CN101942119B - Modified starch catalyzed by compound bio-enzymes and preparation method and application thereof - Google Patents
Modified starch catalyzed by compound bio-enzymes and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a preparation method and application of modified starch catalyzed by compound bio-enzymes. The modified starch is a non-toxic environment-friendly new material prepared by modifying raw plant starch by starch modifying assistants and compound bio-enzyme catalysts through special processes. The invention adopts the following technical scheme: the compound bio-enzyme catalysts are adopted to improve the reaction rate, shorten the reaction time and simplify the production process; and molecular recombination, namely grafting, is simultaneously carried out when the required viscosity is achieved, thus improving the use performance of the starch, reducing the use quantity of the assistants and reducing COD emission. The modified starch is widely applied to such fields as disposable environment-friendly tableware, wrappers, non-woven fabrics, pulp for paper-making, industrial and agricultural membranes, fabrics warp sizing, especially to fabrics warp sizing, and can replace PVA and other size.
Description
Technical field
The present invention relates to a kind of treated starch preparation method and its usage, particularly a kind of compound biological enzyme catalytic modification starch preparation method and uses thereof.
Background technology
Starch resource is abundant, low price, but native starch had both been expanded the purposes space because the restriction of inherent nature can not be satisfied the processing requirement of many aspects through the starch after the sex change, had improved economic worth again.
Treated starch is to utilize the means of physics, chemistry or enzyme to change the character of native starch, through molecule cut-out, rearrangement, oxidation or in molecule, introduce the starch derivative that character that substituting group makes changed, strengthens or had new property.Treated starch possesses environmental protection, energy-conservation, characteristics such as performance is good because of it; And then be widely used in fields such as environmental friendly material, disposable environmental protection tableware, wrapping material, food, pharmacy, papermaking sizing, non-woven fabrics, textile warp starching, toy for children, be an important branch in starch deep processing field.
Warp sizing is one very important operation in the textile industry, and the type of stock of main utilization is at present: treated starch, Z 150PH (PVA), acrylic acid or the like (EAA, EEA).The description of homemade three big slurries is more comprehensive, but low-levelly repeats morely, and high quality, high performance stable product are rare, and the competition between the international and domestic slurry enterprise is also unusual fierce.
Because PVA has good film-forming properties, adhesivity reaches and the characteristics of other slurry intermiscibility; The slurry that once was considered to " ideal "; The enhancing of warp thread, wear-resisting, subtract and stretch etc. on the overall target, have no a kind of natural or synthetic slurry to be equal to it so far.But the deadly defect of PVA is the non-feature of environmental protection, is called " unclean slurry " by people, and some countries of Europe have prohibited the grey cloth import that contains the PVA slurry.Another problem is that the PVA destarch is difficult for moving back fully only, and this has also hindered its use.
It is with a long history that ative starch is used for the textile warp starching, but compare with PVA, has many deficiencies.In order to overcome the shortcoming of ative starch, the investigator utilizes the characteristics of starch molecular structure, and starch is carried out sex change, to improve the performance of ative starch.
China began modified starch is developed faster from the eighties in last century, now can produce to be suitable for weaving all kinds of complete converted starch (acidolysis, oxidation), esterification, etherificate, crosslinked and graft starch.Along with improving constantly of modified starch state of the art, the modified starch consumption has accounted for about 70% of starch total flow, and is wherein maximum with the converted starch consumption, accounts for about 80% of modified starch.This is because this kind of starch can be according to the requirement of different fabrics and sizing equipment (like the high pressure starching); Produce the product (dense low sticking) of different viscosity series like height; Basically can satisfy the requirement of general big kind fabric warp sizing, secondly the converted starch production technology is uncomplicated, and price is also more cheap.
The kind of treated starch is a lot of at present, but the mode of sex change is different, and its quality, performance are also different, like phosphate ester starch, adopts the phosphoric acid salt degeneration methods, and the phosphoric acid salt usage quantity is too high, and the COD discharging exceeds standard, and consumption directly influences quality product less again.Sumstar 190, because chemical ingredientss such as use urea, oxygen-consumption is big when in producing the mashing off process, reacting, and service life of equipment and human body are had harm.Denaturated starch by acid because production process is to adopt the liquid acid infusion method to produce, technology very complicacy and cycle long, the energy consumption height, the production process environmental pollution is serious, does not fit into current friendly environment society.Therefore, how utilizing biotechnology, is raw material with the ative starch, develops high performance treated starch, no matter from environmental angle still from the economic benefit angle, all be a very urgent task.It can alleviate human degree of dependence to these Nonrenewable resources such as oil and coals.
