CN112724353A - Ultra-stable polyurethane waterproofing agent and preparation method thereof - Google Patents
Ultra-stable polyurethane waterproofing agent and preparation method thereof Download PDFInfo
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- CN112724353A CN112724353A CN202011406105.9A CN202011406105A CN112724353A CN 112724353 A CN112724353 A CN 112724353A CN 202011406105 A CN202011406105 A CN 202011406105A CN 112724353 A CN112724353 A CN 112724353A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- 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
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/6505—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6511—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/32 or polyamines of C08G18/38 compounds of group C08G18/3203
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- 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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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- 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
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/02—Natural fibres, other than mineral fibres
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/10—Repellency against liquids
- D06M2200/12—Hydrophobic properties
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- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses an ultra-stable polyurethane waterproofing agent and a preparation method thereof, belonging to the field of textile auxiliaries and comprising the following raw materials in percentage by mass: 1-50% of a hydrophobic compound having a linking group of formula I, 1-70% of a compound having formula II, 1-50% of a compound having formula III, 5-70% of a solvent, 0.01-5% of a catalyst, and 1-50% of a surfactant. In the polyurethane waterproof component, the molecular weight of the polyurethane waterproof agent can be greatly improved through the structure of the formula (II), so that the waterproof effect is greatly improved, and the compound has a special tree structure and can greatly enhance the stability of the polyurethane waterproof agent.
Description
Technical Field
The invention relates to an ultra-stable polyurethane waterproof agent and a preparation method thereof, belonging to the field of textile auxiliary agents.
Background
With the improvement of production and living standards, people have higher and higher requirements on the performance of fabrics, and waterproof fabrics are one of the fabrics. The fluorine-containing acrylate polymer has excellent waterproof and oilproof effects and is widely applied to the surface of textile base materials, but the fluorine-containing acrylate polymer can generate substances harmful to human bodies and ecological environment in the using process, so that the use is limited, and the price of the fluorine-containing acrylate polymer is relatively expensive.
The fluoride-free waterproof agent is harmless to the environment, low in price and good in waterproof effect, and is more and more popular among people. The types of the current fluorine-free water-proofing agent include alkane long-chain type, acrylate polymer, organopolysiloxane and polyurethane type. Polyurethane waterproof agents have been widely used in the textile industry due to their excellent water-and oil-repellency, excellent compatibility, and high cost performance. However, the isocyanate reaction capability in the polyurethane waterproofing agent is too strong, so that the polyurethane waterproofing agent is easy to generate a floating flock phenomenon in the use process, waterproof spots are easy to generate on the cloth surface, and the waterproof effect of the fabric is greatly reduced.
Patent document WO2014/160906 relates to a fluorine-free water repellent, comprising a polyurethane compound of an isocyanate and a fatty acid ester, the polyurethane of the isocyanate and the fatty acid ester having excellent washing fastness, but the stability and water repellent effect of the water repellent are limited due to the poor stability of the isocyanate; patent document CN107407047A relates to a fluorine-free water repellent, which is a polyurethane compound containing isocyanate ester and acrylate, but the water repellent effect is affected by the water repellent stain on the cloth surface caused by the poor stability of isocyanate.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides an ultra-stable polyurethane waterproofing agent and a preparation method thereof, which can improve the waterproofing effect of the polyurethane waterproofing agent and improve the stability of use and storage.
In order to achieve the purpose, the ultra-stable polyurethane waterproof agent adopted by the invention comprises the following raw materials in percentage by mass: 1-50% of a hydrophobic compound having a linking group of formula I, 1-70% of a compound having formula II, 1-50% of a compound having formula III, 5-70% of a solvent, 0.01-5% of a catalyst, and 1-50% of a surfactant;
wherein, formula I is Q-NHC (O) -X-, formula II is (ABn) m (II), formula III is-R6Z；
Q in Q-NHC (O) -X-is selected from one of linear chain, cyclic or acyclic alkylene, and X is at least one of-R1, -C (O) R1- (CH)2CH2O)N(CH(CH3)CH2O)mR2、-(CH2CH2O)n(CH(CH3)CH2O) m C (O) R1, or a mixture thereof; wherein each n is independently 0 to 20, each m is independently 0 to 20, and m + n is greater than 0;
n in the (ABn) m is independently 1 to 3, m is independently 0 to 1000;
a is selected from ethylene carbonate or propylene carbonate, B is selected from R4Si (R5)3, R4 is selected from aminoalkyl, R5 is selected from-OCH or-OCH2CH3；
R6 of the-R6Z comprises at least one of saturated group-C1 to C30 straight chain or branched alkyl group, hydroxyl group-C1 to C30 straight chain or branched alkyl group, hydroxyl functional straight chain or branched C1 to C30 polyether, amine functional straight chain or branched organosilane alkane, amine functional C1 to C30 branched or branched alkyl group, and Z is selected from-NH, -OH, -COOH, -SH, -O (CH)2CH2O)s(CH(CH3CH2O) t-H, each s is independently 0 to 20, each t is independently 0 to 20, and s + t is greater than 0.
