CN103922944A - Cross-linkable quaternary ammonium salt water-soluble cationic monomer as well as preparation method and application thereof - Google Patents
Cross-linkable quaternary ammonium salt water-soluble cationic monomer as well as preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a cross-linkable water-soluble cationic monomer as well as a preparation method and application thereof. The traditional quaternary ammonium salt water-soluble cationic monomer is prepared by the two methods of carrying out cationization on natural polymer or polymerizing a monomer and then carrying out cationization, but the cationization degrees of the polymers obtained by the two methods are both lower and can not reach the industrially needed performance. The cross-linkable water-soluble cationic monomer is prepared by virtue of the following steps: on the basis of utilizing alkyl secondary amine, epoxyhalopropane, allyl tertiary amine and dilute acid as raw materials, carrying out substitution reaction, ring-opening reaction, solution removing and the like. The cross-linkable water-soluble cationic monomer can be polymerized with an olefinic unsaturated comonomer to form a cross-linkable copolymer or homopolymer, and the homopolymer and the copolymer based on the cross-linkable water-soluble cationic monomer have the advantages that the cation content is high and adjustable, the molecular weight is large, the cation degree is high, the homopolymer and the copolymer can be well dissolved in water and can generate strong intermolecular interaction with various polar materials and the like.
Description
Technical field
The invention belongs to cationic monomer field, relate to crosslinkable soluble quaternary ammonium cationoid compound, quaternary ammonium salt water-soluble cationic monomer of especially a kind of two ends polymerizable and band crosslinked group (hydroxyl) and its preparation method and application.
Background technology
Cationic polymers is a kind of important functional high molecule material, and it has cationic characteristic in macromolecular structure, thereby is all widely used in a lot of fields.The common Application Areas of cationic polymers comprises: in textile dyeing and finishing industry as laking agent, static inhibitor and sterilant; In daily-use chemical industry industry as the agent of anti-dyestuff colour contamination, colour protecting agent, antistatic softening agent and antiseptic-germicide etc.; In paper industry as paper strengthening agent, printing-ink retention aid etc.; In sewage disposal as cationic flocculant, sludge dehydrating agent; In oilfield applications as drilling fluid, oil field emulsifying agent etc.
At present, study more cationic polymers have QAS polymer, quaternary alkylphosphonium salt polymkeric substance and season sulfosalt polymkeric substance, most widely used, product category is maximum is QAS polymer.From current synthetic technology, the preparation of industrial this cationoid polymkeric substance generally all adopts carries out cationization by natural polymers or by first monomer polymerization and then these two kinds of methods of cationization, but the cation ionization degree of the polymkeric substance that these two kinds of methods obtain is all lower, does not reach industrial required performance.Therefore in order to improve the cation ionization degree of product, the synthetic exactly polymerizable cationic monomer of best bet and then carry out polymerization, so not only the cationic degree of polymkeric substance is high, and molecular weight and cationic degree all adjustable.Conventional cationic polymerization monomer mainly contains at present: dimethyl diallyl ammonium chloride (DMDAAC), methylacryoyloxyethyl alkyl dimethyl ammonium chloride (DMAEMA), Epicholorohydrin and acrylamide etc.As the people such as Daniher with the multipolymer of DMDAAC:N-n-methylolacrylamide=80:20 as laking agent use, result shows, this material is fine to the tint retention of substantive dyestuff, brings up to 4～5 grades for 3 grades that calico staining can be when not processing with laking agent; The people such as Lv Shenghua are used as flocculation agent acrylamide (AM) with the multipolymer of DMDAAC, have good flocculating effect, and this base polymer is also used in shampoo; The cationic copolymer of the propylene phthalein amine that the people such as Zhang Long are synthetic and propylene phthalein oxygen ethyl alkyl dimethyl ammonium chloride, has good flocculation ability, and its throwing out is obviously better than inorganic flocculating agent; People is also taking epoxy chloropropane, polyethylene polyamine as raw material for horse happiness equality, has synthesized organic cationic polymer, and the performance such as anti-swollen, flocculation and inhibition to it studies, and discovery polymkeric substance has good inhibition etc. to hydration and expansion of clay.
