CN113957719A - Organic silicon polyurethane waterproof moisture permeable coating agent and preparation method and finishing process thereof - Google Patents
Organic silicon polyurethane waterproof moisture permeable coating agent and preparation method and finishing process thereof Download PDFInfo
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- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- 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
- D06M15/572—Reaction products of isocyanates with polyesters or polyesteramides
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/61—Polysiloxanes
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- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
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- C08G18/6659—Compounds of group C08G18/42 with compounds of group C08G18/34
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- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- D06M2101/16—Synthetic fibres, other than mineral fibres
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- D06M2200/35—Abrasion, pilling or fibrillation resistance
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- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
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- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/50—Modified hand or grip properties; Softening compositions
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Abstract
The invention discloses an organic silicon polyurethane waterproof moisture permeable coating agent and a preparation method and a finishing process thereof, the carboxylic acid ammonium salt modified organic silicon polyurethane water pressure resistant coating agent prepared by the invention has the characteristics of good film forming property, good stability, good water resistance, strong adhesion and the like, and can improve the tearing strength of fabrics when being finished on the fabrics, endow the fabrics with the performances of softness, wear resistance, crease resistance and the like, and does not influence the whiteness of the fabrics. Meanwhile, the preparation process is simple and convenient, and the reaction conditions are mild. From the molecular structure of the product, the hydroxyl silicone oil and the polyurethane are subjected to graft copolymerization, so that certain film-forming water resistance and flexibility are endowed. BTCA reacts with liquid ammonia in a certain proportion to generate ammonium carboxylate, ammonium radicals are generated, a part of carboxyl is reserved, the carboxyl reacts with modified polyurethane, the modified polyurethane is arranged on the fabric, the ammonium radicals are converted into ammonia gas under the condition of high-temperature baking, the carboxyl is generated, the water solubility is reduced, a firm film is formed and attached to the fabric, and the water pressure resistance is further improved.
Description
Technical Field
The invention belongs to the field of organic silicon polyurethane, and particularly relates to an organic silicon polyurethane waterproof moisture-permeable coating agent, and a preparation method and a finishing process thereof.
Background
The polyurethane is a high molecular polymer containing urethane groups (-NHCOO-) or isocyanate groups (-NCO) in molecular chains, has excellent performance, has the advantages of good low-temperature stability, friction resistance, chemical medicine resistance and the like, and is widely applied to the fields of textiles, buildings, national defense and the like. With the enhancement of environmental protection consciousness of people, the traditional solvent type polyurethane is gradually replaced by the waterborne polyurethane, and the waterborne polyurethane has the advantages of good flexibility, easy modification, easy processing and the like. However, due to the introduction of hydrophilic groups, the water resistance of the waterborne polyurethane is poor, and the hand feeling is hard when the waterborne polyurethane is finished on the fabric. The hydroxyl silicone oil has a unique chemical structure of a Si-O chain, has low surface energy, and forms a graft copolymer with polyurethane when being used as a modifier, and is enriched to the surface in the film forming process, so that the surface energy of a coating is reduced, the hydrophobicity is enhanced, and the finished fabric has excellent performances of water resistance, softness and the like. And reacting ammonium carboxylate obtained by neutralizing reaction of BTCA and partial liquid ammonia with the modified waterborne polyurethane to obtain the organosilicon water pressure resistant coating agent. After the finishing agent is finished on the fabric, under the condition of high-temperature baking, the coating agent generates carboxylic acid, the water solubility is reduced, a formed film is firmly fixed on the fabric, the fabric is endowed with the performances of softness, abrasion resistance, crease resistance and the like, and the water resistance effect is also achieved. The hydroxyl silicone oil modification and the ammonium carboxylate modification are carried out on the waterborne polyurethane, so that the waterborne polyurethane has the advantages of the hydroxyl silicone oil modification and the ammonium carboxylate modification, and the purposes of environmental protection, good water pressure resistance, good film forming property and the like are achieved.
