CN103485238B - The method of paper strengthening agent is prepared in a kind of corncob modification - Google Patents
The method of paper strengthening agent is prepared in a kind of corncob modification Download PDFInfo
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- CN103485238B CN103485238B CN201310449300.3A CN201310449300A CN103485238B CN 103485238 B CN103485238 B CN 103485238B CN 201310449300 A CN201310449300 A CN 201310449300A CN 103485238 B CN103485238 B CN 103485238B
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Abstract
A method for paper strengthening agent is prepared in corncob modification, and corncob pulverizes obtained 80 object maize cob meals; Be mixed with the aqueous solution with the glacial acetic acid of maize cob meal 20wt% ~ 30wt% and the sodium chlorite of 20wt% ~ 30wt%, maize cob meal processes 50 ~ 70 minutes at 75 ~ 80 DEG C of temperature in the described aqueous solution; Add and use the glacial acetic acid of maize cob meal 20wt% ~ 30wt% and the sodium chlorite of 20wt% ~ 30wt%, at 75 ~ 80 DEG C of temperature, continue process 50 ~ 70 minutes; Intermediate cools, filter, be washed with water to washing lotion not in acid, obtained white intermediate product; White intermediate product is joined the suspension making 5wt% ~ 12wt% in 60V% ~ 90V% ethanol; Add the NaOH of white intermediate product oven-dry weight 0.6 ~ 1.2 weight portion and the sodium chloroacetate ethanolic solution of 0.8 ~ 1.5 weight portion, at 60 ~ 80 DEG C of temperature, white intermediate product was through carboxy methylation 70 ~ 150 minutes; After filtration, with after the washing of 75V% ~ 95V% ethanolic solution, obtained paper strengthening agent.
Description
Technical field
The present invention relates to the paper strengthening agent of paper technology, particularly a kind of take corncob as the production method of Material synthesis paper strengthening agent, is specifically related to the corncob method of modifying being used as paper strengthening agent.
Background technology
China is large agricultural country, string aboundresources.Corncob is the fruit axle after corn ear sloughs seed.Corn yield, can the corncob of by-product 2,000 ten thousand tons every year at 1.1 ~ 1.3 hundred million tons, but corncob is as a kind of agricultural wastes, multiplexly at present makes fuel, causes very large waste.At present, all conduct a research around corncob deep processing and comprehensive utilization both at home and abroad, develop the new way of a series of corncob comprehensive process.Along with the continuous enhancing of China's scientific and technological strength, the field of deep of corncob constantly expands, and current many products achieve suitability for industrialized production, makes this waste material obtain recycling.Along with corn yield improves day by day, the amount of corncob improves greatly, and continue the reproducible corncob of research and development and prepare Biodegradable material or chemicals, to plant resources, high-valued and environmental protection is extremely important.
Summary of the invention
The object of the present invention is to provide a kind of corncob modification to prepare the method for paper strengthening agent, the chemical group contained by corncob, specific aim is transformed, and obtained nanoscale paper strengthening agent, can strengthen the intensity of paper.
In order to solve the problems of the technologies described above, the method for paper strengthening agent is prepared in a kind of corncob modification provided by the invention, at least comprises the following steps:
1) corncob pulverizes obtained 80 object maize cob meals;
2) be mixed with the aqueous solution with the described glacial acetic acid of maize cob meal 20wt% ~ 30wt% and the sodium chlorite of 20wt% ~ 30wt%, maize cob meal processes 50 ~ 70 minutes at 75 ~ 80 DEG C of temperature in the described aqueous solution;
3) after upper step process, add the described glacial acetic acid of maize cob meal 20wt% ~ 30wt% and the sodium chlorite of 20wt% ~ 30wt%, at 75 ~ 80 DEG C of temperature, continue process 50 ~ 70 minutes;
4) intermediate after upper step process cools, filter, be washed with water to washing lotion not in acid, obtained white intermediate product;
5) white intermediate product is joined the suspension making 5wt% ~ 12wt% in 60V% ~ 90V% ethanol; Add the NaOH of white intermediate product oven-dry weight 0.6 ~ 1.2 weight portion and the sodium chloroacetate of 0.8 ~ 1.5 weight portion, wherein said sodium chloroacetate is dissolved in after in the ethanolic solution of its weight 20 ~ 60 times of 95V% and adds, at 60 ~ 80 DEG C of temperature, described white intermediate product was through carboxy methylation 70 ~ 150 minutes.
