CN101058647A - Method of preparing modified starch composition - Google Patents

Method of preparing modified starch composition Download PDF

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Publication number
CN101058647A
CN101058647A CN 200710049242 CN200710049242A CN101058647A CN 101058647 A CN101058647 A CN 101058647A CN 200710049242 CN200710049242 CN 200710049242 CN 200710049242 A CN200710049242 A CN 200710049242A CN 101058647 A CN101058647 A CN 101058647A
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paper
acid amides
add
charged ion
starch
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CN100572434C (en
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汪春江
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Sichuan spring Paper Technology Co., Ltd.
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NEIJIANG CHUNJIANG PAPER INDUSTRY Co Ltd
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Abstract

The invention discloses a making method of starch composition of retention reinforcer in the paper making course, which comprises the following steps: fatting; ionizing; ripening; improving the fiber and fill retention rate as well as the physical strength and surface property of paper.

Description

A kind of preparation method of modified starch composition
Technical field
The present invention relates to a kind of preparation method who improves fiber, filler retention, improves the auxiliary agent of paper physical intensity and paper surface properties that is applicable to, especially in papermaking, be used as that kind of starch preparation of compositions method of fortifier.
Background technology
The application of papermaking chemical product is to the benefit that improves paper industry and improve the quality of products significant.China is papermaking big country, but China's paper industry raw material is based on grass fiber.The characteristics of grass fiber are that staple length is short, intensity is low, cause the low and high-grade paper of can not manufacturing paper with pulp of fiber utilization rate in the pulping and papermaking processes.Therefore, to have a papermaking chemical product of specific function significant to China's paper industry in development and application.In paper, Mierocrystalline cellulose is made the pulp suspension thing, then paper pulp is placed screen cloth to make fibre orientation and filters liquid, and through behind the screen cloth, paper further reduces moisture content in the between centers extruding, has just become paper through last drying again.Typically, the paper that fresh paper pulp makes is than the paper of the equal in quality paper intensity height that makes of slurrying again, and the intensity of every circulation primary paper will reduce, and therefore, people have found the additive that increases paper strength.Know, by being that the wet end of paper technology adds additive and can increase strength of paper in paper pulp.Can use starch or poly-hydroxy high molecular polymer as filler or caking agent, usually, by adding ionic group these molecules be carried out modification, thereby increase cementability.
Starch based is frequently used in paper industry as paper making additive, and progressively become second largest raw material in the paper production, all kinds of starch based auxiliary agents of the annual consumption of whole world paper-making industry have reached ten million ton, in paper industry, it is main that what use is ative starch, yin, yang ion type starch and amphoteric starch, but commonly used be cationic starch and amphoteric starch.Such as.In the paper making additive that wet end of machine uses, retention aid can improve filler retention, reduce the slurry consumption; Flocculating aids can improve sheet drainage, reduce cylinder air pressure in the paper making, cut down the consumption of energy, and creates conditions for improving paper machine speed; Flocculation agent can reduce the fiber that runs off in the plain boiled water, and toughener then can improve the physical index of paper;
But the usually mutual contradiction of the effect of above-mentioned various chemical assistants for example is the treated starch as fortifier, and the effect of retention and flocculation is good more, and keeping of filler and fiber fines is just high more, and these have disadvantageous effect to strength of paper.Enhancing and retention sometimes are a pair of paradox, in the time of enhanced, all be attended by the appearance of retention function, strengthen to such an extent that mechanism is to increase hydrophilic point or binding site, so generation along with above-mentioned phenomenon, cohesion begins to take place, will produce certain retention effect, when the retention effect was excessive, fiber fines of keeping and filler particles increased, reduced the mean length of fiber, when improving intensity and retention, its tearability can a bit be transferred at certain, and is on a declining curve, so enhancing and retention only can reach the enhanced purpose when tearability does not take place significantly to descend.
For many years, the contradiction used of fortifier is that retention can not help filter, help the filter can not enhanced contradiction.This contradiction is perplexing the technician of paper industry always, still, up to now, does not have the people that this was proposed the scheme of solution as yet.
Summary of the invention
The preparation method who the objective of the invention is to overcome the shortcoming of above-mentioned prior art and a kind of fortifier is provided, the starch composites that adopts this method preparation can also improve the physical strength and the surface property of paper simultaneously except improving effectively fiber, the filler retention.
The object of the present invention is achieved like this:
1) fatization: to water content is to add in 10% the flour starch to be equivalent to the salt of starch weight 5-10%, the soda ash of 5-10%, the colophonium powder of 0.3-0.7%, mix slowly heating of back, be warmed up to 70-80 ℃ in 1-1.5 hour, isothermal reaction 1-3 hour, esterification reaction finished;
