CN102675573B - Meta-acid liquid dicyandiamide-formaldehyde polymer and application thereof in printing and dyeing industry - Google Patents
Meta-acid liquid dicyandiamide-formaldehyde polymer and application thereof in printing and dyeing industry Download PDFInfo
- Publication number
- CN102675573B CN102675573B CN 201210153455 CN201210153455A CN102675573B CN 102675573 B CN102675573 B CN 102675573B CN 201210153455 CN201210153455 CN 201210153455 CN 201210153455 A CN201210153455 A CN 201210153455A CN 102675573 B CN102675573 B CN 102675573B
- Authority
- CN
- China
- Prior art keywords
- dyhard
- yuban
- liquid
- acid
- slant acidity
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Abstract
The invention provides a meta-acid liquid dicyandiamide-formaldehyde polymer. The polymer is obtained through direct reaction of 100 parts of dicyandiamide, 158-162 parts of formaldehyde solution with mass concentration being 36%, 65-68 parts of ammonium chloride and 20-24 parts of inorganic strong acid with mass concentration being 20% by weight and is characterized by controlling the pH value of the reaction system to 5-5.2 when the temperature of the reaction system re-drops to 84-85 DEG C after reaching 93-95 DEG C. The polymer has strong activity and dispersive capacity in water and good stability, can greatly improve the fastness of the dyes when serving as a dye fixing agent and has high discoloration rate when serving as a flocculant of printing and dyeing wastewater. The printing and dyeing wastewater treated with the polymer can reach the standard of direct discharge. Besides, the polymer has simple preparation method, high reaction speed in the preparation process, good controllability and high yield and is beneficial to popularization and application.
Description
Technical field
The present invention relates to a kind of polymkeric substance, especially relate to a kind of Dyhard RU 100 yuban, more specifically relate to the liquid Dyhard RU 100 yuban of a kind of slant acidity.The invention still further relates to the application of the liquid Dyhard RU 100 yuban of this slant acidity in dyeing industry.
Background technology
The Dyhard RU 100 yuban is important cationic polymers of a class and cationic chemical auxiliary agent, Application Areas is extensive, as the flocculation agent of the laking agent that in printing and dyeing industry, is used as dyestuff and dyeing waste water, in paper industry, be used as the wet end toughener, in leather industry, be used as leather retanning agent, in the styrene-butadiene rubber(SBR) production process, be used as emulsion coagulation agent etc.The Dyhard RU 100 yuban is by Dyhard RU 100 and oxymethylene polymerization and get, and traditional preparation method feeds intake Dyhard RU 100, formaldehyde in certain proportion, under the katalysis of acid chlorization ammonium, carries out hydroxymethylation and polycondensation simultaneously.Less by Dyhard RU 100-yuban extent of polymerization in aqueous phase system that the traditional preparation process method obtains, the adsorptive power of products therefrom a little less than, in printing and dyeing industry, during as the flocculation agent of the laking agent of dyestuff and wastewater treatment, can influence giving full play to of its treatment effect and performance characteristic.Therefore, some experts and scholar successively propose by adding the 3rd component it to be carried out a plurality of technical schemes of modification, also the someone proposes to strengthen the technical scheme that density improves the polymerization degree, all these schemes can both obtain certain effect, but the equal more complicated of technological process, and need special equipment, so cost is higher.Applicant of the present invention is 01129968.1 November 22 calendar year 2001 to the State Intellectual Property Office application and the patent No. of obtaining the authorization, name is called the patent of invention of " a kind of flocculation agent of dye wastewater treatment using ", employing alum is disclosed as Dyhard RU 100 and oxymethylene polymerization catalyst for reaction, can obtain to have the technical scheme of the very strong adsorptive power and the Dyhard RU 100 yuban of better solubleness, the polymkeric substance of this invention is to removing the color in the waste water from dyestuff, effect is splendid, the waste water from dyestuff that this polymer treatment of process is crossed, its filtrate colourity can be reduced to 40-100 doubly, reaches direct emission standards; If the laking agent of this polymkeric substance as textile dyeing used, the ability that also has good raising dyeing fastness, but, tend to make fabric to have than the local phenomenon that whiting occurs of dark colour, so generally do not use as laking agent in printing and dyeing because this polymkeric substance contains aluminum ion.