6) after filtration, with paper strengthening agent obtained after the washing of 75V% ~ 95V% ethanolic solution.
Further, the method for paper strengthening agent, step 4 are prepared in described corncob modification) in filter the filtered fluid that obtains and be back to step 2) in.
The beneficial effect that the present invention brings: adopt sodium chlorite process to make it particle and diminish, reach nanoscale, sodium chloroacetate in the basic conditions, hydroxycarboxymethyl in nano-scale particle is changed into carboxymethyl, when paper strengthening agent add to manufacture paper with pulp in paper pulp time, the adhesion between paper pulp fiber can be strengthened, thus improve the physical strength of paper.With agricultural wastes corncob for raw material, realize the comprehensive utilization of renewable agricultural wastes resource.
Accompanying drawing explanation
Accompanying drawing is used to provide a further understanding of the present invention, and form a application's part, schematic description and description of the present invention, for explaining the present invention, does not form inappropriate limitation of the present invention.In the accompanying drawings:
Fig. 1 is the reinforcing agent granular size figure that embodiment obtains;
Fig. 2 is the graph of a relation of carboxyl-content and folding strength;
Fig. 3 is the relation of carboxyl-content and burst index;
Fig. 4 is the relation of carboxyl-content and tear index;
Fig. 5 is the relation of carboxyl-content and tensile index.
Detailed description of the invention
Embodiment 1: by obtained for corncob grinding and sieving 80 object maize cob meals; Be mixed with the aqueous solution with the described glacial acetic acid of maize cob meal 25wt% and the sodium chlorite of 25wt%, maize cob meal processes 60 minutes at 75 DEG C of temperature in the described aqueous solution; Continue to add the described glacial acetic acid of maize cob meal 25wt% and the sodium chlorite of 25wt%, maize cob meal continues process 50 minutes at 80 DEG C of temperature; The intermediate obtained after process cools, filter, be washed with water to washing lotion not in acid, obtained white intermediate product; White intermediate product is joined in the ethanol of 60V%, make the suspension of 5wt%; Add the described NaOH of white intermediate product oven-dry weight 0.6 weight portion and the sodium chloroacetate of 0.8 weight portion, wherein said sodium chloroacetate adds after being dissolved in and making solution in the ethanol of its weight 20 times of 95V% again, described white intermediate product at 60 DEG C of temperature through carboxy methylation 70 minutes, wash with 75V% ethanolic solution, finally with the washing of 95V% ethanolic solution, filtration drying obtains described paper strengthening agent.After tested, carboxyl-content is 160.0mmol/kg, and C element mass percentage is 29.90%.
Embodiment 2: by obtained for corncob grinding and sieving 80 object maize cob meals; Be mixed with the aqueous solution with the described glacial acetic acid of maize cob meal 30wt% and the sodium chlorite of 30wt%, maize cob meal processes 50 minutes at 80 DEG C of temperature in the described aqueous solution; Continue to add the described glacial acetic acid of maize cob meal 20wt% and the sodium chlorite of 20wt%, maize cob meal continues process 70 minutes at 75 DEG C of temperature; The intermediate obtained after process cools, filter, be washed with water to washing lotion not in acid, obtained white intermediate product; White intermediate product is joined the suspension making 8wt% in 70V% ethanol, add the described NaOH of white intermediate product oven-dry weight 0.8 weight portion and the sodium chloroacetate of 1.0 weight portions, wherein said sodium chloroacetate adds after being dissolved in and making solution in the ethanol of its weight 30 times of 95V% again, described white intermediate product is at 70 DEG C of temperature, through carboxy methylation 90 minutes, with the washing of 75V% ethanolic solution, finally with the washing of 95V% ethanolic solution, filtration drying obtains described paper strengthening agent.After tested, the carboxyl-content of the paper strengthening agent obtained is 192.3mmol/kg, and C element mass percentage is 29.23%.
