CN109989270A - A kind of high bound starch slurry and preparation method thereof - Google Patents
A kind of high bound starch slurry and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B30/00—Preparation of starch, degraded or non-chemically modified starch, amylose, or amylopectin
- C08B30/12—Degraded, destructured or non-chemically modified starch, e.g. mechanically, enzymatically or by irradiation; Bleaching of starch
- C08B30/18—Dextrin, e.g. yellow canari, white dextrin, amylodextrin or maltodextrin; Methods of depolymerisation, e.g. by irradiation or mechanically
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B31/00—Preparation of derivatives of starch
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F218/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
- C08F218/02—Esters of monocarboxylic acids
- C08F218/04—Vinyl esters
- C08F218/08—Vinyl acetate
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
- C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C08G81/021—Block or graft polymers containing only sequences of polymers of C08C or C08F
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/28—Treatment by wave energy or particle radiation
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/01—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural macromolecular compounds or derivatives thereof
- D06M15/03—Polysaccharides or derivatives thereof
- D06M15/11—Starch or derivatives thereof
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2303/00—Characterised by the use of starch, amylose or amylopectin or of their derivatives or degradation products
- C08J2303/02—Starch; Degradation products thereof, e.g. dextrin
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/02—Natural fibres, other than mineral fibres
- D06M2101/04—Vegetal fibres
- D06M2101/06—Vegetal fibres cellulosic
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Abstract
The present invention provides a kind of high bound starch slurries and preparation method thereof, belong to weaving Size Technology field, and the present invention adds water to be gelatinized, obtains gelatinized starch after cornstarch is carried out radiation treatment；Vinylacetate, acrylic acid and initiator are mixed and carry out polymerization reaction, obtains copolymer；The copolymer, gelatinized starch and ammonium ceric nitrate aqueous solution are mixed and carry out graft copolymerization, obtains high bound starch slurry after adding alkali neutralization.The present invention reacts easy to control, obtained copolymer molecule chain is longer, and flexibility is more preferable using acrylic acid and vinyl acetate copolymerized；The present invention is compared using single catalyst ammonium ceric nitrate catalysis graft copolymerization with many body system mixed catalyst, and uncontrollable factor is few, reaction process milder, high-efficient.High bound starch slurry of the invention reaches 83.9N to the adhesion strength of pure cotton, reaches 119.42N to the adhesion strength of polyester-cotton blend, and the flexibility for forming serous coat is preferable.
Description
Technical field
The invention belongs to weave to use Size Technology field, and in particular to a kind of high bound starch slurry and preparation method thereof.
Background technique
Textile process process is that fiber elder generation spun yarn is made into cloth again, before yarn is made into cloth, warp thread palpus starching, to improve yarn
Weavability, make that yarn is phozy in the weaving process, few broken end；Except seldom a part of strand, high twist yarn and some textured filaments
Warp thread is not required to starching, and the warp thread of other forms all needs starching.After the completion of weaving process, the slurry on fabric will will affect fabric
Water absorbing properties also will affect the dye quality of product, in order to reduce the consumption of dye chemical drug product, therefore need desizing before dyeing.Print
Waste water caused by kiering desizing typically constitutes from 40% or so of dyeing waste water total amount, various slurry degradation objects, acid, Soft flocks in dye
Equal organic pollutants account for about the half of total amount.Desized wastewater is in alkalinity more, and pH is that 9~13, COD average value can reach 8000mg/L
Left and right；It is difficult that treatment of dyeing wastewater is got up, and a large amount of accumulation, make the deteriorating water quality of contaminated water, influence in the environment
The activity of gas microorganism, it has also become one of biggish pollution sources of textile industry.
Currently, textile warp starching mainly uses starch, PVA and acrylic acid three categories slurry.The appearance of PVA, solves
The filming performance of the sizing of hydrophobic fibre, PVA brilliance is considered as the revolution of warp yarn sizing；But PVA is difficult to drop
Solution pollutes the environment, it is considered to be not environmentally slurry.Acrylic size also has good film forming, and serous coat is soft
Soft, no pollution to the environment has been widely used in warp yarn sizing；But acrylic size has biggish moisture absorption sticky again, no
It can be used alone as main slurry.
