Environment-friendly polyester modified waterproof agent as well as preparation method and application thereof

Abstract

The invention discloses an environment-friendly polyester modified waterproof agent as well as a preparation method and application thereof. Comprising the following raw materials: 2-20% of double-end hydroxyalkyl silicone oil with the molecular weight of 1000-5000, 5-20% of epsilon-caprolactone, 0.001-1% of an organic bismuth catalyst, 5-70% of an organic solvent, 1-20% of isocyanate, 0.01-2% of an environment-friendly catalyst, 0.05-1% of organic amine, 0.5-3% of an environment-friendly end-capping reagent, 1-50% of an emulsifier and 0.1-2% of acid. According to the waterproof agent, polyester modified hydroxyalkyl silicone oil with an ultra-long molecular chain is introduced, the prepared waterproof agent contains a silicone oil component, a fabric can be endowed with soft hand feeling and does not become hard, white marks caused by hand grasping are greatly reduced, meanwhile, an environment-friendly end-capping reagent is introduced, the end-capping reagent is unblocked during high-temperature setting, unblocked isocyanate can generate a cross-linking effect with fiber molecules, and the waterproof effect is good. Therefore, the waterproof effect and the washability of the fiber are improved.

Description

Technical Field

[0001] The invention relates to an environmentally friendly polyester modified waterproofing agent and a preparation method and application thereof, belonging to the field of textile auxiliaries. Background Art

[0002] Fluorinated acrylate polymers are widely used on the surface of textile substrates due to their excellent waterproof and oil-proof effects. However, they produce substances harmful to the human body and the ecological environment during use, so their use has been restricted. In addition, fluorinated acrylate polymers are relatively expensive. Fluorine-free waterproofing agents are becoming more and more popular because they are harmless to the environment and cheap. Currently, the types of fluorine-free waterproofing agents include long-chain alkanes, acrylate polymers, organopolysiloxanes, and polyurethanes. Polyurethane waterproofing agents have good waterproofness and compatibility, and are relatively cheap. They have begun to be widely used in the textile industry.

[0003] At present, some manufacturers increase the amount of polyurethane waterproofing agent during processing to obtain excellent waterproofing effect when using polyurethane waterproofing agent. However, during the waterproofing process, it is found that the fabric will have white scratches after shaping, the hand feels hard, and the waterproof and washable effect is poor. This is because the polyurethane waterproofing agent product has poor cross-linking. When the dosage is large, the waterproofing agent and the fabric do not react chemically during the shaping process, but only accumulate on the fiber surface to form a dense and repeated film layer, resulting in obvious hand scratches. Moreover, most polyurethane waterproofing agents on the market use dehydrated sorbitan stearate as the main raw material, and dehydrated sorbitan stearate feels hard, so the fabric feels worse and has poor washability after being treated with the polyurethane waterproofing agent. This phenomenon is particularly obvious on some chemical fiber fabrics and high-density fabrics. For example, an existing patent discloses a super-stable polyurethane waterproofing agent and a preparation method thereof (CN112724353A), wherein the main waterproofing components are sorbitan trioleate + isocyanate, the silicone oil connected contains amino groups, and the remaining isocyanate is connected through the amino groups. The amount of silicone oil connected is not much, and the hand feel is improved, but the waterproofing agent made of sorbitan trioleate + isocyanate has obvious hand scratches.

[0004] In addition, patent document WO2014 / 160906 relates to a fluorine-free waterproofing agent, comprising a polyurethane compound of isocyanate and fatty acid ester, the polyurethane of isocyanate and fatty acid ester has excellent wash resistance, but due to the poor cross-linking of isocyanate, the treated fabric has serious white marks and the hand feel becomes obviously harder; patent document CN107407047A relates to a fluorine-free waterproofing agent, comprising a polyurethane compound of isocyanate and acrylate, but due to the poor compatibility of isocyanate and acrylate, the fabric has obvious waterproof spots, poor wash resistance, and thickening occurs during storage. Summary of the invention

[0005] In view of the problems existing in the above-mentioned prior art, the present invention provides an environmentally friendly polyester modified waterproofing agent and a preparation method and application thereof.

