CN107400176A - Hydroxypropyl cation guar gum and its water-medium semi-dry method preparation method and use - Google Patents

Hydroxypropyl cation guar gum and its water-medium semi-dry method preparation method and use Download PDF

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CN107400176A
CN107400176A CN201710771441.5A CN201710771441A CN107400176A CN 107400176 A CN107400176 A CN 107400176A CN 201710771441 A CN201710771441 A CN 201710771441A CN 107400176 A CN107400176 A CN 107400176A
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melon
parts
hydroxypropyl
cationic
preparation
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罗彤彤
孙立田
姜长辉
陈雁南
刘凯
吴萌
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Beijing General Research Institute of Mining and Metallurgy
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Beijing General Research Institute of Mining and Metallurgy
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
    • C08B37/006—Heteroglycans, i.e. polysaccharides having more than one sugar residue in the main chain in either alternating or less regular sequence; Gellans; Succinoglycans; Arabinogalactans; Tragacanth or gum tragacanth or traganth from Astragalus; Gum Karaya from Sterculia urens; Gum Ghatti from Anogeissus latifolia; Derivatives thereof
    • C08B37/0087—Glucomannans or galactomannans; Tara or tara gum, i.e. D-mannose and D-galactose units, e.g. from Cesalpinia spinosa; Tamarind gum, i.e. D-galactose, D-glucose and D-xylose units, e.g. from Tamarindus indica; Gum Arabic, i.e. L-arabinose, L-rhamnose, D-galactose and D-glucuronic acid units, e.g. from Acacia Senegal or Acacia Seyal; Derivatives thereof
    • C08B37/0096—Guar, guar gum, guar flour, guaran, i.e. (beta-1,4) linked D-mannose units in the main chain branched with D-galactose units in (alpha-1,6), e.g. from Cyamopsis Tetragonolobus; Derivatives thereof
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H11/00—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only
    • D21H11/12—Pulp from non-woody plants or crops, e.g. cotton, flax, straw, bagasse
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
    • D21H17/24—Polysaccharides
    • D21H17/31—Gums
    • D21H17/32—Guar or other polygalactomannan gum
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/06—Paper forming aids
    • D21H21/10—Retention agents or drainage improvers

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Molecular Biology (AREA)
  • General Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Biochemistry (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Coloring Foods And Improving Nutritive Qualities (AREA)

Abstract

The invention provides hydroxypropyl cation guar gum and a preparation method and application thereof by a water-medium semi-dry method, wherein the method comprises the following steps: (1) adding guar endosperm slices into hot water, adding alkalizer water solution under protection of protective gas, soaking for alkalization to obtain alkalized guar endosperm slices; (2) adding a cationic etherifying agent aqueous solution into the alkalized guar endosperm slices, and reacting to obtain cationic guar endosperm slices; (3) adding a phase transfer catalyst into a cationic intermediate, adding an alkoxy etherifying agent under the protection of protective gas, reacting, then cooling to room temperature, and adjusting the pH value of the material to be weak acid to weak alkali to prepare hydroxypropyl cationic guar endosperm fragments; (4) the hydroxypropyl cationic guar gum finished product is prepared by coarse crushing, drying, crushing, screening and homogenizing. The preparation method of the invention does not use organic solvent, greatly reduces the cost, has safe and environment-friendly production process and simple synthesis process.

Description

A kind of hydroxypropyl cationic melon bean gum and its water-borne semidry method preparation method and application
Technical field
The invention belongs to paper pulp retention and drainage aid agent field, and in particular to prepare wood pulp and straw pulp by raw material of melon bean gum System and papermaking-method reconstituted tobaccos manufacture paper with pulp during retention and drainage aid agent method, more particularly to a kind of hydroxypropyl cationic melon Bean gum and its water-borne semidry method preparation method and application.
Background technology
The commonly used modified starch of paper industry and PAMC are as retention and drainage aid agent at present, but the country forms sediment Powder raw material source is differed, and species is various, and straight chain and amylopectin ratios are different, therefore has a strong impact on the steady of its modified product quality It is qualitative, limit its popularization and application.Domestic larger paper mill must not oneself from the production of external major company wet end adjuvant, so as to make Into paper cost increase.On the other hand, PAMC not easily biological-degradable, residual monomer has certain toxicity, in life Apply flexibly and be restricted in the application of paper and high-grade paper.And the white water recycling containing PAMC can cause positive electricity Enrichment, fleeces congeal into group, influence the stability of formation of sheet and system of manufacturing paper with pulp.