Starch have the characteristics that abundance, it is cheap, be easy to degrade etc. meet current environmental requirement, in this regard, many
Research worker is using starch as substrate, by various methods physically or chemically to starch conversion: as using high low viscosity original
The means such as starch blending, acidified starch, oxidized starch, graft copolymerization have synthesized diversified environmental protection starch type slurry.China
A kind of method for improving starch size adhesive strength is disclosed in patent CN201710605460.0, first by starch respectively through carboxylic first
Base etherificate and propionate two-step reaction, are made oil/water amphiphilic starch derivative, then by oil/water amphiphilic starch derivative
Adhesion promotor is mixed to get with hydroxyl plasticizers and amino plasticizer；The table using oil/water amphiphilic starch is described
Face activity improves starch size to the wetability of fiber and is impregnated with degree, and plasticizer reduces the brittleness that fiber and starch are glued, from
And the adhesive strength of starch size is improved, although to can be improved starch size to a certain extent short to terylene for the method for the patent
The adhesive strength of fiber, but there are still manufacturing process that more complicated, plasticizer is difficult to the disadvantage degraded, adhesion strength is inadequate.
Therefore, researching and developing a kind of simple starch conversion method and improving the adhesion strength that starch size itself forms serous coat has important meaning
Justice.
Summary of the invention
In view of this, the present invention provides it is an object of that present invention to provide a kind of high bound starch slurry and preparation method thereof
Preparation method step it is simple, reaction is mild, and without using plasticizer, the starch size of preparation has very high adhesiveness and good
Good flexibility, it is more conducively environmentally friendly.
In order to achieve the above-mentioned object of the invention, the present invention the following technical schemes are provided:
The present invention provides a kind of preparation methods of high bound starch slurry, comprising the following steps:
(1) add water gelatinization after cornstarch being carried out radiation treatment, obtain gelatinized starch；
(2) vinylacetate, acrylic acid and initiator are mixed and carries out polymerization reaction, obtain copolymer；
(3) copolymer, gelatinized starch and ammonium ceric nitrate aqueous solution are mixed and carries out graft copolymerization, add alkali neutralization
After obtain high bound starch slurry；
The limitation of the not no time sequencing of the step (1) and step (2).
Preferably, the irradiation bomb of radiation treatment is in the step (1)60Co- γ, irradiation dose are 4~40kGy.
Preferably, it is 4~9 times of cornstarch weight that the amount of water is added in the step (1), and the temperature of the gelatinization is 95
~98 DEG C, the time is 30~35min.
Preferably, initiator is azo-bis-iso-dimethyl and/or azodiisobutyronitrile in the step (2).
Preferably, the mass ratio of vinylacetate, acrylic acid and initiator is 300~400:100:1 in the step (2)
~2.
Preferably, the temperature of polymerization reaction is 69 DEG C in the step (2), and the time is 30~50min.
Preferably, the mass ratio of copolymer and gelatinized starch is 2.3~2.5:1 in the step (3).
Preferably, the concentration of ammonium ceric nitrate aqueous solution is 4~6wt.% in the step (3)；The ammonium ceric nitrate is water-soluble
The quality of ammonium ceric nitrate is the 1.2~1.8% of the copolymer and cornstarch gross mass in liquid.
Preferably, the temperature of graft copolymerization is 50~60 DEG C in the step (3), and the time is 3.5~4h.
The present invention provides the high bound starch slurries described in above-mentioned technical proposal.
The utility model has the advantages that
The present invention provides a kind of preparation methods of high bound starch slurry, add water after cornstarch is carried out radiation treatment
Gelatinization, obtains gelatinized starch；Vinylacetate, acrylic acid and initiator are mixed and carry out polymerization reaction, obtains copolymer；By institute
It states copolymer, gelatinized starch and the mixing of ammonium ceric nitrate aqueous solution and carries out graft copolymerization, obtain high adherency shallow lake after adding alkali neutralization
Slurry material.It is not easy to control to avoid Vinyl Acetate Monomer self-polymeric reaction using acrylic acid and vinyl acetate copolymerized by the present invention
The shortcomings that, the strand of obtained vinyl acetate-acrylic copolymer is longer, and flexibility is more preferable, and being grafted on starch can
Significantly improve the adhesiveness and flexibility of starch；And the present invention is anti-using single catalyst (ammonium ceric nitrate) catalysis graft copolymerization
It answers, in conventional method by the way of many body system mixed catalyst, uncontrollable factor is less, and grafting of the invention is total
Poly- reaction process is mild, more efficient.
Starching test result in embodiment shows that high bound starch slurry prepared by the present invention has pure cotton and polyester-cotton blend
Good adhesion property reaches 83.9N to the adhesion strength of the end 40S coarse sand pure cotton, reaches to the adhesion strength of the end 45S coarse sand polyester-cotton blend
To 119.42N, and the flexibility for forming serous coat is preferable, breaking strength > 36.41N/mm2, elongation at break > 3.62%；Phase
It is substantially improved in terms of adhesion strength than unmodified cornstarch, it being capable of substitution for PVA slurry, more environment-friendly advantage.
Specific embodiment
The present invention provides a kind of preparation methods of high bound starch slurry, comprising the following steps:
(1) add water gelatinization after cornstarch being carried out radiation treatment, obtain gelatinized starch；
(2) vinylacetate, acrylic acid and initiator are mixed and carries out polymerization reaction, obtain copolymer；
(3) copolymer, gelatinized starch and ammonium ceric nitrate aqueous solution are mixed and carries out graft copolymerization, add alkali neutralization
After obtain high bound starch slurry；
The limitation of the not no time sequencing of the step (1) and step (2).
The present invention adds water gelatinization after cornstarch is carried out radiation treatment, obtains gelatinized starch.In the present invention, the jade
The preferred < 15wt.% of the moisture content of rice starch；The irradiation bomb of the radiation treatment is preferably60Co- γ, irradiation dose are preferably 4
~40kGy, more preferably 20~40kGy, further preferably 30~40kGy.The present invention uses60Co- γ is as irradiation bomb, energy
It is enough that modification effectively is played to the starch chain structure of cornstarch, cause changes of free radicals, amylase activity is promoted to enhance, fits
For large-scale starch conversion.
After the completion of radiation treatment, the cornstarch after irradiation is added water to be gelatinized by the present invention, obtains gelatinized starch.In the present invention
In, described plus water amount is preferably 4~9 times, more preferable 6~8 times of cornstarch weight.In the present invention, the gelatinization
Temperature is preferably 95~98 DEG C, and more preferably 96 DEG C；The time of gelatinization is preferably 30~35min, more preferably 33min.At this
In invention, after the cornstarch after the irradiation adds water, it is preferably warming up to gelatinization point in 10min, in the temperature-rise period
It needs quickly to stir, then continues heating in 95~98 DEG C and be gelatinized with moderate-speed mixer；After the completion of the gelatinization, the present invention is excellent
Choosing is stirred at low speed, and continues to keep the temperature 30min, the present invention preferably be gelatinized and is passed through nitrogen in insulating process and protects.This hair
It is bright to container used in gelatinization process, agitating mode and stirring rate without particular/special requirement, can prevent heating from generating agglomeration, keep
It is uniformly dispersed；In the present invention, gelatinization and isothermal holding can further degradable starch macromolecular, keep its evengranular
In aqueous solution, the graft copolymerization conducive to the promotion later period is gone on smoothly for dispersion.
Vinylacetate, acrylic acid and initiator are mixed and carry out polymerization reaction by the present invention, obtain copolymer.In the present invention
In, the initiator is preferably azo-bis-iso-dimethyl and/or azodiisobutyronitrile；The vinylacetate, acrylic acid
Mass ratio with initiator is preferably 300~400:100:1~2, more preferably 320~380:100:1.2~1.8；It is described poly-
The temperature for closing reaction is preferably 69 DEG C, and the time is preferably 30~50min, more preferably 40min；The present invention is preferably in stirring condition
Lower carry out polymerization reaction, the revolving speed of the stirring is preferably 200rpm；The present invention preferably under nitrogen protection and stirring condition into
Row polymerization reaction, the revolving speed of the stirring are preferably 200rpm.The present invention is avoided using acrylic acid and vinyl acetate copolymerized
Vinyl Acetate Monomer self-polymeric reaction disadvantage not easy to control, the present invention generate the reaction of vinyl acetate-acrylic copolymer
Time is easy to control, and the strand of obtained vinyl acetate-acrylic copolymer is longer, and flexibility is more preferable.