The main defects of some organic silicon coating agents on the market at present are as follows: firstly, the film-forming property and the water resistance are not good enough, and the finishing effect after washing is not obvious. Second, some silicone polyurethane coating agents have no practical value in finishing light and thin fabrics because they cause a decrease in tear strength of the fabrics. Therefore, the development of the organic silicon polyurethane solvent-free coating agent which is simple and convenient to operate, environment-friendly and safe in product performance and excellent in service performance has great significance. The invention can be applied to 10D nylon base cloth and can simultaneously process comfortable, solvent-free, down-proof, waterproof and moisture-permeable down fabric.
Disclosure of Invention
The purpose of the invention is as follows: in order to solve the defects of the prior art, the invention provides an organic silicon polyurethane waterproof moisture permeable coating agent, a preparation method and a finishing process thereof, which can improve the tearing strength of the fabric, have good water resistance and endow the fabric with soft hand feeling.
The technical scheme is as follows: the organic silicon polyurethane waterproof moisture-permeable coating agent comprises the following components in parts by mass: 166 parts of polycarbonate polyol 124, 6-8 parts of hydroxyl silicone oil, 15-20 parts of isophorone diisocyanate, 1.5-2.5 parts of 1, 4-butanediol, 0.50-0.55 part of dibutyl tin dilaurate, 15-21 parts of 1,2,3, 4-butane tetracarboxylic acid, 0.5-0.8 part of ammonia water and 80-100 parts of deionized water.
As an optimization: the polycarbonate polyols provide hydrophilicity, solvent free.
As an optimization: the molecular weight of the hydroxyl silicone oil is 3000.
A preparation method of an organic silicon polyurethane waterproof moisture-permeable coating agent comprises the following steps:
(1) preparation procedure of carboxylic acid ammonium salt:
adding 1 in a certain proportion into a reaction kettleReacting 2,3, 4-butanetetracarboxylic acid with liquid ammonia at normal temperature for a certain time to obtain ammonium carboxylate, and controlling-COOH to convert into-COONH4The conversion rate is 50-60%;
(2) the preparation process of the carboxylic acid ammonium salt modified organosilicon polyurethane water pressure resistant coating agent comprises the following steps:
adding dehydrated polycarbonate dihydric alcohol and isophorone diisocyanate into a reaction kettle provided with a thermometer and a reflux device, then dropwise adding hydroxyl silicone oil and 1, 4-butanediol into the reaction kettle, and adding N2Under the protection of (1), heating to a certain temperature, adding a catalyst of dibutyl tin dilaurate, reacting for a certain time, cooling to room temperature, and adding sodium bisulfite NaHSO3And (3) carrying out end-capping reaction, finally adding deionized water, stirring at a high speed and emulsifying to obtain an organic silicon polyurethane emulsion, and reacting with the prepared ammonium carboxylate at a certain temperature to obtain the ammonium carboxylate modified organic silicon polyurethane water pressure resistant coating agent.
As an optimization: in the preparation process of the carboxylic acid ammonium salt, the reaction time is 30 min.
As an optimization: in the preparation process of the ammonium carboxylate modified organosilicon polyurethane water pressure resistant coating agent, N is2Under the protection of (2), the temperature rise is 75 ℃; adding a catalyst dibutyl tin dilaurate for reaction for 2-2.5 h; the reaction time for the capping reaction was 40 min.
A finishing process of an organic silicon polyurethane waterproof moisture-permeable coating agent comprises the following steps of: nylon base cloth → coating and scraping → drying and film forming → baking and shaping → finished product; wherein, the ammonium carboxylate and the organosilicon polyurethane emulsion are obtained according to a certain proportion according to a prescription, cloth samples are finished according to process conditions, and the following coating slurry is required to be prepared:
90-100g/L of carboxylic acid ammonium salt modified organic silicon polyurethane water pressure resistant coating agent SSP;
1-2g/L of low molecular polyethylene glycol;
20-30g/L of ultraviolet-proof finishing agent UV-BS.
