CN109750503A - A kind of siliceous water repellent finishing agent - Google Patents
A kind of siliceous water repellent finishing agent Download PDFInfo
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Abstract
The invention discloses a kind of siliceous water repellent finishing agents, the siliceous water repellent finishing agent is formed by organosilicon-modified acrylate emulsion and organic silicon modified polyurethane emulsion blending, wherein, organosilicon-modified acrylate emulsion 86-122 parts, 72-94 parts of organic silicon modified polyurethane lotion；Using Si (CH3)3The organosilicon function monomer of group substantially increases the stability of emulsion polymerization, increases the content of silicon in polymer, make distributing equilibrium of the organosilicon in polymer molecular chain, enhance the water repellency of polymer since its steric hindrance is big, does not hydrolyze.Using the complementarity on polyurethane and polyacrylate performance, two kinds of lotions are subjected to composite, obtain the excellent composite finishing agent of water repellency.By introducing Diacetone Acrylamide, adipic dihydrazide in lotion, after two kinds of emulsion blendings, can crosslink sites in increase system, improve it is self-crosslinking can, form medium temperature self-cross linking type finishing agent, can suitably reduce baking temperature.
Description
Technical field
The present invention relates to a kind of water repellent finishing agents, and in particular to the water repellent finishing agent of organosilicon is applied to textile field.
Background technique
Water repellent finishing agent is widely used in function textile finishing technique, and common finishing agent is fluorine resin.Fluorine class
Finishing agent has the characteristics of low concentration, high effect, and to ambient stables such as strong acid, highly basic, high temperature.But fluoride compound has environment
There is lasting harmfulness.
Compared with fluorine compounds, organosilicon water repellent has lower surface tension, only needs relatively low amount that can reach very
Good water repellent effect, moreover, organosilicon is environmental-friendly, heat-resisting, weather-proof.But the mechanical strength of organosilicon, adhesive force are slightly worse.
Acrylate, polyurethane resin have excellent film forming, adhesive force is strong, weatherability, heat resistance, corrosion resistance,
Flexibility is excellent, is widely used in textile industry.
For this purpose, in conjunction with the respective advantage of organosilicon and acrylate, polyurethane, to form floride-free textile water repellent finish
Agent.
Summary of the invention
The object of the present invention is to provide a kind of siliceous water repellent finishing agents, and organosilicon is risen in conjunction with acrylate, polyurethane
Come, forms floride-free, environmentally protective textile water repellent finishing agent.
To achieve the above object, the present invention adopts the following technical scheme that.
A kind of siliceous water repellent finishing agent, it is characterised in that: the siliceous water repellent finishing agent is by organosilicon-modified acrylic
Ester lotion is formed with organic silicon modified polyurethane emulsion blending, wherein 86-122 parts of organosilicon-modified acrylate emulsion, organic
72-94 parts of silicon modified polyurethane lotion；
The organosilicon-modified acrylate emulsion, the preparation method is as follows:
(1) by 1.6 parts of fatty alcohol polyoxyethylene ether AEO-9,0.7 part of alkylphenol-polyethenoxy (10) ether OP-10,3.8 parts
Lauryl sodium sulfate SDS and 124 parts of water are stirred and dissolved into aqueous solution；32 parts of methyl methacrylates, 13 parts of acrylic acid are added
Ethyl ester, 45 parts of butyl acrylates, 16 parts of octadecyl acrylates, 12 parts of bi-end-blocking vinyl silicone oils, 18 parts of Functional silicones lists
Body (as shown in formula a), 6 parts of Diacetone Acrylamide, after being sufficiently mixed, high-speed stirred emulsification forms pre-emulsion；
(2) in the reactor that blender, condensing unit, nitrogen protection device are housed, 72 parts of water, 0.8 part of fat are added
Alcohol polyoxyethylene ether AEO-9,0.3 part of alkylphenol-polyethenoxy (10) ether OP-10,2.3 parts of lauryl sodium sulfate SDS, dissolution；
