CN105037679A - Cationic type polyurethane modified organosilicon water repellent agent and preparation method and application thereof - Google Patents

Cationic type polyurethane modified organosilicon water repellent agent and preparation method and application thereof Download PDF

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Publication number
CN105037679A
CN105037679A CN201510610960.4A CN201510610960A CN105037679A CN 105037679 A CN105037679 A CN 105037679A CN 201510610960 A CN201510610960 A CN 201510610960A CN 105037679 A CN105037679 A CN 105037679A
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type polyurethane
polyurethane modified
organic silicon
modified organic
cation type
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CN105037679B (en
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周向东
黄斌
易辉
李福泉
林江
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Suzhou Yisite New Material Technology Co Ltd
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Suzhou Yisite New Material Technology Co Ltd
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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
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
    • 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
    • C08G18/08—Processes
    • C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
    • C08G18/0809—Manufacture of polymers containing ionic or ionogenic groups containing cationic or cationogenic groups
    • C08G18/0814—Manufacture of polymers containing ionic or ionogenic groups containing cationic or cationogenic groups containing ammonium groups or groups forming them
    • 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
    • C08G18/2805—Compounds having only one group containing active hydrogen
    • C08G18/285—Nitrogen containing compounds
    • C08G18/286—Oximes
    • 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
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
    • C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
    • 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
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6633—Compounds of group C08G18/42
    • C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • C08G18/6644—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203 having at least three hydroxy groups
    • 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
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6633—Compounds of group C08G18/42
    • C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6648—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38
    • C08G18/6655—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3271
    • 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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
    • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
    • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
    • 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
    • D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
    • D06M15/653—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain modified by isocyanate compounds
    • 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
    • D06M2101/04—Vegetal fibres
    • D06M2101/06—Vegetal fibres cellulosic
    • 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
    • D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M2101/32—Polyesters
    • 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

Abstract

The invention discloses a cationic type polyurethane modified organosilicon water repellent agent and a preparation method and application thereof. The method comprises the steps of adding isophorone diisocyanate into polyester diol and trimethylolpropane which are subjected to dewatering and drying treatment for reaction, then adding a cation chain extender N-methyldiethanolamine, sealing part of the isocyanate groups with methyl ethyl ketoxime, conducting reaction with the obtained part of isocyanate groups, the sealed polyurethane prepolymers and amino-polysiloxane, conducting neutralizing and solvent removing, and obtaining the emulsion of the cationic type polyurethane modified organosilicon water repellent agent. The process is simple, the textile is good in waterproof performance after arrangement, and the appetency between the water repellent agent and the fabric is high; meanwhile, the soft chains and hard chains in the polyurethane modified organosilicon molecules are prone to microphase separation, and the textile feels flexible and elastic; in addition, in the high temperature curing process, the unsealed isocyanate groups react with active groups of the fabric, and the washing resistance of the textile can be improved remarkably.

Description

Cation type polyurethane modified organic silicon water repllents and preparation method thereof and application
Technical field
The present invention relates to textile auxiliary's synthesis technical field, be specifically related to a kind of cation type polyurethane modified organic silicon water repllents and preparation method thereof and application.
Background technology
Under normal circumstances, human consumer, according to the needs of product end-use, requires that waterproof fabrics has fire-retardant, moisture-inhibiting, the function such as ventilative simultaneously.Although the organic fluorine class water-resisting agent that to be current effect best, but the contact angle of fabric only has about 120 ° after it arranges, if waterproof and the fire-retardant afterfinish method all adopting routine, because waterproofing and fire-retardant finish influence each other comparatively large, be difficult to make fabric have good waterproof and flame retardant effect simultaneously.In recent years, field of textiles is proposed " super-hydrophobic textile ", and " super-hydrophobic " refers to that water droplet is stablized contact angle at textile surface and is greater than 150 °.The working method of super-hydrophobic textile is generally the surface tissue form of imitating lotus leaf, fabric is created a nanometer or the rough surface of micron order and covers one deck hydrophobic material, making textiles have the ultra-hydrophobicity of similar lotus leaf.
