CN104420372A - Formaldehyde-free color-fixing agent for DMDAAC-AM-HEA copolymer and preparation method of color-fixing agent - Google Patents
Formaldehyde-free color-fixing agent for DMDAAC-AM-HEA copolymer and preparation method of color-fixing agent Download PDFInfo
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Abstract
The invention discloses a formaldehyde-free color-fixing agent for a DMDAAC-AM-HEA copolymer and a preparation method of the color-fixing agent. The formaldehyde-free color-fixing agent comprises the following components in parts by mass: 90-110 parts of dimethyl dipropenyl ammonium chloride, 12-20 parts of acrylamide, 6-10 parts of hydroxyethyl acrylate, 1.6-2.3 parts of persulfate, 0.45-0.85 part of hydrosulphite, 0.10-0.18 part of heavy metal ion capture agent and the balance of water. The dimethyl dipropenyl ammonium chloride is selected as a main monomer and is subjected to solution copolymerization with water-soluble acrylamide and hydroxyethyl acrylate so as to form a quaternary ammonium polymer with positive ions, so that the prepared color-fixing agent is environmental friendly, safe and good in color-fixing effect.
Description
Technical field
The present invention relates to the technical field of textile auxiliary, particularly relate to formaldehyde-free color fixing agent of a kind of DMDAAC-AM-HEA copolymer and preparation method thereof.
Background technology
Color-fixing agent a kind ofly improves the dyestuff auxiliary agent that color moisture resistant fastness is used on fabric, indispensable dyeing post-treatment agent when being direct dyes, REACTIVE DYES dye cellulose fibre.In recent years, along with the development of science and technology, dyeing and finishing technique have also been obtained significant raising, due to the raising of the expansion of World Textile trade and people's living standard, environmental consciousness, requires that textiles is comfortable, clean, safety.
From 20 century 70s, after Germany takes the lead in releasing blue angels plan, some developed countries states such as () such as Japan, the U.S. pass in succession through and implement about the various indexs of laws and regulations to textiles limit in the world.Green Textiles requires the dye material prohibitting the use carcinogenic, teratogenesis and biological degradability difference and some aromatic amine intermediate to produce in dyeing and printing process, also requires the auxiliary agent that uses containing heavy metal ion simultaneously and does not produce free formaldehyde.The Green Additives epoch that such as aldehyde-free colour stabilizer KS day by day strengthens in environmental consciousness are announced to the world splendidly.Existing formaldehyde-free color fixing agent adopts epoxychloropropane, dicyandiamide and diethylenetriamine to be raw material mostly, by the high polymer of condensation.And epoxychloropropane has severe toxicity, in preparation process, volatile gas is very large to harm, and it is very strict to production requirement in building-up process.In addition, the colour fixation of these color-fixing agent is undesirable, and these govern the process of industrialization of aldehyde-free colour stabilizer.
Summary of the invention
In view of this, one aspect of the present invention provides a kind of formaldehyde-free color fixing agent of DMDAAC-AM-HEA copolymer, and this color-fixing agent obtains by polymerisation in solution the color-fixing agent Environmental Safety that quaternary ammonium salt polymer makes to obtain with water-soluble monomer, and colour fixation is strong.
A formaldehyde-free color fixing agent for DMDAAC-AM-HEA copolymer, comprises in mass fraction: the water of 90 ~ 110 parts of dimethyl-dipropenyl ammonium chlorides, 12 ~ 20 parts of acrylamides, 6 ~ 10 parts of hydroxy-ethyl acrylates, 1.6 ~ 2.3 parts of persulfates, 0.45 ~ 0.85 part of bisulfites, 0.10 ~ 0.18 part of heavy metal ion agent for capturing and surplus.
Wherein, comprise in mass fraction: the water of 100 parts of dimethyl-dipropenyl ammonium chlorides, 16 parts of acrylamides, 8 parts of hydroxy-ethyl acrylates, 1.89 parts of persulfates, 0.63 part of bisulfites, 0.14 part of heavy metal ion agent for capturing and surplus.
Wherein, the mass fraction of described water is 140 ~ 280 parts.
Wherein, described heavy metal ion agent for capturing is the high polymer of dithiocarbamates polyvinyl alcohol.