[0006] In order to achieve the above-mentioned purpose, the environmentally friendly polyester modified waterproofing agent adopted by the present invention comprises the following raw materials, by mass percentage: 2-20% of double-terminal hydroxyl silicone oil with a molecular weight of 1000-5000, 5-20% of ε-caprolactone, 0.001-1% of organic bismuth catalyst, 5-70% of organic solvent, 1-20% of isocyanate, 0.01-2% of environmentally friendly catalyst, 0.05-1% of organic amine, 0.5-3% of environmentally friendly end-capping agent, 1-50% of emulsifier and 0.1-2% of acid.

[0007] Preferably, the structural formula of the double-terminated hydroxyl silicone oil with a molecular weight of 1000-5000 is:

[0008]

[0009] Where R = (C2H4O) m .

[0010] Preferably, the organic solvent is methyl isobutyl ketone (MIBK).

[0011] Preferably, the isocyanate is at least one of hexamethylene diisocyanate biuret, hexamethylene diisocyanate homopolymer, toluene diisocyanate trimer and 3-isocyanato or methyl-3,4,4-trimethylcyclohexyl isocyanate trimer, preferably DESMODUR N-3300 and DESMOUR N100 from Bayer.

[0012] Preferably, the environmentally friendly catalyst is an organic bismuth catalyst.

[0013] Preferably, the organic amine is an amine having a single hydroxyl group, and is at least one of N,N-dimethylethanolamine and N,N-diethylethanolamine.

[0014] Preferably, the environmentally friendly end-capping agent is methyl isobutyl ketone oxime.

[0015] Preferably, the emulsifier is at least one of a cationic surfactant, a nonionic surfactant and an amphoteric surfactant; and the acid is at least one of acetic acid, formic acid and glycolic acid.

[0016] The second aspect of the present invention provides a method for preparing the environmentally friendly polyester modified waterproofing agent, comprising the following steps:

[0017] S1. Preparation of polyester modified hydroxyl-alkyl silicone oil: adding double-terminal hydroxyl-alkyl silicone oil with a molecular weight of 1000-5000 and ε-caprolactone into a reactor, heating to 60-80° C. under nitrogen protection, adding an organic bismuth catalyst, heating to 150-180° C. for reaction for 5-10 hours, cooling to 70-90° C., and distilling low-boiling products under reduced pressure to obtain polyester modified hydroxyl-alkyl silicone oil;

[0018] S2. Add the polyester modified hydroxyl silicone oil prepared in step S1 to a flask, heat it to 50-70°C, add an organic solvent, stir evenly, continue to add isocyanate and an environmentally friendly catalyst, heat it to 70-90°C for reaction for 1-2h, add an organic amine, continue to keep warm at 70-90°C for 1-3h, add an environmentally friendly end-capping agent, keep warm at 60-70°C for 1-2h until the isocyanate reaction is complete, add an emulsifier, stir evenly, add 50-70°C acid, stir evenly, homogenize the mixture, remove the solvent by distillation, filter the product, and obtain an environmentally friendly polyester modified waterproofing agent.

[0019] The third aspect of the present invention provides a use of the environmentally friendly polyester modified waterproofing agent in fabric treatment.

[0020] Mechanism of the present invention:

[0021] By introducing polyester-modified hydroxyl silicone oil with ultra-long molecular chains, the waterproofing agent obtained contains silicone oil components, which can give the fabric a soft feel, will not harden, and greatly reduce white marks caused by hand scratches. At the same time, an environmentally friendly blocking agent is introduced. The blocking agent is unblocked during high-temperature setting. The unblocked isocyanate can cross-link with the fiber molecules and firmly bond to the fiber, thereby improving the waterproof effect and washability of the fiber.

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

[0023] (1) The waterproof performance of the present invention is mainly provided by the polyester-modified hydroxyalkyl silicone oil and isocyanate with ultra-long molecular chains. Compared with the commonly used waterproofing agents on the market, the present invention contains silicon-oxygen bonds generated by the reaction, which can provide excellent soft hand feel, significantly improve hand scratches, and is connected with amine. The remaining isocyanate is blocked with a blocking agent. When the product is finalized, the blocking agent is unblocked, and the cross-linking property with the fiber is better. A soft silicone oil layer will be formed on the fiber surface, which can significantly improve hand scratches and has better waterproof and wash resistance. The molecular weight of the waterproofing agent of the present invention is large, and the waterproof effect is significantly improved.

