CN103922944B - A kind of crosslinkable quaternary ammonium salt water-soluble cationic monomer and its preparation method and application - Google Patents

A kind of crosslinkable quaternary ammonium salt water-soluble cationic monomer and its preparation method and application Download PDF

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CN103922944B
CN103922944B CN201410128942.8A CN201410128942A CN103922944B CN 103922944 B CN103922944 B CN 103922944B CN 201410128942 A CN201410128942 A CN 201410128942A CN 103922944 B CN103922944 B CN 103922944B
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water
cationic monomer
soluble cationic
monomer
quaternary ammonium
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CN103922944A (en
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张红燕
金鲜花
项宝军
张丽阳
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Zhejiang Chuanhua Daily Necessities Co ltd
Zhejiang Chuanhua Functional New Material Co ltd
Transfar Zhilian Co Ltd
Hangzhou Transfar Fine Chemicals Co Ltd
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Zhejiang Transfar Co Ltd
Hangzhou Transfar Commodity Co Ltd
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Abstract

The invention discloses a kind of crosslinkable water-soluble cationic monomer and its preparation method and application.Existing quaternary ammonium salt water-soluble cationic monomer the most all uses and natural polymers carries out cationization or monomer is first polymerized cationization both approaches the most again, but the cation ionization degree of the polymer obtained by both approaches is the most relatively low, do not reach industrial required performance.Crosslinkable water-soluble cationic monomer of the present invention is to be that raw material is prepared by steps such as substitution reaction, ring-opening reaction and desolventizings by alkyl secondary amine, epoxyhalopropane, pi-allyl tertiary amine and diluted acid.The crosslinkable water-soluble cationic monomer of the present invention can aggregate into crosslinkable copolymer or homopolymer with olefinic unsaturated comonomer, and homopolymer with it as base and copolymer have that cations is high and adjustable, molecular weight is big, cationic degree is high, can dissolve well and the advantages such as strong intermolecular interaction can occur with various polarity material in water.

Description

A kind of crosslinkable quaternary ammonium salt water-soluble cationic monomer and its preparation method and application
Technical field
The invention belongs to cationic monomer field, relate to crosslinkable soluble quaternary ammonium cationoid compound, especially one Plant quaternary ammonium salt water-soluble cationic monomer of two ends polymerizable and band crosslinked group (hydroxyl) and its preparation method and application.
Background technology
Cationic polymer is a kind of important functional high molecule material, and it has cationic characteristic in macromolecular structure, Thus be widely used in many fields.The common application of cationic polymer includes: in textile dyeing and finishing industry Middle as color fixing agent, antistatic additive and antibacterial;As anti-dyestuff colour contamination agent, colour fixative, anti-quiet in daily-use chemical industry industry Electricity softening agent and antibacterial etc.;As paper strengthening agent, printing-ink retention agent etc. in paper industry;In sewage disposal As cationic flocculant, sludge dehydrating agent;As drilling fluid, oil field emulsifying agent etc. in oilfield applications.
At present, studying more cationic polymer has QAS polymer, quaternary alkylphosphonium salt polymer and season sulfosalt polymer, should With the widest, product category most be QAS polymer.In terms of current synthetic technology, industrial this kind of cationic polymerization The preparation of thing the most all uses and natural polymers carries out cationization or monomer is first polymerized cationization the most again Both approaches, but the cation ionization degree of the polymer obtained by both approaches is the most relatively low, does not reaches industrial required Performance.Therefore to improve the cation ionization degree of product, it is right that best bet synthesizes polymerizable cationic monomer exactly After be polymerized again, the most not only the cationic degree of polymer is high, and molecular weight and cationic degree are the most adjustable.The most conventional Cationic polymerization monomer mainly have: dimethyl diallyl ammonium chloride (DMDAAC), methylacryoyloxyethyl dimethyl chloride Change ammonium (DMAEMA), chloropropylene oxide and acrylamide etc..Such as Daniher et al. DMDAAC:N-n-methylolacrylamide=80:20 Copolymer show as color fixing agent use, result, this material is fine to the tint retention of direct dyes, and calico staining can be by not 3 grades when processing with color fixing agent bring up to 4~5 grades;Lv Shenghua et al. is used as acrylamide (AM) with the copolymer of DMDAAC Flocculant, has good flocculating effect, and this base polymer is also used in shampoo;The propylene phthalein amine of Zhang Long et al. synthesis With the cation copolymer of propylene phthalein oxygen ethyl alkyl dimethyl ammonium chloride, having good flocculation ability, its flocculation is obvious It is better than inorganic flocculating agent;Horse happiness equality people, also with epoxychloropropane, polyethylene polyamine as raw material, has synthesized organic cation and has gathered Compound, and it is prevented, and the performances such as swollen, flocculation and inhibition are studied, find that hydration and expansion of clay is had well by polymer Inhibition etc..