In the technical scheme of above formaldehyde-free color fixing agent, compound selects dimethyl-dipropenyl ammonium chloride (DMDAAC), acrylamide (AM) and hydroxy-ethyl acrylate (HEA) to be monomer, three kinds of monomers are all containing unsaturated group propenyl, generable radical polymerization, can copolymer be obtained, can homopolymers be obtained again.The present invention passes through the proportioning of control three monomer based on the product of copolymer.Dimethyl-dipropenyl ammonium chloride, due to containing highdensity electric charge, can make during copolymerization introduce CATION in copolymer and produce tint retention.Dimethyl diallyl ammonium chloride is difficult to all be polymerized to the larger polymer of relative molecular mass, this may be containing more active allylic hydrogen in cationic monomer, make activated centre be easy to chain transfer reaction occurs, the allyl radical simultaneously produced has stronger from inhibition.But it but can the triallylamine high with reactivity and allyl alcohol copolymerization.The hydroxyl that hydroxy-ethyl acrylate contains can reduce the gel in polymeric solution thus improve the stability of polymeric solution.What deserves to be explained is, main based on block copolymer, random copolymer in the copolymer of three monomers, the product of a small amount of graft copolymer and alternate copolymer, wherein block copolymer is the copolymer products of target of the present invention.
Persulfate and bisulfites is selected to be the initator of oxidation/reduction system.Bisulfites can slow down persulfate as reductant and discharge free radical, thus makes chain reaction more steady.Select suitable initiator amount.When initiator amount is lower, in reaction system, free radical number is less, and rate of chain growth is lower, causes reaction conversion ratio lower not high with relative molecular mass that is copolymerization product; Along with the increase of initiator amount, cause free radical increased number, chain growth probability and speed all increase, and Copolymer molecular weight also obviously increases; But when initiator amount is too many, free radical number is too much in reaction system, and reaction speed is accelerated, and the collision between free radical and stopping of chain are also accelerated, cause Polymer Molecular Weight to decline and molecular vibrational temperature broadens, polymer performance declines.
Select heavy metal ion agent for capturing as chelating agent, effectively can catch the heavy metal ion impurities such as copper ion and zinc ion of some trace in solution, not only can avoid the adverse effect that the dyeing of these heavy metal ion impurities to dyestuff causes, the more important thing is can the proper extension free radical time-to-live, promote thoroughly carrying out of polymerisation, thus improve the overall viscosity of product.Heavy metal ion agent for capturing of the present invention is preferably the high polymer that heavy metal ion agent for capturing is dithiocarbamates polyvinyl alcohol, and the degree of polymerization is 500 ~ 2000.This heavy metal ion agent for capturing both cocoa, see method synthesis disclosed in Chinese patent CN101173019A, directly can buy again the commercially available metal ion capturing agent MCP of this patent application unit
tM.
Take water as solvent.Water provides place for polymerisation, and the mass fraction of water is preferably 140 ~ 280 parts.If the consumption of water is too much, the number of free radical that produces in solution can be made too low, and cause the speed of polymerisation too small, the conversion ratio of monomer is too small.Otherwise the consumption of water is very few, number of free radical can be made excessive, the chance that free radical collides increases, and polymerisation is too violent and be difficult to control, and makes the gel too much viscosity of augmenting response system in solution, when viscosity increases to a certain degree, just have and produce implode phenomenon.
The present invention provides on the other hand a kind of formaldehyde-free color fixing agent of DMDAAC-AM-HEA copolymer, and the method obtains by polymerisation in solution the color-fixing agent Environmental Safety that quaternary ammonium salt polymer makes to obtain with water-soluble monomer, and colour fixation is strong.
Prepare a method for above-mentioned CATION formaldehyde-free color fixing agent, comprise the following steps:
(1) in mass fraction, 90 ~ 110 parts of dimethyl-dipropenyl ammonium chlorides, 12 ~ 20 parts of acrylamides, 6 ~ 10 parts of hydroxy-ethyl acrylates are dissolved in water and are made into monomer solution, and 1.6 ~ 2.3 parts of persulfates, 0.45 ~ 0.85 part of bisulfites are dissolved in water and are made into initiator solution;
(2) in the solution of dissolving 0.10 ~ 0.18 part of heavy metal ion agent for capturing, add the described monomer solution of part and the described initiator solution of part, under constantly stirring condition, heat up and polymerisation in this solution is started;
(3) drop in the solution of polymerization reaction take place in step (2) by the described monomer solution of residue and the described initiator solution of residue, after dropwising, cooling stops polymerisation.
