CN103437246A - Paper strengthening agent, and preparation method and application thereof - Google Patents
Paper strengthening agent, and preparation method and application thereof Download PDFInfo
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- CN103437246A CN103437246A CN2013103889728A CN201310388972A CN103437246A CN 103437246 A CN103437246 A CN 103437246A CN 2013103889728 A CN2013103889728 A CN 2013103889728A CN 201310388972 A CN201310388972 A CN 201310388972A CN 103437246 A CN103437246 A CN 103437246A
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Abstract
The invention belongs to the technical field of production of modified starch, and particularly relates to a paper strengthening agent, and a preparation method and application thereof. The preparation method of the paper strengthening agent comprises the following steps: mixing waxy rice starch, distilled water and an expansion inhibitor into starch suspension; dropwise adding aqueous alkali into the starch suspension to alkalify after the components of the starch suspension are evenly mixed; slowly dropwise adding a cationic etherifying agent solution to the alkalified solution, and carrying out heating reaction; cooling at room temperature after the reaction; dropwise adding acetic acid to neutralize, carrying out vacuum filtration, washing by an ethanol solution, drying an obtained solid mater, and crushing after drying so as to obtain the paper strengthening agent. The prepared paper strengthening agent is prepared into a solution and then added to a wet part of a paper machine in proportion, so that the physical strength of produced paper can be improved.
Description
Technical field
The invention belongs to the production technical field of converted starch, be specifically related to a kind of paper making intensifier and preparation method thereof and application.
Background technology
China's converted starch industry is started late, and production capacity is lower, before 2000 domestic converted starch annual production all below 200,000 tons, domestic consumption height dependence on import, the import interdependency is more than 30%.And the kind of home products and quality be meeting the market requirement fully.
Cationic starch mainly contains tertiary amine salt and quaternary ammonium salt.The cationic starch gelatinization point is low, be easy to disperse, and viscosity is high, Heat stability is good.Therefore be widely used in the fields such as papermaking, weaving, food, oil, binder, mining industry, sewage disposal and cosmetics.Quaternary ammonium cation starch, no matter under acidity or alkali condition, all be cationic, copy paper in particularly suitable, under alkalescence or acid condition, the today developed rapidly in the neutral papermaking technology, it is just becoming indispensable paper making additive, is also that the current scope of application is the widest, the maximum a kind of converted starch of consumption.
What the converted starch result of use was best at present is the cationic starch of high side chain, and glutinous rice starch, because amylopectin content in its structure is higher, receives people's concern in recent years day by day, becomes gradually the focus of research.The raw material of at present common manufacture paper grade (stock) cationic starch reinforcing agent has cornstarch, tapioca, wheaten starch or farina etc.Not yet have at present and take glutinous rice starch and prepare the method report of paper making intensifier as raw material.
Summary of the invention
Primary and foremost purpose of the present invention is to provide a kind of preparation method of paper making intensifier, and the method be take glutinous rice starch and prepared and be applicable to the paper making intensifier that paper industry requires by wet method as main raw material;
The paper making intensifier that provides above-mentioned preparation method to make is provided;
A further object of the present invention is to provide the application of above-mentioned paper making intensifier.
Purpose of the present invention is achieved through the following technical solutions:
A kind of preparation method of paper making intensifier comprises following operating procedure:
(1) size mixing: glutinous rice starch, expansion inhibitor and distilled water are mixed into to starch suspension; Described expansion inhibitor is 15% of starch weight, and described distilled water is 2.5 times of starch weight;
(2) alkalization: the alkali wiring solution-forming that will be equivalent to glutinous rice starch weight 3～5% is added drop-wise in the starch suspension of step (1), under 30 ℃ of conditions, alkalizes 15～30 minutes;
(3) etherificate: the cationic etherifying agent that will be equivalent to glutinous rice starch weight 6～8% is mixed with in the starch suspension after solution is added drop-wise to step (2) alkalization, and time for adding is 30～45 minutes, is warming up to 85～90 ℃ of reactions 105～120 minutes;
(4) neutralization, suction filtration, washing, drying: in the starch suspension after step (3) etherificate, the acetic acid that the dropping concentration expressed in percentage by volume is 10% is neutralized to pH=6.5～7.0, vacuum filtration, the ethanol water washing that the volume fraction of take is 60～80%, the solid content obtained, 40～50 ℃ of lower vacuumizes, crushed after being dried obtains paper making intensifier.
The described expansion inhibitor of step (1) is sodium chloride.