Melon bean gum is a kind of natural galactomannan gum, from the melon beans kind for originating in the ground such as Yunnan, Xinjiang, India Extract and obtain in the endosperm of son.Melon bean gum main chain is formed by mannose for element connection, and side chain is made up of single galactolipin, it The molecular structure similar with cellulose determines it and the natural sympathy of cellulose.Melon bean gum is used for paper industry, is improving While paper fiber fines and filler retention and drainage effect, the evenness of paper is not influenceed, so as to not reduce its strength character.Melon Youngster's bean gum natural plants seed source and outstanding biodegradability alleviate the problem of environmental pollution of paper industry, meet clear Clean production, environment-friendly theory.
Although melon bean gum has water-soluble and thickening property well, often there are following shortcomings：Can not be instant soon Swollen and hydration, dissolution velocity are slow；Thickening capabilities are poor, and water insoluble matter content is high.These shortcomings make the application of melon bean gum by very Big limitation makes it can extensive use, it is necessary to change its physicochemical property by chemical modification method.Each monose of melon bean gum is put down There are three activity hydroxies, under certain condition, these three activity hydroxies can be etherified, be esterified or oxidation reaction, be prepared into Various ethers, ester derivant and oxide.
The modified-reaction of producer is carried out for rubber powder both at home and abroad at present, first adds albumen tablet by being hydrated, crushing Then work is modified reaction in ethanol or aqueous isopropanol, finally carries out crushing and processing again, be modified into rubber powder Melon bean gum finished product.This technique belongs to two step solvent methods, and process route is numerous and diverse, and this two step has hydration and crushes this in being modified Two processes are relatively low using chemical solvent, product substitution values such as ethanol, isopropanols.
The content of the invention
To solve the above problems, it is an object of the invention to provide a kind of hydroxypropyl cationic melon bean gum and its water-borne half-dried Method preparation method and application.The preparation method of the present invention is greatly reduced without using organic solvent, cost, production process safety collar Protect；Synthesis technique is simple, and intermediate products need not isolate and purify, and can directly carry out subsequent reactions；Made full use of in building-up process Reaction heat, energy expenditure is reduced, the hydroxypropyl cationic melon bean gum transparency being prepared is high, there is suitable hydroxypropyl to take Dai Du and degree ofacationic substitution, water insoluble matter content are low.
For the above-mentioned purpose, the present invention uses following technological means：
A kind of water-borne semidry method preparation method of hydroxypropyl cationic melon bean gum, comprises the following steps：
(1) hydrating alkalization：Melon beans albumen tablet is added in hot water, under protective gas protection, adds basifier The aqueous solution, immersion alkalization, alkalization melon beans albumen tablet is made；
(2) positive ionization：The cationic etherifying agent aqueous solution is added to obtained alkalization melon beans embryo in step (1) In newborn piece, reaction, cation melon beans albumen tablet is made；
(3) hydroxypropylation reacts：Phase transfer catalyst is added to the cation melon beans albumen tablet that step (2) obtains In, under protective gas protection, alkoxy etherifying agent is added, reaction, then cools to room temperature, and adjust material pH value to 6 ~10, hydroxypropyl cationic melon beans albumen tablet is made；
(4) hydroxypropyl cationic melon beans albumen tablet made from step (3) is through coarse crushing, drying, crushing, screening, homogeneous, system Obtain hydroxypropyl cationic melon bean gum finished product.
Hydroxypropyl in the hydroxypropyl cationic melon bean gum molecule that the present invention is prepared by above-mentioned particular step is assigned Its significant fast hydrating dissolving swelling feature is given, makes it be adapted to add use in the form of dry powder or slurries.It has and fibre The similar functional group of structure is tieed up, paper pull-up and linting can be reduced by showing good adhesive effect；Excellent dyestuff and filler Retention performance, reduce filler loss；Beating degree is reduced, and the straight mixed and disorderly unordered long and short fiber of whole and reason can be entangled, it is steady to improve wet end It is qualitative, improve every physical and chemical index of paper.
Basifier, cationic etherifying agent, phase transfer catalyst and alkoxy etherifying agent used can be in above-mentioned steps General basifier, cationic etherifying agent, phase transfer catalyst and alkoxy etherifying agent in such technology.