Wherein, the temperature of described polymerisation is 70 ~ 80 DEG C.
Wherein, 5 ~ 20% monomer solutions and 5 ~ 10% initiator solutions are added in described step (2).
Wherein, described polymerisation drips the described monomer solution of residue and the described initiator solution of residue after starting 30 ~ 60min, the time of described dropping is 1 ~ 3h; Described dropwise after stop polymerisation after 2 ~ 4h.
Wherein, describedly in the solution of dissolving 0.10 ~ 0.18 part of heavy metal ion agent for capturing, add the described monomer solution of part and the described initiator solution of part is specially: in the solution of dissolving 0.10 ~ 0.18 part of heavy metal ion agent for capturing, add the described monomer solution of part, then adjust ph, disposablely after being warming up to 65 ~ 70 DEG C adds the described initiator solution of part.
Wherein, described pH value is 6 ~ 7.
In the technical scheme of above preparation method, the feed way of monomer is continuous mode stage by stage, because this feed way can make the monomer in reaction be in " hunger " state preferably, therefore can significantly improve the conversion ratio of monomer.
Polymeric reaction temperature is 70 ~ 80 DEG C.Along with reaction temperature raises, conversion ratio improves constantly, and the inherent viscosity of polymer first rises and then reduces.This is because the decomposition rate of the change major effect initator of polymeric reaction temperature, when low temperature, raise with temperature, decomposition of initiator speed is accelerated gradually, creates more primary group of free radicals, promotes that chain propagation reaction is carried out.On monomer molecule chain, c h bond is relatively more active, and hydrogen atom is easy to be replaced by free radical chain tra nsfer occurs.But temperature is too high, chain termination and chain transfer reaction aggravation, Polymer Molecular Weight declines, and polymer property degree of carrying declines, but temperature raises, and polymerisation is still being carried out, and monomer conversion also just improves constantly.
Selective polymerization reaction total time is 3.5 ~ 8h.Here namely reaction time refer to the time of monomer dropping, twice, the front and back isothermal reaction temporal summation of monomer dropping.The starting stage of reaction, living radical is more, and polymerization rate is comparatively determined, and reaction conversion ratio also has obvious growth; After reaction reaches certain hour, living radical is fewer and feweri, and rate of chain growth is also more and more less, and polymerisation tends to be steady, and the relative molecular mass of polymer increases little.
DMDAAC-TAA-AA copolymer formaldehyde-free color fixing agent of the present invention comprises in mass fraction: comprising: the water of 90 ~ 110 parts of dimethyl-dipropenyl ammonium chlorides, 12 ~ 20 parts of acrylamides, 6 ~ 10 parts of hydroxy-ethyl acrylates, 1.6 ~ 2.3 parts of persulfates, 0.45 ~ 0.85 part of bisulfites, 0.10 ~ 0.18 part of heavy metal ion agent for capturing and surplus.Select dimethyl-dipropenyl ammonium chloride to be main monomer, form with cationic quaternary ammonium salt polymer with water miscible acrylamide and hydroxy-ethyl acrylate generation solution copolymerization, thus obtained color-fixing agent Environmental Safety, colour fixation is strong.
Detailed description of the invention
The present invention is described in further detail in conjunction with the embodiments respectively below.
Pulp furnish as described in the following Examples prepares polyquaternium color-fixing agent according to following steps:
(1) dimethyl-dipropenyl ammonium chloride of metering, acrylamide and hydroxy-ethyl acrylate are added in beaker add suitable quantity of water and fully stir and make it dissolve to be made into monomer solution.Metering persulfate and bisulfites are added in beaker and is dissolved in 10ml water and is made into initiator solution.Being poured in beaker to add water by metering heavy metal ion agent for capturing makes it fully dissolve.
(2) heavy metal ion agent for capturing solution and 5 ~ 20% monomer solutions are poured into be equipped with in the four-hole boiling flask of suitable quantity of water, then use watery hydrochloric acid adjust ph to 6 ~ 7.On four bottlenecks of four-hole boiling flask, install thermometer, electric blender, spherical condensation tube constant pressure funnel respectively, start electric blender, control speed of agitator is 150 ~ 250rpm.When temperature rises to 65 ~ 70 DEG C, disposablely add 5 ~ 10% initiator solutions, pour constant pressure funnel into after remaining monomer solution and initiator solution being mixed for subsequent use simultaneously, after the temperature stabilization in question response solution, start constant temperature polymerisation.
