CN1085279C - Non-wood fibre paper strengthening agent - Google Patents
Non-wood fibre paper strengthening agent Download PDFInfo
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- CN1085279C CN1085279C CN99113918A CN99113918A CN1085279C CN 1085279 C CN1085279 C CN 1085279C CN 99113918 A CN99113918 A CN 99113918A CN 99113918 A CN99113918 A CN 99113918A CN 1085279 C CN1085279 C CN 1085279C
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Abstract
The present invention relates to a non-wood fiber paper strengthening agent, which is a multiple modified starch derivative which is obtained through the following reaction that a. alkali catalyst, a cation etherifying agent and starch carry out cation etherification reaction, with the replacement degree from 0.010 to 0.035; b. anion esterifying agent is sprayed, phosphoric acid is used for adjusting a pH value, and anion reaction is carried out to lead the replacement degree to be from 0.005 to 0.030; c. 10% of starch is added into the strengthening agent, and strengthening reaction is carried out; a product is obtained through post-treatment. The product of the present invention can improve a breaking length and a breaking resistance degree of finished paper by 15 to 20%, saves wood pulp by 10 to 20%, has certain remaining aiding and filtering aiding effects, and has wide application range.
Description
Non-wood-fiber mainly is meant the paper grade (stock) fiber made from straw, awns bar, reed, straw, bagasse, mao bamboon and waste paper.Because non-wood-fiber is short, so paper strength is poor, has become a difficult problem in the paper-making industry.American documentation literature discloses as the cationic starch technology of reinforcing agent such as US2813093 and US 2876217, anion acid ester starch technology such as US2929520 and US3077469 etc., amphoteric starch derivative technology such as US4093510, common type reinforcing agent technology such as US5104487.Above-mentioned technology all strengthens at lumber fibre, and wherein cationic starch, phosphate ester starch lack the antijamming capability to non-wood-fiber impurity chemical substance, to the non-wood-fiber DeGrain; Though the amphoteric starch effect is better than cationic starch and phosphate ester starch, because manufacturing technique cost height, not penetration and promotion as yet so far; Though and the common type technology can improve effect, to add respectively when using, it is inconvenient that the user feels.
The objective of the invention is in order to overcome the deficiency of above-mentioned prior art, provide a kind of and can improve effectively with the paper of non-wood-fiber manufacturing and the non-wood-fiber paper making intensifier of cardboard physical strength.
The present invention is a kind of multicomponent modified starch derivative, obtains by following reaction:
A) CATION etherification reaction: reaction can be adopted solvent method, wet method, dry method, semidry method, and the present invention adopts semidry process.Under the base catalyst effect, cationic etherifying agent is sprayed on the starch powder, make fully evenly mixedly, temperature is at 30～90 ℃, and common 50～80 ℃, reacted 0.5～10 hour, common 4～6 hours, making CATION etherificate base substitution value was 0.010～0.035;
B) anionization reaction: reaction can be adopted wet method, dry method, the present invention's dry method.Add anion esterification agent at spray below 50 ℃, and transfer pH value to 4～8 (measuring under mixture pH value 3% concentration) with acid catalyst, after stirring, with the pneumatic conveying drying method material moisture content is reduced to 5～8%, at 80～160 ℃, under common 120～140 ℃, reacted 1～6 hour, common 2～4 hours, making anion esterification base substitution value was 0.005～0.030, is cooled to 40～60 ℃ then;
C) help strong reaction: the strength assistant agent of amount of starch 1～10% is added and evenly mixed, at room temperature 0.5～4 hour reaction time, common 1～3 hour, post processing promptly got non-wood fibre paper strengthening agent.
Product of the present invention can also improve by controlling following parameter, and promptly CATION etherificate base substitution value is 0.015～0.030, and anion esterification base substitution value is 0.010～0.025, and strength assistant agent is 1.5～5.0% of an amount of starch.
Cationic etherifying agent is 2-diethylamino diethylaluminum monochloride (DEC), 2,3-glycidyl diethylamide, 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride, 4-chloro-2 butylene trimethyl ammonium chlorides, β-chloropropyl trimethyl ammonium chloride;
Base catalyst is potassium hydroxide, calcium hydroxide, NaOH, magnesium hydroxide or two kinds mixture wherein; Acid catalyst is a kind of in hydrochloric acid, sulfuric acid and the phosphoric acid.