Preferably, in the preparation method of the present invention, basifier described in step (1) is sodium hydroxide, potassium hydroxide, carbon In sour sodium or sodium acid carbonate any one or at least two mixture.
Preferably, in terms of parts by weight, relative to 100 parts of melon beans albumen tablets, the dosage of step (1) described hot water is 50 ~300 parts, for example, 70 parts, 90 parts, 120 parts, 150 parts, 190 parts, 210 parts, 240 parts, 270 parts, 295 parts etc., basifier Dosage is 0.5~30 part, for example, 0.8 part, 1.5 parts, 3 parts, 6 parts, 11 parts, 16 parts, 21 parts, 26 parts, preferably 29 parts etc., hot water Dosage is 100~160 parts, and basifier dosage is 1~15 part.
In the present invention, the temperature of hot water described in step (1) is 60~70 DEG C, such as 60 DEG C, 63 DEG C, 65 DEG C, 68 DEG C Or 70 DEG C.
Preferably, the mass concentration of the basifier aqueous solution be 10%~80%, for example, 14%, 18%, 25%, 30%th, 36%, 41%, 48%, 55%, 61%, 70%, 75% etc., preferably 20%~50%.
Preferably, the time of the immersion alkalization is more than 0.05h, for example, 0.08h, 0.15h, 0.22h, 0.3h, 0.45h, 0.6h, 0.8h etc., preferably 0.1~0.5h.
Preferably, in the preparation method of the present invention, cationic etherifying agent described in step (2) is the chloro- 2- hydroxypropyls of 3- In trimethyl ammonia chloride amine, arsenic thiamine hydrochloride, quinoline hydrochloride or 2,3- epoxypropyl trimethylammonium chloride amine any one or extremely Few two kinds mixture.
Preferably, in terms of parts by weight, relative to 100 parts of step (1) melon beans albumen tablets, step (2) described sun The dosage of the ion etherifying agent aqueous solution be 0.5~30 part, for example, 0.7 part, 0.9 part, 1.5 parts, 3 parts, 6 parts, 9 parts, 12 parts, 15 Part, preferably 18 parts etc., 1~20 part.
Preferably, the mass concentration of the cationic etherifying agent aqueous solution be 50%~90%, 52%, 55%, 59%, 65%th, 71%, 76%, 80%, 85% etc., preferably 70%.
Preferably, the temperature of the reaction be 40~90 DEG C, 42 DEG C, 46 DEG C, 50 DEG C, 54 DEG C, 58 DEG C, 62 DEG C, 69 DEG C, 72 DEG C, 76 DEG C, preferably 84 DEG C, 88 DEG C etc., 55~75 DEG C；The time of reaction is 1~10h, for example, 1.5h, 3h, 6h, 9h etc., Preferably 2~4h.
Preferably, in the preparation method of the present invention, phase transfer catalyst described in step (3) is 4 bromide And/or hexadecyl benzyl dimethly ammonium chloride.
Preferably, alkoxy etherifying agent described in step (3) is oxirane, expoxy propane, epoxy butane, epoxy chloropropionate In alkane any one or at least two mixture.
Preferably, in terms of parts by weight, relative to 100 parts of step (1) melon beans albumen tablets, step (3) described phase The dosage of transfer catalyst be 0~15 part but not include 0, for example, 0.2 part, 0.7 part, 0.9 part, 1.5 parts, 3 parts, 6 parts, 9 parts, 12 parts, 14 parts etc., preferably 0~10 part, the dosage of the alkoxy etherifying agent are 0.5~25 part, for example, 0.7 part, 0.9 Part, 1.5 parts, 3 parts, 6 parts, 9 parts, 12 parts, 15 parts, preferably 18 parts, 23 parts etc., 1~18 part.
Preferably, the time of the reaction is more than 0.5h, for example, 0.7h, 1.2h, 1.5h, 2.0h, 2.5h etc., preferably For 1~3h.
Preferably, material used in regulation material pH value is acidic materials, preferably in hydrochloric acid, acetic acid, boric acid, citric acid It is a kind of or at least two mixture.
In the present invention, step (3) the regulation material pH value to 6~10, such as 6.2,6.4,6.6,7.1,7.4, 7.7th, 8,8.3,8.5,9,9.4,9.8 etc., it is preferable that regulation material pH value to 6~8, further preferred 6.5~7.5.
Preferably, step (1) and step (3) described protective gas are nitrogen or argon gas.
