CN1431360A - Fiber modifier for cellulose, its preparation and application - Google Patents
Fiber modifier for cellulose, its preparation and application Download PDFInfo
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- CN1431360A CN1431360A CN 03114881 CN03114881A CN1431360A CN 1431360 A CN1431360 A CN 1431360A CN 03114881 CN03114881 CN 03114881 CN 03114881 A CN03114881 A CN 03114881A CN 1431360 A CN1431360 A CN 1431360A
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Abstract
A modifier with 400-1700 of average molecular weight for cellulose fibre is prepared through reaction between polyepoxy chloropropane and bimethylamine in mole ratio of 1:(1-3), and features no obvious cationic nature and high water solubility. It can increase the dyeability and color fixing rate and decrease environmental pollution.
Description
Technical field
The present invention relates to the textile printing and dyeing technology, specifically a kind of cellulose fiber modifier, preparation method and application, this modifier is a kind of poly-epoxychloropropane dimethylamine derivative that does not have cationic.
Background technology
Poly-epoxychloropropane dimethylamine derivative (PECH-amine) is by epoxychloropropane polymerization in advance as a kind of cellulose fiber cation modifier, and then make with the dimethylamine amination.Hydrin (PECH) is used widely in textile finishing as a kind of elastomer, simultaneously, utilize chloromethyl and ammoniate reaction in the PECH polymer can make cationization, water miscible polyepichlorohydrin amine thing, with the difference of dimethylamine consumption, can obtain the polymer of different amido content:
PECH-amine has multiple reactive group and cation position: keep the part chlorine atom in the polymer, polymer can with cellulose fibre generation covalent bonds; The protonated back of amido forms positively charged ammonium salt under the acid condition, therefore, can improve the dye-uptake of anionic dye (direct dyes, REACTIVE DYES, ACID DYES and leuco vat dye etc.) greatly with this reagent pretreatment of fiber cellulose fiber, reduce discharging (the DMLewis and KA Mcilroy of dyeing waste-water, Chemical modification of cellulosic fibres to enhancedyeability, Rev.Prog.Coloration, 1997, (27): 5～17; RB Chavan and DPChattopadhyay, Cationization of cotton for improved dyeability, ColourageAnnual, 1998:127～133; O.Junger and K.Schafer, Cationisation of lyocell, Melliand English, 1999 (3): E50～E53; TS Wu and KM Chen, New cationic agentsfor improving the dyeability of cellulose fibres, JSDC, 1993 (108): 388～394; TS Wu and KM Chen, New cationic agents for improving the dyeabilityof cellulose fibres, JSDC, 1993, (109): 153～158).
But directly there are many problems in application,
First, because modifier amino-contained or nitrogen-atoms are more, so chloromethyl is less in the PECH-amine molecule, the reactivity of modifier and cellulose fibre is also not too high, when dye strength is higher than 0.5%o.w.f., dyeing still need be with salt, but also owing to contain amino or nitrogen-atoms is more, easily yellowing of modified fibre.
The second, because used polymer molecular weight is bigger, modification often occurs in the surface, and preliminary treatment is inhomogeneous very easily to cause uneven dyeing, more obvious when dye strength is low.
The 3rd, cellulose fibre behind the cationization and anionic dye are because of electrostatic attraction, and everybody thorny problem is for many years perplexed in the uneven dyeing that dyeing rate causes too soon especially, also are that the cationization cotton can not really be realized industrialized main reason.
Summary of the invention
The purpose of this invention is to provide a kind of cellulose fiber modifier that does not have cationic, this cellulose fiber modifier is a kind of polyepichlorohydrin amine thing, and modifier molecules amount and nitrogen content are moderate, have good water-solubility, but do not have tangible cationic.Therefore, under the prerequisite that guarantees level-dyeing property, can improve dye-uptake and the degree of fixation of modified fibre greatly to anionic dye.
Purpose of the present invention also provides a kind of preparation method of above-mentioned cellulose fiber modifier.
Another object of the present invention provides a kind of technique for applying of above-mentioned cellulose fiber modifier.