Enzyme is a kind of natural efficient green catalyzer that extensively is present in, and utilizes enzyme that the research that ative starch carries out modification is all had relevant report at home and abroad.For example, domestic existing research report and the patented claim (publication number CN1911966) that utilizes amylorrhexis to handle emulsified starch also has the patented claim (publication number CN101319053) that utilizes saccharifying enzyme to handle the suspension preparation porous-starch of starch.
Publication number is that the invention of CN1911966 relates to a kind of pretreatment method of starch; Starch reaction efficient and modified starch stability are improved greatly, but it needs elder generation that starch is added water accent breast, and enzymolysis time is 2～6 hours; And need to regulate the pH value of starch emulsion, the technology more complicated.
Publication number be CN101011119 disclosure of the Invention a kind of corn-rice refined powder and preparation method thereof of enzymeization, its complex process, and enzymeization was for up to 40～50 hours.
Publication number be CN101319053 disclosure of the Invention a kind of preparation method of fatty acid stephanoporate starch ester, need earlier ative starch to be prepared into porous-starch and carry out enzymeization again, also relate to starch and size mixing, the reaction times is long.
Summary of the invention
For defectives such as the preparation time length that solves enzyme treated starch in the prior art, complex process, modified effect differences, the object of the invention aims to provide a kind of compound bio enzymically modified starch.
In order to achieve the above object, the present invention adopts following technical scheme:
The present invention adopts acid and ester under little water condition, plant ative starch hydroxyl to be carried out esterification, utilizes the compound bio catalyzer to improve speed of reaction, shortens the reaction times, simplifies production technique.To carry out molecular recombination simultaneously under the required viscosities be grafting reaching, and can improve the use properties of product, reduces the auxiliary agent usage quantity, and can reduce the quantity discharged of COD.
Concrete, the present invention provides a kind of preparation method of compound bio enzymically modified starch, is
1) gets the plant ative starch; The compound biological enzyme that add the acids starch conversion auxiliary agent account for ative starch butt weight 0.3%～3%, accounts for ative starch butt weight 0.2%～3% is as catalyzer; Pour in the mixing device; Spray into the water that accounts for ative starch butt weight 0.1%～5%, under 0 ℃～68 ℃ and atmospheric pressure state, the reaction certain hour reaches required viscosity number;
2) add the ester kind of starch plasticizing adjuvant account for ative starch butt weight 1%～10%, account for the supplementary thickener of ative starch butt weight 0.1%～2% after; Be warming up to 80 ℃～180 ℃ and carry out enzyme-deactivating and grafting; Regulate pH value 6～8, stop heating, stir, post reaction mixture is entered in the material water cooler cool off; Leave standstill detection, promptly get.
Wherein, said plant ative starch comprises but is not limited in W-Gum, tapioca(flour), the yam starch one or more.
Said acids starch conversion auxiliary agent is that diprotic acid, organic acid, the lipid acid to human non-toxic is formed, and specifically is in hexanodioic acid, sebacic acid, pentanedioic acid, nonane diacid, Hydrocerol A, tartrate, LAURIC ACID 99 MIN, myristic acid, Triple Pressed Stearic Acid, the oleic acid one or more.Its add-on is preferably and accounts for ative starch butt weight 0.8%～1%.
Said compound biological enzyme catalyzer comprises but is not limited in AMS, glucoamylase, aspartic protease, lypase, cellulase, P-FAD, the Nitrile hydratase two or more.Its add-on is preferably and accounts for ative starch butt weight 2%～3%.
The said water that sprays into is preferably and accounts for ative starch butt weight 0.6～2%.Preferred 60 ℃～68 ℃ of temperature of reaction.Reaction times is different, then obtains the enzyme treated starch of different viscosity; The preferred reaction times can be 10～60 minutes, more preferably 25～45 minutes.
