CN111040105A - Soft fluorine-free waterproof agent and preparation method thereof - Google Patents
Soft fluorine-free waterproof agent and preparation method thereof Download PDFInfo
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- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
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Abstract
The invention belongs to the technical field of printing and dyeing auxiliaries, and particularly relates to a soft fluorine-free waterproof agent and a preparation method thereof. The fluorine-free waterproof agent provided by the invention is a nano fluorine-free waterproof agent emulsion formed by block copolymerization of dimer acid, polyol, aliphatic isocyanate and a crosslinking monomer. Meanwhile, hexamethylene diisocyanate trimer is used as a raw material, N-methyldiethanolamine is used as a water-soluble monomer, butanone oxime is used as a blocking agent, and the synthesized water-dispersible isocyanate emulsion is used as a cross-linking agent. And the modified nano fluorine-free water repellent emulsion is compounded and modified, blocked isocyanate is deblocked under a certain temperature condition, the deblocked isocyanate reacts with a crosslinking monomer in the water repellent, and a low surface tension state is formed after crosslinking and film forming, so that wetting and penetration of water drops are effectively prevented, and finally a novel fluorine-free water repellent finishing agent is formed. The fluorine-free waterproof agent provided by the invention can improve the washing fastness and the waterproof property of the preservative, and is soft in hand feeling and good in elasticity.
Description
Technical Field
The invention belongs to the technical field of printing and dyeing auxiliaries, and particularly relates to a soft fluorine-free waterproof agent and a preparation method thereof.
Background
The waterproof agent is a functional finishing agent, and the fabric finished by the waterproof agent has water repellency and is widely applied to the fields of clothing, umbrellas, tents and the like. The traditional water repellent is perfluoroalkyl acrylate polymer emulsion (commonly known as C8 water repellent), and the water repellent has excellent water and oil resistance, excellent washing resistance and lower cost. However, the fluorine-containing water repellent has been limited in use because of the presence of PFOS, PFOA and other substances which cause serious environmental pollution. The fluoride-free waterproof agent has the advantages of good waterproof performance and less environmental pollution, and is a research hotspot in related fields. The prior fluorine-free water repellent has the problems of hard hand feeling, easy hand mark and insufficient washability, and is intended to develop a novel environment-friendly fluorine-free water repellent product with high washability and soft hand feeling, and the waterproof performance of the novel environment-friendly fluorine-free water repellent product reaches or approaches the level of the traditional C8 water repellent, and the waterproof performance of the novel environment-friendly fluorine-free water repellent product is soft to hand feeling and has washability reaching or exceeding the level of a fluorine-containing water repellent.
At present, the fluorine-containing waterproof and oil-proof agent is definitely forbidden to be used in 2020, so that the development of a high-performance fluorine-free waterproof agent is urgent, and particularly, the high-washability fluorine-free waterproof agent with soft hand feeling is an indispensable functional finishing agent for finishing various functional textiles, so that the development of the fluorine-free waterproof agent with low environmental hazard is necessary.
The Chinese patent application CN109988264A discloses a fluorine-free water-proofing agent, a preparation method and an application thereof, wherein the fluorine-free water-proofing agent is mainly formed by mixing a fluorine-free copolymer, a surfactant, a cosolvent, paraffin and water, has an excellent water-proofing effect, can endow a fabric with good hand feeling, and improves the washing resistance of the fabric. However, this water repellent is not wash-resistant and has a hard hand.
In conclusion, the fluoride-free waterproof agent in the prior art generally has the defects of hard hand feeling, easy scratch, insufficient washability, poor waterproof performance and the like.
Disclosure of Invention
The invention aims to provide a soft fluorine-free waterproof agent and a preparation method thereof aiming at the defects in the prior art. The fluorine-free waterproof agent provided by the invention is comfortable in hand feeling, mild to skin and sufficient in washing resistance.
In order to achieve the purpose, the invention adopts the technical scheme that:
a polyurethane emulsion is prepared by the following steps:
mixing ricinoleic acid dimer and aliphatic isocyanate according to the weight ratio of 58-70: mixing the components in a ratio of 30-42, taking acetone as a solvent, carrying out a polymerization reaction at 60-80 ℃, adding 2-8% dimethylolbutyric acid for chain extension after reacting for 2-4 hours, keeping the temperature for 1-2 hours, cooling to 45 ℃, adding pure water at a rotating speed of 12000rpm, and emulsifying for 15-20 min to obtain the water-soluble polyurethane emulsion with the particle size of 80-120 nm.