Preferably, the preparation method of the present invention comprises the following steps：
(1) hydrating alkalization：In terms of parts by weight, 100 parts of melon beans albumen tablets through cleaning are added to 100~160 In part hot water, under nitrogen protection, 1~15 part of 20%~50% basifier aqueous solution of addition concentration, immersion alkalization 0.1~ 0.5h, alkalization melon beans albumen tablet is made；
(2) positive ionization：It is that the 70% cationic etherifying agent aqueous solution adds by 1~20 part of concentration in terms of parts by weight Enter into the obtained alkalization melon beans albumen tablet of step (1), under the conditions of temperature is 55~75 DEG C, react 2~4h, be made sun from Sub- melon beans albumen tablet；
(3) hydroxypropylation reacts：In terms of parts by weight, 0~10 portion of phase transfer catalyst is added to cation melon beans Albumen tablet, under nitrogen protection, 1~18 portion of alkoxy etherifying agent is added, exothermic heat of reaction makes temperature of charge is spontaneous to be raised to 50~75 DEG C, 1~3h is reacted, then cools to room temperature, and with material pH value is adjusted to 6.5~7.5, hydroxypropyl cationic melon beans are made Albumen tablet；
(4) by hydroxypropyl cationic melon beans albumen tablet made from step (3) through coarse crushing, drying, crushing, screening, homogeneous, Hydroxypropyl cationic melon bean gum finished product is made.
On the other hand, the invention provides the hydroxypropyl cationic melon beans being prepared by preparation method as described above Glue.
Quaternary ammonium cation is both carried in the hydroxypropyl cationic melon bean gum molecule that the present invention is prepared, has been grafted again non- Ion hydroxylpropyl groups.Cationic characteristic adds the relative molecular mass of moderate control, makes product of the present invention than other retention agents Paper stock shaping and shear problem can more be efficiently solved.It has similar plants fibrocyte structure, thus has very to fiber Good affinity；It can be adsorbed in fiber surface rapidly, reduce and neutralize the charge of fiber surface, make slurry current potential to grade electricity Position is close, reduces the mutually exclusive power between particle and between fiber, and by mixed and disorderly unordered fiber it is well-balanced arrange and group The neat solid netted bridge crosslinking structure of synthesis.
Hydroxypropyl cationic melon bean gum prepared by the present invention meets water in room temperature can quickly be dissolved into settled solution, with changing Property starch chemicals compare, it is not necessary to high temperature be gelatinized, it is simple to operate, beneficial to reduce energy consumption and reduce equipment investment；Present invention production Product antibiont degradation capability improved compared with melon bean gum original powder it is very big, the aqueous solution room temperature place one week it is not corrupt non-degradable, Retention and drainage effect is unaffected, and starch base retention and drainage aid agent must prepare the same day use same day, and otherwise performance obtains not To guarantee.Its dosage can be adjusted according to the addition of the different component of paper pulp, beating degree and other auxiliary agents, so as to play Synergistic function, expand the applicable paper kind scope of product of the present invention, such as tobacco sheets by paper making method, high-grade cigarette paper.
On the other hand, the invention provides hydroxypropyl cationic melon bean gum as described above as paper pulp retention aid and filtering aid The application of agent.
Preferably, the hydroxypropyl cationic melon bean gum dosage is the 0.1%~0.5% of quality of finished paper, such as 0.1%th, 0.15%, 0.2%, 0.25%, 0.3%, 0.4% or 0.5%.
The hydroxypropyl cationic melon bean gum of the present invention can be applied as paper pulp with retention and drainage aid agent, improve drainage Property, it is easy to increase copy paper speed, improves overall production efficiency；Anionic impurity can be separated, improve Retention, improve plain boiled water System purification degree；Press dewatering pressure is helped to increase that, shortens and bakees the time；There is peptizaiton to fiber, be uniformly distributed fiber, Improve paper strength；Strengthen the dye light stability energy of paper；In plain boiled water will not aggregation deposition, improve Wet-end stability, subtract Few discharge of wastewater.
Relative to prior art, the invention has the advantages that：
The features of the present invention is preparing hydroxypropyl cationic melon bean gum using water-borne semidry method, without using organic solvent, Cost is greatly reduced, production process safety and environmental protection；Synthesis technique is simple, and intermediate products need not isolate and purify, and can directly carry out Subsequent reactions；Reaction heat is made full use of in building-up process, reduces energy expenditure.