Anionics are sodium dihydrogen phosphate, sodium hydrogen phosphate, or their compound;
Strength assistant agent is formic acid, acetic acid, adipic acid, aceticanhydride, chloroacetic chloride or its mixture.When selecting the mixture of acetic acid and aceticanhydride for use, its mol ratio is 1: 2.
Product of the present invention can effectively prevent the interference of impurity in the non-wood-fiber, its cardinal principle is that the anion substituent of starch molecule helps to eliminate and is an impediment to starch in the non-wood-fiber system and is adsorbed on those heteroions on the fiber, and cationic substituent is shielded; Otherwise; cationic substituent can be eliminated the interference of anionic impurity in the non-wood-fiber system effectively in the starch molecule; and anion substituent in the molecule is shielded; the result that this yin, yang ion substituent is coordinated mutually; add the effect that helps strong basis group, make non-wood-fiber is produced appreciable results.
When product of the present invention is used, can prevent the interference of hydridization material in the non-wood-fiber effectively in non-wood-fiber, also have certain retention, help the filter effect.Wood pulp and straw pulp than constant prerequisite under, can make fracture length and bursting strength improve 15～20%, be the paper of (70: 30) for wood pulp and straw pulp proportioning, under the constant prerequisite of assurance paper quality, saving wood pulp 10～20%.Product of the present invention has extensive applicability, except that non-wood-fiber, mixed pulp, wood pulp is all had good effect.Product of the present invention is not only applicable to acid papermaking, in being applicable to too, alkaline paper-making.
Product of the present invention adopts semidry method-dry method-semidry process preparation, has avoided the phase mutual interference between the different substituents effectively, has reduced production cost simultaneously, has improved reaction efficiency, has solved the three wastes problem in producing.
It is that main raw material carries out modification that product of the present invention adopts starch, and starch can be the product that barley, wheat, potato, corn, cassava, cassava, rice etc. are made, respectively by cationization, and anion and help strong three phases to realize.
Following examples are illustrated the present invention more fully, but not as restriction of the present invention, in addition, umber in the following example and percentage all are in oven-dry weight (unless otherwise indicated).
Embodiment 1
Get 4.7 parts of β-chloropropyl trimethyl ammonium chloride, mix for 1.8 parts, spray then on 162 parts of cornstarchs, fully stir mixedly, and be warmed up to 70 ℃, be incubated 4 hours with NaOH; Cool to 50 ℃ and transfer pH value to 7.0 (the mixture pH value is measured) under 3% concentration with phosphoric acid, spray 20 parts in sodium dihydrogen phosphate and sodium hydrogen phosphate (1: 1) mixture (concentration is 10%) again, after stirring, with the pneumatic conveying drying method material moisture content is reduced to 7%, be warming up to 125 ℃ again, preserved moisture 2 hours, cooling again is when being cooled to 50 ℃; PH value to 7.5 and moisture content are regulated in 30 parts of (concentration 10%) reactions of the spray acetic acid and aceticanhydride (1: the 2) aqueous solution 2 hours, and post processing gets product of the present invention.
Embodiment 2
Get 5.5 parts of 3-chloro-2-hydroxypropyl-trimethyl ammonium chlorides, mix for 2.0 parts with potassium hydroxide, spray then on 162 portions of wheaten starches, stir, and be warmed up to 73 ℃, be incubated 4 hours, cool to 50 ℃ and transfer pH value with 6.5, spray sodium dihydrogen phosphate and sodium hydrogen phosphate (1: 1) mixture again, 25 parts (concentration is 10%) with sulfuric acid, after mixing, with the pneumatic conveying drying method material moisture content is reduced to 6.5%, be warming up to 127 ℃ again, be incubated 2 hours, cooling again, when being cooled to 50 ℃, the spray acetic acid and 30 parts of aceticanhydride (1: the 2) aqueous solution (concentration 10%) reacted 2 hours, regulate pH value to 7.0, post processing promptly gets product of the present invention.
Product of the present invention application conditions in non-wood-fiber:
1, the addition of product is 0.3～2.5%, and more suitable scope is 0.5～2.0%, is preferably 0.8～1.8%.
2, the gelatinization concentration 3～8% of product, preferably 5%, be uniformly dispersed with cold water earlier, stir and be warming up to 90～95 ℃, be incubated 20～30 minutes.
3, the interpolation concentration 0.5～2.0% of product is preferably 0.8～1.5%.
Application example 1:
Product with the embodiment of the invention 1 carries out gelatinization earlier: claim 1 duplicate samples, add 99 parts of cold water and stir that water-bath is raised to gelatinization in 90～95 ℃ of water, is incubated 20 minutes, takes out cooling.