The described alkali of step (2) is NaOH, potassium hydroxide or calcium hydroxide.
The described cationic etherifying agent of step (3) is 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride or 2,3-epoxypropyltrimethylchloride chloride.
A kind of paper making intensifier prepared according to above-mentioned preparation method.
Described paper making intensifier is mixed with solution and adds in proportion the paper machine wet end to improve the application of product paper strength.Paper making intensifier is mixed with to the solution that concentration is 0.001g/ml, adds in the paper machine wet pulp in 0.2%, 0.4%, 0.6% or 0.8% the ratio with respect to the absolute dried paper pulp quality, can improve the intensity of paper.
The present invention has following advantage and effect with respect to prior art:
(1) paper making intensifier production technology of the present invention is reasonable, through sizing mixing, the accurate control of the process system such as alkalization, etherificate, neutralization, suction filtration, washing, drying, make glutinous rice starch there is cationic characteristic, gelatinization point and the retrogradation of glutinous rice starch have been reduced simultaneously, its effect can reach the paper industry requirement fully, can effectively improve paper strength;
(2) the present invention be take glutinous rice starch and is prepared paper making intensifier as raw material, has expanded the scope of application of glutinous rice starch, has enriched the kind of paper making intensifier;
(3) the paper making intensifier viscosity that prepared by the present invention is moderate, and stability is high, and paste liquid transparency is better, and substitution value is low, strengthens effective;
(4) paper making intensifier of the present invention can reduce cationic starch consumption in paper-making process, reduces costs, and increases economic benefit.
The specific embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited to this.
Embodiment 1
(1) size mixing: by the distilled water of 50g glutinous rice starch and 125ml, 7.5g sodium chloride, be mixed into starch suspension.
(2) alkalization: 3% the sodium hydroxide solution of 50ml is added drop-wise in the starch suspension of step (1), and under 30 ℃ of conditions, alkalization is 15 minutes.
(3) etherificate: by 2 of 70ml mass fraction 3%, 3-epoxypropyltrimethylchloride chloride solution slowly is added drop-wise in the starch suspension after step (2) alkalization, and time for adding 30 minutes is warming up to 85 ℃ of reactions 105 minutes.
(4) neutralization, suction filtration, washing, drying: in the starch suspension after step (3) etherificate, the acetic acid that the dropping concentration expressed in percentage by volume is 10% is neutralized to pH=6.5～7.0, vacuum filtration, the ethanol water washing that the volume fraction of take is 60% 5 times, the solid content obtained is placed on to vacuum drying chamber interior dry under 40 ℃, crushed after being dried obtains paper making intensifier.
The paper making intensifier that step (4) is obtained is mixed with the solution that concentration is 0.001g/ml to be added in paper according to the amount with respect to absolute dried paper pulp quality 0.2%, and measures burst index, tear index, the tensile index of the paper of manufacturing paper with pulp and compare with blank pattern.
The present embodiment paper making intensifier substitution value is 0.012, uses the pattern of this paper making intensifier to improve 9.4% than blank pattern burst index, and tear index raising 8.5%, tensile index improve 5.9%.
Embodiment 2
(1) size mixing: by the distilled water of 50g glutinous rice starch and 125ml, 7.5g sodium chloride, be mixed into starch suspension.
(2) alkalization: 5% the sodium hydroxide solution of 50ml is added drop-wise in the starch suspension of step (1), and under 30 ℃ of conditions, alkalization is 20 minutes.
(3) etherificate: by 2 of 75ml mass fraction 3%, 3-epoxypropyltrimethylchloride chloride solution slowly is added drop-wise in the starch suspension after step (2) alkalization, and time for adding 35 minutes is warming up to 87 ℃ of reactions 120 minutes.
(4) neutralization, suction filtration, washing, drying: in the starch suspension after step (3) etherificate, the acetic acid that the dropping concentration expressed in percentage by volume is 10% is neutralized to pH=6.5～7.0, vacuum filtration, the ethanol water washing that the volume fraction of take is 70% 5 times, the solid content obtained is placed on to vacuum drying chamber interior dry under 45 ℃, crushed after being dried obtains paper making intensifier.
The paper making intensifier that step (4) is obtained is mixed with the solution that concentration is 0.001g/ml to be added in paper according to the amount with respect to absolute dried paper pulp quality 0.4%, and measures burst index, tear index, the tensile index of the paper of manufacturing paper with pulp and compare with blank pattern.
