CN109750503B - Silicon-containing water repellent finishing agent - Google Patents
Silicon-containing water repellent finishing agent Download PDFInfo
- Publication number
- CN109750503B CN109750503B CN201811594589.7A CN201811594589A CN109750503B CN 109750503 B CN109750503 B CN 109750503B CN 201811594589 A CN201811594589 A CN 201811594589A CN 109750503 B CN109750503 B CN 109750503B
- Authority
- CN
- China
- Prior art keywords
- parts
- emulsion
- organic silicon
- silicon modified
- diisocyanate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Abstract
The invention discloses a silicon-containing water repellent finishing agent, which is formed by blending organic silicon modified acrylate emulsion and organic silicon modified polyurethane emulsion, wherein 86-122 parts of organic silicon modified acrylate emulsion and 72-94 parts of organic silicon modified polyurethane emulsion are used as the water repellent finishing agent; using Si (CH)3)3The organosilicon functional monomer of the group has large steric hindrance and is not hydrolyzed, so that the emulsion polymerization stability is greatly improved, the silicon content in the polymer is increased, the organosilicon is uniformly distributed in the polymer molecular chain, and the water repellency of the polymer is enhanced. By utilizing the complementarity of the performances of polyurethane and polyacrylate, the two emulsions are blended and compounded to obtain the composite finishing agent with excellent water repellency. By introducing diacetone acrylamide and adipic dihydrazide into the emulsion, after the two emulsions are blended, crosslinking sites in a system can be increased, the self-crosslinking performance is improved, a medium-temperature self-crosslinking finishing agent is formed, and the baking temperature can be properly reduced.
Description
Technical Field
The invention relates to a water repellent finishing agent, in particular to a water repellent finishing agent of organic silicon, which is applied to the field of textiles.
Background
The water repellent finishing agent is widely used in the finishing process of functional textiles, and the commonly used finishing agent is fluorine-containing resin. The fluorine finishing agent has the characteristics of low concentration and high effect, and is stable to strong acid, strong alkali, high temperature and other environments. Fluorine-based compounds, however, have a continuing environmental hazard.
Compared with fluorine compounds, the organosilicon water repellent has lower surface tension, can achieve good water repellent effect only by lower amount, and is environment-friendly, heat-resistant and weather-resistant. However, silicone is slightly inferior in mechanical strength and adhesion.
The acrylate and polyurethane resin have excellent film forming property, strong adhesive force, excellent weather resistance, heat resistance, corrosion resistance and flexibility, and can be widely applied to the textile industry.
For this purpose, the respective advantages of organosilicon, acrylate and polyurethane are combined to form the fluorine-free textile water repellent finishing agent.
Disclosure of Invention
The invention aims to provide a silicon-containing water repellent finishing agent, which combines organic silicon, acrylate and polyurethane to form a fluorine-free, green and environment-friendly textile water repellent finishing agent.
In order to achieve the purpose, the invention adopts the following technical scheme.
A silicon-containing water repellent finishing agent is characterized in that: the silicon-containing water repellent finishing agent is formed by blending organic silicon modified acrylate emulsion and organic silicon modified polyurethane emulsion, wherein 86-122 parts of organic silicon modified acrylate emulsion and 72-94 parts of organic silicon modified polyurethane emulsion are mixed;
the preparation method of the organic silicon modified acrylate emulsion comprises the following steps:
(1) stirring and dissolving 1.6 parts of fatty alcohol-polyoxyethylene ether AEO-9, 0.7 part of alkylphenol polyoxyethylene (10) OP-10, 3.8 parts of Sodium Dodecyl Sulfate (SDS) and 124 parts of water to form an aqueous solution; adding 32 parts of methyl methacrylate, 13 parts of ethyl acrylate, 45 parts of butyl acrylate, 16 parts of octadecyl acrylate, 12 parts of double-end vinyl silicone oil, 18 parts of functional organic silicon monomer (shown as a formula a) and 6 parts of diacetone acrylamide, fully mixing, and stirring at a high speed for emulsification to form a pre-emulsion;
(2) adding 72 parts of water, 0.8 part of fatty alcohol-polyoxyethylene ether AEO-9, 0.3 part of alkylphenol polyoxyethylene (10) OP-10 and 2.3 parts of sodium dodecyl sulfate SDS into a reactor provided with a stirrer, a condensing device and a nitrogen protection device, and dissolving;
(3) adding 1/4 volumes of pre-emulsion into a reactor, stirring and heating to 78 ℃, adding 0.2 parts of initiator and 2 parts of water solution, and continuing to perform heat preservation reaction for 30min after blue light appears;
