CN103242458B - Double-etherification modified starch and preparation method thereof - Google Patents
Double-etherification modified starch and preparation method thereof Download PDFInfo
- Publication number
- CN103242458B CN103242458B CN201310200603.1A CN201310200603A CN103242458B CN 103242458 B CN103242458 B CN 103242458B CN 201310200603 A CN201310200603 A CN 201310200603A CN 103242458 B CN103242458 B CN 103242458B
- Authority
- CN
- China
- Prior art keywords
- starch
- parts
- modified starch
- etherificate
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Abstract
The invention discloses double-etherification modified starch and a preparation method thereof. The double-etherification modified starch is prepared from the following raw materials in parts by weight: 100 parts of starch, 0.010-0.020 part of epoxy chloropropane, 0.8-1.2 parts of water, 0.08-0.12 part of acrylic acid polyacrylamide, 16-18 parts of sodium chloroacetate, 7-8 parts of solid sodium hydroxide and 4-6 parts of industrial alcohol. The preparation method comprises the following steps of: adding the epoxy chloropropane into the starch at first; dispersing by using the acrylic acid polyacrylamide; carrying out a crosslinking reaction, wherein the pH value of the crosslinking reaction is controlled to be 10-10.5, and the temperature of the crosslinking reaction is 50-60 DEG C; then carrying out a carboxymethyl reaction; and adding the sodium chloroacetate, the solid sodium hydroxide and the industrial alcohol, wherein the pH is controlled to be 11-11.5, the reaction temperature is 50-80 DEG C, and the reaction time is 3-5 hours. According to the preparation method, a semi-dry method is adopted for production, and as intracytoplasmic addition, the modified starch is used by matching with cationic starch, so that the total consumption of the starch is lowered, and the quality of paper is greatly improved; and the modified starch is used as a coating starch bonding agent, and does not need gelatinization compared with common coating starch, so that the using effect of the modified starch is improved.
Description
Technical field
The invention belongs to technical field of fine, particularly a kind of bis ether modified starch and preparation method.
Background technology
Modified starch is subject to the favor of paper industry because of its natural nonstaining property.The fast development of China's paper industry is undoubtedly for the modified starch enterprise of China provides the huge market space.Along with paper product are to superior, diversified future development, improving constantly of paper machine speed, and paper waste ratio used constantly increases and causes the every intensity index of paper to decline in papermaking, these factors all to the modified starch of paper making additive propose higher, more carefully, tighter functionalization requirement.Interpolation cationic starch in conventional slurry, coating starch (oxidation acidifying class) has been difficult to adapt to papermaking enterprise, especially produces the enterprise requirements of high-grade paper.
Bis ether modified starch (carboxymethyl starch) is that starch is first cross-linked through etherificate the product formed through carboxymethyl etherification more in the basic conditions.Domestic production method general is at present: 1, dry method and starch, solid caustic soda, and solid sodium chloroacetate mixes, and reaction forms, and the advantage done like this is that pollution is little, and shortcoming is that reaction efficiency is low, reacts uneven.2, wet method, it is produce with water dispersion that generation gets low product, and high substitution value product is then with solvent method, and the advantage done like this is that product is even, but cost is high, pollutes large;
The function that bis ether modified starch is similar to carboxymethyl cellulose mutual, can be used as dispersion agent, tackiness agent, emulsifying agent, water-holding agent, membrane-forming agent, ropiness increasing agent etc., has the good reputation of " industrial monosodium glutamate ".Bis ether modified starch is as a kind of paper making intensifier, and compare with coating starch with the cationic starch used at present, its sexual valence has ten parts of obvious advantages.
Summary of the invention
The object of the present invention is to provide a kind of employing Semi-dry process technique, make simple, pollute little, cost is low, its cold water solubles is applied in paper plant, easy to use, namely can be used as slurry in add, two can coat binding use, there is bis ether modified starch and the preparation method of the incomparable effect of other modified starch.
One of technical solution of the present invention: a kind of bis ether modified starch, be prepared from by following raw material: starch 100 parts, epoxy chloropropane 0.010-0.020 part, 0.8-1.2 parts, water, vinylformic acid polyacrylamide 0.08-0.12 part, sodium chloroacetate 16-18 parts, solid caustic soda 7-8 parts, industrial spirit 4-6 parts.