(3) pre-emulsion of 1/4 volume is added into reactor, stirring is warming up to 78 DEG C, 0.2 part of initiator and 2 are added
The aqueous solution of part water after there is blue light, continues insulation reaction 30min；
(4) solution of remaining pre-emulsion and 0.6 part of initiator and 6 parts of water is added dropwise, controls rate of addition, makes to be added dropwise
Journey is completed in 2-3h；
(5) after dripping, 85 DEG C are warming up to, and supplement the solution of 0.1 part of initiator and 1 part of water, isothermal reaction 2h；
(6) cool down, pH value is adjusted to 7 with ammonium hydroxide, organosilicon-modified acrylate emulsion is made；
The organic silicon modified polyurethane lotion, the preparation method comprises the following steps:
A, equipped with blender, thermometer, condenser pipe reactor in, be added 1600 parts of polyalcohols through dehydration,
200 parts of both-end hydroxyl straight chain dimethicones, 446 parts of diisocyanate, 18 parts of double organic hydroxy silicate monomers (as shown in formula b),
0.52 part of dibutyl tin dilaurate, 100 DEG C are stirred to react 5h；
B, 60 DEG C are cooled to, 94 parts of carboxyl type chain extenders, 400 parts of acetone are added, the reaction was continued 3h；
C, 15 parts of alcohols small molecule chain extenders, chain extending reaction 2h is added；
D, 8 parts of adipic dihydrazides are added, end capping reaction, time 2h are carried out to both-end NCO group；
E, reaction terminates to be cooled to 40 DEG C, is added in 60 parts of triethylamines and 45min, and base polyurethane prepolymer for use as is made；
F, under high-speed stirred, 8000 parts of deionized waters is added using substep addition method and are emulsified, after emulsification, decompression
Acetone is removed, organic silicon modified polyurethane lotion is obtained.
The bi-end-blocking vinyl silicone oil CH2=CH-Si (CH3)2O[(CH3)2SiO]n(CH3)2Si-CH=CH2N=
20-40。
The polyalcohol is polyethylene oxide ether dihydric alcohol, polyoxypropylene dihydric alcohol, polytetrahydrofuran ether binary
One of alcohol, adipic acid system polyester-diol, aromatic polyester polyol, polycaprolactone polyol, polycarbonate glycol are more
Kind.
The diisocyanate is toluene di-isocyanate(TDI), methyl diphenylene diisocyanate, two isocyanide of isophorone
Acid esters, hexamethylene diisocyanate, dicyclohexyl methyl hydride diisocyanate, naphthalene diisocyanate, paraphenylene diisocyanate, 1,
One of 4- cyclohexane diisocyanate is a variety of.
The carboxyl type chain extender is the one or two of dihydromethyl propionic acid, dimethylolpropionic acid.
The alcohols small molecule chain extender is ethylene glycol, in 1,4-butanediol (BDO), hexylene glycol, diglycol
At least one.
The silicon-containing monomer that organosilicon-modified acrylate, polyurethane use in the prior art is mostly vinylsiloxane coupling
Agent, due to containing hydrolyzable groups Si-O-C, in emulsion polymerization process, a degree of hydrolysis, contracting can occur for these groups
It closes, to be excessively crosslinked between making polymer molecule and lead to polymerization reaction unstability, it is difficult to obtain newborn compared with the polymer of high silicon content
Liquid.Although taking measures, the organic silicon monomer contents such as delay dropwise addition in the course of the polymerization process, addition hydrolysis inhibitor to be only capable of
Account for 2-5%, it is difficult to obtain effective modified effect.Present invention employs Si (CH3)3The organosilicon function monomer of group, due to it
Steric hindrance is big, does not hydrolyze, and substantially increases the stability of emulsion polymerization, increases the content of silicon in polymer, and makes organic
Distribution of the silicon in polymer molecular chain is more balanced, effectively enhances the water repellency of polymer.
Organosilicon in water repellent finishing agent of the present invention is by forming side group, silicon oxygen subchain with the methyl that silicon atom is connected directly
Molecular backbone is formed, because silicon oxygen bond angle is big, is easy freely to revolve around silicon oxygen bond with high ionic, coupled methyl
Turn, so that polymer molecular chain has preferable flexibility.In addition, siloxanes has lower surface tension, it, can after arranging fabric
Reach excellent water repellent effect.