Along with the continuous appearance of industrial expansion, especially emerging industry, people's demand to Cationic Polymers Containing Quaternary Ammonium Salts Amount also can be greatly increased, and compared with demand, the domestic research to novel quaternary ammonium salt cationic polymer also seems fewer, And mostly it is confined to the common monomers such as DMDAAC, AM, chloropropylene oxide, the major part sun that performance is more preferable, topology update is clever Ion monomer relies primarily on import.These factors constrain the research of domestic Cationic Polymers Containing Quaternary Ammonium Salts the most to some extent Progress with exploitation.Therefore for adapting to the needs of China's modern industry, develop novel polymerizable cationic monomer and show already Obtain the most necessary.
Summary of the invention
An object of the present invention is to provide a kind of polymerizable, can dissolve well in water and can be with various polarity material There is the quaternary ammonium salt water-soluble cationic monomer of strong intermolecular interaction.
For reaching above-mentioned purpose, the technical solution used in the present invention is as follows: a kind of crosslinkable quaternary ammonium salt water-soluble cationic list Body, it is for having the compound of structure shown in formula (1):
In formula: R1And R2It is respectively and independently selected from C1~C6One, preferably C in alkyl1~C3One in alkyl;X is F, Cl, Br or I, preferably Cl or Br.
Crosslinkable water-soluble cationic monomer of the present invention, it is that a kind of two ends band double bond can carry out radical polymerization Quarternary ammonium salt compound, introduces water-soluble reaction group hydroxy simultaneously in structure.
Double bond is all contained at the two ends being primarily due to molecular structure, and it can carry out copolymerization with olefinic class monomer, the polymer of gained: (1) cationic degree is high, owing to just containing cation in cross-linking water-soluble cationic monomer molecular structure of the present invention Group, therefore in homopolymer with it as base or copolymer almost each construction unit containing cation group;(2) Molecular weight is big, and the cationic monomer designed by the present invention can carry out radical polymerization with other olefinic class monomer, not only can gather Closing out the bigger polymer of various desired structure molecular weight and the adjustable molecular weight of polymer, correspondingly its cationic degree also may be used Adjust;(3) cationic monomer of the present invention, possibly together with more crosslinkable water soluble group in its molecular structure Hydroxyl, so can not only improve the water solublity of heavy polymer and can also strengthen the homopolymer with it as base or copolymer And the compatibility between other polar substances and intermolecular active force, improve the properties of product.
As carried out being polymerized the cationic polymer obtained as fixation using cross-linking water-soluble cationic monomer of the present invention Agent use, owing to dye molecule is usually anionic compound, polymer and dyestuff can occur color lake between the two, can prevent dye Material comes off from fabric because of ionizing and hydrolyzes, thus improves color fastness;In addition polymer molecular weight is big, can be at fabric table Face film forming, covers caducous dyestuff, and the crosslinkable groups hydroxyl in polymer molecular structure can also be tied with cotton fiber simultaneously Activity hydroxy in structure reacts, and produces covalent bond, makes color fixing agent can anchor at fabric face firmly together with dyestuff, Thus effectively improve the dyefastness of each side.
Cross-linking water-soluble cationic monomer of the present invention carry out being polymerized the cationic polymer that obtains can also and other The high molecular polymer of anionic carries out compounding and as bafta soaping agent use, and described cationic polymer can be with molten Dyestuff in liquid forms complex, and by the synergism of other raw materials, can effectively prevent dyestuff to be again deposited on fiber Surface, the removal of the most unreacted loose colour, white ground releasing performance can be accomplished well simultaneously.
As the colour fixative used time in detergent, owing to cross-linking water-soluble cationic monomer of the present invention polymerization obtains Polymer cation degree is high, it easily with the chromogenesis complex on clothing surface, make the dyestuff on medicated clothing be difficult to dissolve in and wash Washing in liquid, thus reach tint retention, it also can prevent pigment to be infected with to medicated clothing table with the chromogenesis complex in solution Face, plays the effect preventing dye transfer, thus plays anti-colour contamination effect.
