CN106279447A - A kind of preparation method of the ultra-fine starch adhesive of papermaking coating graininess - Google Patents
A kind of preparation method of the ultra-fine starch adhesive of papermaking coating graininess Download PDFInfo
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- CN106279447A CN106279447A CN201610613702.6A CN201610613702A CN106279447A CN 106279447 A CN106279447 A CN 106279447A CN 201610613702 A CN201610613702 A CN 201610613702A CN 106279447 A CN106279447 A CN 106279447A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B31/00—Preparation of derivatives of starch
- C08B31/003—Crosslinking of starch
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B31/00—Preparation of derivatives of starch
- C08B31/003—Crosslinking of starch
- C08B31/006—Crosslinking of derivatives of starch
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- C—CHEMISTRY; METALLURGY
- 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
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J103/00—Adhesives based on starch, amylose or amylopectin or on their derivatives or degradation products
- C09J103/04—Starch derivatives
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/10—Coatings without pigments
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/36—Coatings with pigments
- D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
- D21H19/54—Starch
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
- D21H21/16—Sizing or water-repelling agents
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- C—CHEMISTRY; METALLURGY
- 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
- 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
-
- C—CHEMISTRY; METALLURGY
- 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
- C08J2303/00—Characterised by the use of starch, amylose or amylopectin or of their derivatives or degradation products
- C08J2303/04—Starch derivatives
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Biochemistry (AREA)
- Materials Engineering (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Paper (AREA)
Abstract
The present invention relates to pulp technology for making paper, disclose the preparation method of a kind of ultra-fine starch adhesive of papermaking coating graininess.It is characterized in that: with starch as raw material, with water or alcohol water mixed system as disperse medium, carry out extra-fine grinding with grinder, before selecting to grind simultaneously, in or rear three difference crosslinking Treatment, finally it is centrifuged, washs, is dried, obtain the ultra-fine starch granules being suitable for being coated with.When grinding with water for medium, dispersion liquid solid content 10～15%, during with alcohol-water mixture for medium, dispersion liquid solid content 15～20%；Mill pearl diameter 0.1～1.2mm；Turbine disk linear velocity 4～16m/s；Starch granules granularity size 100～300nm after grinding.Preparation method of the present invention is easy and simple to handle, and raw material sources are the most renewable, and products obtained therefrom particle diameter is little, and part substitutes styrene-butadiene latex and allocates that paint viscosity is low, rheological characteristic good into；Be conducive to alleviating styrene-butadiene latex resource scarcity pressure, contribute to reducing coating cost, alleviating carbon emission.
Description
Technical field
The present invention relates to a kind of preparation method of pulp technology for making paper, be specifically related to a kind of ultra-fine starch of papermaking paint
The preparation method of granule adhesive.
Background technology
In papermaking coating raw material, adhesive is most important ingredient.Determining the viscosity of coating, rheological characteristic, guarantor
Aqueous and aspect hardening time, it plays conclusive effect, the printing performance of coating paper is had important impact simultaneously.With
The development of paper coating processes, the kind of coating adhesive the most gradually occurs to change.Synthetic latex adhesive belongs to
Petroleum chemicals, resource is non-renewable, belongs to high carbon emission product, relatively costly；Be coated with starch source in crops Semen Maydis or
The raw materials such as potato starch, its resource is the most renewable, has low-carbon emission characteristic, and cost is relatively low；Therefore, in recent years, form sediment
Powder application in papermaking paint gets more and more.
At present, the starch used by coating mostly is modified starch, by powdery, water-fast starch at 80～90 DEG C during application
Under the conditions of gelatinizing, its concentration below 40%, 35～30% relatively conventional, seriously limit the raising of coating solids；It addition,
People apply discovery in practice, and the membership that adds of starch makes the high shear rheological behavior of coating be deteriorated, thus affect coating operating
Property；The coating of application coating starch is in coating paper dry run, and the starch dry shrinkage that rises of profit is serious, to sheet gloss and
Print gloss has large effect, also can produce flaw in printing etc.；Gelatinized starch mixes dispersion with pigment particles, does not has nanometer
Starch dispersion uniform, therefore, its application gained surface strength of paper is relatively low.
The starch another kind of application form in coating is biological latex.So-called biological latex, has two kinds to there is shape at present
Formula: liquid and powdery.Liquid bio latex is domestic have been applied, and it is the method by chemical modification, makes starch long-chain break
Split, then carry out certain crosslinking Treatment gained；This kind of biological latex 50% is admittedly the most relatively low containing viscosity, illustrates that its chain is disconnected serious；
Practice confirms: even if giving certain crosslinking Treatment, and the application of its Paper Coating is still very big on strength character impact, does not reaches external
ECO biogum breast performance level.External ECO biology latex is the nanoscale powdered granule starch that presently, there are, and it is to pass through spiral shell
The mode of rotation extruding, is aided with certain crosslinking, plasticising process (introducing method), and a kind of pre-gelatinized starch produced, its particle diameter is big
Little 50～150nm, and have the following characteristics that
(1) its adhesion strength performance is close to latex, and the adhesion strength of conventional coating starch is only the half of latex.
(2) having the viscosity characteristics similar with the class coating in latex, paper machine operation performance is stable；
(3) optical property and the printing performance etc. of paper can be improved, as the appearance of flaw in printing can be reduced.
(4) with reproducible if corn starch etc. is as raw material, wide material sources, price is cheaper than latex；
(5) can be the most water-soluble during application, it is not necessary to gelatinizing, solid content may be up to 40%.
Although ECO biology latex has the most preferably application performance, but owing to it is foreign patent product, at present
Domestic application price is higher, for the most domestic paper mill control cost relatively strict in the case of, extensively application is restricted.
Starch material carries out grainy treatment, and conventional method has spray drying method, high pressure alcohol method, normal temperature and pressure alcohol alkali
Method etc..Patent CN1076729 (application number 98126389.5) is referred to the preparation method of a kind of granular starch dissolvable in cold water.Should
The basic feature of method described in patent is: with 45～65 (weight) % alcoholic solution as suspending agent, add starch, solid content be 10～
25 (weight) %, adds solid alkali, and temperature of charge is 30～40 DEG C, carries out αization normal pressure and modifies 10～60 minutes, with in alkyd
Wash with rear alcoholic solution, be dried to obtain product.Its product cold water solubility can reach 95%.What above-mentioned patent proposed prepares granule
The method not mentioned starch granules granularity size of shape starch dissolvable in cold water, and it is mainly used in food, medicine, cosmetics etc.
In industry, product level is higher, price is high, is not suitable for applying in papermaking paint.
Publication " application in art paper topcoating of the cold water soluble coating starch " (paper and papermaking .2013,32 (9):
50-54.) proposing, domestic manufacturer utilizes biomass starch for raw material, gives birth to through chemistry and micronization modification
Output cold water soluble coating starch, its granular size is distributed in 100～200nm scopes more, and sample is powdered, moisture
12%, cold water soluble is preferable, it is possible in dry powder form with pigment common distribution dispensing.But this paper is not mentioned or teaching
Concrete production technology, and in paper to the Application research of product also only in laboratory aspect, the production practices of serialization do not have
Relate to.
Patent CN103496151 (application number 201310468623.7) discloses the system of a kind of papermaking coating nano-starch
Preparation Method.Described in this patent, method basic feature is: starch material passes through twin (double) screw extruder (ten with the mixed dispersion liquid of auxiliary agent
Two joint cylinders) extruding, at protelum cylinder, inject cross-linking agent with liquid spray gun, by extruder discharging opening after material extruding,
Again drying, cool down, pulverize after obtain be coated with nano-starch.This invents coating nano-starch mean diameter 50-obtained
250nm, even particle size distribution, and there is the features such as solid content is high, viscosity is low, good fluidity, cohesion are strong, easy to use, can
Substitute the styrene-butadiene latex of 30-60%, improve paper performance, reduce cost, beneficially environmental protection.Above-mentioned prepare nano-starch method be
By the way of screw extrusion, extrusion process adds cross-linking agent.
Summary of the invention
It is an object of the invention to provide the preparation method of a kind of ultra-fine starch adhesive of papermaking coating graininess, pass through
The method of mechanical lapping obtains the crystal granular starch of super-refinement, this crystal granular starch can directly with pigment mixing split batch charging, use
Synthetic latex in part substitutes coating；This technical method is easy and simple to handle, and products obtained therefrom particle diameter is little, joined paint viscosity is low,
Rheological characteristic is good, adapts to coating large arch dam and the requirement of high speed coating machine.In order to realize this purpose, adopt the following technical scheme that:
(1) with ative starch or modified starch as base material, it is aided with enzyme pretreatment and crosslinking Treatment, under agitation, with water
Or water is abrasive media with ethanol system, using grinder to carry out mechanical lapping, the ultra-fine starch granules granularity size obtained can
Reach 100～300nm, the most concentrated, washed, obtain product after drying.
(2) above-mentioned raw materials used in, ative starch can be corn starch, tapioca, potato starch；Modified starch can
To be esterification starch, Oxytarch, pre-gelatinized starch.
(3) first carry out suitable enzyme pretreatment before starch ground, Starch Fraction chain rupture can be made, to crosslinking and grinding be all
Favourable.Enzyme pretreatment condition: temperature is 30～40 DEG C, pH value 6～10, amylase consumption 0.1%～1%, pretreatment time
0.5h。
(4) method of crosslinking Treatment is divided into three kinds according to the difference of crosslinking time point: the first is that before grinding, crosslinking is located in advance
Reason, general choosing is after the enzymatic treatment；The second is to grind 1～2h, starch certain chain rupture, exposes more polyhydroxy, at this moment
Add cross-linking agent to cross-link, be then further continued for being ground to target particles size；The third is to grind to reach after granularity requirements again
Cross-link.
(5) mechanical lapping used medium has two kinds of selections: aqueous systems or water and ethanol mixed system；When abrasive media is water
Time, starch dispersion is liquid-solid contains 10～15%；When abrasive media is water and ethanol mixed system, starch dispersion is liquid-solid containing up to 15
～20%.
(6) with grinder, starch carried out mechanical lapping, grinder turbine disk linear velocity 4～16m/s, grinding pressure 0.1
～0.4bar, temperature 10～20 DEG C, screen cloth mesh 0.13mm or 0.4mm, grinding bead diameter 0.1～1.2mm.
(7) cross-linking agent used by crosslinking Treatment grinding different time points has esterification class and the crosslinking of etherification reaction class
Agent.
(8) needed for starch ground reaches ultra-fine grain size requirements, milling time is 2～5h；During with ative starch for raw material,
Milling time is relatively long；On the contrary, during with modified starch for raw material, milling time is relatively short.
(9) concentration of products obtained therefrom after grinding, washing use high speed rotating centrifuge to carry out, rotating speed 3500～4000r/
Min, the time 10～20min；Being dried of product is carried out in an oven, temperature 45～50 DEG C, the time 3～6h.
The ultra-fine starch granules that the present invention is prepared with polishing and pigment mixing split batch charging, part substitutes synthetic latex,
Preferable application performance can be reached.As good in coating water retention, viscosity is low, ways and methods such as optical property keeps good, strong
Degree stable performance.This application with ultra-fine starch granules part replacement petrochemical industry latex both can alleviate the pressure of resource scarcity, again
Coating cost can be reduced；Meanwhile, the exploitation of ultra-fine starch granules and application have adapted to the idea of development of low-carbon economy, have the biggest
Development prospect.
Detailed description of the invention
In conjunction with embodiment, the invention will be further described, but is not limited with embodiment.
Embodiment 1
First carry out native cornstarch cross-linking pretreatment.Weigh a certain amount of starch, be added to the water the dispersion making 40%
Liquid, adds the anhydrous Na of 3% (relative starch oven-dry weight) in advance in water2CO3Make protective agent, add a certain amount of NaOH regulation simultaneously
Dispersion liquid pH, between 10～11, adds the cross-linking agent of 5% (relative starch oven-dry weight), stirs continuously in 50 DEG C of thermostat water baths
Mixing reaction 3h, reaction terminates to neutralize and sucking filtration, washing, finally pulverizes filter cake and is dried, to be ground.
Grinder loads mill pearl, grinds pearl diameter 0.4mm, and mill pearl material ratio is 4: 1, connects feed liquid circulation line, by above-mentioned
Starch after crosslinking, with water as medium, is configured to the dispersion liquid that starch solids is 15%, and grinder rotating speed is 9m/s, pressure
0.2～0.4bar, temperature 15～20 DEG C, continuously grinding 5h, D50 granularity is 238nm, low-shear viscosity be 307cps (20 DEG C,
60rpm)；After grinding, dispersion liquid is with 4000r/min speed rotating centrifugal, and washs with ethanol replacement several times, dried
To product.
Embodiment 2
Starch crosslinking preprocess method as described in specific embodiment 1, except for the difference that raw material is modified starch, cross-linking reaction
Time is 6h.
Grinder loads mill pearl, grinds pearl diameter 0.4mm, and mill pearl material ratio is 4: 1, connects feed liquid circulation line, by above-mentioned
Esterification modification starch after crosslinking makes, for medium, the dispersion liquid that solid content is 14% with water, and grinder rotating speed is 9m/s, pressure
0.15～0.25bar, temperature 12～18 DEG C, continuously grinding 2h, D50 granularity is 167nm, low-shear viscosity be 228cps (20 DEG C,
60rpm)；After grinding, dispersion liquid is with 4000r/min speed rotating centrifugal, and washs with ethanol replacement several times, dried
To product.
Embodiment 3
Starch crosslinking pretreatment mode is with the process in embodiment 2.
Grinder loads mill pearl, grinds pearl diameter 0.4mm, and mill pearl material ratio is 4: 1, connects feed liquid circulation line, by above-mentioned
Esterification modification starch after crosslinking, to make, for medium, the dispersion liquid that solid content is 20% containing the alcohol-water solution of 20% ethanol, grinds
Machine rotating speed is 9m/s, pressure 0.15～0.4bar, temperature 15～20 DEG C, and continuously grinding 2h, D50 granularity is 198nm, and low sheraing sticks
Degree is 146cps (20 DEG C, 60rpm)；After grinding, dispersion liquid is with 4000r/min speed rotating centrifugal, and puts with ethanol several times
Change clothes and wash, obtain product after drying.
Embodiment 4
Weigh a certain amount of esterification modification starch and make, for medium, the dispersion liquid that starch solids is 12% with water, such as above-mentioned reality
Execute grinding condition listed by example to be ground；As continuously grinding 1h, midway adds 5% (relative starch over dry in grinding system
Amount) cross-linking agent, agitation cycle reaction 0.5h, continue grind 1h, measure D50 granularity be 161nm, low-shear viscosity is 178cps
(20 DEG C, 60rpm)；After grinding, dispersion liquid is with 4000r/min speed rotating centrifugal, and washs with ethanol replacement several times, dry
Product is obtained after dry.
By above-mentioned prepared products application in coating, after tested, coating and ways and methods index are as shown in the table.Warp
Contrast finds, makes ultra-fine starch granules by oneself and has good coating water retention energy, adds the formula coating paper of ultra-fine starch granules
Performance such as print gloss and picking speed are all good than the formula adding conventional coating starch and domestic biological latex, and add
The performance formula adding ECO particular biological latex is close.As can be seen here, ultra-fine starch granules has a good application prospect.
The performance formula that the different adhesive part of table 1 substitutes latex compares
Note: 1# coating is whole latex system
2# coating is that 2 parts of ultra-fine starch granuless substitute 2 parts of latex
3# coating is that 2 parts of conventional coating starch substitute 2 parts of latex
4# coating is that 2 parts of domestic biological latex substitute 2 parts of latex
5# coating is that 2 parts of ECO biology latex substitute 2 parts of latex.
Claims (9)
1. the papermaking coating preparation method of ultra-fine starch granules, it is characterised in that with ative starch or modified starch as base
Material, is aided with enzyme pretreatment and crosslinking Treatment, under agitation, with water or water with ethanol system as abrasive media, use and grind
Machine carries out mechanical lapping, and the granule size of the ultra-fine starch granules of gained can reach 100～300nm, concentrated, washed, be dried
To product.
The papermaking coating the most according to claim 1 preparation method of ultra-fine starch granules, it is characterised in that ative starch bag
Include corn starch, tapioca, potato starch；Modified starch includes esterification starch, Oxytarch, pre-gelatinized starch.
The papermaking coating the most according to claim 1 preparation method of ultra-fine starch granules, it is characterised in that enzyme pretreatment
Temperature is 30～40 DEG C, pH value 6～10, amylase consumption 0.1%～1%, pretreatment time 0.5h.
The papermaking coating the most according to claim 1 preparation method of ultra-fine starch granules, it is characterised in that crosslinking Treatment
Method be divided into three kinds by the time point difference selecting crosslinking, be respectively before grinding in crosslinking pretreatment, process of lapping at crosslinking
Reason and grinding reaches after granularity requirements crosslinking Treatment again.
The papermaking coating the most according to claim 1 preparation method of ultra-fine starch granules, it is characterised in that grind and select
Medium be aqueous systems or water and ethanol mixed system；When abrasive media is water, starch dispersion is liquid-solid containing being 10～15%；When
When abrasive media is water and ethanol mixed system, starch dispersion is liquid-solid containing up to 15～20%.
The papermaking coating the most according to claim 1 preparation method of ultra-fine starch granules, it is characterised in that use grinder
Starch is carried out mechanical lapping, grinder turbine disk linear velocity 4～16m/s, grinding pressure 0.1～0.4bar, temperature 10～20
DEG C, screen cloth mesh 0.13mm or 0.4mm, grinding bead diameter 0.1～1.2mm.
The papermaking coating the most according to claim 1 preparation method of ultra-fine starch granules, it is characterised in that crosslinking Treatment
Cross-linking agent used has esterification class and etherification reaction class cross-linking agent.
The papermaking coating the most according to claim 1 preparation method of ultra-fine starch granules, it is characterised in that starch ground
Needed for reaching ultra-fine grain size requirements, milling time is 2～5h.
The papermaking coating the most according to claim 1 preparation method of ultra-fine starch granules, it is characterised in that product dense
Contracting, washing use high speed rotating centrifuge to carry out, rotating speed 3500～4000r/min；Being dried of product is carried out in an oven, temperature
45～50 DEG C.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108018739A (en) * | 2017-12-14 | 2018-05-11 | 广东省造纸研究所 | A kind of nano-starch adhesive and preparation method thereof |
| CN112439538A (en) * | 2020-10-16 | 2021-03-05 | 中南林业科技大学 | Method for separating starch with different particle sizes |
| CN112482083A (en) * | 2020-11-24 | 2021-03-12 | 中国制浆造纸研究院有限公司 | Starch-based compound capable of improving oil resistance of paper |
| US11525217B2 (en) | 2019-12-17 | 2022-12-13 | Westrock Mwv, Llc | Coated paper and paperboard structures |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108018739A (en) * | 2017-12-14 | 2018-05-11 | 广东省造纸研究所 | A kind of nano-starch adhesive and preparation method thereof |
| US11525217B2 (en) | 2019-12-17 | 2022-12-13 | Westrock Mwv, Llc | Coated paper and paperboard structures |
| CN112439538A (en) * | 2020-10-16 | 2021-03-05 | 中南林业科技大学 | Method for separating starch with different particle sizes |
| CN112439538B (en) * | 2020-10-16 | 2022-08-05 | 中南林业科技大学 | Method for separating starch with different particle sizes |
| CN112482083A (en) * | 2020-11-24 | 2021-03-12 | 中国制浆造纸研究院有限公司 | Starch-based compound capable of improving oil resistance of paper |
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