[0024] (2) The present invention uses organic bismuth catalysts to meet environmental protection requirements.

[0025] (3) The present invention introduces an organic amine with a special structure into the waterproofing agent, which can cationize the waterproofing agent and greatly increase the stability of the waterproofing agent; at the same time, the amine can provide a certain hand feel, which is helpful to improve the hand feel and hand scratches.

[0026] (4) The present invention uses an environmentally friendly blocking agent, methyl isobutyl ketone oxime, to block some of the unreacted isocyanate groups. The blocking agent is unblocked during high-temperature setting, and the unblocked isocyanate can cross-link with the fabric molecules, greatly improving the waterproof effect and washability of the fabric. DETAILED DESCRIPTION

[0027] In order to make the objectives, technical solutions and advantages of the present invention more clear, the technical solutions of the present application are described in detail through embodiments below. It should be understood that the embodiments of the present application and the specific features in the embodiments are detailed descriptions of the technical solutions of the present application, rather than limitations on the technical solutions of the present application. In the absence of conflict, the embodiments of the present application and the technical features in the embodiments can be combined with each other.

[0028] Example 1

[0029] A method for preparing polyester-modified hydroxyalkyl silicone oil comprises the following steps:

[0030] Assemble a dry four-necked round-bottom flask, a thermocouple, a mechanical stirrer, a nitrogen inlet, a condenser and a gas outlet together, add 100 g of double-terminal hydroxyl silicone oil (molecular weight 2000, Zhejiang Yingke YK-2862-2K) and 117.2 g of ε-caprolactone into the flask, and under nitrogen protection, heat up to 70°C, add 0.02 g of organic bismuth catalyst, heat up to 160°C, keep warm at 160°C for 7 h, cool to 80°C, and distill low-boiling products under reduced pressure to obtain white solid polyester-modified hydroxyl silicone oil.

[0031] Example 2

[0032] A method for preparing polyester-modified hydroxyalkyl silicone oil comprises the following steps:

[0033] Assemble a dry four-necked round-bottom flask, a thermocouple, a mechanical stirrer, a nitrogen inlet, a condenser and a gas outlet together, add 100 g of double-terminal hydroxyl silicone oil (molecular weight 4000, Zhejiang Yingke YK-2862-4K) and 85.6 g of ε-caprolactone into the flask, and under nitrogen protection, heat up to 70°C, add 0.02 g of organic bismuth catalyst, heat up to 170°C, keep warm at 170°C for 7 h, cool to 80°C, and distill low-boiling products under reduced pressure to obtain white solid polyester-modified hydroxyl silicone oil.

[0034] Example 3

[0035] A method for preparing an environmentally friendly polyester modified waterproofing agent comprises the following steps:

[0036] In a dry four-necked round-bottom flask (equipped with a thermocouple, a mechanical stirrer, a nitrogen inlet, a condenser and a gas outlet), 100 g of the polyester-modified hydroxyalkyl silicone oil obtained in Example 1 was added, the temperature was raised to 60 ° C and melted evenly, 140 g of MIBK (methyl isobutyl ketone) was added, stirred and dissolved evenly, and 14 g of DESMODUR N100 from Bayer was continued to be added, the reaction mixture was heated to 70 ° C, 0.05 g of organic bismuth was added, and the mixture was kept warm at 75 ° C for 1 h, 0.7 g of N, N-dimethylethanolamine was added, and the mixture was kept warm at 75 ° C for 2 h, cooled to 60 ° C, 5 g of environmentally friendly end-capping agent methyl isobutyl ketone oxime was added dropwise, and the mixture was kept warm at 65 ° C for 2 h. When the reactant was tested to be negative for active isocyanate, 8.3 g of octadecyl dimethyl ammonium chloride, 3 g of AEO-9, stir well, add a mixture of 300g 60℃ water and 1g acetic acid, and stir the mixture at 60℃ for 1 hour, then homogenize the mixture twice at 4000psi, remove MIBK by distillation, filter the product, and dilute to 20% solid content.