Polyurethane has an excellent mechanical property, excellent cold resistance, wearability and elasticity, but its heat-resisting quantity, water-fast
Property it is poor, polyacrylate has the characteristic of preferable gloss, water resistance and resistance to outdoor aging, but hardness is big, adhesion, soft
Poor toughness.Using the complementarity on polyurethane and polyacrylate performance, by organic-silicon-modified acrylate to polyurethane cream
Liquid carries out composite, obtains the excellent polyurethane-acrylate composite finishing agent of water repellency.
By being introduced into Diacetone Acrylamide (DAAM) in acrylic acid ester emulsion, introducing adipyl in polyaminoester emulsion
Hydrazine (ADH), after two kinds of emulsion blendings, when high temperature forms a film, can crosslink sites in increase system, thus improve water-based emulsion from
Cross-linking properties forms medium temperature self-cross linking type finishing agent, can suitably reduce baking temperature.
Specific embodiment
Component raw material of the present invention, unit " part " refer to " mass parts ".
Functional silicones monomer involved by the present invention, the preparation method of double organic hydroxy silicate monomers are as follows.
The Functional silicones monomer, by 2- (trimethylsiloxy group) ethanol amine and methacrylic acid isocyanates second
Ester reaction is made, and method is as follows:
In the reactor that blender, thermometer, condenser pipe are housed, the 2- (trimethylsiloxy group) through dehydration is added
Ethanol amine, methacrylic acid isocyanate, dibutyl tin dilaurate, 100 DEG C are stirred to react 5h, obtain the function of the key containing C=C
It can property organic silicon monomer；The molar ratio 1:1 of 2- (trimethylsiloxy group) ethanol amine, methacrylic acid isocyanate, February
The quality of dilaurylate accounts for the 0.4% of reaction monomers gross mass.Involved reaction process is such as shown in (1).
Wherein, 2- (trimethylsiloxy group) ethanol amine the preparation method comprises the following steps: with mechanical stirring, thermometer reactor
In, ethanol amine is put into, agitation and dropping hexamethyldisilazane, in 5~50 DEG C of 0.5~2h of reaction, end of reaction is filtered through decompression
Obtain 2- (trimethylsiloxy group) ethanol amine.The molar ratio of ethanol amine and hexamethyldisilazane is 2:1.
Double organic hydroxy silicate monomers are reacted by diethanol amine, NaOH, trim,ethylchlorosilane to be made, and preparation method is such as
Under:
The NaOH aqueous solution of diethanol amine and 0.4mol/L are added to the three-necked flask with blender, reflux condensing tube
In, it is then slowly added to trim,ethylchlorosilane into flask, after charging, 80min is reacted at 70 DEG C, is evaporated under reduced pressure, removes
Extra water and unreacted diethanol amine are removed, N- diethanol-trimethyl silicane (double organic hydroxy silicate monomers) is obtained；Wherein, institute
The diethanol amine of addition and the molar ratio of trim,ethylchlorosilane are 1.1:1, and trim,ethylchlorosilane and NaOH molar ratio are 1:1.Instead
Answer process such as shown in (2).