Water repllents at present for textiles is mainly fluorocarbon polymer and silicoorganic compound.Fluorine carbon water repllents can give weaving grade low surface tension, and what have excellence refuses water effect; But it is expensive, and there is PFOS, PFOA problem in eight carbon fluorine, has potential threat to human body and environment.Silicone based water repllents has unique chemical structure, can form the hydrophobic layer with low surface tension at fiber surface, gives the feel of refusing water effect and softness that textiles is excellent; Meanwhile, its cheaper starting materials, good biocompatibility, has been subject to the favor of more and more investigator.
Intermolecular Van der Waals force and hydrogen bonded is relied between traditional organosilicon water repllents and fiber, chemical finishing agent is difficult to react with fiber, chemical finishing agent only covers fiber surface, the water-wash resistance and the dry cleaning resistance that arrange rear textiles are poor, though add the binding strength that linking agent can improve chemical finishing agent and fiber, improve certain performance, but the function reduction of textiles air-moisture-permeable can be caused, the decline of textiles added value can be brought; After arranging, textile touch shows slightly single simultaneously, cannot meet people to textiles sliding bullet, submissive demand simultaneously.
Summary of the invention
The object of this invention is to provide a kind of preparation method of cation type polyurethane modified organic silicon water repllents, the cation type polyurethane modified organic silicon water repllents prepared thus has excellent water repellency, after making arrangement again, textiles has excellent wash durability simultaneously, and give arrangement textiles favorable elasticity, fabric is not fluorine-containing and free formaldehyde also.
To achieve the above object of the invention, the technical solution used in the present invention is:
A preparation method for cation type polyurethane modified organic silicon water repllents, is characterized in that, comprise the following steps:
(1) polyester diol, TriMethylolPropane(TMP) and organo-tin compound are added in reactor, under nitrogen atmosphere, regulate temperature of reaction to be 55 ~ 60 DEG C; Then isoflurane chalcone diisocyanate is dripped; Then regulate temperature of reaction to be 85 ~ 90 DEG C, react 2 ~ 3 hours; Then temperature of reaction is regulated to be 60 ~ 65 DEG C; Add positively charged ion chainextender and tetrahydrofuran (THF) again, continue reaction 1 ~ 2 hour; Then in reaction solution, add methyl ethyl ketoxime, continue reaction 1 ~ 1.5 hour, obtain base polyurethane prepolymer for use as; With the quality that the quality sum of polyester diol and isoflurane chalcone diisocyanate is reactant, the mass ratio of reactant, trihydroxy methyl propane, organo-tin compound and positively charged ion chainextender is 1: (0.01 ~ 0.03): (0.0001 ~ 0.0002): (0.06 ~ 0.09);
(2) amino silicones is added in the reactor with tetrahydrofuran (THF); Then above-mentioned base polyurethane prepolymer for use as is added, under nitrogen atmosphere, in 20 ~ 30 DEG C of reactions 1 ~ 2 hour; Then Glacial acetic acid is added; Again except namely desolventizing obtains cation type polyurethane modified organic silicon water repllents.
In technique scheme, the molecular-weight average of described polyester diol is 960 ~ 1388, and the molecular-weight average of described amino silicones is 5000 ~ 8000, and the structural formula of amino silicones is:
Wherein 65≤n≤105.Based on the fabric after this cation type polyurethane modified organic silicon water repllents prepared arranges, both there is good water repellency, again there is good elasticity.
In technique scheme, in step (1), described organo-tin compound is dibutyl tin laurate; Described polyester diol is polyneopentyl glycol adipate glycol; Described positively charged ion chainextender is N methyldiethanol amine; The quality of tetrahydrofuran (THF) is 5 ~ 15% of reactant quality; By mol, methyl ethyl ketoxime consumption is 30 ~ 40% with isocyanate-based compound in reaction solution; The mol ratio of the isocyanate group of isoflurane chalcone diisocyanate and the hydroxyl of polyester diol is (1.1 ~ 1.3): 1.The chemical structural formula of gained base polyurethane prepolymer for use as is:
Wherein, R is ; R1 is , 4≤m≤6.