(4) dropwise adding the rest of the pre-emulsion and a solution of 0.6 part of initiator and 6 parts of water, and controlling the dropwise adding speed to complete the dropwise adding process within 2-3 h;
(5) after the dropwise adding, heating to 85 ℃, supplementing a solution of 0.1 part of initiator and 1 part of water, and reacting for 2 hours at constant temperature;
(6) cooling, and adjusting the pH value to 7 by ammonia water to prepare organic silicon modified acrylate emulsion;
the preparation method of the organic silicon modified polyurethane emulsion comprises the following steps:
a. 1600 parts of dehydrated polyol, 200 parts of double-end hydroxyl straight chain dimethyl silicone oil, 446 parts of diisocyanate, 18 parts of dihydroxy organic silicon monomer (shown as a formula b) and 0.52 part of dibutyltin dilaurate are added into a reactor provided with a stirrer, a thermometer and a condenser and stirred for reaction for 5 hours at the temperature of 100 ℃;
b. cooling to 60 ℃, adding 94 parts of carboxyl chain extender and 400 parts of acetone, and continuing to react for 3 hours;
c. adding 15 parts of alcohol micromolecule chain extender, and carrying out chain extension reaction for 2 hours;
d. adding 8 parts of adipic acid dihydrazide, and carrying out end-capping reaction on a double-end NCO group for 2 hours;
e. after the reaction is finished, cooling to 40 ℃, adding 60 parts of triethylamine for neutralization for 45min to obtain a polyurethane prepolymer;
f. and (2) under high-speed stirring, adding 8000 parts of deionized water by a step-by-step addition method for emulsification, and after the emulsification is finished, removing acetone under reduced pressure to obtain the organic silicon modified polyurethane emulsion.
The double-end vinyl silicone oil CH2＝CH-Si(CH3)2O[(CH3)2SiO]n(CH3)2Si-CH＝CH2n＝20-40。
The polyalcohol is one or more of polyethylene oxide ether dihydric alcohol, polypropylene oxide ether dihydric alcohol, polytetrahydrofuran ether dihydric alcohol, adipic acid polyester diol, aromatic polyester polyol, polycaprolactone polyalcohol and polycarbonate diol.
The diisocyanate is one or more of toluene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, naphthalene diisocyanate, p-phenylene diisocyanate and 1, 4-cyclohexane diisocyanate.
The carboxyl chain extender is one or two of dimethylolpropionic acid and dimethylolbutyric acid.
The alcohol micromolecule chain extender is at least one of ethylene glycol, 1, 4-Butanediol (BDO), hexanediol and diethylene glycol.
In the prior art, silicon-containing monomers adopted by organosilicon modified acrylate and polyurethane are mostly vinyl siloxane coupling agents, and due to the fact that the monomers contain hydrolyzable groups Si-O-C, the groups can be hydrolyzed and condensed to a certain degree in the emulsion polymerization process, so that excessive crosslinking among polymer molecules causes instability of polymerization reaction, and polymer emulsion with high silicon content is difficult to obtain. Although measures such as delaying the dropwise addition, adding a hydrolysis inhibitor, and the like are taken during the polymerization, the content of the silicone monomer can only be 2 to 5%, and it is difficult to obtain an effective modification effect. The invention adopts Si (CH)3)3The organosilicon functional monomer of the group has large steric hindrance and is not hydrolyzed, so that the emulsion polymerization stability is greatly improved, the silicon content in the polymer is increased, the organosilicon is more uniformly distributed in the molecular chain of the polymer, and the water repellency of the polymer is effectively enhanced.
The organosilicon in the water repellent finishing agent of the invention forms a side group by methyl directly connected with silicon atoms, and a silicon-oxygen molecular chain forms a molecular main chain, and because the silicon-oxygen bond angle is large and has extremely high ionicity, the methyl connected with the silicon-oxygen bond is easy to freely rotate around the silicon-oxygen bond, so that the polymer molecular chain has better flexibility. In addition, the siloxane has lower surface tension, and after the fabric is finished, an excellent water repellent effect can be achieved.
The polyurethane has excellent mechanical properties, excellent cold resistance, wear resistance and elasticity, but has poor high temperature resistance and water resistance, and the polyacrylate has the characteristics of good luster, water resistance and outdoor aging resistance, but has high hardness, poor adhesiveness and poor flexibility. By utilizing the complementarity of the performances of polyurethane and polyacrylate, the polyurethane emulsion is blended and compounded with the acrylate modified by organic silicon, and the polyurethane-acrylate composite finishing agent with excellent water repellency is obtained.