Said ester kind of starch modified additive is one or more in butyl stearate, tributyl citrate, dioctyl maleate, water-soluble polyester, the sorbitol ester.Its add-on is preferably and accounts for ative starch butt weight 4%～5%.
Said supplementary thickener is one or more in chitosan, chitin, sodium-alginate, guar gum, the gum arabic etc.Its add-on is preferably and accounts for ative starch butt weight 0.6%～0.8%.
Said enzyme-deactivating and grafted temperature are preferably 140 ℃～150 ℃, and the time of enzyme-deactivating is for reaching after the deactivation temperature 3～10 minutes, preferred 8～10 minutes.Said adjusting pH value can adopt the sodium hydroxide of Yi Bingchunan or food grade.
Said mixing device is a high-speed mixer, perhaps adopts starch conversion pot provided by the invention, and said starch conversion pot is to install water-cooled condenser additional in the oily mould temperature control machine with the high-speed mixer of prior art, to reach the purpose of control temperature of charge.
The present invention also provides the compound bio for preparing by said method enzymically modified starch, drying-free, the water cut of gained treated starch≤10%.
Another object of the present invention is to provide said compound bio enzymically modified starch in textile warp starching, disposable environmental protection tableware, wrapping material, toy for children, non-woven fabrics, the industrial or agricultural application with film, papermaking sizing field.
Preparing method's work simplification of compound biological enzyme catalytic modification starch of the present invention, equipment is easy to operate, and the reaction times is short; Modification efficiency is high, and production cost is low, does not use the phosphoric acid salt catalyzer; Non-wastewater discharge has efficient, energy-saving and emission-reduction, environmental protection, low cost and other advantages.Prepared its main performance index of enzyme treated starch SSU can substitute the PVA slurry.
Description of drawings
Fig. 1 is preparing method's schema of compound bio enzymically modified starch provided by the invention;
Fig. 2 is the influence of reaction times to compound bio enzymically modified starch viscosity of the present invention;
Fig. 3 changes the influence to textile adhesive power for the viscosity of the compound bio enzymically modified starch that the inventive method is produced;
Fig. 4 changes the influence to polyester-cotton blend 65/35 adhesive power for the viscosity of the compound bio enzymically modified starch that the inventive method is produced;
The compound bio enzymically modified starch disposable material production process figure that Fig. 5 produces for the inventive method;
Fig. 6 is the supporting condensing surface synoptic diagram of employed modification pot in the preferred embodiment of the invention.
Description of drawings: 1-high temperature heat conductive oil inlet is connected with the outlet of high-speed mixer pot cover; The outlet of 2-thermal oil is connected with oily die heater; 3-condensing surface circulating water outlet; 4-condensing surface recirculated water inlet has also been installed a SV, and this valve is connected with oily die heater temperature control system; The 5-condensing surface is connected support with oily mould temperature.
Embodiment
Below in conjunction with specific embodiment above-mentioned preparation method is further described, but embodiment of the present invention is not limited only to this.
Starch is made up of amylose starch and pulullan, and amylose starch is commonly referred to chain starch, and its structure is through-1 between AGU; 4 glycoside bonds connect, and the pulullan structure is through-1,6 glycoside bonds and-1 between AGU; 4 glycoside bonds connect, and its vent is changed to-1,6 glycoside bond.Because the structure of chain starch and pulullan is different, so the chain starch content is different, starch structure is also different with character.
Enzymic catalytic reaction has the height specificity, reaction conditions is gentle, speed of response is fast, biodegradability.Enzyme can significantly be accelerated the speed of some chemical reaction, shortens reaction greatly and arrives the required time of balance, is issued to the reaction that trim point needs several hrs in no enzyme situation, under enzyme catalysis, possibly need only just can reach several seconds.Consider the composition and the constructional feature of ative starch, the present invention has adopted the compound bio enzyme catalyst, has wherein comprised AMS, aspartic protease, lypase, glucoamylase, cellulase, P-FAD, Nitrile hydratase etc.Wherein, glycase can catalyzed degradation starch, and its molecular weight is reduced; The proteinic degraded of proteolytic enzyme in can catalysis starch reduces Protein content in the starch; Lypase can catalysis starch hydroxyl esterification or the like.