[0037] Example 4

[0038] A method for preparing an environmentally friendly polyester modified waterproofing agent comprises the following steps:

[0039] In a dry four-necked round-bottom flask (equipped with a thermocouple, a mechanical stirrer, a nitrogen inlet, a condenser and a gas outlet), 88 g of the polyester-modified hydroxyalkyl silicone oil obtained in Example 2 was added, the temperature was raised to 60 ° C and melted evenly, 90 g of MIBK (methyl isobutyl ketone) was added, stirred and dissolved evenly, 12.5 g of Bayer's DESMODUR N100 was continued to be added, the reaction mixture was heated to 70 ° C, 0.05 g of organic bismuth was added, and the mixture was kept warm at 75 ° C for 1 h, 0.5 g of N, N-dimethylethanolamine was added, and the mixture was kept warm at 75 ° C for 2 h, cooled to 60 ° C, 3.2 g of environmentally friendly end-capping agent methyl isobutyl ketone oxime was added dropwise, and the mixture was kept warm at 70 ° C for 2 h. When the reactant was tested to be negative for active isocyanate, 8.3 g of octadecyl dimethyl ammonium chloride and 3 g of AEO-9 were added, stirred evenly, and 300 g of A mixture of 60°C water and 1 g of acetic acid was prepared, and the mixture was stirred at 60°C for 1 hour, then the mixture was homogenized twice at 4000 psi, MIBK was removed by distillation, the product was filtered, and diluted to 20% solid content.

[0040] Example 5

[0041] A method for preparing an environmentally friendly polyester modified waterproofing agent comprises the following steps:

[0042] In a dry four-necked round-bottom flask (equipped with a thermocouple, a mechanical stirrer, a nitrogen inlet, a condenser and a gas outlet), 150 g of the polyester-modified hydroxyalkyl silicone oil obtained in Example 1 was added, the temperature was raised to 60° C. and melted evenly, 160 g of MIBK (methyl isobutyl ketone) was added, stirred and dissolved evenly, 16 g of DESMODUR N100 was continued to be added, the reaction mixture was heated to 70° C., 0.05 g of organic bismuth was added, and the mixture was kept warm at 75° C. for 1 h, 0.75 g of N,N-dimethylethanolamine was added, and the mixture was kept warm at 75° C. for 2 h, the temperature was lowered to 60° C., 3.6 g of methyl isobutyl ketone oxime was added dropwise, and the mixture was kept warm at 65° C. for 2 h. When the reactant was tested to be negative for active isocyanate, 8.3 g of octadecyl dimethyl ammonium chloride, 3 g of AEO-7, stir well, add a mixture of 300g 60℃ water and 1g acetic acid, and stir the mixture at 60℃ for 1 hour, then homogenize the mixture twice at 4000psi, remove MIBK by distillation, filter the product, and dilute to 20% solid content.

[0043] Example 6

[0044] A method for preparing an environmentally friendly polyester modified waterproofing agent comprises the following steps:

[0045] In a dry four-necked round-bottom flask (equipped with a thermocouple, a mechanical stirrer, a nitrogen inlet, a condenser and a gas outlet), 150 g of the polyester-modified hydroxyalkyl silicone oil obtained in Example 2 was added, the temperature was raised to 60° C. and melted evenly, 160 g of MIBK (methyl isobutyl ketone) was added, stirred and dissolved evenly, 10 g of DESMODUR N100 was added, the reaction mixture was heated to 70° C., 0.05 g of organic bismuth was added, and the mixture was kept warm at 75° C. for 1 h, 0.5 g of N,N-dimethylethanolamine was added, and the mixture was kept warm at 75° C. for 2 h, the temperature was lowered to 60° C., 12 g of methyl isobutyl ketone oxime was added dropwise, and the mixture was kept warm at 60° C. for 2 h. When the reactant was tested to be negative for active isocyanate, 8.3 g of octadecyl dimethyl ammonium chloride, 3 g of AEO-7, stir well, add a mixture of 300g 60℃ water and 1g acetic acid, and stir the mixture at 60℃ for 1 hour, then homogenize the mixture twice at 4000psi, remove MIBK by distillation, filter the product, and dilute to 20% solid content.

