Preparation and application of polyether polyamide polysiloxane finishing agent
By synthesizing polyether polyamide polysiloxane finishing agent with a specific structure, the problems of uneven distribution of finishing agents on the fabric in the prior art are solved, and the excellent moisture absorption, breathability and sweating properties of the fabric are achieved.
Patent Information
- Application Number
- CN202411760366.9
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-12-03
- Publication Date
- 2025-03-07
Smart Images
Figure CN119570039A_ABST
Abstract
Description
Technical Field
[0001] The invention mainly relates to the technical field of chemical industry, and specifically relates to the preparation and application of a polyether polyamide polysiloxane finishing agent. Background Art
[0002] Polyether polyamide polysiloxane finishing agent is a multifunctional finishing agent, which is widely used in fabric finishing to improve the softness, hydrophilicity, antistatic properties and other properties of fabrics. When combined with nylon fibers, it can condense into a film or cross-link with the fibers to keep the fabric hydrophilic for a long time.
[0003] Based on the existing technology, there are several technical defects: 1. The ratio or chain length of polyamide, polyether and polysiloxane in the finishing agent is unreasonable, which affects the performance of the finishing agent on the fabric, resulting in uneven distribution on the fabric surface or failure to effectively penetrate; 2. The hydrophilic performance is poor, the hydrophilic components in the finishing agent may be insufficient or fail to play an effective role, and the finishing agent layer on the fabric surface may be too dense, hindering the penetration of moisture; 3. Certain components in the finishing agent affect the moisture absorption, air permeability and perspiration performance of the fabric, and fail to effectively improve the pore structure and surface characteristics of the fabric, resulting in a decrease in its moisture absorption and quick-drying performance. Summary of the invention
[0004] Based on this, the purpose of the present invention is to provide a preparation method of a polyether polyamide polysiloxane finishing agent and its application to solve the technical problems raised in the above background technology.
[0005] To achieve the above object, the present invention provides the following technical solutions:
[0006] The first aspect of the present invention provides a polyether polyamide polysiloxane finishing agent having the following structural formula:
[0007]
[0008] Among them: a = 7 to 14; b = 3 to 6; n = 16 to 90; m = 55 to 96; c = 6. a, b, n, m are all natural numbers.
[0009] Preferably, the raw materials for preparing the polyether polyamide polysiloxane finishing agent include: allyl polyether, sodium chloroacetate, hydrogen-containing silicone oil, and amide compound (any one of caprolactam, cinnamamide, and benzamide).
[0010] The second aspect of the present invention provides a method for preparing a polyether polyamide polysiloxane finishing agent, comprising the following steps:
[0011] S1. Synthesis of carboxyl-terminated polyether: tetrahydrofuran and sodium hydride are added to a three-necked flask, stirred to disperse, allyl polyether is dissolved in tetrahydrofuran, added to the three-necked flask under nitrogen protection, and stirred at room temperature until no bubbles are generated; sodium chloroacetate is added, and reacted under nitrogen protection until the material turns yellow; unreacted sodium hydride, sodium chloroacetate and generated sodium chloride are filtered out; tetrahydrofuran is removed by rotary evaporation, hydrochloric acid is added to acidify, and toluene is added to reflux to remove the aqueous phase; toluene is removed by rotary evaporation, and vacuum drying is performed to obtain a yellow viscous substance;
[0012] S2. Synthesis of polyether block polysiloxane copolymer: Add hydrogenated silicone oil and carboxyl-terminated polyether into a three-necked flask, stir and heat to 90°C, add H 2 PtCl 6 Catalyst, heat to 125℃ within 10min, after the material becomes transparent, the reaction is finished and cooled to room temperature;
[0013] S3. Synthesis of polyamide polyether polysiloxane copolymer: add an amide compound in an amount equivalent to that of the carboxyl-terminated polyether, 0.2 wt% phosphorous acid and 10 wt% deionized water into the three-necked flask in step 2, stir and heat to 170°C, keep warm for 5 hours, replace the reflux device with a distillation device, heat to 210°C, keep warm for 2 hours, evacuate for 0.5 hours, cool to 50°C and discharge to obtain a polyamide polyether polysiloxane finishing agent.
[0014] In summary, the present invention mainly has the following beneficial effects:
[0015] The nylon-spandex knitted fabric treated with the polyether polyamide polysiloxane finishing agent prepared by the present invention has excellent softness, smoothness, fineness, resilience and fluffiness; has excellent hydrophilicity, absorbs water instantly, and has good continuous hydrophilicity; gives the fabric excellent moisture absorption, air permeability and perspiration-releasing clothing properties to meet market demand; and at the same time has excellent stability and good compatibility with other additives.
[0016] In addition, the preparation method of the polyether polyamide polysiloxane finishing agent provided by the present invention has a detailed preparation process, a simple operation flow and a high output rate of finished products. DETAILED DESCRIPTION
[0017] The experimental methods in the following examples are conventional methods unless otherwise specified; the experimental raw materials used can be commercially purchased and / or prepared by known means unless otherwise specified, and meet the requirements of standard chemical products unless otherwise specified.
[0018] Example 1
[0019] This embodiment provides a polyether polyamide polysiloxane finishing agent, which is prepared by the following method:
[0020] (1) Synthesis of carboxyl-terminated polyethers:
[0021]
[0022] It should be noted that a=7-14 and b=3-6.
[0023] The synthesis steps are as follows: add 50 ml of tetrahydrofuran to a 500 ml three-necked beaker, add 1.31 g of sodium hydride, i.e. 32.75 mmol, 60% NaH solution, and stir to disperse. Dissolve 10.15 g of allyl polyether in 100 ml of tetrahydrofuran and add 1.31 g of sodium hydride, i.e. 32.75 mmol, 60% NaH solution, and stir to disperse. 2 Add the solution to a three-necked flask under the protection of N. Specifically, add the solution dropwise into a 500 ml three-necked beaker using a constant pressure dropping funnel and stir for 4 h at room temperature until no bubbles are generated. Add 3.41 g of sodium chloroacetate and 2 Under the protection of , react at room temperature for 24 hours, react until the material turns yellow, filter to remove unreacted sodium chloride, sodium chloroacetate and generated NaCl, then remove tetrahydrofuran by rotary evaporation, add 5ml hydrochloric acid to acidify, add 30ml toluene to reflux for 1h to remove the water phase, rotary evaporation to remove toluene, put the product into a vacuum drying oven, dry at room temperature for 24h, and obtain 6.91g of brown-yellow viscous material, with a yield of 67.54%, and a hydroxyl value determination end-capping rate of 96.39%. (for standby)
[0024] (2) Synthesis of polyether block polysiloxane copolymer:
[0025]
[0026] It should be further explained that the hydrogen-containing silicone oil with a hydrogen content of 0.096% and a molecular weight of M W =7802, m=55~96, n=16~90.
[0027] The synthesis steps are as follows: 17.91 g of hydrogenated silicone oil with a hydrogen content of 0.096% and 22.34 g of carboxyl-terminated polyether are added to a three-necked beaker, heated to 90°C with electric stirring, and 5 ppm of H 2 PtCl 6 Catalyst, heat to 125℃ within 10min, continue to react for 1h after the material becomes transparent, and cool to 24-26℃ after the reaction.
[0028] (3) Synthesis of polyamide polyether polysiloxane copolymer:
[0029]
[0030] The synthesis steps are as follows: in the above three-necked flask, add the carboxyl-terminated polyether synthesized in step (1) and 10.15 mmol of caprolactam, and at the same time add 0.2 wt% of nitrous acid and 10 wt% of deionized water, heat to 170°C and keep warm for 5 hours, then replace the reflux device with a distillation device, heat to 210°C and keep warm for 2 hours, finally evacuate, specifically maintain at -0.01 kPa for 0.5 hours, and finally cool to 50°C to complete the preparation. The polyether polyamide polysiloxane finishing agent is obtained.
[0031] Example 2
[0032] (1) Synthesis of carboxyl-terminated polyethers:
[0033] Add 50 ml of tetrahydrofuran and 1.31 g of sodium hydride into a 500 ml three-necked flask, stir to separate, dissolve 10.15 g of allyl polyether in 100 ml of tetrahydrofuran, add to the three-necked flask under nitrogen protection, and stir at room temperature for 4 hours until no bubbles are generated.
[0034] Add 3.41 g of sodium chloroacetate and react under nitrogen for 24 hours until the material turns yellow. Filter out unreacted sodium hydride, sodium chloroacetate and generated sodium chloride, remove tetrahydrofuran by rotary evaporation, add 5 ml of hydrochloric acid to acidify, add 30 ml of toluene and reflux for 1 hour to remove the aqueous phase; rotary evaporation to remove toluene, and vacuum dry for 24 hours to obtain a yellow viscous material.
[0035] (2) Synthesis of polyether block polysiloxane copolymer:
[0036] 17.91 g of hydrogen-containing silicone oil with a hydrogen content of 0.158% and 22.34 g of carboxyl-terminated polyether were added to a three-necked flask, the temperature was raised to 90°C with stirring, and 5 ppm H 2 PtCl 6 Catalyst, heat to 125℃ within 10min, react for 1h after the material becomes transparent, and cool to room temperature after the reaction is completed.
[0037] Among them, it is further explained that 0.158% of hydrogen-containing silicone oil, molecular weight M W =4152, m=55~96, n=16~90.
[0038] (3) Synthesis of polyamide polyether polysiloxane copolymer:
[0039] To the three-necked flask after the reaction of the above polyether block polysiloxane copolymer is completed, add cinnamamide, 0.2wt% phosphorous acid and 10wt% deionized water in an amount equivalent to the carboxyl-terminated polyether, stir and heat to 170°C, keep warm for 5 hours, replace the reflux device with a distillation device, heat to 210°C, keep warm for 2 hours, evacuate (-0.01KPa) for 0.5 hours, cool to 50°C and discharge to obtain a polyether polyamide polysiloxane finishing agent.
[0040] Example 3
[0041] (1) Synthesis of carboxyl-terminated polyethers:
[0042] Add 50 ml of tetrahydrofuran and 1.31 g of sodium hydride into a 500 ml three-necked flask, stir to separate, dissolve 10.15 g of allyl polyether in 100 ml of tetrahydrofuran, add to the three-necked flask under nitrogen protection, and stir at room temperature for 4 hours until no bubbles are generated.
[0043] Add 3.41 g of sodium chloroacetate and react under nitrogen for 24 hours until the material turns yellow. Filter out unreacted sodium hydride, sodium chloroacetate and generated sodium chloride, remove tetrahydrofuran by rotary evaporation, add 5 ml of hydrochloric acid to acidify, add 30 ml of toluene and reflux for 1 hour to remove the aqueous phase; rotary evaporation to remove toluene, and vacuum dry for 24 hours to obtain a yellow viscous material.
[0044] (2) Synthesis of polyether block polysiloxane copolymer:
[0045] 17.91 g of hydrogen-containing silicone oil with a hydrogen content of 0.312% and 22.34 g of carboxyl-terminated polyether were added to a three-necked flask, the temperature was raised to 90°C with stirring, and 5 ppm of H 2 PtCl 6 Catalyst, heat to 125℃ within 10min, react for 1h after the material becomes transparent, and cool to room temperature after the reaction is completed.
[0046] Among them, it is further explained that 0.312% of hydrogen-containing silicone oil, molecular weight M W =5196, m=55~96, n=16~90.
[0047] (3) Synthesis of polyamide polyether polysiloxane copolymer:
[0048] To the three-necked flask after the reaction of the above polyether block polysiloxane copolymer is completed, add benzamide, 0.2wt% phosphorous acid and 10wt% deionized water in the same amount as the carboxyl-terminated polyether, stir and heat to 170°C, keep warm for 5 hours, replace the reflux device with a distillation device, heat to 210°C, keep warm for 2 hours, evacuate (-0.01KPa) for 0.5 hours, cool to 50°C and discharge to obtain a polyether polyamide polysiloxane finishing agent.
[0049] Application comparison test experiment
[0050] Materials: Example 1, Example 2, Example 3, similar finishing agent A on the market, similar finishing agent B on the market, nylon-spandex knitted fabric (82% nylon, 18% spandex, weight 190g / ㎡)
[0051] Process: two dips and two rolls → drying (105°C) → heat setting (170°C for 60s) → testing.
[0052] The treated nylon-spandex knitted fabrics were tested for their moisture absorption, quick-drying, hydrophilicity, washing durability, drying rate, and soft and fluffy feel.
[0053] (1) Water drop diffusion time test: refer to the method of national standard GB / T 21655.1-2023.
[0054] Table 1 Comparative test results of drip diffusion time
[0055] Finishing agent Before washing Wash 5 times Wash 10 times Blank fabric ＞180s ＞180s ＞180s Example 1 ＜1s ＜1s ＜1s Example 2 ＜1s ＜1s ＜1s Example 3 ＜1s ＜1s 1.5s Similar finishing agents on the market A ＜1s ＜1s 2.3s Similar finishing agent on the market B ＜1s 1.8s 4.2s
[0056] Note: The diffusion time of water droplets is measured in seconds (S). The shorter the diffusion time of water droplets, the better the hygroscopicity. Data < 1s is instantaneous hygroscopicity.
[0057] As shown in Table 1, the nylon-spandex knitted fabric treated with the polyamide polyether polysiloxane finishing agent prepared by the present invention has excellent hydrophilicity, absorbs water instantly, and has good continuous hydrophilicity;
[0058] (2) Drying rate test (temperature 21.4°C, humidity 65%): refer to the method of national standard GB / T 21655.1-2023.