By introducing diacetone acrylamide (DAAM) into the acrylate emulsion and Adipic Dihydrazide (ADH) into the polyurethane emulsion, the crosslinking sites in the system can be increased during high-temperature film formation after the two emulsions are blended, so that the self-crosslinking performance of the aqueous emulsion is improved, the medium-temperature self-crosslinking finishing agent is formed, and the baking temperature can be properly reduced.
Detailed Description
The unit "part" of the component raw materials related to the invention refers to "part by mass".
The preparation method of the functional organosilicon monomer and the dihydroxy organosilicon monomer is as follows.
The functional organic silicon monomer is prepared by the reaction of 2- (trimethylsiloxy) ethanolamine and isocyanate ethyl methacrylate, and the method comprises the following steps:
adding dehydrated 2- (trimethylsiloxy) ethanolamine, ethyl methacrylate and dibutyltin dilaurate into a reactor provided with a stirrer, a thermometer and a condenser, and stirring at 100 ℃ for 5 hours to react to obtain a functional organic silicon monomer containing C ═ C bonds; the molar ratio of the 2- (trimethylsiloxy) ethanolamine to the isocyanate ethyl methacrylate is 1:1, and the mass of the dibutyltin dilaurate accounts for 0.4 percent of the total mass of the reaction monomers. The involved reaction process is shown as (1).
The preparation method of the 2- (trimethylsiloxy) ethanolamine comprises the following steps: adding ethanolamine into a reactor with a mechanical stirrer and a thermometer, stirring and dropwise adding hexamethyldisilazane, reacting at 5-50 ℃ for 0.5-2 h, and obtaining 2- (trimethylsiloxy) ethanolamine through decompression and filtration after the reaction is finished. The molar ratio of ethanolamine to hexamethyldisilazane was 2: 1.
The dihydroxy organic silicon monomer is prepared by reacting diethanolamine, NaOH and trimethylchlorosilane, and the preparation method comprises the following steps:
adding diethanolamine and 0.4mol/L NaOH aqueous solution into a three-neck flask with a stirrer and a reflux condenser, slowly adding trimethylchlorosilane into the flask, reacting at 70 ℃ for 80min after the addition is finished, carrying out reduced pressure distillation, removing redundant water and unreacted diethanolamine, and obtaining N-diethanol-trimethyl silicon (dihydroxyorganosilicon monomer); wherein, the molar ratio of the added diethanol amine to the added trimethyl chlorosilane is 1.1:1, and the molar ratio of the trimethyl chlorosilane to the NaOH is 1: 1. The reaction process is shown as (2).
Example 1:
a silicon-containing water repellent finishing agent is formed by blending organic silicon modified acrylate emulsion and organic silicon modified polyurethane emulsion, wherein 86 parts of organic silicon modified acrylate emulsion and 72 parts of organic silicon modified polyurethane emulsion are mixed;
the preparation method of the organic silicon modified acrylate emulsion comprises the following steps:
(1) stirring and dissolving 1.6 parts of AEO-9 fatty alcohol polyoxyethylene ether, 0.7 part of OP-10 alkylphenol polyoxyethylene (10) ether, 3.8 parts of SDS sodium dodecyl sulfate and 124 parts of water into an aqueous solution; adding 32 parts of methyl methacrylate, 13 parts of ethyl acrylate, 45 parts of butyl acrylate, 16 parts of octadecyl acrylate, 12 parts of double-end vinyl silicone oil, 14 parts of functional organic silicon monomer and 6 parts of diacetone acrylamide, fully mixing, and stirring at a high speed for emulsification to form a pre-emulsion;
(2) adding 72 parts of water, 0.8 part of AEO-9 fatty alcohol polyoxyethylene ether, 0.3 part of OP-10 alkylphenol polyoxyethylene (10) ether and 2.3 parts of SDS sodium dodecyl sulfate into a reactor provided with a stirrer, a condensing device and a nitrogen protection device, and dissolving;
(3) adding 1/4 volumes of pre-emulsion into a reactor, stirring and heating to 78 ℃, adding 0.2 parts of initiator and 2 parts of water solution, and continuing to perform heat preservation reaction for 30min after blue light appears;
(4) dropwise adding the rest of the pre-emulsion and a solution of 0.6 part of initiator and 6 parts of water, and controlling the dropwise adding speed to complete the dropwise adding process within 2-3 h;
(5) after the dropwise adding, heating to 85 ℃, supplementing a solution of 0.1 part of initiator and 1 part of water, and reacting for 2 hours at constant temperature;
(6) cooling, and adjusting the pH value to 7 by ammonia water to prepare organic silicon modified acrylate emulsion;