After obtaining gelatinized starch and copolymer, the present invention mixes the copolymer, gelatinized starch and ammonium ceric nitrate aqueous solution
It closes and carries out graft copolymerization, obtain the high flexible starch size of adherency after adding alkali neutralization.In the present invention, the copolymer and paste
The mass ratio for changing starch is preferably 2.3~2.5:1, more preferably 2.4:1；The concentration of the ammonium ceric nitrate aqueous solution is preferably 4
~6wt.%, more preferably 5wt.%；In the ammonium ceric nitrate aqueous solution quality of ammonium ceric nitrate be preferably the copolymer and
The 1.2~1.8% of cornstarch gross mass, more preferably 1.5%.In the present invention, the temperature of the graft copolymerization is excellent
50~60 DEG C, more preferably 55 DEG C are selected as, the time is preferably 3.5~4h, more preferably 4h；The present invention preferably in nitrogen protection and
Graft copolymerization is carried out under stirring condition；The revolving speed of the stirring is preferably 300rpm.
Gelatinized starch after heat preservation is preferably cooled to 50~60 DEG C by the present invention, and gelatinization then is added in copolymer and is formed sediment
In powder, then the initiation grafting copolyreaction of ammonium ceric nitrate aqueous solution is added dropwise into the mixture of gelatinized starch and copolymer；In this hair
In bright, the time for adding of the ammonium ceric nitrate aqueous solution is preferably 1.5~2h；The graft copolymerization time of the invention is from nitric acid
Calculating when cerium aqueous ammonium starts to be added dropwise.
The present invention carries out graft copolymerization using single catalyst, mixes compared to using many body system of different catalytic mechanisms
For the mode of catalyst, uncontrollable factor of the present invention is less, and the time for adding by controlling catalyst amount and catalyst,
Can to avoid because catalyst be added it is too fast caused by early arrive at the defect of chain termination step, graft copolymerization mistake of the invention
Cheng Wenhe, grafting efficiency is higher, and the modified starch of generation has good adhesiveness, and flexibility also improves.
After the completion of graft copolymerization, the present invention adds alkali neutralization into graft copolymerization liquid, obtains high bound starch slurry
Material.In the present invention, the alkali is preferably sodium hydrate aqueous solution；The mass concentration of the sodium hydrate aqueous solution is preferably
25%, for the present invention by adding acrylic acid extra in alkali neutralization graft copolymerization liquid, described plus alkali neutralization endpoint pH is excellent
It is selected as 6.2~6.8, more preferably 6.5.
The present invention provides the high bound starch slurry described in above-mentioned technical proposal, the number of modified starch is equal in the slurry
Molecular weight is 1.2e5~3.5e5, grafting rate > 85%, relative to unmodified starch, acrylic size and PVA, the present invention
High bound starch slurry formed serous coat after have good adhesiveness and preferable flexibility.
A kind of high bound starch slurry provided by the invention and preparation method thereof is carried out below with reference to embodiment detailed
Illustrate, but they cannot be interpreted as limiting the scope of the present invention.
Embodiment 1
A kind of high bound starch slurry, preparation the following steps are included:
(1) extracting corn starch (moisture content 14%) 300g is placed in60The irradiation of Co- γ irradiation field, irradiation dose 4kGy are added
The water for irradiating 9 times of weight of powder, is put in glass reaction kettle, leads to nitrogen protection, and temperature rises to 95 DEG C from room temperature, is gelatinized 30 minutes,
And it keeps the temperature 30 minutes and obtains gelatinized starch；
(2) take monomer 700g (vinylacetate 550g, acrylic acid 150g) and azo-bis-iso-dimethyl 2g in 69 DEG C
Polymerization reaction 40 minutes in water-bath, lead to nitrogen protection, and speed of agitator 200rpm obtains copolymer；
(3) gelatinized starch of step (1) is cooled to 55 DEG C and copolymer is uniformly mixed, it is 5wt.% that concentration, which is then added dropwise,
Ammonium ceric nitrate aqueous solution catalysis graft copolymerization (contain ammonium ceric nitrate 15g), control drips off in 2h, the logical nitrogen protection of whole process,
Speed of agitator 300rpm, reacts 2h again after being added dropwise；It is cooled to room temperature after the reaction was completed, the hydrogen that concentration is 25wt.% is added dropwise
It is 6.5 that aqueous solution of sodium oxide, which is neutralized to pH value, obtains high bound starch slurry.
