A silicone finish for fabrics and a method for its preparation

Abstract

The application belongs to the field of polymers, and discloses a preparation method of a silicone finishing agent for fabrics, which comprises the following steps: step 1: synthesizing a first intermediate and a second intermediate; and step 2: taking the first intermediate, the second intermediate and a compound containing a mercapto group as reaction monomers to perform a reaction in a solvent, and obtaining the silicone finishing agent after removing the solvent; the weight ratio of the first intermediate, the second intermediate and the compound containing a mercapto group is 100-200:10-100:1-5. On the basis of existing development experience, the application retains an intermediate modified by an amino silicone oil, and simultaneously introduces an intermediate containing multiple functional groups, so that a silicone finishing agent with good water repellency, good hand feeling and good durability is synthesized in the presence of a compound containing a mercapto group.

Description

Technical Field

[0001] This invention relates to the field of polymers, and more particularly to an organosilicon finishing agent for fabrics and its preparation method. Background Technology

[0002] Fabric finishing agents can be classified into hydrophilic and hydrophobic types based on their hydrophilicity or hydrophobicity; amino-containing silane coupling agents are used in both types of fabric finishing agents.

[0003] For example, regarding hydrophilic fabric finishing agents, the applicant's earlier application, publication number CN106319975B, is a patent application for a hydrophilic cooling skin-feel finishing agent for cotton fabrics and its preparation method. The application uses an aminosilane coupling agent in a silicone oil-based hydrophilic modified amino silicone oil. In this modified amino silicone oil, hydroxyl epoxy polyether is additionally used as a hydrophilic agent.

[0004] A hydrophobic fabric finishing agent, as seen in patent application CN105256588A, is a honeycomb structure organosilicon waterproof finishing agent and its preparation method, which uses N-β-aminoethyl-γ-aminopropylmethyldimethoxysilane as one of the emulsifiers.

[0005] In this field, the main purpose of loading amino silicone oil as a modifier onto silicone oil is to improve stability through the action of silane coupling agents. For example, in an earlier patent application, publication number CN101446038B, entitled "Deepening and Brightening Agent for Fabrics and its Production Method," a method is used to produce the deepening and brightening agent by introducing a small amount of N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane functional groups into the structure. The synthesis process is unique, and the product has excellent stability.

[0006] In the process of developing hydrophobic fabric finishing agents, we discovered that the incorporation of amino silicone oil into silicone oil segments also plays a very important role in improving the hydrophobic properties of hydrophobic fabric finishing agents.

[0007] Therefore, the technical problem solved by this application is: how to further improve the water-repellent properties of hydrophobic fabric finishing agents. Summary of the Invention

[0008] The purpose of this invention is to provide an organosilicon finishing agent for fabrics and its preparation method. Based on existing development experience, this invention retains the intermediate of amino silicone oil modification and introduces an intermediate containing multiple functional groups. In the presence of a mercapto-containing compound, an organosilicon finishing agent with good water repellency, good hand feel and good durability is synthesized.

[0009] To achieve the above objectives, this application discloses:

[0010] A method for preparing an organosilicon finishing agent for fabrics includes the following steps:

[0011] Step 1: Synthesize the first intermediate and the second intermediate;

[0012] Step 2: Using the first intermediate, the second intermediate, and the mercapto-containing compound as reactants, the reaction is carried out in a solvent, and the organosilicon finishing agent is obtained after removing the solvent;

[0013] The weight ratio of the first intermediate, the second intermediate, and the mercapto-containing compound is 100~200:10~100:1~5;

[0014] The first intermediate is synthesized from hydrogen-containing silicone oil, an olefinic acid with 12-18 carbon atoms, a C12-C18 alkyl acrylate, and a functional monomer having an ethylene oxide group and an unsaturated group; the hydrogen content of the first monomer is 0.1-1 wt%.

[0015] The second intermediate is an amino-modified polyorganosiloxane;

[0016] The thiol-containing compound has a C10-C18 alkyl group.

[0017] In the above preparation method, the amino-modified polyorganosiloxane is obtained by reacting octamethylcyclotetrasiloxane and N-β-(aminoethyl)-γ-aminopropylmethyldimethoxysilane in the presence of a catalyst;

[0018] The N-β-(aminoethyl)-γ-aminopropylmethyldimethoxysilane is equivalent to 10-20 wt% of octamethylcyclotetrasiloxane.

[0019] In the above preparation method, the catalyst is potassium hydroxide, sodium hydroxide or lithium hydroxide; the catalyst is equivalent to 0.01~1 wt% of octamethylcyclotetrasiloxane.