Cellulose fiber modifier of the present invention is a kind of polyepichlorohydrin amine thing that does not have cationic, and it has following structural formula:
Wherein, mean molecule quantity is 400～1700, is recommended as 450～1500, and the mol ratio of Hydrin and dimethylamine is 1: 1～3, the content 1.5～4% of modifier nitrogen.
The preparation method of above-mentioned cellulose fiber modifier of the present invention, in organic solvent and molecular formula be BF
3O (C
2H
5)
2The etherate of trifluoroboron catalyst exist down, epoxychloropropane react 4-20 hour when room temperature, dry must faint yellow Hydrin.Wherein the mol ratio of epoxychloropropane and etherate of trifluoroboron is 20～30: 1, and recommending mol ratio is 25～30: 1.
Be that 1: 1～3 material proportion carries out aminating reaction more by weight with Hydrin and dimethylamine: dimethylamine dropwises in 1 hour prior to 70～100 ℃, continued aminating reaction again 5～10 hours, amination finishes the back and removes unreacted amine, promptly gets product of the present invention.Remove unreacted amine, be preferably in method dry in the vacuum drying chamber.
Because cellulose fiber modifier molecular weight and nitrogen content are moderate in the method for the present invention, modifier has good water-solubility, does not but have tangible cationic, therefore, under the prerequisite that guarantees level-dyeing property, can improve dye-uptake and the degree of fixation of modified fibre greatly to anionic dye.Dyeing can be carried out under neutrality, salt-free condition, makes cleaning dye salt-free substantially in the dyeing waste-water, no dyestuff become possibility.Specifically: the rate of addition of control epoxychloropropane slowly carries out reaction, with the molecular weight and the distribution of control Hydrin at normal temperatures; The amination degree of control Hydrin and dimethylamine makes the nitrogen content of modifier reach desirable state.
Cellulose fiber modifier of the present invention has preferably and leaves many chloromethyl active groups in heat endurance, water-soluble, the big molecule, do not have tangible cationic.Before and after the cellulose fibre modification, total color difference Δ E (comprising poor, the hue difference of deep or light poor, gorgeous degree) separately is very approaching for dyeing.As before the modification cotton dyeing with surfactant A ES pre-soaked processing, the level-dyeing property of dyeing and through-dyeing even also good than unmodified cotton.And under alkali condition, good reactivity is arranged with cellulosic molecule, and preliminary treatment is with one bathing infusion process, rolling-the baking method, and modified effect is all more satisfactory, especially one bathes infusion process, and is all very high to the dye-uptake of direct dyes and chemically-reactive dyes.For chemically-reactive dyes, one bathes K/S value after the infusion process modification has improved 20～70 times before than modification, also more much bigger than direct dyes raising multiples (3～9 times).And modified fibre can be with direct dyes, chemically-reactive dyes dyeing under neutral, salt-free condition, and dye-uptake adds the much taller of 30g/L sodium chloride dyeing than unmodified fibers.Even can exhaust fully directly freezing the following dye bath of two dye strength 2%o.w.f. of yellow G, reactive brilliant red M8B.Reduce or avoided the discharging and the pollution of electrolyte and hydrolised dye, be particularly useful for ecological environment, lay strong basis for realizing cleaning dye technology.Adopt cellulose fiber modifier of the present invention and method, modified fibre not only can dye under neutrality, salt-free condition, can also reach higher degree of fixation in fixation under the neutrallty condition.The soaping fastness of chemically-reactive dyes has improved 2 grades.
Before and after the modification of description of drawings Fig. 1 cellulose fibre and the direct Fig. 2 cellulose fibre modification front and back and the substantivity of directly freezing yellow G of reactive brilliant red M8B
The specific embodiment
To help to understand the present invention by following embodiment, but not limit content of the present invention.
Embodiment 1
(1) raw material:
(a) monomer: epoxychloropropane (AR), the Shanghai phenanthrene reaches industry and trade Co., Ltd
(b) solvent: carbon tetrachloride (AR), Chinese Song Kai Industrial Co., Ltd.
