CN102295707B - Low viscosity carboxymethyl starch, and its preparation method and application - Google Patents
Low viscosity carboxymethyl starch, and its preparation method and application Download PDFInfo
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Abstract
The invention discloses low viscosity carboxymethyl starch for textile size, and its preparation method and application, relating to the field of chemistry. The preparation method for the low viscosity carboxymethyl starch comprises the following steps: mixing starch, alkali, alcohol and hydrogen peroxide, carrying out stirring for 15 to 30 min, adding a solid oxidant and continuing stirring for reaction for 15 to 30 min; adding solid sodium chloroacetate when the temperature of a reaction system naturally rises to 50 to 60 DEG C, and allowing the obtained mixture for reaction for 100 to 120 min; adding glacial acetic acid and carrying out stirring for 15 to 25 min; removing alcohol in the reaction system by heating and distilling under vacuum, and carrying out screening, crushing and mixing. The raw materials for the low viscosity carboxymethyl starch comprise, by weight, 900 parts of starch, 80 to 100 parts of alcohol, 15 to 25 parts of alkali, 18 to 12 parts of hydrogen peroxide, 1.0 part to 2.0 parts of the solid oxidant, 90 to 120 parts of sodium chloroacetate and 7 to 10 parts of glacial acetic acid. The preparation method provided in the invention needs no consumption of water resource and is free of treatment of waste water; consumed small amount of alcohol can be recovered completely through eventual distillation. The low viscosity carboxymethyl starch provided in the invention has good viscosity stability when applied in textile size and meets requirements for sizing processing.
Description
Technical field
The present invention relates to chemical field, be specially a kind of low-viscosity carboxymethyl starch that is used for spinning sizing agent and preparation method thereof.
Background technology
In recent years, various circles of society advocate low-carbon economy to the reinforcement of environmental consciousness, walk the road of green low consumed Sustainable development.The exhaustion day by day of petroleum resources, people are to studying the development and use growing interest of the recyclable materials that substitutes petroleum resources.PVA in textile sizing (polyvinyl alcohol) still occupies very big proportion, and the manufacturing of PVA too relies on petroleum resources, in starching is used, the time of sizing mixing is long, also need high temperature, caustic soda during destarch, and it is clean to be difficult for stripping fully, the desized wastewater of PVA has a strong impact on environment.PVA is from being fabricated onto courses of industrialization of incompatibility low-carbon (LC) green of a series of processes such as application.Chinese cotton textile industry association in 1997 proposes " high quality, multi-functional, few component, seriation.Less since usefulness and the developing direction without PVA.Some advanced enterprises and technician develop the high-performance slurry that substitutes PVA successively through studying assiduously.
Starch is the preferred material that substitutes PVA, is reproducible natural resources, also has many deficiencies but compare with PVA on performance.In its macromolecular chain, introduce different hydrophilic or hydrophobic groupings, improve its performance, the target that to remedy its deficiency to the fiber adhesive power be the investigator.
Carboxymethyl etherification starch is exactly the different positions introducing carboxymethyl at the pyrans group of starch.From the water react system, to the solvent phase reaction system, the investigator has improved the etherificate substitution value of carboxymethyl starch (CMS), has improved the performance of modified starch widely.From the experimental phase to the industrialized scale development, carboxymethyl etherification starch is subjected to the welcome of slurry and textile enterprise day by day.
The research of carboxymethyl starch has had the history in more than 100 year, be widely used in food or additive for papermaking at present, the carboxymethyl starch of low degree of substitution can be with being the water wet production, shortcoming is that the technological process of production is long, need with a large amount of water logging bubble, washing, produce a large amount of trade effluents, environment is posed a big pressure, very not environmental protection of production process.
For the carboxymethyl starch of producing high substitution value must be reacted in by the alcohol of starch suspension in liquid phase at a large amount of alcohol, remove concentrated starch with centrifugal then, if obtain low-ash carboxymethyl starch (ash content≤0.5%), also must repeatedly remove liquid, the more unnecessary alcohol in the vacuum distilling product with alcohol (70-80%) repetitive scrubbing.In order to obtain low viscous carboxymethyl starch, ative starch also must add the strong oxidizer hydrogen peroxide and carry out pre-treatment, just carboxymethylation then.This technology also exists the technological process of production long, and spirit solvent consumption height also has the problem of sewage disposal, reduces the viscosity of starch.Final product and alcohol consumption ton consumption ratio are 3～5: 1.