The invention also provides a special crosslinking agent for the soft fluorine-free waterproof agent, which comprises the following components in percentage by weight: 15-25% of hexamethylene diisocyanate trimer, 5-8% of N-methyldiethanolamine, 1-3% of butanone oxime, 0.5-1% of cosolvent and 63-78.5% of purified water.
Preferably, the soft fluorine-free waterproof special cross-linking agent consists of the following components in percentage by weight: 20% of hexamethylene diisocyanate trimer, 7% of N-methyldiethanolamine, 2% of butanone oxime, 0.8% of cosolvent and 70.2% of purified water.
Preferably, the cosolvent is composed of isooctyl alcohol, acetamide and calcium lactate according to a mass ratio of 1-3: 2-4: 7 to 9.
Preferably, the cosolvent is composed of isooctyl alcohol, acetamide and calcium lactate according to a mass ratio of 2: 3: 8.
The invention also provides a preparation method of the special crosslinking agent for the soft fluorine-free waterproof agent, which comprises the following steps: the preparation method comprises the following steps of reacting hexamethylene diisocyanate trimer, N-methyldiethanolamine, butanone oxime and a cosolvent at 50-60 ℃ for 45-90min, cooling to 35-40 ℃, stirring at 12000rpm, adding purified water, continuously stirring for 20-30 min, and uniformly mixing to obtain the hexamethylene diisocyanate trimer.
The invention also provides a soft fluorine-free waterproof agent, which comprises the following components in percentage by weight: 75-90% of polyurethane emulsion and 10-25% of special cross-linking agent.
The invention also provides a preparation method of the soft fluorine-free waterproof agent, which comprises the following steps: mixing the polyurethane emulsion with a special cross-linking agent at the temperature of 25 ℃, and stirring for 30min at the rotating speed of 800rpm to obtain the polyurethane emulsion.
In the invention, dimer acid, polyol, crosslinking monomer and aliphatic isocyanate are creatively used for block copolymerization to form the nano fluorine-free waterproof agent emulsion, and the particle size of the emulsion is between 100 and 150nm, so that the emulsion has excellent water dispersibility. In addition, the invention surprisingly discovers that the water-dispersible blocked isocyanate is prepared by blocking the cross-linking agent with butanone oxime and is compounded with polyurethane emulsion, so that the polymer can be subjected to a cross-linking reaction under a certain temperature condition, namely, the polymer is quickly cross-linked to form a film in the baking process, and good washing resistance and water resistance can be obtained.
Further, the polyurethane structure of the application is a water-dispersible polyurethane emulsion which is obtained by screening dimer acid and aliphatic isocyanate with special structures, and obtaining specific particle size under the condition of specific using amount of a water-dispersible chain extender, wherein the particle size distribution is concentrated at about 100 nm; the polyurethane emulsion prepared by the method is added with a cross-linking agent, so that the elasticity and the softness of the fluorine-free waterproof agent can be improved.
Compared with the prior art, the soft fluorine-free waterproof agent has the following advantages:
(1) the soft fluorine-free waterproof agent provided by the invention is prepared by compounding water-dispersible blocked isocyanate and polyurethane emulsion, and the finally prepared waterproof agent has good washing resistance and waterproof performance;
(2) the soft fluorine-free waterproof agent provided by the application adopts dimer acid and aliphatic isocyanate with special structures to prepare polyurethane emulsion, so that the elasticity and the softness of the waterproof agent are greatly improved;
(3) the soft fluorine-free waterproof agent provided by the application is simple in preparation method, low in cost and low in surface tension during formation, and can effectively prevent wetting and penetration of water drops.
Detailed Description
The present invention is further explained with reference to the following specific examples, but it should be noted that the following examples are only illustrative of the present invention and should not be construed as limiting the present invention, and all technical solutions similar or equivalent to the present invention are within the scope of the present invention. Unless otherwise specified, the technical means used in the examples are conventional means well known to those skilled in the art, and the raw materials used are commercially available products.
Example 1A crosslinking agent for a Soft fluorine-free waterproofing agent
The crosslinking agent special for the soft fluorine-free waterproof agent comprises the following components in percentage by weight: 15% of hexamethylene diisocyanate trimer, 5% of N-methyldiethanolamine, 1% of butanone oxime, 0.5% of cosolvent and 78.5% of purified water; the cosolvent is composed of isooctyl alcohol, acetamide and calcium lactate according to a mass ratio of 1: 2: 7.