As an improvement, Q in the Q-NHC (O) -X-is selected from at least one of hexamethylene diisocyanate biuret, hexamethylene diisocyanate homopolymer, toluene diisocyanate trimer and 3-isocyanato or methyl-3, 4, 4-trimethylcyclohexyl isocyanate trimer.
In the improvement, X in the Q-NHC (O) -X-is at least one selected from sorbitan trioleate, sorbitan tristearate, polysorbate monostearate, trialkyl citrate and dipentaerythritol.
In the improvement, B in the (ABn) m is at least one of aminopropyltrimethoxysilane, aminopropyltriethoxysilane, aminoethylaminopropyltrimethoxysilane, aminoethylaminopropyltriethoxysilane, phenylaminomethyltriethoxysilane or phenylaminomethyltrimethoxysilane.
In the improvement, the-R6Z adopts at least one of ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, butanediol, polytetrahydrofuran, monoethanolamine, diethanolamine, triethanolamine, N-dimethylaminoethanol, stearic acid, propanolamine, lauric acid or dodecyl mercaptan.
As an improvement, the solvent adopts at least one of ketones, benzenes and esters.
In the improvement, at least one of dibutyltin dilaurate, organic bismuth, ferric chloride and dimethyltin dineodecanoate is adopted as the catalyst.
As an improvement, the surfactant is at least one of a cationic surfactant, a nonionic surfactant or an amphoteric surfactant.
As an improvement, the cationic surfactant adopts at least one of octadecyl ammonium acetate, dodecyl trimethyl ammonium chloride, hexadecyl trimethyl ammonium chloride and octadecyl trimethyl ammonium chloride; the nonionic surfactant comprises at least one of polyethylene glycol monolaurate, polyethylene glycol monostearate, sorbitan monolaurate and sorbitan monooleate.
In addition, the invention also provides a preparation method of the ultra-stable polyurethane waterproofing agent, which comprises the steps of adding sugar alcohol into a flask, heating to 100 ℃ and 150 ℃, carrying out reduced pressure distillation and dehydration, then cooling to room temperature, adding isocyanate and a solvent, uniformly stirring, heating to 40-90 ℃, adding 90% of the total amount of the catalyst, carrying out heat preservation for 1-5 hours, adding a compound with a formula II, adding the rest of the catalyst, carrying out heat preservation for 1-5 hours at 40-90 ℃, adding a compound with a formula III, carrying out heat preservation at 40-90 ℃ until the isocyanate reaction is finished, adding 50-90% of the weight of the product after the isocyanate reaction and a surfactant with a formula amount, stirring to be fully mixed, carrying out homogenization or ultrasonic treatment, and removing the solvent to obtain the ultra-stable polyurethane waterproofing agent.
The reaction mechanism of the present invention: in the polyurethane waterproof component, the molecular weight of the polyurethane waterproof agent can be greatly improved through the structure of the formula (II), so that the waterproof effect is greatly improved, and the compound has a special tree structure and can greatly enhance the stability of the polyurethane waterproof agent.
Drawings
Fig. 1 is a water-repellent picture grade chart of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below. It should be understood, however, that the description herein of specific embodiments is only intended to illustrate the invention and not to limit the scope of the invention.
