CN102653922B - Starch slurry with acrylic ester copolymer block and preparation method thereof - Google Patents
Starch slurry with acrylic ester copolymer block and preparation method thereof Download PDFInfo
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Abstract
The invention provides starch slurry with acrylic ester copolymer blocks and a preparation method thereof and belongs to a preparation technology of slurry for use in warp starching in spinning. The molecular chain of the starch slurry comprises rigid starch molecular chain blocks and soft acrylic ester copolymer blocks; and the mass percent of the acrylic ester copolymer blocked on the starch molecular chain to the starch is 4% to 40%. The preparation method of the starch slurry comprises the following two steps: synchronization and blocking of the acrylic ester copolymer, i.e. firstly, synchronizing the acrylic ester copolymer; secondly plasticating the starch and the acrylic ester copolymer in an internal mixer in the presence of inert gas; further being subjected to shearing action of a screw extruder; forming free groups on two polymer molecules; and performing reciprocal chiasma and coupling so as to obtain the starch slurry with the acrylic ester copolymer blocks. The slurry provided by the invention is high in adhesivity, good in fur stickness, soft in slurry film, easy to deslurry, easy to degrade and capable of replacing PVA (Polyvinyl Alcohol).
Description
technical field
The present invention relates to a kind of slurry that is applicable to warp sizing and preparation method thereof, propose a kind of starch size and preparation method with acrylate copolymer block, belong to the slurry preparing technical field that textile warp starching is used.
Background technology
At present, the slurry for warp sizing mainly contains starch, polyvinyl alcohol (PVA), polyacrylic slurry.It is the most frequently used slurry during sizing is produced that sex change powder forms sediment, and its source is abundant, relative low price, environmentally friendly, is easily degraded by microorganisms, and can adopt biology enzyme destarch, and destarch waste liquid is little to ambient influnence.But its serous coat is crisp hard, to polyster fibre poor adhesion, has had a strong impact on its result of use.
In recent years, the speed of production of Sizing machines and loom is more and more faster, and this has higher requirement to slurry.The increase of Sizing machines and loom speed, the adhesion of inevitable requirement slurry is stronger, slurry film strength and pliability are higher, ABRASION RESISTANCE is better, to increase the anti-wear performance of warp thread, reduce filoplume, improve intensity, the elasticity and the extension at break that keep warp thread, thus reduction is weaved end breakage rate, is enhanced productivity, improves product quality.
On the other hand, in the formula of size using, also temporarily be unable to do without at present PVA pulp components in warp sizing is produced.Although the regularity of PVA strand is high, size film property is good, can enhance productivity, but destarch is difficult, is difficult for moving back completely clean, and very difficult biodegradation, just the material that becomes generally acknowledged contaminated environment after destarch, a large amount of PVA, along with desized wastewater enters rivers and lakes, constitutes a serious threat to ecological environment, become the greatest contamination source of weaving and printing and dyeing, so must the use in sizing is produced be limited PVA.Yet sizing production practices show, in the starching of high-leveled and difficult kind warp thread is produced, if reduce simply PVA consumption, tend to occur various quality problems.Although China just clearly proposed to use no or little the slashing technique developing direction of PVA as far back as 1997, to realize the production that cleans of warp sizing, but the 20% left and right ，Er U.S. that China still accounts for whole slurry use amounts for the PVA of warp sizing at present only accounts for 11% left and right.Not affecting under the prerequisite of sizing quality, how effectively to reduce the PVA consumption in warp sizing production, is a very urgent task.
Ative starch is carried out to chemical modification, a kind of effective way that become and improved starch size sizing performance, reduces PVA usage of sizing agent.Zhu Zhifeng etc. (ZL 03 1 13350.9) carry out the sex change of quaternary ammonium etherificate again to crosslinked starch, keeping on the basis of slurries Heat stability is good, by introducing hydroxypropyl-trimethyl ammonium chloride functional group, overcome the side effect that crosslinked sex change produces, increase its adhesive performance to fiber, improved sizing performance.In order to make modified starch size can adapt to the low temperature starching requirement of the heat-sensitive chaines such as wool, viscose glue, dyed yarn, Zhu Zhifeng etc. (ZL 200810109024.5) disclose a kind of method of starch being carried out to multiple esterification sex change, the multiple esterification modified starch size obtaining, even carry out sizing at 60～80 ℃, the mobility of slurries and Heat stability is good, gel resistance is strong, can on cotton formula Sizing machines, meet the low temperature starching requirement of the heat-sensitive chaines such as wool, viscose glue, dyed yarn.