The preparation process of the special crosslinking agent for the soft fluorine-free waterproof agent comprises the following steps: reacting hexamethylene diisocyanate trimer, N-methyldiethanolamine, butanone oxime and cosolvent at 50 ℃ for 45min, cooling to 35 ℃, stirring at 12000rpm, adding purified water, continuously stirring for 20min, and uniformly mixing to obtain the product.
Example 2A crosslinking agent for a soft fluorine-free waterproofing agent
The crosslinking agent special for the soft fluorine-free waterproof agent comprises the following components in percentage by weight: 20% of hexamethylene diisocyanate trimer, 7% of N-methyldiethanolamine, 2% of butanone oxime, 0.8% of cosolvent and 70.2% of purified water; the cosolvent is composed of isooctyl alcohol, acetamide and calcium lactate according to a mass ratio of 2: 3: 8.
The preparation process of the special crosslinking agent for the soft fluorine-free waterproof agent comprises the following steps: the hexamethylene diisocyanate tripolymer, the N-methyldiethanolamine, the butanone oxime and the cosolvent react for 60min at the temperature of 55 ℃, the temperature is reduced to 38 ℃, the mixture is stirred at the rotating speed of 12000rpm, the purified water is added, the stirring is continued for 25min, and the mixture is uniformly mixed, so that the hexamethylene diisocyanate tripolymer, the N-methyldiethanolamine, the butanone oxime and the cosolvent are obtained.
Example 3A crosslinking agent for a Soft fluorine-free waterproofing agent
The crosslinking agent special for the soft fluorine-free waterproof agent comprises the following components in percentage by weight: 25% of hexamethylene diisocyanate trimer, 8% of N-methyldiethanolamine, 3% of butanone oxime, 1% of cosolvent and 63% of purified water. The cosolvent is composed of isooctyl alcohol, acetamide and calcium lactate according to a mass ratio of 3: 4: 9.
The preparation process of the special crosslinking agent for the soft fluorine-free waterproof agent comprises the following steps: reacting hexamethylene diisocyanate trimer, N-methyldiethanolamine, butanone oxime and cosolvent at 60 ℃ for 90min, cooling to 40 ℃, stirring at 12000rpm, adding purified water, continuously stirring for 30min, and uniformly mixing to obtain the product.
Example 4A Soft fluorine-free Water repellent
The soft fluorine-free waterproof agent comprises the following components in percentage by weight: 75% of polyurethane emulsion and 25% of special cross-linking agent prepared by the method described in example 1.
The preparation method of the soft fluorine-free waterproof agent comprises the following steps:
s1, mixing ricinoleic acid dimer and aliphatic isocyanate according to the weight ratio of 58: mixing in proportion of 30, taking acetone as a solvent, carrying out a polymerization reaction at 60 ℃, adding 2% dimethylolbutyric acid for chain extension after reacting for 2 hours, keeping the temperature for 1 hour, cooling to 45 ℃, adding pure water at a rotating speed of 12000rpm, and emulsifying for 15min to obtain a water-soluble polyurethane emulsion with a particle size of 80 nm;
s2, mixing the polyurethane emulsion obtained in the step S1 with the special cross-linking agent prepared in the embodiment 1 at the temperature of 25 ℃, and stirring for 30min at the rotating speed of 800rpm to obtain the polyurethane emulsion.
Example 5A Soft fluorine-free Water repellent
The soft fluorine-free waterproof agent comprises the following components in percentage by weight: 82% of polyurethane emulsion and 18% of special cross-linking agent prepared by the method described in example 2.
The preparation method of the soft fluorine-free waterproof agent comprises the following steps:
s1, mixing ricinoleic acid dimer and aliphatic isocyanate according to the weight ratio of 65: mixing the raw materials in a proportion of 37, taking acetone as a solvent, carrying out a polymerization reaction at 70 ℃, adding 5% dimethylolbutyric acid for chain extension after reacting for 3 hours, keeping the temperature for 1.5 hours, cooling to 45 ℃, adding pure water at a rotating speed of 12000rpm, and emulsifying for 18min to obtain a water-soluble polyurethane emulsion with a particle size of 100 nm;
s2, mixing the polyurethane emulsion obtained in the step S1 with the special cross-linking agent prepared in the embodiment 2 at the temperature of 25 ℃, and stirring for 30min at the rotating speed of 800rpm to obtain the polyurethane emulsion.