(3) when after polymerisation 30 ~ 60min, open constant pressure funnel valve to start to drip remaining monomer solution and initiator solution mixed liquor, control drip evenly fast and dropwise at 1 ~ 3h, then after isothermal reaction 2 ~ 4h, cooling stops polymerisation, and the viscous liquid that obtained yellowish is transparent is the formaldehyde-free color fixing agent of DMDAAC-AM-HEA copolymer.
Embodiment 1
Each pulp furnish is as follows:
Table note: MCP-1 heavy metal ion agent for capturing is the MCP that Guangzhou Nasen Chemical Co., Ltd. produces
tMone of model of series of products, following examples all with.
Polymeric reaction temperature is 70 DEG C; Polymerisation starts after starting 60min to drip residual monomer solution and initiator solution, and time for adding is 1h, and after dropwising rear 4h, cooling stops polymerisation.
Embodiment 2
Each pulp furnish is as follows:
Polymeric reaction temperature is 80 DEG C; Polymerisation starts after starting 30min to drip residual monomer solution and initiator solution, and time for adding is 2.5h, and after dropwising rear 3h, cooling stops polymerisation.
Embodiment 3
Each pulp furnish is as follows:
Polymeric reaction temperature is 75 DEG C; Polymerisation starts after starting 45min to drip residual monomer solution and initiator solution, and time for adding is 105min, and after dropwising rear 210min, cooling stops polymerisation.
Embodiment 4
Each pulp furnish is as follows:
Polymeric reaction temperature is 73 DEG C; Polymerisation starts after starting 40min to drip residual monomer solution and initiator solution, and time for adding is 2h, and after dropwising rear 200min, cooling stops polymerisation.
Embodiment 5
Each pulp furnish is as follows:
Polymeric reaction temperature is 76 DEG C; Polymerisation starts after starting 50min to drip residual monomer solution and initiator solution, and time for adding is 160min, and after dropwising rear 150min, cooling stops polymerisation.
Embodiment 6
Each pulp furnish is as follows:
Polymeric reaction temperature is 75 DEG C; Polymerisation starts after starting 40min to drip residual monomer solution and initiator solution, and time for adding is 2h, and after dropwising rear 200min, cooling stops polymerisation.
The color-fixing agent molecular weight of EX1600G type GPC to embodiment 1 ~ 6 adopting agate scientific & technical corporation of the U.S. hundred million to produce is measured.
Measure with reference to the monomer conversion of following methods to embodiment 1 ~ 6:
Take 0.3g color-fixing agent, be placed in baking oven and dry to constant weight at 110 DEG C, then:
Monomer conversion=(after drying color-fixing agent quality × each raw material components gross mass)/(before drying color-fixing agent quality × nonvolatile feed components quality); Here, nonvolatile feed components refers to other raw material components than water.
Adopt the color-fixing agent of embodiment 1 ~ 6 to fabric fixation, be specially: select 28tex × 28tex, 425 × 228/10cm is textile material, this fabric REACTIVE DYES (K/S=26.04) dyes black products.With 1.5%(owf) color-fixing agent, pH be 3 ~ 9, temperature be 50 DEG C at by infusion process fixation 20min post-drying.The method of fabric after fixation by GB/T3921-2008 " textile color stability examination is soaped and tested: soaping fastness " is measured soaping fastness; According to the method for pressing GB/T3920-2008 " textile color stability is tested: crock fastness ", friction jail is measured.
Each performance of the color-fixing agent of embodiment 1 ~ 6 is as follows:
As can be seen from the above table, the properties of the color-fixing agent of embodiment 6 is best, and the composition of raw materials described in embodiment 6 and the technological parameter of preparation are the present invention most preferably person.
It should be noted that and understand, when not departing from the spirit and scope of accompanying claim the present invention for required protection, various amendment and improvement can be made to the present invention of foregoing detailed description.Therefore, the scope of claimed technical scheme is not by the restriction of given any specific exemplary teachings.