In addition, to close reaction be also starch to be carried out to a kind of important method of modification to starch graft copolymer.Ma Yanming (200610066984.9) has synthesized degradable starch graft copolymer, can replace part PVA slurry for warp sizing.Zhu Zhifeng etc. (ZL 2,007 1 0024110.1) have invented a kind of pretreatment method of starch that can improve grafting starch grafting efficiency: by starch material is carried out to etherificate preliminary treatment, on starch polymer, introduce the allyl atomic group that contains carbon-to-carbon double bond, then etherification starch and vinyl monomer are carried out to graft copolymerization under initator effect, can obviously improve the grafting efficiency of grafting starch, and significantly increase the content of graft copolymer in grafting starch, effectively improved the sizing performance of grafting starch.The people (200810042900.7) such as Guo's wax plum have invented a kind of graft starch and clean method for preparing thereof that improves side shoot formation that have, adopt the graft starch for cellulose fibre warp sizing of Semi-dry process, accomplish production process non-wastewater discharge, improved production efficiency.
Yet graft starch also exists some defects at present.The main chain of graft starch is still the circulus of the surplus base of glucose, so main chain shows very strong rigidity, compliance is poor, even if exist flexible grafted branches, can not change the attribute of main chain rigidity.On the other hand, as graft copolymerization must be take water as decentralized medium, product needs to filter, washs and dries, and technological process is long; Produce a large amount of waste water, cause environmental problem or increase wastewater treatment expense; The a large amount of heat energy of drying course consumption, cost raises.So, in the urgent need to developing, a kind ofly can under non-water environment, on starch molecule main chain, introduce the production technology of synthetic molecules chain, so that shortened process reduces energy consumption, reduce and pollute, enhance productivity.
Summary of the invention
The object of the present invention is to provide a kind of preparation method with the starch size of acrylate copolymer block.By the prepared block copolymerization starch size of the inventive method, there is adhesiveness high, filoplume sticking nature is good, and serous coat is soft, is easy to destarch, is easy to degraded, has the ability that replaces PVA.The production procedure of the inventive method is short, and production efficiency is high, and production cost is low and energy consumption is little, pollution-free.
Technical scheme of the present invention is to adopt block technology to solve the crisp hard defect of starch main chain, make starch and acrylate copolymer jointly form main chain, main chain is no longer all starch structure, but formed by two parts, the starch molecular chain of rigidity and flexible acrylate segment form jointly.The body of this block copolymer will form the structure of micron-scale phase separation, the microcell that starch hard segment can form, its glass transition temperature mutually
t gheight is born the effect of physical point of attachment in serous coat, meets the requirement of intensity, and can stablize outward appearance cun chi; Flexible acrylate segment will form amorphous microcell, and the possibility of deformation is provided, and meet the requirement of toughness of material.As can be seen here, Starch with Acrylic Acid ester block copolymer can produce larger deformation under the prerequisite that intermolecular slippage does not occur, and starch serous coat is carried out toughness reinforcing, is conducive to overcome the crisp hard defect of starch.This inhomogenous phase structure; make starch serous coat in macroscopic view, there is the good physical and mechanical properties that hard, soft two class segments provide, for protection warp thread, avoid exterior mechanical wearing and tearing and lay a good foundation, thereby improved the weavability of sizing; reduced and weaved end breakage rate, improved loom efficiency.
The present invention realizes its goal of the invention by the following technical solutions:
A starch size with acrylate copolymer block, described starch size molecular backbone is not all starch structure, but is comprised of two parts, the starch molecule segment of rigidity and flexible acrylate copolymer segment form jointly; The acrylate copolymer of block on starch molecular chain is 4%-40% to the quality percentage of starch.
Above-mentioned a kind of starch size with acrylate copolymer block, described starch comprises ative starch, oxidized starch, esterification starch and etherification starch; Described esterification starch can be organic phosphate starch, Acetylated potato starch, urethane starch; Described etherification starch can be carboxymethyl starch, cationic starch.