Embodiment 1:
A kind of siliceous water repellent finishing agent, by organosilicon-modified acrylate emulsion and organic silicon modified polyurethane emulsion blending
It forms, wherein 86 parts of organosilicon-modified acrylate emulsion, 72 parts of organic silicon modified polyurethane lotion；
The organosilicon-modified acrylate emulsion, the preparation method is as follows:
(1) by 1.6 parts of AEO-9 fatty alcohol polyoxyethylene ether, 0.7 part of OP-10 alkylphenol-polyethenoxy (10) ether, 3.8 parts
SDS lauryl sodium sulfate and 124 parts of water are stirred and dissolved into aqueous solution；32 parts of methyl methacrylates, 13 parts of acrylic acid are added
Ethyl ester, 45 parts of butyl acrylates, 16 parts of octadecyl acrylates, 12 parts of bi-end-blocking vinyl silicone oils, 14 parts of Functional silicones lists
Body, 6 parts of Diacetone Acrylamide, after being sufficiently mixed, high-speed stirred emulsification forms pre-emulsion；
(2) in the reactor that blender, condensing unit, nitrogen protection device are housed, 72 parts of water, 0.8 part of AEO-9 are added
Fatty alcohol polyoxyethylene ether, 0.3 part of OP-10 alkylphenol-polyethenoxy (10) ether, 2.3 parts of SDS lauryl sodium sulfate, dissolution；
(3) pre-emulsion of 1/4 volume is added into reactor, stirring is warming up to 78 DEG C, 0.2 part of initiator and 2 are added
The aqueous solution of part water after there is blue light, continues insulation reaction 30min；
(4) solution of remaining pre-emulsion and 0.6 part of initiator and 6 parts of water is added dropwise, controls rate of addition, makes to be added dropwise
Journey is completed in 2-3h；
(5) after dripping, 85 DEG C are warming up to, and supplement the solution of 0.1 part of initiator and 1 part of water, isothermal reaction 2h；
(6) cool down, pH value is adjusted to 7 with ammonium hydroxide, organosilicon-modified acrylate emulsion is made；
The organic silicon modified polyurethane lotion, the preparation method comprises the following steps:
A, in the reactor that blender, thermometer, condenser pipe are housed, 1600 parts of poly- tetrahydro furans through dehydration are added
It mutters dihydric alcohol (molecular weight 2000), 200 parts of both-end hydroxyl straight chain dimethicones (molecular weight 3000), 446 parts of different Buddhist Lovell ketone two
Isocyanates, 18 parts of double organic hydroxy silicate monomers, 0.52 part of dibutyl tin dilaurate, 100 DEG C are stirred to react 5h；
B, 60 DEG C are cooled to, 94 parts of dihydromethyl propionic acids, 400 parts of acetone are added, the reaction was continued 3h；
C, 15 parts of 1,4-butanediol, chain extending reaction 2h is added；
D, 8 parts of adipic dihydrazides are added, end capping reaction, time 2h are carried out to both-end NCO group；
E, reaction terminates to be cooled to 40 DEG C, is added in 60 parts of triethylamines and 45min, and base polyurethane prepolymer for use as is made；
F, under high-speed stirred, 8000 parts of deionized waters is added using substep addition method and are emulsified, after emulsification, decompression
Acetone is removed, organic silicon modified polyurethane lotion is obtained.
Embodiment 2:
A kind of siliceous water repellent finishing agent, by organosilicon-modified acrylate emulsion and organic silicon modified polyurethane emulsion blending
It forms, wherein 104 parts of organosilicon-modified acrylate emulsion, 84 parts of organic silicon modified polyurethane lotion；
The organosilicon-modified acrylate emulsion, the preparation method is as follows:
(1) by 1.6 parts of AEO-9 fatty alcohol polyoxyethylene ether, 0.7 part of OP-10 alkylphenol-polyethenoxy (10) ether, 3.8 parts
SDS lauryl sodium sulfate and 124 parts of water are stirred and dissolved into aqueous solution；32 parts of methyl methacrylates, 13 parts of acrylic acid are added
Ethyl ester, 45 parts of butyl acrylates, 16 parts of octadecyl acrylates, 12 parts of bi-end-blocking vinyl silicone oils, 14 parts of Functional silicones lists
Body, 6 parts of Diacetone Acrylamide, after being sufficiently mixed, high-speed stirred emulsification forms pre-emulsion；
(2) in the reactor that blender, condensing unit, nitrogen protection device are housed, 72 parts of water, 0.8 part of AEO-9 are added
Fatty alcohol polyoxyethylene ether, 0.3 part of OP-10 alkylphenol-polyethenoxy (10) ether, 2.3 parts of SDS lauryl sodium sulfate, dissolution；
(3) pre-emulsion of 1/4 volume is added into reactor, stirring is warming up to 78 DEG C, 0.2 part of initiator and 2 are added
The aqueous solution of part water after there is blue light, continues insulation reaction 30min；
(4) solution of remaining pre-emulsion and 0.6 part of initiator and 6 parts of water is added dropwise, controls rate of addition, makes to be added dropwise