An ultra-stable polyurethane waterproofing agent comprises the following raw materials in percentage by mass: 1-50% of a hydrophobic compound having a linking group of formula I, 1-70% of a compound having formula II, 1-50% of a compound having formula III, 5-70% of a solvent, 0.01-5% of a catalyst, and 1-50% of a surfactant;
wherein, the formula I is Q-NHC (O) -X-, the formula II is (ABn) m (II), the formula III is-R6Z；
Said Q is a monovalent, divalent or polyvalent moiety selected from the group consisting of linear, cyclic or acyclic alkylene groups employing at least one group containing alkoxy groups, phenyl groups, alkylene oxides, urethanes, ureas, biurets, uretdiones, cyclized isocyanates, allophanates or isocyanurates, and moiety Q may be formed from an isocyanate, diisocyanate or polyisocyanate compound in which all isocyanate groups NCO have been removed;
such compounds include, but are not limited to: hexamethylene diisocyanate biuret, hexamethylene diisocyanate homopolymer, toluene diisocyanate trimer, and trimers of 3-isocyanato and methyl-3, 4-trimethylcyclohexyl isocyanate, preferably DESMODUR N-3300, DESMODUR N-3600, DESMODUR N100, DESMODUR N-75D, etc., from Bayer corporation; wherein the compound is present in an amount of 5 to 50% by weight, based on the weight of the entire invention, preferably: 5-30 wt%, more preferably 5-20 wt%;
said X is at least oneA residue of a cyclic or acyclic sugar alcohol substituted with: -R1, -C (O) R1- (CH)2CH2O)N(CH(CH3)CH2O)mR2、-(CH2CH2O)n(CH(CH3)CH2O)mC (O) R1; or mixtures thereof;
wherein each n is independently 0 to 20; each m is independently 0 to 20; and m + n is greater than 0;
each R1 is independently a straight or branched chain hydrocarbyl group having 5-29 carbons optionally including at least 1 unsaturated bond;
and each R2 is independently-H, a straight or branched chain hydrocarbyl group having 6 to 30 carbons, and optionally containing at least 1 unsaturated bond; or mixtures thereof;
wherein; such compounds include, but are not limited to: mono-, di-and tri-substituted sorbitan stearates or sorbitol behenates such as sorbitan trioleate, sorbitan tristearate, polysorbate and polysorbate monostearate, trialkyl citrates, dipentaerythritol esters, wherein the compounds represent 10 to 90% by weight of the total invention, preferably: 20-80 wt%, more preferably 20-60 wt%;
for (ABn) m, the chemical formula is
Wherein each n is independently 1 to 3, and each m is independently 0 to 1000; a is selected from ethylene carbonate or propylene carbonate, B is selected from R4Si (R5)3, R4 is selected from aminoalkyl, R5 is selected from-OCH3；-OCH2CH3；
Compounds B include, but are not limited to: aminopropyltrimethoxysilane, aminopropyltriethoxysilane, aminoethylaminopropyltrimethoxysilane, aminoethylaminopropyltriethoxysilane, phenylaminomethyltriethoxysilane, phenylaminomethyltrimethoxysilane, etc.; the introduction of the compound can greatly improve the molecular weight of the polyurethane waterproofing agent, thereby greatly improving the waterproofing effect, and the compound has a special tree structure and can greatly improve the stability of the polyurethane waterproofing agent; wherein the compound is present in an amount of 1 to 70 wt%, preferably 1 to 30 wt%, more preferably 1 to 20 wt% based on the weight of the entire invention;
for, -R6Z (III);
z is selected from-NH, -OH, -COOH, -SH, -O (CH)2CH2O)s(CH(CH3CH2O) t-H, etc.;
wherein R6 employs a-C1 to C30 linear or branched alkyl group containing at least one saturated group, a hydroxyl C1 to C30 linear or branched alkyl group, a hydroxyl functional linear or branched C1 to C30 polyether, an amine functional linear or branched organosilane; amine functional C1 to C30 branched or branched alkyl;
such compounds include, but are not limited to: ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, butylene glycol, polytetrahydrofuran, monoethanolamine, diethanolamine, triethanolamine, N-dimethylaminoethanol, stearic acid, propanolamine, lauric acid, dodecanethiol; wherein the compound is present in an amount of 1 to 50% by weight, preferably: 1 to 30% by weight, more preferably 1 to 10% by weight.
In addition to the above components, the present invention is carried out in the presence of an organic solvent, typically an organic solvent that is not reactive with isocyanate groups, such compounds including but not limited to: ketones, benzenes, esters; for convenience and availability, ketones are preferred, more preferably: methyl isobutyl ketone (MIBK); wherein the compound is present in an amount of 5 to 70% by weight, based on the weight of the entire invention, preferably: 5 to 50 wt%, more preferably 5 to 40 wt%.