Embodiment 3: by obtained for corncob grinding and sieving 80 object maize cob meals; Be mixed with the aqueous solution with the described glacial acetic acid of maize cob meal 20wt% and the sodium chlorite of 20wt%, maize cob meal processes 60 minutes at 78 DEG C of temperature in the described aqueous solution; Continue to add the described glacial acetic acid of maize cob meal 30wt% and the sodium chlorite of 30wt%, maize cob meal continues process 60 minutes at 77 DEG C of temperature; The intermediate obtained after process cools, filter, be washed with water to washing lotion not in acid, obtained white intermediate product; White intermediate product is joined the suspension making 10wt% in 80V% ethanol, add the described NaOH of white intermediate product oven-dry weight 1.0 weight portion and the sodium chloroacetate of 1.2 weight portions, wherein said sodium chloroacetate adds after being dissolved in and making solution in the ethanol of its weight 45 times of 95V% again, described white intermediate product at 70 DEG C of temperature through carboxy methylation 110 minutes, wash with 75V% ethanolic solution, finally with the washing of 95V% ethanolic solution, filtration drying obtains described paper strengthening agent.After tested, the carboxyl-content obtaining paper strengthening agent is 218.5mmol/kg, and C element mass percentage is 29.02%.
Embodiment 4: by obtained for corncob grinding and sieving 80 object maize cob meals; Be mixed with the aqueous solution with the described glacial acetic acid of maize cob meal 22wt% and the sodium chlorite of 22wt%, maize cob meal processes 60 minutes at 78 DEG C of temperature in the described aqueous solution; Continue to add the described glacial acetic acid of maize cob meal 28wt% and the sodium chlorite of 28wt%, maize cob meal continues process 60 minutes at 77 DEG C of temperature; The intermediate obtained after process cools, filter, be washed with water to washing lotion not in acid, obtained white intermediate product; The suspension of 12wt% is made in 90%V% ethanol, add the described NaOH of white intermediate product oven-dry weight 1.2 weight portion and the sodium chloroacetate of 1.5 weight portions, described sodium chloroacetate adds after being dissolved in and making solution in the ethanol of its weight 60 times of 95V% again, described white intermediate product at 80 DEG C of temperature through carboxy methylation 130 minutes, wash twice with 75V% ethanolic solution, finally wash once with 95V% ethanolic solution, filtration drying obtains described paper strengthening agent.After tested, the carboxyl-content obtaining paper strengthening agent is 211.8mmol/kg, and C element mass percentage is 29.16%.
Popular Kraft pulp water is discongested rear making beating to 40 ° of SR, be diluted to the concentration of 2 ‰, add the aluminum sulfate of absolute dried paper pulp 0.5wt%, regulate the pH value to 5 of slurry, add the paper strengthening agent that absolute dried paper pulp 1wt% embodiment 1 ~ 4 is obtained, after stirring, copy by conventional sheet forming apparatus method (QB/T3703-99) of the preparation of paper pulp laboratory page and get quantitative 60g/m
2page.At 105 DEG C after slaking 20min, equilibrium water conten 24h under constant temperature and humidity condition, tests by mensuration constant rate of extension method (100mm/min) (GB/T22898-2008), the mensuration (GB/T455-2002) of paper and paperboard tearability of paper and paperboard tensile strength, the mensuration (GB/T454-2002) of paper bursting strength, mensuration (GB/T457-2008) method of paper and paperboard folding strength.
Reference examples: be identical poplar slurry and experimental condition, the trial-production sheet paper products when not adding paper strengthening agent provided by the invention.
Test result is as following table:
Fig. 1 is the reinforcing agent granular size figure that embodiment obtains, and reaches nano-scale.Nano level paper strengthening agent not only has the usefulness of general reinforcing agent, also can due to nano effect, to the enhancing better effects if of paper.
Fig. 2 embodies the effect tendency of carboxyl-content content to paper folding strength.Along with the increase of carboxyl-content, folding strength is in rear downward trend of first rising.
Fig. 3 embodies the effect tendency of carboxyl-content to paper burst index.Along with the increase of carboxyl-content, paper burst index is in downward trend slightly after first rising.
Fig. 4 embodies the effect tendency of carboxyl-content to paper tear index.Along with the increase of carboxyl-content, paper tear index is in rear downward trend of first rising.
