CN103242459B - Crosslinked amphoteric starch and preparation method thereof - Google Patents
Crosslinked amphoteric starch and preparation method thereof Download PDFInfo
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- CN103242459B CN103242459B CN201310200329.8A CN201310200329A CN103242459B CN 103242459 B CN103242459 B CN 103242459B CN 201310200329 A CN201310200329 A CN 201310200329A CN 103242459 B CN103242459 B CN 103242459B
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Abstract
The invention discloses a preparation method of crosslinked amphoteric starch, which is implemented by carrying out oxidation, crosslinking, etherification and esterification on the main raw material corn starch. The preparation method is characterized by comprising the following steps: modifying the original starch by oxidation and crosslinking, wherein oxydol and sodium hexametaphosphate are respectively used as an oxidizer and a crosslinking agent; cationizing with 3-chloro-2-hydroxypropyltrimethylammonium chloride; and finally, esterifying by adding sodium dihydrogen phosphate to obtain the crosslinked amphoteric starch, wherein urea is used as a stabilizer in the esterification reaction process. The invention mainly has the characteristics of low sizing cost, high stability of the product paste, acid/alkali resistance, high shearing resistance, strong adhesive force, favorable film formation property, favorable compatibility with other chemical assistants, favorable binding force with aluminum ions and fibers due to amphoteric ions connected to the molecular chain, high adhesive residue rate and service efficiency, obviously improves the paper surface properties, and is especially suitable for producing secondary fibers, paper made by a high-speed paper machine, and high-grade paper.
Description
Technical field
The invention belongs to technical field of fine, particularly one is cross-linked amphoteric starch and preparation method.
Background technology
Amphoteric starch: refer to the compound of ative starch through the process of physics and chemistry method.Amphoteric starch is an important kind in modified starch, applies more and more extensive in papermaking.Simultaneously conventional amphoteric starch connects anions and canons group on starch molecule.The common etherification technology of cation group is quaternary ammonium salt wet method etherificate, as " replacement of amphoteric starch and the research of moisture-absorbing moisture-keeping performance relation " (daily chemical industry 2004,34(2) .97-99) to report with starch be parent, 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride and Mono Chloro Acetic Acid are properties-correcting agent, synthesize the high soluble amphoteric starch of different degree of substitution by carboxymethyl by clean semidry process.
The research of current amphoteric starch mainly concentrates on the introducing of anionic group.Negatively charged ion replaces main employing two kinds of group-phosphate anions and carboxylic ions.Phosphorylation is the process processing starch with phosphoric acid salt under certain condition.Wherein phosphoric acid salt can be tripoly phosphate sodium STPP, potassium permanganate, persulphate etc.As document " dry process of oxidation composite starch phosphoric acid ester " (foodstuffs industry science and technology 2004,25(8) .124-125) describe hydrogen peroxide the pneumatolysis of starch and tripolyphosphate.Document " preparation of cassava carboxylicesters amphoteric starch and synthesis mechanism " (South China Science & Engineering University's journal: natural science edition 2008,36(11) .68-73) " a kind of novel papermaking wet end carboxylic acid type amphoteric starch preparation technology " (Paper Science & Technology, 2008(1)) then report and use clorox carboxylated.
Usually by the massfraction of water and the difference of states of matter in reaction system, the synthesis of amphoteric starch is divided into 3 large classes, i.e. wet method, dry method and semidrying synthesis.Document " replacement of amphoteric starch and the research of moisture-absorbing moisture-keeping performance relation " (daily chemical industry 2004,34(2) .97-99), " semidrying prepares the high research in conjunction with phosphorus starch acid esters " (Guangxi University's journal: natural science edition, 2003,28(3) .186-189), " phosphate type amphoteric starch structure properties and the enhancement to paper thereof " (Chinese papermaking, 2008,27(12) .20-23) method that adopts is exactly dry method.The documents and materials that comprehensive analysis retrieves and with point of the present invention comparative analysis after reach a conclusion: domesticly have no the bibliographical information adopting following explained hereafter to be cross-linked amphoteric starch: by cross-linking modified for ative starch initial oxidation, using hydrogen peroxide and Sodium hexametaphosphate 99 as oxygenant and linking agent, cationization is carried out again with 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride, using urea as stablizer, finally add the obtained crosslinked amphoteric starch of biphosphate sodium esterization.