Embodiment 2
A kind of high bound starch slurry improves irradiation dose relative to embodiment 1, preparation the following steps are included:
(1) extracting corn starch (moisture content 14%) 300g is placed in the irradiation of 60Co- γ irradiation field, and irradiation dose 20kGy adds
The water for entering to irradiate 9 times of weight of powder is put in glass reaction kettle, leads to nitrogen protection, and temperature rises to 95 DEG C from room temperature, is gelatinized 30 points
Clock, and keep the temperature 30 minutes and obtain gelatinized starch；
(2) take monomer 700g (vinylacetate 550g, acrylic acid 150g) and azo-bis-iso-dimethyl 2g in 69 DEG C
Polymerization reaction 40 minutes in water-bath, lead to nitrogen protection, and speed of agitator 200rpm obtains copolymer；
(3) gelatinized starch of step (1) is cooled to 55 DEG C and copolymer is uniformly mixed, concentration, which is then added dropwise, is
The ammonium ceric nitrate aqueous solution catalysis graft copolymerization (containing ammonium ceric nitrate 15g) of 4.5wt.%, control is dripped off in 2h, the logical nitrogen of whole process
Gas shielded, speed of agitator 300rpm, reacts 2h again after being added dropwise；It is cooled to room temperature after the reaction was completed, concentration, which is added dropwise, is
It is 6.3 that the sodium hydrate aqueous solution of 25wt.%, which is neutralized to pH value, obtains high bound starch slurry.
Embodiment 3
A kind of high bound starch slurry improves irradiation dose relative to embodiment 2, preparation the following steps are included:
(1) extracting corn starch (moisture content 14%) 300g is placed in the irradiation of 60Co- γ irradiation field, and irradiation dose 40kGy adds
The water for entering to irradiate 9 times of weight of powder is put in glass reaction kettle, leads to nitrogen protection, and temperature rises to 95 DEG C from room temperature, is gelatinized 30 points
Clock, and keep the temperature 30 minutes and obtain gelatinized starch；
(2) take monomer 700g (vinylacetate 550g, acrylic acid 150g) and azo-bis-iso-dimethyl 2g in 69 DEG C
Polymerization reaction 40 minutes in water-bath, lead to nitrogen protection, and speed of agitator 200rpm obtains copolymer；
(3) gelatinized starch of step (1) is cooled to 55 DEG C and copolymer is uniformly mixed, it is 4wt.% that concentration, which is then added dropwise,
Ammonium ceric nitrate aqueous solution catalysis graft copolymerization (contain ammonium ceric nitrate 15g), control drips off in 2h, the logical nitrogen protection of whole process,
Speed of agitator 300rpm, reacts 2h again after being added dropwise；It is cooled to room temperature after the reaction was completed, the hydrogen that concentration is 25wt.% is added dropwise
It is 6.5 that aqueous solution of sodium oxide, which is neutralized to pH value, obtains high bound starch slurry.
Embodiment 4
A kind of high bound starch slurry, the dosage of catalyst is increased relative to embodiment 3, and preparation includes following step
It is rapid:
(1) extracting corn starch (moisture content 14%) 300g is placed in the irradiation of 60Co- γ irradiation field, and irradiation dose 40kGy adds
The water for entering to irradiate 9 times of weight of powder is put in glass reaction kettle, leads to nitrogen protection, and temperature rises to 95 DEG C from room temperature, is gelatinized 30 points
Clock, and keep the temperature 30 minutes and obtain gelatinized starch；
(2) take monomer 700g (vinylacetate 550g, acrylic acid 150g) and azo-bis-iso-dimethyl 3g in 69 DEG C
Polymerization reaction 40 minutes in water-bath, lead to nitrogen protection, and speed of agitator 200rpm obtains copolymer；
(3) gelatinized starch of step (1) is cooled to 55 DEG C and copolymer is uniformly mixed, it is 6wt.% that concentration, which is then added dropwise,
Ammonium ceric nitrate aqueous solution catalysis graft copolymerization (contain ammonium ceric nitrate 17g), control drips off in 2h, the logical nitrogen protection of whole process,
Speed of agitator 300rpm, reacts 2h again after being added dropwise；It is cooled to room temperature after the reaction was completed, the hydrogen that concentration is 25wt.% is added dropwise
It is 6.8 that aqueous solution of sodium oxide, which is neutralized to pH value, obtains high bound starch slurry.