Other working methods have solvent phase single stage method etc.The solvent phase single stage method be starch in ethanol, starch, caustic soda, oxidant reaction system, earlier alkalization oxidation for some time, progressively add Mono Chloro Acetic Acid; In the reaction process, pH value descends gradually, at last to about 9.Such method, early stage, step of reaction system alkalescence was too strong, and starch turns to be yellow easily, and along with reaction is carried out, moisture increases in the system, the easy local gelatinization of starch.The integrated bulk of starch meeting stirs resistance and increases severely, and is prone to accidents.Therefore can only prepare on a small quantity in the laboratory, suitability for industrialized production danger is bigger.
Summary of the invention
The present invention aims to provide a kind of preparation method of low-viscosity carboxymethyl starch, and resulting carboxymethyl starch can be used as spinning sizing agent.
The preparation method may further comprise the steps:
(1) starch, alkali, alcohol and hydrogen peroxide are mixed, stirs and add the solid oxidizing agent restir after 15～30 minutes and reacted 15～30 minutes; Stirring velocity 50～60rpm;
Add the solid sodium chloroacetate when (2) the question response system temperature rises to 50～60 ℃ naturally, reacted 100～120 minutes;
(3) adding Glacial acetic acid stirred 15～25 minutes;
(4) alcohol in the reaction system is removed in the heating under vacuum distillation, and screening is pulverized and mixed;
Described each raw material weight is: 900 parts of starch, 80～100 parts of alcohol, 15～25 parts in alkali, 18～12 parts in hydrogen peroxide, 1.0～2.0 parts of solid oxidizing agents, 90～120 parts of sodium chloroacetates, 7～10 parts in Glacial acetic acid.
Preferably, starch is the corn ative starch; Alkali is NaOH or KOH; Solid oxidizing agent is a persulphate.
By the low-viscosity carboxymethyl starch of method for preparing, viscosity stability＞85.0%, pH value are 8.0～9.0, substitution value 0.1-0.13, and viscosity 4.0～8.0mPa.S can be used as the preparation spinning sizing agent.
The adding of solid oxidizing agent (persulphate) has improved the more low viscous carboxymethyl starch of oxidation efficiency production, replaces continuing to add liquid oxidizer, makes production safer.Need repeatedly add hydrogen peroxide because produce low viscous modified starch, add oxygenant at every turn and all the moisture that last time added must be removed by adding thermal distillation, replenish the fresh alcohol and the mixed solution of hydrogen peroxide.Under high temperature, strong oxidizer, the alcohol condition, set off an explosion easily.This technology is as long as once add alcohol and hydrogen peroxide, and oxidising process maintains cold condition, and oxidation efficiency continues to reduce starch viscosity by additional solid oxidizing agent inadequately, and does not introduce redundant moisture, and is relatively more difficult when removing liquid so as not to last distillation.
This patent adopts the solvent phase production carboxymethyl starch of low alcohol to oil ratio, selected the powerful box reactor that stirs of band for use, broken through the cost misgivings on using, on spinning sizing agent is used, substituted the PVA use and replaced effect preferably, recently finished watching and enough to meet the need of market from sexual valence.The carboxymethyl starch substitution value 0.10～0.13 of technical grade, the size film property excellence of comparing with other modified starch, a large amount of PVA of replacement use in textile sizing, and market response is good.Spirit solvent is produced not consume water resources mutually, no wastewater treatment.A small amount of alcohol that consumes reclaims fully by last distillation.Without water resources, there is not discharge of wastewater to handle.Spinning sizing agent is used the medium viscosity good stability, satisfies the slashing technique requirement, can meet the requirement in producer and market fully, the sizing costs 10-15% that descended, and weaving efficiency is also than higher; Adopt the spinning sizing agent prescription of this low viscosity carboxymethyl cellulose, do not contain PVA, reduce of the influence of textiles destarch sewage environment.