[0046] Comparative Example 1

[0047] In a dry four-necked round-bottom flask (equipped with a thermocouple, a mechanical stirrer, a nitrogen inlet, a condenser and a gas outlet), add 120 g of sorbitan tristearate, heat to 60°C and melt evenly, add 160 g of MIBK, stir and dissolve evenly, continue to add 24 g of DESMODUR N100, heat the reaction mixture to 70°C, add 0.1 g of dibutyltin dilaurate, keep warm at 75°C for 4 hours, when the reactant is tested negative for active isocyanate, add 8.3 g of octadecyl dimethyl ammonium chloride and 3 g of AEO-7, stir evenly, add a mixture of 300 g of 60°C water and 1 g of acetic acid, and stir the mixture at 60°C for 1 hour, then homogenize the mixture twice at 4000 psi, remove MIBK by distillation, filter the product, and dilute to 20% solid content.

[0048] Fabric treatment

[0049] The products obtained in Examples 3-6 can be used in combination with other surface treatment agents. The environmentally friendly polyester modified waterproofing agent of the present invention can be applied to various fabrics such as natural fibers, synthetic fibers, and artificial fibers by adding water to dilute the solid content to about 0.1-10%. The application method can be coating, dipping, spraying, padding, roller coating, or a combination of methods.

[0050] Specific method: The treated material is roller-dyed by setting the solid content concentration to 0.1-10% as a roller dyeing bath. Next, excess liquid is removed with a slurry roller, and the material is usually dried at a temperature of 80-120°C for 1 minute to 1 hour, preferably aged at 170°C for about 1 minute to complete the waterproofing treatment.

[0051] Waterproof effect test

[0052] The water repellency test was performed to determine the water repellency (according to AATCC 22). The water repellency is indicated by the water repellency No. (as shown in Table 1 below. The suffix "+" attached to the numerical value indicates a performance slightly better than that indicated by the numerical value).

[0053] Table 1 Spray-proof water

[0054] Waterproof NO. state 100(Level 5) The surface is not wet and there are no water drops on the surface 90(Level 4) The surface is not wetted, but there are water droplets on the surface 80(Level 3) Only small, linked areas of the exposed surface are wetted 70(Level 2) Half of the exposed surface is wet 50(Level 1) The entire surface is wetted

[0055] Washing durability test of water resistance:

[0056] According to JIS L-0217-103 method, wash with 40℃ detergent for 25 minutes (5 minutes * HL, 4 times in a row), dehydrate for 3 minutes, rinse for 2 minutes, dehydrate for 3 minutes, rinse for 2 minutes, dehydrate for 3 minutes, dehydrate for 3 minutes, and drum dry to evaluate the waterproof effect. Repeat this procedure 4 times and test the effect after washing 5 times, 10 times, and 20 times.

[0057] The waterproof evaluation of the emulsions prepared in Examples 3-6 and Comparative Example 1 is shown in Table 2 below.

[0058] Table 2 Evaluation of waterproof effect of each embodiment (waterproofing agent dosage: 20g / L)

[0059]

[0060]

[0061] Hand scratch test: Five-finger scratch test, that is, using five fingers to scratch the surface of the fiber after the waterproofing agent treatment, and visually comparing the visibility of the scratches, as shown in Table 3 below.

[0062] Table 3 Visibility of hand scratches

[0063] NO. state Level 4 Completely scratch-free Level 3 Slightly visible scratches Level 2 Visible scratches Level 1 Obvious scratches

[0064] The hand scratch evaluation of the emulsions prepared in Examples 3-6 and Comparative Example 1 is shown in Tables 4 and 5 below.

[0065] Table 4 Evaluation of hand scratch effect of each embodiment (waterproofing agent dosage: 20g / L)

[0066] Fabric / Example Example 3 Example 4 Example 5 Example 6 Comparative Example 1 blank Polyester Level 3 Level 3.5 Level 3 Level 3 Level 1 Level 4 nylon Level 3.5 Level 3 Level 3 Level 3.5 Level 1 Level 4

[0067] Table 5 Hand feel rating of each embodiment (waterproofing agent dosage: 20 g / L)

[0068] Fabric / Example Example 3 Example 4 Example 5 Example 6 Comparative Example 1 blank cotton Level 5 Level 4.5 Level 4 Level 4.5 Level 3 Level 1

[0069] Note: The higher the feel rating, the softer the feel.

