A solvent-free self-emulsifying water-resistant softener, and its preparation method and application

Abstract

The invention discloses a solvent-free self-emulsifying water-resistant softener, a preparation method and application thereof, and belongs to the field of polymer preparation. The invention pre-blocks the NCO active group, unblocks the NCO active group during the fabric finishing and drying process, reacts the active group with the hydroxyl group on the fabric, and firmly fixes the softener on the fabric surface through chemical bonds without being washed away; in addition, polyether polyol and silicone oil containing active hydrogen groups are reacted with diisocyanate at the same time, and the reaction process is controlled by a catalyst to obtain polymers with different molecular arrangements, so that the use of solvents can be avoided in the production process, and hydrophilic groups are introduced, so that the use of emulsifiers can be avoided when preparing the emulsion, and the polymer itself can be self-emulsified with water to form a stable softener emulsion product.

Description

Technical Field

[0001] The invention belongs to the field of softener preparation, in particular to a solvent-free self-emulsifying water-resistant softener, a preparation method and application thereof. Background Art

[0002] Softener is one of the main auxiliaries used in the fabric finishing process, which is directly related to the user's feel and touch when using. After the 1970s, with the development of organosilicon chemistry, organosilicon softeners have developed rapidly as a new type of polymer softener. Compared with traditional non-silicone softeners, organosilicon softeners show better softening properties because the Si-O bond has a lower rotational free energy than the C-O bond. Therefore, they are quickly adopted by textile companies and gradually replace traditional non-silicone softeners to become the leading softener variety.

[0003] Silicone softeners have gone through four generations of products. The fourth generation of linear block copolymer modified silicone softeners began around 2000. It combines the advantages of the first three generations of products and avoids the problems of the first three generations of products. It is a new type of silicone softener product with excellent comprehensive performance. In view of the many advantages of the fourth generation of linear block multi-polymer modified silicone softeners, some domestic chemical additives manufacturers are also focusing on research and development, and similar products are already on sale in the market. At present, the research on silicone-polyurethane copolymers is the most popular.

[0004] However, the organic silicon-polyurethane softener currently on the market generally prepares polyether polyol and diisocyanate into prepolymers, then reacts the prepolymers with organic silicon oil, and finally emulsifies to obtain the softener product. This method contains solvents or emulsifiers during production or use. As people pay more and more attention to environmental protection, the presence of organic solvents or emulsifiers causes great harm to people and the environment. At the same time, the performance of organic silicon-polyurethane softeners currently on the market in terms of washability still cannot meet people's needs. Generally, the softness will drop from level 5 to level 2-3 after washing 10 times. After washing 15 times, the softness of the fabric will drop to level 1. Users can clearly feel that the fabric has become less soft and the feel has deteriorated. Summary of the invention

[0005] In order to overcome the above technical defects, the present invention provides a solvent-free self-emulsifying water-resistant softener, a preparation method and application thereof, so as to solve the problems involved in the background technology.

[0006] The present invention provides a method for preparing a solvent-free self-emulsifying water-resistant softener, comprising:

[0007] Step 1, add polyether polyol and silicone oil containing active hydrogen groups into a reaction flask, heat to 120° C., and evacuate to remove water;

[0008] Step 2: Cool the material in step 1 to 50-100°C, preferably 60-70°C; add diisocyanate, the reaction temperature is 50-80°C, the reaction time is 1-4 hours; the reaction temperature is preferably 55-75°C, the reaction time is preferably 1-3 hours

[0009] Step 3, adding a catalyst to the material of step 2, the reaction temperature is 50-80°C, and the reaction time is 1-4 hours; the reaction temperature is preferably 55-75°C, and the reaction time is preferably 1-3 hours;

[0010] Step 4, adding a chain extender to the material of step 3, the reaction temperature is 50-80°C, the reaction time is 1-4 hours, and the active intermediate is prepared; the reaction temperature is preferably 55-75°C, and the reaction time is preferably 1-3 hours;

[0011] Step 5, adding a blocking agent to the material of step 4, the reaction temperature is 70-90°C, and the reaction time is 1-4 hours; the reaction temperature is preferably 75-85°C, and the reaction time is preferably 1-3 hours;

[0012] Step 6: Add deionized water to the material in step 5 for self-emulsification, the emulsification temperature is 20-60° C., and the emulsification time is 1-4 hours; the emulsification temperature is preferably 30-50° C., and the emulsification time is preferably 2-3 hours.