In addition to color fixing agent, soaping agent component and colour fixative, with cross-linking water-soluble cationic monomer of the present invention as base Homopolymer or copolymer can also be widely used in the fields such as oil exploitation, papermaking, mining, textile printing and dyeing, sewage disposal.
The two of the purpose of the present invention are to provide the preparation side of a kind of above-mentioned crosslinkable quaternary ammonium salt water-soluble cationic monomer Method, it is substituted by the epoxyhalopropane shown in the alkyl secondary amine shown in Formulas I, Formula II, the pi-allyl tertiary amine shown in formula III, Open loop, solvent removal step synthesize quaternary ammonium salt water-soluble cationic monomer,
Wherein R1And R2It is respectively and independently selected from C1~C6One in alkyl, X is F, Cl, Br or I, and synthetic route is as follows:
Wherein R1、R2With the implication of X as hereinbefore.
The preparation method of above-mentioned crosslinkable quaternary ammonium salt water-soluble cationic monomer, it comprises the following steps: 1) add under room temperature Adding epoxyhalopropane and water, and rise high-temperature to 30~50 DEG C, dropping mass concentration is the alkyl secondary amine aqueous solution of 33~50%, After dripping off at 30~50 DEG C insulation reaction 8~10 hours, then decompression is distilled off unreacted monomer and water, obtains compound IV;2) by step 1) the compound IV that obtains is cooled to less than 20 DEG C, and add diluted acid regulation material pH value to 4~5, drip Add pi-allyl tertiary amine and to control system temperature be 30~50 DEG C, after dripping off at 30~50 DEG C insulation reaction 8~10h, then subtract Pressure distillation, to remove unreacted monomer and water, obtains described crosslinkable quaternary ammonium salt water-soluble cationic monomer;
In abovementioned steps, the mol ratio of alkyl secondary amine, epoxyhalopropane and pi-allyl tertiary amine is: 1.0:2.0~2.8:2.0~ 3.0, diluted acid consumption is the 5~13wt% of material total amount.
As preferably, aqueous hydrochloric acid solution that described diluted acid selects mass concentration to be 36.5% or the ice vinegar that mass concentration is 33% One or both combinations in aqueous acid.
The three of the purpose of the present invention are to carry out above-mentioned quaternary ammonium salt water-soluble cationic monomer being polymerized the homopolymer obtained or being total to Polymers, is applied in oil exploitation, papermaking, mining, textile printing and dyeing, daily-use chemical industry, sewage disposal or sewage decoloring field.
Described crosslinkable water-soluble cationic monomer is polymerized by the present invention, using its homopolymer as bafta fixation Colour fixative in agent, soaping agent component and detergent uses and illustrates for special case.
Above-mentioned quaternary ammonium salt water-soluble cationic monomer carries out being polymerized the cationic polymer obtained and is applied to cotton as color fixing agent During the fixation processing and sorting of fabric, infusion process or padding method is used to process technique, when using infusion process to process, color fixing agent consumption Being 0.5~5.0%, bath raio is 1:5~50, and working liquid ph is 5.0~7.0, and color fixing temperature is 40~70 DEG C, fixation Time is 20~30min;When using padding method to process, color fixing agent consumption is 1~50g/l, and liquid carrying rate is 30~150%, roasting Drying temperature is 100~170 DEG C.
Above-mentioned quaternary ammonium salt water-soluble cationic monomer carries out being polymerized the cationic polymer that obtains should as the complex of dyestuff (as the component of soaping agent) time in the soaping agent of bafta, it is polymerized the cationic polymer obtained and is directly compounded In soaping agent, the consumption of cationic polymer is the 0.1~2.0% of soaping agent gross mass.
Above-mentioned quaternary ammonium salt water-soluble cationic monomer carries out being polymerized the cationic polymer obtained and is applied to wash as colour fixative When washing in agent, being polymerized the cationic polymer obtained and directly compound in detergent, the consumption of cationic polymer is washing The 0.1~1.0% of agent gross mass.