In technique scheme, in step (2), the mol ratio of the isocyanate group of base polyurethane prepolymer for use as and the amido of amino silicones is 1: (2 ~ 2.2); The quality of tetrahydrofuran (THF) be base polyurethane prepolymer for use as and amino silicones quality and 20 ~ 30%; Underpressure distillation is utilized to remove desolventizing.
In preferred technical scheme, in step (1), described polyester diol adds in reactor after drying treatment again; Isoflurane chalcone diisocyanate dropwised in 2 ~ 3 hours.Dripping too fast meeting causes sudden and violent poly-, drips the molecular weight distribution that can affect production efficiency and product slowly.
In technical scheme disclosed by the invention, isocyanate group and hydroxyl, amino, oximido have higher reactivity; First, the long-chain representative examples of saturated aliphatic dibasic alcohol adopting hydrophobicity stronger is soft monomer, isoflurane chalcone diisocyanate is hard monomer, N methyldiethanol amine is cationic chainextender, TriMethylolPropane(TMP) is linking agent, methyl ethyl ketoxime is end-capping reagent, by designing feed ratio and the order of addition(of ingredients) of different material, the base polyurethane prepolymer for use as that composite part terminal isocyanate group is closed; Then, the isocyanate group in performed polymer and the amino in polysiloxane molecule react, and carry out modification to polysiloxane; Finally add Glacial acetic acid, obtain cation type polyurethane modified organic silicon water repllents; Therefore the invention also discloses the cation type polyurethane modified organic silicon water repllents prepared according to the preparation method of above-mentioned cation type polyurethane modified organic silicon water repllents; The chemical structural formula of described cation type polyurethane modified organic silicon water repllents is as follows:
Wherein R is ; R 1for , 4≤m≤6, R 2for , 65≤n≤105.
The isocyanate group deblocking when baking arrangement be closed in the cation type polyurethane modified organic silicon water repllents that the invention discloses, again isocyanate group is discharged, and react with the active group on fabric fibre, thus make to form chemical bonding between water repellent finishing agent and fabric, solve existing finishing composition and the defect of planting fabric fibre bonding force difference.Therefore the invention also discloses the application of cation type polyurethane modified organic silicon water repllents in fabric water repellent finish; Described fabric is cotton fabric, polyester piece good or polyester-cotton fabric.
Because technique scheme is used, the present invention compared with prior art has following advantages:
1, the present invention utilizes methyl ethyl ketoxime isocyanate-terminated to part in base polyurethane prepolymer for use as, in the cation type polyurethane modified organic silicon water repllents molecule of synthesis, there is blocked isocyanate base, when textile baking arranges, deblocking discharges isocyanate group, and react with the active group on fiber and generate stable chemical bond, can significantly improve and arrange the wash durability that water effect refused by textiles, after washing 10 times, water repellency still reaches 90/ point.
2, in cation type polyurethane modified organic silicon water repllents disclosed by the invention, polyester diol, as the soft chain segment of urethane, effectively can improve the water repellency of polyurethane-modified organosilicon membrane; Easily there is microphase-separated in soft in polyurethane-modified silicone molecules, hard segment, effectively can increase the rebound resilience arranging textiles, improve single soft feel, wrinkle recovery angle reaches about 200 degree.
3, the present invention introduces positively charged ion chainextender N methyldiethanol amine first in base polyurethane prepolymer for use as, synthesis has the polyurethane-modified organosilicon water repllents of cationic, effectively can increase water repllents and interfibrous avidity, and improve the stability of modification water repllents.
4, cation type polyurethane modified organic silicon water repllents disclosed by the invention has excellent elasticity, low-temperature flexibility, solvent resistance at the film that fabric face is formed, with electronegative fiber, there is excellent avidity, the reactivity certain with fiber surface group tool; The water repellency of arrangement textiles can be improved and improve feel, increasing rebound resilience, also can improve textiles after arranging and refuse the washing fastness of water.