Summary of the invention
The object of the present invention is to provide a kind of is main raw material with W-Gum, initial oxidation, then is cross-linked, etherificate, finally carries out esterification, is mainly used in paper industry as the crosslinked amphoteric starch of Surface Size and preparation method.
Technical solution of the present invention: a kind of preparation method of crosslinked amphoteric starch, take W-Gum as main raw material, initial oxidation, then be cross-linked, esterification, finally carry out etherificate, by cross-linking modified for ative starch initial oxidation, using hydrogen peroxide and Sodium hexametaphosphate 99 as oxygenant and linking agent, then carry out cationization with 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride, finally add the obtained crosslinked amphoteric starch of biphosphate sodium esterization, esterification reaction process is using urea as stablizer.
Being specially: a kind of preparation method of crosslinked amphoteric starch, take ative starch as main raw material, initial oxidation, then is cross-linked, etherificate, finally carries out esterification, is prepared by following raw material, get ative starch 100 parts;
(1) be oxidized:
In described 100 parts of ative starchs, add oxidant hydrogen peroxide 4.5-5.5 parts, solid caustic soda 0.10-0.20 part, 0.005-0.015 part, copper sulfate, pH value controls 9.5-10, and oxidizing reaction temperature rests in 60 DEG C-75 DEG C, oxidation time: 1.5-2.5 hour;
(2) crosslinked:
After step (1) reaction terminates, add linking agent Sodium hexametaphosphate 99 0.015-0.020 part, soda ash 0.25-0.35 part, crosslinking reaction temperature 115 DEG C-125 DEG C, cross-linking reaction time: 2-3 hour, pH value controls at 8-9;
(3) etherificate:
After step (2) reaction terminates, add etherifying agent 3.8-4.2 parts, mass concentration is the liquid caustic soda 3.5-4.0 parts of 30%, etherification reaction temperature 65 DEG C-75 DEG C, etherification reaction time 3-4 hour, and pH value controls at 10.7-11.3;
(4) esterification:
After step (3) reaction terminates, add SODIUM PHOSPHATE, MONOBASIC 1.8-2.2 parts, soda ash 0.25-0.35 part, 0.45-0.55 part, urea, urea is as stablizer, and pH value controls at 8-9, esterification reaction temperature 125 DEG C-135 DEG C, reaction time of esterification 1.8-2.2 hours;
After step (4) reaction terminates, obtain crosslinked amphoteric starch.
Preferred: to be prepared by following raw material, get ative starch 100 parts;
(1) be oxidized:
In described 100 parts of ative starchs, add oxidant hydrogen peroxide 5 parts, solid caustic soda 0.15 part, 0.01 part, copper sulfate, pH value controls 9.5-10, and oxidizing reaction temperature rests in 60 DEG C-72 DEG C, oxidation time: 1.5-2 hour;
(2) crosslinked:
After step (1) reaction terminates, add linking agent Sodium hexametaphosphate 99 0.02 part, soda ash 0.3 part, crosslinking reaction temperature 115 DEG C-125 DEG C, cross-linking reaction time: 2-2.5 hour, pH value controls at 8-9;
(3) etherificate:
After step (2) reaction terminates, add etherifying agent 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride 4 parts, mass concentration is the liquid caustic soda 3.8 parts of 30%, etherification reaction temperature 65 DEG C-75 DEG C, etherification reaction time 3-3.5 hour, and pH value controls at 10.7-11.3;
(4) esterification
After step (3) reaction terminates, add SODIUM PHOSPHATE, MONOBASIC 2 parts, soda ash 0.3 part, 0. 5 parts, urea, urea is as stablizer, and pH value controls at 8-9, esterification reaction temperature 125 DEG C-135 DEG C, reaction time of esterification 2 hours;
After step (4) reaction terminates, obtain crosslinked amphoteric starch.
Described ative starch is W-Gum.
Described etherifying agent is 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride.
The application that crosslinked amphoteric starch prepared by the preparation method of described a kind of crosslinked amphoteric starch is produced at White Board.