Full reed pulp is carried out craft copies sheet, the interpolation order: in reed pulp, add the product 1.5% of embodiment earlier, stirred 1 minute, add alum 2% again, add anion dispersion rosin size 0.5% then, last filled its effect of 20% talcum powder:
| Sample 1 | Quantitatively (g/m2) | Average pulling force (g) | Fracture length (m) | Raising rate (%) |
| Blank | 64.55 | 2263 | 2338 | |
| Embodiment 1 sample | 66.54 | 3150 | 3156 | 34.99 |
| Embodiment 2 samples | 67.89 | 3320 | 3260 | 39.44 |
Application example 2:
Bleached wheat straw pulp is carried out craft copy sheet.Adopt the talcum powder as filler, sizing agent is anion dispersion rosin size and alum, and reinforcing agent adopts embodiment 1 product, first gelatinization before using, and its interpolation order and consumption:
Retention and enhancing effect:
| Sample 1 | Quantitative (g/m 2) | Average pulling force (g) | Fracture length (m) | Raising rate (%) | Filler retention (%) |
| Blank | 58.07 | 3975 | 4564 | 63.9 | |
| Cationic starch | 60.91 | 4757 | 5207 | 14.09 | 71.3 |
| Embodiment 1 product | 60.31 | 4972 | 5497 | 20.44 | 84.2 |
Application example 3:
Natural color pulp is carried out craft copy sheet, earlier the product of the embodiment of the invention 2 is pressed aforementioned gelatinization, adding concentration is 1%, interpolation is in proper order: add present embodiment 2 products 1.5% earlier, stirred 1 minute, add alum 2% again, add anion dispersion rosin size 0.5% at last, its effect:
| Sample 1 | Quantitative (g/m 2) | Average pulling force (g) | Fracture length (m) | Growth rate (%) |
| Blank | 77.96 | 4983 | 4261 | |
| Cationic starch | 77.91 | 6224 | 5326 | 24.99 |
| Embodiment 2 samples | 77.82 | 6958 | 5961 | 39.90 |
Application example 4:
Practical application effect in paper plant
(1) operating condition
Slurry: sulfate wood pulp and sulfate bamboo pulp
Paper machine: 2100mm multi-cylinder long mesh paper machine
The speed of a motor vehicle: 100～105m/min
Paper kind: 80g/m
2Sack kraft paper
The interpolation order and the addition of various chemical addition agents
The gelatinizing method of sample is by preceding described, and adding concentration is 1%.
(2) effect
| Wet end furnish | Addition (%) | Quantitative (g/m 2) | Tensile strength (horizontal stroke) (KN/m) | Raising rate (%) | |
| Bamboo pulp | Wood pulp | ||||
| 22 | 78 | 0 | 75 | 2.63 | 25.10 |
| 22 | 78 | 1.5 | 80.5 | 3.29 | |
| 36 | 64 | 0 | 78 | 2.43 | 30.4 |
| 36 | 64 | 1.5 | 82 | 3.17 | |
| 42 | 58 | 0 | 77.5 | 2.17 | 23.50 |
| 42 | 58 | 1.5 | 96 | 2.68 | |
Claims (7)
1, a kind of non-wood fibre paper strengthening agent is characterized in that obtaining by following reaction:
A) CATION etherification reaction: under the base catalyst effect, cationic etherifying agent is sprayed on the starch powder, make fully to mix evenly, temperature was reacted 4～6 hours at 50～80 ℃, and making CATION etherificate base substitution value is 0.010～0.035;
B) anionization reaction: add anion esterification agent at spray below 50 ℃, and after transferring pH value to 4～8 (the mixture pH value is being measured under 3% concentration) to stir with acid catalyst, with the pneumatic conveying drying method material moisture is reduced to 5～8%, be warming up to 120～140 ℃ again, reacted 2～4 hours, making anion esterification base substitution value is 0.005～0.030, is cooled to 40～60 ℃ then;
C) help strong reaction: the reinforcing agent that adds starch consumption 1～10% is also evenly mixed, and reaction is 1-3 hour under the room temperature, and post processing promptly gets non-wood fibre paper strengthening agent.
2, non-wood fibre paper strengthening agent as claimed in claim 1 is characterized in that its described CATION etherificate base substitution value is 0.015～0.030, and anion esterification base substitution value is 0.010～0.025, and the consumption of strength assistant agent is 1.5～5.0% of an amount of starch.