A preparation method with the starch size of acrylate copolymer block, described preparation method comprises two steps of block of synthetic and acrylate copolymer and the starch of acrylate copolymer emulsion;
(1) acrylate copolymer emulsion is synthetic
First emulsifying agent is added in deionized water and stirring and dissolving, add acrylic acid, butyl acrylate and three kinds of monomers of butyl methacrylate, stirring and emulsifying obtains monomer emulsion; Get persulfate initiator, with deionized water dissolving, be made into the solution that mass concentration is 2%-20%, obtain initiator solution; In normal-pressure reaction kettle, put into deionized water, temperature rises to 70 ℃, stops heating; Under stirring, start to drip described monomer emulsion and initiator solution, open reflux, in dropping process, keeping reaction temperature is 70-75 ℃; Monomer emulsion and initiator solution dropwise, and continue under agitation reaction, treat that temperature is raised to 90 ℃～95 ℃, then react 0.5-2h, are cooled to below 50 ℃, add ammonia neutralization to pH6-7, obtain described acrylate copolymer emulsion;
(2) block of acrylate copolymer and starch
The block of acrylate copolymer and starch is that starch and acrylate copolymer are first plasticated with banbury under inert gas shielding, through screw extruder, shear again, on two kinds of polymer macromolecules, form free radical, and then cross coupling obtains the starch size by acrylate copolymer block mutually; Concrete grammar be by the synthetic acrylate copolymer emulsion of step (1) and starch jointly under inert gas shielding; in 25-60 ℃, with banbury, plasticate after 0.5-4h; through screw extruder extruding, shearing, resulting solid powdery product, is described starch size after crushed again.
Described a kind of preparation method with the starch size of acrylate copolymer block, described emulsifying agent is the combination of nonionic emulsifier and anionic emulsifier; Described nonionic emulsifier can be: the OPEO (OP) that polyoxyethylene sorbitan fatty acid ester, ethylene oxide condensation number are 7-15 and polyoxyethylene nonylphenol ether (NP), or any several mixture in them; Polyoxyethylene sorbitan fatty acid ester is Tween-40, Tween-60, Tween-80; Described anionic emulsifier is: sodium alkyl sulfate, sodium alkyl sulfonate, sodium alkyl benzene sulfonate, or any several mixture in them; Described sodium alkyl sulfate, sodium alkyl sulfonate and sodium alkyl benzene sulfonate, when the atomicity of alkyl carbon is 12-18, the anionic emulsifier that can be used as acrylic acid synthesizing ester copolymer is used.
Described a kind of preparation method with the starch size of acrylate copolymer block, three kinds of monomers of acrylic acid synthesizing ester copolymer, the mass percent that is acrylic acid, butyl acrylate, butyl methacrylate is: acrylic acid 7%-8%, butyl acrylate 66%-84%, butyl methacrylate 9%-27%; Prepare in monomer emulsion, the mass ratio of three kinds of monomers, deionized water, emulsifying agent is: three kinds of monomers: deionized water: emulsifying agent=100:50:0.6-1.2; Described persulfate initiator is one or both the composition in ammonium persulfate, potassium peroxydisulfate, and the weight of initator is the 0.2%-2% of three kinds of total monomer weights; The weight of the deionized water adding in advance in described reactor is 2/5～1/2 of three kinds of total monomer weights.
Described a kind of preparation method with the starch size of acrylate copolymer block, the mass ratio of acrylate copolymer and starch is: 5-30:70-95.
Described a kind of preparation method with the starch size of acrylate copolymer block, it is under inert gas shielding that banbury is plasticated, banburying 0.5-4h under 25-60 ℃ and 10-100 rev/min of condition.
Described a kind of preparation method with the starch size of acrylate copolymer block, the extruding of screw extruder, shearing are under inert gas shielding, at screw speed 80-120 rev/min, temperature 110-150 ℃, under the condition of pressure 1-5MPa, carry out.
Described a kind of preparation method with the starch size of acrylate copolymer block, described starch comprises ative starch, oxidized starch, esterification starch and etherification starch; Described esterification starch can be organic phosphate starch, Acetylated potato starch, urethane starch; Described etherification starch can be carboxymethyl starch, cationic starch.
Described a kind of preparation method with the starch size of acrylate copolymer block, described monomer emulsion and initiator solution dropwise respectively in 1.5-2.5h.
The present invention utilizes power chemism, makes two kinds of polymer form block copolymer.Starch and acrylate copolymer are through plasticating and pushing, and under enough powerful shearing force effect, starch and acrylate copolymer main chain will rupture, and form chain free radical, and then cross coupling becomes block copolymer mutually.Shear action forms the process of cross coupling formation block copolymer between free radical and free radical, and available following chemical equation represents:
Shear action produces free radical:
Cross coupling between free radical forms block copolymer:
In formula: A
gurepresent the glucose unit in starch molecular chain; M
1, M
2represent the construction unit in acrylate copolymer strand; M represents M
1or M
2.
Under the effect of mechanical shear stress, the main chain in starch and side chain all can rupture.By the coupling of these starch main chains and side chain free radical, can make the ratio of side chain and straight chain in starch change, amylopectin content reduces, and amylose content increases.Therefore, starch, after strong mechanical force is sheared, exists with straight chain form substantially.When starch and acrylate copolymer are accepted shear action jointly, can obtain the block copolymer that amylose and shorter polyacrylate segment form.Obviously, the shared ratio of submissive acrylate segment is larger, and serous coat is more soft.