Has the advantages that: the specific advantages of the invention are as follows:
(1) the water pressure resistant coating agent of the ammonium carboxylate modified organosilicon polyurethane prepared by the invention has the characteristics of good film forming property, good stability, good water resistance, strong adhesion and the like, can improve the tearing strength of fabrics after being finished on the fabrics, endows the fabrics with the performances of softness, wear resistance, crease resistance and the like, and does not influence the whiteness of the fabrics. Meanwhile, the preparation process is simple and convenient, and the reaction conditions are mild.
(2) From the molecular structure of the product, the hydroxyl silicone oil and the polyurethane are subjected to graft copolymerization, so that certain film-forming water resistance and flexibility are endowed. BTCA reacts with liquid ammonia in a certain proportion to generate ammonium carboxylate, ammonium radicals are generated, a part of carboxyl is reserved, the carboxyl reacts with modified polyurethane, the modified polyurethane is arranged on the fabric, the ammonium radicals are converted into ammonia gas under the condition of high-temperature baking, the carboxyl is generated, the water solubility is reduced, a firm film is formed and attached to the fabric, and the water pressure resistance is further improved.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below so that those skilled in the art can better understand the advantages and features of the present invention, and thus the scope of the present invention will be more clearly defined. The embodiments described herein are only a few embodiments of the present invention, rather than all embodiments, and all other embodiments that can be derived by one of ordinary skill in the art without inventive faculty based on the embodiments described herein are intended to fall within the scope of the present invention.
Examples
The invention relates to a preparation method of ammonium carboxylate modified organic silicon polyurethane waterproof moisture-permeable coating agent, which is mainly used for the after-finishing process of fabrics and improves the properties of fabric hand feeling, tearing strength and the like. The water-dispersed PU contains more polar groups with large cohesive energy, such as carbamate groups, carbamido groups and the like, and can generate more hydrogen bonds under the action of strong static electricity to form hydrogen bond crosslinking (secondary crosslinking), so that the PU elastomer has physical and mechanical properties, such as high modulus, tensile strength and the like.
The carboxylic acid ammonium salt modified organic silicon polyurethane hydraulic pressure resistant coating agent comprises the following components in parts by weight: 166 parts of polycarbonate polyol 124, 6-8 parts of hydroxyl silicone oil, 15-20 parts of isophorone diisocyanate, 1.5-2.5 parts of 1, 4-butanediol, 0.50-0.55 part of dibutyl tin dilaurate, 15-21 parts of 1,2,3, 4-butane tetracarboxylic acid, 0.5-0.8 part of ammonia water and 80-100 parts of deionized water.
Wherein the polycarbonate polyol provides hydrophilicity and solvent-free. The molecular weight of the hydroxyl silicone oil is 3000.
The preparation method comprises the following steps:
(1) preparation procedure of carboxylic acid ammonium salt:
1,2,3, 4-butanetetracarboxylic acid and liquid ammonia are added into a reaction kettle in a certain proportion to react for a certain time at normal temperature to prepare ammonium carboxylate, and-COOH is controlled to be converted into-COONH4The conversion rate is 50-60%.
(2) The preparation process of the carboxylic acid ammonium salt modified organosilicon polyurethane water pressure resistant coating agent comprises the following steps:
adding dehydrated polycarbonate dihydric alcohol and isophorone diisocyanate into a reaction kettle provided with a thermometer and a reflux device, then dropwise adding hydroxyl silicone oil and 1, 4-butanediol into the reaction kettle, and adding N2Under the protection of (1), heating to a certain temperature, adding a catalyst of dibutyl tin dilaurate, reacting for a certain time, cooling, adding sodium bisulfite for end-capping reaction, finally adding deionized water, stirring at a high speed for emulsification to obtain an organic silicon polyurethane emulsion, and reacting with the prepared ammonium carboxylate at a certain temperature to obtain the ammonium carboxylate modified organic silicon polyurethane water pressure-resistant coating agent SSP.