3, non-wood fibre paper strengthening agent as claimed in claim 1, it is characterized in that described cationic etherifying agent is 2-diethylamino diethylaluminum monochloride, 2,3-glycidyl diethylamide, 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride, 4-chloro-2-butylene trimethyl ammonium chloride, β-chloropropyl trimethyl ammonium chloride.
4, non-wood fibre paper strengthening agent as claimed in claim 1 is characterized in that described base catalyst is potassium hydroxide, calcium hydroxide, NaOH, magnesium hydroxide or two kinds mixture wherein.
5, non-wood fibre paper strengthening agent as claimed in claim 1 is characterized in that described anion esterification agent is sodium dihydrogen phosphate, sodium hydrogen phosphate, or their compound.
6, non-wood fibre paper strengthening agent as claimed in claim 1 is characterized in that described acid catalyst is a kind of in hydrochloric acid, sulfuric acid and the phosphoric acid.
7, non-wood fibre paper strengthening agent as claimed in claim 1 is characterized in that described strength assistant agent is the mixture of acetic acid and aceticanhydride, and its mol ratio is 1: 2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99113918A CN1085279C (en) | 1999-07-27 | 1999-07-27 | Non-wood fibre paper strengthening agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99113918A CN1085279C (en) | 1999-07-27 | 1999-07-27 | Non-wood fibre paper strengthening agent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1281920A CN1281920A (en) | 2001-01-31 |
| CN1085279C true CN1085279C (en) | 2002-05-22 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN99113918A Expired - Lifetime CN1085279C (en) | 1999-07-27 | 1999-07-27 | Non-wood fibre paper strengthening agent |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101724083B (en) * | 2010-01-15 | 2013-05-08 | 广西大学 | Method for producing modified starch |
| CN102477100B (en) * | 2010-11-23 | 2013-12-25 | 兰州瑞特变性淀粉科技有限公司 | Esterification-etherification dual-modified starch and solid phase preparation method thereof |
| CN102587208B (en) * | 2011-12-31 | 2014-07-09 | 杭州纸友科技有限公司 | Method for manufacturing anti-interference recycled paper reinforcing agent |
| CN102942633B (en) * | 2012-12-11 | 2014-12-03 | 广西民族大学 | Clean production method of compound modified starch |
| CN106120448B (en) * | 2016-07-13 | 2017-12-26 | 广西梧州市明阳生化科技有限公司 | A kind of preparation method of composite modified starch |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4093510A (en) * | 1977-04-07 | 1978-06-06 | The United States Of America As Represented By The Secretary Of Agriculture | Xanthated starch amine paper additives |
| US5104487A (en) * | 1988-09-02 | 1992-04-14 | Betz Paper Chem., Inc. | Papermaking using cationic starch and naturally anionic polysacchride gums |
-
1999
- 1999-07-27 CN CN99113918A patent/CN1085279C/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4093510A (en) * | 1977-04-07 | 1978-06-06 | The United States Of America As Represented By The Secretary Of Agriculture | Xanthated starch amine paper additives |
| US5104487A (en) * | 1988-09-02 | 1992-04-14 | Betz Paper Chem., Inc. | Papermaking using cationic starch and naturally anionic polysacchride gums |
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| Publication number | Publication date |
|---|---|
| CN1281920A (en) | 2001-01-31 |
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Assignee: Zhiyou Science & Technology Co., Ltd., Hangzhou Assignor: Hangzhou Chemical and Engineering Institute Contract fulfillment period: 2008.7.1 to 2018.6.30 Contract record no.: 2008330000639 Denomination of invention: Non-wood fibre paper strengthening agent Granted publication date: 20020522 License type: Exclusive license Record date: 2008.9.24 |
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Free format text: EXCLUSIVE LICENCE; TIME LIMIT OF IMPLEMENTING CONTACT: 2008.7.1 TO 2018.6.30 Name of requester: ZHIYOU SCIENCE & TECHNOLOGY CO., LTD., HANGZHOU Effective date: 20080924 |
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Owner name: HANGZHOU RESEARCH INSTITUTE OF CHEMICAL TECHNOLOGY Free format text: FORMER OWNER: HANGZHOU INST. OF CHEMICAL ENGINEERING Effective date: 20121015 |
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Effective date of registration: 20121015 Address after: 310014 lime dam No. 7, Zhejiang, Hangzhou Patentee after: Hangzhou Research Institute of Chemical Technology Co., Ltd. Address before: Hushu lime dam of Hangzhou city in Zhejiang province 310014 No. 7 Patentee before: Hangzhou Chemical and Engineering Institute |
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