The present invention is carried out in the presence of a catalyst, such compounds include, but are not limited to: dibutyltin dilaurate; organic bismuth, ferric chloride, dimethyltin dineodecanoate, and the like; wherein the compound is present in an amount of 0.01 to 2 wt%, preferably 0.01 to 1.5 wt%, more preferably 0.01 to 1 wt% based on the weight of the entire invention.
The invention needs to add a surfactant after the polymerization is finished, and the surfactant can be one or a mixture of a plurality of cationic, nonionic or amphoteric surfactants.
Wherein the nonionic surfactant comprises polyethylene glycol monolaurate, polyethylene glycol monostearate, sorbitan monolaurate, sorbitan monooleate, etc.; the cationic surfactant comprises octadecyl ammonium acetate, dodecyl trimethyl ammonium chloride, hexadecyl trimethyl ammonium chloride, octadecyl trimethyl ammonium chloride and the like; the surfactant is present in an amount of 1 to 50 wt%, preferably 1 to 20 wt%, more preferably 1 to 10 wt% based on the weight of the whole invention.
Example 1
The preparation method of the ultra-stable polyurethane waterproof agent comprises the following steps:
1) preparation of dendrimer-organosilane
Adding 178.3g of aminopropyl trimethoxysilane into a dry four-neck round-bottom flask (provided with a thermocouple, a mechanical stirrer, a nitrogen inlet, a condenser and a gas outlet), stirring, slowly dropwise adding 88g of ethylene carbonate at room temperature, stirring uniformly at room temperature for 24 hours under the protection of nitrogen until the viscosity of the mixture is increased, then heating to 90 ℃, preserving heat for 2 hours, and cooling to obtain colorless to light yellow wax;
2) preparation of polyurethane waterproofing agent
Adding 23g of sorbitan trioleate into a dry four-neck round-bottom flask (provided with a thermocouple, a mechanical stirrer, a nitrogen inlet, a condenser and a gas outlet), heating to 110 ℃, distilling under reduced pressure for 1.5 hours, cooling to 40 ℃, continuously adding 14g of DESMODUR N100 and 100g of MIBK, heating the reaction mixture to 70 ℃, adding 0.1g of dibutyltin dilaurate, preserving heat at 75 ℃ for 2 hours, adding 10g of the product prepared in the step 1) and 0.1g of dibutyltin dilaurate, preserving heat at 75 ℃ for 2 hours, adding 5g of polyethylene glycol 400, and continuously preserving heat at 75 ℃ for 4 hours;
when the reaction was tested negative for reactive isocyanate, 100g of deionized water, 10g of octadecyl dimethyl ammonium chloride, 5g of AEO7 were added and the mixture was stirred at 65 ℃ for 1 hour each, then the mixture was homogenized 2 times at 4000psi, MIBK was removed by distillation, the product was filtered and diluted to 20% solids.
Example 2
The preparation method of the ultra-stable polyurethane waterproof agent comprises the following steps:
1) preparation of dendrimer-organosilane
221.4g of aminopropyltriethoxysilane is added into a dry four-neck round-bottom flask (provided with a thermocouple, a mechanical stirrer, a nitrogen inlet, a condenser and a gas outlet), stirring is started, 88g of ethylene carbonate is slowly dropped at room temperature, stirring is carried out uniformly for 24h at room temperature under the protection of nitrogen until the viscosity of the mixture is increased, then the temperature is raised to 90 ℃ and kept for 2h, and the temperature is lowered to obtain colorless to light yellow wax;
2) preparation of polyurethane waterproofing agent
Adding 30g of sorbitan trioleate into a dry four-neck round-bottom flask (provided with a thermocouple, a mechanical stirrer, a nitrogen inlet, a condenser and a gas outlet), heating to 110 ℃, distilling under reduced pressure for 1.5 hours, cooling to 40 ℃, continuously adding 16g of DESMODUR N100 and 150g of MIBK, heating the reaction mixture to 70 ℃, adding 0.1g of dibutyltin dilaurate, preserving heat at 75 ℃ for 2 hours, adding 15g of the product prepared in the step 1) and 0.1g of dibutyltin dilaurate, preserving heat at 75 ℃ for 2 hours, adding 10g of polyethylene glycol 400, and continuously preserving heat at 70-75 ℃ for 4 hours;
