CN103709364A - Preparation method of quaternary ammonium salt chitosan and organic silicon composite modified cationic water-based polyurethane fixing agent - Google Patents
Preparation method of quaternary ammonium salt chitosan and organic silicon composite modified cationic water-based polyurethane fixing agent Download PDFInfo
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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
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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
- C08G18/0804—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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4081—Mixtures of compounds of group C08G18/64 with other macromolecular compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
- C08G18/6484—Polysaccharides and derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6681—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6688—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3271
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
- D06P5/02—After-treatment
- D06P5/04—After-treatment with organic compounds
- D06P5/08—After-treatment with organic compounds macromolecular
Abstract
The invention relates to the technical field of fixing agent, and provides a preparation method of quaternary ammonium salt chitosan and organic silicon composite modified cationic water-based polyurethane fixing agent. When being used for a fixing aftertreatment process of textile printing and dyeing, the fixing agent prepared through the method can effectively enhance dry/wet rubbing color fastness of textile. The preparation method mainly comprises the following steps: (1) performing quaternary ammonium salt chitosan modified polyurethane prepolymer reaction; (2) performing organic silicon terminating reaction; and (3) neutralizing, and performing ionizing reaction.
Description
Technical field
The present invention relates to laking agent technical field, relate in particular to the preparation method of a kind of Quaternary Ammonium Salt of Chitosan and the composite modified cation water-borne polyurethane color fixing agent of organosilicon.
Background technology
Cotton fabric adopts after anionic dyestuff dyeing, conventionally will carry out fixation treatment, to improve its wet treatment colour fastness.Tradition laking agent is eliminated owing to containing free formaldehyde, and novel non-formaldehyde laking agent continues to bring out.Use different laking agent can improve the colour fastness of dissimilar dyestuff on fabric, while adopting general aldehyde-free colour stabilizer, if it is still very difficult so far above to improve 3 grades of wet rubbing fastness.
Urethane is a class laking agent that paid close attention to by people, and water-borne polyurethane color fixing agent refers to take the polyurethane dispersions system that water is medium.As novel non-formaldehyde laking agent, it forms film by sticking to dye molecule surface, and can react with active group on dye well fiber, thereby improves the crock fastness of fabric.Its not only have do not fire, the advantage such as nontoxic, free from environmental pollution, save energy, but also improved the performance such as wear resistance, shrink resistance, waterproof and moisture permeability of DYED FABRICS.Yet because aqueous polyurethane synthesis material mostly is bifunctional compound, and its in building-up process grafting ionic group, therefore exist poor water resistance after simple aqueous polyurethane film forming, the shortcoming such as thermostability is not good enough and glossiness is not good enough.
Therefore in order better to improve the over-all properties of water-borne polyurethane color fixing agent, the character of combination dye and fabric carries out to aqueous polyurethane the focus that modification has become current research.
Summary of the invention
Therefore, for above content, the invention provides the preparation method of a kind of Quaternary Ammonium Salt of Chitosan and the composite modified cation water-borne polyurethane color fixing agent of organosilicon, utilize the laking agent that the method makes to be applied to fabric printing fixation last handling process, can effectively improve the dry wet friction colour fastness of fabric.
