CN103696320B - A kind of preparation technology of oxidative cationic size-press starch - Google Patents
A kind of preparation technology of oxidative cationic size-press starch Download PDFInfo
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Abstract
The present invention discloses a kind of preparation technology of oxidative cationic size-press starch, it is characterized in that, tapioca is with after oxidizing, and the molecule of oxidized starch generates carbonyl, meanwhile, has also caused polymerisation of dissociating; Cationic starch is that oxidized starch and quaternary ammonium salt cationic chemical reagent (chloro-2 hydroxypropyl-trimethyl ammonium chlorides of 3-) carry out etherification reaction generation in the basic conditions; By recombination reaction, namely starch oxidation reaction and etherification reaction combine, and obtain oxidation quaternary ammonium cation starch; Production process adopts the pollution-free dry process of vacuum; The oxidation quaternary ammonium cation starch of different viscosities, different degree of substitution, i.e. oxidative cationic size-press starch can be synthesized by the ratio of adjustment starch, oxidant, etherifying agent three.Non-wastewater discharge of the present invention, environmental protection, properties of product are stablized, and can meet high-speed paper machine applying glue requirement, paper product steady quality, can substitute inlet surface size-press starch completely, and can reduce paper cost.
Description
Technical field
The invention belongs to field of fine chemical, relate to the agent of a kind of paper grade (stock) oxidative cationic starch surface sizing, particularly a kind of preparation technology of oxidative cationic size-press starch.
Background technology
Along with paper products are to superior, diversified future development, improving constantly of paper machine speed, proposes higher thinner functionalization requirement to converted starch.Size-press starch is the kind that in papermaking converted starch, quality requirement is higher, China for the research and development starting comparatively external evening of New Modified Starch, although and traditional size-press starch is of a great variety, there is many deficiencies in quality.Such as: Acid denaturation, oxidized starch adopt wet method acidifying, oxidative deformation, and the film forming of its product, mobility, adhesion strength, stability are all not ideal enough, and affect applying glue operation, the applying glue requirement of high-speed paper machine can not be met.Along with the development of large high-speed paper machine, size-press starch is proposed to the requirement updated, and oxidative cationic starch is also known as oxidative cationic size-press starch, this novel modified starch is just obtaining the concern of paper industry with the performance of its good stable, and will become one of Research Emphasis of environment friendly and pollution-free size-press starch of new generation.But whole dependence on import before this series products, as the A55 series size-press starch etc. of the 78-8088 series size-press starch of national of the United States Starch Company, Dutch AVEBE company, the only import volume of 2010 more than 40,000 tons nearby.
When paper industry is increasingly competitive, improves raw material class and quality, guarantee its serviceability and stability thereof, active demand that reduction paper cost has become paper industry.If the production domesticization realizing vacuum dry process production oxidative cationic starch is significant, the wide market space will be had.
But the oxidative cationic starch of vacuum dry process is still in the starting stage of research in China, temporarily also do not see there is relevant launch products, the particularly domestic bibliographical information having no employing vacuum dry process suitability for industrialized production oxidative cationic starch.Country does not also formulate relevant national standard or industry standard with regard to this series products.Therefore, significant for adopting the technological development of vacuum dry process suitability for industrialized production oxidative cationic starch.
Summary of the invention
The object of the invention is to select the tapioca of high-quality, oxidant, etherifying agent as raw material, adopt vacuum dry process reaction still production technology, through initial oxidation, again etherificate, rear recombination reaction, produce environmental protection, stable performance, the surface sizing agent for paper making of high-speed paper machine applying glue requirement can be met, thus a kind of preparation technology of oxidative cationic size-press starch is provided.
The present invention is achieved through the following technical solutions:
A preparation technology for oxidative cationic size-press starch, tapioca is with after oxidizing, and the molecule of oxidized starch generates carbonyl, meanwhile, has also caused polymerisation of dissociating; Cationic starch is that oxidized starch and quaternary ammonium salt etherifying agent carry out etherification reaction generation in the basic conditions; By recombination reaction, namely starch oxidation reaction and etherification reaction combine, and obtain oxidation quaternary ammonium cation starch; Production process adopts the pollution-free dry process of vacuum; The oxidation quaternary ammonium cation starch of different viscosities, different degree of substitution, i.e. oxidative cationic size-press starch can be synthesized by the ratio of adjustment starch, oxidant, etherifying agent three.
