CN103739776A - Amphiprotic polyhydroxyl polymer for inorganic superfine fiber papermaking and preparation method thereof - Google Patents
Amphiprotic polyhydroxyl polymer for inorganic superfine fiber papermaking and preparation method thereof Download PDFInfo
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- CN103739776A CN103739776A CN201410000864.3A CN201410000864A CN103739776A CN 103739776 A CN103739776 A CN 103739776A CN 201410000864 A CN201410000864 A CN 201410000864A CN 103739776 A CN103739776 A CN 103739776A
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Abstract
The invention relates to an amphiprotic polyhydroxyl polymer for inorganic superfine fiber papermaking and a preparation method thereof. The preparation method comprises the steps: for a polyhydroxy polymer containing acylamino on a main chain, introducing a cationic group on the main chain by using a reaction of an epoxy group with the acylamino, and hydrolyzing under an alkaline condition through the acylamino to prepare the amphiprotic polyhydroxyl polymer. The preparation method comprises the steps: for a polyhydroxy polymer without containing acylamino on a main chain, introducing a cationic group on the main chain by using a reaction of hydroxyl and an epoxy group under an alkaline condition, and preparing the amphiprotic polyhydroxyl polymer by using the reaction activity of the hydroxyl and the function of an anionic reagent. When being applied to inorganic superfine fiber paper pulp, the amphiprotic polyhydroxyl polymer prepared by adopting the preparation method is capable of improving the dispersibility of inorganic superfine fiber in water due to a synergistic effect of cations and anions of the amphiprotic polyhydroxyl polymer and a hydrogen bond network structure, and improving the strength of inorganic superfine fiber paper.
Description
Technical field
The present invention relates to inorganic ultrafine fiber paper grade (stock) both sexes polyhydroxylated polymer and preparation method thereof, specifically, is that graft modification macromolecular chain is prepared both sexes polyhydroxylated polymer for the preparation method of paper strengthening agent, belongs to polymer analog assistant field.
Background technology
Inorganic ultrafine fiber is a kind of inorganic hybrid oxide fibre, and fiber surface exists considerable weak acid point and alkaline point simultaneously, and integral body is electronegativity, is dispersed in water, and the group of being polymerized to easily attracts each other between fiber, wads a quilt with cotton.The surface active groups of inorganic ultrafine fiber is few, intensity is low, poor with organic consistency, itself and mixed the copying of vegetable fibre are applied in paper-making process, need to add various properties-correcting agent, as surface treatment agent, softening agent for fibres, dispersing agent for fibre, fiber enhancer etc., in the hope of obtaining the similar xylon of inorganic fibre, can in water, there is good dispersiveness, increase the bonding force of inorganic fibre and xylon.
Bonding force between non-ionic type polyhydroxylated polymer (as polyvinyl alcohol, starch etc.) and inorganic ultrafine fiber a little less than, in paper-making process, retention is low.When both sexes polyhydroxylated polymer and inorganic ultrafine fiber blend, inorganic ultrafine fiber surface with negative charge and the cation group in amphiphilic polymers can be by electrostatic attraction, make inorganic ultrafine fiber surface parcel one deck polyhydroxylated polymer " coat ", and in both sexes polyhydroxylated polymer, between anionic group, producing electrostatic repulsion, the inorganic ultrafine fiber that makes to be organised after parcel can better disperse in water.From the ultimate principle of xylon papermaking, the hydrogen bond action between fiber has crucial impact to paper strength, and the formation of hydrogen bond mainly relies on intermolecular hydroxyl effect.Thereby after inorganic ultrafine fiber surface is wrapped up by polyhydroxylated polymer, can make between inorganic ultrafine fiber self and and xylon between the intensive hydrogen bond network structure of height of formation, improved and joined the intensity that copy paper is opened.Therefore study both sexes polyhydroxylated polymer pluronic polymer and become the gordian technique of inorganic ultrafine fiber in papermaking application.