2) ionization: add the urea powder that is equivalent to starch weight 8-12% in the mixture after esterification reaction finishes, add negatively charged ion acid amides liquid that is equivalent to starch weight 8-12% and the positively charged ion acid amides liquid that is equivalent to starch weight 8-12% after mixing again, stirring is warming up to 80-95 ℃, reacted 3-4 hour, ion reaction finishes;
3) slaking: in the composition that ion reaction finishes, feed hydrogen, keep hydrogen pressure, after slaking 1-3 hour, reduce to normal temperature and promptly get modified starch composition at 0.1-0.2MPa.
Need to prove that above-mentioned preparation process is all carried out in closed reactor.
The modified starch composition that adopts the present invention to make, the use in papermaking is the same with routine, still needs earlier through dilution use after the gelatinization, being about to 5 parts of modified starch compositions joins in 95 parts of clean waters, have stir and the reactor of heating unit in thorough mixing, make it to form outstanding mix body after, slowly heat again, be heated to after temperature is 85-90 ℃, stop to stir and heating, left standstill slaking 15-30 minute, thermalization finishes, with about this liquid thin up to 2%, can use.
The present invention has following advantage than background technology:
Adopt the modified starch composition of method provided by the invention preparation, flucculation structure is firm, anti-shearing force is strong, and cohesive force height more is not subjected to stock pump and torrent to kick a little influence, compensation effect harmony.The component diversification contains the various active group, by charge ion effect and bridging function, take complete little super coacervation, make the hemicellulose in the paper pulp, wandering fibre graft copolymerization, it is bonding that filler particles and fiber are at first flocculated, form reticulated structure, thereby improved the mean value of staple length, not only improved keeping of fiber fines and filler effectively, avoided running off, also improved simultaneously the physical strength of paper effectively, improved the visual appearance of paper, reduced cost significantly, reduced consuming.And reduced suspended substance, and reduced environmental pollution, can reduce long stapled consumption, improve the drainage effect, reduce brachycephaly.
Embodiment
Be the detailed description that the present invention is carried out below, but these examples can not limit the present invention's scope required for protection.
Embodiment 1:
1) fatization: the colophonium powder of mistake 100 mesh sieves that in water content is the mealy corn starch of 10% 700 weight parts, adds soda ash, 2.1 weight parts of salt, 35 the weight part of 35 weight parts, mix slowly heating of back, in 1 hour, be warmed up to 70 ℃, isothermal reaction 1 hour, esterification reaction finishes;
2) ionization: the urea powder that adds 56 weight parts in the mixture after esterification reaction finishes, the negatively charged ion acid amides liquid that contains activeconstituents 60% and the positively charged ion acid amides liquid that contains activeconstituents 60% that is equivalent to starch weight 56 weight parts that add 56 weight parts after mixing again, stirring is warming up to 80 ℃, reacted 3 hours, ion reaction finishes;
3) slaking: feed hydrogen in the composition that ion reaction finishes, keep hydrogen pressure at 0.1MPa, slaking was reduced to normal temperature and is promptly got modified starch composition after 3 hours;
Above-mentioned preparation process is all carried out in closed reactor.
After according to preceding method this modified starch composition being prepared into 2% the aqueous solution, make an addition in the paper-making process according to ordinary method, be about to dilute the paper pulp that configures and deliver in the paper machine, add the aqueous solution of this modified starch composition, net filter then, dehydration, squeezing are drying to obtain paper.
In order to demonstrate,prove the retention enhancement of this modified starch composition, according to different modified starch composition add-ons, the 70g/m that adopts aforesaid method to make 2Common writing paper, the result is as follows:
Treated starch add-on (kg/t paper) Substance (g/m 2) Whiteness (%) Become paper ash part (%) Fracture length (m)
0 70.1 78 12.5 2720
8 72.0 79 15.6 3070
12 72.5 81 16.3 3120
20 72.7 81.8 18.4 3270
As can be known from the above table, add modified starch composition deeply after, it becomes paper whiteness to improve, ash has improved 6.2 percentage points at most, and fracture length is up to 3270m, and more the added-time has not been improved 520m, can improve about 19%, illustrate that this modified starch composition has higher retention and enhancement simultaneously.
Embodiment 2:
1) fatization: soda ash, 4.9 weight parts that in water content is the powdery tapioca (flour) of 10% 700 weight parts, add salt, 70 the weight part of 70 weight parts cross 100 mesh sieves colophonium powder, mix slowly heating of back, in 1.5 hours, be warmed up to 80 ℃, isothermal reaction 3 hours, esterification reaction finishes;
2) ionization: the urea powder that adds 84 weight parts in the mixture after esterification reaction finishes, the negatively charged ion acid amides liquid that contains activeconstituents 60% and the positively charged ion acid amides liquid that contains activeconstituents 60% that is equivalent to starch weight 84 weight parts that add 70 weight parts after mixing again, stirring is warming up to 95 ℃, reacted 4 hours, ion reaction finishes;
3) slaking: feed hydrogen in the composition that ion reaction finishes, keep hydrogen pressure at 0.2MPa, slaking was reduced to normal temperature and is promptly got modified starch composition after 1 hour;
Above-mentioned preparation process is all carried out in closed reactor.