For achieving the above object, the present invention is achieved by the following technical solutions: the preparation method of a kind of Quaternary Ammonium Salt of Chitosan and the composite modified cation water-borne polyurethane color fixing agent of organosilicon, comprises the following steps:
(1) Quaternary Ammonium Salt of Chitosan modified polyurethane prepolymer reaction: by the polyvalent alcohol monomer of 30～45 weight parts at 89～92 ℃, 1～1.2h dewaters under 0.08～0.10MPa vacuum tightness, regulate pre-polymerization temperature to 70～80 ℃, the isocyanate-monomer that adds 20～28 weight parts of drying, the Quaternary Ammonium Salt of Chitosan monomer of 1～5 weight part and the catalyzer of 0.3～0.5 weight part, drip the cationic hydrophilic monomer of 2～7 weight parts simultaneously, wherein cationic hydrophilic monomer is 30%～35% with solvent cut to massfraction in advance, time for adding is 2～3h, obtain the Quaternary Ammonium Salt of Chitosan modified polyurethane prepolymer that contains terminal isocyanate group, in prepolymerization reaction process, controlling R value is 1.50～2.50, in reaction process by adding solvent to regulate the viscosity of prepolymer, wherein R value refers to the mol ratio of NCO/OH, and wherein NCO is isocyanate group, and OH is the hydroxyl summation of polyvalent alcohol, Quaternary Ammonium Salt of Chitosan monomer and cationic hydrophilic monomer,
(2) organosilicon end capping reaction: by the Quaternary Ammonium Salt of Chitosan modified polyurethane prepolymer that contains terminal isocyanate group being synthesized in step (1) under 60～80 ℃ of water bath condition, add aminosilane monomer end-capping reagent, adopt infrared spectroscopic determination NCO content, reach some reaction of theoretical value R=1.05～1.30 and finish;
(3) neutralization, ion reaction: the product that step (2) is obtained is cooled to below 40 ℃, according to degree of neutralization, add neutralizing agent to neutralize stirring, making degree of neutralization is 110～120%, stir ionization 0.5～1 h, according to solid content, add deionized water, high-speed stirring is disperseed 10～15 min, obtains outward appearance and is light yellow transparent or semitransparent, the modified cation water-borne polyurethane color fixing agent that solid content is 30%～40%.
Further improve and be: the consumption of the middle aminosilane monomer end-capping reagent of described step (2) is according to the theoretical R value before end-blocking and finally require the R value of product to determine.
Further improve and be: the described polyvalent alcohol monomer in step (1) is polyether polyol or polyester polyol or polyester polyethers polyol blend; Described Quaternary Ammonium Salt of Chitosan monomer is HACC or carboxy-methyl hydroxy propyl trimethyl ammonium chloride chitosan; Described isocyanate-monomer be in isophorone diisocyanate (IPDI), tolylene diisocyanate (TDI), 4,4 '-diphenylmethanediisocyanate (MDI), poly methylene poly phenyl poly isocyanate (PAPI), hexamethylene diisocyanate (HDI), Methylcyclohexyl diisocyanate (HTDI) any one or two or more with arbitrarily than the mixture mixing; Described catalyzer is dibutyl tin laurate, sad pressure tin, triethylamine, diethylenetriamine, dimethyl cetylamine, two dimethyl amine benzyl ethyl ether, nitrogen Ethylmorphine quinoline, trolamine, thanomin, pyridine or N, any one in N '-lutidine; Described cationic hydrophilic monomer be in nitrogen methyldiethanolamine, diethanolamine, pyridyl diethanolamine, trolamine, tri-isopropanolamine, nitrogen ethyldiethanolamine, diisopropanolamine (DIPA) any one or two or more with arbitrarily than the mixture mixing; Described solvent is any one in 1-Methyl-2-Pyrrolidone (NMP), DMF (DMF), butanone, acetone, toluene, ethyl acetate.
Further improve and be: the structural formula of described HACC is:
Wherein, n is 0 to 310 integer.
Further improve and be: the structural formula of described carboxy-methyl hydroxy propyl trimethyl ammonium chloride chitosan is following two kinds:
The first the second
Wherein, n is 0 to 310 integer.
Further improve and be: aminosilane monomer described in step (2) is any one in 3-TSL 8330 KH540, γ-aminopropyl triethoxysilane KH550 and N-β-(aminoethyl)-γ-aminopropyl methyl dimethoxysilane KH602.
Further improve and be: the neutralizing agent described in step (3) is any one in Glacial acetic acid, dilute hydrochloric acid, dilute sulphuric acid, phosphoric acid, methyl-sulfate.