the preparation method of the organic silicon modified polyurethane emulsion comprises the following steps:
a. 1600 parts of polytetrahydrofuran diol (molecular weight 2000), 200 parts of double-end hydroxyl straight-chain dimethyl silicone oil (molecular weight 3000), 446 parts of isophorone diisocyanate , 18 parts of dihydroxy organosilicon monomer and 0.52 part of dibutyltin dilaurate which are subjected to dehydration treatment are added into a reactor provided with a stirrer, a thermometer and a condenser tube, and stirred and reacted for 5 hours at 100 ℃;
b. cooling to 60 ℃, adding 94 parts of dimethylolpropionic acid and 400 parts of acetone, and continuing to react for 3 hours;
c. adding 15 parts of 1, 4-butanediol, and carrying out chain extension reaction for 2 hours;
d. adding 8 parts of adipic acid dihydrazide, and carrying out end-capping reaction on a double-end NCO group for 2 hours;
e. after the reaction is finished, cooling to 40 ℃, adding 60 parts of triethylamine for neutralization for 45min to obtain a polyurethane prepolymer;
f. and (2) under high-speed stirring, adding 8000 parts of deionized water by a step-by-step addition method for emulsification, and after the emulsification is finished, removing acetone under reduced pressure to obtain the organic silicon modified polyurethane emulsion.
Example 2:
a silicon-containing water repellent finishing agent is formed by blending organic silicon modified acrylate emulsion and organic silicon modified polyurethane emulsion, wherein 104 parts of organic silicon modified acrylate emulsion and 84 parts of organic silicon modified polyurethane emulsion are mixed;
the preparation method of the organic silicon modified acrylate emulsion comprises the following steps:
(1) stirring and dissolving 1.6 parts of AEO-9 fatty alcohol polyoxyethylene ether, 0.7 part of OP-10 alkylphenol polyoxyethylene (10) ether, 3.8 parts of SDS sodium dodecyl sulfate and 124 parts of water into an aqueous solution; adding 32 parts of methyl methacrylate, 13 parts of ethyl acrylate, 45 parts of butyl acrylate, 16 parts of octadecyl acrylate, 12 parts of double-end vinyl silicone oil, 14 parts of functional organic silicon monomer and 6 parts of diacetone acrylamide, fully mixing, and stirring at a high speed for emulsification to form a pre-emulsion;
(2) adding 72 parts of water, 0.8 part of AEO-9 fatty alcohol polyoxyethylene ether, 0.3 part of OP-10 alkylphenol polyoxyethylene (10) ether and 2.3 parts of SDS sodium dodecyl sulfate into a reactor provided with a stirrer, a condensing device and a nitrogen protection device, and dissolving;
(3) adding 1/4 volumes of pre-emulsion into a reactor, stirring and heating to 78 ℃, adding 0.2 parts of initiator and 2 parts of water solution, and continuing to perform heat preservation reaction for 30min after blue light appears;
(4) dropwise adding the rest of the pre-emulsion and a solution of 0.6 part of initiator and 6 parts of water, and controlling the dropwise adding speed to complete the dropwise adding process within 2-3 h;
(5) after the dropwise adding, heating to 85 ℃, supplementing a solution of 0.1 part of initiator and 1 part of water, and reacting for 2 hours at constant temperature;
(6) cooling, and adjusting the pH value to 7 by ammonia water to prepare organic silicon modified acrylate emulsion;
the preparation method of the organic silicon modified polyurethane emulsion comprises the following steps:
a. 1600 parts of polypropylene oxide ether glycol (molecular weight 3000), 200 parts of double-end hydroxyl straight-chain dimethyl silicone oil (molecular weight 3000), 446 parts of hexamethylene diisocyanate, 18 parts of dihydroxy organosilicon monomer and 0.52 part of dibutyltin dilaurate which are subjected to dehydration treatment are added into a reactor provided with a stirrer, a thermometer and a condenser tube, and stirred and reacted for 5 hours at the temperature of 100 ℃;
b. cooling to 60 ℃, adding 94 parts of dimethylolbutyric acid and 400 parts of acetone, and continuing to react for 3 hours;
c. adding 15 parts of hexanediol, and carrying out chain extension reaction for 2 hours;
d. adding 8 parts of adipic acid dihydrazide, and carrying out end-capping reaction on a double-end NCO group for 2 hours;
e. after the reaction is finished, cooling to 40 ℃, adding 60 parts of triethylamine for neutralization for 45min to obtain a polyurethane prepolymer;
f. and (2) under high-speed stirring, adding 8000 parts of deionized water by a step-by-step addition method for emulsification, and after the emulsification is finished, removing acetone under reduced pressure to obtain the organic silicon modified polyurethane emulsion.