Chinese patent CN101215807 discloses a kind of preparation method of cationic polyvinyl alcohol paper intensifier, after first this invention dissolves polyvinyl alcohol solid particulate in water, add cationic etherifying agent (3-chloro-2-hydroxypropyl-trimethyl ammonium chloride or 2,3-epoxypropyltrimethylchloride chloride) polyvinyl alcohol is carried out to cationization, finally in positively charged ion polyvinyl alcohol solution, add polymerization crosslinking monomer, system pH is adjusted to slightly acidic.Crosslinked retention after Ionization Modification is greatly improved, and has improved dry epistasis and the wet epistasis of paper.
Chinese patent CN102924635 discloses a kind of preparation method of modified cation polyvinyl alcohol, and it is that under mineral alkali effect, grafting polyvinyl alcohol is prepared cationic polyvinyl alcohol to employing dewatering cationic reagent epoxypropyl dimethyl alkyl ammomium chloride (wherein alkyl carbon atom quantity is at least 6).This invention, by introduce the hydrophobic alkyl of long-chain in polyvinyl alcohol molecule, utilizes its intermolecular chain entanglement to form physical cross-linked network, and polyvinyl alcohol has been played to certain enhancing toughening effect.
Chinese patent CN1982232 discloses a kind of preparation method of the organic cation flocculating agent containing hydrophobic grouping, it utilizes the chlorine on epoxy chloropropane introduce the tertiary amine of different chain length or introduce new hydrophobic grouping and synthesize quaternary ammonium salt, and the open loop activity of recycling epoxy chloropropane obtains quaternary ammonium salt monomer with acrylamide graft.By controlling the proportioning of this quaternary ammonium salt monomer and acrylamide monomer, regulate the cationic degree of flocculation agent, thereby obtain having the organic cation flocculating agent of different hydrophobic groupings, different cationic degree and limiting viscosity.
Chinese patent CN101747465 discloses a kind of preparation method of poly-hydroxy auxiliary agent of fly ash fiber paper making, it take the ethylene glycol monoallyl ether that contains hydroxyl and the MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride of cation quaternary ammonium group is monomer, and in the aqueous solution, radical polymerization preparation obtains fly ash fiber paper making poly-hydroxy auxiliary agent.
The cation modifying that the content that above-mentioned various invention relates to is polyhydroxylated polymer, is applied in inorganic ultrafine fiber paper-making process when polymer-modified, easily causes that the wadding of fiber is polymerized to group, reduces fibre paper intensity.And the both sexes polyhydroxylated polymer of the present invention's design is applied in the paper-making process of inorganic ultrafine fiber, on the one hand inorganic ultrafine fiber surface with negative charge and the quaternary ammonium salt cationic in amphiphilic polymers by electrostatic attraction, make inorganic ultrafine fiber surface parcel one deck polyhydroxylated polymer " coat ", the hydrogen bond action producing between hydroxyl make between fiber self and and xylon between the intensive hydrogen bond network structure of height of formation, improved and joined the intensity that copy paper is opened; On the other hand, in amphiphilic polymers, between anionic group, produce electrostatic repulsion, can be in water between the inorganic ultrafine fiber that makes to be organised after parcel stably dispersing.
Summary of the invention
The object of the invention is to prepare a kind of inorganic ultrafine fiber paper grade (stock) both sexes polyhydroxylated polymer, be applied in paper-making process, can improve the dispersiveness of inorganic ultrafine fiber in water, improve paper strength and the retention of paper making additive in the process of manufacturing paper with pulp.