The hydroxypropyl cationic melon bean gum that the present invention is prepared has the high grade of transparency, and its hydroxypropyl substitution value is 0.05 ~0.30, degree ofacationic substitution is 0.05~0.10, and water insoluble matter content is low, and it is molten to be quickly dissolved into clarification in room temperature chance water Liquid, it is not necessary to which high temperature is gelatinized, simple to operate, and beneficial to reducing energy consumption and reducing equipment investment, the aqueous solution places one week not in room temperature Corruption is non-degradable.
The hydroxypropyl cationic melon bean gum that the present invention is prepared can be applied as paper pulp with retention and drainage aid agent, Drainability is improved, is easy to increase copy paper speed, improves overall production efficiency；Anionic impurity can be separated, improve Retention, Improve white-water system degree of purification；Press dewatering pressure is helped to increase that, shortens and bakees the time；There is peptizaiton to fiber, make fiber It is uniformly distributed, improves paper strength, the dye light stability energy of strong paper, web part of paper machine drainage rate can be made effectively to be controlled System, retention is improved, is had broad application prospects.
Embodiment
For the present invention is better described, technical scheme is readily appreciated, of the invention is typical but non-limiting Embodiment is as follows：
Embodiment 1
(1) melon beans albumen tablet and 110kg hot water of the 100kg through cleaning are sequentially added into kneader, is filled in evacuation Under the conditions of nitrogen, the sodium hydrate aqueous solution 5kg of concentration 40%, immersion alkalization 0.5h are then added；
(2) the 15kg concentration 70%3- chloro-2-hydroxypropyl-trimethyl ammonium chlorides aqueous solution is added, is 55 DEG C of conditions in temperature Under, react 1.5h；
(3) 2.5kg 4 bromides are added, under the conditions of nitrogen charging is evacuated, adds 12kg expoxy propane, exothermic heat of reaction Make temperature of charge is spontaneous to be raised to 65 DEG C, react 1h, then cool to room temperature, and material pH value is adjusted to 7.0 with acetic acid, hydroxyl is made Propyl group cation melon beans albumen tablet；
(4) hydroxypropyl cationic melon bean gum finished product is made through coarse crushing, drying, crushing, screening, homogeneous, packaging again.
After testing, hydroxypropyl substitution value is 0.25 in product, degree ofacationic substitution 0.10, the mass fraction of water-insoluble For 3%.
Embodiment 2
(1) melon beans albumen tablet and 120kg hot water of the 100kg through cleaning are sequentially added into kneader, is filled in evacuation Under the conditions of nitrogen, the aqueous sodium carbonate 4.5kg of concentration 40%, immersion alkalization 0.4h are then added；
(2) the 10kg concentration 70%3- chloro-2-hydroxypropyl-trimethyl ammonium chlorides aqueous solution is added, is 50 DEG C of conditions in temperature Under, react 1.5h；
(3) 2.5kg hexadecyl benzyl dimethly ammonium chlorides are added, under the conditions of nitrogen charging is evacuated, adds 18kg epoxies Ethane, exothermic heat of reaction make temperature of charge is spontaneous to be raised to 68 DEG C, react 1h, then cool to room temperature, and adjust material with citric acid Hydroxypropyl cationic melon beans albumen tablet is made to 7.5 in pH value；
(4) hydroxypropyl cationic melon bean gum finished product is made through coarse crushing, drying, crushing, screening, homogeneous, packaging again.
After testing, hydroxypropyl substitution value is 0.30 in product, degree ofacationic substitution 0.08, the mass fraction of water-insoluble For 2%.
Embodiment 3
(1) melon beans albumen tablet and 140kg hot water of the 100kg through cleaning are sequentially added into kneader, is filled in evacuation Under the conditions of nitrogen, the potassium hydroxide aqueous solution 3.8kg of concentration 40%, immersion alkalization 0.3h are then added；
(2) 12kg concentration 70%2,3- epoxypropyl trimethylammonium chlorides amine aqueous solution are added, under the conditions of temperature is 45 DEG C, React 1.2h；
(3) 2.5kg hexadecyl benzyl dimethly ammonium chlorides are added, under the conditions of nitrogen charging is evacuated, adds 16kg epoxies Chloropropane, exothermic heat of reaction make temperature of charge is spontaneous to be raised to 60 DEG C, react 1.2h, then cool to room temperature, and adjusted with citric acid Hydroxypropyl cationic melon beans albumen tablet is made to 7.3 in material pH value；
(4) hydroxypropyl cationic melon bean gum finished product is made through coarse crushing, drying, crushing, screening, homogeneous, packaging again.