Journey is completed in 2-3h；
(5) after dripping, 85 DEG C are warming up to, and supplement the solution of 0.1 part of initiator and 1 part of water, isothermal reaction 2h；
(6) cool down, pH value is adjusted to 7 with ammonium hydroxide, organosilicon-modified acrylate emulsion is made；
The organic silicon modified polyurethane lotion, the preparation method comprises the following steps:
A, in the reactor that blender, thermometer, condenser pipe are housed, 1600 parts of polycyclic oxygen third through dehydration are added
Alkane ether dihydric alcohol (molecular weight 3000), 200 parts of both-end hydroxyl straight chain dimethicones (molecular weight 3000), 446 parts of hexa-methylenes
Diisocyanate, 18 parts of double organic hydroxy silicate monomers, 0.52 part of dibutyl tin dilaurate, 100 DEG C are stirred to react 5h；
B, 60 DEG C are cooled to, 94 parts of dimethylolpropionic acids, 400 parts of acetone are added, the reaction was continued 3h；
C, 15 parts of hexylene glycols, chain extending reaction 2h is added；
D, 8 parts of adipic dihydrazides are added, end capping reaction, time 2h are carried out to both-end NCO group；
E, reaction terminates to be cooled to 40 DEG C, is added in 60 parts of triethylamines and 45min, and base polyurethane prepolymer for use as is made；
F, under high-speed stirred, 8000 parts of deionized waters is added using substep addition method and are emulsified, after emulsification, decompression
Acetone is removed, organic silicon modified polyurethane lotion is obtained.
Embodiment 3:
A kind of siliceous water repellent finishing agent, by organosilicon-modified acrylate emulsion and organic silicon modified polyurethane emulsion blending
It forms, wherein 122 parts of organosilicon-modified acrylate emulsion, 94 parts of organic silicon modified polyurethane lotion；
The organosilicon-modified acrylate emulsion, the preparation method is as follows:
(1) by 1.6 parts of AEO-9 fatty alcohol polyoxyethylene ether, 0.7 part of OP-10 alkylphenol-polyethenoxy (10) ether, 3.8 parts
SDS lauryl sodium sulfate and 124 parts of water are stirred and dissolved into aqueous solution；32 parts of methyl methacrylates, 13 parts of acrylic acid are added
Ethyl ester, 45 parts of butyl acrylates, 16 parts of octadecyl acrylates, 12 parts of bi-end-blocking vinyl silicone oils, 14 parts of Functional silicones lists
Body, 6 parts of Diacetone Acrylamide, after being sufficiently mixed, high-speed stirred emulsification forms pre-emulsion；
(2) in the reactor that blender, condensing unit, nitrogen protection device are housed, 72 parts of water, 0.8 part of AEO-9 are added
Fatty alcohol polyoxyethylene ether, 0.3 part of OP-10 alkylphenol-polyethenoxy (10) ether, 2.3 parts of SDS lauryl sodium sulfate, dissolution；
(3) pre-emulsion of 1/4 volume is added into reactor, stirring is warming up to 78 DEG C, 0.2 part of initiator and 2 are added
The aqueous solution of part water after there is blue light, continues insulation reaction 30min；
(4) solution of remaining pre-emulsion and 0.6 part of initiator and 6 parts of water is added dropwise, controls rate of addition, makes to be added dropwise
Journey is completed in 2-3h；
(5) after dripping, 85 DEG C are warming up to, and supplement the solution of 0.1 part of initiator and 1 part of water, isothermal reaction 2h；
(6) cool down, pH value is adjusted to 7 with ammonium hydroxide, organosilicon-modified acrylate emulsion is made；
The organic silicon modified polyurethane lotion, the preparation method comprises the following steps:
A, in the reactor that blender, thermometer, condenser pipe are housed, 1600 parts of polycarbonate through dehydration are added
Glycol (molecular weight 2000), 200 parts of both-end hydroxyl straight chain dimethicones (molecular weight 3000), 446 parts of diphenyl methanes two are different
Cyanate, 18 parts of double organic hydroxy silicate monomers, 0.52 part of dibutyl tin dilaurate, 100 DEG C are stirred to react 5h；
B, 60 DEG C are cooled to, 94 parts of dihydromethyl propionic acids, 400 parts of acetone are added, the reaction was continued 3h；
C, 15 parts of ethylene glycol, chain extending reaction 2h is added；
D, 8 parts of adipic dihydrazides are added, end capping reaction, time 2h are carried out to both-end NCO group；
E, reaction terminates to be cooled to 40 DEG C, is added in 60 parts of triethylamines and 45min, and base polyurethane prepolymer for use as is made；
F, under high-speed stirred, 8000 parts of deionized waters is added using substep addition method and are emulsified, after emulsification, decompression
Acetone is removed, organic silicon modified polyurethane lotion is obtained.
