CN104831562A - Hydroxypropyl carboxymethyl waxy corn starch acid dye printing paste and preparation method - Google Patents
Hydroxypropyl carboxymethyl waxy corn starch acid dye printing paste and preparation method Download PDFInfo
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- CN104831562A CN104831562A CN201510222145.0A CN201510222145A CN104831562A CN 104831562 A CN104831562 A CN 104831562A CN 201510222145 A CN201510222145 A CN 201510222145A CN 104831562 A CN104831562 A CN 104831562A
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Abstract
The invention discloses a hydroxypropyl carboxymethyl waxy corn starch acid dye printing paste which is prepared from the following raw materials, by weight, 95-105 parts of waxy corn starch, 190-210 parts of an ethanol aqueous solution, 4-8 parts of sodium hydroxide, 20-25 parts of epoxypropane and 14-21 parts of chloroacetic acid. A preparation method of the paste comprises the following steps: uniformly dissolving waxy corn starch in the ethanol aqueous solution, and carrying out an alkalization reaction by adding sodium hydroxide; carrying out an etherification reaction by adding epoxypropane after the alkalization reaction is finished; adding chloroacetic acid after the etherification reaction is finished, heating to 65-75 DEG C and reacting for 2-3 h; cooling to 25-35 DEG C after the reaction is finished, adjusting pH value of the reaction system to neutral by using hydrochloric acid, washing, carrying out suction filtration, drying at 80 DEG C, and crushing to obtain the product. When used in acid dye printing, the product has high tinctorial yield, good contour sharpness and high de-paste ratio. The acid dye printing paste provided by the invention can be used in acid dye printing, is biodegradable and meets requirements of eco-environmental protection.
Description
Technical field
The invention belongs to the preparing technical field of ACID DYES printing gum, be specifically related to a kind of solvent method and prepare hydroxypropyl carboxy methyl waxy corn starch ACID DYES printing gum.
Background technology
Require during ACID DYES stamp that thickener possesses good acid-proof alkaline, and conventional sodium alginate, carboxymethyl cellulose, carboxymethyl starch thickener all belong to anionic paste, its acid and alkali resistance is very poor, when pH value is lower, in molecule ,-COONa changes-COOH into, cause its viscosity to reduce, produce gelatin phenomenon.In addition the effect of the thickener such as sodium alginate not anticalcium magnesium ion, and the mordant that some acid mordant dyes use is mostly containing heavy metal ion.Convention acidic reactive dye printing paste, mainly based on guar gum and derivative thereof, in recent years, affects by supply-demand relationship, and the price of guar gum significantly rises, and researchers start to seek new ACID DYES printing gum.
Waxy corn starch is almost all made up of amylopectin, compared with other starch, and the expansive force of waxy corn starch, transparency, viscosity is large and filming performance is good, has shear shinning, and its stability of sticking with paste liquid is also fine, easy to digest, not easily aging, be the fabulous raw material of industry.But without processing modified waxy corn starch to pH value, all unstable in temperature and storage, its range of application is limited by very large.The character of modified waxy corn starches, increases its some functional character or introduces new characteristic, makes it more meet commercial Application requirement, and waxy corn starch is all fully utilized in each field.
In prior art, useful dry method and wet processing prepare hydroxypropul starch, the hydroxypropyl carboxy methyl starch of low degree of substitution, and dry method and solvent method prepare carboxymethyl starch.And the hydroxypropyl carboxy methyl starch substitution value of current most of researcher's synthesis is lower, the product hydroxypropyl substitution value of preparation is mostly lower than 0.1, and cold water is insoluble or water-soluble poor, is mainly used in spinning sizing agent, food additives etc.The hydroxypropyl carboxy methyl starch of dry process, impurity in products is more, and reaction efficiency is low, and product need carry out washing impurity-removing with a large amount of organic reagents, complex procedures, and dry process reaction requires higher to reaction condition, otherwise the danger of easily blasting.The hydroxypropyl carboxy methyl starch of Moist chemical synthesis, product substitution value is lower, with the addition of a large amount of salts as swelling inhibitor in reaction system.Wet production condition is also wayward, if it is improper that the conditions such as temperature, starch concentration, catalyst amount control, very easily make product generation gelatin phenomenon, for subsequent technique brings extreme difficulties, and this method reaction efficiency is low, water consumption, power consumption are greatly, simultaneously owing to adding a large amount of salt, also comparatively serious to the corrosion of equipment.