Utilize the characteristics that biological enzyme reacts only needs under little water condition, (promptly to spray into the water that accounts for ative starch butt weight 0.1-5%) with regard to the ability catalyzed reaction, the present invention has adopted the testing program of dry method modification starch, uses existing high-speed mixer to react.In the preferred embodiment of the present invention, be easy to generate mechanical shearing self-friction temperature when overcoming modification and raise and be unfavorable for enzymatic problem, the present invention reequips high-speed mixer.The starch conversion pot is to be with the high-speed mixer of heating unit to convert by existing technology; In order to help realizing processing requirement of the present invention; Installed a water-cooled condenser (seeing accompanying drawing 6) additional in the oily mould temperature control machine to the high-speed mixer of prior art, reached the purpose of temperature of charge control, the concrete arrangement is: a pot body is vertical circle; Interior band stainless steel chuck, high temperature heat conductive oil circulation heating.The top is made up of pot cover, venting port, feeding mouth, and the below is that discharge port is connected with the material water cooler.Wheeled spiral shell dish blade is equipped with in the bottom of a pan, satisfies the required speed ratio of technology through the frequency control motor transmission.The below of chuck is the thermal oil inlet, and the top of chuck is provided with the interior oil pipe that links to each other with oily die heater of thermal oil outlet having increased connection pot cover chuck, and circulation heating or condensation come controlled temperature.This machine when temperature of charge rising, viscosity increased, electric current increase, passes through computer auto-control rotating speed according to the requirement that technology is required through the PLC programming Control, reduces mechanical torque.CPU transmits rapidly to instruct and increases or turn reducing speed when electric current decline certain value is accomplished in the material modification; When guaranteeing that motor runs well, guaranteed carrying out smoothly of under little water condition enzymic catalytic reaction, can increase work efficiency; When the temperature of technique initialization reaches; The starch-based material that modify and graft is accomplished is disposed to the cooling of material water cooler automatically and substitutes, and enzyme generally just demonstrates high catalytic activity under lesser temps (20～65 degree), and loses activity next being prone to of comparatively high temps (surpassing 80 degree); Therefore; After the biological enzyme reaction process is accomplished, can directly heat up and impel the inactivation of biological enzyme agent in the system, thereby reach the purpose of control treated starch quality.
In addition, through in ative starch, adding the starch conversion auxiliary agent, under temperature of reaction,, can impel between plant amylum molecule and the auxiliary agent molecule to react through the shear force of mechanical means; In addition, adopt the small molecules internal plasticization, can improve the use properties of starch.The modified additive that the present invention adopts can play the reduction molecular weight, carry out molecular recombination effects such as (comprising esterification, grafting) in the modifying process of starch.The purpose of wherein starch being carried out the acidolysis modification is to reduce the viscosity of farinaceous size, is through with the hydrolysis of acid catalysis starch polymer glucoside key, has reduced the molecular weight of starch and has realized.Just because of having reduced viscosity, the working concentration of acidified starch is greatly improved.This performance is favourable for sizing technique.And the activity that little an amount of acid and water can keep enzyme under the lesser temps guarantees catalytic efficiency (, after modified-reaction is accomplished, can adopt an amount of alkali to be adjusted to neutrality.And the ester class in the modified additive can play esterification to starch, accomplishing the required reaction times when reaching required viscosity number, heats up and carries out enzyme-deactivating, grafting, and accomplish simultaneously and utilize thickening material to carry out the reorganization of grafting equimolecular.
Preparing method's schema of compound bio enzymically modified starch provided by the invention is as shown in Figure 1.Used plant ative starch gets final product for the GB one-level.
Below in conjunction with embodiment the present invention is further specified, but do not limit the scope of the invention.
Extracting corn starch 150kg adds hexanodioic acid 0.65kg, oleic acid 0.30kg, Triple Pressed Stearic Acid 0.25kg; Glucoamylase 2.5kg, cellulase 2kg pours in the starch conversion pot, opens the starch conversion Pot devices; Spray into the water of 3kg, 60 ℃ of atmospheric pressure states reacted 30 minutes down through the effect of mechanical-physical shearing force, added tributyl citrate 5kg; Sorbitol ester 2.5kg, chitosan 0.75kg, guar gum 0.15kg are warming up to 150 ℃ again and carried out enzyme-deactivating and grafting in mixing 8 minutes, add 1kg sodium hydroxide (food grade) and regulate pH value 6-8; Stop heating, stir stopping device, post reaction mixture is entered in the material water cooler cool off, leave standstill detection; Record (NDJ-79 type detector is at 95 ℃, and 6% solid content is measured down) below the viscosity number 10mpa.s, promptly get enzyme treated starch (SSU-1).