Those skilled in the art generally believes, why the polymerization degree is less for Dyhard RU 100-yuban that employing traditional preparation process method obtains, reason is the carrying out along with reaction, the acid of using as catalyzer constantly is consumed, cause constantly rising of pH value in the mixed system, be unfavorable for further carrying out of polycondensation, synthetic Dyhard RU 100-formaldehyde just aggressiveness has stronger hydrophobicity, causes in aqueous phase system polymerization degree degree less.The present patent application people adds sulfuric acid as catalyzer from resol polymerization process, can be under the situation of not getting rid of reaction water, form in this phenomenon of superpolymer fast and take a hint, through constantly test, discovery is adopting ammonium chloride to add a certain amount of rare inorganic acid in as the Dyhard RU 100-formaldehyde reaction system of catalyzer, and the pH value of control reaction system, can obtain to have strong activity and the good Dyhard RU 100 yuban of solvability.
Summary of the invention
The purpose of this invention is to provide that a kind of activity is strong, solvability good and prepare the liquid Dyhard RU 100 yuban of simple slant acidity.
Another object of the present invention provides the application of the liquid Dyhard RU 100 yuban of above-mentioned slant acidity in dyeing industry.
For realizing above purpose, the liquid Dyhard RU 100 yuban of slant acidity of the present invention is to be that 100 parts of Dyhard RU 100s, mass concentration are that 36% formalin 158-162 part, ammonium chloride 65-68 part and mass concentration are that inorganic acid 20-24 part of 20% obtains with following method by components by weight percent:
(1) above-mentioned Dyhard RU 100, ammonium chloride, formaldehyde are poured in the reaction vessel successively, poured into above-mentioned inorganic acid again and react;
When reducing to 84-85 ℃ again after (2) temperature in the question response container reaches 93-95 ℃, the pH value of measured reaction system, if the pH value of reaction system is at 5-5.2, then allow the temperature of reaction system reduce to room temperature, if, then adding a small amount of Dyhard RU 100 less than 5, the pH value regulates, if the pH value is greater than 5.2, then add a small amount of formaldehyde and regulate, allow the temperature of reaction system reduce to room temperature again.
Above-mentioned inorganic acid preferably sulfuric acid.
The above-mentioned inorganic acid preferably sulfuric acid and the mixing acid of nitric acid or phosphoric acid, sulfuric acid mixes with volume ratio 1 ︰ 1 with nitric acid or phosphoric acid.
In order to reduce the evaporation of moisture, in the aforesaid method, after pouring inorganic acid into, reaction vessel is sealed.
Because the reaction of Dyhard RU 100 and formaldehyde is the reaction of heat absorption back heat release earlier, at colder weather, in order to shorten the reaction times, in the aforesaid method, after pouring inorganic acid into, begin heating when being stirred to the reaction container bottom sediment-free, when treating that temperature rises to 20 ℃, stop heating.
For the better polymerization degree that increases the Dyhard RU 100 yuban, the temperature of above-mentioned reaction system at room temperature continues reaction three days after reducing to room temperature again.
The liquid Dyhard RU 100 yuban of above-mentioned slant acidity in dyeing industry as the application of dye fixing agent.
The liquid Dyhard RU 100 yuban of above-mentioned slant acidity in dyeing industry as the application of printing and dying industry wastewater flocculating agent.
The liquid Dyhard RU 100 yuban of slant acidity of the present invention, in the reaction system of Dyhard RU 100, formaldehyde and ammonium chloride, add a certain amount of rare inorganic acid, make under the situation that the acidity of ammonium chloride is constantly consumed in formaldehyde and Dyhard RU 100 polymerization process, the polymerization degree of reactant still can constantly increase, form superpolymer at last, and keep reaction system to be in the state of slant acidity all the time, can make Dyhard RU 100 formaldehyde superpolymer remain higher activity again.The liquid Dyhard RU 100 yuban of slant acidity of the present invention, has the strong active and dispersive ability in water, and good stability, during as the dye fixing agent, can improve the dyefastness of dyestuff greatly, during as the flocculation agent of dyeing waste water, the percent of decolourization height, dyeing waste water through polymer treatment of the present invention is crossed can reach direct emission standards; In addition, the liquid Dyhard RU 100 yuban of slant acidity of the present invention, the preparation method is simple, and the preparation process speed of response is fast, controllability good and recovery rate is high, helps applying.