After testing, hydroxypropyl substitution value is 0.15 in product, degree ofacationic substitution 0.10, the mass fraction of water-insoluble For 4%.
Embodiment 4
(1) melon beans albumen tablet and 50kg hot water of the 100kg through cleaning are sequentially added into kneader, is evacuating nitrogen charging Under the conditions of, then add the potassium hydroxide aqueous solution 0.5kg of concentration 80%, immersion alkalization 0.05h；
(2) the epoxypropyl trimethylammonium chloride amine aqueous solution of 30kg concentration 90% is added, under the conditions of temperature is 95 DEG C, reaction 1h；
(3) 1kg arsenic thiamine hydrochloride is added, under the conditions of nitrogen charging is evacuated, adds 25kg oxirane, exothermic heat of reaction makes thing Material temperature degree is spontaneous to be raised to 70 DEG C, reacts 0.5h, then cools to room temperature, and adjusts material pH value to 6.0 with citric acid, and hydroxyl is made Propyl group cation melon beans albumen tablet；
(4) hydroxypropyl cationic melon bean gum finished product is made through coarse crushing, drying, crushing, screening, homogeneous, packaging again.
After testing, hydroxypropyl substitution value is 0.05 in product, degree ofacationic substitution 0.08, the mass fraction of water-insoluble For 6%.
Embodiment 5
(1) melon beans albumen tablet and 300kg hot water of the 100kg through cleaning are sequentially added into kneader, is filled in evacuation Under the conditions of nitrogen, the potassium hydroxide aqueous solution 30kg of concentration 10%, immersion alkalization 1h are then added；
(2) the quinoline hydrochloride aqueous solution of 1kg concentration 50% is added, under the conditions of temperature is 40 DEG C, reacts 10h；
(3) 15kg 4 bromides are added, under the conditions of nitrogen charging is evacuated, adds 0.5kg epoxy butanes, exothermic heat of reaction Make temperature of charge is spontaneous to be raised to 75 DEG C, react 5h, then cool to room temperature, and material pH value is adjusted to 8.0 with citric acid, be made Hydroxypropyl cationic melon beans albumen tablet；
(4) hydroxypropyl cationic melon bean gum finished product is made through coarse crushing, drying, crushing, screening, homogeneous, packaging again.
After testing, hydroxypropyl substitution value is 0.20 in product, degree ofacationic substitution 0.05, the mass fraction of water-insoluble For 2%.
Embodiment 6
In the present embodiment, hydroxypropyl cationic melon bean gum embodiment 1-5 being prepared is as paper pulp retention Filter aid uses, and method is as follows：
Strengthen retention and drainage aid agent using the hydroxypropyl cationic melon bean gum that embodiment 1-5 is prepared as cigarette paper, Addition be about into paper 0.1%~0.5% (the hydroxypropyl cationic melon bean gum dosage that each embodiment is prepared is all provided with Be set to 0%, 0.1%, 0.2%, 0.3%, 0.5%), its mass fraction is no more than 1% as far as possible during dissolving.It can add after dissolving in advance In high deckered stock chest after to mashing, web part of paper machine drainage rate can be made to be effectively controlled, improve retention, improve dandyprat Runnability, improve paper strength.
Mainly include the following steps that：
1) powder stores：The storage tank of one constant volume is set, electronic scale is set under storage tank, according to liquid total amount and proportioning It is required that accurate control plus powder amount.Screw feeder is set in storage tank, uses frequency modulator to enter with certain frequency controlled motor when to powder Row stirring at low speed, prevent the phenomenon for powder of not putting up a bridge.
2) powder supplies：Use frequency modulator to control accurate pressure feeding spiral with certain frequency, realize rubber powder it is uniform, continuously to Material, discharging opening are connected by plastic flexible pipe with Hi-mixer.
3) pigment mix：Clear water enters Hi-mixer by booster pump, and rubber powder is sucked Hi-mixer by negative pressure In mixed with water.
4) glue being mixed to form enters in preparation tank, stirs 14~15min, leads to steam and heats 2~3min, makes glue temperature Degree reaches 34~35 DEG C, then tapping to fluid reservoir, entirely matches somebody with somebody 21~22min of liquid process.
5) glue enters fluid reservoir, continues with 50~60rpm stirring at low speed, in the Liquid level that robot control system(RCS) is set Under, enter through screw rod solution feed pump from lower end and use tank, continue with 50~60rpm stirring at low speed.
