibration peak of Si-C, 1114.81cm-1 and 1008.73cm -1 The characteristic absorption peaks are -Si-O-Si and -COC, indicating that a polyether-modified amino silicone oil product has been synthesized.

[0050] Table 1 below shows the performance test results of the polyether-modified amino silicone oil products prepared in the examples of the present invention.

[0051] Table 1 shows the PEG content and water content of polyether modified amino silicone oil products

[0052] Example Example 1 Example 2 Example 3 Example 4 Example 5 PEG content% 2.008 2.441 4.120 4.190 0.273 Water content% 0.556 0.235 0.375 0.470 0.708

[0053] As can be seen from Table 1, the polyether-modified aminosilicone oil product prepared by the method of the present invention has the advantages of high reaction selectivity and high product purity. Under the process parameter conditions of Examples 1 to 5, the by-product content of Example 4 is the highest among the prepared products, but it does not exceed 5%, and the by-product content in Example 5 is only 0.98%. This fully demonstrates that the polyether-modified aminosilicone oil has a low degree of side reaction. Under the conditions of better process parameters, the total amount of by-product PEG and water content can be reduced to less than 1% by using the method of the present invention.

[0054] Example 6

[0055] Taking Example 1 as an example, the polyether-modified amino silicone oil product prepared by the method of the present invention is subjected to application performance tests, including whiteness test, softness test, and softness grade test. The test methods and test results (Table 2) are as follows:

[0056] (1) Whiteness test: Use a fully automatic whiteness meter to test the finished brown cotton cloth and compare it with a blank sample. The difference in whiteness between the finished brown cotton cloth and the blank sample is small, indicating that the color change of the finished brown cotton cloth is small.

[0057] (2) Softness test: The finished brown cotton cloth and the blank cotton cloth were measured using a Drick DPK119 softness tester. The finished brown cotton cloth was softer than the blank cotton cloth, indicating that the finished brown cotton cloth had better softness.

[0058] (3) Softness level test: The finished brown cotton cloth is sorted according to the softness level from bad to good, i.e., 1-5. Fifty people are randomly selected to touch the finished brown cotton cloth with their hands and compare it with the blank brown cotton cloth to judge the softness level of the cotton cloth. The cloth with the highest softness level judged by the number of people is used as the standard.

[0059] AEO 3A mixed surfactant was prepared with FMEE-Ⅱ and FMEE-Ⅱ as surfactants in the ratio of 2:8 and 3:7, and an emulsion was prepared with the mixed surfactant accounting for 5wt%, 10wt%, 15wt% and the polyether amino silicone oil accounting for 10wt%. The emulsion was then diluted to a bath liquid with a silicone oil content of 0.6wt%. The bath liquid was poured onto brown cotton cloth to test its whiteness and softness.

[0060] Table 2 is the performance test results of brown cotton cloth after softening agent finishing in Example 1

[0061]

[0062] It can be seen from Table 2 that the bath liquid prepared with mixed surfactants of different proportions and contents can effectively improve the softness of the cotton cloth and the color change is small when it is finished on brown cotton cloth. Compared with the unfinished brown cotton cloth, the difference in whiteness of the finished brown cotton cloth is small, indicating that this polyether amino silicone oil product has a small effect on the color change of the cotton cloth. Compared with the unfinished brown cotton cloth, as the proportion of mixed surfactants increases, the softness of the finished brown cotton cloth decreases more, and the softness level increases to 2-3, which indicates that when preparing silicone oil emulsion, the more the proportion of mixed surfactants, the smaller the particle size of the prepared silicone oil emulsion, so it can better penetrate into the fiber pores and improve the softness of the fiber.

[0063] The various embodiments in this specification are described in a progressive manner, and each embodiment focuses on the differences from other embodiments. The same or similar parts between the various embodiments can be referenced to each other.

[0064] The above description of the disclosed embodiments enables one skilled in the art to implement or use the present invention. Various modifications to these embodiments will be apparent to one skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the present invention. Therefore, the present invention will not be limited to the embodiments shown herein, but rather to the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. A method for preparing polyether-modified amino silicone oil, Features: Amino silicone oil and homogeneous calcium-based catalyst are added into a high-pressure reactor under negative pressure, nitrogen is introduced to replace the air in the reactor, and then the reaction temperature is increased to 160°C-180°C, ethylene oxide is introduced, and the reaction is carried out under a reaction pressure of 0.3MPa-0.5MPa. After the reaction is completed, the temperature in the reactor is reduced to 60°C-80°C, and nitrogen is introduced to purge the polyether-modified amino silicone oil product.

2. The method for preparing polyether-modified amino silicone oil according to claim 1, Features: The amino silicone oil is any one of a side chain type diamino silicone oil, a side chain type monoamino silicone oil, and an amino-terminated amino silicone oil.

3. The method for preparing polyether-modified amino silicone oil according to claim 2, Features: The amino silicone oil is any one of the compounds shown in the following molecular structural formulas: In formula (1) and (2), R 1 =NH 2 or NHCH 2 CH 2 NH 2 ,x is a positive integer between 1 and 300, y is a positive integer between 1 and 60, and z is a positive integer between 1 and 270.

4. The method for preparing polyether-modified amino silicone oil according to claim 3, Features: The reaction synthesis route is as follows: In the above reaction, R 1 =NH 2 or NHCH 2 CH 2 NH 2 , a is a positive integer from 1 to 30, b is a positive integer from 1 to 30, c is a positive integer from 1 to 30, d is a positive integer from 1 to 30, e is a positive integer from 1 to 50, f is a positive integer from 1 to 50, x is a positive integer from 1 to 300, y is a positive integer from 1 to 60, and z is a positive integer from 1 to 270.

5. The method for preparing polyether-modified amino silicone oil according to claim 1, Features: The homogeneous calcium-based catalyst uses raw materials of organic calcium salt, fatty alcohol and alcohol ether to react at 60°C-150°C under the protection of inert gas, and then adds organic acid to react for 1-3 hours to obtain a product of milky white liquid with pH <7.

6. The method for preparing polyether-modified amino silicone oil according to claim 1, Features: The amount of the homogeneous catalyst added is 1%-5% of the total mass of the amino silicone oil and ethylene oxide.

7. The method for preparing polyether-modified amino silicone oil according to claim 1, Features: The reaction is concluded when the pressure in the reactor drops below 0.1 MPa and remains constant.

8. The method for preparing polyether-modified amino silicone oil according to claim 1, Features: In the polyether modified amino silicone oil product, the content of polyether modified amino silicone oil is ≥90%.

9. A fabric finishing agent, It is characterized in that The effective components contain 10wt.% of polyether-modified aminosilicone oil, 15wt.% of composite surfactant, and the balance is deionized water; the polyether-modified aminosilicone oil is obtained by the preparation method of polyether-modified aminosilicone oil according to any one of claims 1 to 8.

10. The fabric finishing agent according to claim 9, Features: The composite surfactant is surfactant AEO 3 and FMEE-Ⅱ in a mass ratio of 2:8 to 3:7 to obtain a mixture.

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