Summary of the invention
Technical problem to be solved by this invention be prepare that ACID DYES printing gum reaction efficiency is low for prior art, complex procedures and the high defect of cost, a kind of preparation method of hydroxypropyl carboxy methyl waxy corn starch ACID DYES printing gum is provided, utilize solvent method, carry out composite modified to waxy corn starch, cold water-soluble, thickener mobility and saturating net are all better, transparency is higher, meets the requirement of ACID DYES printing gum.
For solving the problems of the technologies described above, the present invention by the following technical solutions: a kind of preparation method of hydroxypropyl carboxy methyl waxy corn starch ACID DYES printing gum, step is as follows:
A kind of hydroxypropyl carboxy methyl waxy corn starch ACID DYES printing gum, it is made up of the raw material of following portions by weight: waxy corn starch 95 ~ 105 parts, ethanol water 190 ~ 210 parts, 4 ~ 8 parts, NaOH, expoxy propane 20 ~ 25 parts, monoxone 14 ~ 21 parts; The hydroxypropyl substitution value (MS) of described hydroxypropyl carboxy methyl cornstarch ACID DYES printing gum is 0.30 ~ 0.40, and degree of substitution by carboxymethyl (DS) is 0.2 ~ 0.3.
A preparation method for hydroxypropyl carboxy methyl waxy corn starch ACID DYES printing gum, step is as follows:
(1) waxy corn starch is joined in ethanol water, be stirred to waxy corn starch and be dispersed in ethanol water, then add NaOH, quaternization 25 ~ 35min under the condition of 20 ~ 30 DEG C;
(2) quaternization adds expoxy propane after terminating, and is warming up to 60 ~ 75 DEG C and carries out etherification reaction 8 ~ 10h after stirring;
(3) etherification reaction is cooled to 45 ~ 55 DEG C after terminating, and then adds monoxone, is warming up to 65 ~ 75 DEG C of reaction 2 ~ 3h after stirring;
(4) reaction is cooled to 25 ~ 35 DEG C after terminating, and regulates pH value of reaction system to neutral with hydrochloric acid, namely obtains hydroxypropyl carboxy methyl waxy corn starch and be applied to ACID DYES stamp after washing, suction filtration, 80 DEG C of oven dry, pulverizing.
In described step (1), the bath raio of waxy corn starch and ethanol water is 1:2.
In described step (1), the mass fraction of ethanol water is 70 ~ 95%.
NaOH distilled water in described step (1) dissolves and is cooled to room temperature.
Hydroxypropyl carboxy methyl waxy corn starch ACID DYES printing gum is used for ACID DYES stamp.
Beneficial effect of the present invention: (1) raw material of the present invention waxy corn starch is full amylopectin, relative to common starch as: tapioca, wheaten starch and common corn starch etc., waxy corn starch viscosity is high, and anti-aging, transparency is good.Former waxy corn starch not cold water solubles, can not be used for printing gum, must pass through modification.(2) hydroxypropyl waxy corn starch belongs to non-ionic starch analog derivative, forms the ehter bond of strong stability between starch and the hydroxypropyl molar of nonionic, makes hydroxypropul starch have good acid-proof alkaline.And in the hydroxypropyl molar of high substituted degree, introduce more hydrophilic radical hydroxypropyl, reduce the internal hydrogen bond strength of starch granules structure, make it be easy to expand, gelatinization is easy, and cold water-soluble is good, thickener good fluidity, saturating net is also better, and transparency is higher, meets the requirement of printing gum.(3) hydroxypropyl carboxy methyl waxy corn starch is further modification on the basis of preparing hydroxypropyl waxy corn starch, and the carboxymethyl group introducing strong polarity can improve the de-paste of thickener.Product had both possessed the acid-proof alkaline of hydroxypropyl waxy corn starch, possessed again the key property of carboxymethyl waxy corn starch.Hydroxypropyl substitution value (MS) is between 0.30 ~ 0.40, and when degree of substitution by carboxymethyl (DS) is between 0.2 ~ 0.3, hydroxypropyl carboxy methyl waxy corn starch has good resistance to acids and bases, viscosity is high, dissolubility good, good fluidity.(4) when hydroxypropyl carboxy methyl waxy corn starch ACID DYES printing gum of the present invention is used for ACID DYES stamp, tinctorial yield is high, contour sharpness good, de-paste rate is high, feel is good, after stamp, overall target is excellent, may be used for ACID DYES stamp, and starch material is abundant, low price, easily biological-degradable, when environmental problem comes into one's own day by day, this invention meets the requirement of ecological, environmental protective, result of study has also expanded the novelty teabag of converted starch, and industrial value is high.