The present embodiment paper making intensifier substitution value is 0.013, uses the pattern of this paper making intensifier to improve 11.0% than blank pattern burst index, and tear index improves 10.1%, and tensile index improves 7.5%.
Embodiment 3
(1) size mixing: by the distilled water of 100g glutinous rice starch and 250ml, 15g sodium chloride, be mixed into starch suspension.
(2) alkalization: 3% the aqua calcis of 100ml is added drop-wise in the starch suspension of step (1), and under 30 ℃ of conditions, alkalization is 25 minutes.
(3) etherificate: by 2 of 160ml mass fraction 3%, 3-epoxypropyltrimethylchloride chloride solution slowly is added drop-wise in the starch suspension after step (2) alkalization, and time for adding 40 minutes is warming up to 90 ℃ of reactions 115 minutes.
(4) neutralization, suction filtration, washing, drying: in the starch suspension after step (3) etherificate, the acetic acid that the dropping concentration expressed in percentage by volume is 10% is neutralized to pH=6.5～7.0, vacuum filtration, the ethanol water washing that the volume fraction of take is 75% 5 times, the solid content obtained is placed on to vacuum drying chamber interior dry under 50 ℃, crushed after being dried obtains paper making intensifier.
The paper making intensifier that step (4) is obtained is mixed with the solution that concentration is 0.001g/ml to be added in paper according to the amount with respect to absolute dried paper pulp quality 0.6%, and measures burst index, tear index, the tensile index of the paper of manufacturing paper with pulp and compare with blank pattern.
The present embodiment paper making intensifier substitution value is 0.022, uses the pattern of this paper making intensifier to improve 12.4% than blank pattern burst index, and tear index improves 11.3%, and tensile index improves 9.2%.
Embodiment 4
(1) size mixing: by the distilled water of 100g glutinous rice starch and 250ml, 15g sodium chloride, be mixed into starch suspension.
(2) alkalization: 5% the aqua calcis of 100ml is added drop-wise in the starch suspension of step (1), and under 30 ℃ of conditions, alkalization is 30 minutes.
(3) etherificate: by 2 of 170ml mass fraction 3%, 3-epoxypropyltrimethylchloride chloride solution slowly is added drop-wise in the starch suspension after step (2) alkalization, and time for adding 45 minutes is warming up to 90 ℃ of reactions 110 minutes.
(4) neutralization, suction filtration, washing, drying: in the starch suspension after step (3) etherificate, the acetic acid that the dropping concentration expressed in percentage by volume is 10% is neutralized to pH=6.5～7.0, vacuum filtration, the ethanol water washing that the volume fraction of take is 80% 5 times, the solid content obtained is placed on to vacuum drying chamber interior dry under 50 ℃, crushed after being dried obtains paper making intensifier.
The paper making intensifier that step (4) is obtained is mixed with the solution that concentration is 0.001g/ml to be added in paper according to the amount with respect to absolute dried paper pulp quality 0.8%, and measures burst index, tear index, the tensile index of the paper of manufacturing paper with pulp and compare with blank pattern.
The present embodiment paper making intensifier substitution value is 0.021, uses the pattern of this paper making intensifier to improve 15.7% than blank pattern burst index, and tear index improves 13.2%, and tensile index improves 11.5%.
Embodiment 5
(1) size mixing: by the distilled water of 50g glutinous rice starch and 125ml, 7.5g sodium chloride, be mixed into starch suspension.
(2) alkalization: 3% the potassium hydroxide solution of 80ml is added drop-wise in the starch suspension of step (1), and under 30 ℃ of conditions, alkalization is 15 minutes.
(3) etherificate: the 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride solution of 100ml mass fraction 3% slowly is added drop-wise in the starch suspension after step (2) alkalizes, and time for adding 30 minutes, be warming up to 85 ℃ of reactions 105 minutes.
(4) neutralization, suction filtration, washing, drying: in the starch suspension after step (3) etherificate, the acetic acid that the dropping concentration expressed in percentage by volume is 10% is neutralized to pH=6.5～7.0, vacuum filtration, the ethanol water washing that the volume fraction of take is 65% 5 times, the solid content obtained is placed on to vacuum drying chamber interior dry under 40 ℃, crushed after being dried obtains paper making intensifier.
The paper making intensifier that step (4) is obtained is mixed with the solution that concentration is 0.001g/ml to be added in paper according to the amount with respect to absolute dried paper pulp quality 0.2%, and measures burst index, tear index, the tensile index of the paper of manufacturing paper with pulp and compare with blank pattern.