Preferred: preparation technology is as follows:
(1), oxidation reaction:
Get 1000 weight portion tapiocas, putting into dry process reaction still volumetric concentration is that the dilution alkali lye of 3-5% sprays into starch, adjust pH is 8 ± 1, then clorox is sprayed, the consumption that clorox is is the 4%-6% of tapioca, stirs rear extracting vacuum, and vacuum is 300-500Pa, be heated to 60-65 DEG C, reaction 1.5-2 hour.
(2), etherificate recombination reaction:
After oxidized starch reaction terminates, dry process reaction device bleeds off vacuum, directly sprays into the mixture of alkali and quaternary ammonium salt etherifying agent, and the substitution value of oxidative cationic size-press starch is 0.01-0.02, quaternary ammonium salt etherifying agent consumption is the 3%-4% of tapioca, and the mol ratio of quaternary ammonium salt and alkali is 1.5-1.7; Chemicals has sprayed rear stirring, vacuumizes 300-500 Pa, is warmed up to 65-70 DEG C simultaneously, reaction 1.8-2.5 hour.
Described quaternary ammonium salt etherifying agent is chloro-2 hydroxypropyl-trimethyl ammonium chlorides of 3-.
The present invention, by regulating starch, oxidant, the proportion adjustment viscosity of etherifying agent three, substitution value, adopts initial oxidation, again etherificate, rear composite modified technique, meanwhile, adopts vacuum dry technology for production to make
productgrade is reached advanced world standards, non-wastewater discharge, environmental protection.Properties of product are stablized, high-speed paper machine applying glue requirement can be met, now produce test products, by following the tracks of the effect of the purple emerging paper industry in Suzhou, Zhenjiang JinDong Paper Co., Ltd, Guangxi Zhi Deng enterprise of Yong Kai candy paper group, steady quality, inlet surface size-press starch can be substituted completely, and can paper cost be reduced, sum up its serviceability feature as follows:
1, tapioca protein content is low, and precipitation is few, and cohesive force is strong, sticks with paste liquid not easily corrupt, non-foam, free from extraneous odour;
2, gelatinization point is low, and gelatinization speed is fast, and stick with paste liquid good fluidity, the features such as stability is high, good film-forming property, can adapt to the needs of modern high-speed paper machine applying glue application development, effectively can prevent into paper in printing process, fall hair, dry linting phenomenon;
3, dispersive property is good, excellent to various fiber adhesive performance, has good compatibility with other auxiliary agents, partly or entirely can replace the expensive chemical products such as casein, PVA, reduces gluing cost;
4, because it is with positive charge, closely hydrophobic layer overlay film can be formed in conjunction with infiltrated fiber gap And on surface with the surface with negative electrical charge fiber, to the significantly raising increasing the resistance to water of paper and paperboard, surface strength, folding strength, fracture length, smoothness, and to improving into the printing performance Be very effective of paper.
5, adopt unique vacuum dry process to produce in preparation process, emit no waste water.
6, its physical and chemical performance has very wide excursion, and the peculiar physical and chemical performance shown is as biological degradability, superabsorbency, strong ion adsorption capacity etc., and for making full use of biomass resource, the crisis of alleviating petroleum resources increasingly exhausted is very helpful.There is good social benefit and considerable economic benefit, there is wide DEVELOPMENT PROSPECT.
Accompanying drawing explanation
Fig. 1 is present invention process flow chart.
Fig. 2 is the SEM photo of paper after oxidative cationic starch surface sizing of the present invention.
Fig. 3 is the SEM photo of paper after cationic starch top sizing of the prior art.
Detailed description of the invention
The each raw material of the present invention and parameter all can be implemented in technical solution of the present invention.By the following examples can the invention will be further described, but scope of the present invention is not limited to following embodiment.
Embodiment 1:
(1), oxidation reaction:
Get 1000 weight portion tapiocas, putting into dry process reaction still volumetric concentration is that the dilution alkali lye of 3-5% sprays into starch, adjust pH is 9, then clorox is sprayed, the consumption that clorox is is 5% of tapioca, stirs rear extracting vacuum, and vacuum is 300-500Pa, be heated to 60 DEG C, react 2 hours.