Detailed description of the invention
Embodiment 1
The preparation method of the hydroxypropyl carboxy methyl waxy corn starch ACID DYES printing gum of the present embodiment, step is as follows:
(1) 95g waxy corn starch being joined 190mL mass fraction is in the ethanol water of 70%, is stirred to waxy corn starch and is dispersed in ethanol water, then add 4g NaOH, quaternization 35min under the condition of 20 DEG C;
(2) quaternization adds 20g expoxy propane after terminating, and is warming up to 60 DEG C and carries out etherification reaction 10h after stirring;
(3) etherification reaction is cooled to 45 DEG C after terminating, and then adds 14g monoxone, is warming up to 65 DEG C of reaction 3h after stirring;
(4) reaction is cooled to 25 DEG C after terminating, and regulates pH value of reaction system to neutral with hydrochloric acid, namely obtains hydroxypropyl carboxy methyl waxy corn starch and be applied to ACID DYES stamp after washing, suction filtration, 80 DEG C of oven dry, pulverizing.
Embodiment 2
A kind of hydroxypropyl carboxy methyl waxy corn starch ACID DYES printing gum, is characterized in that it is made up of the raw material of following portions by weight: waxy corn starch 95 ~ 105 parts, ethanol water ~ 210 part, 4 ~ 8 parts, NaOH, expoxy propane 20 ~ 25 parts, monoxone 14 ~ 21 parts; The hydroxypropyl substitution value of described hydroxypropyl carboxy methyl cornstarch ACID DYES printing gum is 0.30 ~ 0.40, and degree of substitution by carboxymethyl is 0.2 ~ 0.3.
The preparation method of the hydroxypropyl carboxy methyl cornstarch ACID DYES printing gum of the present embodiment, step is as follows:
(1) 100g waxy corn starch being joined 200mL mass fraction is in the ethanol water of 80%, is stirred to waxy corn starch and is dispersed in ethanol water, then add 6g NaOH, quaternization 30min under the condition of 25 DEG C;
(2) quaternization adds 22g expoxy propane after terminating, and is warming up to 70 DEG C and carries out etherification reaction 9h after stirring;
(3) etherification reaction is cooled to 50 DEG C after terminating, and then adds 18g monoxone, is warming up to 70 DEG C of reaction 2.5h after stirring;
(4) reaction is cooled to 30 DEG C after terminating, and regulates pH value of reaction system to neutral with hydrochloric acid, namely obtains hydroxypropyl carboxy methyl waxy corn starch ACID DYES printing gum after washing, suction filtration, 80 DEG C of oven dry, pulverizing.
Embodiment 3
The preparation method of the hydroxypropyl carboxy methyl cornstarch ACID DYES printing gum of the present embodiment, step is as follows:
(1) 105g waxy corn starch being joined 210mL mass fraction is in the ethanol water of 95%, is stirred to waxy corn starch and is dispersed in ethanol water, then add 8g NaOH, quaternization 25min under the condition of 30 DEG C;
(2) quaternization adds 25g expoxy propane after terminating, and is warming up to 75 DEG C and carries out etherification reaction 8h after stirring;
(3) etherification reaction is cooled to 55 DEG C after terminating, and then adds 21g monoxone, is warming up to 75 DEG C of reaction 2h after stirring;
(4) reaction is cooled to 35 DEG C after terminating, and regulates pH value of reaction system to neutral with hydrochloric acid, namely obtains hydroxypropyl carboxy methyl waxy corn starch ACID DYES printing gum after washing, suction filtration, 80 DEG C of oven dry, pulverizing.