Be prepared from by following raw material: starch 100 parts, epoxy chloropropane 0.015 part, 1 part, water, vinylformic acid polyacrylamide 0.1 part, sodium chloroacetate 17 parts, solid caustic soda 7.6 parts, industrial spirit 5 parts.
Technical solution of the present invention two: a kind of preparation method of bis ether modified starch, mixed with solid caustic soda by starch, epoxy chloropropane and sodium chloroacetate, spray into reactor reaction by alcohol and water dissolution and form, it is characterized in that being prepared by following raw material, get starch 100 parts;
(1) etherificate is cross-linked:
In described 100 parts of starch, first 0.010-0.020 part epoxy chloropropane, put into 0.8-1.2 parts of water, for subsequent use with 0.08-0.12 part of vinylformic acid polyacrylamide dispersion, cross-linking process first uses 0.08-0.12 part of solid caustic soda that starch pH value is adjusted to 10-10.5, again scattered epoxy chloropropane is sprayed in the starch of modulated good pH value, in 50-60 degree reaction 1-2 hour, namely complete etherificate cross-linking process;
(2) etherificate carboxymethylation:
At the end of etherificate is crosslinked, first adds 6.92-7.88 parts, powder caustic soda, then spray industrial spirit 4-6 parts, then add sodium chloroacetate 16-18 parts, pH value controls at 11-11.5, temperature of reaction 50-80 degree, reaction times 3-5 hour, namely completes the etherificate carboxymethylation stage, obtains bis ether modified starch.
The present invention adopts Semi-dry process, add as in slurry, with cationic starch with the use of, not only reduce the total consumption of starch, and significantly improve paper quality, use as coating starch tackiness agent, compare with general coating starch, not only do not need gelatinization, and the powder and water-holding agent that need use when making coating can be saved.Its result of use is improved.
Employing dual-ether method manufactures, and both through etherificate Gao Lian, again through etherificate carboxymethylation, the use properties of product is obtained further perfect, its production technique and using method have one's own knack.The present invention is new through looking into, and has novelty.And the present invention adopts Semi-dry process technique, process environments is excellent, energy-saving and cost-reducing, production cost is low, and technique is simple, constant product quality, pilot reacts excellent after putting on market and using, compare with common cationic starch, coating starch, folding endurance significantly improves, and printing, wear resistance etc. are clearly better.Especially be applicable to secondary stock, the production of high-speed paper machine and high-grade paper, its cost performance has sizable advantage, has wide market development space in China.
Bis ether modified starch of the present invention is in coated manila, when preparing coating, directly can mix the tackiness agent such as Some substitute butadiene-styrene rubber in powder, and it add also without the need to adding water-holding agent, dispersion agent, compare with general coating starch, its not gelatinization, but also eliminate the input of water-holding agent, dispersion agent, the effect of use is very.Compare with general coating starch, environmental protection is laborsaving, province consumes, save money.
The present invention, in boxboard and tissue paper, adds as in slurry, directly adds machine chest, the paper be ferreted out, compare with simple cationic starch, and the raising of its physical index can be more significantly many.And be of wide application, in White Board, when making coating, directly added in coating by the bis ether modified starch that the present invention produces, every part of alternative 3.5 parts of butadiene-styrene rubber class tackiness agents of bis ether modified starch, substitution rate is high, and economic benefit is fairly obvious.
Embodiment
The present invention specifically can be implemented by the technology illustrated in summary of the invention, and reaches effect of the present invention, can be conducted further description by the following examples to the present invention, but scope of the present invention is not limited to following embodiment.
Embodiment 1: be preferably prepared from by following raw material: starch 100 parts, epoxy chloropropane 0.015 part, 1 part, water, vinylformic acid polyacrylamide 0.1 part, sodium chloroacetate 17 parts, solid caustic soda 7.6 parts, industrial spirit 5 parts.
The preparation method of bis ether modified starch, is prepared by following raw material, gets starch 100 parts;
(1) etherificate is cross-linked:
In described 100 parts of starch, first 0.015 part of epoxy chloropropane, put into 1 part of water, for subsequent use with 0.1 part of vinylformic acid polyacrylamide dispersion, cross-linking process first with 0.1 part of solid caustic soda, starch pH value is adjusted to 10-10.5, again scattered epoxy chloropropane is sprayed in the starch of modulated good pH value, in 50-60 degree reaction 1-2 hour, namely complete etherificate cross-linking process;
(2) etherificate carboxymethylation:
At the end of etherificate is crosslinked, first adds 7.5 parts, powder caustic soda, then spray industrial spirit 5 parts, then add sodium chloroacetate 17 parts, pH value controls at 11-11.5, temperature of reaction 50-80 degree, in 4 hours reaction times, complete the etherificate carboxymethylation stage, obtain bis ether modified starch.