[0059] Table 2 Drying rate comparison test results g / h
[0060] Finishing agent Before washing Wash 5 times Wash 10 times Blank fabric 0.15 0.09 0.04 Example 1 0.3 0.28 0.25 Example 2 0.3 0.26 0.20 Example 3 0.28 0.24 0.18 Similar finishing agents on the market A 0.28 0.22 0.15 Similar finishing agent on the market B 0.26 0.21 0.13
[0061] Note: The drying rate is expressed in grams per hour (g / h). The larger the drying rate, the better the moisture absorption and perspiration wicking performance.
[0062] As shown in Table 2, the nylon-spandex knitted fabric treated with the polyamide polyether polysiloxane finishing agent prepared by the present invention has an excellent drying rate, giving the fabric excellent moisture absorption, air permeability, and sweat-wicking clothing properties;
[0063] (3) Hand feel performance test: refer to the method of enterprise standard SC-YY-013
[0064] Table 3 Hand feel performance comparison test results
[0065] Finishing agent soft fluffy Blank fabric 1 1 Example 1 4-5 4-5 Example 2 4-5 4 Example 3 4 4 Similar finishing agents on the market A 4 3 Similar finishing agent on the market B 3-4 3
[0066] Note: The touch performance is rated by at least 5 experienced people. 1 to 5 points represent the touch comparison results, 5 points represent the best, and 1 point represents the worst.
[0067] As shown in Table 3, the nylon-spandex knitted fabric treated with the polyamide polyether polysiloxane finishing agent prepared by the present invention has an excellent hand feel and imparts excellent skin-friendly properties to the fabric;
[0068] (4) Stability test
[0069] Table 4 Stability application comparison test results
[0070] Finishing agent pH = 3 pH=11 Sodium sulfate (20g / L) Dye (2%) Fixing agent (20g / L) Example 1 Stablize Stablize Stablize Stablize Stablize Example 2 Stablize Stablize Stablize Stablize Stablize Example 3 Stablize Stablize Stablize Stablize Stablize Similar finishing agents on the market A Stablize Stablize Stablize Stablize precipitation Similar finishing agent on the market B Stablize precipitation Stablize precipitation Stablize
[0071] As shown in Table 3, the polyamide polyether polysiloxane finishing agent of the present invention has excellent acid, alkali and salt resistance stability, and good compatibility with other additives.
[0072] The above embodiments are only for illustrating the technical idea of the present invention, and cannot be used to limit the protection scope of the present invention. Any changes made on the basis of the technical solution in accordance with the technical idea proposed by the present invention shall fall within the protection scope of the present invention.
Claims
1. Preparation of a polyether polyamide polysiloxane finishing agent, characterized in that , comprising the following preparation steps: S1. Synthesis of carboxyl-terminated polyether: tetrahydrofuran and sodium hydride are added to a three-necked flask, and stirred to disperse them. Allyl polyether is dissolved in tetrahydrofuran, and added to the three-necked flask under nitrogen protection, and stirred at room temperature until no bubbles are generated; sodium chloroacetate is added, and reacted under nitrogen protection until the material turns yellow; unreacted sodium hydride, sodium chloroacetate and generated sodium chloride are filtered out; tetrahydrofuran is removed by rotary evaporation, hydrochloric acid is added to acidify, and toluene is added to reflux to remove the aqueous phase; toluene is removed by rotary evaporation, and vacuum drying is performed to obtain a yellow viscous substance. S2. Synthesis of polyether block polysiloxane copolymer: Add hydrogenated silicone oil and carboxyl-terminated polyether into a three-necked flask, stir and heat to 90°C, add H2PtCl6 catalyst, heat to 125°C within 10 minutes, and when the material becomes transparent, the reaction is terminated and cooled to room temperature. S3. Synthesis of polyamide polyether polysiloxane copolymer: add amide compound in the same amount as carboxyl-terminated polyether, 0.2wt% phosphorous acid and 10wt% deionized water into a three-necked flask, stir and heat to 170°C, keep warm for 5h, replace the reflux device with a distillation device, heat to 210°C, keep warm for 2h, vacuum for 0.5h, cool to 50°C and discharge to obtain polyamide polyether polysiloxane finishing agent.
2. The preparation of a polyether polyamide polysiloxane finishing agent according to claim 1, characterized in that: The hydrogen-containing silicone oil is specifically a hydrogen-containing silicone oil with a hydrogen content of 0.096% to 0.312%.
3. The preparation of a polyether polyamide polysiloxane finishing agent according to claim 1, characterized in that: The amide compound is specifically any one of caprolactam, cinnamamide and benzamide.
4. The preparation of a polyether polyamide polysiloxane finishing agent according to claim 1, characterized in that: The vacuuming is specifically -0.01 KPa.
5. The preparation of a polyether polyamide polysiloxane finishing agent according to claim 1, characterized in that: The room temperature is specifically 24-26°C.