After according to preceding method this modified starch composition being prepared into 2% the aqueous solution, make an addition in the paper-making process according to ordinary method, be about to dilute the paper pulp that configures and deliver in the paper machine, add the aqueous solution of this modified starch composition, net filter then, dehydration, squeezing are drying to obtain paper.
In order to demonstrate,prove the retention enhancement of this modified starch composition, according to different modified starch composition add-ons, the fluting board that adopts aforesaid method to make, wherein, it is raw material that paper pulp adopts waste and old boxboard, the result is as follows:
Treated starch add-on (kg/t paper) Substance (g/m 2) Ring crush index (N, m/g) Fracture length (m)
0 136 78 2250
10 141 79 2780
20 142 81 3065
As can be known from the above table, after adding modified starch composition deeply, its ring crush index has improved 1.35N, m/g, fracture length is up to 3270m, and more the added-time has not been improved 815m, improved 25% and 36% respectively, its intensity improves very obvious, and when utilizing waste and old regeneration fluting board, this modified starch composition still has higher retention and enhancement simultaneously.
Embodiment 3:
1) fatization: soda ash, 3.3 weight parts that in water content is the mealy corn starch of 10% 700 weight parts, add salt, 50 the weight part of 50 weight parts cross 100 mesh sieves colophonium powder, mix slowly heating of back, in 1.5 hours, be warmed up to 75 ℃, isothermal reaction 2 hours, esterification reaction finishes;
2) ionization: the urea powder that adds 75 weight parts in the mixture after esterification reaction finishes, the negatively charged ion acid amides liquid that contains activeconstituents 60% and the positively charged ion acid amides liquid that contains activeconstituents 60% that is equivalent to starch weight 60 weight parts that add 65 weight parts after mixing again, stirring is warming up to 90 ℃, reacted 3 hours, ion reaction finishes;
3) slaking: feed hydrogen in the composition that ion reaction finishes, keep hydrogen pressure at 0.2MPa, slaking was reduced to normal temperature and is promptly got modified starch composition after 1 hour;
Above-mentioned preparation process is all carried out in closed reactor.
After according to preceding method this modified starch composition being prepared into 2% the aqueous solution, make an addition in the paper-making process according to ordinary method, be about to dilute the paper pulp that configures and deliver in the paper machine, add the aqueous solution of this modified starch composition, net filter then, dehydration, squeezing are drying to obtain paper.
In order to demonstrate,prove the retention enhancement of this modified starch composition, according to different modified starch composition add-ons, the 50g/m that adopts aforesaid method to make 2Double gummed paper, wherein, it is raw material that paper pulp adopts bamboo, the result is as follows:
Treated starch add-on (kg/t paper) Substance (g/m 2) Whiteness (%) Tear index (m.N.m/g) Degree of resistance to demolition (inferior) Fracture length (m) Smoothness (S)
0 52.0 89 5.44 16 3676.7 3067.7
10 54.0 89 5.40 24 4049 3653.4
15 54.5 89.1 5.39 27 4252 3650
20 55.0 89.3 5.30 32 4350 3752
As can be known from the above table, after adding modified starch composition deeply, its Substance increases to some extent, tear index is constant substantially, and degree of resistance to demolition significantly improves, and has overcome bamboo pulp and has given birth to the crisp weakness that easily splits off, its fracture length is up to 3270m, more the added-time has not been improved 18%m, and it is poor to have changed one-tenth paper two sides, has proved that this modified starch composition has the effect of improving into the paper surface property.
Embodiment 4:
1) fatization: soda ash, 2.9 weight parts that in water content is the mealy corn starch of 10% 700 weight parts, add salt, 55 the weight part of 55 weight parts cross 100 mesh sieves colophonium powder, mix slowly heating of back, in 1.5 hours, be warmed up to 70 ℃, isothermal reaction 2 hours, esterification reaction finishes;
2) ionization: the urea powder that adds 70 weight parts in the mixture after esterification reaction finishes, the negatively charged ion acid amides liquid that contains activeconstituents 60% and the positively charged ion acid amides liquid that contains activeconstituents 60% that is equivalent to starch weight 70 weight parts that add 70 weight parts after mixing again, stirring is warming up to 85 ℃, reacted 3 hours, ion reaction finishes;
3) slaking: feed hydrogen in the composition that ion reaction finishes, keep hydrogen pressure at 0.2MPa, slaking was reduced to normal temperature and is promptly got modified starch composition after 1 hour;
Above-mentioned preparation process is all carried out in closed reactor.
After according to preceding method this modified starch composition being prepared into 2% the aqueous solution, make an addition in the paper-making process according to ordinary method, be about to dilute the paper pulp that configures and deliver in the paper machine, add the aqueous solution of this modified starch composition, net filter then, dehydration, squeezing are drying to obtain paper.
In order to demonstrate,prove the retention enhancement of this modified starch composition, according to different modified starch composition add-ons, the 70g/m that adopts aforesaid method to make 2Bamboo pulp kraft paper, wherein, it is raw material that paper pulp adopts bamboo, the result is as follows:
Treated starch add-on (kg/t paper) Substance (g/m 2) Bursting strength (kpa) Tearability (Mn) Degree of resistance to demolition (inferior)
0 68 190 450 18
8 70 235 440 30
10 71 256 425 43
As can be known from the above table, after adding modified starch composition deeply, its Substance increases to some extent, illustrate that retention improves, bursting strength and degree of resistance to demolition significantly improve, overcome bamboo pulp and given birth to the crisp weakness that easily splits off, proved that this modified starch composition has good retention and the effect of improving into the paper surface property.