Embodiment
(1) method for making embodiment
Embodiment 1
Get 100 gram Dyhard RU 100s, 66 gram ammonium chlorides and 160 milliliters of mass concentrations are that 36% formaldehyde is poured in 500 milliliters the beaker that has thermometer together, pour 20 milliliters of mass concentrations again into and be 20% sulfuric acid, and beaker is sealed; During the reaction beginning, temperature descends, temperature begins to rise after a while, after reaching 93-95 ℃, temperature begins to descend, when treating that temperature is reduced to 85 ℃, take the pH value of sealing the detection reaction system apart, if the pH value is between 5-5.2, then allow reaction system continue to reduce to room temperature, if, then adding a small amount of Dyhard RU 100 less than 5, the pH value regulates, if the pH value is greater than 5.2, then adding a small amount of formaldehyde regulates, allow the temperature of reaction system reduce to room temperature again, promptly getting outward appearance is the transparent product A of little Huang, at room temperature continues reaction and obtains product B after three days.
Aforesaid method is suitable for the weather of comparison sweltering heat, and entire reaction course is about 30 minutes.
Aforesaid method also is suitable for raw-material detection, when the temperature of reaction system is reduced to 85 ℃ and pH value at 5-5.2, get the standardized solution (0.2%) of a cuvette weak acid dye, draw reactant with suction pipe and directly carry out titration, after stirring clarification in a minute, if upper strata filtrate is light red, colourity is below 100 times, prove that then Dyhard RU 100 purity reaches requirement (purity of general commercially available Dyhard RU 100 is about 99%), otherwise the purity that promptly proves Dyhard RU 100 does not reach requirement, need readjust the feed ratio of each component.
Embodiment 2
With 100 gram Dyhard RU 100s, 68 gram ammonium chlorides, 158 milliliters of mass concentrations are that 36% formaldehyde and 20 milliliters of mass concentrations are that 20% sulfuric acid is poured in 500 milliliters the beaker that has thermometer successively, begin heating at the bottom of being stirred to glass during sediment-free, when treating that temperature rises to 20 ℃, stop heating, rely on reaction heat to keep the required heat of polycondensation, after beaker internal reaction thing reached 93-95 ℃, temperature began to descend, when treating that temperature is reduced to 85 ℃, the pH value of detection reaction system, if the pH value between 5-5.2, then allows reaction system continue to reduce to room temperature, if the pH value is less than 5, then adding a small amount of Dyhard RU 100 regulates, regulate if the pH value, then adds a small amount of formaldehyde greater than 5.2, allow reaction system reduce to room temperature again, promptly getting outward appearance is the transparent products C of little Huang, at room temperature continues reaction and obtains product D after three days;
Aforesaid method is suitable for colder weather, also is suitable for suitability for industrialized production, and the process that rises to 93-95 ° of C from 20 ° of C is about 2 minutes.
Sulfuric acid dosage in the aforesaid method can be that the sulfuric acid of 1 ︰ 1 and nitric acid mixing acid replace by volume ratio, or is that sulfuric acid and the phosphoric acid mixing acid of 1 ︰ 1 replaces the final product quality basically identical by volume ratio.
(2) Application Example
1, the product that the foregoing description 1-2 is obtained uses as the dye fixing agent, and the performance synopsis of itself and conventional laking agent is as follows:
| Laking agent | Outward appearance | The pH value | Water-soluble | Stability | Washing fastness |
| Commercially available laking agent | The yellow transparent mucus | 5－7 | Yi Rong | Stable | 3－4 |
| Product A | The transparent mucus of little Huang | 5－5.2 | Yi Rong | Stable | ? 3－4 |
| Product B | The transparent mucus of little Huang | 5－5.2 | Yi Rong | Stable | ? 4－5 |
| Products C | The transparent mucus of little Huang | 5－5.2 | Yi Rong | Stable | ? 3－4 |
| Product D | The transparent mucus of little Huang | 5－5.2 | Yi Rong | Stable | ? 4－5 |
As can be seen from the above table, the liquid Dyhard RU 100 yuban of slant acidity of the present invention is suitable with at present commercially available laking agent performance, and washing fastness is better than commercially available laking agent.Because present commercially available laking agent complicated process of preparation, strict to equipment, thereby production cost height, the liquid Dyhard RU 100 yuban of slant acidity of the present invention adopts common chemical industry equipment, and preparation technology is simple, product recovery rate height, production cost is low, has good market outlook.