Embodiment 4
Hydroxypropyl carboxy methyl starch thickener is prepared, wherein waxy corn starch 100g, ethanol water 190mL, distilled water 10g by the step of embodiment 1, NaOH is 6g, 30 DEG C of alkalization 30min, and expoxy propane is 20g, 75 DEG C of reaction 8h, monoxone is 14g, 70 DEG C of reaction 2h.
Embodiment 5
Hydroxypropyl carboxy methyl starch thickener is prepared, wherein waxy corn starch 100g, ethanol water 190mL, distilled water 10g by the step of embodiment 2, NaOH is 6g, 30 DEG C of alkalization 30min, and expoxy propane is 25g, 75 DEG C of reaction 10h, monoxone is 21g, 70 DEG C of reaction 3h.
Embodiment 6
Prepare hydroxypropyl carboxy methyl starch thickener, wherein waxy corn starch 100g, ethanol water 190mL, distilled water 10g by embodiment 2, NaOH is 6g, 30 DEG C of alkalization 30min, and expoxy propane is 20g, 75 DEG C of reaction 8h, and monoxone is 21g, 70 DEG C of reaction 3h.
Embodiment 7
Hydroxypropyl carboxy methyl Waxy Maize Starch Pastes material is prepared, wherein waxy corn starch 100g, ethanol water 190mL, distilled water 10g by embodiment 3, NaOH is 6g, 30 DEG C of alkalization 30min, and expoxy propane is 25g, 75 DEG C of reaction 10h, monoxone is 14g, 70 DEG C of reaction 2h.
Sample prepared by above-mentioned 1 ~ 7 embodiment prepares former paste → modulation mill base (ACID DYES 3 parts by mass fraction 6%, 5 parts, urea, 3 parts, ammonium sulfate, former paste 80 parts, distilled water 9 parts) → stamp → oven dry (60 DEG C) → decatize (105 DEG C, 20min) → buck washes (sodium carbonate 3g/L) → cold wash → soap boiling (soap flakes 1g/L, soda ash 3g/L, builder 3g/L, 50 DEG C, 5min) → hot water wash → cold wash → oven dry (60 DEG C) → test fabric printing quality.
Properties of sample index prepared by above-mentioned 1 ~ 7 embodiment and seeing the following form for ACID DYES printing tests effect.
The above is only preferred embodiments of the present invention, different embodiments can find out hydroxypropyl carboxy methyl Waxy Maize Starch Pastes material hydroxypropyl substitution value (MS) 0.3 ~ 0.4, degree of substitution by carboxymethyl (DS) between 0.2 ~ 0.3 time, sample indices is excellent, best for ACID DYES stamp resultant effect.
Claims (6)
1. a hydroxypropyl carboxy methyl waxy corn starch ACID DYES printing gum, is characterized in that it is made up of the raw material of following portions by weight: waxy corn starch 95 ~ 105 parts, ethanol water 190 ~ 210 parts, 4 ~ 8 parts, NaOH, expoxy propane 20 ~ 25 parts, monoxone 14 ~ 21 parts; The hydroxypropyl substitution value of described hydroxypropyl carboxy methyl cornstarch ACID DYES printing gum is 0.30 ~ 0.40, and degree of substitution by carboxymethyl is 0.2 ~ 0.3.