5, cation type polyurethane modified organic silicon water repllents preparation method disclosed by the invention is simple, easy handling, and have the advantage that production cost is low and operability is stronger, preparation time is short; Raw material composition rationally, prepare the excellent product performance that technique obtains, after washing 10 times, water repellency is still excellent, overcome existing organosilicon water repllents unstable, with the defect of fiber bonding force difference, turn avoid the harm that fluorine material brings, simultaneously not containing free formaldehyde, be applicable to suitability for industrialized production.
Accompanying drawing explanation
Fig. 1 is the infrared spectrogram of cation type polyurethane modified organic silicon water repllents prepared by embodiment 1;
Fig. 2 is the infrared spectrogram of cation type polyurethane modified organic silicon water repllents prepared by embodiment 2;
Fig. 3 is the infrared spectrogram of cation type polyurethane modified organic silicon water repllents prepared by embodiment 3.
Embodiment
Below in conjunction with embodiment and accompanying drawing, the invention will be further described:
Embodiment 1
1, by through the dried 48g polyneopentyl glycol adipate glycol (molecular weight is 960) of vacuum hydro-extraction, 2.25g TriMethylolPropane(TMP), 0.015g dibutyl tin laurate adds agitator is housed, in the reaction vessel of thermometer and condensation reflux unit, open and stir and logical nitrogen protection, be heated to 55 DEG C, 39.31g isoflurane chalcone diisocyanate is added drop-wise in reaction vessel gradually, within 2 hours, drip, 90 DEG C are warming up to after dropwising, be incubated 2 hours, be cooled to 60 DEG C, add 8.04gN-methyldiethanolamine and 6g tetrahydrofuran (THF) viscosity reduction, be incubated 1.5 hours, add again 1.68g methyl ethyl ketoxime by system 35% isocyanate-terminated, react 1 hour, obtain the base polyurethane prepolymer for use as that part isocyanic ester is closed.
2, under nitrogen protection, in the reaction vessel that agitator, thermometer, condensation reflux unit are housed, by-NCO and-NH 2amount of substance is than being 1:2, add the 347g amino silicones (molecular-weight average is 8000) that 110g tetrahydrofuran (THF) dissolves, slowly add the base polyurethane prepolymer for use as obtained in 100g step 1, at 30 DEG C, insulation reaction is after 1 hour, add 6.76g Glacial acetic acid, underpressure distillation is except desolventizing again, obtains the cation type polyurethane modified organic silicon water repllents that molecular-weight average is 20100.
See accompanying drawing 1, it is the infrared spectrum of above-mentioned cation type polyurethane modified organic silicon water repllents.3762cm in figure -1place is the weak absorbing peak of primary amine groups, 3322cm -1place is N-H stretching vibration peak, 1736cm -1place is the C=O stretching vibration peak of carbamate and ester group, 1667cm -1place is the C=N stretching vibration peak of methyl ethyl ketoxime blocked isocyanate base, 1527cm -1the N-H formation vibration that place is carbamate and C-N stretching vibration peak, 1262cm -1place is C-O stretching vibration in ester group and-Si-CH 3the sum of fundamental frequencies peak of middle methyl formation vibration, 1098cm -1place is the charateristic avsorption band of Si-O-Si, 804cm -1place is the stretching vibration peak of Si-C, simultaneously 2270cm -1near do not occur showing the absorption peak of-NCO to have obtained polyurethane-modified organosilicon water repllents.
Embodiment 2
1, by through the dried 58g polyneopentyl glycol adipate glycol (molecular weight is 1174) of vacuum hydro-extraction, 2.25g TriMethylolPropane(TMP), 0.015g dibutyl tin laurate adds agitator is housed, in the reaction vessel of thermometer and condensation reflux unit, open and stir and logical nitrogen protection, be heated to 60 DEG C, 41.83g isoflurane chalcone diisocyanate is added drop-wise in reaction vessel gradually, within 3 hours, drip, 85 DEG C of insulations 3 hours are warming up to after dropwising, 65 DEG C are cooled to when-NCO content no longer reduces, add 7.35gN-methyldiethanolamine and 12g tetrahydrofuran (THF) viscosity reduction, be incubated 1 hour, add again 1.58g methyl ethyl ketoxime by system 40% isocyanate group envelope close, react 1.5 hours, obtain the base polyurethane prepolymer for use as that part isocyanate group is closed.