2, the product that the foregoing description 1-2 is obtained uses as the flocculation agent of dyeing waste water
Getting the direct water of weak acid dye, to be mixed with mass concentration be aqueous dye solutions (colourity is more than 2000 a times) cuvette of 0.2%, with the dilution of the product of embodiment 1-2 10% solution, with directly being added drop-wise in the aqueous dye solutions after the suction pipe absorption, stir after one minute phenomenon that obtains such as following table:
| Flocculation agent | Stirred 1 minute after dripping flocculation agent | Colourity |
| Product A | A large amount of flosss generate, and the filtrate on upper strata, clarification back is light red slightly | Below 100 times |
| Product B | A large amount of flosss generate, and the filtrate on upper strata, clarification back is colourless | Below 10 times |
| Products C | A large amount of flosss generate, and the filtrate on upper strata, clarification back is light red slightly | Below 100 times |
| Product D | A large amount of flosss generate, and the filtrate on upper strata, clarification back is colourless | Below 10 times |
As can be seen from the above table, adopt the flocculation agent of the liquid Dyhard RU 100 yuban of slant acidity of the present invention as dyeing waste water, the medicament delivery amount is few, treatment effect is good, colourity at 2000 to 3000 times waste water after the liquid Dyhard RU 100 yuban of slant acidity of the present invention is handled, the colourity of its filtrate is below 100 times, reaches direct emission standards.
Claims (2)
1. the liquid Dyhard RU 100 yuban of a slant acidity is to be that 100 parts of Dyhard RU 100s, mass concentration are that 36% formalin 158-162 part, ammonium chloride 65-68 part and mass concentration are that inorganic acid 20-24 part of 20% obtains with following method by components by weight percent:
(1) above-mentioned Dyhard RU 100, ammonium chloride, formaldehyde are poured in the reaction vessel successively, poured into above-mentioned inorganic acid again and react;
When reducing to 84-85 ℃ again after (2) temperature in the question response container reaches 93-95 ℃, the pH value of measured reaction system, if the pH value of reaction system is at 5-5.2, then allow the temperature of reaction system reduce to room temperature, promptly obtain the liquid Dyhard RU 100 yuban of slant acidity, if the pH value is less than 5, then add a small amount of Dyhard RU 100, if the pH value greater than 5.2, then adds a small amount of formaldehyde, allow reaction system reduce to room temperature again.
2. the liquid Dyhard RU 100 yuban of slant acidity according to claim 1, it is characterized in that: described inorganic acid is a sulfuric acid.
3. the liquid Dyhard RU 100 yuban of slant acidity according to claim 1, it is characterized in that: described inorganic acid is the mixing acid of sulfuric acid and nitric acid or phosphoric acid, sulfuric acid mixes with volume ratio 1 ︰ 1 with nitric acid or phosphoric acid.
4. according to claim 2 or the liquid Dyhard RU 100 yuban of 3 described slant acidity, it is characterized in that: in the described method, step (1) is sealed reaction vessel after pouring inorganic acid into.
5. according to claim 2 or the liquid Dyhard RU 100 yuban of 3 described slant acidity, it is characterized in that: in the described method, step (1) begins heating when being stirred to the reaction container bottom sediment-free after pouring inorganic acid into, when treating that temperature rises to 20 ℃, stop heating.
6. according to claim 2 or the liquid Dyhard RU 100 yuban of 3 described slant acidity, it is characterized in that: the temperature of described reaction system at room temperature continues reaction three days after reducing to room temperature again.
The liquid Dyhard RU 100 yuban of the arbitrary described slant acidity of a claim 1-6 in dyeing industry as the application of dye fixing agent.