when the reaction was tested negative for reactive isocyanate, 100g of deionized water, 10g of octadecyl dimethyl ammonium chloride, 5g of AEO7 were added and the mixture was stirred at 65 ℃ for 1 hour, then the mixture was homogenized at 4000psi for 2 times, MIBK was removed by distillation, the product was filtered, diluted to 20% solids content
Example 3
The preparation method of the ultra-stable polyurethane waterproof agent comprises the following steps:
1) preparation of dendrimer-organosilane
221.4g of aminopropyltriethoxysilane is added into a dry four-neck round-bottom flask (provided with a thermocouple, a mechanical stirrer, a nitrogen inlet, a condenser and a gas outlet), stirring is started, 102.1g of propylene carbonate is slowly dropped at room temperature, stirring is uniformly carried out at room temperature for 12h under the protection of nitrogen until the viscosity of the mixture is increased, then the temperature is raised to 90 ℃ and kept for 2h, and the temperature is lowered to obtain colorless to light yellow wax;
2) preparation of polyurethane waterproofing agent
Adding 30g of sorbitan trioleate into a dry four-neck round-bottom flask (provided with a thermocouple, a mechanical stirrer, a nitrogen inlet, a condenser and a gas outlet), heating to 110 ℃, distilling under reduced pressure for 1.5 hours, cooling to 40 ℃, continuously adding 16g of DESMODUR N100 and 150g of MIBK, heating the reaction mixture to 70 ℃, adding 0.1g of dibutyltin dilaurate, preserving heat at 75 ℃ for 2 hours, adding 15g of the product prepared in the step 1) and 0.1g of dibutyltin dilaurate, preserving heat at 75 ℃ for 2 hours, adding 10g of polyethylene glycol 400, and continuously preserving heat at 70-75 ℃ for 4 hours;
when the reaction was tested negative for reactive isocyanate, 100g of deionized water, 10g of octadecyl dimethyl ammonium chloride, 5g of AEO7 were added and the mixture was stirred at 65 ℃ for 1 hour each, then the mixture was homogenized 2 times at 4000psi, MIBK was removed by distillation, the product was filtered and diluted to 20% solids.
Comparative example 1
Adding 30g of sorbitan trioleate into a dry four-neck round-bottom flask (provided with a thermocouple, a mechanical stirrer, a nitrogen inlet, a condenser and a gas outlet), heating to 110 ℃, distilling under reduced pressure for 1.5 hours, cooling to 40 ℃, continuously adding 16g of DESMODUR N100 and 150g of MIBK, heating the reaction mixture to 70 ℃, adding 0.1g of dibutyltin dilaurate, preserving heat at 75 ℃ for 2 hours, adding 10g of polyethylene glycol 400, and continuously preserving heat at 70-75 ℃ for 4 hours;
when the reaction was tested negative for reactive isocyanate, 100g of deionized water, 10g of octadecyl dimethyl ammonium chloride, 5g of AEO7 were added and the mixture was stirred at 65 ℃ for 1 hour each, then the mixture was homogenized 2 times at 4000psi, MIBK was removed by distillation, the product was filtered and diluted to 20% solids.
Comparative example 2
Adding 30g of sorbitan trioleate into a dry four-neck round-bottom flask (provided with a thermocouple, a mechanical stirrer, a nitrogen inlet, a condenser and a gas outlet), heating to 110 ℃, distilling under reduced pressure for 1.5 hours, cooling to 40 ℃, continuously adding 16g of DESMODUR N100 and 150g of MIBK, heating the reaction mixture to 70 ℃, adding 0.1g of dibutyltin dilaurate, preserving heat at 75 ℃ for 2 hours, adding 60g of German bike BKY370 and 0.1g of dibutyltin dilaurate, preserving heat at 75 ℃ for 2 hours, adding 10g of polyethylene glycol 400, and continuously preserving heat at 70-75 ℃ for 4 hours;
when the reaction was tested negative for reactive isocyanate, 100g of deionized water, 10g of octadecyl dimethyl ammonium chloride, 5g of AEO7 were added and the mixture was stirred at 65 ℃ for 1 hour each, then the mixture was homogenized 2 times at 4000psi, MIBK was removed by distillation, the product was filtered and diluted to 20% solids.
Fabric treatment
The prepared product can be compounded with other surface treatment agents for use. The polymer of the invention is diluted to solid content of about 0.1-10% by adding water, and is suitable for fabrics such as natural fibers, synthetic fibers, artificial fibers and the like. The application method can adopt coating, dipping, spraying, padding, roll coating or combination method.