2, under nitrogen protection, in the reaction vessel that agitator, thermometer, condensation reflux unit are housed, by-NCO and-NH 2amount of substance is than being 1:2.2, add the 145g amino silicones (molecular-weight average is 5000) that 56g tetrahydrofuran (THF) dissolves, slowly add the base polyurethane prepolymer for use as in 117g step 1, at 25 DEG C, insulation reaction is after 1.5 hours, add 7.39g Glacial acetic acid, underpressure distillation is except desolventizing again, obtains the cation type polyurethane modified organic silicon water repllents that molecular-weight average is 14600.
See accompanying drawing 2, it is the infrared spectrum of above-mentioned cation type polyurethane modified organic silicon water repllents.3771cm in figure -1place is the weak absorbing peak of primary amine groups, 3320cm -1place is N-H stretching vibration peak, 1732cm -1place is the C=O stretching vibration peak of carbamate and ester group, 1663cm -1place is the C=N stretching vibration peak of methyl ethyl ketoxime blocked isocyanate base, 1528cm -1the N-H formation vibration that place is carbamate and C-N stretching vibration peak, 1261cm -1place is C-O stretching vibration in ester group and-Si-CH 3the sum of fundamental frequencies peak of middle methyl formation vibration, 1096cm -1place is the charateristic avsorption band of Si-O-Si, 801cm -1place is the stretching vibration peak of Si-C, simultaneously 2270cm -1near do not occur showing the absorption peak of-NCO to have obtained polyurethane-modified organosilicon water repllents.
Embodiment 3
1, by through the dried 69g polyneopentyl glycol adipate glycol (molecular weight is 1388) of vacuum hydro-extraction, 2.25g TriMethylolPropane(TMP), 0.02g dibutyl tin laurate adds agitator is housed, in the reaction vessel of thermometer and condensation reflux unit, open and stir and logical nitrogen protection, be heated to 65 DEG C, 39.72g isoflurane chalcone diisocyanate is added drop-wise in reaction vessel gradually, within 2.5 hours, drip, 85 DEG C of insulations 2.5 hours are warming up to after dropwising, 60 DEG C are cooled to when-NCO content no longer reduces, add 7.4gN-methyldiethanolamine and 17g tetrahydrofuran (THF) viscosity reduction, be incubated 2 hours, add again 1.87g methyl ethyl ketoxime by system 30% isocyanate group close, react 1 hour, obtain the base polyurethane prepolymer for use as that part isocyanate group is closed.
2, under nitrogen protection, in the reaction vessel that agitator, thermometer, condensation reflux unit are housed, by-NCO and-NH 2amount of substance is than being 1:2.1, the 300g amino silicones molecular-weight average adding the dissolving of 120g tetrahydrofuran (THF) is 6000), slowly add the base polyurethane prepolymer for use as in 110g step 1, at 20 DEG C, insulation reaction is after 2 hours, add 7.32g Glacial acetic acid, underpressure distillation is except desolventizing again, obtains the cation type polyurethane modified organic silicon water repllents that molecular-weight average is 17500.
See accompanying drawing 3, it is the infrared spectrum of above-mentioned cation type polyurethane modified organic silicon water repllents.3765cm in figure -1place is the weak absorbing peak of primary amine groups, 3314cm -1place is N-H stretching vibration peak, 1719cm -1place is the C=O stretching vibration peak of carbamate and ester group, 1671cm -1place is the C=N stretching vibration peak of methyl ethyl ketoxime blocked isocyanate base, 1533cm -1the N-H formation vibration that place is carbamate and C-N stretching vibration peak, 1257cm -1place is C-O stretching vibration in ester group and-Si-CH 3the sum of fundamental frequencies peak of middle methyl formation vibration, 1089cm -1place is the charateristic avsorption band of Si-O-Si, 809cm -1place is the stretching vibration peak of Si-C, simultaneously 2270cm -1near do not occur showing the absorption peak of-NCO to have obtained polyurethane-modified organosilicon water repllents.