Along with industrial expansion, especially the continuous appearance of emerging industry, people also can increase greatly to the demand of Cationic Polymers Containing Quaternary Ammonium Salts, compared with demand, domestic the research of novel quaternary ammonium salt cationic polymkeric substance is also seemed to fewer, and be mostly confined to the common monomers such as DMDAAC, AM, Epicholorohydrin, the main dependence on import of cationic monomer that most of performance is better, topology update is clever.These factors have all restricted the progress of the research and development of domestic Cationic Polymers Containing Quaternary Ammonium Salts to some extent.Therefore for adapting to the needs of China's modern industry, the polymerizable cationic monomer of development of new seems very necessary already.
Summary of the invention
The quaternary ammonium salt water-soluble cationic monomer that one of object of the present invention is to provide a kind of polymerizable, can dissolves and can occur with various polarity material well strong molecular interaction in water.
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 monomer, and it is for having the compound of structure shown in formula (1):
In formula: R
1and R
2independently be selected from respectively C
1～C
6a kind of in alkyl, preferably C
1～C
3one in alkyl; X is F, Cl, Br or I, preferably Cl or Br.
Crosslinkable water-soluble cationic monomer of the present invention, it is the quarternary ammonium salt compound that band two keys in a kind of two ends can carry out radical polymerization, has introduced water-soluble reaction group-hydroxyl in structure simultaneously.
First because two keys are all contained at the two ends of molecular structure, it can carry out copolymerization with olefinic class monomer, the polymkeric substance of gained: (one) cationic degree is high, owing to just containing cation group in crosslinkable water-soluble cationic monomer molecular structure of the present invention, therefore in the homopolymer taking it as base or multipolymer, almost each structural unit contains cation group; (2) molecular weight is large, the designed cationic monomer of the present invention can carry out radical polymerization with other olefinic class monomer, it is adjustable that not only polymerizable goes out the molecular weight of polymkeric substance that various desired structure molecular weight are larger but also polymkeric substance, and correspondingly its cationic degree is also adjustable; (3) cationic monomer of the present invention, in its molecular structure, also contain more crosslinkable water soluble group-hydroxyl, can not only improve like this water-soluble of high-molecular weight polymer and can also strengthen compatibleness and the intermolecular reactive force between homopolymer or multipolymer and other polar material taking it as base, improve the properties of product.
The cationic polymers that polymerization obtains as crosslinkable water-soluble cationic monomer of the present invention is carried out is used as laking agent, because dye molecule is generally anionic compound, can there is color lake between the two in polymkeric substance and dyestuff, can prevent that dyestuff from coming off and being hydrolyzed from fabric because of ionization, thereby improve colour fastness; In addition polymericular weight is large, can be in fabric face film forming, cover caducous dyestuff, crosslinkable groups hydroxyl in polymer molecular structure can also react with the activity hydroxy in cotton fiber structure simultaneously, produce covalent linkage, make laking agent can anchor at firmly fabric face together with dyestuff, thereby effectively improve the dyefastness of each side.
Crosslinkable water-soluble cationic monomer of the present invention carries out the cationic polymers that polymerization obtains and can also carry out composite and use as the soaping agent of cotton fabric with the high molecular polymer of other anionic, described cationic polymers can with solution in dyestuff form complex compound, and by the synergy of other raw materials, can effectively prevent that dyestuff is deposited on fiber surface again, be conducive to the removal of unreacted loose colour, can accomplish well that Bai Difang is stained with performance simultaneously.
As the colour protecting agent used time in washing composition, the polymer cation degree obtaining due to crosslinkable water-soluble cationic monomer of the present invention polymerization is high, it very easily with the lip-deep chromogenesis complex compound of clothing, make the dyestuff on clothing be difficult for dissolving in washings, thereby reach tint retention, it also can with solution in chromogenesis complex compound, prevent that pigment is infected with to clothing surface, play the effect that prevents dye transfer, thereby play anti-colour contamination effect.
Except laking agent, soaping agent component and colour protecting agent, homopolymer or multipolymer taking crosslinkable water-soluble cationic monomer of the present invention as base can also be widely used in the fields such as oily exploitation, papermaking, mining, textile printing and dyeing, sewage disposal.