Extracting corn starch 150kg adds hexanodioic acid 0.65kg, oleic acid 0.30kg, Triple Pressed Stearic Acid 0.25kg; Glucoamylase 2.5kg, cellulase 2kg pours in the starch conversion pot, opens the starch conversion Pot devices; Spray into the water of 3kg, 60 ℃ of atmospheric pressure states reacted 40 minutes down through the effect of mechanical-physical shearing force, added tributyl citrate 5kg; Sorbitol ester 2.5kg, chitosan 0.75kg, guar gum 0.15kg are warming up to 150 ℃ again and carried out enzyme-deactivating and grafting in mixing 8 minutes, add 1kg sodium hydroxide (food grade) and regulate pH value 6-8; Stop heating, stir stopping device, post reaction mixture is entered in the material water cooler cool off, leave standstill detection; Record (NDJ-79 type detector is at 95 ℃, and 6% solid content is measured down) below the viscosity number 5mpa.s, promptly get enzyme treated starch (SSU-2).
Get yam starch 150kg, add sebacic acid 0.40kg, myristic acid 0.60kg, LAURIC ACID 99 MIN 0.50kg; AMS 1.5kg, aspartic protease 1.2kg, lypase 1kg pours in the starch conversion pot; Open the starch conversion Pot devices, spray into the water of 1kg, 60 ℃ of atmospheric pressure states reacted 30 minutes down through the mechanical shear stress effect; Add butyl stearate 2.50kg, water-soluble polyester 5kg, chitin 1kg, gum arabic 0.2kg are warming up to 150 ℃ of stirrings again and carried out enzyme-deactivating and grafting in 10 minutes; Add 1.25kg sodium hydroxide (food grade) and regulate pH value 6-8, stop heating, stirring, stopping device enters post reaction mixture in the material water cooler and to cool off; Leave standstill detection, record viscosity number 8mpa.s following (NDJ-79 type detector is at 95 ℃, and 6% solid content is measured down) and promptly get.
Get yam starch 150kg, add sebacic acid 0.40kg, myristic acid 0.60kg, LAURIC ACID 99 MIN 0.50kg; AMS 1.5kg, aspartic protease 1.2kg, lypase 1kg pours in the starch conversion pot; Open the starch conversion Pot devices, spray into the water of 1kg, 60 ℃ of atmospheric pressure states reacted 45 minutes down through the mechanical shear stress effect; Add butyl stearate 2.50kg, water-soluble polyester 5kg, chitin 1kg, gum arabic 0.2kg are warming up to 150 ℃ of stirrings again and carried out enzyme-deactivating and grafting in 10 minutes; Add 1.25kg sodium hydroxide (food grade) and regulate pH value 6-8, stop heating, stirring, stopping device enters post reaction mixture in the material water cooler and to cool off; Leave standstill detection, record viscosity number 3mpa.s following (NDJ-79 type detector is at 95 ℃, and 6% solid content is measured down) and promptly get.
Get tapioca(flour) 150kg, add nonane diacid 1.30kg, Triple Pressed Stearic Acid 0.25kg, Hydrocerol A 0.20kg; P-FAD 2kg, Nitrile hydratase 1kg pours in the starch conversion pot, opens the starch conversion Pot devices; Spray into the water of 2.5kg, cut effect through machinery under 68 ℃ of atmospheric pressure states, reacted 25 minutes, add dioctyl maleate 1.50kg; Water-soluble polyester 6kg, sodium-alginate 0.75kg, guar gum 0.15kg are warming up to 145 ℃ of stirrings again and carried out enzyme-deactivating and grafting in 8 minutes, add the 0.5kg Yi Bingchunan and regulate pH value 6-8; Stop heating, stir, stopping device enters post reaction mixture in the material water cooler and to cool off; Leave standstill detection, record viscosity number 15mpa.s following (NDJ-79 type detector is at 95 ℃, and 6% solid content is measured down) and promptly get.