The present invention selects power chemical synthesis to carry out block to starch, and preparation has the starch size of acrylate block.First starch and acrylate copolymer are plasticated in banbury, then pass through the shear action of double screw extruder, form two kinds of free radicals on two kinds of polymer macromolecules, cross coupling obtains the starch size by acrylate copolymer block.Regulate the mass ratio of two kinds of polymer, the ratio of hard and soft chain segment in capable of regulating product strand, changes the crisp hard defect of starch serous coat.The innovative point of this technique is to adopt Semi-dry process, and production process produces without the three wastes, produces continuously, and the production time is short, and efficiency is high.Production process does not need to filter, washs and dries, and production cost is low.
Compare with PVA, by the prepared starch size of the inventive method, have adhesiveness high, filoplume docile is good, for warp sizing, can replace PVA.In adhesiveness, ABRASION RESISTANCE, pliability and the aspect such as water-soluble, all have obvious advantage, and be easy to destarch, the slurry in waste liquid is easy to fast degradation, belongs to Eco-Fashion type slurry.Its manufacture craft feature is produced continuously, and the production time is short, production efficiency is high, energy consumption is low, it is little to pollute.
The specific embodiment
In conjunction with the embodiment providing, production method of the present invention is illustrated, but is not formed any restriction to protection domain of the present invention:
embodiment mono-:
(1) acrylate copolymer is synthetic:
A, preparation monomer emulsion: by the lauryl sodium sulfate of the NP-10 of 4Kg and 2Kg, drop into and be equipped with in the high-speed stirred tank of 250Kg deionized water, stirring and dissolving.Then drop into successively acrylic acid 35Kg, butyl acrylate 330Kg, butyl methacrylate 135Kg, fully emulsified 20 minutes, obtains monomer emulsion;
B, preparation initiator solution: take ammonium persulfate initiator 5Kg, put into 95Kg deionized water and dissolve, obtain initiator solution;
C, combined polymerization: in 1 cube of normal-pressure reaction kettle, drop into, 230Kg deionized water, rises to 70 ℃ by temperature of reaction kettle, stops heating; Then start to drip monomer emulsion and the initiator solution in the present embodiment, prepared, open reflux, maintenance reaction temperature is 70-75 ℃.The rate of addition of controlling monomer emulsion and initiator solution dropwises respectively monomer emulsion and initiator solution in 1.5-2.5h.Then continue reaction, treat that temperature is raised to 90 ℃～95 ℃, then react 60 minutes, be cooled to 50 ℃, add ammonia neutralization to pH6-7, adding deionized water to adjust mass percent concentration is 40% to obtain described acrylate copolymer emulsion.
(2) block of starch:
By 80Kg Acetylated potato starch (A366, the production of the emerging Chemical Co., Ltd. in Qinyang; DS=0.02) with 50Kg the present embodiment in the solids content the prepared acrylate copolymer emulsion that is 40% (mass ratio of acrylate copolymer and starch is: 20:80), under nitrogen protection, at 50 ℃, plasticate 90 minutes; Again product after plasticating is dropped in screw extruder, under 150 ℃, 3MPa, 80 revs/min of conditions of screw speed, shear, extrude.The solid powdery product of gained after pulverizing, is described starch size.Acetone extract method shows, in product, block is 22.8% at the acrylate copolymer of starch molecular chain to the quality percentage of starch; Product viscosity is 8mPas.
embodiment bis-
(1) acrylate copolymer is synthetic:
A, preparation monomer emulsion: by the sodium hexadecyl sulfate of the Tween-40 of 2Kg and 1Kg, drop into and be equipped with in the high-speed stirred tank of 250Kg deionized water, stirring and dissolving.Then drop into successively acrylic acid 35Kg, butyl acrylate 330Kg, butyl methacrylate 135Kg, fully emulsified 20 minutes, obtains monomer emulsion;
B, preparation initiator solution: take ammonium persulfate initiator 1Kg, put into 49Kg deionized water and dissolve, obtain initiator solution;
C, combined polymerization: in 1 cube of normal-pressure reaction kettle, drop into, 230Kg deionized water, rises to 70 ℃ by temperature of reaction kettle, stops heating; Then start to drip monomer emulsion and the initiator solution in the present embodiment, prepared, open reflux, maintenance reaction temperature is 70-75 ℃.The rate of addition of controlling monomer emulsion and initiator solution dropwises respectively monomer emulsion and initiator solution in 1.5-2.5h.Then continue reaction, treat that temperature is raised to 90 ℃～95 ℃, then react 30 minutes, be cooled to 50 ℃, add ammonia neutralization to pH6-7, adding deionized water to adjust mass percent concentration is 40% to obtain described acrylate copolymer emulsion.