By adopting aforementioned techniques scheme, the invention has the beneficial effects as follows: operational path of the present invention can be divided into three steps: the first step is the reaction of Quaternary Ammonium Salt of Chitosan modified polyurethane prepolymer, by polyvalent alcohol monomer, Quaternary Ammonium Salt of Chitosan monomer, cationic hydrophilic monomer and isocyanic ester, carry out prepolymerization reaction, generate Quaternary Ammonium Salt of Chitosan modified polyurethane prepolymer; Second step is organosilicon end capping reaction, adopts excessive isocyanate reaction after aminosilane monomer and pre-polymerization, makes part isocyanic ester inactivation at normal temperatures; The 3rd step is acid neutralization, and ion reaction, according to the requirement of degree of neutralization and solid content, carries out acid neutralization to the performed polymer after end-blocking, and be emulsifiable in water, forms Quaternary Ammonium Salt of Chitosan and the composite modified cation aqueous polyurethane emulsion of organosilicon.
In the modified cation water-borne polyurethane color fixing agent that adopts method of the present invention to prepare, contain a large amount of center of positive charge and hydrogen bond center, can be combined into ionic linkage with the negative charge of cellulose fiber peacekeeping dyestuff, the siloxane structure of simultaneously introducing, its siloxane bond can form cross-linking system in fabric face hydrolysis, thereby improve thermotolerance, water tolerance and the snappiness of aqueous polyurethane cured film, and the feel of giving fabric sofetening, the water-repellancy of fabric also makes moderate progress; In addition, have quaternary ammonium salt cationic group and silicon hydroxyl (SiOH) in product structure, wherein quaternary ammonium salt cationic group has stronger polarity, can form with the anionic reactive of dyestuff insoluble dye salt precipitation, thus the dyestuff on fixed fabric; Silicon hydroxyl (SiOH) has stronger reactive behavior, can with the active group hydroxyl (OH) of dyestuff on fabric, amino (NH
2) isoreactivity group carries out dehydration reaction in dry process, forms Chemical bond, thereby the dyestuff further on fixed fabric.Owing to also having introduced organosilicon segment on product structure, therefore to compare with the laking agent of other types, the fabric after product treatment of the present invention not only has more flexibility, smoothness, and has further improved the fastness to wet rubbing of fabric.
Product application of the present invention is in spinning post-finishing process, and environmental protection, containing formaldehyde, and have antimicrobial health care function, meet modern's life requirement, treated fabric fastness to wet rubbing can reach 4 grades, dry fastness can reach 5 grades, good hand touch, on color and luster without impact.
Embodiment
Below with reference to specific embodiment, describe embodiments of the present invention in detail, to the present invention, how utilisation technology means solve technical problem whereby, and the implementation procedure of reaching technique effect can fully understand and implement according to this.
If do not specialize, the conventional means that the technique means adopting in embodiment is well known to those skilled in the art, the reagent adopting and product are also and can business obtain.The source of agents useful for same, trade(brand)name and be necessary to list its moiety person are all indicated when occurring first.
Embodiment mono-
A preparation method for Quaternary Ammonium Salt of Chitosan and the composite modified cation water-borne polyurethane color fixing agent of organosilicon, comprises the following steps:
20.0 g polyoxypropyleneglycols (N220) are added in reaction vessel, mix and blend, thermostatically heating under 90 ℃ of oil bath conditions, vacuumize dehydration 1 h, vacuum tightness is 0.098MPa, be cooled to 80 ℃, add 11.1 g IPDI, 1.94 g HACCs and di-n-butyltin dilaurate 0.15 g, drip 1.2 g nitrogen-methyl glycol amine (being 35% with acetone diluted to massfraction), until the nco value in system obtains prepolymer while substantially reaching theoretical value, theoretical R value is 1.56, then be cooled to 60 ℃, add 3-TSL 8330 (KH540) 1.55 g, treat that end capping is complete, theoretical R value is 1.20.Oil bath is cooled to 40 ℃, with acetone (approximately 3～5 g) dilution, reduces viscosity, slowly adds 0.73 g Glacial acetic acid neutralize ions (degree of neutralization is 120%) reaction 0.5 h; Finally under 1500 r/min high-speed stirring, add 85.0 g deionized waters, reaction 0.5 h, obtaining theoretical solid content is 30.13%, light yellow transparent emulsion.Wherein, degree of neutralization refers to the molar percentage of neutralizing agent and cationic hydrophilic monomer.