Example 6A Soft fluorine-free Water repellent
The soft fluorine-free waterproof agent comprises the following components in percentage by weight: 90% of polyurethane emulsion and 10% of special cross-linking agent prepared by the method described in example 3.
The preparation method of the soft fluorine-free waterproof agent comprises the following steps:
s1, mixing ricinoleic acid dimer and aliphatic isocyanate according to the weight ratio of 70: 42, mixing in proportion, taking acetone as a solvent, carrying out a polymerization reaction at 80 ℃, adding 8% dimethylolbutyric acid for chain extension after 4 hours of reaction, keeping the temperature for 2 hours, cooling to 45 ℃, adding pure water at a rotating speed of 12000rpm, and emulsifying for 20 minutes to obtain a polyurethane emulsion which has a particle size of 120nm and is easily soluble in water;
s2, mixing the polyurethane emulsion obtained in the step S1 with the special cross-linking agent prepared in the embodiment 2 at the temperature of 25 ℃, and stirring for 30min at the rotating speed of 800rpm to obtain the polyurethane emulsion.
Comparative example 1A Soft fluorine-free Water repellent
The soft fluorine-free waterproof agent comprises the following components in percentage by weight: 82% of polyurethane emulsion and 18% of special cross-linking agent;
the proprietary crosslinker is similar to example 2; the difference from the example 2 is that the cosolvent in the comparative example 1 is prepared by isooctanol, acetamide and calcium lactate according to the mass ratio of 1: 1: 1.
The procedure for preparing the soft type fluorine-free water repellent was the same as in example 5.
Comparative example 2A Soft fluorine-free Water repellent
The soft fluorine-free waterproof agent comprises the following components in percentage by weight: 82% of polyurethane emulsion and 18% of special cross-linking agent;
the proprietary crosslinker is similar to example 2; the difference from example 2 is that no butanone oxime was included in comparative example 2.
The procedure for preparing the soft type fluorine-free water repellent was the same as in example 5.
Test example 1 Performance test
1. Test samples: examples 4 to 6 Soft fluorine-free Water repellent
2. The test method comprises the following steps: the fluorine-free water repellent agents obtained in examples 4 to 6 were subjected to the average particle diameter, mechanical stability and storage stability tests.
Wherein, the mechanical stability is that a fluoride-free water repellent is added into an l0mL centrifugal tube, the centrifugal tube is centrifuged for 30 minutes at 3000r/min, and the unstable phenomena of floating, layering, precipitation and the like of the fluoride-free water repellent are observed.
Storage stability: the aqueous dispersion was stored at 40 ℃ for 1 month, and the occurrence of sedimentation was observed.
Evaluation criteria for storage stability: o: no generation of agglomerates
△ little coagulum generation
X: generate a lot of aggregates
3. And (3) test results: the specific test results are shown in table 1.
TABLE 1 fluoride-free water repellent Performance test results
| Test ofSample (I) | Average particle diameter/nm | Mechanical stability | Storage stability |
| Example 4 | 80 | Stabilization | Ο |
| Example 5 | 120 | Stabilization | Ο |
| Example 6 | 100 | Stabilization | Ο |
As is clear from Table 1, the fluorine-free water repellent prepared by the present invention has good mechanical stability and storage stability.
Test example 2 Water resistance test
1. Test samples: fluorine-free water repellent agents obtained in examples 4 to 6 and comparative examples 1 to 2; foreign product waterproof agent R3; pure cotton white yarn card cloth; baolan 65, 35 polyester cotton yarn card cloth.
2. The test method comprises the following steps:
respectively diluting a test sample into the concentrations of 80g/L, 100g/L and 120g/L by using deionized water, soaking pure cotton white yarn card cloth in the diluent for 15 minutes, rolling the card cloth once by using a padder, wherein the liquid carrying rate is 100 percent, and after the process of one-soaking-one-rolling, shaping the cotton cloth at 180 ℃ for 1min to obtain the cotton cloth treated by the fluorine-free waterproof agent.