The preparation of inorganic ultrafine fiber paper grade (stock) both sexes polyhydroxylated polymer adopts respectively two kinds of preparation methods as described below due to the difference of main polymer chain:
(
) preparation of the both sexes polyhydroxylated polymer of amide-containing on main chain: first in reactor, add main chain amide-containing polyhydroxylated polymer and solvent, being warming up to 50～100 degrees Celsius of dissolvings, to be made into massfraction be 1～30 % polymers soln, in insulation downhill reaction still, add epoxy-cationic reagent, stirring reaction 1～10 hour, then with the sodium hydroxide solution regulator solution pH that massfraction is 5～40 %, be 10～13, quaternization is more than 10 minutes, be down to room temperature, hydrochloric acid regulates reaction solution pH to neutral, dehydrated alcohol precipitation, suction filtration, dry, obtain both sexes polyhydroxylated polymer product,
(
) the not preparation of the both sexes polyhydroxylated polymer of amide-containing on main chain: first in reactor, add main chain not amide-containing polyhydroxylated polymer and solvent, being warming up to 50～100 degrees Celsius of dissolvings, to be made into massfraction be 1～30 % polymers soln, insulation is lower is 10～13 with the sodium hydroxide solution regulator solution pH that massfraction is 5～40 %, alkalization is more than 10 minutes, then in reactor, add epoxy-cationic reagent, stirring reaction 1～10 hour, in alkaline condition downhill reaction still, add anionization reagent again, stirring reaction 1～10 hour, be down to room temperature, hydrochloric acid regulates reaction solution pH to neutral, dehydrated alcohol precipitation, suction filtration, dry, obtain both sexes polyhydroxylated polymer product.
Described inorganic ultrafine fiber, refers to the ultra-fine fibre of being manufactured by inorganic oxide, comprises ultra-fine rock wool, ultra-fine ceramic fibre, ultrafine slag fiber, superfined flyash fiber, ultra-fine red mud fiber.
On described main chain, amide-containing polyhydroxylated polymer refers to acrylamide and hydroxyl ethylenic unsaturation hydrocarbon monomer or comprises the multipolymer of other function monomers, comprises acrylamide-acrylicacid hydroxyl ethyl ester multipolymer, acrylamide-hydroxyethyl methylacrylate multipolymer, acrylamide-ethylene glycol monoallyl ether multipolymer, acrylamide-acrylicacid hydroxyl ethyl ester-acrylic copolymer, acrylamide-hydroxyethyl methylacrylate-sodium acrylate copolymer, acrylamide-ethylene glycol monoallyl ether-acrylic copolymer.
On described main chain, amide-containing polyhydroxylated polymer does not comprise polyvinyl alcohol, Poly(Hydroxyethyl Methacrylate), poly hydroxy ethyl acrylate, Hydroxyethyl acrylate-acrylic copolymer.
Described epoxy-cationic reagent comprises aliphatic chain alkyl epoxy propyl-dimethyl alkyl ammomium chloride or nitrogen heterocyclic ring epoxypropyl ammonium chloride, particularly, described aliphatic chain alkyl epoxy propyl-dimethyl alkyl ammomium chloride comprises epoxypropyltrimethylchloride chloride, epoxypropyl dimethyl hexyl ammonium chloride, epoxypropyl dimethyl-octa ammonium chloride, epoxypropyl dimethyl decyl ammonium chloride, epoxypropyl dimethyl lauryl ammonium chloride, epoxypropyl dimethyl tetradecyl ammonium chloride; Described nitrogen heterocyclic ring epoxypropyl ammonium chloride comprises epoxypropyl pyridine chlorination ammonium, epoxypropyl N-Methylimidazole ammonium chloride, epoxypropyl N-methylmorpholine ammonium chloride, epoxypropyl quinoline ammonium chloride.
Described anionization reagent comprises Mono Chloro Acetic Acid, the chloro-2-sulphur of 3-propionic acid, 3-chlorine-2-hydroxyl propanesulfonate, tripoly phosphate sodium STPP, maleic anhydride, succinyl oxide.
Described solvent comprises a kind of or its mixture in water, dimethyl sulfoxide (DMSO), dehydrated alcohol.