(2), etherificate recombination reaction:
After oxidized starch reaction terminates, dry process reaction device bleeds off vacuum, directly spray into the mixture of alkali and chloro-2 hydroxypropyl-trimethyl ammonium chlorides of 3-, the substitution value of oxidative cationic size-press starch is 0.01-0.02, the chloro-2 hydroxypropyl-trimethyl ammonium chloride consumptions of 3-are the 3%-4% of tapioca, and the mol ratio of chloro-2 hydroxypropyl-trimethyl ammonium chlorides of 3-and alkali is 1.5-1.7; Chemicals has sprayed rear stirring, vacuumizes 300-500 Pa, is warmed up to 65-70 DEG C simultaneously, reacts 2 hours.
one, laboratory report
1, main raw material physicochemical property
(1) tapioca
Moisture (%) :≤14.0
Protein (butt) (%) :≤0.20
Ash content (butt) (%) :≤0.2
Sulfur dioxide (%) :≤0.004
Fineness (100 order sieving rates, %): >=99
Acidity (in and 100 grams of over dry tapiocas consume the amount of 0.1mol/LNaOH, mL) :≤18.0
Outward appearance: white, has gloss
Smell: there is the smell that tapioca is intrinsic, free from extraneous odour
(2) other main raw materials are chemical industrial product oxidant, etherifying agent etc.
, oxidative cationic starch know-why
(1), the oxidizing rear title oxidized starch of starch, while generating carbonyl in the molecule of oxidized starch, also caused polymerisation of dissociating.
(2), cationic starch is that oxidized starch and quaternary ammonium salt cationic chemical reagent (chloro-2 hydroxypropyl-trimethyl ammonium chlorides of 3-) carry out etherification reaction generation in the basic conditions.Claim quaternary ammonium salt cationic starch.
(3), starch oxidation reacts and etherification reaction combines title recombination reaction, and its product claims oxidation quaternary ammonium cation starch.
3, discuss
(1), pH value is on the impact of oxidized starch carboxyl and hydroxy radical content
The anion of starch, the anion of hypochlorite are when higher pH value, and the latter preponderates.Two like magnetic poles repel each other, reaction is difficult to carry out, and alkalescence increases, and reaction speed declines.
In neutrality, subacidity or alkalescence medium, hypochlorite is mainly in non-dissociated state, and starch is in neutral.The hypochlorite of non-dissociated can produce starch hypochlorous acid ester and water, and ester decomposes generation oxidation product and hydrogen chloride.
React under different pH condition, mensuration---COOH from---ratio of CHO is different, as shown in table 1.
Table 1:
pH value is on the impact of oxidized starch carboxyl and carbonyl content
Under different pH condition during oxidized starch, the carboxyl-content of product increases with pH value and increases, and reaches peak, then decline when pH value 9, but carbonyl content increases with pH value and declines rapidly.It is preferred for obtaining pH value 7-9.
(2), cationic etherifying agent consumption is on the impact of substitution value
Be raw material with tapioca, after initial oxidation, etherificate is under reaction temperature is 65 DEG C and the reaction time is the condition of 2 h, and the consumption having investigated etherifying agent is on the impact of cationic starch nitrogen content and substitution value (DS), and result is as shown in table 2.
table 2, cationic etherifying agent consumption are on the impact of nitrogen content and substitution value
As can be seen from Table 2, along with the increase of cationic etherifying agent consumption, the nitrogen content of the cationic starch of generation rises gradually, and substitution value increases gradually.
(3), the comparison of top sizing effect
Table 3 is the situation of the paper surface properties after different starch varieties top sizing.
the surface property of paper after table 3, top sizing
Note: a, b, c are respectively substitution value 0. 020, the oxidative cationic starch of 0. 015,0. 010.
As can be seen from Table 3, the surface strength of cation surface sizing paper, smoothness, tensile strength have had significant raising than acidified starch and oxidized starch generally, can improve the printing effect of paper with oxidative cationic starch as Cypres; For the oxidative cationic starch of same kind, along with the increase of glue application solution concentration and the moderate of substitution value, the surface effect of sized paper also significantly improves; Wherein substitution value DS is that the sizing efficiency of the cationic starch of 0.015 is best, and the surface strength of paper after its applying glue, smoothness, tensile strength are higher, and the sizing efficiency of simple oxidized starch is the poorest.In practice, substitution value DS is that the sizing efficiency of the cationic starch of 0.01-0.02 is excellent.
(4), the scanning electron microscopic observation on paper sizing surface
In order to the form on interfibrous connection after studying applying glue and surface, observe paper surface situation and fibre morphology thereof with ESEM (SEM).Fig. 2 and Fig. 3 is respectively the SEM photo of paper after oxidative cationic starch of the present invention and existing cationic starch top sizing.