The cotton cloth is washed once by 13g of WOB washing powder at 40 ℃ for 20 minutes in a Siemens roller washing machine, and then is thrown dry after washing. And respectively recording the waterproof performance of the fabric after 5 times, 10 times and 20 times of washing before, after and after washing.
The test process of the baolan 65 and 35 polyester cotton yarn card cloth is the same as the test operation of the pure cotton white yarn card cloth.
3. And (3) test results: the specific test results are shown in tables 2, 3, 4 and 5.
TABLE 2 initial Water resistance of pure Cotton white yarn card cloth
TABLE 3 Water resistance of pure cotton white yarn-card cloth at treatment of different test samples
TABLE 4 initial Water-proof Properties of Baolan 65, 35 polyester-cotton yarn cloth
TABLE 5 waterproof Properties of Baolan 65 and 35 polyester cotton yarn cloth for treating different test samples
As is apparent from tables 2, 3, 4 and 5, the fluorine-free waterproofing agents obtained in examples 4 to 6 of the present invention have excellent waterproofing performance as compared with the waterproofing agent R3 available in foreign countries, and particularly, the fluorine-free waterproofing agent of example 4 still has excellent waterproofing performance after washing 20 times, so that example 4 is the most preferable example of the present invention; the waterproofing agent prepared in the comparative example 1 has the advantages that the solubility of the substance is reduced due to the change of the proportion of the cosolvent, and the end capping agent is removed in the comparative example 2, so that the waterproofing performance is greatly reduced.
It should be noted that the above-mentioned embodiments are only preferred embodiments of the present invention, and the present invention is not limited thereto, and although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that modifications and equivalents can be made in the technical solutions described in the foregoing embodiments, or some technical features can be replaced. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (8)
1. The polyurethane emulsion is characterized by comprising the following preparation methods:
mixing ricinoleic acid dimer and aliphatic isocyanate according to the weight ratio of 58-70: mixing the components in a ratio of 30-42, taking acetone as a solvent, carrying out a polymerization reaction at 60-80 ℃, adding 2-8% dimethylolbutyric acid for chain extension after reacting for 2-4 hours, keeping the temperature for 1-2 hours, cooling to 45 ℃, adding pure water at a rotating speed of 12000rpm, and emulsifying for 15-20 min to obtain the water-soluble polyurethane emulsion with the particle size of 80-120 nm.
2. A special crosslinking agent for a soft fluorine-free waterproof agent is characterized by comprising the following components in percentage by weight: 15-25% of hexamethylene diisocyanate trimer, 5-8% of N-methyldiethanolamine, 1-3% of butanone oxime, 0.5-1% of cosolvent and 63-78.5% of purified water.
3. The crosslinking agent special for the soft fluorine-free waterproof agent as claimed in claim 2, which is characterized by comprising the following components in percentage by weight: 20% of hexamethylene diisocyanate trimer, 7% of N-methyldiethanolamine, 2% of butanone oxime, 0.8% of cosolvent and 70.2% of purified water.
4. The crosslinking agent special for the soft fluorine-free waterproofing agent according to claim 2 or 3, wherein the cosolvent is composed of isooctanol, acetamide and calcium lactate according to a mass ratio of 1-3: 2-4: 7 to 9.
5. The crosslinking agent special for the soft fluorine-free waterproofing agent according to claim 4, wherein the cosolvent is composed of isooctanol, acetamide and calcium lactate in a mass ratio of 2: 3: 8.
6. A method for preparing the crosslinking agent special for the soft fluorine-free waterproof agent according to any one of claims 2 to 5, which is characterized by comprising the following steps: the preparation method comprises the following steps of reacting hexamethylene diisocyanate trimer, N-methyldiethanolamine, butanone oxime and a cosolvent at 50-60 ℃ for 45-90min, cooling to 35-40 ℃, stirring at 12000rpm, adding purified water, continuously stirring for 20-30 min, and uniformly mixing to obtain the hexamethylene diisocyanate trimer.
7. A soft fluorine-free waterproof agent is characterized by comprising the following components in percentage by weight: 75-90% of the polyurethane emulsion as defined in claim 1 and 10-25% of the special cross-linking agent as defined in claim 2.
8. A method for preparing the flexible fluorine-free water repellent according to claim 7, which comprises the steps of: mixing the polyurethane emulsion with a special cross-linking agent at the temperature of 25 ℃, and stirring for 30min at the rotating speed of 800rpm to obtain the polyurethane emulsion.
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