By cation type polyurethane modified organic silicon water repllents prepared by embodiment 1 ~ 3, by following finishing technique to cotton, wash/cotton and Polyester Textiles arranges, and the water repellency of textiles before and after arranging, rebound resilience, washing fastness to be tested.
Finishing technique: dressing liquid concentration is 50g/L(water repllents solid content is 30%), bath raio is 30:1.Padding finishing liquid (two leachings two are rolled, mangle expression 80%) → dry (90 DEG C, 2min) → bake (160 DEG C, 1min).
Measure of merit:
The water repellency of textiles is arranged by AATCC22-2005 " textiles water repellency is tested: spraying process " test; The rebound resilience of textiles is arranged by GB/T3819-1997 " mensuration of textile fabric wrinkle recovery property replys horn cupping " test; The wash durability of textiles is arranged by GB/T8629-2001 " Textile Test home washings and drying program " test.
The cation type polyurethane modified organic silicon water repllents prepared of embodiment 1 ~ 3 cotton, wash/the application performance test result of cotton and Polyester Textiles is as shown in table 1, table 2, table 3.
The salient features of table 1 cotton fabric after cation type polyurethane modified organic silicon water repllents arranges
/ main property the performance of cotton fabric washed by table 2 after cation type polyurethane modified organic silicon water repllents arranges
The salient features of table 3 polyester piece good after cation type polyurethane modified organic silicon water repllents arranges
To sum up, the film that the cation type polyurethane modified organic silicon water repllents adopting method of the present invention to prepare is formed has excellent elasticity, low-temperature flexibility, solvent resistance, with electronegative fiber, there is excellent avidity, can react with fabric fibre surface group simultaneously; The water repellency of arrangement textiles can be improved and improve feel, increasing rebound resilience, also can improve textiles after arranging and refuse the washing fastness of water.The more important thing is, after washing 10 times, the water repellency of yarn fabric still excellent, feel is still soft, this has no report in the prior art.

Claims (10)

1. a preparation method for cation type polyurethane modified organic silicon water repllents, is characterized in that, comprises the following steps:
(1) polyester diol, TriMethylolPropane(TMP) and organo-tin compound are added in reactor, under nitrogen atmosphere, regulate temperature of reaction to be 55 ~ 60 DEG C; Then isoflurane chalcone diisocyanate is dripped; Then regulate temperature of reaction to be 85 ~ 90 DEG C, react 2 ~ 3 hours; Then temperature of reaction is regulated to be 60 ~ 65 DEG C; Add positively charged ion chainextender and tetrahydrofuran (THF) again, continue reaction 1 ~ 2 hour; Then in reaction solution, add methyl ethyl ketoxime, continue reaction 1 ~ 1.5 hour, obtain base polyurethane prepolymer for use as; With the quality that the quality sum of polyester diol and isoflurane chalcone diisocyanate is reactant, the mass ratio of reactant, trihydroxy methyl propane, organo-tin compound and positively charged ion chainextender is 1: (0.01 ~ 0.03): (0.0001 ~ 0.0002): (0.06 ~ 0.09);
(2) amino silicones is added in the reactor with tetrahydrofuran (THF); Then above-mentioned base polyurethane prepolymer for use as is added, under nitrogen atmosphere, in 20 ~ 30 DEG C of reactions 1 ~ 2 hour; Then Glacial acetic acid is added; Again except namely desolventizing obtains cation type polyurethane modified organic silicon water repllents.