2. a preparation method for hydroxypropyl carboxy methyl waxy corn starch ACID DYES printing gum according to claim 1, is characterized in that step is as follows:
(1) waxy corn starch is joined in ethanol water, be stirred to waxy corn starch and be dispersed in ethanol water, then add NaOH, quaternization 25 ~ 35min under the condition of 20 ~ 30 DEG C;
(2) quaternization adds expoxy propane after terminating, and is warming up to 60 ~ 75 DEG C and carries out etherification reaction 8 ~ 10h after stirring;
(3) etherification reaction is cooled to 45 ~ 55 DEG C after terminating, and then adds monoxone, is warming up to 65 ~ 75 DEG C of reaction 2 ~ 3h after stirring;
(4) reaction is cooled to 25 ~ 35 DEG C after terminating, and regulates pH value of reaction system to neutral with hydrochloric acid, namely obtains hydroxypropyl carboxy methyl waxy corn starch ACID DYES printing gum after washing, suction filtration, 80 DEG C of oven dry, pulverizing.
3. the preparation method of hydroxypropyl carboxy methyl waxy corn starch ACID DYES printing gum according to claim 2, is characterized in that: in described step (1), the bath raio of waxy corn starch and ethanol water is 1:2.
4. the preparation method of hydroxypropyl carboxy methyl waxy corn starch ACID DYES printing gum according to claim 2, is characterized in that: in described step (1), the mass fraction of ethanol water is 70 ~ 95%.
5. the preparation method of hydroxypropyl carboxy methyl waxy corn starch ACID DYES printing gum according to claim 2, is characterized in that: the NaOH distilled water in described step (1) dissolves and is cooled to room temperature.
6. hydroxypropyl carboxy methyl waxy corn starch ACID DYES printing gum according to claim 1 is used for ACID DYES stamp.
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Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
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CN105274872A (en) * | 2015-10-27 | 2016-01-27 | 华南理工大学 | Acid printing paste and preparation method and application thereof |
CN105507032A (en) * | 2016-01-13 | 2016-04-20 | 北京中纺化工股份有限公司 | Printing paste for imitating wax printing and preparation method thereof |
CN108130756A (en) * | 2017-12-18 | 2018-06-08 | 苏州昕能胶体技术有限公司 | A kind of modified tamarind gum printing gum and preparation method thereof |
CN109267383A (en) * | 2018-08-10 | 2019-01-25 | 湖北达雅生物科技股份有限公司 | Disperse stamp composite paste material and preparation method thereof |
CN110090202A (en) * | 2019-06-10 | 2019-08-06 | 哈尔滨坤丰生物工程有限公司 | A kind of pea hydroxypropyl carboxy methyl starch hollow capsule and preparation method |
CN110846908A (en) * | 2019-11-19 | 2020-02-28 | 湖州世合纺织有限公司 | Accelerating agent suitable for natural dye and use method thereof |
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2015
- 2015-05-05 CN CN201510222145.0A patent/CN104831562A/en active Pending
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
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CN105274872A (en) * | 2015-10-27 | 2016-01-27 | 华南理工大学 | Acid printing paste and preparation method and application thereof |
CN105274872B (en) * | 2015-10-27 | 2017-06-06 | 华南理工大学 | A kind of acid printing gum and its preparation method and application |
CN105507032A (en) * | 2016-01-13 | 2016-04-20 | 北京中纺化工股份有限公司 | Printing paste for imitating wax printing and preparation method thereof |
CN105507032B (en) * | 2016-01-13 | 2017-12-19 | 北京中纺化工股份有限公司 | It is a kind of to be used to imitate printing gum of wax printing flower and preparation method thereof |
CN108130756A (en) * | 2017-12-18 | 2018-06-08 | 苏州昕能胶体技术有限公司 | A kind of modified tamarind gum printing gum and preparation method thereof |
CN109267383A (en) * | 2018-08-10 | 2019-01-25 | 湖北达雅生物科技股份有限公司 | Disperse stamp composite paste material and preparation method thereof |
CN110090202A (en) * | 2019-06-10 | 2019-08-06 | 哈尔滨坤丰生物工程有限公司 | A kind of pea hydroxypropyl carboxy methyl starch hollow capsule and preparation method |
CN110846908A (en) * | 2019-11-19 | 2020-02-28 | 湖州世合纺织有限公司 | Accelerating agent suitable for natural dye and use method thereof |
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Application publication date: 20150812 |