Two of object of the present invention is to provide a kind of preparation method of above-mentioned crosslinkable quaternary ammonium salt water-soluble cationic monomer, its by the allyl group tertiary amine shown in the alkyl secondary amine shown in formula I, the epoxyhalopropane shown in formula II, formula III be substituted, open loop, desolventizing step synthesize quaternary ammonium salt water-soluble cationic monomer
Wherein R
1and R
2independently be selected from respectively C
1～C
6a kind of in alkyl, X is F, Cl, Br or I, and synthetic route is as follows:
Wherein R
1, R
2with 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 epoxyhalopropane and water under normal temperature, and temperature to 30～50 DEG C that raise, the alkyl secondary amine aqueous solution that dropping mass concentration is 33～50%, after dripping off at 30～50 DEG C insulation reaction 8～10 hours, unreacted monomer and water are removed in underpressure distillation again, obtain compound IV; 2) by step 1) compound IV that obtains is cooled to below 20 DEG C, add diluted acid to regulate material pH value to 4～5, dripping allyl group tertiary amine hierarchy of control temperature is 30～50 DEG C, after dripping off at 30～50 DEG C insulation reaction 8～10h, underpressure distillation, to remove unreacted monomer and water, obtains described crosslinkable quaternary ammonium salt water-soluble cationic monomer again;
In abovementioned steps, the mol ratio of alkyl secondary amine, epoxyhalopropane and allyl group tertiary amine is: 1.0:2.0～2.8:2.0～3.0, diluted acid consumption is 5～13wt% of material total amount.
As preferably, it is one or both combinations in 36.5% aqueous hydrochloric acid or the mass concentration glacial acetic acid aqueous solution that is 33% that described diluted acid is selected mass concentration.
Three of object of the present invention is that above-mentioned quaternary ammonium salt water-soluble cationic monomer is carried out to homopolymer or the multipolymer that polymerization obtains, and is applied in oily exploitation, papermaking, mining, textile printing and dyeing, daily-use chemical industry, sewage disposal or sewage decoloring field.
Described crosslinkable water-soluble cationic monomer is carried out polymerization by the present invention, and the colour protecting agent in taking its homopolymer as cotton fabric laking agent, soaping agent component and washing composition uses as special case and describes.
Above-mentioned quaternary ammonium salt water-soluble cationic monomer carries out cationic polymers that polymerization obtains while being applied to the fixation processing and sorting of cotton fabric as laking agent, adopt pickling process or padding method treatment process, while adopting pickling process to process, laking agent consumption is 0.5～5.0%; bath raio is 1:5～50; working fluid pH value is 5.0～7.0, and color fixing temperature is 40～70 DEG C, and the fixation time is 20～30min; While adopting padding method to process, laking agent consumption is 1～50g/l, and liquid carrying rate is 30～150%, and baking temperature is 100～170 DEG C.
Above-mentioned quaternary ammonium salt water-soluble cationic monomer carries out cationic polymers that polymerization obtains be applied in the soaping agent of cotton fabric during as the complex compound of dyestuff (as the component of soaping agent), the cationic polymers that institute's polymerization obtains is directly composite in soaping agent, and the consumption of cationic polymers is 0.1～2.0% of soaping agent total mass.
Above-mentioned quaternary ammonium salt water-soluble cationic monomer carries out cationic polymers that polymerization obtains while being applied in washing composition as colour protecting agent, the cationic polymers that institute's polymerization obtains is directly composite in washing composition, and the consumption of cationic polymers is 0.1～1.0% of washing composition total mass.
In above-mentioned application, the polymerization process of described cationic polymers is as follows: add at normal temperatures described water-soluble cationic monomer and water and be warming up to 80～85 DEG C, drip initiator, insulation reaction 3～5h at 80～85 DEG C, cooling, discharging, can obtain required cationic polymers, it is that 50% hydrogen peroxide, Diisopropyl azodicarboxylate hydrochloride, Potassium Persulphate, ammonium persulphate or ammonium persulphate and sodium bisulfite are the composition of 3:1 in molar ratio that described initiator is selected mass concentration, and the consumption of initiator is 0.1～1.5wt% of monomer total amount.