[0020] In the above preparation method, the synthesis process of the amino-modified polyorganosiloxane is as follows: under the protection of an inert gas, octamethylcyclotetrasiloxane, N-β-(aminoethyl)-γ-aminopropylmethyldimethoxysilane and catalyst are added to a reactor and reacted at 100-150°C for 2-7 hours.

[0021] In the above preparation method, the weight ratio of the hydrogen-containing silicone oil, the olefinic acid with 12 to 18 carbon atoms, the C12 to C18 alkyl acrylate, and the functional monomer with ethylene oxide group and unsaturated group is 100:15 to 30:10 to 20:15 to 25.

[0022] In the above preparation method, the synthesis process of the first intermediate is as follows: adding hydrogen-containing silicone oil, olefinic acid with 12 to 18 carbon atoms, C12 to C18 alkyl ester of acrylic acid, and functional monomers with ethylene oxide groups and unsaturated groups into a reactor, and reacting at 55 to 95°C for 3 to 8 hours in the presence of a platinum catalyst.

[0023] In the above preparation method, the hydrogen-containing silicone oil is obtained by reacting octamethylcyclotetrasiloxane, high-hydrogen silicone oil, and hexamethyldisiloxane; the hydrogen content of the high-hydrogen silicone oil is 1.5~2.5wt%; and the hexamethyldisiloxane is equivalent to 0.5~5wt% of the weight of octamethylcyclotetrasiloxane.

[0024] In the above preparation method, the solvent is ethanol, and the solvent is equivalent to 0.5 to 1.5 times the weight of the first intermediate.

[0025] In the above preparation method, the mercapto-containing compound is dodecyl mercaptohydride and / or tert-dodecyl mercaptohydride; the functional monomer having an ethylene oxide group and an unsaturated group is allyl glycidyl ether and / or allyl polyoxypropylene glycidyl ether.

[0026] Meanwhile, the present invention also discloses an organosilicon finishing agent, which is prepared by any of the methods described above.

[0027] This application has at least the following beneficial effects:

[0028] Based on existing development experience, this invention retains the intermediates for amino silicone oil modification and introduces intermediates containing multiple functional groups. In the presence of thiol-containing compounds, an organosilicon finishing agent with good water repellency, good feel, and good durability was synthesized. Detailed Implementation

[0029] The present invention will now be clearly and completely described in conjunction with embodiments thereof. It should be noted that, unless otherwise specified in the embodiments, conditions are performed under conventional conditions or conditions recommended by the manufacturer. Reagents or instruments whose manufacturers are not specified are all commercially available products. Unless otherwise specified, all parts used in the embodiments of the present invention are parts by weight.

[0030] Part 1: Synthesis of the First Intermediate

[0031] The synthesis of the first intermediate includes the following steps:

[0032] Step 1: Synthesis of hydrogen-containing silicone oil;

[0033] Octamethylcyclotetrasiloxane (D4), high-hydrogen silicone oil (2wt% hydrogen content), hexamethyldisiloxane, and catalyst (acidic clay) were added to a four-necked flask. The mixture was kept at 50°C for 8 hours and then filtered to obtain the hydrogen-containing silicone oil.

[0034] Step 2: Synthesis of the first intermediate;

[0035] Hydrogen-containing silicone oil, dodecenoic acid, allyl glycidyl ether, allyl polyoxypropyl glycidyl ether (molecular weight: 300-1000), and octadecyl acrylate were added to a four-necked flask. Under the action of a platinum catalyst (Castel platinum complex), the mixture was kept at 70°C for 5 hours to obtain the first intermediate.

[0036] The formulas are shown in Tables 1 and 2.

[0037] Table 1 Formulation table for the synthesis of hydrogen-containing silicone oil (Unit: parts by weight)

[0038] Hydrogen-containing silicone oil 1 100 100 0.5 1 1% Hydrogen-containing silicone oil 2 100 50 2 2 0.67% Hydrogen-containing silicone oil 3 100 30 3 3 0.45% Hydrogen-containing silicone oil 4 100 10 4 4 0.18% Hydrogen-containing silicone oil 5 100 5 5 5 0.1%

[0039] Table 2 Formulation table for the synthesis of the first intermediate (unit: parts by weight)

[0040]

[0041] First intermediate 9

[0042] It is largely the same as the first intermediate 3, except that it uses an equal weight of octadecenoic acid to replace dodecenoic acid.

[0043] The product was named First Intermediate 9.

[0044] First intermediate 10

[0045] It is largely the same as the first intermediate 3, except that it uses lauryl acrylate to replace octadecyl acrylate by weight.