Example 3:
a silicon-containing water repellent finishing agent is formed by blending organic silicon modified acrylate emulsion and organic silicon modified polyurethane emulsion, wherein 122 parts of organic silicon modified acrylate emulsion and 94 parts of organic silicon modified polyurethane emulsion are mixed;
the preparation method of the organic silicon modified acrylate emulsion comprises the following steps:
(1) stirring and dissolving 1.6 parts of AEO-9 fatty alcohol polyoxyethylene ether, 0.7 part of OP-10 alkylphenol polyoxyethylene (10) ether, 3.8 parts of SDS sodium dodecyl sulfate and 124 parts of water into an aqueous solution; adding 32 parts of methyl methacrylate, 13 parts of ethyl acrylate, 45 parts of butyl acrylate, 16 parts of octadecyl acrylate, 12 parts of double-end vinyl silicone oil, 14 parts of functional organic silicon monomer and 6 parts of diacetone acrylamide, fully mixing, and stirring at a high speed for emulsification to form a pre-emulsion;
(2) adding 72 parts of water, 0.8 part of AEO-9 fatty alcohol polyoxyethylene ether, 0.3 part of OP-10 alkylphenol polyoxyethylene (10) ether and 2.3 parts of SDS sodium dodecyl sulfate into a reactor provided with a stirrer, a condensing device and a nitrogen protection device, and dissolving;
(3) adding 1/4 volumes of pre-emulsion into a reactor, stirring and heating to 78 ℃, adding 0.2 parts of initiator and 2 parts of water solution, and continuing to perform heat preservation reaction for 30min after blue light appears;
(4) dropwise adding the rest of the pre-emulsion and a solution of 0.6 part of initiator and 6 parts of water, and controlling the dropwise adding speed to complete the dropwise adding process within 2-3 h;
(5) after the dropwise adding, heating to 85 ℃, supplementing a solution of 0.1 part of initiator and 1 part of water, and reacting for 2 hours at constant temperature;
(6) cooling, and adjusting the pH value to 7 by ammonia water to prepare organic silicon modified acrylate emulsion;
the preparation method of the organic silicon modified polyurethane emulsion comprises the following steps:
a. 1600 parts of polycarbonate diol (molecular weight 2000), 200 parts of double-end hydroxyl straight-chain dimethyl silicone oil (molecular weight 3000), 446 parts of diphenylmethane diisocyanate, 18 parts of dihydroxy organosilicon monomer and 0.52 part of dibutyltin dilaurate which are subjected to dehydration treatment are added into a reactor provided with a stirrer, a thermometer and a condenser tube, and stirred and reacted for 5 hours at the temperature of 100 ℃;
b. cooling to 60 ℃, adding 94 parts of dimethylolpropionic acid and 400 parts of acetone, and continuing to react for 3 hours;
c. adding 15 parts of ethylene glycol, and carrying out chain extension reaction for 2 hours;
d. adding 8 parts of adipic acid dihydrazide, and carrying out end-capping reaction on a double-end NCO group for 2 hours;
e. after the reaction is finished, cooling to 40 ℃, adding 60 parts of triethylamine for neutralization for 45min to obtain a polyurethane prepolymer;
f. and (2) under high-speed stirring, adding 8000 parts of deionized water by a step-by-step addition method for emulsification, and after the emulsification is finished, removing acetone under reduced pressure to obtain the organic silicon modified polyurethane emulsion.
The silicon-containing water repellent finishing agent is formed by blending organic silicon modified acrylate emulsion and organic silicon modified polyurethane emulsion, and the stability of the mixed emulsion has a direct relation with the performance of the emulsion. The stability of the blended emulsions was tested using the following method.