(c) catalyst: etherate of trifluoroboron (CR), the Shanghai phenanthrene reaches industry and trade Co., Ltd
(d) aminating agent: 33% dimethylamine agueous solution (CR), Chinese Medicine (group) Shanghai chemical reagent
Company
(2) operation sequence:
Earlier in the 500ml three-necked bottle, add 100mlCCl
4, 8ml BF
3O (C
2H
5)
2, 200 gram epoxychloropropane divide slow, evenly dropping in 6 hours in 29 ℃.Reaction is put 60 ℃ of vacuumizes of Rotary Evaporators after finishing, and gets faint yellow Hydrin.
Again with Hydrin and dimethylamine by weight 2: 3) material proportion carry out aminating reaction: dimethylamine dropwises in 1 hour prior to 80～95 ℃, drips to continue aminating reactions 8 hours in 80～95 ℃ again after finishing, and amination finishes.In vacuum drying chamber, separate unreacted amine, promptly get final products.
Embodiment 2PECH-amine bathes the modification of high temperature infusion process to cellulose fibre one
Plain weave bleached cotton cloth 40
s* 40
s
Modification formula of liquid: modifier (molecular weight M
n1,380, nitrogen content 2.55%) concentration 1～4g/L
NaOH 2～4g/L bath raio: 1: 50
Heating curve: bleached cotton cloth is warming up to 95 ℃ at 40 ℃ by 2 ℃ of per minutes, is incubated 50 minutes, is cooled to room temperature, running water flushing, drying at room temperature.
Embodiment 3
Dyeing before and after the modification under salt-free, the neutrallty condition of cellulose fibre
Dyeing prescription: dyestuff: directly freeze yellow G (C.I.Direct Yellow 12) (vapour crust)
Reactive Brilliant Red M-8B (vapour crust)
Direct dark green NB (vapour crust)
Reactive turquoise blue M-GB (vapour crust)
Dye strength: 1.5% (o.w.f.)
Bath raio: the dyeing heating curve was with embodiment 2 in 1: 50.Absorbance is recorded by 721 type spectrophotometers, and the K/S value is measured by deta color SF600 color measurement and color match instrument.Experimental result: as table 1
K/S value and the dye uptake of table 1 modification cotton and unmodified cotton
| Modifier concentration (g/L) | NaOH 4g/L in 1.5% (o.w.f.) reactive red M8B modification liquid | 1.5% (o.w.f.) directly freezes NaOH 4g/L in the yellow G modification liquid | ||
| ????K/S | Dye uptake | ????K/S | Dye uptake | |
| ????0 | ????0.21 | ?????/ | ????3.0 | ????/ |
| ????1 | ????12.12 | ?????64.71％ | ????22.07 | ????66.76％ |
| ????2 | ????14.32 | ?????92.27％ | ????25.82 | ????90.00％ |
| ????3 | ????15.56 | ?????97.70％ | ????26.29 | ????95.15％ |
| ????4 | ????16.31 | ?????98.53％ | ????27.26 | ????97.82％ |
Cotton salt-free dyeing of embodiment 4 modifications and unmodified cotton have salt dyeing
Colouring method such as embodiment 3, the result is shown in table 2 and Fig. 1～2.
The cotton neutrality with unmodified cotton of table 2 modification dyes
The unmodified cotton modification cotton of unmodified cotton
Dyestuff (1.5%o.w.f.) (not with salt) (NaCl 30g/L) (not with salt)
K/S??????????K/S??????????????K/S
Directly freeze yellow G 2.97 14.52 25.66
Direct dark green NB 4.96 8.59 13.83
Reactive Brilliant Red M-8B 0.57 3.79 11.71
Reactive turquoise blue M-GB 0.21 3.37 14.11
The comparison of embodiment 5 modifier of the present invention and market like product
Modifier: DE-Z cellulose cation modifier: dimethylene three ammonia that Donghua University produces and the reaction of epoxychloropropane
Concentration: 5g/L, bath raio: 1: 20Cm cellulose cation modifier: the quaternary ammonium compound that printing and dyeing research institute in Shanghai produces
Concentration: 20g/L, bath raio: 1: 50CA-1 cellulose cation modifier: the aminating agent that printing and dyeing research institute in Shanghai produces
Concentration: 6g/L, bath raio: 1: 50
Cellulose modified dose of (molecular weight M of the present invention
n1,380, nitrogen content 2.55%)
Concentration: 2g/L, bath raio: 1: 50
Dyestuff: Reactive Brilliant Red M-8B, 2%o.w.f.