(2) block of starch:
By 70Kg organic phosphate starch (FZ, the production of Zanhuang, Shijiazhuang starch Co., Ltd; DS=0.02) with 75Kg the present embodiment in the solids content the prepared acrylate copolymer emulsion that is 40% (mass ratio of acrylate copolymer and starch is: 30:70), throw in banbury simultaneously, 1h plasticates in argon gas at 60 ℃, again the product after plasticating is dropped in screw extruder, at 110 ℃, pressure is controlled under 2MPa, 90 revs/min of conditions of screw speed and shears, extrudes.Resulting solid powdery product after pulverizing, is described starch size.Acetone extract method shows, in product, block is 39.2% at the acrylate copolymer of starch molecular chain to the quality percentage of starch; Product viscosity is 12mPas.
embodiment tri-
(1) acrylate copolymer is synthetic:
A, preparation monomer emulsion: by the sodium stearyl sulfate of the Tween-60 of 3Kg and 1Kg, drop into and be equipped with in the high-speed stirred tank of 250Kg deionized water, stirring and dissolving.Then drop into successively acrylic acid 40Kg, butyl acrylate 410Kg, butyl methacrylate 50Kg, fully emulsified 30 minutes, obtains monomer emulsion;
B, preparation initiator solution: take ammonium persulfate initiator 10Kg, put into 40Kg deionized water and dissolve, obtain initiator solution;
C, combined polymerization: in 1 cube of normal-pressure reaction kettle, drop into, 230Kg deionized water, rises to 70 ℃ by temperature of reaction kettle, stops heating; Then start to drip monomer emulsion and the initiator solution in the present embodiment, prepared, open reflux, maintenance reaction temperature is 70-75 ℃.The rate of addition of controlling monomer emulsion and initiator solution dropwises respectively monomer emulsion and initiator solution in 1.5-2.5h.Then continue reaction, treat that temperature is raised to 90 ℃～95 ℃, then react 120 minutes, be cooled to 50 ℃, add ammonia neutralization to pH6-7, adding deionized water to adjust mass percent concentration is 40% to obtain described acrylate copolymer emulsion.
(2) block of starch:
By 85Kg carboxymethyl starch (JYD-SH, the production of Zaozhuang long-range starch Co., Ltd; DS=0.03) and the solids content of preparing in the 37.5Kg the present embodiment acrylate copolymer emulsion that is 40% (mass ratio of acrylate copolymer and starch is: 15:85); drop in banbury simultaneously; under nitrogen protection at 40 ℃; plasticate 90 minutes; again the product after plasticating is dropped in screw extruder; at 130 ℃, pressure is controlled under 100 revs/min of conditions of 3MPa screw speed and shears, extrudes.Resulting solid powdery product after pulverizing, is described starch size.Acetone extract method shows, in product, block is 16.0% at the acrylate copolymer of starch molecular chain to the quality percentage of starch; Product viscosity is 9mPas.
embodiment tetra-
(1) acrylate copolymer is synthetic:
A, preparation monomer emulsion: by the dodecyl sodium sulfate of the OP-15 of 3Kg and 1Kg, drop into and be equipped with in the high-speed stirred tank of 250Kg deionized water, stirring and dissolving.Then drop into successively acrylic acid 38Kg, butyl acrylate 390Kg, butyl methacrylate 72Kg, fully emulsified 30 minutes, obtains monomer emulsion;
B, preparation initiator solution: take ammonium persulfate initiator 1.1Kg, put into 20Kg deionized water and dissolve, obtain initiator solution;
C, combined polymerization: in 1 cube of normal-pressure reaction kettle, drop into, 230Kg deionized water, rises to 70 ℃ by temperature of reaction kettle, stops heating; Then start to drip monomer emulsion and the initiator solution in the present embodiment, prepared, open reflux, maintenance reaction temperature is 70-75 ℃.The rate of addition of controlling monomer emulsion and initiator solution dropwises respectively monomer emulsion and initiator solution in 1.5-2.5h.Then continue reaction, treat that temperature is raised to 90 ℃～95 ℃, then react 40 minutes, be cooled to 50 ℃, add ammonia neutralization to pH6-7, adding deionized water to adjust mass percent concentration is 40% to obtain described acrylate copolymer emulsion.