[0013] Preferably or alternatively, the molecular weight of the polyether polyol is 200 to 8000, preferably 1000 to 4000;

[0014] The polyether polyol is selected from one or more of polyethylene glycol and polypropylene glycol;

[0015] Preferably or optionally, the organic silicone oil can be selected from one or more of hydroxy silicone oil and amino silicone oil; further preferably, the organic silicone oil is hydroxy silicone oil, and the hydroxy content of the hydroxy silicone oil is 0.2-5.0%, preferably 1.0-4.0%,

[0016] Preferably or optionally, the diisocyanate may be one or more of isophorone diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate and the like;

[0017] Preferably or optionally, the molar ratio of the isocyanate groups in the diisocyanate to the active hydrogen groups in the silicone oil is between 1.0 and 3.0.

[0018] Preferably or optionally, the catalyst may be one or more of organotin and organobismuth catalysts;

[0019] The chain extender may be one or more of ethylenediamine and butanediol;

[0020] The sealing agent may be selected from one or more of acetanilide, cyclohexanone oxime, methyl ethyl ketone oxime, and ethyl salicylate.

[0021] Preferably or optionally, the feed ratio of each raw material, in parts by mass, is

[0022] 40-90 parts of polyether polyol; 10-60 parts of hydroxy silicone oil; 5-50 parts of diisocyanate; 0-0.15 parts of catalyst; 0-1 parts of chain extender; 1-20 parts of blocking agent.

[0023] Preferably or optionally, the amount of deionized water added accounts for 20-85 wt % of the softener emulsion.

[0024] In a second aspect, the present invention also provides a softener obtained by the preparation method of the solvent-free self-emulsifying water-resistant softener.

[0025] In a third aspect, the present invention also provides a solvent-free self-emulsified water-resistant softener for use in the fields of fabric finishing, leather and papermaking.

[0026] The present invention relates to a solvent-free self-emulsifying water-resistant softener, a preparation method and application thereof, which have the following beneficial effects compared with the prior art:

[0027] 1. Good washing resistance. It has active reaction groups and can be used in fabric, leather, papermaking post-processing, etc. In the post-processing drying high temperature section, generally 100-200°C, the -NCO active group will be unblocked and react chemically with the hydroxyl groups on the fabric fibers, so that the softener can be firmly fixed on the surface and not easily washed off. After washing 15 times, it can still maintain level 5 softness, after washing 25 times, it can still maintain level 4 softness, and after washing 35 times, it can still maintain level 3 or above softness, which greatly improves the feel of the fabric.

[0028] 2. Wide range of applications. Since it can react with fiber hydroxyl groups, it is suitable for various fiber products.

[0029] 3. Solvent-free, environmentally friendly product. In the production process, polyether polyols, silicone oil containing active hydrogen groups and diisocyanate are reacted at the same time, and the reaction process is controlled by catalysts to obtain polymers with different molecular arrangements, so that solvents can be avoided in the production process, and emulsifiers can be avoided when preparing emulsions. The polymer itself can self-emulsify with water to form a stable softener emulsion product.

[0030] 4. The present invention performs sealing treatment on the active groups in the softener, and the product will not be inactivated due to long-term storage during storage.