Mechanical stability of the emulsion: performing an accelerated separation test on the emulsion by using a centrifugal machine, placing a test tube containing the emulsion in the centrifugal machine, operating at 1000r/min for 10min at the beginning, observing whether a precipitate exists or not, and if the precipitate exists, failing to pass the speed stability test; then the emulsion in the rest test tubes is operated for 10min at 2000r/min, and the precipitation condition is observed; then, the operation is carried out for 10min at 3000r/min, and if no precipitation still appears in the test tube, the stability of the emulsion is good. The test conditions of the samples of examples 1-3 are shown in table 1 below.
Table 1 results of mechanical stability of the samples of the examples
The organosilicon modified acrylate emulsion and the organosilicon modified polyurethane emulsion are uniform and stable, the surface tension of the two emulsions is similar, the compatibility after mixing is good, the phenomena of layering and phase separation do not occur, and the uniform and stable emulsion state can still be maintained after high-speed centrifugation.
In order to investigate the performances of water repellency, moisture permeability, strength, chlorine resistance and the like of the silicon-containing water repellent finishing agent in the embodiment, the water repellent finishing is carried out on the polyester fabric by using the silicon-containing water repellent finishing agent in the embodiment of the invention, and the process flow is as follows: soaking (5min) → double soaking and double rolling (the rolling retention rate is 100%) → pre-baking (100 ℃, 2min) → baking (150 ℃, 3 min). The fabric comprises the following components: 100% of terylene, specification: 50D.
Waterproof performance: tested according to the method described in AATCC-22-2017. Spraying method: the water temperature is 27 ℃; washing procedure: and (3) washing at 27 ℃, performing conventional washing, hanging and airing, and washing with water for 20 times.
The moisture permeability is tested according to the GB/T12704-.
The tearing strength is carried out according to the GB/T3917.1-2009 coating fabric tearing strength test method.
The results of the above performance tests are shown in table 2.
Table 2 results of performance tests of the silicon-containing water repellent finish of examples
From the test results in table 2, it can be seen that after the water repellent finishing agent is coated, the fabric has high strength, excellent waterproof performance, good moisture permeability and no stuffiness when the fabric is taken.
Claims (5)
1. A silicon-containing water repellent finishing agent is characterized in that: the silicon-containing water repellent finishing agent is formed by blending organic silicon modified acrylate emulsion and organic silicon modified polyurethane emulsion, wherein 86-122 parts of organic silicon modified acrylate emulsion and 72-94 parts of organic silicon modified polyurethane emulsion are mixed;
the preparation method of the organic silicon modified acrylate emulsion comprises the following steps:
(1) stirring and dissolving 1.6 parts of AEO-9 fatty alcohol-polyoxyethylene ether, 0.7 part of OP-10 alkylphenol polyoxyethylene ether, 3.8 parts of SDS sodium dodecyl sulfate and 124 parts of water into an aqueous solution; adding 32 parts of methyl methacrylate, 13 parts of ethyl acrylate, 45 parts of butyl acrylate, 16 parts of octadecyl acrylate, 12 parts of double-end vinyl silicone oil, 18 parts of functional organic silicon monomer and 6 parts of diacetone acrylamide, fully mixing, and stirring at a high speed for emulsification to form a pre-emulsion; the structural formula of the functional organosilicon monomer is shown as a;
(2) adding 72 parts of water, 0.8 part of AEO-9 fatty alcohol polyoxyethylene ether, 0.3 part of OP-10 alkylphenol polyoxyethylene ether and 2.3 parts of SDS sodium dodecyl sulfate into a reactor provided with a stirrer, a condensing device and a nitrogen protection device, and dissolving;
(3) adding 1/4 volumes of pre-emulsion into a reactor, stirring and heating to 78 ℃, adding 0.2 parts of initiator and 2 parts of water solution, and continuing to perform heat preservation reaction for 30min after blue light appears;
(4) dropwise adding the rest of the pre-emulsion and a solution of 0.6 part of initiator and 6 parts of water, and controlling the dropwise adding speed to complete the dropwise adding process within 2-3 h;
(5) after the dropwise adding, heating to 85 ℃, supplementing a solution of 0.1 part of initiator and 1 part of water, and reacting for 2 hours at constant temperature;