Embodiment 5
A kind of high bound starch slurry, has replaced azodiisobutyronitrile relative to embodiment 4, it is water-soluble to accelerate ammonium ceric nitrate
The rate of addition of liquid, preparation the following steps are included:
(1) extracting corn starch (moisture content 14%) 300g is placed in the irradiation of 60Co- γ irradiation field, and irradiation dose 40kGy adds
The water for entering to irradiate 9 times of weight of powder is put in glass reaction kettle, leads to nitrogen protection, and temperature rises to 95 DEG C from room temperature, is gelatinized 30 points
Clock, and keep the temperature 30 minutes and obtain gelatinized starch；
(2) take monomer 700g (vinylacetate 550g, acrylic acid 150g) and azodiisobutyronitrile 3g in 69 DEG C of water-baths
Middle polymerization reaction 40 minutes, leads to nitrogen protection, and speed of agitator 200rpm obtains copolymer；
(3) gelatinized starch of step (1) is cooled to 55 DEG C and copolymer is uniformly mixed, concentration, which is then added dropwise, is
The ammonium ceric nitrate aqueous solution catalysis graft copolymerization (containing ammonium ceric nitrate 17g) of 5.5wt.%, control is dripped off in 1.5h, and whole process is logical
Nitrogen protection, speed of agitator 300rpm, reacts 2h again after being added dropwise；It is cooled to room temperature after the reaction was completed, concentration, which is added dropwise, is
It is 6.5 that the sodium hydrate aqueous solution of 25wt.%, which is neutralized to pH value, obtains high bound starch slurry.
The high bound starch slurry sample prepared to the embodiment of the present invention 1~5 is tested for the property:
Adhesion strength test: high bound starch slurry prepared by the embodiment of the present invention 1~5 is dissolved in water according to 1% concentration
In, it is configured to 5 parts of solution；It heats, stirs evenly in 95 DEG C of thermostat water bath respectively.After 0.5h, start sizing；It selects respectively
With pure cotton dandy roving and polyester-cotton blend dandy roving.It is lightly wound on metal framework, yarn external force is not given during yarn, to
With test rove item number at least 30 every time.
Ready sample is immersed in well-done slurries, manual time-keeping is pressed, impregnates 5min (in order to make rove starching
Uniformly, just, each dipping 2.5min) when, frame is taken out, naturally dry is hung, the water of rove item is kept in dry process
It is flat；The pure cotton dried and polyester-cotton blend rove item are carefully cut, separately in case test in valve bag.The present invention uses
The adhesion strength of YG028 universal testing machine test sample, clamp distance 50mm, tensile speed 100mm/min, concrete outcome are shown in
Table 1.
Serous coat flexility test: by the embodiment of the present invention 1~5 prepare high bound starch slurry be configured to 3% it is molten
Liquid, water-bath under conditions of 95 DEG C, mashing off 1.5h；50 DEG C are cooled to after slurries are cooked, pour mask at room temperature naturally cools to
Film molding；Serous coat is cut into uniform strip, guarantees that length is greater than 10cm, width is in 5mm or so.It is placed in constant temperature and humidity room
Balance is for 24 hours；With the thickness of every serous coat of vernier caliper measurement, (thickness, takes its average value as serous coat at every serous coat measurement three
Thickness).The present invention tests its breaking strength and elongation at break (sample holder distance on YG028 universal testing machine
100mm, decrease speed 500mm/min), every kind of serous coat is tested 30 times, its average value is calculated.
The breaking strength calculation formula of serous coat is as follows: serous coat breaking strength=serous coat ultimate strength/(serous coat average thickness *
5mm), concrete outcome is shown in Table 1.