According to the invention, hydrophilic compounds polycarbonate dihydric alcohol, 1, 4-butanediol and ammonium carboxylate are mixed, after film forming, the hydrogen bond action of hydrophilic groups and water vapor molecules is utilized, and the water vapor molecules are transferred from the side with high humidity to the side with low humidity through macromolecular thermal motion to be released, so that the moisture permeability purpose is achieved. The hydrophilic groups become "channels" or "steps" through which the water vapor molecules are transported. Meanwhile, hydroxyl silicone oil is introduced into the system, so that the defect that the polyurethane coating agent has hard hand feeling is overcome.
The product of the invention has moderate viscosity: 22-25 pas without solvent, if the viscosity of the coating adhesive is too high, the fluidity of the coating adhesive is too poor, so that uneven stripes of the coating appear on the cloth surface, and the cloth surface effect is influenced; if the viscosity of the coating paste is too low and the fluidity is too good, the amount of coating paste falling off is greatly increased.
The post-finishing process of the fabric is as follows: direct dry coating: nylon base cloth → coating and scraping → drying and film forming → baking and shaping → finished product; wherein, the ammonium carboxylate and the organosilicon polyurethane emulsion are obtained according to a certain proportion according to a prescription, cloth samples are finished according to process conditions, and the following coating slurry is required to be prepared:
90-100g/L of carboxylic acid ammonium salt modified organic silicon polyurethane water pressure resistant coating agent SSP;
1-2g/L of low molecular polyethylene glycol;
20-30g/L of ultraviolet-proof finishing agent UV-BS.
Wherein, the low molecular polyethylene glycol has the functions of osmosis and high-temperature volatilization, does not influence the waterproof performance, and prevents the residual surfactant on the cloth cover from damaging the waterproof performance.
The ultraviolet-proof finishing agent UV-BS has excellent ultraviolet absorption effect, and simultaneously endows the fabric with good softness, antistatic performance and the like.
The properties of the 10D nylon used were as follows: low-density weaving, light weight, elasticity and shape keeping.
The final product properties of the invention were as follows: water pressure resistance is 1500mm, uvioresistant UPF value is 50+, hand feeling is 2-3 grade, no down is drilled, moisture permeability and air permeability are as follows: 3.5 g/(m)2·24h)。
Detailed description of the preferred embodiment 1
(1) Preparation procedure of carboxylic acid ammonium salt:
1,2,3, 4-butanetetracarboxylic acid and liquid ammonia in a certain proportion are added into a reaction kettle to react for 30min at normal temperature, and then dehydration is carried out to obtain the ammonium carboxylate. The specific synthesis reaction equation is as follows.
(2) The preparation process of the organic silicon polyurethane coating agent comprises the following steps:
adding dehydrated polycarbonate dihydric alcohol and isophorone diisocyanate into a reaction kettle provided with a thermometer and a reflux device, then dropwise adding hydroxyl silicone oil and 1, 4-butanediol into the reaction kettle, and adding N2Under the protection of (1), heating to 75 ℃, adding a catalyst dibutyl tin dilaurate, reacting for 2-2.5h, cooling to room temperature, and adding NaHSO3And (3) carrying out end-capping reaction for 40min, finally adding deionized water, and stirring and emulsifying at a high speed to obtain the organic silicon polyurethane coating agent. The specific synthesis reaction equation is as follows.
The reaction of the ammonium carboxylate salt and the silicone polyurethane emulsion at elevated temperature is as follows:
the water pressure resistant coating agent of the ammonium carboxylate modified organosilicon polyurethane prepared by the invention has the characteristics of good film forming property, good stability, good water resistance, strong adhesion and the like, can improve the tearing strength of fabrics after being finished on the fabrics, endows the fabrics with the performances of softness, wear resistance, crease resistance and the like, and does not influence the whiteness of the fabrics. Meanwhile, the preparation process is simple and convenient, and the reaction conditions are mild.