6) glue is from tank is used under the conveying of frequency conversion screw solution feed pump, by filter, into paper stock system.Range of flow 40 ~60min/L, determined according to indexs such as Substance, intensity, air permeability, the coefficient of variation.On average, glue is from into liquid storage Tank starts, and into paper stock system, the time is about 2h.
The effect that the hydroxypropyl cationic melon bean gum that embodiment 1-5 is prepared is used as paper pulp with retention and drainage aid agent As shown in table 1.
Table 1
The hydroxypropyl cationic melon bean gum of the present invention can make web part of paper machine drainage rate it can be seen from the result of table 1 It is effectively controlled, improves retention.
Applicant state, the present invention by the embodiment come illustrate the present invention hydroxypropyl cationic melon bean gum and its Water-borne semidry method preparation method and application, but the invention is not limited in above-described embodiment, that is, do not mean that the present invention must be according to Bad above-described embodiment could be implemented.Person of ordinary skill in the field is it will be clearly understood that any improvement in the present invention, to this hair The equivalence replacement of bright each raw material of product and the addition of auxiliary element, the selection of concrete mode etc., all fall within the protection model of the present invention Within the scope of enclosing and disclosing.

Claims (10)

1. a kind of water-borne semidry method preparation method of hydroxypropyl cationic melon bean gum, it is characterised in that methods described includes as follows Step：
(1) hydrating alkalization：Melon beans albumen tablet is added in hot water, under protective gas protection, it is water-soluble to add basifier Liquid, immersion alkalization, alkalization melon beans albumen tablet is made；
(2) positive ionization：The cationic etherifying agent aqueous solution is added to obtained alkalization melon beans albumen tablet in step (1) In, reaction, cation melon beans albumen tablet is made；
(3) hydroxypropylation reacts：Phase transfer catalyst is added in the cation melon beans albumen tablet that step (2) obtains, Under protective gas protection, alkoxy etherifying agent is added, reaction, then cools to room temperature, and adjust material pH value to 6~10, Hydroxypropyl cationic melon beans albumen tablet is made；
(4) hydroxyl is made through coarse crushing, drying, crushing, screening, homogeneous in hydroxypropyl cationic melon beans albumen tablet made from step (3) Propyl group cation melon bean gum finished product.
2. preparation method according to claim 1, it is characterised in that basifier described in step (1) is sodium hydroxide, hydrogen In potassium oxide, sodium carbonate or sodium acid carbonate any one or at least two mixture；
Preferably, in terms of parts by weight, relative to 100 parts of melon beans albumen tablets, the dosage of step (1) described hot water for 50~ 300 parts, the dosage of basifier is 0.5~30 part, and preferably amount of hot water is 100~160 parts, and basifier dosage is 1~15 part.
3. preparation method according to claim 1 or 2, it is characterised in that the temperature of hot water described in step (1) be 60~ 70℃；
Preferably, the mass concentration of the basifier aqueous solution described in step (1) is 10%~80%, preferably 20%~50%；
Preferably, the time of the immersion alkalization is more than 0.05h, preferably 0.1~0.5h.
4. according to the preparation method described in claim any one of 1-3, it is characterised in that cation described in step (2) is etherified Agent is the chloro- 2- Hydroxyproyl Trimethyls ammonium chlorides of 3-, arsenic thiamine hydrochloride, quinoline hydrochloride or 2,3- epoxypropyl trimethylammonium chloride amine In any one or at least two mixture；
Preferably, in terms of parts by weight, relative to 100 parts of step (1) melon beans albumen tablets, step (2) described cation The dosage of the etherifying agent aqueous solution is 0.5~30 part, preferably 1~20 part；
Preferably, the mass concentration of the cationic etherifying agent aqueous solution is 50%~90%, preferably 70%.
5. according to the preparation method described in claim any one of 1-4, it is characterised in that the temperature reacted described in step (2) For 40~90 DEG C, preferably 55~75 DEG C；The time of reaction is 1~10h, preferably 2~4h.
6. according to the preparation method described in claim any one of 1-5, it is characterised in that phase transfer catalysis (PTC) described in step (3) Agent is 4 bromide and/or hexadecyl benzyl dimethly ammonium chloride；
Preferably, alkoxy etherifying agent described in step (3) is in oxirane, expoxy propane, epoxy butane, epoxychloropropane Any one or at least two mixture.