Embodiment
Embodiment 1
In the box reactor (volume 3000L) of band strong mixer, add 900kg corn ative starch, 16kg NaOH, 18kg hydrogen peroxide and 82kg alcohol, stir and be sprinkled into the 1.8kg Sodium Persulfate after 20 minutes, continue to stir 25 minutes, when treating that temperature is elevated to 52 ℃ naturally, add the 105kg sodium chloroacetate, react and added 10kg Glacial acetic acid continuation stirring reaction after 100 minutes 20 minutes.Stirring velocity is 50～60rpm.
Open steam valve, be heated to 65 ℃ and continue to vacuumize that (pressure 0.7～0.9atm) makes complete volatile matter distillation of alcohol and recovery in the reactor.
Screening behind the blowing, pulverizing (sieve underfill aperture 2.0～3.0mm), mixing.
Embodiment 2
In the box reactor (volume 3000L) of band strong mixer, add 900kg corn ative starch, 25kg NaOH, 15kg hydrogen peroxide and 98kg alcohol, stir and be sprinkled into the 1.0kg Sodium Persulfate after 20 minutes, continue to stir 20 minutes, when treating that temperature is elevated to 57 ℃ naturally, add the 95kg sodium chloroacetate, react and added 7kg Glacial acetic acid continuation stirring reaction after 100 minutes 20 minutes.
Open steam valve, be heated to 65 ℃ and continue to vacuumize, make complete volatile matter distillation of alcohol and recovery in the reactor.
Screening behind the blowing, pulverizing (sieve underfill aperture 2.0～3.0mm), mixing.
Embodiment 3
In the box reactor (volume 3000L) of band strong mixer, add 900kg corn ative starch, 25kg KOH, 12kg hydrogen peroxide and 90kg alcohol, stir and be sprinkled into the 2.0kg Sodium Persulfate after 20 minutes, continue to stir 20 minutes, when treating that temperature is elevated to 57 ℃ naturally, add the 120kg sodium chloroacetate, react and added 8kg Glacial acetic acid continuation stirring reaction after 100 minutes 20 minutes.
Open steam valve, be heated to 65 ℃ and continue to vacuumize, make complete volatile matter distillation of alcohol and recovery in the reactor.
Screening behind the blowing, pulverizing (sieve underfill aperture 2.0～3.0mm), mixing.
Embodiment 1～3 product, outward appearance are that white or yellow powder are granular, fugitive constituent≤14.0%, and viscosity stability＞85.0%, pH value are 8.0～9.0, substitution value 0.1-0.13, viscosity 4.0～8.0mPa.S.
The measuring method of substitution value is that acid base neutralization titration analysis or mantoquita complex-precipitation are analyzed.
The detection method of viscosity stability is with reference to weaving modified starch size quality industry standard commonly used (2000 editions, tentative).
NDJ-79 type rotational viscosimeter detects viscosity, carries out with reference to the method for GB 12098-89.
Infrared spectroscopy, embodiment 1～3 product and ative starch compare, and at wave number 1600 places carbonyl unsymmetrically peak are arranged, and have coupling to give birth to the carbonyl symmetrical peak simultaneously at wave number 1400 places.
Embodiment 4
A kind of polyester-cotton fabric (the outlet European market bans use of PVA), production description: T/C 63 " 21
s* 21
s100 * 551/1.This kind difficulty mainly is that the warp-wise tightness is big, and filoplume is many.
If use the PVA starching, filling a prescription is: PVA 50kg, ative starch 40kg, wax disk(-sc) 2kg, properties-correcting agent (as amylase, reducing the viscosity of ative starch when being used to size mixing) 4kg, liquid propene 10kg; Weaving efficiency 91%.
Use the prepared low-viscosity carboxymethyl starch of embodiment 1 instead, prescription is: carboxymethyl starch 75kg, the PE-23 (liquid polyester of solids content 25wt%, Shanghai C﹠D Industrial Co., Ltd.) 25kg, wax disk(-sc) 2kg, NP-350 (the liquid propene class slurry of solids content 25wt%, Shanghai C﹠D Industrial Co., Ltd.) 10kg.Weaving efficiency 95.7%.
In the present embodiment, carboxymethyl starch replaces PVA fully, has reduced the sizing cost of textile mills, and production efficiency also improves.Without PVA, and cost is compared reduction by 14.8% with aforesaid prescription, can meet the requirement in producer and market fully.