(6) cooling, and adjusting the pH value to 7 by ammonia water to prepare organic silicon modified acrylate emulsion;
the preparation method of the organic silicon modified polyurethane emulsion comprises the following steps:
a. 1600 parts of dehydrated polyol, 200 parts of double-end hydroxyl straight chain dimethyl silicone oil, 446 parts of diisocyanate, 18 parts of dihydroxy organosilicon monomer and 0.52 part of dibutyltin dilaurate are added into a reactor provided with a stirrer, a thermometer and a condenser, and stirred and reacted for 5 hours at the temperature of 100 ℃; the structural formula of the dihydroxy organosilicon monomer is shown as b;
b. cooling to 60 ℃, adding 94 parts of carboxyl chain extender and 400 parts of acetone, and continuing to react for 3 hours;
c. adding 15 parts of alcohol micromolecule chain extender, and carrying out chain extension reaction for 2 hours;
d. adding 8 parts of adipic acid dihydrazide, and carrying out end-capping reaction on a double-end NCO group for 2 hours;
e. after the reaction is finished, cooling to 40 ℃, adding 60 parts of triethylamine for neutralization for 45min to obtain a polyurethane prepolymer;
f. under high-speed stirring, 8000 parts of deionized water is added by a step-by-step addition method for emulsification, and after the emulsification is finished, acetone is removed under reduced pressure to obtain the organic silicon modified polyurethane emulsion
2. The silicon-containing water repellent finish according to claim 1, characterized in that: the polyalcohol is one or more of polyethylene oxide ether dihydric alcohol, polypropylene oxide ether dihydric alcohol, polytetrahydrofuran ether dihydric alcohol, adipic acid polyester diol, aromatic polyester polyol, polycaprolactone polyalcohol and polycarbonate diol.
3. The silicon-containing water repellent finish according to claim 1, characterized in that: the diisocyanate is one or more of toluene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, naphthalene diisocyanate, p-phenylene diisocyanate and 1, 4-cyclohexane diisocyanate.
4. The silicon-containing water repellent finish according to claim 1, characterized in that: the carboxyl chain extender is one or two of dimethylolpropionic acid and dimethylolbutyric acid.
5. The silicon-containing water repellent finish according to claim 1, characterized in that: the alcohol micromolecule chain extender is at least one of ethylene glycol, 1, 4-butanediol, hexanediol and diethylene glycol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811594589.7A CN109750503B (en) | 2018-12-25 | 2018-12-25 | Silicon-containing water repellent finishing agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811594589.7A CN109750503B (en) | 2018-12-25 | 2018-12-25 | Silicon-containing water repellent finishing agent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109750503A CN109750503A (en) | 2019-05-14 |
| CN109750503B true CN109750503B (en) | 2021-04-30 |
Family
ID=66403958
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811594589.7A Active CN109750503B (en) | 2018-12-25 | 2018-12-25 | Silicon-containing water repellent finishing agent |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109750503B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111424431A (en) * | 2019-12-18 | 2020-07-17 | 广州市增城区实验中学 | Fluorine-free hydrophobic cotton fabric finishing agent and method for finishing cotton fabric by using same |
| CN111978476B (en) * | 2020-08-25 | 2022-09-27 | 青岛大学 | Sulfonic acid/carboxylic acid type silicon-containing polyurethane acrylate water repellent agent and preparation and application thereof |
| 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 |
| CN114933681B (en) * | 2022-05-16 | 2023-11-21 | 杭州美高华颐化工有限公司 | Isocyanate modified polyacrylate fluorine-free waterproof agent and preparation method thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1268919B1 (en) * | 2000-04-04 | 2006-06-21 | Schoeller Textil AG | Finish of textile fibres, tissues and fabrics |
| CN1854165A (en) * | 2005-04-20 | 2006-11-01 | 广州宏昌胶粘带厂 | Organic silicon modified aqueous polyurethane |
| CN101544738A (en) * | 2009-04-30 | 2009-09-30 | 中山大学 | Room-temperature self-crosslinking water-soluble polyurethane acrylic resin and preparation method and application thereof |
| CN104194610A (en) * | 2014-09-11 | 2014-12-10 | 北京东方雨虹防水技术股份有限公司 | Self-crosslinked one-component polyurethane waterproofing coating |
| CN105175642A (en) * | 2015-09-25 | 2015-12-23 | 三棵树涂料股份有限公司 | Self-crosslinking polyurethane-acrylate composite emulsion and preparation method thereof |