Fig. 5 embodies the effect tendency of carboxyl-content to paper tensile index.Along with the increase of carboxyl-content, paper tensile index is in rear downward trend of first rising.
Result shows: the increase of the carboxyl-content of the paper strengthening agent obtained along with nanoscale corncob modified product, and the dry tensile strength of paper in rear downward trend of first rising, but changes not obvious; Burst index, tear index and dry tensile strength similar trend; Folding strength is downward trend slightly after first significantly rising, but all good than the performance of reference examples, after carboxy methylation, the water-soluble increase of nanoscale corncob modified product, add nano effect, the adhesion between fiber is increased, and tensile index, folding strength and bursting strength also increase thereupon.But the carboxy methylation time lengthens, and carboxyl-content declines slightly, paper strength change is very little.Preferably add the sodium chloroacetate of white intermediate product oven-dry weight 0.8 ~ 1.2 weight portion, the carboxymethyl content 160.0 ~ 218.5mmol/kg of the paper strengthening agent that 70 ~ 110 minutes reaction time obtained, has good technique effect.
Obviously, the invention is not restricted to above preferred embodiment, in the spirit that also can limit in the claims in the present invention and description, carry out conversion and the improvement of various ways, can same technical problem be solved, and obtain the technique effect of expection, therefore not repeat.Those of ordinary skill in the art can from content disclosed by the invention directly or all schemes associated, as long as within the spirit limited in claim, also belong to protection scope of the present invention.
Claims (2)
1. a method for paper strengthening agent is prepared in corncob modification, it is characterized in that, at least comprises the following steps:
1) corncob pulverizes obtained 80 object maize cob meals;
2) be mixed with the aqueous solution with the described glacial acetic acid of maize cob meal 20wt% ~ 30wt% and the sodium chlorite of 20wt% ~ 30wt%, maize cob meal processes 50 ~ 70 minutes at 75 ~ 80 DEG C of temperature in the described aqueous solution;
3) after upper step process, add the described glacial acetic acid of maize cob meal 20wt% ~ 30wt% and the sodium chlorite of 20wt% ~ 30wt%, at 75 ~ 80 DEG C of temperature, continue process 50 ~ 70 minutes;
4) intermediate after upper step process cools, filter, be washed with water to washing lotion not in acid, obtained white intermediate product;
5) white intermediate product is joined the suspension making 5wt% ~ 12wt% in 60V% ~ 90V% ethanol; Add the NaOH of white intermediate product oven-dry weight 0.6 ~ 1.2 weight portion and the sodium chloroacetate of 0.8 ~ 1.5 weight portion, described sodium chloroacetate is dissolved in after in the ethanolic solution of its weight 20 ~ 60 times of 95V% and adds, at 60 ~ 80 DEG C of temperature, described white intermediate product was through carboxy methylation 70 ~ 150 minutes;
6) after filtration, with after the washing of 75V% ~ 95V% ethanolic solution, obtained paper strengthening agent.
2. the method for paper strengthening agent is prepared in corncob modification according to claim 1, it is characterized in that: step 4) in filter the filtered fluid that obtains and be back to step 2) in.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102852035A (en) * | 2012-08-27 | 2013-01-02 | 北京林业大学 | Paper reinforcing agent, and production and usage method thereof |
| CN102852036A (en) * | 2012-08-27 | 2013-01-02 | 北京林业大学 | Cationic paper reinforcing agent, and production method and usage method thereof |
| CN102852037A (en) * | 2012-08-27 | 2013-01-02 | 北京林业大学 | Paper reinforcing agent prepared from flotation deinking residue fiber, and production and usage method thereof |
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| CN102852035A (en) * | 2012-08-27 | 2013-01-02 | 北京林业大学 | Paper reinforcing agent, and production and usage method thereof |
| CN102852036A (en) * | 2012-08-27 | 2013-01-02 | 北京林业大学 | Cationic paper reinforcing agent, and production method and usage method thereof |
| CN102852037A (en) * | 2012-08-27 | 2013-01-02 | 北京林业大学 | Paper reinforcing agent prepared from flotation deinking residue fiber, and production and usage method thereof |
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