Textile product detects through ITS (International Testing Service) and does not contain PVA fully, meets the ecological check of the International Textile Oeko-Tex of association standard.
Embodiment 5
Produce JC 62 " 50
s* 50
s134 * 79 poplin cloth fabric varieties.Slasher sizing machine HS40, slasher sizing machine speed 40m/ branch, air-jet weaving 700rpm.
Formula of size is as follows: NP-350 liquid propene 25kg, KS-51 (wax disk(-sc)) 5kg, embodiment 2 low-viscosity carboxymethyl starch 100kg, Sumstar 190 25kg; Do not use PVA, weaving efficiency 92.8%.
Embodiment 6
Another kind JC 51.2 " 40
s* 40
s148 * 62 poplin cloth.Slasher sizing machine HS40, slasher sizing machine speed 40m/ branch, air-jet weaving 700rpm.
Formula of size is as follows: NP-350 liquid propene 25kg, KS-51 (wax disk(-sc)) 5kg, embodiment 3 low-viscosity carboxymethyl starch 50kg, Sumstar 190 50kg; Weaving efficiency 92%.Do not use PVA, reduce of the influence of textiles destarch sewage environment.
Claims (5)
1. the preparation method of low-viscosity carboxymethyl starch is characterized in that, comprises the steps:
(1) starch, alkali, alcohol and hydrogen peroxide are mixed, stirs and add the solid oxidizing agent restir after 15～30 minutes and reacted 15～30 minutes;
Add the solid sodium chloroacetate when (2) the question response system temperature rises to 50～60 ℃ naturally, reacted 100～120 minutes;
(3) adding Glacial acetic acid stirred 15～25 minutes;
(4) add thermal distillation under the vacuum condition and remove alcohol in the reaction system, screening is pulverized also and is mixed;
Described each raw material weight is: 900 parts of starch, 80～100 parts of alcohol, 15～25 parts in alkali, 18～12 parts in hydrogen peroxide, 1.0～2.0 parts of solid oxidizing agents, 90～120 parts of sodium chloroacetates, 7～10 parts in Glacial acetic acid;
Described solid oxidizing agent is a persulphate, and described alkali is NaOH or KOH.
2. the preparation method of the described low-viscosity carboxymethyl starch of claim 1 is characterized in that, described starch is corn ative starch or wheat ative starch.
3. the preparation method of the described low-viscosity carboxymethyl starch of claim 1 is characterized in that, stirring velocity 50～60rpm described in the step (1).
4. a low-viscosity carboxymethyl starch is characterized in that, by each described method preparation of claim 1～3, and viscosity stability＞85.0%, the pH value is 8.0～9.0, substitution value 0.1-0.13, viscosity 4.0～8.0mPa.S.
5. the application of the described low-viscosity carboxymethyl starch of claim 4 aspect the preparation spinning sizing agent.
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| CN104592404A (en) * | 2015-02-03 | 2015-05-06 | 漯河市恒瑞加友食品科技有限公司 | Physical oxidative carboxymethyl composite modified starch and preparation method thereof |
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| CN1923852A (en) * | 2006-08-28 | 2007-03-07 | 南昌大学 | One-step method of preparing oxidated carboxymethyl starch sodium from sweet potato starch |
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Effective date of registration: 20140224 Address after: The 215505 Jiangsu Economic Development Zone of Xishan province high tech Industrial Park Road two South Road to glue Yang Dongsheng West, West (East) Patentee after: XIDA (WUXI) BIOTECHNOLOGY CO.,LTD. Address before: 201617 Shanghai Songjiang District Li Tower Private Economic Development Zone Patentee before: SHANGHAI C & D IND Co.,Ltd. |
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Effective date of registration: 20230928 Address after: Floor 2, No. 10, Lane 658, Jinzhong Road, Changning District, Shanghai, 200000 Patentee after: Xinxida (Shanghai) Biotechnology Co.,Ltd. Address before: 215505 High tech Industrial Park in Xishan Economic Development Zone, Jiangsu Province, south of Jiaoyang Road and west of Dongsheng Second Road (East Zone) Patentee before: XIDA (WUXI) BIOTECHNOLOGY CO.,LTD. |