In above-mentioned application, the polymerization of described cationic polymer is as follows: add at normal temperatures described water solublity sun from Sub-monomer and water are also warming up to 80~85 DEG C, drip initiator, insulation reaction 3~5h at 80~85 DEG C, cooling, discharging, I.e. available required cationic polymer, hydrogen peroxide, azo two isobutyl that described initiator selects mass concentration to be 50% Nitrile hydrochlorate, potassium peroxydisulfate, Ammonium persulfate. or Ammonium persulfate. and sodium sulfite are the compositions of 3:1 in molar ratio, cause The consumption of agent is the 0.1~1.5wt% of monomer total amount.
The cross-linking water-soluble cationic monomer of the present invention has the advantages that (one) cationic degree is high, due to this Bright described cross-linking water-soluble cationic monomer molecular structure just contains cation group, the therefore homopolymer with it as base Or almost each construction unit contains cation group in copolymer;(2) molecular weight is big, the sun designed by the present invention Ion monomer can carry out radical polymerization with other olefinic class unsaturated monomer, and not only polymerizable goes out the poly-of various desired structure Compound and the adjustable molecular weight of polymer, correspondingly its cationic degree is the most adjustable;(3) cation mono of the present invention Possibly together with crosslinkable water soluble group hydroxyl in its molecular structure of body, the water of heavy polymer so can not only be improved Dissolubility, and the compatibility between the homopolymer with it as base or copolymer and other polar substances and intermolecular can also be strengthened Active force, improve product properties.
The raw material preparing cross-linking water-soluble cationic monomer of the present invention is conventional chemical products, low cost, Er Qiehe Become simple for process, preparation condition gentleness safety.
Carry out being polymerized with cross-linking water-soluble cationic monomer of the present invention and prepare cationic polymer and traditional sun Ionomer preparation compares, and cost significantly reduces;The cationic polymer that polymerization obtains is except as color fixing agent, soaping agent Outside component and colour fixative, it is also possible to be widely used in oil exploitation, papermaking, mining, textile printing and dyeing, daily-use chemical industry, sewage In the fields such as process or sewage decoloring.
Detailed description of the invention
Below by embodiment, the present invention is further illustrated, it is therefore intended that is more fully understood that present disclosure, therefore, The cited case is not limiting as protection scope of the present invention.
Embodiment 1
1, the preparation of crosslinkable water-soluble cationic monomer
Epoxychloropropane 2.0mol is added in the four-hole bottle equipped with condensing reflux pipe, thermometer, Dropping funnel and agitator, Water 10ml, liter high-temperature is to 30 DEG C, and at 30 DEG C, dimethylamine 1.0mol(of dropping 33% is in terms of the molal quantity of dimethylamine), After dripping off at 30 DEG C insulation reaction 10 hours, then decompression distillation is to remove unreacted monomer and water.Be cooled to 20 DEG C with Under, add 33% glacial acetic acid aqueous solution 42.9g regulation material pH value to 4~5, be slowly added dropwise DMAA 2.0mol And to control system temperature be 30 DEG C, after dripping off at 30 DEG C insulation reaction 10h, decompression distillation with remove unreacted monomer and Water i.e. obtains required crosslinkable water-soluble cationic monomer.
2, polyreaction
In the four-hole bottle equipped with condensing reflux pipe, thermometer, Dropping funnel and agitator, crosslinkable synthesized by addition Water-soluble cationic monomer 100g, water 150g, be warming up to 80 DEG C, drips 50% hydrogen peroxide 0.2g, after dripping off at 80 DEG C After insulation reaction 5h, cooling can be prepared by required cationic polymer.
Embodiment 2
1, the preparation of crosslinkable water-soluble cationic monomer
Epoxy bromopropane 2.8mol is added in the four-hole bottle equipped with condensing reflux pipe, thermometer, Dropping funnel and agitator, Water 10ml, liter high-temperature, to 30 DEG C, drips methyl-propyl amine 1.0mol(the rubbing with methyl-propyl amine of 50% at 30 DEG C Your number meter), after dripping off at 30 DEG C insulation reaction 10 hours, then decompression distillation is to remove unreacted monomer and water.Cooling To less than 20 DEG C, add 36.5% aqueous hydrochloric acid solution 26.9g regulation material pH value to 4~5, be slowly added dropwise methyl-propyl alkene Propyl group amine 3.0mol to control system temperature be 30 DEG C, after dripping off at 30 DEG C insulation reaction 10h, decompression distillation is to remove Unreacted monomer and water i.e. obtain required crosslinkable water-soluble cationic monomer.