Embodiment 6
Get tapioca(flour) 150kg, add nonane diacid 1.30kg, Triple Pressed Stearic Acid 0.25kg, Hydrocerol A 0.20kg; P-FAD 2kg, Nitrile hydratase 1kg pours in the starch conversion pot, opens the starch conversion Pot devices; Spray into the water of 2.5kg, cut effect through machinery under 68 ℃ of atmospheric pressure states, reacted 35 minutes, add dioctyl maleate 1.50kg; Water-soluble polyester 6kg, sodium-alginate 0.75kg, guar gum 0.15kg are warming up to 145 ℃ of stirrings again and carried out enzyme-deactivating and grafting in 8 minutes, add the 0.5kg Yi Bingchunan and regulate pH value 6-8; Stop heating, stir, stopping device enters post reaction mixture in the material water cooler and to cool off; Leave standstill detection, record viscosity number 7mpa.s following (NDJ-79 type detector is at 95 ℃, and 6% solid content is measured down) and promptly get.
The treated starch water cut of prepared as stated above embodiment 1-6 all is lower than 10%, the drying-free program, thus make work simplification.Through check, its performance index with the modified starch paste of producing with ordinary method contrast, and are as shown in table 1 below:
Table 1
Warp sizing is one of main application of treated starch, and adhesion strength is to estimate the important indicator of starch finishing effect.
The factor that influences adhesion strength mainly comprises: the 1) structural form of macromolecular chain, 2) kindliness of macromolecular chain, 3) viscosity (molecular weight).The macromolecular structural form of slurry has tangible influence to the adhesion property of slurry.The polymer molecule that has long-chain branch, end group quantity is more, end group obviously than segment more easily to the adherend internal divergence, so help to improve adhesion property.The polymer molecular chain kindliness is good, will help the diffusion motion of this molecular chain, helps to improve bond strength.The factor of impact polymer molecular chain kindliness mainly contains backbone structure, substituent polarity, intermolecular reactive force and temperature etc.Slurry viscosity is low, and then the good fluidity of slurries helps fiber is sprawled, and helps to form the tight contact of molecular level, helps improving bond strength.
General for the same superpolymer that is used for warp sizing, its molecular weight is low, and slurry viscosity is low, good fluidity, wetting favourable to warp thread; But force of cohesion is low, and adhesion strength is not high.Relative molecular weight is high, and force of cohesion is big, but is unfavorable for slurries wetting to warp thread because slurry viscosity is high, makes slurries molecular diffusion difficulty, also can not get the adhesion strength of the best.Therefore, the molecular weight that has only slurries is in certain scope, and slurries just have good penetration property and bigger force of cohesion, thereby higher adhesion strength is arranged.
Ative starch is a relative molecular weight up to 100,000 natural high moleculer eompound.And this macromole is to be flocked on together with the granule shape, in water, can form the very big mashed prod of viscosity, and is mobile poor, thereby to the poor permeability of warp thread, is difficult to directly be used for warp sizing.
In view of the foregoing, in the process of the test of utilizing the enzyme treated starch, emphasis has been followed the tracks of the changing conditions of the viscosity of treated starch with the reaction times.Viscosity tester is the NDJ-79 rotational viscosimeter.
One, the reaction times is to the influence of viscosity
By above-mentioned preparation method, under the identical situation of other reaction conditionss, the different reaction times obtains the enzyme treated starch of different viscosity.Like the preparation method of embodiment 1 and 2, slurries heat through thermostat water bath, and concentration of slurry is 6%, and slurry temperature is set in 93 ℃～95 ℃ insulation 1h, uses viscosity tester to be the NDJ-79 rotary viscosity design determining.Fig. 2 has provided respectively through reacting the slurry viscosity of the treated starch preparation that obtains in 30 minutes and 40 minutes.Obviously, the reaction times is very remarkable to the influence of viscosity.
Through measuring, concentration is that the viscosity of 6% serial slurries of enzyme treated starch (SSU) is 3～10mpd.s, and wherein the slurry viscosity of the code name SSU-1 of embodiment 1 is 6～10mpd.s, belongs to the LV slurries.The slurry viscosity of the code name SSU-2 of embodiment 2 is 3～5mpd.s, belongs to the ultra-low viscosity slurries.According to the requirement of textile sizing technical recipe solid content, the user uses after can regulating viscosity voluntarily.
