CN103724441A - Guanidine salt grafted starch multifunctional papermaking additive and preparation method thereof - Google Patents
Guanidine salt grafted starch multifunctional papermaking additive and preparation method thereof Download PDFInfo
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- CN103724441A CN103724441A CN201410010234.4A CN201410010234A CN103724441A CN 103724441 A CN103724441 A CN 103724441A CN 201410010234 A CN201410010234 A CN 201410010234A CN 103724441 A CN103724441 A CN 103724441A
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Abstract
The invention discloses a guanidine salt grafted starch multifunctional papermaking additive and a preparation method thereof. The method comprises the following steps: adding starch into a sodium periodate solution, heating and reacting for 4 hours, filtering the product, washing and drying to obtain dialdehyde starch; dispersing the dialdehyde starch in distilled water, adding a guanidine salt and reacting at a certain temperature for 2 hours, filtering the product, washing, drying, and obtaining guanidine salt grafted starch; and finally, coating the guanidine salt grafted starch on the paper surface, and preparing high-strength high-antibacterial property functional paper. The guanidine salt grafted starch multifunctional papermaking additive is coated on the paper surface, so that the paper simultaneously has high strength and high antibacterial property, and the two defects of low strength and low antibacterial property of the paper are improved. Therefore, the multifunctional papermaking additive has high application value.
Description
Technical field
The present invention relates to a kind ofly for paper grade (stock) multifunctional assistant, specifically, relate to multi-functional paper making additive of a kind of guanidinesalt graft starch and preparation method thereof.
Background technology
In paper industry, starch occupies an important position.Starch can be used for wet end to be added, and can play the effects such as enhancing, retention aid and filter aid; For the top sizing of paper, can improve the surface strength of paper and improve printing performance; For painting processing paper, can improve printing performance and the printing effect of paper.In addition, starch have aboundresources, low price, supply stable, easy to use, can chemical modification and the advantage such as biological degradation.Therefore, starch and derivative product thereof are widely used in paper industry.Starch has amylose starch and amylopectin two classes.Amylose starch is containing a hundreds of glucose unit, and amylopectin is containing several thousand glucose units.In native starch straight chain account for 20%～26%, it is solubility, remaining is amylopectin.When detecting with iodine solution, amylose starch liquid manifests blueness, becomes reddish-brown when amylopectin contacts with iodine.Because starch itself is without any anti-microbial effect, can not give paper anti-microbial property, therefore, after using starch, easily cause bacteria breed and breeding in paper, thereby harm people's is healthy.
Summary of the invention
The object of the invention is to improve starch itself without the deficiency of anti-microbial property, multi-functional paper making additive of a kind of novel guanidinesalt graft starch and preparation method thereof is provided.
For realizing object of the present invention, the technical scheme adopting is: the preparation method of the multi-functional paper making additive of a kind of guanidinesalt graft starch of the present invention, comprises the steps:
(1) starch is joined in 0.1-5mol/L sodium periodate solution, reacting by heating under 30-60 ° of C, obtains dialdehyde starch after product is filtered, washs and be dried; The mol ratio of described sodium periodate and starch is 1:1-2;
(2) step (1) gained dialdehyde starch is dispersed in distilled water, adds guanidinesalt and react under 30-70 ° of C, after product is filtered, washs and be dried, obtain guanidinesalt graft starch; The mol ratio of described guanidinesalt and dialdehyde starch is 1:1-20.Its synthetic chemistry formula figure is shown in Fig. 1.
The volumetric molar concentration of the above-mentioned sodium periodate solution of the present invention is 0.7 mol/L preferably, and the mol ratio of described guanidinesalt and dialdehyde starch is preferably 1:1-10.
Guanidinesalt of the present invention can be Walaphage, Guanidinium hydrochloride etc., preferably Guanidinium hydrochloride.
The multi-functional paper making additive of guanidinesalt graft starch of the present invention is to be prepared from by above-mentioned the inventive method.
The present invention's starch used can amylose starch, also can be amylopectin, the starch described in embodiments of the invention refers to " amylopectin ".
With respect to prior art, tool of the present invention has the following advantages:
China's paper industry is just experiencing raw material of papermaking fiber, paper product specification of quality, the adjustment of paper product kind, paper technology and equipment, and starch has become paper industry one of the indispensable papermaking chemical product that improves the quality of products, reduces production costs.But utilize antiseptic-germicide treated starch, make starch there is high-efficiency antimicrobial performance and have not been reported.The present invention is directed to current starch itself without the deficiency of anti-microbial property, first utilize sodium periodate that starch oxidation is become to dialdehyde starch, by schiff base reaction, guanidinesalt is grafted on dialdehyde starch again, thereby make starch there is anti-microbial property, finally this treated starch is applied to paper surface, thereby when improving paper tensile strength, also can give paper high-efficiency antimicrobial performance.