Crosslinkable water-soluble cationic monomer of the present invention has following beneficial effect: (one) cationic degree is high, owing to just containing cation group in crosslinkable water-soluble cationic monomer molecular structure of the present invention, therefore in the homopolymer taking it as base or multipolymer, almost each structural unit contains cation group; (2) molecular weight is large, and the designed cationic monomer of the present invention can carry out radical polymerization with other olefinic class unsaturated monomer, and not only polymerizable goes out the polymkeric substance of various desired structures but also the molecular weight of polymkeric substance is adjustable, and correspondingly its cationic degree is also adjustable; (3) in its molecular structure of cationic monomer of the present invention, also contain crosslinkable water soluble group-hydroxyl, can not only improve like this water-soluble of high-molecular weight polymer, and can also strengthen compatibleness and the intermolecular reactive force between homopolymer or multipolymer and other polar material taking it as base, improve the properties of product.
The raw material of preparing crosslinkable water-soluble cationic monomer of the present invention is conventional Chemicals, and cost is low, and synthesis technique is simple, the gentle safety of preparation condition.
Carry out polymerization with crosslinkable water-soluble cationic monomer of the present invention and prepare cationic polymers and compare with the preparation of traditional cationic polymers, cost significantly reduces; The cationic polymers that polymerization obtains, except as laking agent, soaping agent component and colour protecting agent, can also be widely used in the fields such as oily exploitation, papermaking, mining, textile printing and dyeing, daily-use chemical industry, sewage disposal or sewage decoloring.
Embodiment
Below by embodiment, the present invention is further illustrated, and object is to understand better content of the present invention, and therefore, the cited case does not limit the scope of the invention.
Embodiment 1
1, the preparation of crosslinkable water-soluble cationic monomer
Add epoxy chloropropane 2.0mol to being equipped with in the four-hole bottle of condensing reflux pipe, thermometer, dropping funnel and agitator, water 10ml, rising temperature to 30 DEG C, at 30 DEG C, drip 33% the dimethylamine 1.0mol(mole number in dimethylamine), after dripping off at 30 DEG C insulation reaction 10 hours, then underpressure distillation is to remove unreacted monomer and water.Be cooled to below 20 DEG C, add 33% glacial acetic acid aqueous solution 42.9g to regulate material pH value to 4～5, slowly dripping DMAA 2.0mol hierarchy of control temperature is 30 DEG C, after dripping off at 30 DEG C insulation reaction 10h, underpressure distillation obtains required crosslinkable water-soluble cationic monomer to remove unreacted monomer and water.
2, polyreaction
To being equipped with in the four-hole bottle of condensing reflux pipe, thermometer, dropping funnel and agitator, add crosslinkable water-soluble cationic monomer 100g, the water 150g of synthesized, be warming up to 80 DEG C, drip 50% hydrogen peroxide 0.2g, after dripping off, at 80 DEG C after insulation reaction 5h, cooling can make required cationic polymers.
Embodiment 2
1, the preparation of crosslinkable water-soluble cationic monomer
Add epoxy bromopropane 2.8mol to being equipped with in the four-hole bottle of condensing reflux pipe, thermometer, dropping funnel and agitator, water 10ml, rising temperature to 30 DEG C, at 30 DEG C, drip 50% the methyl-propyl amine 1.0mol(mole number in methyl-propyl amine), after dripping off at 30 DEG C insulation reaction 10 hours, then underpressure distillation is to remove unreacted monomer and water.Be cooled to below 20 DEG C, add 36.5% aqueous hydrochloric acid 26.9g to regulate material pH value to 4～5, slowly dripping methyl-propyl allyl amine 3.0mol hierarchy of control temperature is 30 DEG C, after dripping off at 30 DEG C insulation reaction 10h, underpressure distillation obtains required crosslinkable water-soluble cationic monomer to remove unreacted monomer and water.
2, polyreaction
To being equipped with in the four-hole bottle of condensing reflux pipe, thermometer, dropping funnel and agitator, add crosslinkable water-soluble cationic monomer 100g, the water 150g of synthesized, be warming up to 80 DEG C, drip 50% Diisopropyl azodicarboxylate hydrochloride aqueous solution 0.2g, after dripping off, at 85 DEG C after insulation reaction 5h, cooling can make required cationic polymers.