The siliceous water repellent finishing agent of the present invention is total to by organosilicon-modified acrylate emulsion and organic silicon modified polyurethane lotion
Mixed to form, emulsion intercalation method has direct relationship to the performance of lotion after mixing.Using following method to the lotion of blending
Stability is tested.
The mechanical stability of lotion: acceleration separation test is carried out to lotion using centrifuge, the test tube for filling lotion is set
In centrifuge, precipitating has been seen whether after running 10min when initial with 1000r/min, can't pass the speed if having precipitating
Stability test；10min is run with 2000r/min to the lotion in remaining test tube again, observes precipitation status；Then again with
3000r/min runs 10min and illustrates that emulsion intercalation method is good if not precipitating yet in test tube.Embodiment 1-3 sample
Test case is as shown in table 1 below.
1 embodiment sample machinery stability result of table
Organosilicon-modified acrylate emulsion, organic silicon modified polyurethane lotion are uniform and stable, the surface of two kinds of lotions
Power is similar, and compatibility is good after mixing, does not occur layering, phenomenon of phase separation, uniform and stable cream is still able to maintain after high speed centrifugation
Liquid status.
To investigate the performances such as the siliceous water repellent finishing agent water repellent of embodiment, moisture-inhibiting, strength, chlorine-resistant, by institute of the embodiment of the present invention
It states siliceous water repellent finishing agent and water repellent finish, process flow has been carried out to polyester fabric are as follows: infiltration (5min) → second dipping and rolling (is rolled remaining
Rate 100%) → preliminary drying (100 DEG C, 2min) → bake (150 DEG C, 3min).Fabric ingredient: 100% terylene, specification: 50D*50D.
Waterproof performance: the test of the method referring to documented by AATCC-22-2017.Spray process: 27 DEG C of water temperature；Washing procedure:
27 DEG C, conventional wash, hang airing is washed 20 times.
Water vapour permeability is tested referring to GB/T 12704-2009 method.
Tearing brute force is carried out referring to GB/T3917.1-2009 coated fabric tearing brute force test method.
The test result of above-mentioned performance is as shown in table 2.
The siliceous water repellent finishing agent properties test result of 2 embodiment of table
From the test result of table 2 it is found that the strength of fabric is higher, and the waterproof performance of fabric is excellent after coating water repellent finishing agent
It is good, and it will not generate feeling of oppression and heat when the fabric is taken with good penetrability.