One, technical indicator
1, outward appearance: white or pale yellow powder;
2, moisture content: <13%;
3, pH value (6% solution): 11 ± 0.5;
4, fineness (80 mesh sieve percent of pass) >=95 parts;
5, substitution value: 0.45-0.65;
6, viscosity: 6%(DNJ-79) >=10mpas.
Two, mechanism is used
Bis ether modified starch of the present invention has excellent dispersiveness, cohesiveness, when adding in paper pulp in effect slurry, make paper pulp fiber mix evenly, copy fibre array when selecting more unordered (normally manufacture paper with pulp paper time, fibre array mostly can along head box stream slurry order ordered arrangement, the folding of paper will be affected like this and tear), because the membership that adds of bis ether modified starch of the present invention changes this manufacturing paper with pulp property condition, thus the physical index of paper can be improved, as coating adhesive, because bis ether modified starch characteristic of the present invention causes not only very economically to reduce the tackiness agents such as butadiene-styrene rubber, and dispersion agent and water-holding agent can not be used, raising quality is reduced costs clearly.
Claims (4)
1. a preparation method for bis ether modified starch, is mixed with solid caustic soda by starch, epoxy chloropropane and sodium chloroacetate, sprays into reactor reaction and forms, it is characterized in that being prepared by following raw material, get starch 100 parts by alcohol and water dissolution;
(1) etherificate is cross-linked:
In described 100 parts of starch, first 0.010-0.020 part epoxy chloropropane, put into 0.8-1.2 parts of water, for subsequent use with 0.08-0.12 part of vinylformic acid polyacrylamide dispersion, cross-linking process first uses 0.08-0.12 part of solid caustic soda that starch pH value is adjusted to 10-10.5, again scattered epoxy chloropropane is sprayed in the starch of modulated good pH value, in 50-60 degree reaction 1-2 hour, namely complete etherificate cross-linking process;
(2) etherificate carboxymethylation:
At the end of etherificate is crosslinked, first adds 6.92-7.88 parts, powder caustic soda, then spray industrial spirit 4-6 parts, then add sodium chloroacetate 16-18 parts, pH value controls at 11-11.5, temperature of reaction 50-80 degree, reaction times 3-5 hour, namely completes the etherificate carboxymethylation stage, obtains bis ether modified starch.
2. the preparation method of a kind of bis ether modified starch according to claim 1, is characterized in that being prepared by following raw material, gets starch 100 parts;
(1) etherificate is cross-linked:
In described 100 parts of starch, first 0.015 part of epoxy chloropropane, put into 1 part of water, for subsequent use with 0.1 part of vinylformic acid polyacrylamide dispersion, cross-linking process first with 0.1 part of solid caustic soda, starch pH value is adjusted to 10-10.5, again scattered epoxy chloropropane is sprayed in the starch of modulated good pH value, in 50-60 degree reaction 1-2 hour, namely complete etherificate cross-linking process;
(2) etherificate carboxymethylation:
At the end of etherificate is crosslinked, first adds 7.5 parts, powder caustic soda, then spray industrial spirit 5 parts, then add sodium chloroacetate 17 parts, pH value controls at 11-11.5, temperature of reaction 50-80 degree, in 4 hours reaction times, complete the etherificate carboxymethylation stage, obtain bis ether modified starch.
3. the bis ether modified starch prepared of the preparation method of a kind of bis ether modified starch according to claim 1.