As can be seen from Fig. 2 and Fig. 3, after oxidative cationic starch of the present invention applying glue, surface fiber is still more loose, fiber and Inter-fiber voids larger, due to the capillarity in space, glue can infiltrate the hole of paper very well, and the fiber of paper surface combines tightr, and fiber and fiber stick together tightly, thus the capillarity reduced because space causes, effectively reduce the speed that liquid infiltrates page, thus realize good water resistant effect, also improve paper smoothness; And existing cationic starch due to viscosity high, glue can not gap well between infiltrated fiber, and when particularly to carry out mass fraction be the cationic starch glue top sizing of 5%, glue viscosity is large, and glue is uneven.
conclusion
(1) starch falls in glutinous processing procedure, and the factor such as clorox consumption, reaction temperature, reaction time all has considerable influence to viscosity, strictly should control, makes it reach suitable viscosity scope; During cationization, the etherifying agent consumption also corresponding consumption than common cation starch is little.
(2) when consumption is identical, oxidative cationic starch of the present invention has than cationic starch and the better top sizing effect of oxidized starch, and after applying glue, the smoothness of paper, surface strength and tensile strength have raising by a relatively large margin.
(3) oxidative cationic starch of the present invention is compared with existing cationic starch, and its viscosity is low, good stability.Therefore, oxidative cationic starch of the present invention has good surface sizability.
two, survey report
Institute of Analysis of Jiangxi Province assay:
Claims (3)
1. a preparation technology for oxidative cationic size-press starch, is characterized in that, preparation technology is as follows:
(1), oxidation reaction:
Get 1000 weight portion tapiocas, putting into dry process reaction still volumetric concentration is that the dilution alkali lye of 3-5% sprays into starch, adjust pH is 8 ± 1, then clorox is sprayed, the consumption of clorox is the 4%-6% of tapioca, stirs rear extracting vacuum, and vacuum is 300-500Pa, be heated to 60-65 DEG C, reaction 1.5-2 hour;
(2), etherificate recombination reaction:
After oxidized starch reaction terminates, dry process reaction device bleeds off vacuum, directly sprays into the mixture of alkali and quaternary ammonium salt etherifying agent, and the substitution value of oxidative cationic size-press starch is 0.01-0.02, quaternary ammonium salt etherifying agent consumption is the 3%-4% of tapioca, and the mol ratio of quaternary ammonium salt and alkali is 1.5-1.7; Chemicals has sprayed rear stirring, vacuumizes 300-500Pa, is warmed up to 65-70 DEG C simultaneously, reaction 1.8-2.5 hour.
2. the preparation technology of a kind of oxidative cationic size-press starch according to claim 1, is characterized in that:
(1), oxidation reaction:
Get 1000 weight portion tapiocas, putting into dry process reaction still volumetric concentration is that the dilution alkali lye of 3-5% sprays into starch, adjust pH is 8, then clorox is sprayed, the consumption of clorox is 5% of tapioca, stirs rear extracting vacuum, and vacuum is 300-500Pa, be heated to 60 DEG C, react 2 hours;
(2), etherificate recombination reaction:
After oxidized starch reaction terminates, dry process reaction device bleeds off vacuum, directly sprays into the mixture of alkali and quaternary ammonium salt etherifying agent, and the substitution value of oxidative cationic size-press starch is 0.01-0.02, quaternary ammonium salt etherifying agent consumption is the 3%-4% of tapioca, and the mol ratio of quaternary ammonium salt and alkali is 1.5-1.7; The mixture of alkali and quaternary ammonium salt etherifying agent
Spray rear stirring, vacuumized 300-500Pa, be warmed up to 65-70 DEG C simultaneously, reacted 2 hours.
3. the preparation technology of a kind of oxidative cationic size-press starch according to claim 1 and 2, is characterized in that, described quaternary ammonium salt etherifying agent is chloro-2 hydroxypropyl-trimethyl ammonium chlorides of 3-.
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| CN106905487B (en) * | 2017-03-15 | 2019-01-18 | 晋州市大成变性淀粉有限公司 | A kind of preparation process of waterproof size-press starch |
| CN110656536A (en) * | 2019-05-17 | 2020-01-07 | 江西红星变性淀粉有限公司 | Novel oxidized cationic sizing starch |
| CN110172105B (en) * | 2019-05-22 | 2021-09-21 | 华南理工大学 | Method for improving reaction efficiency of dry/semi-dry starch and etherifying agent |
| CN111409154B (en) * | 2020-05-07 | 2021-07-06 | 广西祥盛家居材料科技股份有限公司 | Method for producing veneer shaving board |
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