The present embodiment paper making intensifier substitution value is 0.017, uses the pattern of this paper making intensifier to improve 9.2% than blank pattern burst index, and tear index raising 8.4%, tensile index improve 6.6%.
Embodiment 6
(1) size mixing: by the distilled water of 50g glutinous rice starch and 125ml, 7.5g sodium chloride, be mixed into starch suspension.
(2) alkalization: 4% the potassium hydroxide solution of 50ml is added drop-wise in the starch suspension of step (1), and under 30 ℃ of conditions, alkalization is 20 minutes.
(3) etherificate: the 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride solution of 100ml mass fraction 3% slowly is added drop-wise in the starch suspension after step (2) alkalizes, and time for adding 35 minutes, be warming up to 87 ℃ of reactions 110 minutes.
(4) neutralization, suction filtration, washing, drying: in the starch suspension after step (3) etherificate, the acetic acid that the dropping concentration expressed in percentage by volume is 10% is neutralized to pH=6.5～7.0, vacuum filtration, the ethanol water washing that the volume fraction of take is 70% 5 times, the solid content obtained is placed on to vacuum drying chamber interior dry under 45 ℃, crushed after being dried obtains paper making intensifier.
The paper making intensifier that step (4) is obtained is mixed with the solution that concentration is 0.001g/ml to be added in paper according to the amount with respect to absolute dried paper pulp quality 0.4%, and measures burst index, tear index, the tensile index of the paper of manufacturing paper with pulp and compare with blank pattern.
The present embodiment paper making intensifier substitution value is 0.019, uses the pattern of this paper making intensifier to improve 10.7% than blank pattern burst index, and tear index raising 9.7%, tensile index improve 8.5%.
Embodiment 7
(1) size mixing: by the distilled water of 100g glutinous rice starch and 250ml, 15g sodium chloride, be mixed into starch suspension.
(2) alkalization: 5% the sodium hydroxide solution of 100ml is added drop-wise in the starch suspension of step (1), and under 30 ℃ of conditions, alkalization is 25 minutes.
(3) etherificate: the 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride solution of 190ml mass fraction 3% slowly is added drop-wise in the starch suspension after step (2) alkalizes, and time for adding 40 minutes, be warming up to 90 ℃ of reactions 115 minutes.
(4) neutralization, suction filtration, washing, drying: in the starch suspension after step (3) etherificate, the acetic acid that the dropping concentration expressed in percentage by volume is 10% is neutralized to pH=6.5～7.0, vacuum filtration, the ethanol water washing that the volume fraction of take is 75% 5 times, the solid content obtained is placed on to vacuum drying chamber interior dry under 50 ℃, crushed after being dried obtains paper making intensifier.
The paper making intensifier that step (4) is obtained is mixed with the solution that concentration is 0.001g/ml to be added in paper according to the amount with respect to absolute dried paper pulp quality 0.6%, and measures burst index, tear index, the tensile index of the paper of manufacturing paper with pulp and compare with blank pattern.
The present embodiment paper making intensifier substitution value is 0.019, uses the pattern of this paper making intensifier to improve 11.9% than blank pattern burst index, and tear index raising 11.2%, tensile index improve 10.1%.
Embodiment 8
(1) size mixing: by the distilled water of 100g glutinous rice starch and 250ml, 15g sodium chloride, be mixed into starch suspension.
(2) alkalization: 4% the aqua calcis of 100ml is added drop-wise in the starch suspension of step (1), and under 30 ℃ of conditions, alkalization is 30 minutes.
(3) etherificate: the 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride solution of 200ml mass fraction 3% slowly is added drop-wise in the starch suspension after step (2) alkalizes, and time for adding 45 minutes, be warming up to 90 ℃ of reactions 120 minutes.
(4) neutralization, suction filtration, washing, drying: in the starch suspension after step (3) etherificate, the acetic acid that the dropping concentration expressed in percentage by volume is 10% is neutralized to pH=6.5～7.0, vacuum filtration, the ethanol water washing that the volume fraction of take is 80% 5 times, the solid content obtained is placed on to vacuum drying chamber interior dry under 50 ℃, crushed after being dried obtains paper making intensifier.
The paper making intensifier that step (4) is obtained is mixed with the solution that concentration is 0.001g/ml to be added in paper according to the amount with respect to absolute dried paper pulp quality 0.8%, and measures burst index, tear index, the tensile index of the paper of manufacturing paper with pulp and compare with blank pattern.