The add-on of described epoxy-cationic reagent, with the mol ratio of amide group segment repeating unit in amide-containing polyhydroxylated polymer on main chain is: 1:10～4:1; With on main chain not in amide-containing polyhydroxylated polymer the mol ratio of hydroxyl segment repeating unit be: 1:10～4:1.
Described anionization reagent dosage, with the mol ratio of hydroxyl segment repeating unit in polyhydroxylated polymer is: 1:10～4:1.
The innovative point of this technology is: on polyhydroxylated polymer fundamental chain, introduce zwitter-ion group, obtain both sexes water-soluble polyhydroxyl polymer.While being applied to inorganic ultrafine fiber paper pulp, on the one hand, cation group on polymer chain easily and the negative charge effect on inorganic ultrafine fiber surface, on inorganic ultrafine fiber surface, form one deck organic coating, negative ion group on polymer segment repels mutually, make easily to form single fiber between inorganic ultrafine fiber and reduce flocculation, improved the dispersiveness of inorganic ultrafine fiber in water; On the other hand, when inorganic ultrafine fiber and vegetable fibre are copied while being applied to papermaking altogether, the hydroxyl hydroxyl easy and vegetable fibre on the inorganic ultrafine fiber surface after organic modification passes through the network structure that hydrogen bond action height of formation is intensive, improved inorganic ultrafine fiber to each other and and vegetable fibre between bonding force, improved the intensity of paper.As a kind of paper grade (stock) reinforcing aids, the introducing of ionic group has also improved the retention of auxiliary agent in paper-making process.
Embodiment
Embodiment 1
By 18.75 grams of acrylamide-acrylicacid hydroxyl ethyl ester multipolymers (wherein, acrylamide segment molar fraction accounts for 50 %, approximately 0.1 mole) add containing in the reactor of 60 grams of water, being warming up to 85 degrees Celsius of stirrings fully dissolves it, add 30.55 grams of epoxypropyl dimethyl lauryl ammonium chlorides (approximately 0.1 mole), under 60 degrees Celsius, react after 3 hours, with massfraction, be that 40 % sodium hydroxide solutions adjusting pH are 10, 50 degrees Celsius are incubated quaternization 1 hour, be down to room temperature, salt acid for adjusting pH is neutral, dehydrated alcohol precipitation, suction filtration, dry, obtain both sexes polyhydroxylated polymer as shown in Figure 1.
Embodiment 2
By 13.80 grams of acrylamide-ethylene glycol monoallyl ether multipolymers (wherein, acrylamide segment molar fraction accounts for 33 %, approximately 0.05 mole) add containing in the reactor of 50 grams of dimethyl sulfoxide (DMSO), being warming up to 95 degrees Celsius of stirrings fully dissolves it, add 25.72 grams of epoxypropyl pyridine chlorination ammoniums (approximately 0.15 mole), under 70 degrees Celsius, react 4 hours, with the sodium hydroxide solution that massfraction is 20 %, regulating pH is 12, 60 degrees Celsius of insulations are alkalized 30 minutes, be down to room temperature, salt acid for adjusting pH is neutral, dehydrated alcohol precipitation, suction filtration, dry, obtain both sexes polyhydroxylated polymer as shown in Figure 2.
Embodiment 3
By 27.30 grams of acrylamide-hydroxyethyl methylacrylate multipolymers (wherein, acrylamide segment molar fraction accounts for 67 %, approximately 0.2 mole) add in the reactor containing 100 grams of dimethyl sulfoxide (DMSO) and 15 grams of dehydrated alcohol mixed solvents, being warming up to 85 degrees Celsius of stirrings fully dissolves it, add 8.73 grams of epoxypropyl N-Methylimidazole ammonium chlorides (approximately 0.05 mole), under 70 degrees Celsius, react after 3 hours, with massfraction, be that 5 % sodium hydroxide solutions adjusting pH are 10, 50 degrees Celsius of insulations are alkalized 30 minutes, be down to room temperature, salt acid for adjusting pH is neutral, dehydrated alcohol precipitation, suction filtration, dry, obtain both sexes polyhydroxylated polymer as shown in Figure 3.