Embodiment 3
1, the preparation of crosslinkable water-soluble cationic monomer
Add epoxy bromopropane 2.0mol to being equipped with in the four-hole bottle of condensing reflux pipe, thermometer, dropping funnel and agitator, water 10ml, rising temperature to 30 DEG C, at 30 DEG C, drip 33% the dimethylamine 1.0mol(mole number in dimethylamine), after dripping off at 30 DEG C insulation reaction 10 hours, then underpressure distillation is to remove unreacted monomer and water.Be cooled to below 20 DEG C, add 33% glacial acetic acid aqueous solution 38.8g to regulate material pH value to 4～5, slowly dripping DMAA 2.0mol hierarchy of control temperature is 30 DEG C, after dripping off at 30 DEG C insulation reaction 10h, underpressure distillation obtains required crosslinkable water-soluble cationic monomer to remove unreacted monomer and water.
2, polyreaction
To being equipped with in the four-hole bottle of condensing reflux pipe, thermometer, dropping funnel and agitator, add crosslinkable water-soluble cationic monomer 100g, the water 150g of synthesized, be warming up to 80 DEG C, drip 50% persulfate aqueous solution 3.0g, after dripping off, at 80 DEG C after insulation reaction 5h, cooling can make required cationic polymers.
Embodiment 4
1, the preparation of crosslinkable water-soluble cationic monomer
Add epoxy bromopropane 2.0mol to being equipped with in the four-hole bottle of condensing reflux pipe, thermometer, dropping funnel and agitator, water 10ml, rising temperature to 50 DEG C, at 50 DEG C, drip 33% the dimethylamine 1.0mol(mole number in dimethylamine), after dripping off at 50 DEG C insulation reaction 8 hours, then underpressure distillation is to remove unreacted monomer and water.Be cooled to below 20 DEG C, add 33% glacial acetic acid aqueous solution 37.7g to regulate material pH value to 4～5, slowly dripping DMAA 2.0mol hierarchy of control temperature is 50 DEG C, after dripping off at 50 DEG C insulation reaction 8h, underpressure distillation obtains required crosslinkable water-soluble cationic monomer to remove unreacted monomer and water.
2, polyreaction
To being equipped with in the four-hole bottle of condensing reflux pipe, thermometer, dropping funnel and agitator, add crosslinkable water-soluble cationic monomer 100g, the water 150g of synthesized, be warming up to 85 DEG C, drip 50% ammonium persulfate aqueous solution 3.0g, after dripping off, at 85 DEG C after insulation reaction 3h, cooling can make required cationic polymers.
Embodiment 5
1, the preparation of crosslinkable water-soluble cationic monomer
Add epoxy chloropropane 2.5mol to being equipped with in the four-hole bottle of condensing reflux pipe, thermometer, dropping funnel and agitator, water 10ml, rising temperature to 50 DEG C, at 50 DEG C, drip 33% the dimethylamine 1.0mol(mole number in dimethylamine), after dripping off at 50 DEG C insulation reaction 8 hours, then underpressure distillation is to remove unreacted monomer and water.Be cooled to below 20 DEG C, add 33% glacial acetic acid aqueous solution 48.9g to regulate material pH value to 4～5, slowly dripping DMAA 3.0mol hierarchy of control temperature is 50 DEG C, after dripping off at 50 DEG C insulation reaction 8h, underpressure distillation obtains required crosslinkable water-soluble cationic monomer to remove unreacted monomer and water.
2, polyreaction
To being equipped with in the four-hole bottle of condensing reflux pipe, thermometer, dropping funnel and agitator, add crosslinkable water-soluble cationic monomer 100g, the water 150g of synthesized, 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 make required cationic polymers.