Applicant states, the present invention illustrates detailed process equipment and process flow process of the present invention by above-described embodiment, but the present invention is not limited to above-mentioned detailed process equipment and process flow process, namely do not mean that the present invention must rely on above-mentioned detailed process equipment and process flow process and could implement.Person of ordinary skill in the field should understand, any improvement in the present invention, to equivalence replacement and the interpolation of auxiliary element, the concrete way choice etc. of each raw material of product of the present invention, all drops within protection scope of the present invention and open scope.
Claims (10)
1. the formaldehyde-free color fixing agent of a DMDAAC-AM-HEA copolymer, it is characterized in that, comprise in mass fraction: the water of 90 ~ 110 parts of dimethyl-dipropenyl ammonium chlorides, 12 ~ 20 parts of acrylamides, 6 ~ 10 parts of hydroxy-ethyl acrylates, 1.6 ~ 2.3 parts of persulfates, 0.45 ~ 0.85 part of bisulfites, 0.10 ~ 0.18 part of heavy metal ion agent for capturing and surplus.
2. formaldehyde-free color fixing agent according to claim 1, it is characterized in that, comprise in mass fraction: the water of 100 parts of dimethyl-dipropenyl ammonium chlorides, 16 parts of acrylamides, 8 parts of hydroxy-ethyl acrylates, 1.89 parts of persulfates, 0.63 part of bisulfites, 0.14 part of heavy metal ion agent for capturing and surplus.
3. formaldehyde-free color fixing agent according to claim 1, is characterized in that, the mass fraction of described water is 140 ~ 280 parts.
4. formaldehyde-free color fixing agent according to claim 1, is characterized in that, described heavy metal ion agent for capturing is the high polymer of dithiocarbamates polyvinyl alcohol.
5. prepare a method for formaldehyde-free color fixing agent according to claim 1, it is characterized in that, comprise the following steps:
(1) in mass fraction, 90 ~ 110 parts of dimethyl-dipropenyl ammonium chlorides, 12 ~ 20 parts of acrylamides, 6 ~ 10 parts of hydroxy-ethyl acrylates are dissolved in water and are made into monomer solution, and 1.6 ~ 2.3 parts of persulfates, 0.45 ~ 0.85 part of bisulfites are dissolved in water and are made into initiator solution;
(2) in the solution of dissolving 0.10 ~ 0.18 part of heavy metal ion agent for capturing, add the described monomer solution of part and the described initiator solution of part, under constantly stirring condition, heat up and polymerisation in this solution is started;
(3) drop in the solution of polymerization reaction take place in step (2) by the described monomer solution of residue and the described initiator solution of residue, after dropwising, cooling stops polymerisation.
6. method according to claim 5, is characterized in that, the temperature of described polymerisation is 70 ~ 80 DEG C.
7. method according to claim 5, is characterized in that, adds 5 ~ 20% monomer solutions and 5 ~ 10% initiator solutions in described step (2).
8. method according to claim 5, is characterized in that, in described step (2), polymerisation drips the described monomer solution of residue and the described initiator solution of residue after starting 30 ~ 60min, and the time of described dropping is 1 ~ 3h; Described dropwise after stop polymerisation after 2 ~ 4h.
9. method according to claim 5, it is characterized in that, describedly in the solution of dissolving 0.10 ~ 0.18 part of heavy metal ion agent for capturing, add the described monomer solution of part and the described initiator solution of part is specially: in the solution of dissolving 0.10 ~ 0.18 part of heavy metal ion agent for capturing, add the described monomer solution of part, then adjust ph, disposablely after being warming up to 65 ~ 70 DEG C adds the described initiator solution of part.
10. method according to claim 9, is characterized in that, described pH value is 6 ~ 7.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108824035A (en) * | 2018-07-05 | 2018-11-16 | 陈国宝 | A kind of fabrics printing and dyeing color fixing agent and preparation method thereof |
| CN115094654A (en) * | 2022-08-23 | 2022-09-23 | 江苏富淼科技股份有限公司 | Polymer color fixing agent and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108824035A (en) * | 2018-07-05 | 2018-11-16 | 陈国宝 | A kind of fabrics printing and dyeing color fixing agent and preparation method thereof |
| CN115094654A (en) * | 2022-08-23 | 2022-09-23 | 江苏富淼科技股份有限公司 | Polymer color fixing agent and preparation method thereof |
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Application publication date: 20150318 |