7. according to the preparation method described in claim any one of 1-6, it is characterised in that in terms of parts by weight, relative to 100 parts Step (1) the melon beans albumen tablet, the dosage of step (3) described phase transfer catalyst for 0~15 part but do not include 0, preferably For 1~10 part, the dosage of the alkoxy etherifying agent is 0.5~25 part, preferably 1~18 part；
Preferably, the time reacted described in step (3) is more than 0.5h, preferably 1~3h；
Preferably, material used in regulation material pH value is acidic materials, preferably hydrochloric acid, acetic acid, boric acid, lemon in step (1) One kind or at least two mixture in acid；
Preferably, material pH value is adjusted to 6~8, preferably 6.5~7.5；
Preferably, step (1) and step (3) described protective gas are nitrogen or argon gas.
8. according to the preparation method any one of claim 1-7, it is characterised in that comprise the following steps：
(1) hydrating alkalization：In terms of parts by weight, 100 parts of melon beans albumen tablets through cleaning are added to 100~160 parts of heat In water, under nitrogen protection, 1~15 part of 20%~50% basifier aqueous solution of concentration, immersion 0.1~0.5h of alkalization, system are added Must be alkalized melon beans albumen tablet；
(2) positive ionization：It is that the 70% cationic etherifying agent aqueous solution is added to by 1~20 part of concentration in terms of parts by weight In the obtained alkalization melon beans albumen tablet of step (1), under the conditions of temperature is 55~75 DEG C, 2~4h is reacted, cation melon is made Youngster's beans albumen tablet；
(3) hydroxypropylation reacts：In terms of parts by weight, 0~10 portion of phase transfer catalyst is added to cation melon beans endosperm Piece, under nitrogen protection, 1~18 portion of alkoxy etherifying agent is added, exothermic heat of reaction makes temperature of charge is spontaneous to be raised to 50~75 DEG C, instead 1~3h is answered, then cools to room temperature, and with material pH value is adjusted to 6.5~7.5, hydroxypropyl cationic melon beans endosperm is made Piece；
(4) hydroxypropyl cationic melon beans albumen tablet made from step (3) is made through coarse crushing, drying, crushing, screening, homogeneous Hydroxypropyl cationic melon bean gum finished product.
9. the hydroxypropyl cationic melon bean gum that the preparation method according to claim any one of 1-8 is prepared.
10. application of the hydroxypropyl cationic melon bean gum according to claim 9 as paper pulp retention and drainage aid agent.
CN201710771441.5A 2017-08-31 2017-08-31 Hydroxypropyl cation guar gum and its water-medium semi-dry method preparation method and use Pending CN107400176A (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109535265A (en) * 2018-11-23 2019-03-29 重庆工商大学 A kind of preparation method of anionic hydroxyethyl cellulose
CN113265009A (en) * 2021-03-31 2021-08-17 矿冶科技集团有限公司 Preparation method of Guanhua bean endosperm rubber powder derivative and derivative thereof

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Publication number Priority date Publication date Assignee Title
CN1757827A (en) * 2005-09-23 2006-04-12 华南理工大学 Hydroxyalkyl cationic guar gum and its preparation method and application
CN101591687A (en) * 2009-06-30 2009-12-02 姜堰市博立生物制品有限公司 A kind of microwave combined enzyme process preparation and refining galactomannan-oligosaccharide technology
CN101787083A (en) * 2010-02-10 2010-07-28 刘东辉 Nonionic cation guar gum and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1757827A (en) * 2005-09-23 2006-04-12 华南理工大学 Hydroxyalkyl cationic guar gum and its preparation method and application
CN101591687A (en) * 2009-06-30 2009-12-02 姜堰市博立生物制品有限公司 A kind of microwave combined enzyme process preparation and refining galactomannan-oligosaccharide technology
CN101787083A (en) * 2010-02-10 2010-07-28 刘东辉 Nonionic cation guar gum and preparation method thereof

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109535265A (en) * 2018-11-23 2019-03-29 重庆工商大学 A kind of preparation method of anionic hydroxyethyl cellulose
CN113265009A (en) * 2021-03-31 2021-08-17 矿冶科技集团有限公司 Preparation method of Guanhua bean endosperm rubber powder derivative and derivative thereof
CN113265009B (en) * 2021-03-31 2023-03-10 矿冶科技集团有限公司 Preparation method of Guanhua bean endosperm rubber powder derivative and derivative thereof

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