Specifically, the water repellent treatment is completed by padding the material to be treated with a padding bath having a solid content of 0.1 to 10%, removing the excess liquid with a squeeze roll, drying the material at a temperature of usually 80 to 120 ℃ for 1 minute to 1 hour, and aging the material at 170 ℃ for about 1 minute.
Test of Water-proof Effect
The water repellent effect (according to AATCC 22) was measured for a water repellent test. The water repellency was expressed as water repellency No. (as shown in table 1 below, the suffix "+" attached to the numerical value indicates a slightly better performance than that indicated by the numerical value).
TABLE 1 spray resistance
| Water repellency NO. | Status of state |
| 100(5 level) | The surface of the shower is not wet and is not stained with water drops |
| 90 (4-grade) | The surface of the drenched liquid is not wetted, but the surface occupies water drops |
| 80 (grade 3) | Linked-only small-area wetting of a showered surface |
| 70 (2-grade) | The surface of the drenched liquid is half wet |
| 50 (level 1) | The drenched surface is totally wetted |
The grade of the water repellent picture is shown in figure 1, ISO 5-the upper layer surface is not wetted and wetted; ISO 4-there is a small amount of irregular wetting or wetting on the upper surface; ISO 3-wetting the upper layer surface at the showering position; ISO 2-partial wetting of the entire upper surface; ISO 1-complete wetting of all upper surface.
The waterproof evaluation of each example of the present invention is shown in tables 2 to 4 below.
TABLE 2 evaluation of the Water-repellency on Cotton cloth
| Examples | No. 1 cloth | No. 2 cloth | No. 3 |
4 th piece of |
5 th cloth | 6 th piece of cloth | No. 7 cloth | 8 th cloth |
| Example 1 | 100 | 100 | 100 | 90 | 90 | 90 | 90 | 90 |
| Example 2 | 100 | 100 | 100 | 90 | 90 | 90 | 90 | 90 |
| Example 3 | 100 | 100 | 100 | 90 | 90 | 90 | 80 | 80 |
| Comparative example 1 | 90 | 80 | 80 | 80 | 70 | 70 | 70 | 50 |
| Comparative example 2 | 100 | 100 | 90 | 90 | 80 | 70 | 50 | 50 |
TABLE 3 evaluation of the Water-repellency on polyester
| Examples | No. 1 cloth | No. 2 cloth | No. 3 |
4 th piece of |
5 th cloth | 6 th piece of cloth | No. 7 cloth | 8 th cloth |
| Example 1 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 90 |
| Example 2 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 |
| Example 3 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 |
| Comparative example 1 | 100 | 100 | 90 | 90 | 90 | 80 | 80 | 70 |
| Comparative example 2 | 100 | 100 | 100 | 100 | 90 | 80 | 70 | 70 |
TABLE 4 evaluation of Water-repellency on Nylon
| Examples | No. 1 cloth | No. 2 cloth | No. 3 |
4 th piece of |
5 th cloth | 6 th piece of cloth | No. 7 cloth | 8 th cloth |
| Example 1 | 100 | 100 | 100 | 100 | 100 | 90 | 90 | 90 |
| Example 2 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 90 |
| Example 3 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 |
| Comparative example 1 | 100 | 90 | 90 | 90 | 70 | 70 | 50 | 50 |
| Comparative example 2 | 100 | 100 | 90 | 90 | 80 | 80 | 70 | 50 |
As can be seen from the above table, the water repellency rating of the urethane repellent component incorporated into the structure of formula II is superior to the water repellent component without the structure of formula II.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, so any modification, equivalent replacement or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. An ultra-stable polyurethane waterproofing agent is characterized by comprising the following raw materials in percentage by mass: 1-50% of a hydrophobic compound having a linking group of formula I, 1-70% of a compound having formula II, 1-50% of a compound having formula III, 5-70% of a solvent, 0.01-5% of a catalyst, and 1-50% of a surfactant;
wherein, the formula I is Q-NHC (O) -X-, the formula II is (ABn) m (II), the formula III is-R6Z；
Q in Q-NHC (O) -X-is selected from one of linear chain, cyclic or acyclic alkylene, and X is at least one of-R1, -C (O) R1- (CH)2CH2O)N(CH(CH3)CH2O)mR2、-(CH2CH2O)n(CH(CH3)CH2O) m C (O) R1, or a mixture thereof; wherein each n is independently 0 to 20, each m is independently 0 to 20, and m + n is greater than 0;
n in the (ABn) m is independently 1 to 3, m is independently 0 to 1000;
a is selected from ethylene carbonate or propylene carbonate, B is selected from R4Si (R5)3, R4 is selected from aminoalkyl, R5 is selected from-OCH or-OCH2CH3；
R6 of the-R6Z comprises at least one of saturated group-C1 to C30 straight chain or branched alkyl group, hydroxyl group-C1 to C30 straight chain or branched alkyl group, hydroxyl functional straight chain or branched C1 to C30 polyether, amine functional straight chain or branched organosilane alkane, amine functional C1 to C30 branched or branched alkyl group, and Z is selected from-NH, -OH, -COOH, -SH, -O (CH)2CH2O)s(CH(CH3CH2O) t-H, each s is independently 0 to 20, each t is independently 0 to 20, and s + t is greater than 0.