The structural formula of described HACC is:
Wherein, n=100.
Embodiment bis-
A preparation method for Quaternary Ammonium Salt of Chitosan and the composite modified cation water-borne polyurethane color fixing agent of organosilicon, comprises the following steps:
20.0 g polyoxypropyleneglycols (N220) are added in reaction vessel, mix and blend, thermostatically heating under 90 ℃ of oil bath conditions, vacuumizes dehydration 1 h, and vacuum tightness is 0.098MPa.Be cooled to 80 ℃, add 11.1 g IPDI, 1.29 g carboxy-methyl hydroxy propyl trimethyl ammonium chloride chitosans and di-n-butyltin dilaurate 0.15 g, drip 1.2 g nitrogen-methyl glycol amine (being 35% with acetone diluted to massfraction), until the nco value in system obtains prepolymer while substantially reaching theoretical value, theoretical R value is 1.78, is then cooled to 60 ℃, adds γ-aminopropyl triethoxysilane (KH550) 1.89 g, band end capping is complete, and theoretical R value is 1.20.Oil bath is cooled to 40 ℃, with acetone (approximately 3～5 g) dilution, reduces viscosity, slowly adds 0.73 g Glacial acetic acid neutralize ions (degree of neutralization is 120%) reaction 0.5 h; Finally under 1500r/min high-speed stirring, add 75.0 g deionized waters, reaction 0.5 h, obtaining theoretical solid content is 32.65%, light yellow transparent emulsion.Wherein degree of neutralization refers to the molar percentage of neutralizing agent and cationic hydrophilic monomer.
The structural formula of carboxy-methyl hydroxy propyl trimethyl ammonium chloride chitosan is:
Wherein, n=150.
Embodiment tri-
A preparation method for Quaternary Ammonium Salt of Chitosan and the composite modified cation water-borne polyurethane color fixing agent of organosilicon, comprises the following steps:
20.0 g polyoxypropyleneglycols (N220) are added in reaction vessel, mix and blend, thermostatically heating under 90 ℃ of oil bath conditions, vacuumizes dehydration 1 h, and vacuum tightness is 0.098MPa.Be cooled to 80 ℃, add 11.1 g IPDI, 0.81 g HACC and di-n-butyltin dilaurate 0.15 g, drip 1.2 g nitrogen-methyl glycol amine (being 35% with acetone diluted to massfraction), until the nco value in system obtains prepolymer while substantially reaching theoretical value, theoretical R value is 2.00, then be cooled to 60 ℃, add N-β-(aminoethyl)-γ-aminopropyl methyl dimethoxysilane (KH602) 2.15 g, band end capping is complete, and theoretical R value is 1.20.Oil bath is cooled to 40 ℃, with acetone (approximately 3～5 g) dilution, reduces viscosity, slowly adds 0.73 g Glacial acetic acid neutralize ions (degree of neutralization is 120%) reaction 0.5 h; Finally under stirring, 1500r/min adds 80.0 g deionized waters, reaction 0.5 h, and obtaining theoretical solid content is 31.12%, light yellow transparent emulsion.Wherein degree of neutralization refers to the molar percentage of neutralizing agent and cationic hydrophilic monomer.
The structural formula of HACC is:
Wherein, n=200.