2. the preparation method of cation type polyurethane modified organic silicon water repllents according to claim 1, is characterized in that: the molecular-weight average of described polyester diol is 960 ~ 1388; The molecular-weight average of described amino silicones is 5000 ~ 8000.
3. the preparation method of cation type polyurethane modified organic silicon water repllents according to claim 1, it is characterized in that: in step (1), described organo-tin compound is dibutyl tin laurate; Described polyester diol is polyneopentyl glycol adipate glycol; Described positively charged ion chainextender is N methyldiethanol amine.
4. the preparation method of cation type polyurethane modified organic silicon water repllents according to claim 1, it is characterized in that: in step (1), the quality of tetrahydrofuran (THF) is 5 ~ 15% of reactant quality; By mol, methyl ethyl ketoxime consumption is 30 ~ 40% with isocyanate-based compound in reaction solution; The mol ratio of the isocyanate group of isoflurane chalcone diisocyanate and the hydroxyl of polyester diol is (1.1 ~ 1.3): 1.
5. the preparation method of cation type polyurethane modified organic silicon water repllents according to claim 1, it is characterized in that: in step (2), the mol ratio of the isocyanate group of base polyurethane prepolymer for use as and the amido of amino silicones is 1: (2 ~ 2.2); The quality of tetrahydrofuran (THF) be base polyurethane prepolymer for use as and amino silicones quality and 20 ~ 30%; Underpressure distillation is utilized to remove desolventizing.
6. the preparation method of cation type polyurethane modified organic silicon water repllents according to claim 1, is characterized in that: in step (1), described polyester diol adds in reactor after drying treatment again; Isoflurane chalcone diisocyanate dropwised in 2 ~ 3 hours.
7. the cation type polyurethane modified organic silicon water repllents prepared of the preparation method of any one cation type polyurethane modified organic silicon water repllents according to claims 1 to 6.
8. cation type polyurethane modified organic silicon water repllents according to claim 7, is characterized in that: the chemical structural formula of described cation type polyurethane modified organic silicon water repllents is as follows:
Wherein R is ; R 1for , 4≤m≤6, R 2for , 65≤n≤105.
9. the application of cation type polyurethane modified organic silicon water repllents in fabric water repellent finish described in claim 8.
10. application according to claim 9, is characterized in that: described fabric is cotton fabric, polyester piece good or polyester-cotton fabric.
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CN108424502A (en) * 2018-02-27 2018-08-21 合肥微晶材料科技有限公司 A kind of multifunctional monomer and the low square resistance flexible transparent conducting film based on it
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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
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CN112745473A (en) * 2021-01-15 2021-05-04 禾瑞（漳州）助剂有限公司 High-water-pressure washing-resistant polyurethane primer resin for textile coating and preparation method thereof
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CN107059405A (en) * 2017-03-01 2017-08-18 苏州依司特新材料科技有限公司 A kind of polyurethane-modified organosilicon water repellent and antibacterial finishing agent, preparation method and application
CN108659187B (en) * 2017-03-30 2021-02-05 合肥工业大学 Hydrophilic/hydrophobic polyurethane based on carbon dioxide regulation and control and preparation method thereof
CN108659187A (en) * 2017-03-30 2018-10-16 合肥工业大学 One kind is based on carbon dioxide regulation and control parent/hydrophobic polyurethane and preparation method thereof
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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
CN112281493A (en) * 2020-11-16 2021-01-29 五邑大学 Fluoride-free waterproof finishing agent and preparation method thereof
CN112745473A (en) * 2021-01-15 2021-05-04 禾瑞（漳州）助剂有限公司 High-water-pressure washing-resistant polyurethane primer resin for textile coating and preparation method thereof
CN114214843A (en) * 2021-12-21 2022-03-22 绍兴兆丰绒织品有限公司 Finishing process of flame-retardant polyester
CN114214843B (en) * 2021-12-21 2024-01-30 绍兴兆丰绒织品有限公司 Finishing process of flame-retardant polyester
CN114261168A (en) * 2021-12-28 2022-04-01 浙江东进新材料有限公司 Waterproof moisture-permeable functional fabric

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