The liquid Dyhard RU 100 yuban of the arbitrary described slant acidity of a claim 1-6 in dyeing industry as the application of printing and dying industry wastewater flocculating agent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201210153455 CN102675573B (en) | 2012-05-17 | 2012-05-17 | Meta-acid liquid dicyandiamide-formaldehyde polymer and application thereof in printing and dyeing industry |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201210153455 CN102675573B (en) | 2012-05-17 | 2012-05-17 | Meta-acid liquid dicyandiamide-formaldehyde polymer and application thereof in printing and dyeing industry |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102675573A CN102675573A (en) | 2012-09-19 |
| CN102675573B true CN102675573B (en) | 2013-07-31 |
Family
ID=46808168
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201210153455 Expired - Fee Related CN102675573B (en) | 2012-05-17 | 2012-05-17 | Meta-acid liquid dicyandiamide-formaldehyde polymer and application thereof in printing and dyeing industry |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102675573B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102895806A (en) * | 2012-10-17 | 2013-01-30 | 滁州市润达溶剂有限公司 | Coagulant and preparation method thereof |
| CN106883671A (en) * | 2017-03-29 | 2017-06-23 | 南宁市青秀区嘉利林化有限公司 | A kind of rosin ink color fixing agent and preparation method thereof |
| CN107100018B (en) * | 2017-04-28 | 2020-05-22 | 晋江市南星印染材料有限公司 | Color fixing agent for acid dye dyeing and preparation method thereof |
| CN109133509B (en) * | 2018-09-05 | 2021-06-04 | 嘉兴市天伦纳米染整有限公司 | Processing system of textile printing and dyeing sewage |
| CN109205750A (en) * | 2018-11-08 | 2019-01-15 | 东江环保股份有限公司江苏分公司 | The efficient flocculating device of dyeing waste water and its application |
| CN110685175B (en) * | 2019-10-14 | 2022-02-08 | 苏州联胜化学有限公司 | Acidic color fixing agent and preparation method and application method thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6627086B2 (en) * | 2001-03-21 | 2003-09-30 | Polymer Ventures, Inc. | Methods of producing polyarylamines and using them for detackifying paint and removing color from aqueous systems |
| CN1162346C (en) * | 2001-11-22 | 2004-08-18 | 张明 | Dye adsorbent and its application in treating dye effluent |
| CN101935094B (en) * | 2010-08-25 | 2012-02-29 | 常州大学 | Method for preparing decoloring flocculant of reactive dye waste water |
-
2012
- 2012-05-17 CN CN 201210153455 patent/CN102675573B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN102675573A (en) | 2012-09-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102675573B (en) | Meta-acid liquid dicyandiamide-formaldehyde polymer and application thereof in printing and dyeing industry | |
| CN105086503B (en) | Common-process production technique of caramel color with color ratio of at least 30000EBC | |
| CN103351047B (en) | Organic-inorganic hybrid flocculant and preparation method thereof | |
| CN104059215A (en) | Preparation method of TDI isocyanurate | |
| CN104292387A (en) | Preparation method of high temperature resistant salt-resistant filtrate reducer | |
| CN109718771A (en) | A kind of bimetal-doped type alumina aerogels and its preparation and application | |
| CN105712865B (en) | Solid citric acid aluminum crosslinker, preparation method and its application | |
| CN104479978A (en) | White spirit aging accelerating agent, aging hastening method and aging tank | |
| CN102515331B (en) | Preparation method of dosage form flocculation decoloring agent | |
| CN101921015A (en) | Novel inorganic-organic composite macromolecular decolorizing flocculant and preparation method thereof | |
| CN103011362B (en) | Preparation method for high-efficiency dye decolorizing agent | |
| CN102040718B (en) | Preparation method of decolorizing flocculant | |
| CN104004151A (en) | Dicyandiamide-formaldehyde polymer and preparation method and applications thereof | |
| CN104045751A (en) | Preparation method of polyvinyl butyral | |
| CN102502932B (en) | High-effective composite flocculant for treating low-turbidity water and preparation method of high-effective composite flocculant | |
| CN106215873B (en) | A kind of preparation method of the adsorbent material with photocatalytic Degradation | |
| CN101746911B (en) | Preprocessing method of hexadecyl trimethyl ammonium bromide for molasses alcohol waste water | |
| CN108339502B (en) | Preparation method of monascus pigment microcapsules | |
| CN103420415B (en) | A kind of preparation method of vanadylic sulfate | |
| CN101298346A (en) | Polysilicate aluminum sulphate flocculant, preparation process and use thereof | |
| TWI735318B (en) | Quick kit and method for detecting activity of dye solution for aluminum anodizing | |
| CN103881415B (en) | A kind of paper grade (stock) compositions of fluorescent whitening agents and preparation method thereof | |
| CN104674576B (en) | A kind of method preparing accelerant based on high glass gall | |
| CN109574885A (en) | A kind of preparation method of low contamination Dispersant MF | |
| CN109020713B (en) | Phosphorus compound fertilizer granulation coloring agent, and preparation method, application and application method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20130731 Termination date: 20140517 |