Embodiment tetra-
A preparation method for Quaternary Ammonium Salt of Chitosan and the composite modified cation water-borne polyurethane color fixing agent of organosilicon, comprises the following steps:
20.0 g polyoxypropyleneglycols (N220) are added in reaction vessel, mix and blend, thermostatically heating under 90 ℃ of oil bath conditions, vacuumizes dehydration 1 h, and vacuum tightness is 0.098MPa.Be cooled to 80 ℃, add 11.1 g IPDI, 0.32 g HACC and di-n-butyltin dilaurate 0.15 g, drip 1.2 g nitrogen-methyl glycol amine (being 35% with acetone diluted to massfraction), until the nco value in system obtains prepolymer while substantially reaching theoretical value, theoretical R value is 2.27, is then cooled to 60 ℃, adds 3-TSL 8330 (KH540) 2.41 g, band end capping is complete, and theoretical R value is 1.20.Oil bath is cooled to 40 ℃, with acetone (approximately 3～5 g) dilution, reduces viscosity, slowly adds 0.73 g Glacial acetic acid neutralize ions (degree of neutralization is 120%) reaction 0.5 h; Finally under stirring, 1500r/min adds 80.0 g deionized waters, reaction 0.5 h, and obtaining theoretical solid content is 30.98%, light yellow transparent emulsion.Wherein degree of neutralization refers to the molar percentage of neutralizing agent and cationic hydrophilic monomer.
The structural formula of HACC is:
Wherein, n=300.
Embodiment five
A preparation method for Quaternary Ammonium Salt of Chitosan and the composite modified cation water-borne polyurethane color fixing agent of organosilicon, comprises the following steps:
20.0 g polyoxypropyleneglycols (N220) are added in reaction vessel, mix and blend, thermostatically heating under 90 ℃ of oil bath conditions, vacuumizes dehydration 1 h, and vacuum tightness is 0.098MPa.Be cooled to 80 ℃, add 11.1 g IPDI, 0.05 g carboxy-methyl hydroxy propyl trimethyl ammonium chloride chitosan and di-n-butyltin dilaurate 0.15 g, drip 1.2 g nitrogen-methyl glycol amine (being 35% with acetone diluted to massfraction), until the nco value in system obtains prepolymer while substantially reaching theoretical value, theoretical R value is 2.46, is then cooled to 60 ℃, adds 3-TSL 8330 (KH540) 2.55 g, band end capping is complete, and theoretical R value is 1.20.Oil bath is cooled to 40 ℃, with acetone (approximately 3～5 g) dilution, reduces viscosity, slowly adds 0.73 g Glacial acetic acid neutralize ions (degree of neutralization is 120%) reaction 0.5 h; Finally under stirring, 1500r/min adds 80.0 g deionized waters, reaction 0.5 h, and obtaining theoretical solid content is 30.90%, light yellow transparent emulsion.Wherein degree of neutralization refers to the molar percentage of neutralizing agent and cationic hydrophilic monomer.
The structural formula of carboxy-methyl hydroxy propyl trimethyl ammonium chloride chitosan is:
Wherein, n=200.
Above-described embodiment products obtained therefrom and two kinds of commercially available laking agent are done to fixation experiment, and test result is as follows:
Remarks: 1. crock fastness testing method is pressed GB/T3920-2008 < < textile color stability test colour fastness to rubbing > > method mensuration;
2. soaping fastness testing method is pressed GB/T3921-2008 < < textile color stability test colour fastness to washing > > method mensuration.
Color fixing agent Y and laking agent G are commercially available.
As can be seen from the above table, the present invention synthesize with two kinds of commercially available laking agent comparisons, consumption is few, dry fastness can significantly improve 1.0～1.5 grades, fastness to wet rubbing can improve 1.0～1.5 grades, and the fabrics feel soft after processing, and its net effect is obviously better than the latter.