Embodiment 4
By 3.75 grams of acrylamide-acrylicacid hydroxyl ethyl ester-acrylic copolymer, (wherein, acrylamide segment molar fraction accounts for 25 %, approximately 0.01 mole; Vinylformic acid segment molar fraction accounts for 25 %, approximately 0.01 mole) add containing in the reactor of 30 grams of water, being warming up to 75 degrees Celsius of stirrings fully dissolves it, add 6.67 grams of epoxypropyl tetradecyl ammonium chlorides (approximately 0.02 mole), under 70 degrees Celsius, react after 6 hours, with massfraction, be that 25 % sodium hydroxide solutions adjusting pH are 11,60 degrees Celsius of insulations are alkalized 30 minutes, be down to room temperature, with salt acid for adjusting pH, be neutral, dehydrated alcohol precipitation, suction filtration, dry, obtain both sexes polyhydroxylated polymer as shown in Figure 4.
Embodiment 5
5.24 grams of polyvinyl alcohol 1799(hydroxyl segments are about to 0.12 mole) add containing in the reactor of 50 grams of water, being warming up to 90 degrees Celsius of stirrings fully dissolves it, reactor is cooled to 60 degrees Celsius, with massfraction, be that 10 % sodium hydroxide solutions regulate pH to 12, insulation alkalization 20 minutes, then in reactor, add 30.55 grams of epoxypropyl dimethyl lauryl ammonium chlorides (approximately 0.1 mole), react and after 6 hours, add 9.45 grams of Mono Chloro Acetic Acids (approximately 0.1 mole), react 5 hours, be cooled to room temperature, salt acid for adjusting pH is neutral, dehydrated alcohol precipitation, suction filtration, dry, obtain both sexes polyhydroxylated polymer as shown in Figure 5.
Embodiment 6
4.88 grams of polyvinyl alcohol 1788(hydroxyl segments are about to 0.1 mole) add containing in the reactor of 50 grams of dimethyl sulfoxide (DMSO), being warming up to 90 degrees Celsius of stirrings fully dissolves it, reactor is cooled to 70 degrees Celsius, with massfraction, be that 30 % sodium hydroxide solutions regulate pH to 12, insulation alkalization 20 minutes, then in reactor, add 9.68 grams of epoxypropyl N-methylmorpholine ammonium chlorides (approximately 0.05 mole), react and after 6 hours, add 7.86 grams of 3-chlorine-2-hydroxyl propanesulfonates (approximately 0.04 mole), adding massfraction is that 30 % sodium hydroxide solutions maintenance pH value of solution are 12, react 6 hours, be cooled to room temperature, salt acid for adjusting pH is neutral, dehydrated alcohol precipitation, suction filtration, dry, obtain both sexes polyhydroxylated polymer as shown in Figure 6.
Embodiment 7
11.60 grams of Poly(Hydroxyethyl Methacrylate) (hydroxyl segment is about 0.1 mole) are added containing in the reactor of 50 grams of water, being warming up to 90 degrees Celsius of stirrings fully dissolves it, reactor is cooled to 70 degrees Celsius, with massfraction, be that 30 % sodium hydroxide solutions regulate pH to 12, insulation alkalization 50 minutes, then in reactor, add 72.30 grams of epoxypropyl dimethyl cetyl chloride ammoniums (approximately 0.2 mole), react and after 6 hours, add 19.65 grams of 3-chlorine-2-hydroxyl propanesulfonates (approximately 0.1 mole), react 6 hours, be cooled to room temperature, salt acid for adjusting pH is neutral, dehydrated alcohol precipitation, suction filtration, dry, obtain both sexes polyhydroxylated polymer as shown in Figure 7.