The present invention with high-grade maize starch for main raw material, the initial oxidation adopting Semi-dry process technique to prepare-crosslinked-etherificate-esterification multiple elements design modified starch, be mainly used in paper industry as Surface Size, principal feature of the present invention has: (1) applying glue cost is low, have in limited time at internal sizing, can further improve sizing efficiency, and alleviate that paper strength caused by internal sizing agent declines, paper machine stains and the problem such as plain boiled water load increase; (2) obviously paper surface properties is improved, as poor in surface strength, water resisting property, two sides, smoothness and printability; (3) ative starch is after polynary sex change, product sticks with paste liquid good stability, acid and alkali-resistance and shearing force impact, bounding force is strong, good film-forming property, good with other chemical assistant consistencies, molecular chain is connected to zwitter-ion, with aluminum ion and fibrous binding force good, brain jelly retention is high, service efficiency is high, is especially applicable to the production of secondary stock, high-speed paper machine papermaking and high-grade paper.
Compared with common paper surface-sizing modified starch, the advantage that the present invention is cross-linked amphoteric starch is: the carboxyl of oxidation cross-linked generation of appropriateness and cross-link bond are beneficial to the stability of sticking with paste liquid, has high stability to the impact of heat, acid, alkali and shearing force; On starch molecule, introduce positively charged ion by etherificate, can increase hydrogen bond between fiber in conjunction with quantity, improve into the tensile strength properties of paper, and be conducive to the ink of adsorption zone negatively charged ion during printing, improve printing effect; Introduce negatively charged ion again by esterification, easily adsorbed by the position that the Tai-Ace S 150 in ply of paper or cation property copolymer have activated with cationic, also can positively charged ion rubbish in effectively shielding system, be combined with fiber to protect cation group.In a word, it is high for top sizing retention that the present invention is cross-linked amphoteric starch, and service efficiency is high, effectively can improve the surface strength of paper, reduce the hair and powder dropping phenomenon of paper, improve the quality scale of product, be especially applicable to the production of secondary stock, high-speed paper machine papermaking and high-grade paper.
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: the preparation method of crosslinked amphoteric starch, is prepared by following raw material, extracting corn starch 100 parts;
(1) be oxidized:
In described 100 parts of W-Gums, add oxidant hydrogen peroxide 5 parts, solid caustic soda 0.15 part, 0.01 part, copper sulfate, pH value controls 9.5-10, and oxidizing reaction temperature rests in 60 DEG C-72 DEG C, oxidation time: 1.5-2 hour;
(2) crosslinked:
After step (1) reaction terminates, add linking agent Sodium hexametaphosphate 99 0.02 part, soda ash 0.3 part, crosslinking reaction temperature 115 DEG C-125 DEG C, cross-linking reaction time: 2-2.5 hour, pH value controls at 8-9;
(3) etherificate:
After step (2) reaction terminates, add etherifying agent 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride 4 parts, mass concentration is the liquid caustic soda 3.8 parts of 30%, etherification reaction temperature 65 DEG C-75 DEG C, etherification reaction time 3-3.5 hour, and pH value controls at 10.7-11.3;
(4) esterification
After step (3) reaction terminates, add SODIUM PHOSPHATE, MONOBASIC 2 parts, soda ash 0.3 part, 0. 5 parts, urea, urea is as stablizer, and pH value controls at 8-9, esterification reaction temperature 125 DEG C-135 DEG C, reaction time of esterification 2 hours;
After step (4) reaction terminates, obtain crosslinked amphoteric starch.
One, embodiment 1 is cross-linked the examining report of amphoteric starch
Two, embodiment 1 is cross-linked the operation report of amphoteric starch
Top sizing can give paper high surface strength, slow down the migration of body paper tackiness agent in coating process, infiltration, originally adopt Sumstar 190 as Surface Size, surface strength is not enough, and it is larger with strength fluctuation in season, after using embodiment 1 to be cross-linked amphoteric starch, intensity and the printing performance of coating are significantly improved.
The condition of production is as follows:
1, pulpwood
Broad-leaved is starched: needle slurry, BOTMP chemical bleaching thermomechanical pulp=80 part: 10 parts: 10 parts
2, top sizing and coating
The quantitative 70g/m of body paper
2; Respectively embodiment 1 is carried out top sizing, resin added 1 g/m with existing after composite with PVA etc. according to a certain percentage after certain factory's Sumstar 190 gelatinization
2; Pattern carries out press polish (50KN/ m after fixed temperature and humidity process
2, normal temperature, 1NIP) after be coated with, glue spread 25 g/m
2.