(2) block of starch:
By 75Kg carbamate starch (DS=0.058, according to the method in following document and step preparation: Zhu Zhifeng, Pan's meeting, Li Wenbin, Kang Cuizhen, the adhesive performance research of starch carbamate, cotton textile technology, 31(3): 5-9, 2003) and the solids content of preparing in the 62.5Kg the present embodiment acrylate copolymer emulsion that is 40% (mass ratio of acrylate copolymer and starch is: 25:75), drop in banbury simultaneously, at 30 ℃, plasticate 120 minutes, again the product after plasticating is dropped in screw extruder, under nitrogen protection at 150 ℃, pressure is controlled under 110 revs/min of conditions of 5MPa screw speed and shears, extrude.Resulting solid powdery product after pulverizing, is described starch size.Acetone extract method shows, in product, block is 30.5% at the acrylate copolymer of starch molecular chain to the quality percentage of starch; Product viscosity is 6mPas.
embodiment five
(1) acrylate copolymer is synthetic:
A, preparation monomer emulsion: by the dodecyl sodium sulfate of the NP-15 of 3Kg and 2Kg, drop into and be equipped with in the high-speed stirred tank of 250Kg deionized water, stirring and dissolving.Then drop into successively acrylic acid 36Kg, butyl acrylate 360Kg, butyl methacrylate 104Kg, fully emulsified 30 minutes, obtains monomer emulsion;
B, preparation initiator solution: take ammonium persulfate initiator 1.2Kg, put into 20Kg deionized water and dissolve, obtain initiator solution;
C, combined polymerization: in 1 cube of normal-pressure reaction kettle, drop into, 230Kg deionized water, rises to 70 ℃ by temperature of reaction kettle, stops heating; Then start to drip monomer emulsion and the initiator solution in the present embodiment, prepared, open reflux, maintenance reaction temperature is 70-75 ℃.The rate of addition of controlling monomer emulsion and initiator solution dropwises respectively monomer emulsion and initiator solution in 1.5-2.5h.Then continue reaction, treat that temperature is raised to 90 ℃～95 ℃, then react 60 minutes, be cooled to 50 ℃, add ammonia neutralization to pH6-7, adding deionized water to adjust mass percent concentration is 40% to obtain described acrylate copolymer emulsion.
(2) block of starch:
By 95Kg cationic starch LG(Handan Xin Jia starch Co., Ltd; DS=0.05) with 12.5Kg embodiment in the solids content the prepared acrylate copolymer emulsion that is 40% (mass ratio of acrylate copolymer and starch is: 5:95); drop in banbury simultaneously; at 25 ℃; plasticate 30 minutes; again the product after plasticating is dropped in screw extruder; under nitrogen protection, at 150 ℃, pressure is controlled under 120 revs/min of conditions of 3MPa screw speed and shears, extrudes.Resulting solid powdery product after pulverizing, is described starch size.Acetone extract method shows, in product, block is 4.3% at the acrylate copolymer of starch molecular chain to the quality percentage of starch; Product viscosity is 22mPas.
embodiment six
(1) acrylate copolymer is synthetic:
A, preparation monomer emulsion: by the neopelex of the OP-10 of 3Kg and 1Kg, drop into and be equipped with in the high-speed stirred tank of 250Kg deionized water, stirring and dissolving.Then drop into successively acrylic acid 35Kg, butyl acrylate 395Kg, butyl methacrylate 70Kg, fully emulsified 30 minutes, obtains monomer emulsion;
B, preparation initiator solution: take ammonium persulfate initiator 2.5Kg, put into 20Kg deionized water and dissolve, obtain initiator solution;
C, combined polymerization: in 1 cube of normal-pressure reaction kettle, drop into, 230Kg deionized water, rises to 70 ℃ by temperature of reaction kettle, stops heating; Then start to drip monomer emulsion and the initiator solution in the present embodiment, prepared, open reflux, maintenance reaction temperature is 70-75 ℃.The rate of addition of controlling monomer emulsion and initiator solution dropwises respectively monomer emulsion and initiator solution in 1.5-2.5h.Then continue reaction, treat that temperature is raised to 90 ℃～95 ℃, then react 50 minutes, be cooled to 50 ℃, add ammonia neutralization to pH6-7, adding deionized water to adjust mass percent concentration is 40% to obtain described acrylate copolymer emulsion.