Claims (5)
1. a kind of siliceous water repellent finishing agent, it is characterised in that: the siliceous water repellent finishing agent is by organosilicon-modified acrylate
Lotion is formed with organic silicon modified polyurethane emulsion blending, wherein and 86-122 parts of organosilicon-modified acrylate emulsion, organosilicon
72-94 parts of modified polyurethane emulsion；
The organosilicon-modified acrylate emulsion, the preparation method is as follows:
(1) by 1.6 parts of AEO-9 fatty alcohol polyoxyethylene ether, 0.7 part of OP-10 alkylphenol-polyethenoxy (10) ether, 3.8 parts of SDS ten
Sodium dialkyl sulfate and 124 parts of water are stirred and dissolved into aqueous solution；Be added 32 parts of methyl methacrylates, 13 parts of ethyl acrylates,
45 parts of butyl acrylates, 16 parts of octadecyl acrylates, 12 parts of bi-end-blocking vinyl silicone oils, 18 parts of Functional silicones monomers, 6 parts
Diacetone Acrylamide, after being sufficiently mixed, high-speed stirred emulsification forms pre-emulsion；Functional silicones monomer structure formula such as a
It is shown；
(2) in the reactor that blender, condensing unit, nitrogen protection device are housed, 72 parts of water, 0.8 part of AEO-9 fat are added
Alcohol polyoxyethylene ether, 0.3 part of OP-10 alkylphenol-polyethenoxy (10) ether, 2.3 parts of SDS lauryl sodium sulfate, dissolution；
(3) pre-emulsion of 1/4 volume is added into reactor, stirring is warming up to 78 DEG C, 0.2 part of initiator and 2 parts of water is added
Aqueous solution, after there is blue light, continue insulation reaction 30min；
(4) solution of remaining pre-emulsion and 0.6 part of initiator and 6 parts of water is added dropwise, controls rate of addition, dropwise addition process is made to exist
It is completed in 2-3h；
(5) after dripping, 85 DEG C are warming up to, and supplement the solution of 0.1 part of initiator and 1 part of water, isothermal reaction 2h；
(6) cool down, pH value is adjusted to 7 with ammonium hydroxide, organosilicon-modified acrylate emulsion is made；
The organic silicon modified polyurethane lotion, the preparation method comprises the following steps:
A, equipped with blender, thermometer, condenser pipe reactor in, 1600 parts of polyalcohols through dehydration, 200 parts are added
Both-end hydroxyl straight chain dimethicone, 446 parts of diisocyanate, 18 parts of double organic hydroxy silicate monomers, 0.52 part of tin dilaurate two
Butyl tin, 100 DEG C are stirred to react 5h；Double organic hydroxy silicate monomer structure formulas are as shown in b；
B, 60 DEG C are cooled to, 94 parts of carboxyl type chain extenders, 400 parts of acetone are added, the reaction was continued 3h；
C, 15 parts of alcohols small molecule chain extenders, chain extending reaction 2h is added；
D, 8 parts of adipic dihydrazides are added, end capping reaction, time 2h are carried out to both-end NCO group；
E, reaction terminates to be cooled to 40 DEG C, is added in 60 parts of triethylamines and 45min, and base polyurethane prepolymer for use as is made；
F, under high-speed stirred, 8000 parts of deionized waters is added using substep addition method and are emulsified, after emulsification, removed under reduced pressure
Acetone obtains organic silicon modified polyurethane lotion.
2. a kind of siliceous water repellent finishing agent according to claim 1, it is characterised in that: the polyalcohol is polycyclic oxygen second
Alkane ether dihydric alcohol, polyoxypropylene dihydric alcohol, polytetrahydrofuran ether dihydric alcohol, adipic acid system polyester-diol, aromatic polyester
One of polyalcohol, polycaprolactone polyol, polycarbonate glycol are a variety of.
3. a kind of siliceous water repellent finishing agent according to claim 1, it is characterised in that: the diisocyanate is toluene
Diisocyanate, methyl diphenylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, two hexamethylenes
One of dicyclohexylmethane diisocyanate, naphthalene diisocyanate, paraphenylene diisocyanate, Isosorbide-5-Nitrae-cyclohexane diisocyanate are more
Kind.
4. a kind of siliceous water repellent finishing agent according to claim 1, it is characterised in that: the carboxyl type chain extender is
The one or two of dihydromethyl propionic acid, dimethylolpropionic acid.
5. a kind of siliceous water repellent finishing agent according to claim 1, it is characterised in that: the alcohols small molecule chain extender
For at least one of ethylene glycol, 1,4-butanediol (BDO), hexylene glycol, diglycol.
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| 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 |
| CN111978476A (en) * | 2020-08-25 | 2020-11-24 | 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 |
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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 |