[0031] The above characteristics indicate that the present invention is suitable for industrial production and has broad application prospects. DETAILED DESCRIPTION

[0032] In the following description, a large number of specific details are provided to provide a more thorough understanding of the present invention. However, it is apparent to those skilled in the art that the present invention can be implemented without one or more of these details. In other examples, in order to avoid confusion with the present invention, some technical features well known in the art are not described. SUMMARY OF THE INVENTION

[0034] The invention adopts polyether polyol, silicone oil and diisocyanate to react to obtain an active intermediate, then performs a blocking treatment on the active group in the active intermediate to obtain a blocked intermediate, and finally performs self-emulsification on the blocked intermediate to obtain a washable softener. By blocking the -NCO active group in advance, the -NCO active group is unblocked during the fabric finishing and drying process, and the active group reacts with the hydroxyl group on the fabric, and can react with the hydroxyl group on the fabric at a certain temperature, and the softener is firmly fixed on the fabric surface through chemical bonds, and will not be washed away. After washing 15 times, the softness of level 5 can still be maintained, after washing 25 times, the softness of level 4 can still be maintained, and after washing 35 times, the softness of level 3 or above can still be maintained, which greatly improves the hand feel of the fabric.

[0035] In the production process of the softener, the polyether polyol and the organic silicone oil containing active hydrogen groups react with diisocyanate at the same time. Since the polyether polyol and the organic silicone oil containing active hydrogen groups have different reaction activities with diisocyanate, the reaction process is controlled by the catalyst diisocyanate and the organic silicone oil containing active hydrogen groups. Specifically, the role of the catalyst is mainly to change the reaction rate of diisocyanate (-NCO) and hydroxyl (-OH). For example, when polyethylene glycol and hydroxyl silicone oil react with isocyanate, when no catalyst is added, isocyanate first reacts with polyethylene glycol and then with hydroxyl silicone oil. When the catalyst is added, isocyanate can react with polyethylene glycol and hydroxyl silicone oil at the same time. The polymer with different molecular arrangements is obtained, so that the use of solvents can be avoided in the production process, and hydrophilic groups are introduced, so that the use of emulsifiers can be avoided when preparing emulsions. The polymer itself can self-emulsify with water to form a stable softener emulsion product.

[0036] The present invention will be further described below in conjunction with embodiments. The examples of the embodiments are intended to explain the present invention and should not be construed as limiting the present invention.

[0037] Example 1

[0038] Add PEG (molecular weight 2000): 107.1g, and hydroxy silicone oil (hydroxyl content 1.7%): 19.5g to the reaction bottle, heat to 120°C, remove water under vacuum for 2 hours, and cool to 65°C. Add isophorone diisocyanate: 19.5g, control the temperature at 65°C, and react for 2 hours. Add bismuth neodecanoate: 0.09g, control the temperature at 70°C, and react for 2 hours. Add chain extender ethylenediamine: 0.7g, control the temperature at 65°C, and continue to react for 2 hours to prepare an active intermediate. Add methyl ethyl ketone oxime: 3.2g to the active intermediate, control the temperature at 80°C, and react for 2 hours to prepare a closed intermediate. Add 350g of deionized water to the closed intermediate, control the temperature at 50°C, emulsify for 2 hours, and obtain homemade sample 1.

[0039] Example 2

[0040] Add PEG (molecular weight 8000): 95.3g, and hydroxy silicone oil (hydroxyl content 1.7%): 42.3g to the reaction bottle, heat to 120°C, remove water under vacuum for 2 hours, and cool to 65°C. Add isophorone diisocyanate: 9.3g, control the temperature at 65°C, and react for 2 hours. Add bismuth neodecanoate: 0.05g, control the temperature at 70°C, and react for 2 hours. Add chain extender ethylenediamine: 0.3g, control the temperature at 65°C, and continue to react for 2 hours to prepare an active intermediate. Add methyl ethyl ketone oxime: 2.8g to the active intermediate, control the temperature at 80°C, and react for 2 hours to prepare a closed intermediate. Add 350.0g of deionized water to the closed intermediate, control the temperature at 50°C, emulsify for 2 hours, and obtain homemade sample 2.