The high bound starch slurry head film properties test of table 1
As a comparison, the present invention uses unmodified cornstarch raw material directly as slurry, using identical test
Method tests adhesion strength, and measuring unmodified cornstarch slurry is 65.9N to the adhesion strength of pure cotton, and the adhesion strength to polyester-cotton blend is
70.2N；PVA slurry on the market is generally 70~75N to the adhesion strength of pure cotton, and the adhesion strength to polyester-cotton blend is 100~115N.
By above embodiments and the data of table 1 it is found that changing in high bound starch slurry prepared by the embodiment of the present invention 1~5
The number-average molecular weight of property starch is in 1.2e5~3.5e5, grafting rate > 85%, test result is shown, provided by the invention high viscous
Attached starch size has a good adhesion strength to rove pure cotton and coarse sand polyester-cotton blend, and the breaking strength of the serous coat by being formed and
Elongation at break data, it can be seen that high bound starch slurry prepared by the embodiment of the present invention 1~5 also has preferably flexible
Property, is substantially improved in terms of adhesion strength compared to unmodified cornstarch, and can substitution for PVA slurry, it is more environmentally friendly excellent
Gesture.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of preparation method of high bound starch slurry, which comprises the following steps:
(1) add water gelatinization after cornstarch being carried out radiation treatment, obtain gelatinized starch；
(2) vinylacetate, acrylic acid and initiator are mixed and carries out polymerization reaction, obtain copolymer；
(3) copolymer, gelatinized starch and ammonium ceric nitrate aqueous solution are mixed and carries out graft copolymerization, obtained after adding alkali neutralization
To high bound starch slurry；
The limitation of the not no time sequencing of the step (1) and step (2).
2. preparation method according to claim 1, which is characterized in that the irradiation bomb of radiation treatment is in the step (1)60Co- γ, irradiation dose are 4~40kGy.
3. preparation method according to claim 1, which is characterized in that in the step (1) plus the amount of water is cornstarch
4~9 times of weight, the temperature of the gelatinization are 95~98 DEG C, and the time is 30~35min.
4. preparation method according to claim 1, which is characterized in that initiator is two isobutyl of azo in the step (2)
Dimethyl phthalate and/or azodiisobutyronitrile.
5. preparation method according to claim 1 or 4, which is characterized in that vinylacetate, propylene in the step (2)
The mass ratio of acid and initiator is 300~400:100:1~2.
6. preparation method according to claim 1, which is characterized in that the temperature of polymerization reaction is 69 in the step (2)
DEG C, the time is 30~50min.
7. preparation method according to claim 1, which is characterized in that copolymer and gelatinized starch in the step (3)
Mass ratio is 2.3~2.5:1.
8. preparation method according to claim 7, which is characterized in that ammonium ceric nitrate aqueous solution is dense in the step (3)
Degree is 4~6wt.%；The quality of ammonium ceric nitrate is the copolymer and cornstarch gross mass in the ammonium ceric nitrate aqueous solution
1.2~1.8%.
9. preparation method according to claim 8, which is characterized in that the temperature of graft copolymerization in the step (3)
It is 50~60 DEG C, the time is 3.5~4h.
10. the high bound starch slurry that any one of claim 1~9 preparation method is prepared.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111607966A (en) * | 2020-04-22 | 2020-09-01 | 山东宏业纺织股份有限公司 | Cotton fiber reinforcing agent |
| 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 |
| CN114351463A (en) * | 2021-12-20 | 2022-04-15 | 滁州天鼎丰非织造布有限公司 | Composite adhesive, application thereof, scour-dispersion-prevention water-filtration non-woven fabric and preparation method thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111607966A (en) * | 2020-04-22 | 2020-09-01 | 山东宏业纺织股份有限公司 | Cotton fiber reinforcing agent |
| CN111607966B (en) * | 2020-04-22 | 2022-08-26 | 山东宏业纺织股份有限公司 | Cotton fiber reinforcement method using fiber reinforcement agent |
| 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 |
| CN114351463A (en) * | 2021-12-20 | 2022-04-15 | 滁州天鼎丰非织造布有限公司 | Composite adhesive, application thereof, scour-dispersion-prevention water-filtration non-woven fabric and preparation method thereof |
| CN114351463B (en) * | 2021-12-20 | 2023-10-31 | 滁州天鼎丰非织造布有限公司 | Composite adhesive, application thereof, anti-water-scattering filter nonwoven fabric and preparation method thereof |
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Application publication date: 20190709 |