| CN105601799A (en) * | 2016-01-05 | 2016-05-25 | 广州中国科学院工业技术研究院 | Core/shell type organosilicone-modified acrylate emulsion and preparation method and application thereof |
| CN108978226A (en) * | 2018-07-17 | 2018-12-11 | 江南大学 | A kind of preparation of polyurethane-modified polyacrylate class water repellent and application method |
-
2018
- 2018-12-25 CN CN201811594589.7A patent/CN109750503B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1268919B1 (en) * | 2000-04-04 | 2006-06-21 | Schoeller Textil AG | Finish of textile fibres, tissues and fabrics |
| CN1854165A (en) * | 2005-04-20 | 2006-11-01 | 广州宏昌胶粘带厂 | Organic silicon modified aqueous polyurethane |
| CN101544738A (en) * | 2009-04-30 | 2009-09-30 | 中山大学 | Room-temperature self-crosslinking water-soluble polyurethane acrylic resin and preparation method and application thereof |
| CN104194610A (en) * | 2014-09-11 | 2014-12-10 | 北京东方雨虹防水技术股份有限公司 | Self-crosslinked one-component polyurethane waterproofing coating |
| CN105175642A (en) * | 2015-09-25 | 2015-12-23 | 三棵树涂料股份有限公司 | Self-crosslinking polyurethane-acrylate composite emulsion and preparation method thereof |
| CN105601799A (en) * | 2016-01-05 | 2016-05-25 | 广州中国科学院工业技术研究院 | Core/shell type organosilicone-modified acrylate emulsion and preparation method and application thereof |
| CN108978226A (en) * | 2018-07-17 | 2018-12-11 | 江南大学 | A kind of preparation of polyurethane-modified polyacrylate class water repellent and application method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109750503A (en) | 2019-05-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109750503B (en) | Silicon-containing water repellent finishing agent | |
| CN109679327B (en) | Nano organic silicon composite polyurethane waterproof emulsion | |
| CN105884999B (en) | Preparation method and products thereof containing hydrophilic and hydrophobic side long-chain modified cation aqueous polyurethane emulsion | |
| CN111393608B (en) | Preparation method of UV-cured organic silicon modified hyperbranched polyurethane material | |
| CN109706746B (en) | Water-repellent polyolefin elastic fabric | |
| CN109371687B (en) | High-flexibility waterborne polyurethane finishing agent for textiles and preparation method thereof | |
| CN108410343B (en) | Water-based bi-component coating | |
| CN111019084A (en) | Water-based moisture-permeable flame-retardant polyurethane emulsion for textiles and preparation method thereof | |
| CN105461862A (en) | One-component water-based cationic polyurethane-fluorinated acrylate resin and preparation method thereof | |
| CN107629188A (en) | A kind of preparation method of combination property high-environmental type modified aqueous polyurethane | |
| CN112593410B (en) | Waterborne imitation coating high-elasticity stiff and smooth finishing agent and preparation method thereof | |
| CN114456348A (en) | Preparation method of waterborne polyurethane for organic silicon modified polyester polyether type leather finishing | |
| CN110734533A (en) | terminal/side fluoroalkyl co-modified polyurethane nano hybrid emulsion and preparation method thereof | |
| EP1883668A1 (en) | Polyurethane/ureas containing pendant alkoxysilane groups | |
| CN108178822A (en) | A kind of preparation method of environment-friendly modified aqueous polyurethane | |
| CN113956434B (en) | Hyperbranched organic amino silicon post-chain extension modified waterborne polyurethane and preparation method thereof | |
| CN108530603B (en) | Mica modified waterborne polyurethane emulsion, adhesive and preparation method thereof | |
| CN103993483B (en) | A kind of tear-proof coating fabric and its preparation process | |
| CN115612029A (en) | Modified cationic aqueous polyurethane dispersion, and preparation method and application thereof | |
| CN109703076B (en) | Preparation method of air pillow fabric | |
| CN108514999B (en) | Spraying process of water-based bi-component paint | |
| KR102572609B1 (en) | Low gloss urethane arcryl hybrid resin composition for textile coating | |
| CN115558082B (en) | Spider silk bionic type high-toughness polyurea, preparation method and coating thereof | |
| CN115536802B (en) | Water-based polylactic acid modified organic silicon polyurethane and preparation method and application thereof | |
| CN109369862A (en) | A kind of fluorine-silicon polyurethane modified acroleic acid water-base resin and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: A water repellent finishing agent containing silicon Effective date of registration: 20210917 Granted publication date: 20210430 Pledgee: Zhejiang Shaoxing Ruifeng Rural Commercial Bank Co.,Ltd. Binhai sub branch Pledgor: ZHEJIANG DONGJIN NEW MATERIAL Co.,Ltd. Registration number: Y2021330001687 |