Dyeing is carried out as embodiment 2, and is neutral, salt-free, and 40 ℃ of initial temperatures rise to 95 ℃ and continuous dye 50min, add 2g/L soap powder (bath raio 1: 100) soap boiling 10min then, and washing is dried in the shade, mensuration K/S value.
Result such as table 3:
Table 3 compares through the K/S value of different modifier modification after stain chromaticities
| The dyeing type | ????K/S |
| Unmodified | ????0.27 |
| The DE-Z modification | ????1.12 |
| ????C mModification | ????1.178 |
| The CA-1 modification | ????1.66 |
| Modifier of the present invention | ????10.14 |
Claims (7)
1, a kind of cellulose fiber modifier that does not have cationic, it has following structural formula:
Wherein, mean molecule quantity is 400～1700, is recommended as 450～1500, and the mol ratio of Hydrin and dimethylamine is 1: 1～3, the content 1.5～4% of modifier nitrogen.
2, a kind of cellulose fiber modifier as claimed in claim 1 is characterized in that mean molecule quantity is 450～1500, and nitrogen content 1.5～4% does not have tangible cationic.
3, the preparation method of a kind of cellulose fiber modifier as claimed in claim 1 is characterized in that in organic solvent and molecular formula is BF
3O (C
2H
5)
2The etherate of trifluoroboron catalyst exist down, epoxychloropropane react 4-20 hour when room temperature, dry must Hydrin, wherein the mol ratio of epoxychloropropane and etherate of trifluoroboron is 20～30: 1; Be that 1: 1～3 material proportion carried out aminating reaction 5～10 hours more by weight with Hydrin and dimethylamine, remove unreacted amine.
4, the preparation of a kind of cellulose fiber modifier as claimed in claim 3 is characterized in that removing unreacted amine and ties up in the vacuum drying chamber dry.
5, a kind of cellulose fiber modifier as claimed in claim 1 is used, and its feature is used for the modification of cellulose fibre, preliminary treatment with a bath infusion process, roll-baking method or the volume method of rolling can both reach fabulous effect.
6, a kind of cellulose fiber modifier as claimed in claim 1 is used, its feature is used for the modification of cellulose fibre, one modified technique of bathing (high temperature) infusion process is: modification formula of liquid: modifier concentration 1～4g/L, NaOH 1～4g/L, bath raio: 1: 10～50, heating curve: 40 ℃ of initial temperature rise to 95 ℃ by 2 ℃ of programming rates of per minute, be incubated 50 minutes, be cooled to room temperature, running water flushing, drying at room temperature.