4. the bis ether modified starch prepared of the preparation method of a kind of bis ether modified starch according to claim 2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310200603.1A CN103242458B (en) | 2013-05-27 | 2013-05-27 | Double-etherification modified starch and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310200603.1A CN103242458B (en) | 2013-05-27 | 2013-05-27 | Double-etherification modified starch and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103242458A CN103242458A (en) | 2013-08-14 |
| CN103242458B true CN103242458B (en) | 2015-07-15 |
Family
ID=48922359
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310200603.1A Expired - Fee Related CN103242458B (en) | 2013-05-27 | 2013-05-27 | Double-etherification modified starch and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103242458B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104804139A (en) * | 2015-05-21 | 2015-07-29 | 南京大学 | Flocculation sterilization difunctional grafting starch water treatment agent and preparation method thereof |
| JP6689675B2 (en) * | 2016-05-31 | 2020-04-28 | 日本食品化工株式会社 | Improved carboxymethylated starch and its use |
| JP6795790B2 (en) * | 2016-06-23 | 2020-12-02 | 荒川化学工業株式会社 | Manufacturing method of paper |
| CN113122163B (en) * | 2021-03-15 | 2022-12-16 | 上海应用技术大学 | Preparation method of corrugated board starch adhesive with low gelatinization temperature |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102229676A (en) * | 2011-05-19 | 2011-11-02 | 江西仁丰农业发展有限公司 | Preparation process of special rubber powder for architectural coating |
| CN102746408A (en) * | 2012-06-18 | 2012-10-24 | 新疆光大山河化工科技有限公司 | Method for preparing hydroxypropyl starch ether |
| CN103059227A (en) * | 2013-01-27 | 2013-04-24 | 桂林理工大学 | Preparation method of crosslinked acrylic graft hydroxypropyl cassava starch |
-
2013
- 2013-05-27 CN CN201310200603.1A patent/CN103242458B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102229676A (en) * | 2011-05-19 | 2011-11-02 | 江西仁丰农业发展有限公司 | Preparation process of special rubber powder for architectural coating |
| CN102746408A (en) * | 2012-06-18 | 2012-10-24 | 新疆光大山河化工科技有限公司 | Method for preparing hydroxypropyl starch ether |
| CN103059227A (en) * | 2013-01-27 | 2013-04-24 | 桂林理工大学 | Preparation method of crosslinked acrylic graft hydroxypropyl cassava starch |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103242458A (en) | 2013-08-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103242458B (en) | Double-etherification modified starch and preparation method thereof | |
| CN103755816B (en) | A kind of preparation method of sodium carboxymethylcellulose | |
| CN102619127A (en) | Environment-friendly high-printability non-woven wallpaper base and preparation method thereof | |
| CN104532660A (en) | Nano-microcrystalline cellulose paint, preparation method thereof, and coated paper prepared using nano-microcrystalline cellulose paint | |
| CN103911885A (en) | Printing and dyeing paste | |
| CN103924457B (en) | A kind of production technology of dyeing paste | |
| CN102887956B (en) | Method for preparing technical grade sodium carboxymethylcellulose with high viscosity and high salt resistance | |
| CN108978296A (en) | A kind of high quality recycled paper processing method | |
| CN102162200B (en) | Retention and drainage aid and preparation method thereof | |
| CN104499371A (en) | High strength impregnation textured paper production process | |
| CN102020720A (en) | High branch cationic starch for papermaking wet end and preparation method thereof | |
| CN107915783A (en) | A kind of method that carboxymethyl cellulose is prepared using waste paper as raw material | |
| CN103397566B (en) | A kind of method utilizing recycled pulp to manufacture hanging raw stock | |
| CN103451993A (en) | Attapulgite clay papermaking additive and preparation method of same | |
| CN101693744A (en) | Preparation technique of polybasic esterification starch | |
| CN103711023A (en) | Method for producing paper for daily use by superhigh-concentration grinding technology | |
| CN102587137A (en) | Novel environment-friendly energy saving spinning sizing agent and preparation method thereof | |
| CN111979810A (en) | Process for preparing cardboard paper by using wood chip fibers | |
| CN104497155A (en) | Modified starch for environment-friendly starch-based wallpaper glue and preparation method of modified starch | |
| CN107254806A (en) | Label leather paper and its preparation method and application | |
| CN103938469A (en) | Method for preparing reactive dyeing and printing paste of linen fabric | |
| CN102532328B (en) | Starch Based Pigments and preparation method thereof, applies coating and the White Board of this Starch Based Pigments | |
| CN112048936B (en) | Method for preparing coating by using biomass, coating and sizing material | |
| CN104153246A (en) | Papermaking sizing starch substitute as well as preparation method and application thereof | |
| CN112538783A (en) | Super-strong glassine base paper and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20150715 Termination date: 20170527 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |