CN110306364A - A kind of starch complex thickener and preparation method thereof - Google Patents
A kind of starch complex thickener and preparation method thereof Download PDFInfo
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- CN110306364A CN110306364A CN201910670742.8A CN201910670742A CN110306364A CN 110306364 A CN110306364 A CN 110306364A CN 201910670742 A CN201910670742 A CN 201910670742A CN 110306364 A CN110306364 A CN 110306364A
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
- D06P1/46—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing natural macromolecular substances or derivatives thereof
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
- D06P1/46—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing natural macromolecular substances or derivatives thereof
- D06P1/48—Derivatives of carbohydrates
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- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
- D06P1/60—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing polyethers
- D06P1/613—Polyethers without nitrogen
- D06P1/6138—Polymerisation products of glycols, e.g. Carbowax, Pluronics
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- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
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- D06P3/34—Material containing ester groups
- D06P3/52—Polyesters
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Abstract
Suitable material technical field of the present invention, a kind of starch complex thickener and preparation method thereof is provided, wherein, the starch complex thickener, the raw material including following parts by weight: 40 ~ 80 parts of starch polymer, 5 ~ 30 parts of carboxymethyl cellulose, bentonite thickener 5-15 parts aqueous, 1 ~ 10 part of xanthan gum, 0.2 ~ 5 part of polyethylene glycol and 0.1 ~ 0.8 part of preservative.The starch complex thickener has the characteristics that paste making rate is high, tinctorial yield is high, quality-high and inexpensive, tasteless nontoxic, environmentally protective；Alternative carboxy methyl hydroxyethyl on the market is etherified tamarind gum thickener, and the dosage of opposite carboxy methyl hydroxyethyl etherificate tamarind gum thickener substantially reduces, and can significantly reduce 35% or more thickener dosage；Simultaneously, the starch complex thickener stability of pigment paste, tinctorial yield are superior to carboxy methyl hydroxyethyl etherificate tamarind gum, so that dye dosage can reduce 5% or more, and, texture after printing and proofing is suitable with carboxy methyl hydroxyethyl etherificate tamarind gum, and cost is also significantly lower than carboxy methyl hydroxyethyl etherificate tamarind gum.
Description
Technical field
The invention belongs to field of material technology more particularly to a kind of starch complex thickener and preparation method thereof.
Background technique
Thickener is the important component of print paste.Its is with higher at paste ability, i.e., with less amount of thickening
The higher thickener of viscosity can be made in agent.Thickener be in print paste dyestuff and chemicals be transmitted to fabric get on load
Body, no thickener cannot make print paste have plasticity, and can not print and dye flower pattern.
Currently, conventional use of printing gum is varied, can be divided into natural class and chemical classes by the source of thickener.Its
In, although natural class thickener has many advantages, such as that printing quality is good and good hand touch, generally existing stability is bad, degradable, makes
With limited disadvantage；Chemical classes thickener is mostly that one or more organic monomers by copolyreaction are prepared into high polymer (such as poly- ammonia
Ester, polypropylene, PVA etc.), its paste making rate of the thickener of organic compound preparation is high, and thickening effect is good, fabric feeling after stamp
It is good, but it is there are salt tolerance is poor, and pollutes big, waste water treatmentntrol difficult, the problem big to environmental hazard.At present by favor
Carboxy methyl hydroxyethyl etherificate tamarind gum is also the printing gum prepared after a kind of natural products is denaturalized, now positive to be widely applied
In the stamp production of dacron.Carboxy methyl hydroxyethyl is etherified the particularly suitable dacron of tamarind gum thickener and uses dispersion
It is used in dyestuff combination superhigh temperature fixation, after the processing of superhigh temperature steam fixation, is also easy to be washed off, so that printing and dyeing
Fabrics feel soft, color is beautiful, but carboxy methyl hydroxyethyl etherificate tamarind gum is due to itself characteristic, exist as
Niff, bitter taste and protein are difficult to the problem of removing and the low disadvantage for causing application cost high of paste making rate.
It can be seen that there are niff, bitter taste, protein to be difficult to remove and at paste for existing thickener
The low problem for causing application cost high of rate.
Summary of the invention
The embodiment of the present invention is designed to provide a kind of starch complex thickener, it is intended to solve existing thickener and exist
Niff, bitter taste, protein are difficult to the problem removed and paste making rate is low to cause application cost high.
The embodiments of the present invention are implemented as follows, a kind of starch complex thickener, the raw material including following parts by weight:
40~80 parts of starch polymer, 5~30 parts of carboxymethyl cellulose, bentonite thickener 5-15 parts aqueous, xanthan gum 1
~10 parts, 0.2~5 part of polyethylene glycol and 0.1~0.8 part of preservative.
The another object of the embodiment of the present invention is a kind of preparation method of starch complex thickener, comprising:
Weigh by weight starch polymer, carboxymethyl cellulose, aqueous bentonite thickener, xanthan gum, polyethylene glycol with
And preservative, it is spare；
By the starch polymer, carboxymethyl cellulose, aqueous bentonite thickener, xanthan gum, polyethylene glycol and prevent
In rotten agent investment blending tank, it is mixed 15~45 minutes, obtains whole mixture；
The whole mixture is sent into humidification storehouse through powder feeding extension set and batcher and carries out abundant atomization process, and is inversely sprayed into
After atomized water, from the humidification orlop portion enter be granulated unit be granulated to get.
Starch complex thickener provided in an embodiment of the present invention, starch molecule amount increase, and molecule salt resistance viscosity stabilization is good, tool
Have that paste making rate is high, high, quality-high and inexpensive, tasteless nontoxic, the environmentally protective and advantageous improvement shop worker's production environment of tinctorial yield etc.
Feature；Alternative carboxy methyl hydroxyethyl on the market is etherified tamarind gum thickener, and opposite carboxy methyl hydroxyethyl is etherified Luo Wang
The dosage of sub- glue thickener substantially reduces, and can significantly reduce 35% or more thickener dosage；Meanwhile the starch complex thickener mill base
Stability, tinctorial yield are superior to carboxy methyl hydroxyethyl etherificate tamarind gum, so that dye dosage can reduce 5% or more, also,
Texture after printing and proofing is suitable with carboxy methyl hydroxyethyl etherificate tamarind gum, and cost is also significantly lower than carboxy methyl hydroxyethyl etherificate
Tamarind gum.
Detailed description of the invention
Fig. 1 is allyl polyoxy alkyl epoxy base ether dosage provided in an embodiment of the present invention to Crosslinked and hydroxypropyl starch viscosity shadow
Ring effect curve figure；
Fig. 2 is that long-chain alkyl alcohol polyethenoxy ether metacrylic acid ester dosage provided in an embodiment of the present invention is crosslinked etherificate
Starch viscosity impact effect curve graph；
Fig. 3 is methyl epichlorohydrin dosage provided in an embodiment of the present invention and hands over after a certain amount of salt is added etherificate
Join starch viscosity impact effect figure；
Fig. 4 is the reaction time provided in an embodiment of the present invention to Crosslinked and hydroxypropyl starch viscosity influence effect curve figure；
Fig. 5 is reaction temperature provided in an embodiment of the present invention to Crosslinked and hydroxypropyl starch viscosity influence effect curve figure；
Fig. 6 is vinyl alkoxy phosphate dosage provided in an embodiment of the present invention to starch polymer viscosity influence effect
Curve graph；
Fig. 7 is viscosity influence effect of the dosage to starch polymer of different copolymer stabilizer provided in an embodiment of the present invention
Curve graph.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to the accompanying drawings and embodiments, right
The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and
It is not used in the restriction present invention.
Starch, cellulose, tamarind etc. are used as natural products, and raw material sources are wide, abundance, but lacking because of itself
(if you need to boiling, paste making rate low, not soluble in water etc.) is fallen into seldom directly as printing gum.It need to generally be alkalized, be hydrolyzed or oxygen
After change, adds monoxone or other medicaments carry out esterification and etherification and react obtained converted starch or cellulose derivative etc., institute
The converted starch or cellulose derivative cold water solubles of preparation, paste making rate it is also higher (general 6%~8% or so), tinctorial yield,
Permeability is also ideal, but there is also it is de- paste it is difficult, not acidproof and and part salt react the problem of.
The embodiment of the present invention is equipped with carboxymethyl cellulose, aqueous by the starch polymer that is prepared with special process
Bentonite thickener, xanthan gum, polyethylene glycol and preservative prepare starch complex thickener, and gained starch complex thickener is deposited
Increase in starch molecule amount, molecule salt resistance viscosity stabilization is good, have paste making rate is high, tinctorial yield it is high, quality-high and inexpensive, tasteless it is nontoxic,
The features such as environmentally protective and advantageous improvement shop worker's production environment；Alternative carboxy methyl hydroxyethyl on the market is etherified Luo Wang
The dosage of sub- glue thickener, opposite carboxy methyl hydroxyethyl etherificate tamarind gum thickener substantially reduces, and can significantly reduce thickener
35% or more dosage；Meanwhile the starch complex thickener stability of pigment paste is etherified tamarind gum, stamp better than carboxy methyl hydroxyethyl
Tinctorial yield after drawing a design is higher than carboxy methyl hydroxyethyl and is etherified tamarind gum, so that dye dosage can reduce 5% or more, also,
Texture after printing and proofing is suitable with carboxy methyl hydroxyethyl etherificate tamarind gum, and cost is also significantly lower than carboxy methyl hydroxyethyl etherificate
Tamarind gum.
In embodiments of the present invention, starch polymer is that branch is connect by Crosslinked and hydroxypropyl starch and acrylic acid, acrylonitrile altogether
After poly- reaction, generate using starch as the copolymer of main chain；And Crosslinked and hydroxypropyl starch is that caustic soda, ethyl alcohol, alkene are equipped with by native starch
Propyl polyoxy alkyl epoxy base ether, long-chain alkyl alcohol polyethenoxy ether metacrylic acid ester, methyl epichlorohydrin are specific anti-
Etherificate crosslinking is carried out under the conditions of answering and is obtained.
In embodiments of the present invention, the etherificate cross-linking process are as follows: 100 parts by weight of native starch are put into kneader device,
10~20 parts by weight of ethanol water that concentration is 50~80% and the caustic soda that concentration is 30% are sequentially added in whipping process
3~10 parts by weight of alcoholic solution, temperature be 25~35 DEG C at stirring 15~after forty minutes, obtain mixture I；In the mixture I
Middle 5~10 parts by weight of addition allyl polyoxy alkyl epoxy base ether, long-chain alkyl alcohol polyethenoxy ether metacrylic acid ester 5~10
Parts by weight, 0.1~1 parts by weight of methyl epichlorohydrin, stirring 15~after forty minutes, pumping, which is expected in reactor tank, is reacted, instead
Answering temperature is 60~120 DEG C, and the reaction time is 60~180 minutes, obtains mixture II；By the mixture II carry out it is cooling, in
With dry and break process to get Crosslinked and hydroxypropyl starch.
In embodiments of the present invention, caustic soda is the reactant of starch quaternization, while being also the catalyst of etherification reaction,
The active group inside starch is activated, in order to obtain the product of more high substituted degree.The dosage of caustic soda is more, the active group of activation
Group is more, but the dosage of caustic soda can excessively make starch that the progress that gelatinization influence is reacted occur.
In embodiments of the present invention, ethyl alcohol can inhibit starch gelatinization as organic solvent, improve the dosage of caustic soda, with
Just the product of more high substituted degree is obtained.
In embodiments of the present invention, allyl polyoxy alkyl epoxy base ether had not only contained unsaturated double-bond but also had contained high activity
Epoxy cardinal extremity, good reactivity makes it under the effect of the catalyst, and etherification reaction easily occurs with starch hydroxyl, increases
The molecular weight of big starch molecule.
In embodiments of the present invention, long-chain alkyl alcohol polyethenoxy ether metacrylic acid ester can be used as alkaline association type thickening
Agent contains the hydrophilic oxyethylene end of the chain in long chain hydrophobic group again, reacts, make with starch molecule under alkaline environment
Molecule chain extension, and reticular structure is formed, improve the hydrophily of product after reaction.The reticular structure that simultaneous reactions are formed also promotes
Each ingredient is sufficiently mixed in system, promotes reaction efficiency and the extent of reaction.
In embodiments of the present invention, the epoxy group that methyl epichlorohydrin contains under alkaline condition, is easily divided with starch
Hydroxyl in son crosslinks reaction, and the salt tolerant and endurance of cutting energy of cross-linking chemistry bond energy intensified response product promote reaction
The stability of product afterwards, but with the increase of crosslinking degree, the chemical bond quantity between starch molecule increases, and can inhibit the swollen of starch
Swollen gelatinization, therefore dosage is easily controlled in the present reaction, it is unsuitable excessive.
Further, graft copolymerization process specifically: by the obtained Crosslinked and hydroxypropyl starch 100 of above-mentioned etherificate cross-linking process
Parts by weight are put into kneader device, and 2~10 weight of ferrous sulfate aqueous solution that concentration is 10% is added in whipping process
Part, it stirs 10~30 minutes, obtains the first mixture；0.1~1 weight of hydrogen peroxide that concentration is 30% is slowly added dropwise in starting metering pump
Part, 40~80 parts by weight of acrylic acid, 10~30 parts by weight of acrylonitrile and 10~20 parts by weight of vinyl alkoxy phosphate in
In first mixture, after stirring 10~30 minutes, it is micro- to the continuous multi-resonant chamber of tunnel type that power is 60~120kw to take out material
It is irradiated reaction in amplitude jet device 15~45 minutes, obtains the second mixture；To second mixture carry out it is cooling, in
With dry and break process to get starch polymer.
In embodiments of the present invention, meeting Zhi Gongju is the chemistry that two kinds of macromoleculars incompatible with each other pass through main chain and branch
Connection is formed by polymer, and usually there are two types of the comprehensive performances of substance for tool, connects fulcrum it is required that existing on main chain polymer chain
Or exist in reaction process and connect fulcrum, by radical reaction mechanism, starch and acrylic acid, acrylonitrile connect branch copolyreaction
Afterwards, it generates using starch as the copolymer of main chain；In addition, meeting Zhi Juhe mostly uses initiator to cause, and common initiator has
Azo-initiator and peroxide type initiators.In its peroxide type initiators, hydrogen peroxide can form two hydrogen-oxygens certainly
It is not used alone generally by base because decomposition activation energy is higher, but the oxidation of partial reduction agent (such as ferrous sulfate) composition is added also
Substance system generates intermediate product free radical to cause polymerization；The activation energy of redox system is lower, to improve reaction speed
Rate reduces reaction temperature, reduces reaction temperature, energy saving.
In embodiments of the present invention, Crosslinked and hydroxypropyl starch is solid phase, and acrylic acid, acrylonitrile are liquid phase, and the two belongs to different
Grafted branches copolyreaction improves the compatibility of reactant, makes to react by vinyl alkoxy phosphate as copolymerization stabilizer
Continual and steady progress.
Further, starch complex thickener the preparation method comprises the following steps: the obtained starch of above-mentioned graft copolymerization process is polymerize
40~80 parts by weight of object, 5~30 parts by weight of carboxymethyl cellulose, 5~15 parts by weight of aqueous bentonite thickener, xanthan gum 1~
10 parts by weight, 0.2~5 parts by weight of polyethylene glycol and preservative 0.1-0.8 parts by weight.It puts into blending tank, is mixed 15
~45 minutes, obtain whole mixture；The whole mixture is sent into humidification storehouse through powder feeding extension set and batcher to be sufficiently atomized, together
When inversely spray into 5~15 parts by weight of atomized water, then from humidification orlop portion enter be granulated unit be granulated to get to mesh number be 20~
The starch complex thickener of 80 mesh.
In embodiments of the present invention, starch polymer has paste making rate high, and salt stability is good, tinctorial yield height and saturating net
Well, the features such as PVI value is higher.In printing gum, different stamp modes has different requirements to the rheological characteristic of thickener, and one
As for, color paste viscosity is high, and PVI value is lower, Yi Yin get it is clear decorative pattern, be suitable for the fine decorative patterns such as printing lines, little Hua, print
When large area figure processed, then PVI value is high that mill base is even more ideal.It is higher that carboxymethyl cellulose and xanthan gum all have paste making rate,
And the characteristics of PVI value lower (wherein xanthan gum PVI value is lower), the resulting starch complex thickener of hybrid combination is carried out, it can
The product for obtaining a variety of difference PVI values, meets different printing technologies.
In embodiments of the present invention, carboxymethyl cellulose and xanthan gum all have paste making rate height, Stability towards electrolytes are good,
The high advantage of color fastness after stamp, but the disadvantage that there is also tinctorial yield is poor, saturating net is poor.It, can after adding polyethylene glycol
Its surface tension is reduced, the wetting ability to fabric is improved, improves tinctorial yield difference and uniformity difference disadvantage.
In embodiments of the present invention, natural minerals (such as bentonite) itself mobility and embrace it is aqueous poor, be individually
It cannot function as printing gum, but its unique mineral structure and crystal chemistry characteristic, there is good suspension stability, thickening
Property, it is blended with other printing gums, improves the rheological characteristic of thickener, enhance the storage stability of thickener, and in reactive dye
When, facilitate mill base not split-phase, keep woven designs clear-cut, improves printing quality.
In embodiments of the present invention, the 5% 30000~100000mpa.s of concentration of aqueous solution viscosity of starch polymer.
In embodiments of the present invention, the 1% concentration of aqueous solution viscosity of carboxymethyl cellulose is 800~2500mpa.s, is taken
Dai Du is 1.0~1.8.
In embodiments of the present invention, 8% concentration of aqueous solution viscosity of the aqueous bentonite thickener >=7500mpa.s.
In embodiments of the present invention, the 1% 800~1600mpa.s of solution viscosity of xanthan gum.
In embodiments of the present invention, the molecular weight polyethylene glycol is 1800~4400.
It is described further below by way of technical effect of the specific embodiment to starch complex thickener of the invention.
The raw materials used information of following specific embodiments and source are as shown in table 1:
Table 1
Embodiment 1
A kind of starch complex thickener, the raw material including following parts by weight:
50 parts of starch polymer, 25 parts of carboxymethyl cellulose, 7 parts of aqueous bentonite thickener, 10 parts of xanthan gum, poly- second two
5 parts of alcohol and 0.3 part of preservative.
Wherein, the starch polymer includes the raw material of following parts by weight:
The hydrogen peroxide 0.1 that 2 parts of ferrous sulfate aqueous solution that 100 parts of Crosslinked and hydroxypropyl starch, concentration are 10%, concentration are 30%
Part, 40 parts of acrylic acid, 10 parts of acrylonitrile and 10 parts of vinyl alkoxy phosphate.
Wherein, the Crosslinked and hydroxypropyl starch includes the raw material of following parts by weight:
The caustic soda alcohol that 10 parts of ethanol water that 100 parts of native starch (cornstarch), concentration are 50%, concentration are 30%
3 parts of solution, 5 parts of allyl polyoxy alkyl epoxy base ether, 8 parts of long-chain alkyl alcohol polyethenoxy ether metacrylic acid ester and methyl
0.1 part of epoxychloropropane.
The starch complex thickener the preparation method comprises the following steps:
Cornstarch is put into kneader device, ethanol water and the concentration that concentration is 50% are added in whipping process
Mixture I is obtained after 25 DEG C are stirred 15 minutes for 30% caustic soda alcoholic solution；Allyl polyoxy alkane is added in the mixture I
Basic ring oxygen ether, long-chain alkyl alcohol polyethenoxy ether metacrylic acid ester and methyl epichlorohydrin are taken out after stirring 15 minutes
Expect in reactor tank and reacted, reaction temperature is 60 DEG C, and the reaction time is 60 minutes, obtains mixture II；By the mixture
II cool down, neutralizes, drying and break process, obtains Crosslinked and hydroxypropyl starch.
Crosslinked and hydroxypropyl starch is put into kneader device, it is water-soluble that the ferrous sulfate that concentration is 10% is added in whipping process
Liquid stirs 10 minutes, obtains the first mixture；Hydrogen peroxide, the acrylic acid, acrylonitrile that concentration is 30% is slowly added dropwise in starting metering pump
And vinyl alkoxy phosphate, in first mixture, stirring after twenty minutes, takes out the tunnel that material is 60kw to power
The continuous multi-resonant chamber microwave radiation equipment of formula is irradiated reaction 30 minutes, obtains the second mixture；To second mixture into
Row is cooling, neutralize, dry and break process is to get starch polymer.It is 42000mpa.s through 5% solution viscosity of detection,
PVI value is 0.55.
Weigh by weight starch polymer, carboxymethyl cellulose, aqueous bentonite thickener, xanthan gum, polyethylene glycol with
And preservative, it is spare；By the starch polymer, carboxymethyl cellulose, aqueous bentonite thickener, xanthan gum, polyethylene glycol
And it in preservative investment blending tank, is mixed 25 minutes, obtains whole mixture；The whole mixture through powder feeding extension set and is given
Material machine is sent into humidification storehouse and is sufficiently atomized, while reverse 8 parts of atomized water of penetrating, then enters pelletizer from the bottom in humidification storehouse
Group is granulated, and obtains the starch complex thickener that mesh number is 60 mesh.
Embodiment 2
A kind of starch complex thickener, the raw material including following parts by weight:
70 parts of starch polymer, 25 parts of carboxymethyl cellulose, 3 parts of aqueous bentonite thickener, 1 part of xanthan gum, poly- second two
0.5 part of alcohol and 0.3 part of preservative.
Wherein, the starch polymer includes the raw material of following parts by weight:
The hydrogen peroxide 0.5 that 5 parts of ferrous sulfate aqueous solution that 100 parts of Crosslinked and hydroxypropyl starch, concentration are 10%, concentration are 30%
Part, 40 parts of acrylic acid, 15 parts of acrylonitrile and 15 parts of vinyl alkoxy phosphate.
Wherein, the Crosslinked and hydroxypropyl starch includes the raw material of following parts by weight:
The caustic soda alcohol that 20 parts of ethanol water that 100 parts of native starch (tapioca), concentration are 50%, concentration are 30%
5 parts of solution, 8 parts of allyl polyoxy alkyl epoxy base ether, 8 parts of long-chain alkyl alcohol polyethenoxy ether metacrylic acid ester and methyl
0.3 part of epoxychloropropane.
The starch complex thickener the preparation method comprises the following steps:
Tapioca is put into kneader device, ethanol water and the concentration that concentration is 50% are added in whipping process
For 30% caustic soda alcoholic solution, 35 DEG C of stirrings after forty minutes, obtain mixture I；Allyl polyoxy alkane is added in the mixture I
Basic ring oxygen ether, long-chain alkyl alcohol polyethenoxy ether metacrylic acid ester and methyl epichlorohydrin are taken out after stirring 15 minutes
Expect in reactor tank and reacted, reaction temperature is 60 DEG C, and the reaction time is 180 minutes, obtains mixture II；By the mixture
II cool down, neutralizes, drying and break process, obtains Crosslinked and hydroxypropyl starch.
Crosslinked and hydroxypropyl starch is put into kneader device, it is water-soluble that the ferrous sulfate that concentration is 10% is added in whipping process
Liquid stirs 20 minutes, obtains the first mixture；Hydrogen peroxide, the acrylic acid, acrylonitrile that concentration is 30% is slowly added dropwise in starting metering pump
And vinyl alkoxy phosphate, in first mixture, stirring after twenty minutes, takes out the tunnel that material is 90kw to power
The continuous multi-resonant chamber microwave radiation equipment of formula is irradiated reaction 30 minutes, obtains the second mixture；To second mixture into
Row is cooling, neutralize, dry and break process is to get starch polymer.It is 63000mpa.s through 5% solution viscosity of detection,
PVI value is 0.57.
Weigh by weight starch polymer, carboxymethyl cellulose, aqueous bentonite thickener, xanthan gum, polyethylene glycol with
And preservative, it is spare；By the starch polymer, carboxymethyl cellulose, aqueous bentonite thickener, xanthan gum, polyethylene glycol
And it in preservative investment blending tank, is mixed 25 minutes, obtains whole mixture；The whole mixture through powder feeding extension set and is given
Material machine is sent into humidification storehouse and is sufficiently atomized, while reverse 10 parts of atomized water of penetrating, then enters granulation from the bottom in humidification storehouse
Unit is granulated, and obtains the starch complex thickener that mesh number is 60 mesh.
Embodiment 3
A kind of starch complex thickener, the raw material including following parts by weight:
50 parts of starch polymer, 25 parts of carboxymethyl cellulose, 3 parts of aqueous bentonite thickener, 2 parts of xanthan gum, poly- second two
5 parts of alcohol and 0.3 part of preservative.
Wherein, the starch polymer includes the raw material of following parts by weight:
The hydrogen peroxide 1 that 5 parts of ferrous sulfate aqueous solution that 100 parts of Crosslinked and hydroxypropyl starch, concentration are 10%, concentration are 30%
Part, 60 parts of acrylic acid, 15 parts of acrylonitrile and 20 parts of vinyl alkoxy phosphate.
Wherein, the Crosslinked and hydroxypropyl starch includes the raw material of following parts by weight:
The caustic soda that 20 parts of ethanol water that 100 parts of native starch (potato starch), concentration are 60%, concentration are 30%
10 parts of alcoholic solution, 10 parts of allyl polyoxy alkyl epoxy base ether, 10 parts of long-chain alkyl alcohol polyethenoxy ether metacrylic acid ester with
And 1 part of methyl epichlorohydrin.
The starch complex thickener the preparation method comprises the following steps:
Potato starch is put into kneader device, it is 60% ethanol water and dense that concentration is added in whipping process
The caustic soda alcoholic solution that degree is 30% obtains mixture I after 30 DEG C are stirred 25 minutes；Allyl polyoxy is added in the mixture I
Alkyl epoxy base ether, long-chain alkyl alcohol polyethenoxy ether metacrylic acid ester and methyl epichlorohydrin, after stirring 30 minutes,
Pumping, which is expected in reactor tank, is reacted, and reaction temperature is 120 DEG C, and the reaction time is 60 minutes, obtains mixture II；By the mixing
Object II cool down, neutralized, drying and break process, obtains Crosslinked and hydroxypropyl starch.
Crosslinked and hydroxypropyl starch is put into kneader device, it is water-soluble that the ferrous sulfate that concentration is 10% is added in whipping process
Liquid stirs 20 minutes, obtains the first mixture；Hydrogen peroxide, the acrylic acid, acrylonitrile that concentration is 30% is slowly added dropwise in starting metering pump
And vinyl alkoxy phosphate, in first mixture, stirring after twenty minutes, takes out the tunnel that material is 90kw to power
The continuous multi-resonant chamber microwave radiation equipment of formula is irradiated reaction 45 minutes, obtains the second mixture；To second mixture into
Row is cooling, neutralize, dry and break process is to get starch polymer.It is 100000mpa.s through 5% solution viscosity of detection,
PVI value is 0.65.
Weigh by weight starch polymer, carboxymethyl cellulose, aqueous bentonite thickener, xanthan gum, polyethylene glycol with
And preservative, it is spare；By the starch polymer, carboxymethyl cellulose, aqueous bentonite thickener, xanthan gum, polyethylene glycol
And it in preservative investment blending tank, is mixed 25 minutes, obtains whole mixture；The whole mixture through powder feeding extension set and is given
Material machine is sent into humidification storehouse and is sufficiently atomized, while reverse 8 parts of atomized water of penetrating, then enters pelletizer from the bottom in humidification storehouse
Group is granulated, and obtains the starch complex thickener that mesh number is 60 mesh.
Embodiment 4
A kind of starch complex thickener, the raw material including following parts by weight:
65 parts of starch polymer, 20 parts of carboxymethyl cellulose, 5 parts of aqueous bentonite thickener, 5 parts of xanthan gum, poly- second two
5 parts of alcohol and 0.3 part of preservative.
Wherein, the starch polymer includes the raw material of following parts by weight:
The hydrogen peroxide 1 that 10 parts of ferrous sulfate aqueous solution that 100 parts of Crosslinked and hydroxypropyl starch, concentration are 10%, concentration are 30%
Part, 80 parts of acrylic acid, 20 parts of acrylonitrile and 20 parts of vinyl alkoxy phosphate.
Wherein, the Crosslinked and hydroxypropyl starch includes the raw material of following parts by weight:
The caustic soda alcohol that 20 parts of ethanol water that 100 parts of native starch (cornstarch), concentration are 80%, concentration are 30%
10 parts of solution, 10 parts of allyl polyoxy alkyl epoxy base ether, 10 parts of long-chain alkyl alcohol polyethenoxy ether metacrylic acid ester and
1 part of methyl epichlorohydrin.
The starch complex thickener the preparation method comprises the following steps:
Cornstarch is put into kneader device, ethanol water and the concentration that concentration is 80% are added in whipping process
For 30% caustic soda alcoholic solution, 30 DEG C of stirrings after twenty minutes, obtain mixture I；Allyl polyoxy alkane is added in the mixture I
Basic ring oxygen ether, long-chain alkyl alcohol polyethenoxy ether metacrylic acid ester and methyl epichlorohydrin are taken out after stirring 30 minutes
Expect in reactor tank and reacted, reaction temperature is 80 DEG C, and the reaction time is 120 minutes, obtains mixture II；By the mixture
II cool down, neutralizes, drying and break process, obtains Crosslinked and hydroxypropyl starch.
Crosslinked and hydroxypropyl starch is put into kneader device, it is water-soluble that the ferrous sulfate that concentration is 10% is added in whipping process
Liquid stirs 20 minutes, obtains the first mixture；Hydrogen peroxide, the acrylic acid, acrylonitrile that concentration is 30% is slowly added dropwise in starting metering pump
And vinyl alkoxy phosphate, in first mixture, stirring after forty minutes, takes out the tunnel that material is 120kw to power
The continuous multi-resonant chamber microwave radiation equipment of formula is irradiated reaction 30 minutes, obtains the second mixture；To second mixture into
Row is cooling, neutralize, dry and break process is to get starch polymer.It is 90000mpa.s through 5% solution viscosity of detection,
PVI value is 0.63.
Weigh by weight starch polymer, carboxymethyl cellulose, aqueous bentonite thickener, xanthan gum, polyethylene glycol with
And preservative, it is spare；By the starch polymer, carboxymethyl cellulose, aqueous bentonite thickener, xanthan gum, polyethylene glycol
And it in preservative investment blending tank, is mixed 25 minutes, obtains whole mixture；The whole mixture through powder feeding extension set and is given
Material machine is sent into humidification storehouse and is sufficiently atomized, while reverse 12 parts of atomized water of penetrating, then enters granulation from the bottom in humidification storehouse
Unit is granulated, and obtains the starch complex thickener that mesh number is 60 mesh.
Embodiment 5
A kind of starch complex thickener, the raw material including following parts by weight:
65 parts of starch polymer, 10 parts of carboxymethyl cellulose, 15 parts of aqueous bentonite thickener, 10 parts of xanthan gum, poly- second
3 parts of glycol and 0.3 part of preservative.
Wherein, the starch polymer includes the raw material of following parts by weight:
The hydrogen peroxide 1 that 5 parts of ferrous sulfate aqueous solution that 100 parts of Crosslinked and hydroxypropyl starch, concentration are 10%, concentration are 30%
Part, 60 parts of acrylic acid, 15 parts of acrylonitrile and 15 parts of vinyl alkoxy phosphate.
Wherein, the Crosslinked and hydroxypropyl starch includes the raw material of following parts by weight:
The burning that 15 parts of ethanol water that 100 parts of native starch (waxy corn starch), concentration are 80%, concentration are 30%
10 parts of alkali alcoholic solution, 10 parts of allyl polyoxy alkyl epoxy base ether, 6 parts of long-chain alkyl alcohol polyethenoxy ether metacrylic acid ester with
And 1 part of methyl epichlorohydrin.
The starch complex thickener the preparation method comprises the following steps:
By waxy corn starch put into kneader device in, in whipping process be added concentration be 80% ethanol water and
The caustic soda alcoholic solution that concentration is 30% obtains mixture I after 30 DEG C are stirred 30 minutes；It is poly- that allyl is added in the mixture I
Oxyalkyl epoxy group ether, long-chain alkyl alcohol polyethenoxy ether metacrylic acid ester and methyl epichlorohydrin stir 30 minutes
Afterwards, pumping, which is expected in reactor tank, is reacted, and reaction temperature is 80 DEG C, and the reaction time is 90 minutes, obtains mixture II；It will be described mixed
It closes object II cool down, neutralize, drying and break process, obtains Crosslinked and hydroxypropyl starch.
Crosslinked and hydroxypropyl starch is put into kneader device, it is water-soluble that the ferrous sulfate that concentration is 10% is added in whipping process
Liquid stirs 20 minutes, obtains the first mixture；Hydrogen peroxide, the acrylic acid, acrylonitrile that concentration is 30% is slowly added dropwise in starting metering pump
And vinyl alkoxy phosphate, in first mixture, stirring after twenty minutes, takes out the tunnel that material is 90kw to power
The continuous multi-resonant chamber microwave radiation equipment of formula is irradiated reaction 45 minutes, obtains the second mixture；To second mixture into
Row is cooling, neutralize, dry and break process is to get starch polymer.It is 72000mpa.s through 5% solution viscosity of detection,
PVI value is 0.58.
Weigh by weight starch polymer, carboxymethyl cellulose, aqueous bentonite thickener, xanthan gum, polyethylene glycol with
And preservative, it is spare；By the starch polymer, carboxymethyl cellulose, aqueous bentonite thickener, xanthan gum, polyethylene glycol
And it in preservative investment blending tank, is mixed 25 minutes, obtains whole mixture；The whole mixture through powder feeding extension set and is given
Material machine is sent into humidification storehouse and is sufficiently atomized, while reverse 10 parts of atomized water of penetrating, then enters granulation from the bottom in humidification storehouse
Unit is granulated, and obtains the starch complex thickener that mesh number is 60 mesh.
1 starch complex thickener printing gum original of test case pastes performance comparison experiment
Luo Wang is etherified to the preparation-obtained starch complex thickener of 1-5 of the embodiment of the present invention and commercially available carboxy methyl hydroxyethyl
Sub- glue (deriving from India, Guangzhou Pu Yang trade Co., Ltd) carries out technical target of the product test, particular technique index and detection
Method is as follows:
Original paste paste making rate: the slurries that preparation viscosity is 45000mpa.s, the solid content of slurries.
Salt stability: a certain amount of former paste liquid for redissolving and preparing is weighed, the reservehao S (nitre of equal quality is added
Base benzene sulfonic acid sodium salt), the viscosity of former paste liquid is detected, is calculated viscosity retention ratio (%).
PVI: with the former paste of the same range of viscosities of NDJ-1 type rotary viscosity design determining in two kinds of revolving speeds of 60r/min, 6r/min
Under viscosity, the PVI value of thickener is calculated as follows, to evaluate its rheological characteristic.
60/ η 6 of PVI=η
Viscosity under η 60=60r/min revolving speed
Viscosity under η 6=6r/min revolving speed
These parameters testing result is as shown in table 2:
Table 2
From table 2 it can be seen that its paste making rate of the starch complex thickener of embodiment 1-5 preparation is above commercially available carboxymethyl hydroxyl
Ethyl is etherified tamarind gum, and salt tolerance is also above carboxy methyl hydroxyethyl etherificate tamarind gum.Wherein, the embodiment of the present invention 3
Preparation-obtained starch complex thickener paste making rate highest, salt stability is good, can reduction by a relatively large margin in actual use
Thickener dosage, save the cost.
2 starch complex thickener printing gum application performance comparative experiments of test case
Luo Wang is etherified to the preparation-obtained starch complex thickener of 1-5 of the embodiment of the present invention and commercially available carboxy methyl hydroxyethyl
After sub- glue prepares mill base, chooses dacron and carries out stamp, printing technology process is as follows:
Plain net scrape-dries (100 DEG C, 3min)-decatize (170 DEG C, 7min)-cold water and rinse-soaps-cold water
It wash-dries.
Technical indicator test is carried out to the product after printing and dyeing, particular technique index and detection method are as follows:
Decorative pattern clarity: decorative pattern clarity refers to the degree that decorative pattern is accurately presented on the fabric, and the sharper pattern the more clear,
Decorative pattern clarity is evaluated using " Pyatyi system " ocular estimate.
Crock fastness: being executed by GB/T3920-2008 standard, measures embodiment 1-5 and commercially available carboxy methyl hydroxyethyl etherificate
The dry fastness and fastness to wet rubbing of tamarind gum.
De- paste rate: after stamp, the quality that will weigh after fabric drying and the quality difference value of the PRINTED FABRIC after washing are knitted than above
The percentage of quality and the fabric quality difference of non-stamp, calculation formula are as follows after weighing after object drying:
De- paste rate=(W1-W2)/(W1-W0) × 100%
W in formula1For the fabric quality after stamp and drying, W2For the quality of the PRINTED FABRIC after washing, W0For non-stamp
Fabric quality.
Feel (texture): the feels such as smooth, soft, elastic using the method evaluation PRINTED FABRIC of " pinch, touch, grabbing " are special
Sign；Using " Pyatyi system " subjective grading method.
Color strength: with the K/S of computer color measurement and color match instrument measurement fabric surface.
Embrace aqueous: fresh filter paper is cut into the strip of 10cm × 2cm, is inserted perpendicularly into 5% former paste, measures liquid after 30min
The height that body rises, highly good less than 0.5cm, it is highly poor greater than 1cm that it is good for, which being highly greater than 0.5cm and being less than 1cm,.
These parameters testing result is as shown in table 3 below:
Table 3
The stamp prepared it can be seen from the test result of table 3 using the starch complex thickener of 1-5 of the embodiment of the present invention
Thickener decorative pattern clarity is high, and dry fastness and fastness to wet rubbing rank are higher, it is good to take off paste property, and color strength is also above carboxylic
Dimethyl hydroxyethyl is etherified tamarind gum, has more apparent advantage.
To sum up, starch complex thickener safety and environmental protection prepared by the present invention, each component synergistic effect, through being granulated rear stability
It is fabulous.The thickener paste making rate of preparation is high, and salt stability is high, can substantially reduce the dosage of thickener.The print paste of preparation is being knitted
Decorative pattern is clear on object, and color strength is high, can reduce the usage amount of mill base.It is easier to clean up after fabric printing, less residue,
Washing times and water consumption can be reduced.Carboxy methyl hydroxyethyl etherificate tamarind can be substituted completely by applying in actual woven printing and dyeing
Glue.
In embodiments of the present invention, the viscosity of starch polymer, PVI value can because medicament dosage and reaction condition (such as
Temperature, time etc.) have certain variation, will lead to finally with the raw mixtures viscosity such as carboxymethyl cellulose, xanthan gum,
The variation of PVI value, for the stabilization for guaranteeing final product starch complex thickener, can suitably according to the viscosity of starch polymer and
PVI value adjusts the usage ratio of each raw material.
Specifically, the stability of product refers to that the viscosity of final product starch complex thickener and stamp take off paste effect
Stablize；The stabilization of viscosity can ensure that the stability of printing gum, not need to adjust with the viscosity change of starch complex thickener
Section thickener opens slurry concentration, reduces worker's workload of print works, the stabilization of PVI value ensure that printing quality.Because of starch polymer
Certain fluctuation can be generated because of the factors such as medicament, environment, machine, artificial in production, as produced with the technique in embodiment 1
Based on starch polymer, viscosity also has certain fluctuation (3.5 ten thousand~5.5 ten thousand mpa.s), and PVI value also has certain
It fluctuates (0.52~0.63), therefore the present invention is to guarantee the stabilization of the viscosity of final product starch complex thickener, it can be to each original
The usage ratio of material carries out certain adjusting, to the starch polymer of same raw material, different viscosities to starch complex thickener
Influence studied (research method are as follows: based on embodiment 1, in addition to the viscosity of each starch polymer is different, other raw materials
Dosage immobilizes, and preparation generates starch complex thickener), specific test result see the table below shown in 4.
Table 4
To sum up, as shown in Table 4, when the starch polymer viscosity prepared is different, according to unified material rate preparation
The viscosity of final product starch complex thickener can generate certain fluctuation；Even if the starch polymer viscosity of preparation is consistent, but PVI
Value difference is more, though close according to the viscosity of the final product starch complex thickener of unified material rate preparation, PVI value is had
A certain distance, these can all cause the unstable of the product of stamp.First it is carried out when producing starch polymer viscosity and
PVI value detects, according to testing result the ratio of adjustment each material of starch complex thickener appropriate, to ensure the viscous of final product
The stabilization of degree and PVI value, it is ensured that the stabilization of the using effect of product.
Further, the present invention found in R&D process in etherificate cross-linking process the content of component used or concentration, with
And the variation of Parameter Conditions influences significantly the property of gained Crosslinked and hydroxypropyl starch in reaction process, therefore to determine that best composition contains
Amount or concentration and Parameter Conditions expand following experimental example 1-7 based on embodiment 1, specific as follows:
Experimental example 1
The concentration of fixed ethanol water is 50%, and dosage is that 10 parts by weight immobilize, except the dosage of caustic soda alcoholic solution
Successively change into 3 parts, 5 parts, 8 parts and 10 especially, other dosings are also that definite value is constant (with embodiment 1), to made
The results are shown in Table 4 for standby obtained Crosslinked and hydroxypropyl starch influence.
Table 5
As known from Table 5, reactant of the caustic soda as starch quaternization, while being also the catalyst of etherification reaction, activation
Active group inside starch, in order to obtain the product of more high substituted degree.When the dosage of caustic soda is more, the active group of activation
Also more, but the dosage of caustic soda can excessively make starch that the progress that gelatinization influence is reacted occur.
Experimental example 2
Except the concentration (dosage) of ethanol water successively change into 50% (10 parts), 60% (10 parts), 80% (10 parts) with
And 80% (20 parts) outside, caustic soda alcoholic solution dosage is that 10 parts by weight immobilize, and other dosings are also that definite value is constant (same
Embodiment 1), on the influence of preparation-obtained Crosslinked and hydroxypropyl starch, the results are shown in Table 6.
Table 6
As known from Table 6, ethyl alcohol can inhibit starch gelatinization as organic solvent, improve the dosage of caustic soda, to obtain more
The product of high substituted degree.
Experimental example 3
In addition to allyl polyoxy alkyl epoxy base ether dosage changes, other dosings are also that definite value is constant (with implementation
Example 1), it is as shown in Figure 1 to the influence result of preparation-obtained Crosslinked and hydroxypropyl starch viscosity.From fig. 1, it can be seen that allyl polyoxy alkane
Basic ring oxygen ether not only containing unsaturated double-bond but also contained the epoxy cardinal extremity of high activity, and good reactivity is urging it
Under the action of agent, etherification reaction easily occurs with starch hydroxyl, increases the molecular weight of starch molecule.
Experimental example 4
Except long-chain alkyl alcohol polyethenoxy ether metacrylic acid ester dosage change in addition to, other dosings be also definite value not
Become (with embodiment 1), it is as shown in Figure 2 to the influence result of preparation-obtained Crosslinked and hydroxypropyl starch viscosity.As can be seen from Figure 2, long
Alkyl group alcohol polyethenoxy ether metacrylic acid ester is used as alkaline association thickener, contains again in long chain hydrophobic group hydrophilic
The property ethylene oxide end of the chain, reacts with starch molecule under alkaline environment, makes molecule chain extension, and form reticular structure, change
The hydrophily of product after kind reaction.Also each ingredient is sufficiently mixed the reticular structure that simultaneous reactions are formed in promotion system, is promoted anti-
Answer efficiency and the extent of reaction.
Experimental example 5
In addition to methyl epichlorohydrin dosage changes, other dosings are also that definite value is constant (with embodiment 1), to institute
The influence result such as table 6 and figure of the Crosslinked and hydroxypropyl starch viscosity and the viscosity retention ratio being added after a certain amount of salt that are prepared
Shown in 3.From table 6 and Fig. 3 it is found that the epoxy group that contains of methyl epichlorohydrin under alkaline condition, easily and starch molecule
In hydroxyl crosslink reaction, the salt tolerant and endurance of cutting energy of cross-linking chemistry bond energy intensified response product, after promoting reaction
The stability of product, but with the increase of crosslinking degree, the chemical bond quantity between starch molecule increases, and can inhibit the expansion of starch
Gelatinization, therefore dosage is easily controlled in the present reaction, it is unsuitable excessive.
Experimental example 6
In addition to the reaction time changes, other process conditions are also that definite value is constant (with embodiment 1), to preparation-obtained
The influence result of Crosslinked and hydroxypropyl starch viscosity is as shown in Figure 4.As can be seen from Figure 4, the viscosity of test powder can be improved by increasing the reaction time,
But after reaching the regular hour, increasing time viscosity can remain unchanged substantially, illustrate that reaction is reached home.
Experimental example 7
In addition to reaction temperature changes, other process conditions are also that definite value is constant (with embodiment 1), to preparation-obtained
The influence result of Crosslinked and hydroxypropyl starch viscosity is as shown in Figure 5.As can be seen from Figure 5, reaction temperature is improved, reaction efficiency can be accelerated, is contracted
Short reaction time, but after temperature promotion to a certain extent, reaction test powder viscosity dramatic decrease can be made.
Further, the present invention is to determine shadow of the dosage to system for connecing branch polymerization process medium vinyl alkoxy phosphate
It rings, based on embodiment 1, expands following experimental example 8, specific as follows:
Experimental example 8
In addition to vinyl alkoxy phosphate dosage changes, other dosings are also that definite value is constant (with embodiment 1),
It is as shown in Figure 6 to the viscosity influence result of preparation-obtained starch polymer.As can be seen from Figure 6, with vinyl alkoxy phosphorus
The viscosity of the addition of acid esters, gained starch polymer slowly rises, when the dosage of vinyl alkoxy phosphate reaches certain journey
After degree, it can make viscosity that downward trend be presented.In addition, Crosslinked and hydroxypropyl starch be solid phase, and acrylic acid, acrylonitrile be liquid phase, two
Person belongs to grafting copolyreaction, it is therefore desirable to which vinyl alkoxy phosphate improves reactant as copolymerization stabilizer
Compatibility makes to react continual and steady progress.
It is worth noting that, the embodiment of the present invention is copolymerized stabilizer as in reacting using vinyl alkoxy phosphate, it is
Progress testing sieve under equal conditions is carried out with allyloxy hydroxypropyl azochlorosulfonate acid sodium, sodium vinyl sulfonate, hydroxyalkyl acrylate to select
Come, the dosage of different copolymer stabilizer as shown in Figure 7 is to the influence curve of viscosity it is found that the same usage amount the case where
Under, it is best to take off paste effect for the starch polymer viscosity highest that vinyl alkoxy phosphate is prepared as stabilizer；I.e. in this hair
Bright embodiment medium vinyl alkoxy phosphate has irreplaceable role as copolymerization stabilizer.
It is worth noting that, the present invention is crosslinked pretreatment by etherificate, then carries out connecing branch, starch molecule amount increases, molecule
Salt resistance viscosity stabilization is more preferable, meanwhile, connect high-efficient a, allyl for the allyl polyoxy alkyl epoxy base ether in etherificate cross-linking process
Acrylonitrile microwave reaction during group and graft copolymerization increases copolymer level in starch, reduces the life of homopolymer
At；Thickening effect is good, effectively improves the paste making rate of subsequent starch complex thickener.
The embodiments described above only express several embodiments of the present invention, and the description thereof is more specific and detailed, but simultaneously
Limitations on the scope of the patent of the present invention therefore cannot be interpreted as.It should be pointed out that for those of ordinary skill in the art
For, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to guarantor of the invention
Protect range.Therefore, the scope of protection of the patent of the invention shall be subject to the appended claims.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Made any modifications, equivalent replacements, and improvements etc., should all be included in the protection scope of the present invention within mind and principle.
Claims (10)
1. a kind of starch complex thickener, which is characterized in that the raw material including following parts by weight:
40 ~ 80 parts of starch polymer, 5 ~ 30 parts of carboxymethyl cellulose, bentonite thickener 5-15 parts aqueous, xanthan gum 1 ~ 10
Part, 0.2 ~ 5 part of polyethylene glycol and 0.1 ~ 0.8 part of preservative.
2. starch complex thickener according to claim 1, which is characterized in that the starch polymer includes following weight
The raw material of number:
100 parts of Crosslinked and hydroxypropyl starch, 2 ~ 10 parts of the ferrous sulfate aqueous solution that concentration is 10%, hydrogen peroxide 0.1 that concentration is 30% ~
1 part, 40 ~ 80 parts of acrylic acid, 10 ~ 30 parts of acrylonitrile and 10 ~ 20 parts of vinyl alkoxy phosphate.
3. starch complex thickener according to claim 2, which is characterized in that the preparation method packet of the starch polymer
It includes:
Crosslinked and hydroxypropyl starch is put into kneader device, and the ferrous sulfate that addition concentration is 10% in whipping process is water-soluble
Liquid stirs 10 ~ 30 minutes, obtains the first mixture；
Hydrogen peroxide, acrylic acid, acrylonitrile and vinyl alkoxy phosphoric acid that concentration is 30% is successively slowly added dropwise in starting metering pump
Ester is in first mixture, after stirring 10 ~ 30 minutes, takes out the continuous multi-resonant chamber of tunnel type that material is 60 ~ 120kw to power
It is irradiated reaction in microwave radiation equipment 15 ~ 45 minutes, obtains the second mixture；
Second mixture cool down, is neutralized, is dried and break process to get.
4. starch complex thickener according to claim 2, which is characterized in that the Crosslinked and hydroxypropyl starch includes following heavy
Measure the raw material of number:
100 parts of native starch, 10 ~ 20 parts of the ethanol water that concentration is 50 ~ 80%, the caustic soda alcoholic solution 3 ~ 10 that concentration is 30%
Part, 5 ~ 10 parts of allyl polyoxy alkyl epoxy base ether, 5 ~ 10 parts of long-chain alkyl alcohol polyethenoxy ether metacrylic acid ester and
0.1 ~ 1 part of methyl epichlorohydrin.
5. starch complex thickener according to claim 4, which is characterized in that the preparation method of the Crosslinked and hydroxypropyl starch
Include:
Native starch is put into kneader device, and it is the ethanol water of 50-80% and dense that concentration, which is added in whipping process,
Degree be 30% caustic soda alcoholic solution, temperature be 25 ~ 35 DEG C at stirring 15 ~ after forty minutes, obtain mixture I；
Allyl polyoxy alkyl epoxy base ether, long-chain alkyl alcohol polyethenoxy ether methyl acid are added in the mixture I
Ester and methyl epichlorohydrin, stirring 15 ~ after forty minutes, pumping, which is expected in reactor tank, is reacted, and reaction temperature is 60 ~ 120
DEG C, the reaction time is 60 ~ 180 minutes, obtains mixture II；
The mixture II cool down, is neutralized, is dried and break process to get.
6. starch complex thickener according to claim 1, which is characterized in that 5% concentration of aqueous solution of starch polymer
30000 ~ 100000mpa.s of viscosity.
7. starch complex thickener according to claim 1, which is characterized in that 1% concentration of carboxymethyl cellulose is water-soluble
Fluid viscosity is 800 ~ 2500mpa.s, and degree of substitution is 1.0 ~ 1.8.
8. starch complex thickener according to claim 1, which is characterized in that aqueous 8% concentration of bentonite thickener
Solution viscosity >=7500mpa.s.
9. starch complex thickener according to claim 1, which is characterized in that 1% solution viscosity 800 of the xanthan gum ~
1600mpa.s。
10. a kind of preparation method of starch complex thickener characterized by comprising
Starch polymer, carboxymethyl cellulose, aqueous bentonite thickener, xanthan gum, polyethylene glycol are weighed by weight and are prevented
Rotten agent, it is spare；
By the starch polymer, carboxymethyl cellulose, aqueous bentonite thickener, xanthan gum, polyethylene glycol and preservative
It puts into blending tank, is mixed 15 ~ 45 minutes, obtains whole mixture；
The whole mixture is sent into humidification storehouse through powder feeding extension set and batcher and carries out abundant atomization process, and inversely sprays into atomization
After water, from the humidification orlop portion enter be granulated unit be granulated to get.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114622426A (en) * | 2022-01-21 | 2022-06-14 | 昌邑华晨纺织印染有限公司 | Preparation method and application of active printing paste containing polyhydroxy chelate |
| CN115279928A (en) * | 2020-05-18 | 2022-11-01 | 日本制铁株式会社 | Method for producing agglomerate and agglomerate |
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2019
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115279928A (en) * | 2020-05-18 | 2022-11-01 | 日本制铁株式会社 | Method for producing agglomerate and agglomerate |
| CN115279928B (en) * | 2020-05-18 | 2024-01-19 | 日本制铁株式会社 | Method for producing agglomerate and agglomerate |
| CN114622426A (en) * | 2022-01-21 | 2022-06-14 | 昌邑华晨纺织印染有限公司 | Preparation method and application of active printing paste containing polyhydroxy chelate |
| CN114622426B (en) * | 2022-01-21 | 2024-05-17 | 昌邑华晨纺织印染有限公司 | Preparation method and application of active printing paste containing polyhydroxy chelate |
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