7, a kind of cellulose fiber modifier as claimed in claim 1 is used, its feature is used for the modification of cellulose fibre, modified fibre is under neutrality, salt-free condition, available anionic dye (direct dyes, chemically-reactive dyes etc.) dyeing, under the prerequisite that guarantees level-dyeing property, obtain high dye-uptake and degree of fixation, the following dye bath of 2%o.w.f. can exhaust fully, is particularly useful for ecological environment.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031148816A CN1190548C (en) | 2003-01-14 | 2003-01-14 | Fiber modifier for cellulose, its preparation and application |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031148816A CN1190548C (en) | 2003-01-14 | 2003-01-14 | Fiber modifier for cellulose, its preparation and application |
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| Publication Number | Publication Date |
|---|---|
| CN1431360A true CN1431360A (en) | 2003-07-23 |
| CN1190548C CN1190548C (en) | 2005-02-23 |
Family
ID=4790513
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB031148816A Expired - Fee Related CN1190548C (en) | 2003-01-14 | 2003-01-14 | Fiber modifier for cellulose, its preparation and application |
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| Country | Link |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100343183C (en) * | 2006-06-06 | 2007-10-17 | 山东大学 | Polyepichlorohydrin-dimethylamine organic polymer coargulator and its preparation technology |
| WO2008141522A1 (en) * | 2007-05-18 | 2008-11-27 | Guangdong Demei Fine Chemicals Co. Ltd. | Modifying and dyeing method of fiber material |
| CN101864668A (en) * | 2010-06-18 | 2010-10-20 | 上海工程技术大学 | Modifier for improving dye-uptake of kawokawofibers, preparation method thereof and use thereof |
| CN102134806A (en) * | 2011-04-27 | 2011-07-27 | 广州湘中纺织助剂有限公司 | Salt-free rolling, baking, dying and low-temperature soaping method for fiber reactive dyes |
| CN104233866A (en) * | 2014-09-17 | 2014-12-24 | 华南理工大学 | Method for cation modification and salt-free dyeing of cellulose fiber fabric |
| CN106758212A (en) * | 2016-12-12 | 2017-05-31 | 上海雅运纺织助剂有限公司 | A kind of modification nonwoven cloth and its preparation and application |
| CN108914548A (en) * | 2018-06-15 | 2018-11-30 | 石家庄天略工业用布有限公司 | A kind of cloth and the preparation method and application thereof with superpower adsorptivity |
| CN114164687A (en) * | 2022-01-13 | 2022-03-11 | 常州纺织服装职业技术学院 | Cotton fabric cationic modifier and application thereof |
-
2003
- 2003-01-14 CN CNB031148816A patent/CN1190548C/en not_active Expired - Fee Related
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100343183C (en) * | 2006-06-06 | 2007-10-17 | 山东大学 | Polyepichlorohydrin-dimethylamine organic polymer coargulator and its preparation technology |
| WO2008141522A1 (en) * | 2007-05-18 | 2008-11-27 | Guangdong Demei Fine Chemicals Co. Ltd. | Modifying and dyeing method of fiber material |
| CN101864668A (en) * | 2010-06-18 | 2010-10-20 | 上海工程技术大学 | Modifier for improving dye-uptake of kawokawofibers, preparation method thereof and use thereof |
| CN101864668B (en) * | 2010-06-18 | 2012-05-30 | 上海工程技术大学 | Modifier for improving dyeing rate of kapok fiber and preparation method and application thereof |
| CN102134806A (en) * | 2011-04-27 | 2011-07-27 | 广州湘中纺织助剂有限公司 | Salt-free rolling, baking, dying and low-temperature soaping method for fiber reactive dyes |
| CN102134806B (en) * | 2011-04-27 | 2012-10-03 | 广州湘中纺织助剂有限公司 | Salt-free rolling, baking, dying and low-temperature soaping method for fiber reactive dyes |
| CN104233866A (en) * | 2014-09-17 | 2014-12-24 | 华南理工大学 | Method for cation modification and salt-free dyeing of cellulose fiber fabric |
| CN104233866B (en) * | 2014-09-17 | 2016-07-06 | 华南理工大学 | A kind of cellulose base fiber fabric is cation-modified and the method for salt-free dyeing |
| CN106758212A (en) * | 2016-12-12 | 2017-05-31 | 上海雅运纺织助剂有限公司 | A kind of modification nonwoven cloth and its preparation and application |
| CN108914548A (en) * | 2018-06-15 | 2018-11-30 | 石家庄天略工业用布有限公司 | A kind of cloth and the preparation method and application thereof with superpower adsorptivity |
| CN114164687A (en) * | 2022-01-13 | 2022-03-11 | 常州纺织服装职业技术学院 | Cotton fabric cationic modifier and application thereof |
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| Publication number | Publication date |
|---|---|
| CN1190548C (en) | 2005-02-23 |
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Assignee: Wuhu Fuchun Dye and Weave Co., Ltd. Assignor: Donghua University Contract record no.: 2011340000178 Denomination of invention: Fiber modifier for cellulose, its preparation and application Granted publication date: 20050223 License type: Exclusive License Open date: 20030723 Record date: 20110726 |
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