Two, viscosity changes the influence to adhesive power
Along with the carrying out of reaction, starch molecule amount and structure thereof and other composition all can change.Therefore, the inventive method is found the carrying out along with modifying process, and the viscosity of treated starch is in continuous decline, and meanwhile, adhesive power also descends along with the decline of viscosity.Fig. 3 demonstrates the changing conditions of the slurries of three kinds of different viscosity treated starches to the clinging power of cotton textiles, and Fig. 4 then is the adhesive power test results of the slurries of these three kinds of different viscosity treated starches to polyester-cotton blend 65/35.
The enzyme treated starch that the inventive method is produced has following purposes:
1, the slurry that starching is used as textile warp.
The purpose of warp sizing is submissive in order to improve its wear resistance and filoplume.Enzyme treated starch of the present invention is suitable for the starching of cotton textiles, polyester-cotton blend and hydrophobic synthetic fibre; Can improve the replacement amount of starch size to PVA; Reach " high dense low sticking ", " two-supremes one is low " (high-count and high-density, high density, LV) starching; Paste the volt filoplume, strengthen the yarn wear resistance, make weaving efficiency improve more than 10%.Compound bio enzymically modified starch warp sizing of the present invention has special excellent permeation performance, and polyester-cotton blend is had the affinity clinging power of similar PVA, has better adhesivity than modified modified starch, phosphate ester starch and acidified starch simultaneously.
2, be used for disposable environmental protection tableware, degradable packaging material, industrial or agricultural with film, toy for children, non-woven fabrics.
By preparation method of the present invention; Starch can be directly and degradable macromolecular material in the starch conversion pot after the modification, as: PLA, PCL; Or superpolymer such as PP, PE 10～30 minutes short mix in the starch conversion pot; Get into successively in the parallel double-screw extruder, through the effect of " low temperature high-shear " power, make that starch fully plastifies, mixing " polymerization solubilising " application " powder single stage method " extruding pelletization (resin) or sheet material.Because after the abundant modification of starch, grafting during with the superpolymer polymerization; The Flow of Goods and Materials performance significantly improves; Can be used for the required material of all kinds of environment protection type disposable articles for use " thermoplastically starch-base biodegradation material "; The thermoplastic shaping mode such as utilize plastics machinery to adopt to press, annotate, blow produce disposable each required based article, like tableware, toy for children, non-woven fabrics, cosmetic package, pharmaceutical product packaging, industrial or agricultural with products such as film, footwear packagings.Its disposable material produce process drawing is as shown in Figure 5.
3, be used for the papermaking sizing.
The enzyme treated starch that the inventive method is produced is a kind of good additive in paper industry, and it can improve the anti-fatigue performance of paper, tension stress, folding resistance and resistance to picking.
Enzyme treated starch method technological process of the present invention is simplified, and equipment is easy to operate, and the reaction times is short; Modification efficiency is high, and production process does not have tangible waste water and gas discharging, and production cost is low; Under little water or few water condition, can react, the treated starch water cut of reaction gained is low, drying-free.The enzyme treated starch of preparation gained is widely used in fields such as disposable environmental protection tableware, wrapping material, toy for children, non-woven fabrics, food, pharmacy, papermaking sizing, textile warp starching.Especially as spinning sizing agent; Be applicable to high and low shift yarn sizings such as cotton textiles, cotton are washed, polyester-cotton blend; Have that convenience for size mixing, energy-conservation solar term, slurry viscosity are stable, good penetrability, adhesive power are strong, going up will be evenly, film phonograph strength is complete, be beneficial to advantages such as feather is submissive, dry powder is lighter, and weaving efficiency is increased significantly, can be less with PVA or without PVA; Cost is practiced thrift in environmental protection.