[0070] Analysis shows that, compared with general polyurethane waterproofing agents, the environmentally friendly polyester modified waterproofing agent of the present invention has excellent waterproof and washability; after being treated with the waterproofing agent of the present invention, the feel of the fiber is significantly improved, and the scratches on the fiber are not obvious.

[0071] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the technical principles of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.

Claims

1. An environmentally friendly polyester modified waterproofing agent, characterized in that: Calculated by mass percentage, it includes the following raw materials: 2-20% of double-terminated hydroxyl silicone oil with a molecular weight of 1000-5000, 5-20% of ε-caprolactone, 0.001-1% of organic bismuth catalyst, 5-70% of organic solvent, 1-20% of isocyanate, 0.01-2% of environmentally friendly catalyst, 0.05-1% of organic amine, 0.5-3% of environmentally friendly end-capping agent, 1-50% of emulsifier, and 0.1-2% of acid.

2. An environmentally friendly polyester modified waterproofing agent according to claim 1, characterized in that: The structural formula of the double-terminated hydroxyl silicone oil with a molecular weight of 1000-5000 is: Where R = (C2H4O) m .

3. The environmentally friendly polyester modified waterproofing agent according to claim 1, characterized in that: The organic solvent is methyl isobutyl ketone.

4. The environmentally friendly polyester modified waterproofing agent according to claim 1, characterized in that: The isocyanate is at least one of hexamethylene diisocyanate biuret, hexamethylene diisocyanate homopolymer, toluene diisocyanate trimer and 3-isocyanato or methyl-3,4,4-trimethylcyclohexyl isocyanate trimer.

5. The environmentally friendly polyester modified waterproofing agent according to claim 1, characterized in that: The environmentally friendly catalyst adopts an organic bismuth catalyst.

6. The environmentally friendly polyester modified waterproofing agent according to claim 1, characterized in that: The organic amine is an amine having a single hydroxyl group, and is at least one of N,N-dimethylethanolamine and N,N-diethylethanolamine.

7. The environmentally friendly polyester modified waterproofing agent according to claim 1, characterized in that: The environmentally friendly end-capping agent is methyl isobutyl ketone oxime.

8. The environmentally friendly polyester modified waterproofing agent according to claim 1, characterized in that: The emulsifier is at least one of a cationic surfactant, a nonionic surfactant and an amphoteric surfactant; the acid is at least one of acetic acid, formic acid and glycolic acid.

9. A method for preparing the environmentally friendly polyester modified waterproofing agent according to any one of claims 1 to 8, characterized in that: The following steps are involved: S1. Preparation of polyester modified hydroxyl-alkyl silicone oil: adding double-terminal hydroxyl-alkyl silicone oil with a molecular weight of 1000-5000 and ε-caprolactone into a reactor, heating to 60-80° C. under nitrogen protection, adding an organic bismuth catalyst, heating to 150-180° C. for reaction for 5-10 hours, cooling to 70-90° C., and distilling low-boiling products under reduced pressure to obtain polyester modified hydroxyl-alkyl silicone oil; S2. Add the polyester modified hydroxyl silicone oil prepared in step S1 to a flask, heat it to 50-70°C, add an organic solvent, stir evenly, continue to add isocyanate and an environmentally friendly catalyst, heat it to 70-90°C for reaction for 1-2h, add an organic amine, continue to keep warm at 70-90°C for 1-3h, add an environmentally friendly end-capping agent, keep warm at 60-70°C for 1-2h until the isocyanate reaction is complete, add an emulsifier, stir evenly, add 50-70°C acid, stir evenly, homogenize the mixture, remove the solvent by distillation, filter the product, and obtain an environmentally friendly polyester modified waterproofing agent.

10. Use of the environmentally friendly polyester modified waterproofing agent according to any one of claims 1 to 8 in fabric treatment.

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