[0041] Example 3

[0042] Add PEG (molecular weight 1000): 80.4g, and hydroxy silicone oil (hydroxyl content 1.7%): 20.1g to the reaction bottle, heat to 120°C, remove water in vacuum for 2 hours, and cool to 65°C. Add isophorone diisocyanate: 34.0g, control the temperature at 65°C, and react for 2 hours. Add bismuth neodecanoate: 0.12g, control the temperature at 70°C, and react for 2 hours. Prepare an active intermediate. Add methyl ethyl ketone oxime: 15.4g to the active intermediate, control the temperature at 80°C, react for 2 hours, and prepare a blocked intermediate. Add 350.0g of deionized water to the blocked intermediate, control the temperature at 50°C, emulsify for 2 hours, and obtain homemade sample 3.

[0043] Example 4

[0044] Add PEG (molecular weight 1500): 58.4g, and hydroxy silicone oil (hydroxy content 1.7%): 58.4g to the reaction bottle, heat to 120°C, remove water under vacuum for 2 hours, and cool to 65°C. Add isophorone diisocyanate: 20.5g, control the temperature at 65°C, and react for 2 hours. Add bismuth neodecanoate: 0.13g, control the temperature at 70°C, and react for 2 hours. Add chain extender ethylenediamine: 0.4g, control the temperature at 65°C, and continue to react for 2 hours to prepare an active intermediate. Add methyl ethyl ketone oxime: 12.2g to the active intermediate, control the temperature at 80°C, and react for 2 hours to prepare a closed intermediate. Add 350.0g of deionized water to the closed intermediate, control the temperature at 50°C, emulsify for 2 hours, and obtain homemade sample 4.

[0045] Example 5

[0046] Add PEG (molecular weight 3000): 81.0g, and hydroxy silicone oil (hydroxyl content 1.7%): 24.3g to the reaction bottle, heat to 120°C, remove water under vacuum for 2 hours, and cool to 65°C. Add isophorone diisocyanate: 28.5g, control the temperature at 65°C, and react for 2 hours. Add bismuth neodecanoate: 0.11g, control the temperature at 70°C, and react for 2 hours. Add chain extender ethylenediamine: 1.2g, control the temperature at 65°C, and continue to react for 2 hours to prepare an active intermediate. Add methyl ethyl ketone oxime: 14.9g to the active intermediate, control the temperature at 80°C, and react for 2 hours to prepare a closed intermediate. Add 350.0g of deionized water to the closed intermediate, control the temperature at 50°C, and emulsify for 2 hours to obtain homemade sample 5.

[0047] Example 6

[0048] Add PEG (molecular weight 1500): 57.0g, and hydroxy silicone oil (hydroxyl content 1.7%): 35.6g to the reaction bottle, heat to 120°C, remove water under vacuum for 2 hours, and cool to 65°C. Add isophorone diisocyanate: 34.8g, control the temperature at 65°C, and react for 2 hours. Add bismuth neodecanoate: 0.11g, control the temperature at 70°C, and react for 2 hours. Add chain extender ethylenediamine: 0.7g, control the temperature at 65°C, and continue to react for 2 hours to prepare an active intermediate. Add methyl ethyl ketone oxime: 21.8g to the active intermediate, control the temperature at 80°C, and react for 2 hours to prepare a closed intermediate. Add 350.0g of deionized water to the closed intermediate, control the temperature at 50°C, and emulsify for 2 hours to obtain homemade sample 1.

[0049] Test example

[0050] The homemade samples in Examples 1 to 6 and the commercial softener samples were tested for softness. Dyeing process: two dipping and two padding (softener dosage 80 g / L, dipping 5 min, padding rate 85%, bath ratio 1:30) → pre-baking (80°C × 3 min) → baking (150°C × 3 min), using woven grey fabric.

[0051] Subjective test of softness: The same fabrics were treated with homemade softeners and commercial softeners under their respective optimal finishing process conditions. The multi-person touch method was used, and the softness level of the fabric with the best touch was set as level 5, and the softness level of the unfinished fabric was set as level 1. Each assessment was conducted by a team of five people, who evaluated by touch with their eyes closed, and compared the finishing effects of the two softeners.