[0046] The product was named First Intermediate 10.

[0047] The synthesis of the second intermediate in the second part includes the following steps:

[0048] D4, N-β-(aminoethyl)-γ-aminopropylmethyldimethoxysilane (hereinafter referred to as amino silicone oil), and catalyst (potassium hydroxide) were added to a four-necked flask and kept at 120°C for 5 hours to obtain amino-modified polyorganosiloxane.

[0049] The formula is shown in Table 3;

[0050] Table 3 Formulation table for the synthesis of the second intermediate (Unit: parts by weight)

[0051] Second intermediate 1 100 10 0.1 Second intermediate 2 100 15 0.5 Second intermediate 3 100 20 1

[0052] Part Three: Synthesis of Fabric Finishing Agents

[0053] The first intermediate, the second intermediate, the mercapto compound, and anhydrous ethanol solvent were added to a four-necked flask and kept at 70°C for 12 hours. The anhydrous ethanol was then concentrated to remove the residue, yielding the organosilicon finishing agent.

[0054] The formula is shown in Table 4;

[0055] Table 4 Formulation table for the synthesis of fabric finishing agents (Unit: parts by weight)

[0056]

[0057] Contrast finishing agent 6

[0058] It is largely the same as fabric finishing agent 1, except that, in the synthesis of the first intermediate monomer 3, octadecyl acrylate is replaced by trifluoroethyl acrylate in equal weight.

[0059] Contrast Finishing Agent 7

[0060] It is largely the same as fabric finishing agent 1, except that in the synthesis of the first intermediate monomer 3, dodecenoic acid is replaced with hexafluorobutyl methacrylate.

[0061] Performance testing

[0062] This invention evaluates each sample in four dimensions: softness to the touch, water resistance, contact angle, and washability. The test methods for each test are as follows:

[0063] Softness of the hand feel: Five professional judges conducted a blind test, comparing the scores with standard hand feel cards (level 1 to 5, with higher levels indicating better softness), and took the average value.

[0064] Waterproofing effect: Pour 250ml of room temperature deionized water into the funnel of the testing instrument and spray it onto the sample fabric over 25-30 seconds. The degree of water penetration on the fabric is then assessed and scored.

[0065] 100—The surface being sprayed was neither wetted nor covered with water droplets.

[0066] 90—The surface being irrigated is not wet, but has water droplets on it.

[0067] 80—The surface being sprayed is only wetted at the spray point.

[0068] 70—Only part of the surface being wetted.

[0069] 60—The entire surface to be wetted

[0070] 0 — The surface being sprayed and the other side are completely wetted.

[0071] Contact angle: The water contact angle (static) was tested according to DB44 / T1872-2016 "Determination of surface wetting properties of textiles - Contact angle method".

[0072] Washability: The fabric was washed according to the household washing and drying procedure for textile experiments (GB / T8629-20015A). After washing, its softness was tested. The number of washes in which the softness decreased by one grade compared to before washing is the wash resistance. (Compare the decrease in hand feel and water resistance after 10 washes).

[0073] The test results are shown in Table 5.

[0074] Table 5 Test Results

[0075] Fabric finishing agent 1 Level 4.5 91 113° 22 times Fabric finishing agent 2 Level 5 92 115° 25 times Fabric finishing agent 3 Level 5 93 116° 23 times Fabric finishing agent 4 Level 4.5 90 111° 20 times Fabric finishing agent 5 Level 4.5 91 112° 21 times Fabric finishing agent 6 Level 4 88 107° 16 times Fabric finishing agent 7 Level 4 89 108° 17 times Fabric finishing agent 8 Level 4.5 91 113° 22 times Fabric finishing agent 9 Level 4.5 90 110° 20 times Fabric finishing agent 10 Level 5 92 115° 24 times Fabric finishing agent 11 Level 4.5 88 109° 19 times Fabric finishing agent 12 Level 4 86 106° 16 times Comparison finishing agent 1 Level 3.5 78 101° 11 times Comparison finishing agent 2 Level 3 74 94° 8 times Contrast finishing agent 3 Level 3 75 96° 9 times Contrast finishing agent 4 Level 2.5 62 83° 3 times Comparison finishing agent 5 Level 3 73 92° 5 times Contrast finishing agent 6 Level 2.5 89 105° 6 times Contrast finishing agent 7 3 87 108° 5 times

[0076] Results analysis:

[0077] 1. Based on the above-mentioned fabric finishing agents 1 to 12, the products of the present invention have good hand feel, waterproof effect and washability;

[0078] 2. By comparing finishing agents 1 to 5, finishing agent 1 showed the best effect, indicating that long-chain fatty acids had the weakest impact on performance. Finishing agents 2 and 3 showed similar effects, indicating that the absence of glycidyl ether flexible segments and long-chain fatty acid esters had a more significant impact on overall performance.