From the molecular structure of the product, the hydroxyl silicone oil and the polyurethane are subjected to graft copolymerization, so that certain film-forming water resistance and flexibility are endowed. BTCA reacts with liquid ammonia in a certain proportion to generate ammonium carboxylate, ammonium radicals are generated, a part of carboxyl is reserved, the carboxyl reacts with modified polyurethane, the modified polyurethane is arranged on the fabric, the ammonium radicals are converted into ammonia gas under the condition of high-temperature baking, the carboxyl is generated, the water solubility is reduced, a firm film is formed and attached to the fabric, and the water pressure resistance is further improved.
Claims (7)
1. The organic silicon polyurethane waterproof moisture permeable coating agent is characterized in that: the organic silicon polyurethane waterproof moisture-permeable coating agent comprises the following components in parts by mass: 166 parts of polycarbonate polyol 124, 6-8 parts of hydroxyl silicone oil, 15-20 parts of isophorone diisocyanate, 1.5-2.5 parts of 1, 4-butanediol, 0.50-0.55 part of dibutyl tin dilaurate, 15-21 parts of 1,2,3, 4-butane tetracarboxylic acid, 0.5-0.8 part of ammonia water and 80-100 parts of deionized water.
2. The silicone polyurethane waterproof moisture-permeable coating agent according to claim 1, characterized in that: the polycarbonate polyols provide hydrophilicity, solvent free.
3. The silicone polyurethane waterproof moisture-permeable coating agent according to claim 1, characterized in that: the molecular weight of the hydroxyl silicone oil is 3000.
4. A method for preparing the organosilicon polyurethane waterproof moisture-permeable coating agent according to claim 1, which is characterized in that: the method comprises the following steps:
(1) preparation procedure of carboxylic acid ammonium salt:
1,2,3, 4-butanetetracarboxylic acid and liquid ammonia are added into a reaction kettle in a certain proportion to react for a certain time at normal temperature to prepare ammonium carboxylate, and-COOH is controlled to be converted into-COONH4The conversion rate is 50-60%;
(2) the preparation process of the carboxylic acid ammonium salt modified organosilicon polyurethane water pressure resistant coating agent comprises the following steps:
adding dehydrated polycarbonate dihydric alcohol and isophorone diisocyanate into a reaction kettle provided with a thermometer and a reflux device, then dropwise adding hydroxyl silicone oil and 1, 4-butanediol into the reaction kettle, and adding N2Under the protection of (1), heating to a certain temperature, adding a catalyst of dibutyl tin dilaurate, reacting for a certain time, cooling to room temperature, and adding sodium bisulfite NaHSO3And (3) carrying out end-capping reaction, finally adding deionized water, stirring at a high speed and emulsifying to obtain an organic silicon polyurethane emulsion, and reacting with the prepared ammonium carboxylate at a certain temperature to obtain the ammonium carboxylate modified organic silicon polyurethane water pressure resistant coating agent.
5. The preparation method of the organosilicon polyurethane waterproof moisture-permeable coating agent according to claim 4, characterized in that: in the preparation process of the carboxylic acid ammonium salt, the reaction time is 30 min.
6. The preparation method of the organosilicon polyurethane waterproof moisture-permeable coating agent according to claim 4, characterized in that: in the preparation process of the ammonium carboxylate modified organosilicon polyurethane water pressure resistant coating agent, N is2Under the protection of (2), the temperature rise is 75 ℃; adding a catalyst dibutyl tin dilaurate for reaction for 2-2.5 h; the reaction time for the capping reaction was 40 min.
7. A finishing process of an organic silicon polyurethane waterproof moisture-permeable coating agent is characterized in that: direct dry coating: nylon base cloth → coating and scraping → drying and film forming → baking and shaping → finished product; wherein, the ammonium carboxylate and the organosilicon polyurethane emulsion are obtained according to a certain proportion according to a prescription, cloth samples are finished according to process conditions, and the following coating slurry is required to be prepared:
90-100g/L of carboxylic acid ammonium salt modified organic silicon polyurethane water pressure resistant coating agent SSP;
1-2g/L of low molecular polyethylene glycol;
20-30g/L of ultraviolet-proof finishing agent UV-BS.
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