[0052] Washing test: Washing test is carried out according to GB / T 8629-2017. Washing effect judgment standard: those that can be washed less than 5 times are non-durable soft finishing, those that can be washed 5-30 times are semi-durable soft finishing, and those that can be washed more than 30 times and still have a certain softening effect are called durable soft finishing.

[0053] Test results:

[0054] softener After finishing Wash 10 times Wash 15 times Wash 25 times Wash 35 times Example 1 Level 5 Level 4 Level 4 Level 3 Level 1 Example 2 Level 5 Level 5 Level 5 Level 4 Level 1 Example 3 Level 5 Level 4 Level 3 Level 2 Level 1 Example 4 Level 5 Level 4 Level 3 Level 3 Level 1 Example 5 Level 5 Level 5 Level 5 Level 4 Level 3 Example 6 Level 5 Level 3 Level 3 Level 1 / Commercial softener Level 5 Level 3 Level 1 / /

[0055] discuss

[0056] The washing resistance of the homemade softener is significantly better than that of the commercially available softener. It can still maintain level 5 softness after washing 15 times, level 4 softness after washing 25 times, and level 3 or above softness after washing 35 times, and has a durable soft finishing effect.

[0057] It should also be noted that the various specific technical features described in the above specific embodiments can be combined in any suitable manner without contradiction. In order to avoid unnecessary repetition, the present invention will not further describe various possible combinations.

Claims

1. A method for preparing a solvent-free self-emulsifying water-resistant softener, characterized in that: include: Step 1, add polyether polyol and hydroxy silicone oil into a reaction flask, heat to 120° C., and evacuate to remove water; the polyether polyol is polyethylene glycol; Step 2, cooling the material in step 1 to 50-100° C., adding diisocyanate, the reaction temperature is 50-80° C., and the reaction time is 1-4 hours; the molar ratio of the isocyanate group in the diisocyanate to the active hydrogen group in the hydroxy silicone oil is between 1.0 and 3.0; Step 3, adding a catalyst to the material in step 2, the reaction temperature is 50-80°C, and the reaction time is 1-4 hours; Step 4, adding a chain extender to the material of step 3, the reaction temperature is 50-80°C, the reaction time is 1-4 hours, to prepare an active intermediate; the chain extender is ethylenediamine; Step 5, adding a blocking agent to the material in step 4, the reaction temperature is 70-90°C, and the reaction time is 1-4 hours; Step 6: Add deionized water to the material in step 5 for self-emulsification at a temperature of 20 to 60° C. for a time of 1 to 4 hours; The feeding ratio of each raw material, calculated by weight, is as follows: 40-90 parts of polyether polyol; 10-60 parts of hydroxy silicone oil; 5-50 parts of diisocyanate; 0-0.15 parts of catalyst; 0-1 parts of chain extender; and 1-20 parts of blocking agent.

2. The method for preparing the solvent-free self-emulsified water-resistant softener according to claim 1, characterized in that: The molecular weight of the polyether polyol is 200-8000.

3. The method for preparing the solvent-free self-emulsified water-resistant softener according to claim 1, characterized in that: The diisocyanate is selected from one or more of isophorone diisocyanate, hexamethylene diisocyanate and xylylene diisocyanate.

4. The method for preparing the solvent-free self-emulsified water-resistant softener according to claim 1, characterized in that: The catalyst may be selected from one or more of organic tin catalysts and organic bismuth catalysts.

5. The method for preparing the solvent-free self-emulsified water-resistant softener according to claim 1, characterized in that: The sealing agent may be selected from one or more of acetanilide, cyclohexanone oxime, methyl ethyl ketone oxime, and ethyl salicylate.

6. The method for preparing the solvent-free self-emulsified water-resistant softener according to claim 1, characterized in that: The amount of deionized water added accounts for 20-85wt% of the softener emulsion.