2, polyreaction
In the four-hole bottle equipped with condensing reflux pipe, thermometer, Dropping funnel and agitator, crosslinkable synthesized by addition Water-soluble cationic monomer 100g, water 150g, be warming up to 80 DEG C, drips 50% azodiisobutyronitrile hydrochlorate aqueous solution 0.2g, After dripping off at 85 DEG C after insulation reaction 5h, cooling can be prepared by required cationic polymer.
Embodiment 3
1, the preparation of crosslinkable water-soluble cationic monomer
Epoxy bromopropane 2.0mol is added in the four-hole bottle equipped with condensing reflux pipe, thermometer, Dropping funnel and agitator, Water 10ml, liter high-temperature is to 30 DEG C, and at 30 DEG C, dimethylamine 1.0mol(of dropping 33% is in terms of the molal quantity of dimethylamine), After dripping off at 30 DEG C insulation reaction 10 hours, then decompression distillation is to remove unreacted monomer and water.Be cooled to 20 DEG C with Under, add 33% glacial acetic acid aqueous solution 38.8g regulation material pH value to 4~5, be slowly added dropwise DMAA 2.0mol And to control system temperature be 30 DEG C, after dripping off at 30 DEG C insulation reaction 10h, decompression distillation with remove unreacted monomer and Water i.e. obtains required crosslinkable water-soluble cationic monomer.
2, polyreaction
In the four-hole bottle equipped with condensing reflux pipe, thermometer, Dropping funnel and agitator, crosslinkable synthesized by addition Water-soluble cationic monomer 100g, water 150g, be warming up to 80 DEG C, drips 50% persulfate aqueous solution 3.0g, after dripping off At 80 DEG C after insulation reaction 5h, cooling can be prepared by required cationic polymer.
Embodiment 4
1, the preparation of crosslinkable water-soluble cationic monomer
Epoxy bromopropane 2.0mol is added in the four-hole bottle equipped with condensing reflux pipe, thermometer, Dropping funnel and agitator, Water 10ml, liter high-temperature is to 50 DEG C, and at 50 DEG C, dimethylamine 1.0mol(of dropping 33% is in terms of the molal quantity of dimethylamine), After dripping off at 50 DEG C insulation reaction 8 hours, then decompression distillation is to remove unreacted monomer and water.Be cooled to 20 DEG C with Under, add 33% glacial acetic acid aqueous solution 37.7g regulation material pH value to 4~5, be slowly added dropwise DMAA 2.0mol And to control system temperature be 50 DEG C, after dripping off at 50 DEG C insulation reaction 8h, decompression distillation with remove unreacted monomer and Water i.e. obtains required crosslinkable water-soluble cationic monomer.
2, polyreaction
In the four-hole bottle equipped with condensing reflux pipe, thermometer, Dropping funnel and agitator, crosslinkable synthesized by addition Water-soluble cationic monomer 100g, water 150g, be warming up to 85 DEG C, drips 50% ammonium persulfate aqueous solution 3.0g, after dripping off At 85 DEG C after insulation reaction 3h, cooling can be prepared by required cationic polymer.
Embodiment 5
1, the preparation of crosslinkable water-soluble cationic monomer
Epoxychloropropane 2.5mol is added in the four-hole bottle equipped with condensing reflux pipe, thermometer, Dropping funnel and agitator, Water 10ml, liter high-temperature is to 50 DEG C, and at 50 DEG C, dimethylamine 1.0mol(of dropping 33% is in terms of the molal quantity of dimethylamine), After dripping off at 50 DEG C insulation reaction 8 hours, then decompression distillation is to remove unreacted monomer and water.Be cooled to 20 DEG C with Under, add 33% glacial acetic acid aqueous solution 48.9g regulation material pH value to 4~5, be slowly added dropwise DMAA 3.0mol And to control system temperature be 50 DEG C, after dripping off at 50 DEG C insulation reaction 8h, decompression distillation with remove unreacted monomer and Water i.e. obtains required crosslinkable water-soluble cationic monomer.
2, polyreaction
In the four-hole bottle equipped with condensing reflux pipe, thermometer, Dropping funnel and agitator, crosslinkable synthesized by addition Water-soluble cationic monomer 100g, water 150g, be warming up to 85 DEG C, drip respectively 50% ammonium persulfate aqueous solution 5.5g with And 5% sodium pyrosulfite 8.0g, after dripping off at 85 DEG C after insulation reaction 5h, cooling can be prepared by required cationic polymerization Thing.
Embodiment 6
1, the preparation of crosslinkable water-soluble cationic monomer
Epoxychloropropane 2.0mol is added in the four-hole bottle equipped with condensing reflux pipe, thermometer, Dropping funnel and agitator, Water 10ml, liter high-temperature is to 50 DEG C, and at 50 DEG C, dimethylamine 1.0mol(of dropping 33% is in terms of the molal quantity of dimethylamine), After dripping off at 50 DEG C insulation reaction 8 hours, then decompression distillation is to remove unreacted monomer and water.Be cooled to 20 DEG C with Under, add 33% glacial acetic acid aqueous solution 42.9g regulation material pH value to 4~5, be slowly added dropwise DMAA 2.0mol And to control system temperature be 50 DEG C, after dripping off at 50 DEG C insulation reaction 8h, decompression distillation with remove unreacted monomer and Water i.e. obtains required crosslinkable water-soluble cationic monomer.
2, polyreaction
In the four-hole bottle equipped with condensing reflux pipe, thermometer, Dropping funnel and agitator, crosslinkable synthesized by addition Water-soluble cationic monomer 100g, water 150g, be warming up to 85 DEG C, drip respectively 50% ammonium persulfate aqueous solution 5.5g and 5% sodium pyrosulfite 8.0g, after dripping off at 85 DEG C after insulation reaction 5h, cooling can be prepared by required cationic polymer.
Embodiment 7
1, the preparation of crosslinkable water-soluble cationic monomer
Epoxychloropropane 2.5mol is added in the four-hole bottle equipped with condensing reflux pipe, thermometer, Dropping funnel and agitator, Water 10ml, liter high-temperature is to 30 DEG C, and at 30 DEG C, the N-hexyl methylamine 1.0mol(of dropping 50% is with N-hexyl methylamine Molal quantity meter), after dripping off at 30 DEG C insulation reaction 10 hours, then decompression distillation is to remove unreacted monomer and water.Fall Temperature to less than 20 DEG C, add 36.5% aqueous hydrochloric acid solution 36.9g regulation material pH value to 4~5, be slowly added dropwise methylhexyl Allyl amine 3.0mol to control system temperature be 30 DEG C, after dripping off at 30 DEG C insulation reaction 10h, decompression distillation is to remove Unreacted monomer and water is gone i.e. to obtain required crosslinkable water-soluble cationic monomer.
2, polyreaction
In the four-hole bottle equipped with condensing reflux pipe, thermometer, Dropping funnel and agitator, crosslinkable synthesized by addition Water-soluble cationic monomer 100g, water 150g, be warming up to 80 DEG C, drips 50% azodiisobutyronitrile hydrochlorate aqueous solution 0.2g, After dripping off at 85 DEG C after insulation reaction 5h, cooling can be prepared by required cationic polymer.
Synthesized cationic polymer is carried out the test of colour fixation as color fixing agent and contrasts with existing color fixing agent Y.
Color fixing condition:
1. cloth used by: a is reactive brilliant red cotton yarn card,bFor reactive turquoise blue cotton yarn card;
2. color fixing process: color fixing agent consumption 3.0% (o.w.f), bath raio 1:20, working liquid ph is 6.0, color fixing temperature 50 DEG C, fixation time 20min, 160 DEG C of drying.
3. fastness method of testing: color fastness to washing: GB/T3921-1997;Crock fastness: GB/T3920-1997;Sweat stain Fastness: AATCC-15-1995;Blister fastness: bath raio l:40, heating in water bath: first the beaker being watered is put into 100 DEG C In boiling water bath, when more than water in the cup temperature rise to 95 DEG C, then cloth is put in beaker, stirring, more than 95 DEG C insulation 5min, Period stirs 3~4 times;Then taking out fabric, and observe the color of water, as colourity is relatively deep, then explanation is faded weight, blister jail It is poor to spend;Otherwise, such as water colorless, then explanation blister fastness is good;Aberration: test with Color Eye7000A;Feel: allow Multidigit experienced hand valuation expert evaluates the feel of fabric from different angles, and 5 grades preferably, and 1 grade worst.
Experimental result see table
Crosslinkable water-soluble cationic monomer homopolymer the most of the present invention can significantly improve activity Reactive brilliant red that dyestuff especially color and luster is more bright-coloured, the color fastness of reactive turquoise blue dyed fabric, such as washable staining fastness, blister Fastness, colour fastness to perspiration all promote 1~2 grade;Colour fastness to rubbing promotes 0.5~1 grade.Of the present invention cross-linking Water-soluble cationic monomer homopolymer the color fastness improving performance of Fabrics Dyed with Reactive Dyes is much better than color fixing agent Y, and After fixation, fabric feeling is the least without impact, chromatic aberration, and beneficially factory checks colors.
Synthesized cationic polymer is compounded with existing acrylic compounds soaping agent (soaping agent A), and by gained To soaping agent carry out soaping the test of effect contrasting with existing market like product.
Soaping condition:
1. cloth used by:aFor reactive brilliant red cotton yarn card,bFor reactive turquoise blue cotton yarn card;
2. soap technique: soaping agent consumption 1g/L, bath raio 1:10, temperature of soaping 90 DEG C, soap time 10min.
3. fastness method of testing: fabric abrasive fastness is according to GB/T3920 1997 " textile color stability test rub resistance Color fastness " test;Color fastness to washing is according to GB/T3921.5 1997 " textile color stability test color fastness to washing: examination Test 5 " test;Evaluation staining fastness, with comparison calico as lining cloth, puts into together with painting cloth and soaps in liquid, in work of soaping Washing under the conditions of skill, the stickers lining cloth of test staining is recorded on Computer color testing instrument K/S value, K/S value is the least, it was demonstrated that Releasing chromatic effect is the best.
Experimental result see table
Crosslinkable water-soluble cationic monomer homopolymer the most of the present invention joins in soaping agent, energy Enough significantly improve the more bright-coloured reactive brilliant red of reactive dye especially color and luster, the color fastness to washing of reactive turquoise blue dyed fabric, resistance to Colorfastness to rubbing and anti-staining performance.Color fastness to washing can promote 0.5~1.5 grade, colour fastness to rubbing (dry and wet fastness) All promote 0.5~1 grade;Anti-staining performance can promote 40~60%.Crosslinkable water-soluble cationic the most of the present invention Monomer homopolymer can significantly improve the properties of soaping agent, and it is similar that its properties of soaping agent obtained after compounding is better than market Product.
Synthesized cationic polymer is carried out as the colour fixative in detergent test and the existing market of effect of color protection Like product contrasts.
Wash conditions:
1. cloth used by: red cotton (the reddest 83), black cotton (Direct black 22), standard white cotton.
2. washing process: slurry is 250ppm hard water, detergent concentration is 2g/l, temperature 30 DEG C, test pieces of cloth For coloured pieces of cloth and each 4 pieces of calico sheet, pieces of cloth specification: 6cm × 6cm, single wash time: 20min, rinse 2 times, Circulation washing times: 10 times, washing facility is RHLQ-III type Terg-O-Tometer, and rotating speed is 120r/min.
3. effect of color protection evaluation methodology: after washing according to experimental condition, reads painting cloth and the chromatic value of calico respectively.Color fixative is imitated Fruit is that after being washed by measurement, painting cloth represents with the color distinction aberration △ E not washing painting cloth, and aberration is the biggest, and painting cloth is described Fading the most serious, the colour fixation of detergent is the poorest;Contrary then colour fixation the best.Dye transfer inhibition effect is then with washing The value of chromatism △ E of rear calico represents, △ E is the lowest, then it represents that transfer to calico from there being the dye molecule washed off painting cloth through solution On amount the fewest, dye transfer inhibition effect is the most obvious.Aberration: test with Color Eye7000A.
Experimental result see table
Data from upper table are it can be seen that the detergent adding the cationic polymer synthesized by the present invention can be effectively improved The color fastness of color cotton, simultaneously can also effectively suppress dyestuff from coloured cotton to the transfer of standard white cotton, its colour fixation and anti- Dye transfer effect is superior to the like product on market.
The above, be only presently preferred embodiments of the present invention.By the cross-linking water solublity sun synthesized by the present invention in embodiment Ion monomer carry out equal coalescence using this homopolymer as color fixing agent, soaping agent component and colour fixative with also simply several in its application Special case, every any simple modification, equivalent variations and modification above example made according to the technical spirit of the present invention, all Fall within the scope of protection of the present invention.

Claims (8)

1. a crosslinkable quaternary ammonium salt water-soluble cationic monomer, it is for having the compound of structure shown in formula (1):
The preparation method of described quaternary ammonium salt water-soluble cationic monomer is as follows: shown in the alkyl secondary amine shown in Formulas I, Formula II Epoxyhalopropane, the pi-allyl tertiary amine shown in formula III is substituted, open loop, that solvent removal step synthesizes quaternary ammonium salt is water-soluble Property cationic monomer,
Wherein, R1And R2It is respectively and independently selected from C1~C6One in alkyl, X is F, Cl, Br or I, and synthetic route is as follows:
The preparation method of described quaternary ammonium salt water-soluble cationic monomer comprises the following steps: 1) add epoxyhalopropane under room temperature And water, and rise high-temperature to 30~50 DEG C, dropping mass concentration is the alkyl secondary amine aqueous solution of 33~50%, after dripping off 30~ Insulation reaction 8~10 hours at 50 DEG C, then decompression is distilled off unreacted monomer and water, obtains compound IV;2) by step 1) the compound IV obtained is cooled to less than 20 DEG C, and addition diluted acid regulation material pH value, to 4~5, drips pi-allyl tertiary amine And to control system temperature be 30~50 DEG C, after dripping off at 30~50 DEG C insulation reaction 8~10h, then decompression distillation is to remove Unreacted monomer and water, obtain described crosslinkable quaternary ammonium salt water-soluble cationic monomer;
In abovementioned steps, the mol ratio of alkyl secondary amine, epoxyhalopropane and pi-allyl tertiary amine is: 1.0:2.0~2.8:2.0~ 3.0, diluted acid consumption is the 5~13wt% of material total amount.
Crosslinkable quaternary ammonium salt water-soluble cationic monomer the most according to claim 1, it is characterised in that described R1And R2It is respectively and independently selected from C1~C3One in alkyl.
Crosslinkable quaternary ammonium salt water-soluble cationic monomer the most according to claim 1, it is characterised in that X is Cl Or Br.
Crosslinkable quaternary ammonium salt water-soluble cationic monomer the most according to claim 1, it is characterised in that described One or two in aqueous hydrochloric acid solution that diluted acid selects mass concentration to be 36.5% or glacial acetic acid aqueous solution that mass concentration is 33% Plant combination.
5. quaternary ammonium salt water-soluble cationic monomer described in any one of claim 1-4 carries out being polymerized the cationic polymer obtained The fixation processing and sorting of bafta it is applied to, it is characterised in that use infusion process or padding method to process technique as color fixing agent, When using infusion process to process, color fixing agent consumption is 0.5~5.0%, and bath raio is 1:5~50, and working liquid ph is 5.0~7.0, Color fixing temperature is 40~70 DEG C, and the fixation time is 20~30min;When using padding method to process, color fixing agent consumption is 1~50g/l, Liquid carrying rate is 30~150%, and baking temperature is 100~170 DEG C.
6. quaternary ammonium salt water-soluble cationic monomer described in any one of claim 1-4 carries out being polymerized the cationic polymer obtained Complex as dyestuff is applied in the soaping agent of bafta, it is characterised in that be polymerized the cationic polymer obtained straight Connecing and compound in soaping agent, the consumption of cationic polymer is the 0.1~2.0% of soaping agent gross mass.
7. quaternary ammonium salt water-soluble cationic monomer described in any one of claim 1-4 carries out being polymerized the cationic polymer obtained It is applied in detergent as colour fixative, it is characterised in that be polymerized the cationic polymer obtained and directly compound detergent In, the consumption of cationic polymer is the 0.1~1.0% of detergent gross mass.
8. the application described in any one of claim 5-7, it is characterised in that the polymerization of described cationic polymer is as follows: Add described water-soluble cationic monomer and water at normal temperatures and be warming up to 80~85 DEG C, dripping initiator, at 80~85 DEG C Lower insulation reaction 3~5h, cooling, discharging, i.e. available required cationic polymer, described initiator selects quality Concentration is hydrogen peroxide, azodiisobutyronitrile hydrochlorate, potassium peroxydisulfate, Ammonium persulfate. or Ammonium persulfate. and the bisulfite of 50% Sodium is the compositions of 3:1 in molar ratio, and the consumption of initiator is the 0.1~1.5wt% of monomer total amount.
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