(2) block of starch:
(mass ratio of acrylate copolymer and starch is the acrylate copolymer emulsion that is 40% by the native cornstarch of 90Kg and the synthetic solids content of 20Kg the present embodiment: 8:90); drop in banbury simultaneously; under nitrogen protection, at 50 ℃, plasticate 240 minutes; again the product after plasticating is dropped in screw extruder; at 150 ℃, pressure is controlled under 3Mpa, 80 revs/min of conditions of screw speed and shears, extrudes.Resulting solid powdery product after pulverizing, is described starch size.Acetone extract method shows, in product, block is 10.9% at the acrylate copolymer of starch molecular chain to the quality percentage of starch; Product viscosity is 3mPas.
embodiment seven
Adopt method and step in embodiment 1, acrylic acid synthesizing ester copolymer, and carry out block with starch, and prepare starch size, difference is that the present embodiment adopts 80Kg oxidized starch, carries out block with acrylate copolymer.Acetone extract method shows, in product, block is 22.2% at the acrylate copolymer of starch molecular chain to the quality percentage of starch; Product viscosity is 8.5mPas.
embodiment eight
Adopt method and step in embodiment 1, acrylic acid synthesizing ester copolymer, and carry out block with starch, and prepare starch size, difference is that the present embodiment adopts 80Kg wheat ative starch, carries out block with acrylate copolymer.Acetone extract method shows, in product, block is 22.8% at the acrylate copolymer of starch molecular chain to the quality percentage of starch; Product viscosity is 9mPas.
embodiment nine
Adopt method and step in embodiment 1, acrylic acid synthesizing ester copolymer, and carry out block with starch, difference be the present embodiment in acrylic ester synthesizing copolymer process the anionic emulsifier that adopts different, the neopelex that the anionic emulsifier that the present embodiment adopts is 0.6Kg and the dodecyl sodium sulfate of 0.4Kg.Acetone extract method shows, in product, block is 22.0% at the acrylate copolymer of starch molecular chain to the quality percentage of starch; Product viscosity is 8.5mPas.
embodiment ten
Adopt method and step in embodiment 1, acrylic acid synthesizing ester copolymer, and carry out block with starch, difference be the present embodiment in acrylic ester synthesizing copolymer process the nonionic emulsifier that adopts different, the nonionic emulsifier that the present embodiment adopts is Tween-80 3Kg; Acetone extract method shows, in product, block is 22.5% at the acrylate copolymer of starch molecular chain to the quality percentage of starch; Product viscosity is 7.5mPas.
embodiment 11
Adopt method and step in embodiment 1, acrylic acid synthesizing ester copolymer, and carry out block with starch, difference be the present embodiment in acrylic ester synthesizing copolymer process the nonionic emulsifier that adopts different, the OP-10 of NP-10,1Kg and the Tween-40 of 1Kg that the nonionic emulsifier that the present embodiment adopts is 1Kg.Acetone extract method shows, in product, block is 22.5% at the acrylate copolymer of starch molecular chain to the quality percentage of starch; Product viscosity is 7.5mPas.
embodiment 12
The starch size that adopts embodiment mono-preparation, is 73.6N to the adhesion of cotton yarn, serous coat elongation at break 3.7%.Be used in the tabby warp sizing of textile C40 * C40 133 * 72, control the rate of sizing 12.5%, the amount of waxing is 0.3%, and at air-jet loom weaving, efficiency reaches 96%.Compare with the formula of size that contains 30%PVA, its sizing quality is identical.
embodiment 13
The starch size that adopts embodiment tetra-preparations, is 116N to the adhesion of wash/cotton fiber, serous coat elongation at break 3.6%.At the warp sizing of wash/cotton 65,/35 45 * 45 110 * 76 fine cloth, control the rate of sizing 13.5%, the amount of waxing is 0.3%, at air-jet loom weaving, efficiency reaches 93%.Compare with the formula of size that contains 45%PVA, its sizing quality is identical.