Embodiment 8
17.60 grams of Poly(Hydroxyethyl Methacrylate) (hydroxyl segment is about 0.15 mole) are added in the reactor containing 60 grams of dimethyl sulfoxide (DMSO) and 20 grams of dehydrated alcohol mixed solvents, being warming up to 95 degrees Celsius of stirrings fully dissolves it, reactor is cooled to 80 degrees Celsius, with massfraction, be that 15 % sodium hydroxide solutions regulate pH to 12, insulation alkalization 1 hour, then in reactor, add 66.46 grams of epoxypropyl quinoline ammonium chlorides (approximately 0.3 mole), react and after 6 hours, add 49.20 grams of maleic anhydrides (approximately 0.5 mole), react 6 hours, be cooled to room temperature, salt acid for adjusting pH is neutral, dehydrated alcohol precipitation, suction filtration, dry, obtain both sexes polyhydroxylated polymer as shown in Figure 8.
Claims (9)
1. inorganic ultrafine fiber paper grade (stock) both sexes polyhydroxylated polymer and preparation method thereof, is characterized in that:
(
) preparation of the both sexes polyhydroxylated polymer of amide-containing on main chain: first in reactor, add main chain amide-containing polyhydroxylated polymer and solvent, be warming up to 50～100 degrees Celsius of dissolvings and be made into the polymers soln that massfraction is 1～30 %, in insulation downhill reaction still, add epoxy-cationic reagent, stirring reaction 1～10 hour, then with the sodium hydroxide solution regulator solution pH that massfraction is 5～40 %, be 10～13, insulation quaternization is more than 10 minutes, be down to room temperature, hydrochloric acid regulates reaction solution pH to neutral, dehydrated alcohol precipitation, suction filtration, dry, obtain both sexes polyhydroxylated polymer product,
(
) the not preparation of the both sexes polyhydroxylated polymer of amide-containing on main chain: first in reactor, add main chain not amide-containing polyhydroxylated polymer and solvent, being warming up to 50～100 degrees Celsius of dissolvings, to be made into massfraction be 1～30 % polymers soln, insulation is lower is 10～13 with the sodium hydroxide solution regulator solution pH that massfraction is 5～40 %, alkalization is more than 10 minutes, then in reactor, add epoxy-cationic reagent, stirring reaction 1～10 hour, in alkaline condition downhill reaction still, add anionization reagent again, stirring reaction 1～10 hour, be down to room temperature, hydrochloric acid regulates reaction solution pH to neutral, dehydrated alcohol precipitation, suction filtration, dry, obtain both sexes polyhydroxylated polymer product.
2. inorganic ultrafine fiber as claimed in claim 1, refers to the ultra-fine fibre of being manufactured by inorganic oxide, comprises ultra-fine rock wool, ultra-fine ceramic fibre, ultrafine slag fiber, superfined flyash fiber, ultra-fine red mud fiber.
3. the polyhydroxylated polymer of amide-containing on main chain as claimed in claim 1, it is characterized in that: on described main chain, amide-containing polyhydroxylated polymer refers to acrylamide and hydroxyl ethylenic unsaturation hydrocarbon monomer or comprises the multipolymer of other function monomers, comprise acrylamide-acrylicacid hydroxyl ethyl ester multipolymer, acrylamide-hydroxyethyl methylacrylate multipolymer, acrylamide-ethylene glycol monoallyl ether multipolymer, acrylamide-acrylicacid hydroxyl ethyl ester-acrylic copolymer, acrylamide-hydroxyethyl methylacrylate-sodium acrylate copolymer, acrylamide-ethylene glycol monoallyl ether-acrylic copolymer.
4. the polyhydroxylated polymer of amide-containing not on main chain as claimed in claim 1, is characterized in that: on described main chain, amide-containing polyhydroxylated polymer does not comprise polyvinyl alcohol, Poly(Hydroxyethyl Methacrylate), poly hydroxy ethyl acrylate, Hydroxyethyl acrylate-acrylic copolymer.