Operational path of the present invention can be divided into three steps: the first step is the reaction of Quaternary Ammonium Salt of Chitosan modified polyurethane prepolymer, by polyvalent alcohol monomer, Quaternary Ammonium Salt of Chitosan monomer, cationic hydrophilic monomer and isocyanic ester, carry out prepolymerization reaction, generate Quaternary Ammonium Salt of Chitosan modified polyurethane prepolymer; Second step is organosilicon end capping reaction, adopts excessive isocyanate reaction after aminosilane monomer and pre-polymerization, makes part isocyanic ester inactivation at normal temperatures; The 3rd step is acid neutralization, and ion reaction, according to the requirement of degree of neutralization and solid content, carries out acid neutralization to the performed polymer after end-blocking, and be emulsifiable in water, forms Quaternary Ammonium Salt of Chitosan and the composite modified cation aqueous polyurethane emulsion of organosilicon.
In the modified cation water-borne polyurethane color fixing agent that adopts method of the present invention to prepare, contain a large amount of center of positive charge and hydrogen bond center, can be combined into ionic linkage with the negative charge of cellulose fiber peacekeeping dyestuff, the siloxane structure of simultaneously introducing, its siloxane bond can form cross-linking system in fabric face hydrolysis, thereby improve thermotolerance, water tolerance and the snappiness of aqueous polyurethane cured film, and the feel of giving fabric sofetening, the water-repellancy of fabric also makes moderate progress; In addition, have quaternary ammonium salt cationic group and silicon hydroxyl (SiOH) in product structure, wherein quaternary ammonium salt cationic group has stronger polarity, can form with the anionic reactive of dyestuff insoluble dye salt precipitation, thus the dyestuff on fixed fabric; Silicon hydroxyl (SiOH) has stronger reactive behavior, can with the active group hydroxyl (OH) of dyestuff on fabric, amino (NH
2) isoreactivity group carries out dehydration reaction in dry process, forms Chemical bond, thereby the dyestuff further on fixed fabric.Owing to also having introduced organosilicon segment on product structure, therefore to compare with the laking agent of other types, the fabric after product treatment of the present invention not only has more flexibility, smoothness, and has further improved the fastness to wet rubbing of fabric.
Product application of the present invention is in spinning post-finishing process, and environmental protection, containing formaldehyde, and have antimicrobial health care function, meet modern's life requirement, treated fabric fastness to wet rubbing can reach 4 grades, dry fastness can reach 5 grades, good hand touch, on color and luster without impact.
Above record, only, for utilizing the embodiment of this origination techniques content, modification, variation that any those skilled in the art use this creation to do, all belong to the scope of the claims that this creation is advocated, and be not limited to those disclosed embodiments.
Claims (7)
1. a preparation method for Quaternary Ammonium Salt of Chitosan and the composite modified cation water-borne polyurethane color fixing agent of organosilicon, is characterized in that, comprises the following steps:
(1) Quaternary Ammonium Salt of Chitosan modified polyurethane prepolymer reaction: by the polyvalent alcohol monomer of 30～45 weight parts at 89～92 ℃, 1～1.2h dewaters under 0.08～0.10MPa vacuum tightness, regulate pre-polymerization temperature to 70～80 ℃, the isocyanate-monomer that adds 20～28 weight parts of drying, the Quaternary Ammonium Salt of Chitosan monomer of 1～5 weight part and the catalyzer of 0.3～0.5 weight part, drip the cationic hydrophilic monomer of 2～7 weight parts simultaneously, wherein cationic hydrophilic monomer is 30%～35% with solvent cut to massfraction in advance, time for adding is 2～3h, obtain the Quaternary Ammonium Salt of Chitosan modified polyurethane prepolymer that contains terminal isocyanate group, in prepolymerization reaction process, controlling R value is 1.50～2.50, in reaction process by adding solvent to regulate the viscosity of prepolymer, wherein R value refers to the mol ratio of NCO/OH, and wherein NCO is isocyanate group, and OH is the hydroxyl summation of polyvalent alcohol, Quaternary Ammonium Salt of Chitosan monomer and cationic hydrophilic monomer,
(2) organosilicon end capping reaction: by the Quaternary Ammonium Salt of Chitosan modified polyurethane prepolymer that contains terminal isocyanate group being synthesized in step (1) under 60～80 ℃ of water bath condition, add aminosilane monomer end-capping reagent, adopt infrared spectroscopic determination NCO content, reach some reaction of theoretical value R=1.05～1.30 and finish;
(3) neutralization, ion reaction: the product that step (2) is obtained is cooled to below 40 ℃, according to degree of neutralization, add neutralizing agent to neutralize stirring, making degree of neutralization is 110～120%, stir ionization 0.5～1 h, according to solid content, add deionized water, high-speed stirring is disperseed 10～15 min, obtains outward appearance and is light yellow transparent or semitransparent, the modified cation water-borne polyurethane color fixing agent that solid content is 30%～40%.