3, paper physical index determining
4, result and discussion
4.1 body paper Performance comparision
4.2 ways and methods compare
4.3 brief summary
(1) utilize embodiment 1 to be cross-linked amphoteric starch and carry out top sizing, it is better than now using Sumstar 190 to the reinforced effects of body paper.
(2) utilize embodiment 1 to be cross-linked amphoteric starch and carry out top sizing, can form more fine and close glued membrane on body paper face, reduce the permeability of White Board, paper smoothness and glossiness are obviously improved.
(3) embodiment 1 is cross-linked process and the data of the production and application of amphoteric starch, and the over-all properties of this product is better than existing Sumstar 190, is improving the object all reaching use in intensity and printability etc.
Claims (3)
1. a preparation method for crosslinked amphoteric starch take ative starch as main raw material, initial oxidation, then is cross-linked, etherificate, finally carries out esterification, it is characterized in that being prepared by following raw material, gets ative starch 100 parts;
(1) be oxidized:
In described 100 parts of ative starchs, add oxidant hydrogen peroxide 4.5-5.5 parts, solid caustic soda 0.10-0.20 part, 0.005-0.015 part, copper sulfate, pH value controls 9.5-10, and oxidizing reaction temperature rests in 60 DEG C-75 DEG C, oxidation time: 1.5-2.5 hour;
(2) crosslinked:
After step (1) reaction terminates, add linking agent Sodium hexametaphosphate 99 0.015-0.020 part, soda ash 0.25-0.35 part, crosslinking reaction temperature 115 DEG C-125 DEG C, cross-linking reaction time: 2-3 hour, pH value controls at 8-9;
(3) etherificate:
After step (2) reaction terminates, add etherifying agent 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride 3.8-4.2 parts, mass concentration is the liquid caustic soda 3.5-4.0 parts of 30%, etherification reaction temperature 65 DEG C-75 DEG C, etherification reaction time 3-4 hour, pH value controls at 10.7-11.3;
(4) esterification:
After step (3) reaction terminates, add SODIUM PHOSPHATE, MONOBASIC 1.8-2.2 parts, soda ash 0.25-0.35 part, 0.45-0.55 part, urea, urea is as stablizer, and pH value controls at 8-9, esterification reaction temperature 125 DEG C-135 DEG C, reaction time of esterification 1.8-2.2 hours;
After step (4) reaction terminates, obtain crosslinked amphoteric starch.
2. the preparation method of a kind of crosslinked amphoteric starch according to claim 1, is characterized in that being prepared by following raw material, gets ative starch 100 parts;
(1) be oxidized:
In described 100 parts of ative starchs, add oxidant hydrogen peroxide 5 parts, solid caustic soda 0.15 part, 0.01 part, copper sulfate, pH value controls 9.5-10, and oxidizing reaction temperature rests in 60 DEG C-72 DEG C, oxidation time: 1.5-2 hour;
(2) crosslinked:
After step (1) reaction terminates, add linking agent Sodium hexametaphosphate 99 0.02 part, soda ash 0.3 part, crosslinking reaction temperature 115 DEG C-125 DEG C, cross-linking reaction time: 2-2.5 hour, pH value controls at 8-9;
(3) etherificate:
After step (2) reaction terminates, add etherifying agent 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride 4 parts, mass concentration is the liquid caustic soda 3.8 parts of 30%, etherification reaction temperature 65 DEG C-75 DEG C, etherification reaction time 3-3.5 hour, and pH value controls at 10.7-11.3;
(4) esterification
After step (3) reaction terminates, add SODIUM PHOSPHATE, MONOBASIC 2 parts, soda ash 0.3 part, 0. 5 parts, urea, urea is as stablizer, and pH value controls at 8-9, esterification reaction temperature 125 DEG C-135 DEG C, reaction time of esterification 2 hours;
After step (4) reaction terminates, obtain crosslinked amphoteric starch.
3. the preparation method of a kind of crosslinked amphoteric starch according to claim 1 and 2, is characterized in that described ative starch is W-Gum.
4. the application that the crosslinked amphoteric starch adopting the preparation method of a kind of crosslinked amphoteric starch described in claim 1 or 2 to prepare is produced at White Board.
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| CN110845635B (en) * | 2019-11-29 | 2022-07-29 | 江苏哈齐诺生物环保科技有限公司 | Preparation method of amphoteric polysaccharide water-absorbing material |
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