Embodiment 6
1, the preparation of crosslinkable water-soluble cationic monomer
Add epoxy chloropropane 2.0mol to being equipped with in the four-hole bottle of condensing reflux pipe, thermometer, dropping funnel and agitator, water 10ml, rising temperature to 50 DEG C, at 50 DEG C, drip 33% the dimethylamine 1.0mol(mole number in dimethylamine), after dripping off at 50 DEG C insulation reaction 8 hours, then underpressure distillation is to remove unreacted monomer and water.Be cooled to below 20 DEG C, add 33% glacial acetic acid aqueous solution 42.9g to regulate material pH value to 4～5, slowly dripping DMAA 2.0mol hierarchy of control temperature is 50 DEG C, after dripping off at 50 DEG C insulation reaction 8h, underpressure distillation obtains required crosslinkable water-soluble cationic monomer to remove unreacted monomer and water.
2, polyreaction
To being equipped with in the four-hole bottle of condensing reflux pipe, thermometer, dropping funnel and agitator, add crosslinkable water-soluble cationic monomer 100g, the water 150g of synthesized, 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 make required cationic polymers.
Embodiment 7
1, the preparation of crosslinkable water-soluble cationic monomer
Add epoxy chloropropane 2.5mol to being equipped with in the four-hole bottle of condensing reflux pipe, thermometer, dropping funnel and agitator, water 10ml, rising temperature to 30 DEG C, at 30 DEG C, drip 50% the N-hexyl methylamine 1.0mol(mole number in N-hexyl methylamine), after dripping off at 30 DEG C insulation reaction 10 hours, then underpressure distillation is to remove unreacted monomer and water.Be cooled to below 20 DEG C, add 36.5% aqueous hydrochloric acid 36.9g to regulate material pH value to 4～5, slowly dripping methyl hexyl allyl amine 3.0mol hierarchy of control temperature is 30 DEG C, after dripping off at 30 DEG C insulation reaction 10h, underpressure distillation obtains required crosslinkable water-soluble cationic monomer to remove unreacted monomer and water.
2, polyreaction
To being equipped with in the four-hole bottle of condensing reflux pipe, thermometer, dropping funnel and agitator, add crosslinkable water-soluble cationic monomer 100g, the water 150g of synthesized, be warming up to 80 DEG C, drip 50% Diisopropyl azodicarboxylate hydrochloride aqueous solution 0.2g, after dripping off, at 85 DEG C after insulation reaction 5h, cooling can make required cationic polymers.
Carry out the test of colour fixation using the cationic polymers of synthesized as laking agent and contrast with existing color fixing agent Y.
Color fixing condition:
1. cloth used: a is reactive brilliant red cotton yarn card,
bfor reactive turquoise blue cotton yarn card;
2. color fixing process: laking agent consumption 3.0% (o.w.f), bath raio 1:20, working fluid pH value is 6.0,50 DEG C of color fixing temperatures, fixation time 20min, 160 DEG C of oven dry.
3. fastness testing method: colour fastness to washing: GB/T3921-1997; Crock fastness: GB/T3920-1997; Perspiration fastness: AATCC-15-1995; Bubble fastness: bath raio l:40, heating in water bath: first the beaker being watered is put into the boiling water bath of 100 DEG C, more than water in the cup temperature rise to 95 DEG C time, then cloth is put into beaker, stir, more than 95 DEG C be incubated 5min, stir during this time 3～4 times; Then take out fabric, and observe the color of water, as darker in colourity, explanation is faded heavily, and bubble fastness is poor; Otherwise, as water colorless, illustrate that bubble fastness is good; Aberration: with Color Eye7000A test; Feel: allow the experienced hand valuation expert of multidigit evaluate the feel of fabric from different angles, 5 grades best, and 1 grade the poorest.
Experimental result sees the following form
Crosslinkable water-soluble cationic monomer homopolymer of the present invention can significantly improve the colour fastness of the reactive dyestuffs reactive brilliant red that especially color and luster is more bright-coloured, reactive turquoise blue DYED FABRICS as can be seen from the above table, as washable staining fastness, bubble fastness, colour fastness to perspiration all promote 1～2 grade; Colour fastness to rubbing promotes 0.5～1 grade.Crosslinkable water-soluble cationic monomer homopolymer of the present invention is much better than color fixing agent Y to the colour fastness improving performance of Fabrics Dyed with Reactive Dyes, and after fixation, fabric feeling is also very little without impact, chromatic aberration, is conducive to factory and checks colors.