The present embodiment paper making intensifier substitution value is 0.020, uses the pattern of this paper making intensifier to improve 13.4% than blank pattern burst index, and tear index raising 12.8%, tensile index improve 11.5%.
Above-described embodiment is preferably embodiment of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under Spirit Essence of the present invention and principle, substitutes, combination, simplify; all should be equivalent substitute mode, within being included in protection scope of the present invention.
Claims (8)
1. the preparation method of a paper making intensifier is characterized in that comprising following operating procedure:
(1) size mixing: glutinous rice starch, expansion inhibitor and distilled water are mixed into to starch suspension; Described expansion inhibitor is 15% of starch weight, and described distilled water is 2.5 times of starch weight;
(2) alkalization: the alkali wiring solution-forming that will be equivalent to glutinous rice starch weight 3～5% is added drop-wise in the starch suspension of step (1), under 30 ℃ of conditions, alkalizes 15～30 minutes;
(3) etherificate: the cationic etherifying agent that will be equivalent to glutinous rice starch weight 6～8% is mixed with in the starch suspension after solution is added drop-wise to step (2) alkalization, and time for adding is 30～45 minutes, is warming up to 85～90 ℃ of reactions 105～120 minutes;
(4) neutralization, suction filtration, washing, drying: in the starch suspension after step (3) etherificate, the acetic acid that the dropping concentration expressed in percentage by volume is 10% is neutralized to pH=6.5～7.0, vacuum filtration, the ethanol water washing that the volume fraction of take is 60～80%, the solid content obtained, 40～50 ℃ of lower vacuumizes, crushed after being dried obtains paper making intensifier.
2. preparation method according to claim 1, it is characterized in that: the described expansion inhibitor of step (1) is sodium chloride.
3. preparation method according to claim 1, it is characterized in that: the described alkali of step (2) is NaOH, potassium hydroxide or calcium hydroxide.
4. preparation method according to claim 1, it is characterized in that: the described cationic etherifying agent of step (3) is 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride or 2,3-epoxypropyltrimethylchloride chloride.
5. the paper making intensifier prepared according to the described method of claim 1～4 any one.
6. paper making intensifier according to claim 5 is in the application that improves the product paper strength.
7. application according to claim 6 is characterized in that: in described application process, paper making intensifier is mixed with to the solution that concentration is 0.001g/ml and adds in proportion the paper machine wet end to.
8. application according to claim 7 is characterized in that: described ratio is with respect to 0.2%, 0.4%, 0.6% or 0.8% of absolute dried paper pulp quality.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104086704A (en) * | 2014-06-13 | 2014-10-08 | 华南理工大学 | Starch grafted acrylamide and preparation method and application thereof |
| CN104861213A (en) * | 2015-05-06 | 2015-08-26 | 金东纸业（江苏）股份有限公司 | Method for preparing complex starch |
| CN106087561A (en) * | 2016-06-13 | 2016-11-09 | 北京林业大学 | A kind of paper strengthening agent and production method thereof |
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| CN101033260A (en) * | 2006-03-10 | 2007-09-12 | 四平帝达变性淀粉有限公司 | Method of preparing quaternary ammonium type cationic starch |
| CN101168569A (en) * | 2007-12-04 | 2008-04-30 | 天津科技大学 | Method for preparing cationic starch with high substitution degree |
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| CN101033260A (en) * | 2006-03-10 | 2007-09-12 | 四平帝达变性淀粉有限公司 | Method of preparing quaternary ammonium type cationic starch |
| CN101168569A (en) * | 2007-12-04 | 2008-04-30 | 天津科技大学 | Method for preparing cationic starch with high substitution degree |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104086704A (en) * | 2014-06-13 | 2014-10-08 | 华南理工大学 | Starch grafted acrylamide and preparation method and application thereof |
| CN104861213A (en) * | 2015-05-06 | 2015-08-26 | 金东纸业（江苏）股份有限公司 | Method for preparing complex starch |
| CN106087561A (en) * | 2016-06-13 | 2016-11-09 | 北京林业大学 | A kind of paper strengthening agent and production method thereof |
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Effective date of registration: 20201118 Address after: 523081 opposite to Lishao office, Yanjiang Avenue, Humen Port chemical industry park, Shatian Town, Dongguan City, Guangdong Province Patentee after: GUANGDONG MAIKERUI CHEMICAL TECHNOLOGY Co.,Ltd. Address before: 510640 Tianhe District, Guangdong, No. five road, No. 381, Patentee before: SOUTH CHINA University OF TECHNOLOGY |