[0079] The absence of the second intermediate has a particularly significant impact on performance, and the effect of thiol compounds on performance is also quite obvious. In this invention, thiol compounds are not only used as chain transfer agents, but also provide long hydrophobic segments, which have a significant impact on the overall performance.

[0080] 3. By comparing finishing agents 6 and 7, it can be seen that the use of fluorinated hydrophobic monomers can improve hydrophobic properties, but the improvement on hand feel and wash resistance is not as good as that of other monomers. In fact, the addition of this fluorinated monomer while retaining other monomers in the reaction has a particularly significant impact on non-hydrophobic properties.

Claims

1. A method for preparing an organosilicon finishing agent for fabrics, characterized in that, Includes the following steps: Step 1: Synthesize the first intermediate and the second intermediate; Step 2: Using the first intermediate, the second intermediate, and the mercapto-containing compound as reactants, the reaction is carried out in a solvent, and the organosilicon finishing agent is obtained after removing the solvent; The weight ratio of the first intermediate, the second intermediate, and the mercapto-containing compound is 100~200:10~100:1~5; The first intermediate is synthesized from hydrogen-containing silicone oil, an olefinic acid with 12-18 carbon atoms, a C12-C18 alkyl acrylate, and a functional monomer having an ethylene oxide group and an unsaturated group; the hydrogen content of the first monomer is 0.1-1 wt%. The second intermediate is an amino-modified polyorganosiloxane; The thiol-containing compound has a C10-C18 alkyl group.

2. The preparation method according to claim 1, characterized in that, The amino-modified polyorganosiloxane is obtained by reacting octamethylcyclotetrasiloxane and N-β-(aminoethyl)-γ-aminopropylmethyldimethoxysilane in the presence of a catalyst; The N-β-(aminoethyl)-γ-aminopropylmethyldimethoxysilane is equivalent to 10-20 wt% of octamethylcyclotetrasiloxane.

3. The preparation method according to claim 2, characterized in that, The catalyst is potassium hydroxide, sodium hydroxide, or lithium hydroxide; the catalyst is equivalent to 0.01 to 1 wt% of octamethylcyclotetrasiloxane.

4. The preparation method according to claim 2, characterized in that, The synthesis process of the amino-modified polyorganosiloxane is as follows: under the protection of an inert gas, octamethylcyclotetrasiloxane, N-β-(aminoethyl)-γ-aminopropylmethyldimethoxysilane and a catalyst are added to a reactor and reacted at 100-150°C for 2-7 hours.

5. The preparation method according to claim 1, characterized in that, The weight ratio of the hydrogen-containing silicone oil, the olefinic acid with 12 to 18 carbon atoms, the C12 to C18 alkyl acrylate, and the functional monomers with ethylene oxide groups and unsaturated groups is 100:15 to 30:10 to 20:15 to 25.

6. The preparation method according to claim 5, characterized in that, The synthesis process of the first intermediate is as follows: adding hydrogen-containing silicone oil, olefinic acid with 12 to 18 carbon atoms, C12 to C18 alkyl ester of acrylic acid, and functional monomers with ethylene oxide groups and unsaturated groups into a reactor, and reacting at 55 to 95°C for 3 to 8 hours in the presence of a platinum catalyst.

7. The preparation method according to claim 6, characterized in that, The hydrogen-containing silicone oil is obtained by reacting octamethylcyclotetrasiloxane, high-hydrogen silicone oil, and hexamethyldisiloxane; the hydrogen content of the high-hydrogen silicone oil is 1.5~2.5wt%; the hexamethyldisiloxane is equivalent to 0.5~5wt% of the weight of octamethylcyclotetrasiloxane.

8. The preparation method according to claim 1, characterized in that, The solvent is ethanol, and the solvent is equivalent to 0.5 to 1.5 times the weight of the first intermediate.

9. The preparation method according to claim 1, characterized in that, The mercapto-containing compound is dodecyl mercaptohydride and / or tert-dodecyl mercaptohydride; the functional monomer having an ethylene oxide group and an unsaturated group is allyl glycidyl ether and / or allyl polyoxypropylene glycidyl ether.

10. An organosilicon finishing agent, characterized in that, It is prepared by the method described in any one of claims 1 to 8.

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