Claims (6)
1. a preparation method with the starch size of acrylate copolymer block, is characterized in that: described preparation method comprises two steps of block of synthetic and acrylate copolymer and the starch of acrylate copolymer;
(1) acrylate copolymer is synthetic
First emulsifying agent is added in deionized water and stirring and dissolving, add acrylic acid, butyl acrylate and three kinds of monomers of butyl methacrylate, three kinds of monomers, the mass percent that is acrylic acid, butyl acrylate, butyl methacrylate is: acrylic acid 7%-8%, butyl acrylate 66%-84%, butyl methacrylate 9%-27%; Stirring and emulsifying obtains monomer emulsion, prepares in monomer emulsion, and the mass ratio of three kinds of monomers, deionized water, emulsifying agent is: three kinds of monomers: deionized water: emulsifying agent=100:50:0.6-1.2; Get persulfate initiator, described persulfate initiator is one or both the composition in ammonium persulfate, potassium peroxydisulfate, the weight of persulfate initiator is the 0.2%-2% of three kinds of total monomer weights, with deionized water dissolving, be made into the solution that mass concentration is 2%-20%, obtain initiator solution; In normal-pressure reaction kettle, put into deionized water, the deionized water weight adding in advance in described reactor is 2/5～1/2 of three kinds of total monomer weights; Temperature rises to 70 ℃, stops heating; Under stirring, start to drip described monomer emulsion and initiator solution, open reflux, in dropping process, keeping reaction temperature is 70-75 ℃; Monomer emulsion and initiator solution dropwise, and continue under agitation reaction, treat that temperature is raised to 90 ℃～95 ℃, then react 0.5-2h, are cooled to below 50 ℃, add ammonia neutralization to pH6-7, obtain described acrylate copolymer emulsion;
(2) block of acrylate copolymer and starch
The block of acrylate copolymer and starch is that starch and acrylate copolymer are first plasticated with banbury under inert gas shielding, through screw extruder, shear again, on two kinds of polymer macromolecules, form free radical, and then cross coupling obtains the starch size by acrylate copolymer block mutually; The mass ratio of acrylate copolymer and starch is: 5-30 ︰ 70-95; Concrete grammar be by the synthetic acrylate copolymer emulsion of step (1) and starch jointly under inert gas shielding; in 25-60 ℃, with banbury, plasticate after 0.5-4h; through screw extruder extruding, shearing, resulting solid powdery product, is described starch size after crushed again.
2. according to a kind of preparation method with the starch size of acrylate copolymer block claimed in claim 1, be characterised in that: described emulsifying agent is at least one the combination at least one and the anionic emulsifier in nonionic emulsifier; Described nonionic emulsifier is: OPEO and polyoxyethylene nonylphenol ether that polyoxyethylene sorbitan fatty acid ester, ethylene oxide condensation number are 7-15; Or arbitrarily several and be the mixture of any mass ratio in them; Described polyoxyethylene sorbitan fatty acid ester is Tween-40, Tween-60, Tween-80; Described anionic emulsifier is: sodium alkyl sulfate or sodium alkyl sulfonate or sodium alkyl benzene sulfonate, or arbitrarily several and be the mixture of any mass ratio in them; The atomicity of the alkyl carbon of described sodium alkyl sulfate, sodium alkyl sulfonate and sodium alkyl benzene sulfonate is 12-18.
3. according to a kind of preparation method with the starch size of acrylate copolymer block claimed in claim 1, it is characterized in that: it is under inert gas shielding that banbury is plasticated banburying 0.5-4h under 25-60 ℃ and 10-100 rev/min of condition.
4. according to a kind of preparation method with the starch size of acrylate copolymer block claimed in claim 1; it is characterized in that: the extruding of screw extruder, shearing are under inert gas shielding; at screw speed 80-120 rev/min, temperature 110-150 ℃, under the condition of pressure 1-5MPa, carry out.
5. according to a kind of preparation method with the starch size of acrylate copolymer block claimed in claim 1, it is characterized in that: described starch comprises ative starch, oxidized starch, esterification starch and etherification starch; Described esterification starch is organic phosphate starch, Acetylated potato starch, urethane starch; Described etherification starch is carboxymethyl starch, cationic starch.
6. according to a kind of preparation method with the starch size of acrylate copolymer block claimed in claim 1, it is characterized in that: described monomer emulsion and initiator solution dropwise respectively in 1.5-2.5h.
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| CN102926198A (en) * | 2012-10-26 | 2013-02-13 | 无锡裕通织造有限公司 | Spinning sizing agent |
| CN103938453B (en) * | 2013-12-19 | 2016-03-16 | 宁波江东索雷斯电子科技有限公司 | A kind of wrap dressing agent and preparation method thereof |
| CN103881613A (en) * | 2014-04-17 | 2014-06-25 | 西达（无锡）生物科技有限公司 | Acrylic acid copolymerization composite adhesive as well as preparation method and application thereof |
| CN109929116A (en) * | 2019-03-28 | 2019-06-25 | 湖北顶新环保生物质材料有限公司 | A kind of Resisting fractre starch size and preparation method thereof |
| CN110512424A (en) * | 2019-08-23 | 2019-11-29 | 广州市迅宏粘合剂有限公司 | A kind of water soluble adhesive and preparation method thereof and its application |
| CN112961293A (en) * | 2021-04-21 | 2021-06-15 | 安徽工程大学 | Preparation method for preparing high-surface-activity amphiphilic grafted starch slurry in two steps, product and application thereof |
| CN114773532B (en) * | 2022-05-17 | 2023-09-29 | 江西宏大化工有限公司 | Modified starch emulsion and preparation method thereof |
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