2. the preparation method of Quaternary Ammonium Salt of Chitosan according to claim 1 and the composite modified cation water-borne polyurethane color fixing agent of organosilicon, is characterized in that: the consumption of the middle aminosilane monomer end-capping reagent of described step (2) is according to the theoretical R value before end-blocking and finally require the R value of product to determine.
3. the preparation method of Quaternary Ammonium Salt of Chitosan according to claim 1 and the composite modified cation water-borne polyurethane color fixing agent of organosilicon, is characterized in that: the described polyvalent alcohol monomer in step (1) is polyether polyol or polyester polyol or polyester polyethers polyol blend; Described Quaternary Ammonium Salt of Chitosan monomer is HACC or carboxy-methyl hydroxy propyl trimethyl ammonium chloride chitosan; Described isocyanate-monomer be in isophorone diisocyanate (IPDI), tolylene diisocyanate (TDI), 4,4 '-diphenylmethanediisocyanate (MDI), poly methylene poly phenyl poly isocyanate (PAPI), hexamethylene diisocyanate (HDI), Methylcyclohexyl diisocyanate (HTDI) any one or two or more with arbitrarily than the mixture mixing; Described catalyzer is dibutyl tin laurate, sad pressure tin, triethylamine, diethylenetriamine, dimethyl cetylamine, two dimethyl amine benzyl ethyl ether, nitrogen Ethylmorphine quinoline, trolamine, thanomin, pyridine or N, any one in N '-lutidine; Described cationic hydrophilic monomer be in nitrogen methyldiethanolamine, diethanolamine, pyridyl diethanolamine, trolamine, tri-isopropanolamine, nitrogen ethyldiethanolamine, diisopropanolamine (DIPA) any one or two or more with arbitrarily than the mixture mixing; Described solvent is any one in 1-Methyl-2-Pyrrolidone (NMP), DMF (DMF), butanone, acetone, toluene, ethyl acetate.
4. the preparation method of Quaternary Ammonium Salt of Chitosan according to claim 3 and the composite modified cation water-borne polyurethane color fixing agent of organosilicon, is characterized in that, the structural formula of described HACC is:
Wherein, n is 0 to 310 integer.
5. the preparation method of Quaternary Ammonium Salt of Chitosan according to claim 3 and the composite modified cation water-borne polyurethane color fixing agent of organosilicon, is characterized in that, the structural formula of described carboxy-methyl hydroxy propyl trimethyl ammonium chloride chitosan is following two kinds:
The first the second
Wherein, n is 0 to 310 integer.
6. according to the Quaternary Ammonium Salt of Chitosan described in claim 1 or 2 or 3 or 4 or 5 and the preparation method of the composite modified cation water-borne polyurethane color fixing agent of organosilicon, it is characterized in that: aminosilane monomer described in step (2) is any one in 3-TSL 8330 KH540, γ-aminopropyl triethoxysilane KH550, N-β-(aminoethyl)-γ-aminopropyl methyl dimethoxysilane KH602.
7. the preparation method of Quaternary Ammonium Salt of Chitosan according to claim 6 and the composite modified cation water-borne polyurethane color fixing agent of organosilicon, is characterized in that: the neutralizing agent described in step (3) is any one in Glacial acetic acid, dilute hydrochloric acid, dilute sulphuric acid, phosphoric acid, methyl-sulfate.
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