2. The ultra-stable polyurethane waterproofing agent according to claim 1, wherein Q in Q-nhc (o) -X "is at least one selected from the group consisting of hexamethylene diisocyanate biuret, hexamethylene diisocyanate homopolymer, toluene diisocyanate trimer and trimer of 3-isocyanato or methyl-3, 4, 4-trimethylcyclohexyl isocyanate.
3. The ultra-stable polyurethane waterproofing agent according to claim 1, wherein X in Q-nhc (o) -X "is at least one selected from sorbitan trioleate, sorbitan tristearate, polysorbate monostearate, trialkyl citrate and dipentaerythritol.
4. The ultra-stable polyurethane waterproofing agent according to claim 1, wherein B in (ABn) m is at least one of aminopropyltrimethoxysilane, aminopropyltriethoxysilane, aminoethylaminopropyltrimethoxysilane, aminoethylaminopropyltriethoxysilane, phenylaminomethyltriethoxysilane or phenylaminomethyltrimethoxysilane.
5. The ultra-stable polyurethane waterproofing agent according to claim 1, wherein said-R6Z employs at least one of ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, butylene glycol, polytetrahydrofuran, monoethanolamine, diethanolamine, triethanolamine, N-dimethylaminoethanol, stearic acid, propanolamine, lauric acid, or dodecanethiol.
6. The ultra-stable polyurethane waterproofing agent according to claim 1, wherein the solvent is at least one of ketones, benzenes, and esters.
7. The ultra-stable polyurethane waterproofing agent according to claim 1, wherein said catalyst is at least one of dibutyltin dilaurate, organic bismuth, ferric chloride and dimethyltin dineodecanoate.
8. The ultra-stable polyurethane waterproofing agent according to claim 1, wherein the surfactant is at least one of a cationic surfactant, a nonionic surfactant or an amphoteric surfactant.
9. The super-stable polyurethane waterproofing agent according to claim 8, wherein the cationic surfactant is at least one of octadecyl ammonium acetate, dodecyl trimethyl ammonium chloride, hexadecyl trimethyl ammonium chloride and octadecyl trimethyl ammonium chloride; the nonionic surfactant comprises at least one of polyethylene glycol monolaurate, polyethylene glycol monostearate, sorbitan monolaurate and sorbitan monooleate.
10. A preparation method of the ultra-stable polyurethane waterproofing agent as claimed in any one of claims 1 to 9, characterized in that sugar alcohol is added into a flask, the temperature is raised to 100-150 ℃, the reduced pressure distillation dehydration is carried out, then the temperature is lowered to room temperature, isocyanate and solvent are added, the stirring is carried out uniformly, the temperature is raised to 40-90 ℃, 90% of the total amount of the catalyst is added, the heat preservation is carried out for 1-5 hours, the compound with the formula II is added, the rest of the catalyst is added, the heat preservation is carried out for 1-5 hours at 40-90 ℃, the compound with the formula III is added, the heat preservation is carried out at 40-90 ℃ until the isocyanate reaction is finished, water accounting for 50-90% of the weight of the product after the isocyanate reaction and surfactant in the formula amount are added, the stirring is carried out until the mixture is fully.
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| CN114164663A (en) * | 2021-12-21 | 2022-03-11 | 广东湛丰精细化工有限公司 | High-performance durable polyurethane polyacrylate waterproof agent and preparation method thereof |
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