Claims (4)

1, a kind of preparation method of modified starch composition is characterized in that carrying out as follows:
1) fatization: to water content is to add in 10% the flour starch to be equivalent to the salt of starch weight 5-10%, the soda ash of 5-10%, the colophonium powder of 0.3-0.7%, mix slowly heating of back, be warmed up to 70-80 ℃ in 1-1.5 hour, isothermal reaction 1-3 hour, esterification reaction finished;
2) ionization: add the urea powder that is equivalent to starch weight 8-12% in the mixture after esterification reaction finishes, add negatively charged ion acid amides liquid that is equivalent to starch weight 8-12% and the positively charged ion acid amides liquid that is equivalent to starch weight 8-12% after mixing again, stirring is warming up to 80-95 ℃, reacted 3-4 hour, ion reaction finishes;
3) slaking: in the composition that ion reaction finishes, feed hydrogen, keep hydrogen pressure, after slaking 1-3 hour, reduce to normal temperature and promptly get modified starch composition at 0.1-0.2MPa;
Above-mentioned preparation process is all carried out in closed reactor.
2, method according to claim 1 is characterized in that the positively charged ion acid amides liquid and the negatively charged ion acid amides liquid weight that add equate in the ion reaction process.
3, method according to claim 1 and 2 is characterized in that the active quantities of described positively charged ion acid amides liquid and negatively charged ion acid amides liquid is 60%.
4, method according to claim 1 is characterized in that described colophonium powder was the meal of 100 mesh sieves.
CNB200710049242XA 2007-06-05 2007-06-05 A kind of preparation method of modified starch composition Expired - Fee Related CN100572434C (en)

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CN1064122A (en) * 1991-02-07 1992-09-02 江西省黎川县纸模工艺厂 The manufacture method of paper conic bobbin for cotton spinning
CN1073450A (en) * 1992-10-07 1993-06-23 王珍 The production method of soluble amphoteric starch and purposes
US6033525A (en) * 1997-10-30 2000-03-07 Moffett; Robert Harvey Modified cationic starch composition for removing particles from aqueous dispersions
US5928474A (en) * 1997-10-30 1999-07-27 E. I. Du Pont De Nemours And Company Modified starch composition for removing particles from aqueous dispersions
US5859128A (en) * 1997-10-30 1999-01-12 E. I. Du Pont De Nemours And Company Modified cationic starch composition for removing particles from aqueous dispersions
DE19832241A1 (en) * 1998-07-17 2000-01-27 Stockhausen Chem Fab Gmbh Modified starch used as retention aid in paper production, obtained by digesting starch material in water in presence of a cationic polymer based on dialkylaminoalkylacrylamide and a particulate mineral additive
CN1085278C (en) * 1999-07-27 2002-05-22 杭州市化工研究所 High-effective filter and retention aid for straw pulp for making paper
US6699363B2 (en) * 2001-11-13 2004-03-02 E. I. Du Pont De Nemours And Company Modified starch and process therefor
MXPA05009123A (en) * 2003-02-27 2006-03-08 Univ Maine Starch compositions and methods of making starch compositions.

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