Claims (11)
1. the preparation method of a compound bio enzymically modified starch is characterized in that
1) gets the plant ative starch; The compound biological enzyme that add the acids starch conversion auxiliary agent account for ative starch butt weight 0.3%～3%, accounts for ative starch butt weight 0.2%～3% is as catalyzer; Pour in the mixing device, spray into the water that accounts for ative starch butt weight 0.1%～5%, under 0 ℃～68 ℃ little water atmospheric pressure states; Under the effect through mechanical shear stress, the dry process reaction certain hour reaches required viscosity number;
2) add the ester kind of starch plasticizing adjuvant account for ative starch butt weight 1%～10%, account for the supplementary thickener of ative starch butt weight 0.1%～2% after; Be warming up to 80 ℃～180 ℃ and carry out enzyme-deactivating and grafting; Regulate pH value 6～8, stop heating, stir, post reaction mixture is entered in the material water cooler cool off; Leave standstill detection, promptly get;
Said acids starch conversion auxiliary agent is made up of diprotic acid, organic acid, lipid acid to human non-toxic; Specifically be several kinds in hexanodioic acid, sebacic acid, pentanedioic acid, nonane diacid, Hydrocerol A, tartrate, LAURIC ACID 99 MIN, myristic acid, Triple Pressed Stearic Acid, the oleic acid, its add-on is to account for 0.8%～1% of ative starch butt weight.
2. the preparation method of compound bio enzymically modified starch as claimed in claim 1 is characterized in that said plant ative starch is selected from one or more in W-Gum, tapioca(flour), the yam starch.
3. the preparation method of compound bio enzymically modified starch as claimed in claim 1 is characterized in that said compound bio enzyme catalyst is selected from two or more in AMS, glucoamylase, aspartic protease, lypase, cellulase, P-FAD, the Nitrile hydratase; Its add-on is to account for 2%～3% of ative starch butt weight.
4. the preparation method of compound bio enzymically modified starch as claimed in claim 1 is characterized in that the said water that sprays into accounts for 0.6～2% of ative starch butt weight; Temperature of reaction is 60 ℃～68 ℃; Reaction times is 10～60 minutes.
5. the preparation method of compound bio enzymically modified starch as claimed in claim 4 is characterized in that the said reaction times is 25～45 minutes.
6. the preparation method of compound bio enzymically modified starch as claimed in claim 1 is characterized in that said ester kind of starch plasticizing adjuvant is one or more in butyl stearate, tributyl citrate, dioctyl maleate, water-soluble polyester, the sorbitol ester; Its add-on is to account for 4%～5% of ative starch butt weight.
7. the preparation method of compound bio enzymically modified starch as claimed in claim 1; It is characterized in that said supplementary thickener is one or more in chitosan, chitin, sodium-alginate, guar gum, the gum arabic, its add-on is for accounting for ative starch butt weight 0.6%～0.8%.
8. the preparation method of compound bio enzymically modified starch as claimed in claim 1, the temperature that it is characterized in that said enzyme-deactivating is 140～150 ℃, the time of enzyme-deactivating is for reaching after the deactivation temperature 3～10 minutes; Said adjusting pH value adopts the sodium hydroxide of Yi Bingchunan or food grade.
9. the preparation method of compound bio enzymically modified starch as claimed in claim 8 is characterized in that the said enzyme-deactivating time is for reaching after the deactivation temperature 8～10 minutes.
10. like the compound bio enzymically modified starch of the said method of claim 1-9 preparation, it is characterized in that the treated starch for preparing, drying-free, the water cut of gained treated starch≤10%.
11. like the purposes of the compound bio enzymically modified starch of the said method of claim 1-9 preparation, it is characterized in that: said enzyme treated starch is used for textile warp starching, disposable environmental protection tableware, wrapping material, toy for children, non-woven fabrics, industrial or agricultural with film, papermaking sizing field.
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| CN109023943A (en) * | 2018-07-14 | 2018-12-18 | 嘉兴市如裕纺织有限公司 | A kind of production technology of all cotton yarn |
| CN109851860B (en) * | 2018-12-13 | 2021-04-30 | 浙江华康药业股份有限公司 | Method for regulating and controlling starch denaturation by sugar alcohol |
| CN112813528A (en) * | 2020-12-30 | 2021-05-18 | 浪莎针织有限公司 | Degradable flame-retardant polylactic acid elastic fiber and preparation method thereof |
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| CN114163695A (en) * | 2021-11-16 | 2022-03-11 | 合肥玉麦康环保科技有限公司 | Method for manufacturing fully biodegradable tableware and production equipment thereof |
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