The cationic polymers of synthesized and existing acrylic acid or the like soaping agent (soaping agent A) are carried out composite, and by the soap test of effect contrasting with existing market like product of obtained soaping agent.
Soaping condition:
1. cloth used:
afor reactive brilliant red cotton yarn card,
bfor reactive turquoise blue cotton yarn card;
2. the technique of soaping: soaping agent consumption 1g/L, bath raio 1:10,90 DEG C of the temperature of soaping, time 10min soaps.
3. fastness testing method: fabric crock fastness is to test according to GB/T3920-1997 " textile color stability test colour fastness to rubbing "; Colour fastness to washing is according to GB/T3921.5-1997 " textile color stability test colour fastness to washing: test 5 " test; Evaluation staining fastness as lining cloth, is put into the liquid of soaping with contrast calico together with painting cloth, washs soaping under processing condition, and the stickers lining cloth of test staining is recorded to K/S value on Computer color testing instrument, and K/S value is less, proves that anti-staining effect is better.
Experimental result sees the following form
Crosslinkable water-soluble cationic monomer homopolymer of the present invention joins in soaping agent as can be seen from the above table, can significantly improve colour fastness to washing, colour fastness to rubbing and the anti-staining performance of the reactive dyestuffs reactive brilliant red that especially color and luster is more bright-coloured, reactive turquoise blue DYED FABRICS.Colour fastness to washing can promote 0.5～1.5 grade, and colour fastness to rubbing (dry wet fastness) all promotes 0.5～1 grade; Anti-staining performance can promote 40～60%.Therefore crosslinkable water-soluble cationic monomer homopolymer of the present invention can obviously improve the properties of soaping agent, and its properties of soaping agent obtaining after composite is better than market like product.
Colour protecting agent using the cationic polymers of synthesized in washing composition protects the test of chromatic effect and contrasts with existing market like product.
Wash conditions:
1. cloth used: red cotton (direct red 83), black cotton (Direct black 22), standard white cotton.
2. washing process: bath water is 250ppm hard water, detergent concentration is 2g/l, 30 DEG C of temperature, test is each 4 of coloured pieces of cloth and calico sheet with pieces of cloth, pieces of cloth specification: 6cm × 6cm, single wash time: 20min, rinsing 2 times, circulation cleaning number of times: 10 times, washing plant is RHLQ-III type Terg-O-Tometer, and rotating speed is 120r/min.
3. protect chromatic effect evaluation method: after test conditions washing, read respectively the colourimetric number of painting cloth and calico.Protecting chromatic effect is that after washing by measurement, painting cloth represents with the color distinction-aberration △ E that does not wash painting cloth, and it is more serious that aberration more illustrates that painting cloth fades, and the colour fixation of washing composition is poorer; Colour fixation is better on the contrary.Anti-dye transfer effect is to represent with the value of chromatism △ E of calico after washing, and △ E is lower, represents from there being dye molecule that painting cloth washes off to transfer to amount on calico through solution lesser, and anti-dye transfer effect is just more obvious.Aberration: with Color Eye7000A test.
Experimental result sees the following form
Data from upper table can be found out, add the washing composition of the cationic polymers of synthesized of the present invention can effectively improve the colour fastness of coloured cotton, can also effectively suppress the transfer of dyestuff from coloured cotton to standard white cotton, its colour fixation and anti-dye transfer effect are all better than the like product on market simultaneously.
The above is only preferred embodiment of the present invention.In embodiment, the crosslinkable water-soluble cationic monomer of synthesized of the present invention is carried out equal coalescence using this homopolymer as laking agent, also several special cases in its application just of soaping agent component and colour protecting agent; any simple modification, equivalent variations and modification that every foundation technical spirit of the present invention is done above embodiment, all fall within the scope of protection of the present invention.
Claims (10)
1. a crosslinkable quaternary ammonium salt water-soluble cationic monomer, it is for having the compound of structure shown in formula (1):
In formula: R
1and R
2independently be selected from respectively C
1～C
6one in alkyl, X is F, Cl, Br or I.