Accompanying drawing explanation
Fig. 1 is the chemical equation figure of the multi-functional paper making additive of guanidinesalt graft starch of the embodiment of the present invention 1 preparation.
Fig. 2 is the infrared spectrogram of ative starch and guanidinesalt graft starch.
Fig. 3 is the affect figure of the coating of guanidinesalt graft starch on paper strength.
Fig. 4 is body paper and the anti-microbial property comparison diagram of White Board to intestinal bacteria (a) and staphylococcus (b), and figure (a) is intestinal bacteria anti-microbial property figure, and figure (b) is staphylococcus anti-microbial property figure.
Embodiment
Below in conjunction with embodiment, the inventive method is described in further detail.It should be noted that, protection scope of the present invention should include but not limited to the disclosed technology contents of the present embodiment.
(1) starch is joined in 1 mol/L sodium periodate solution, reacting by heating 4h under 30 ° of C, obtains dialdehyde starch after product is filtered, washs and be dried; The mol ratio of described sodium periodate and starch is 1:1.
(2) step (1) gained dialdehyde starch is dispersed in distilled water, adds Guanidinium hydrochloride and react 2h under 30 ° of C, after product is filtered, washs and be dried, obtain guanidinesalt graft starch; The mol ratio of described guanidinesalt and dialdehyde starch is 1:1.
Embodiment 2
(1) starch is joined in 1.5 mol/L sodium periodate solutions, reacting by heating 4h under 40 ° of C, obtains dialdehyde starch after product is filtered, washs and be dried; The mol ratio of described sodium periodate and starch is 1:1.2.
(2) step (1) gained dialdehyde starch is dispersed in distilled water, adds Guanidinium hydrochloride and react 2h under 50 ° of C, after product is filtered, washs and be dried, obtain guanidinesalt graft starch; The mol ratio of described guanidinesalt and dialdehyde starch is 1:5.
Embodiment 3
(1) starch is joined in 2 mol/L sodium periodate solutions, reacting by heating 4h under 50 ° of C, obtains dialdehyde starch after product is filtered, washs and be dried; The mol ratio of described sodium periodate and starch is 1:1.5.
(2) step (1) gained dialdehyde starch is dispersed in distilled water, and adds Walaphage (proving like this present invention's also available " Walaphage ") to react 2h under 60 ° of C, after product is filtered, washs and be dried, obtain guanidinesalt graft starch; The mol ratio of described guanidinesalt and dialdehyde starch is 1:10.
Embodiment 4
Performance test:
1, the intensity detection of White Board
By the guanidinesalt graft starch of embodiment 1 preparation, while detecting with iodine solution, it becomes in reddish-brown explanation guanidinesalt graft starch and contains amylopectin.By the infrared spectra Fig. 2 to guanidinesalt graft starch and ative starch, analyze contrast known, in the infrared spectra of guanidinesalt graft starch, occur new absorption peak 1659cm
-1(N-H flexural vibration), show that guanidinesalt is successfully grafted on starch.
The guanidinesalt graft starch of embodiment 1 preparation is applied to paper surface, and the intensity of White Board is measured, result as shown in Figure 3, in figure: DAS-1, DAS-1.4,, DAS-4.7, DAS-25, DAS-62 refer to respectively guanidinesalt graft starch (guanidinesalt grafting amount is respectively 1,1.4,4.7,25,62%).Can find out, because treated starch has much amino and hydroxyl, in drying process, hydroxyl easy and paper fibre forms hydrogen bonded, thereby paper is had to good enhancement, when coating is during DAS-25, the dry strength of paper increases to 75.3 Nm/g from 60.2, has improved 25%; Wet tenacity increases to 4.2 Nm/g from 2.1, has improved 100%.
2, the anti-microbial property of White Board detects
For the multi-functional paper making additive of the explanation novel guanidinesalt graft starch of the present invention is for the anti-microbial property after Paper Coating, measure the anti-microbial property of body paper and White Board.