5. epoxy-cationic reagent as claimed in claim 1, it is characterized in that: described epoxy-cationic reagent comprises aliphatic chain alkyl epoxy propyl-dimethyl alkyl ammomium chloride or nitrogen heterocyclic ring epoxypropyl ammonium chloride, particularly, described aliphatic chain alkyl epoxy propyl-dimethyl alkyl ammomium chloride comprises epoxypropyltrimethylchloride chloride, epoxypropyl dimethyl hexyl ammonium chloride, epoxypropyl dimethyl-octa ammonium chloride, epoxypropyl dimethyl decyl ammonium chloride, epoxypropyl dimethyl lauryl ammonium chloride, epoxypropyl dimethyl tetradecyl ammonium chloride; Described nitrogen heterocyclic ring epoxypropyl ammonium chloride comprises epoxypropyl pyridine chlorination ammonium, epoxypropyl N-Methylimidazole ammonium chloride, epoxypropyl N-methylmorpholine ammonium chloride, epoxypropyl quinoline ammonium chloride.
6. anionization reagent as claimed in claim 1, is characterized in that: described anionization reagent comprises Mono Chloro Acetic Acid, the chloro-2-sulphur of 3-propionic acid, 3-chlorine-2-hydroxyl propanesulfonate, tripoly phosphate sodium STPP, maleic anhydride, succinyl oxide.
7. solvent as claimed in claim 1, is characterized in that: described solvent comprises a kind of or its mixture in water, dimethyl sulfoxide (DMSO), dehydrated alcohol.
8. epoxy-cationic reagent dosage as claimed in claim 1, on epoxy-cationic reagent and main chain, in amide-containing polyhydroxylated polymer, the mol ratio of amide group segment repeating unit is: 1:10～4:1; With on main chain not in amide-containing polyhydroxylated polymer the mol ratio of hydroxyl segment repeating unit be: 1:10～4:1.
9. anionization reagent dosage as claimed in claim 1, with the mol ratio of hydroxyl segment repeating unit in polyhydroxylated polymer is: 1:10～4:1.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104311736A (en) * | 2014-11-05 | 2015-01-28 | 华东理工大学 | Polyhydroxyl polyampholyte and preparation method thereof |
| CN110407974A (en) * | 2019-08-15 | 2019-11-05 | 浙江传化华洋化工有限公司 | A kind of preparation method of cross-linking amphiprotic polyacrylamide polymer |
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| CN101748650A (en) * | 2009-12-17 | 2010-06-23 | 华东理工大学 | Preparation and application method for fly ash fiber and wood fiber mixed dissolving modifier |
| CN101747465A (en) * | 2009-12-17 | 2010-06-23 | 华东理工大学 | Method for preparing polyhydroxy auxiliary agent for fly ash fiber papermaking |
| CN102924635A (en) * | 2011-08-12 | 2013-02-13 | 中国石油化工集团公司 | Modified cationic polyvinyl alcohol and its preparation method |
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2014
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| JPH06192993A (en) * | 1992-12-24 | 1994-07-12 | Mitsui Toatsu Chem Inc | Additive for papermaking |
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| CN101748650A (en) * | 2009-12-17 | 2010-06-23 | 华东理工大学 | Preparation and application method for fly ash fiber and wood fiber mixed dissolving modifier |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104311736A (en) * | 2014-11-05 | 2015-01-28 | 华东理工大学 | Polyhydroxyl polyampholyte and preparation method thereof |
| CN104311736B (en) * | 2014-11-05 | 2016-08-24 | 华东理工大学 | A kind of polyhydroxy polycarboxylic ampholytes and preparation method thereof |
| CN110407974A (en) * | 2019-08-15 | 2019-11-05 | 浙江传化华洋化工有限公司 | A kind of preparation method of cross-linking amphiprotic polyacrylamide polymer |
| CN110407974B (en) * | 2019-08-15 | 2021-09-21 | 浙江传化华洋化工有限公司 | Preparation method of crosslinkable amphoteric polyacrylamide polymer |
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Application publication date: 20140423 |