2. crosslinkable quaternary ammonium salt water-soluble cationic monomer according to claim 1, is characterized in that described R
1and R
2independently be selected from respectively C
1～C
3one in alkyl.
3. crosslinkable quaternary ammonium salt water-soluble cationic monomer according to claim 1, is characterized in that, described X is Cl or Br.
4. the preparation method of quaternary ammonium salt water-soluble cationic monomer described in claim 1-3 any one, its by the allyl group tertiary amine shown in the alkyl secondary amine shown in formula I, the epoxyhalopropane shown in formula II, formula III be substituted, open loop, desolventizing step synthesize quaternary ammonium salt water-soluble cationic monomer
Wherein R
1and R
2independently be selected from respectively C
1～C
6a kind of in alkyl, X is F, Cl, Br or I, and synthetic route is as follows:
R
1and R
2independently be selected from respectively C
1～C
6one in alkyl, X is F, Cl, Br or I.
5. preparation method according to claim 4, it comprises the following steps: 1) add epoxyhalopropane and water under normal temperature, and temperature to 30～50 DEG C that raise, the alkyl secondary amine aqueous solution that dropping mass concentration is 33～50%, after dripping off at 30～50 DEG C insulation reaction 8～10 hours, unreacted monomer and water are removed in underpressure distillation again, obtain compound IV; 2) by step 1) compound IV that obtains is cooled to below 20 DEG C, add diluted acid to regulate material pH value to 4～5, dripping allyl group tertiary amine hierarchy of control temperature is 30～50 DEG C, after dripping off at 30～50 DEG C insulation reaction 8～10h, underpressure distillation, to remove unreacted monomer and water, obtains described crosslinkable quaternary ammonium salt water-soluble cationic monomer again;
In abovementioned steps, the mol ratio of alkyl secondary amine, epoxyhalopropane and allyl group tertiary amine is: 1.0:2.0～2.8:2.0～3.0, diluted acid consumption is 5～13wt% of material total amount.
6. preparation method according to claim 5, is characterized in that, it is one or both combinations in 36.5% aqueous hydrochloric acid or the mass concentration glacial acetic acid aqueous solution that is 33% that described diluted acid is selected mass concentration.
7. described in claim 1-3 any one, quaternary ammonium salt water-soluble cationic monomer carries out cationic polymers that polymerization obtains and is applied to as laking agent the fixation processing and sorting of cotton fabric, it is characterized in that, adopt pickling process or padding method treatment process, while adopting pickling process to process, laking agent consumption is 0.5～5.0%, and bath raio is 1:5～50, and working fluid pH value is 5.0～7.0, color fixing temperature is 40～70 DEG C, and the fixation time is 20～30min; While adopting padding method to process, laking agent consumption is 1～50g/l, and liquid carrying rate is 30～150%, and baking temperature is 100～170 DEG C.
8. described in claim 1-3 any one, quaternary ammonium salt water-soluble cationic monomer carries out the cationic polymers that polymerization obtains and is applied to as the complex compound of dyestuff in the soaping agent of cotton fabric, it is characterized in that, the cationic polymers that institute's polymerization obtains is directly composite in soaping agent, and the consumption of cationic polymers is 0.1～2.0% of soaping agent total mass.
9. described in claim 1-3 any one, quaternary ammonium salt water-soluble cationic monomer carries out the cationic polymers that polymerization obtains and is applied in washing composition as colour protecting agent, it is characterized in that, the cationic polymers that institute's polymerization obtains is directly composite in washing composition, and the consumption of cationic polymers is 0.1～1.0% of washing composition total mass.
10. the application described in claim 7-9 any one, it is characterized in that, the polymerization process of described cationic polymers is as follows: add at normal temperatures described water-soluble cationic monomer and water and be warming up to 80～85 DEG C, drip initiator, insulation reaction 3～5h at 80～85 DEG C, cooling, discharging, can obtain required cationic polymers, it is 50% hydrogen peroxide that described initiator is selected mass concentration, Diisopropyl azodicarboxylate hydrochloride, Potassium Persulphate, ammonium persulphate or ammonium persulphate and sodium bisulfite are the composition of 3:1 in molar ratio, the consumption of initiator is 0.1～1.5wt% of monomer total amount.
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