After the multi-functional paper making additive of novel guanidinesalt graft starch that utilizes embodiment 1 to prepare is coated with paper, White Board and body paper are detected the inhibition of intestinal bacteria and streptococcus aureus respectively, result as shown in Figure 4, DAS-1, DAS-1.4,, DAS-4.7, DAS-25, DAS-62 refer to respectively guanidinesalt graft starch (guanidinesalt grafting amount is respectively 1,1.4,4.7,25,62%).Can find out, compare with body paper, the White Board that has been coated with the multi-functional paper making additive of guanidinesalt graft starch has obvious inhibition zone, so the multi-functional paper making additive of this novel guanidinesalt graft starch has good anti-microbial property to paper.
Claims (4)
1. a preparation method for the multi-functional paper making additive of guanidinesalt graft starch, is characterized in that comprising the steps:
(1) starch is joined in 0.1-5mol/L sodium periodate solution, reacting by heating under 30-60 ° of C, obtains dialdehyde starch after product is filtered, washs and be dried; The mol ratio of described sodium periodate and starch is 1:1-2;
(2) step (1) gained dialdehyde starch is dispersed in distilled water, adds guanidinesalt and react under 30-70 ° of C, after product is filtered, washs and be dried, obtain guanidinesalt graft starch; The mol ratio of described guanidinesalt and dialdehyde starch is 1:1-20.
2. the preparation method of the multi-functional paper making additive of guanidinesalt graft starch according to claim 1, is characterized in that: the volumetric molar concentration of described sodium periodate solution is 0.7 mol/L, and the mol ratio of described guanidinesalt and dialdehyde starch is 1:1-10.
3. the preparation method of the multi-functional paper making additive of guanidinesalt graft starch according to claim 1 and 2, is characterized in that: described guanidinesalt is selected from Walaphage or Guanidinium hydrochloride, preferably Guanidinium hydrochloride.
4. the multi-functional paper making additive of guanidinesalt graft starch, is characterized in that being prepared from by the method described in claim 1 or 2 or 3.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105713131A (en) * | 2014-12-04 | 2016-06-29 | 上海东升新材料有限公司 | Styrene-acrylic emulsion, preparation method and application thereof |
| WO2018011667A1 (en) * | 2016-07-11 | 2018-01-18 | Stora Enso Oyj | Process for creating a foam utilizing an antimicrobial starch within a process for manufacturing a paper or board product |
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| US4427808A (en) * | 1980-07-21 | 1984-01-24 | Ceskoslovenska Akademie Ved | Composite polymeric material for biological and medical applications and the method for its preparation |
| JPS59102939A (en) * | 1982-12-03 | 1984-06-14 | Japan Carlit Co Ltd:The | Aqueous gel substrate and composite containing the same |
| US20080305950A1 (en) * | 2004-09-14 | 2008-12-11 | Archer-Daniels-Midland Company | Guanidinated Polysaccharides, Their Use as Absorbents and Process For Producing Same |
| CN101781467A (en) * | 2009-01-21 | 2010-07-21 | 郑州佰沃生物质材料有限公司 | Biomass-synthetic plastic product and method for preparing same |
| CN103012606A (en) * | 2013-01-09 | 2013-04-03 | 上海富元塑胶科技有限公司 | Modified starch for grafting guazatine oligomer as well as preparation method and application of modified starch |
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2014
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Patent Citations (5)
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| US4427808A (en) * | 1980-07-21 | 1984-01-24 | Ceskoslovenska Akademie Ved | Composite polymeric material for biological and medical applications and the method for its preparation |
| JPS59102939A (en) * | 1982-12-03 | 1984-06-14 | Japan Carlit Co Ltd:The | Aqueous gel substrate and composite containing the same |
| US20080305950A1 (en) * | 2004-09-14 | 2008-12-11 | Archer-Daniels-Midland Company | Guanidinated Polysaccharides, Their Use as Absorbents and Process For Producing Same |
| CN101781467A (en) * | 2009-01-21 | 2010-07-21 | 郑州佰沃生物质材料有限公司 | Biomass-synthetic plastic product and method for preparing same |
| CN103012606A (en) * | 2013-01-09 | 2013-04-03 | 上海富元塑胶科技有限公司 | Modified starch for grafting guazatine oligomer as well as preparation method and application of modified starch |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105713131A (en) * | 2014-12-04 | 2016-06-29 | 上海东升新材料有限公司 | Styrene-acrylic emulsion, preparation method and application thereof |
| WO2018011667A1 (en) * | 2016-07-11 | 2018-01-18 | Stora Enso Oyj | Process for creating a foam utilizing an antimicrobial starch within a process for manufacturing a paper or board product |
| US11001969B2 (en) | 2016-07-11 | 2021-05-11 | Stora Enso Oyj | Process for creating a foam utilizing an antimicrobial starch within a process for manufacturing a paper or board product |
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Application publication date: 20140416 |