CN101747471A - Method for preparing fly ash fiber reinforced modifier - Google Patents
Method for preparing fly ash fiber reinforced modifier Download PDFInfo
- Publication number
- CN101747471A CN101747471A CN200910201320A CN200910201320A CN101747471A CN 101747471 A CN101747471 A CN 101747471A CN 200910201320 A CN200910201320 A CN 200910201320A CN 200910201320 A CN200910201320 A CN 200910201320A CN 101747471 A CN101747471 A CN 101747471A
- Authority
- CN
- China
- Prior art keywords
- hydroxyethyl acrylate
- vinylformic acid
- fly ash
- ash fiber
- aqueous solution
- 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.)
- Granted
Links
Landscapes
- Paper (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a method for preparing a fly ash fiber reinforced modifier, which is characterized by comprising the following steps: firstly, copolymerizing acrylic acid and hydroxy-ethyl acrylate, wherein the copolymerizing method comprises the steps of adding water and sodium hydrogensulfite into a reaction kettle, heating the reaction kettle to 90 DEG C, and then dripping 70 percent mixed monomer aqueous solution of the acrylic acid and the hydroxy-ethyl acrylate and 5 to 15 percent ammonium persulfate aqueous solution into the reaction kettle at the same time; and then adding N,N-dimethyl-1,3-propane diamine into the solution to perform amidation, and finally adding hydrochloric acid into the solution to neutralize the pH of the solution to between 6.5 and 7.5 so as to obtain a polyhydroxy cationic polymer type fly ash fiber reinforced modifier. The polyhydroxy cationic polymer prepared by the method can improve the dispersion property of the fly ash fiber in the water, enhance the binding force between the fly ash fiber and wood pulp fiber or straw pulp fiber, and improve the strength of paper doped with the fly ash fiber.
Description
Technical field
The present invention relates to a kind of preparation method of surface of fly ash fiber properties-correcting agent, specifically, is a kind of preparation method who is used for the polyhydroxy cation polymkeric substance of coal ash fiber papermaking.
Background technology
Common wood pulp or straw pulp paper technology, strength of paper mainly is subjected to the influence of four fundamental factor: the intensity of fiber itself; The intensity of fiber combining; The number of fiber combining or bonded area; The distribution of fiber or fiber dispersion and formation of sheet.Wood pulp or straw pulp are pulled an oar through machinery, fiber is under the effect of extruding and other mechanical forces, to fibrous inside and outside generation conquassation and brooming effect, cause the cut-out and the fibrillation effect of fiber, and make a large amount of water of fiber absorbs and swollen, become more soft and be obedient to, produce more combination and bigger bonded area when causing fiber to be in contact with one another each other.And coal ash fiber has only single independent the existence, be pencil unlike wood pulp or straw pulp fiber, and surface of fly ash fiber is smooth, and it is poor that coal ash fiber reaches to each other with wood pulp or straw pulp fiber combining power.
Chinese patent CN1464020 discloses a kind of latex nano bonding agent.Be characterized in that with emulsifying agent, butyl acrylate, vinylformic acid, n-methylolacrylamide, Hydroxyethyl acrylate, glycidyl acrylate, vinylbenzene, vinyl cyanide, ammonium persulphate and water be raw material, make the product of this invention through emulsification, polymerization, filtration blowing, it is said to can be used for printing and dyeing, stamp ecological textile.
Chinese patent CN1323843 discloses composite epoxy-modified acrylic acid-polyurethane emulsion and preparation technology thereof.This invention utilizes Hydroxyethyl acrylate (HEA) to make the end of the chain base band of aqueous polyurethane that two keys be arranged, the copolyreaction of acrylic monomer and urethane is stablized, caused fast to low temperature down then, make the copolymer emulsion of graft type nucleocapsid structure, and be coated in the kernel of emulsion Resins, epoxy is stable, cold cross-linking solidifies under the effect of organic amine curing agent, and inorganic nanometer powder introduced in this water-based system, thereby prepare organic-inorganic compoiste epoxy-modified acrylic acid-polyurethane copolymer emulsion.
Chinese patent CN101215353 discloses a kind of method of preparing polymer nano micelle by water solution polymerization self-emulsification.This invention utilizes the monomeric strong alternating polymerization tendency of phenylethylene/maleic anhydride, and/or at (methyl) Hydroxyethyl acrylate and/or other (methyl) alkyl acrylate, and/or under the participation to the Vinylstyrene difunctional monomer, do not add any emulsifying agent and inorganic salt and organic solvent, be initiator with the Potassium Persulphate, in the aqueous solution by radical polymerization, directly the polymer nano micelle of preparation adjustable grain control and cross-linking type that is evenly distributed or non-crosslinked type can be used for aspects such as drug loading release, catalysis load.The purification of polymkeric substance and the step of micellization have been saved in this invention, do not introduce organic solvent, easy and simple to handle, cost is low, by regulating monomeric kind of hydrophilic and ratio, initiator amount, to obtain the nano micellar solution of polymer of various size, structure and performance.
Chinese patent CN1580391 discloses a kind of fly ash fiber pulp and has been the papermaking process of raw material.The component and the weight percent content of the fly ash fiber pulp of this invention comprise: tenderizer 1～10%, dispersion agent 1～8%, surface-modifying agent 1～10%, coal ash fiber 20～80%, organic fibre 20～80%, water surplus.Adopting conventional method to be delivered to join on the paper machine above-mentioned fly ash fiber pulp copies paper product, can make paper material.Adopt corresponding national standards that the prepared various paper product of this invention are detected, physicals reaches the equal performance of vegetable fibre paper, is being better than the vegetable fibre paper aspect water tolerance, the corrosion-resistant and fire line.This invention is applicable to industrial-scale production, flyash ultra-fine fibre slurries manufacturing processed non-pollutant discharge, and reduce the papermaking cost.Method of the present invention is given industrial waste with the functionalization utilization, replaces wood pulp, saves log and expends, and is remarkable to the meaning that protects forest resources.
Although foregoing invention is mentioned the flyash ultra-fine fibre and is made paper pulp, all show coal ash fiber and the not strong weakness of vegetable fibre bonding force, can not compare favourably with the intensity of xylon.Therefore invent that a kind ofly with the flyash ultra-fine fibre good combination power to be arranged, can improve the dispersiveness of coal ash fiber in water simultaneously and can increase the consistency of coal ash fiber and wood pulp or straw pulp fiber again, reach the properties-correcting agent that improvement is mixed with the coal ash fiber paper strength be vital, meaning of the present invention just is this.
Summary of the invention
A kind of preparation method of fly ash fiber reinforced modifier, it is characterized in that: earlier vinylformic acid and Hydroxyethyl acrylate mix monomer are carried out copolymerization in aqueous solution of sodium bisulfite, under the initiation of ammonium persulphate, obtain the multipolymer of vinylformic acid and Hydroxyethyl acrylate, again toward wherein adding N, N-dimethyl-1, the 3-propylene diamine carries out amidation, adds hydrochloric acid then and is neutralized to pH 6.5～7.5, obtains the polyhydroxy cation polymkeric substance.
The method that described vinylformic acid and Hydroxyethyl acrylate carry out copolymerization is: add entry and sodium bisulfite earlier in reactor, be warming up to 90 ℃, the ammonium persulfate aqueous solution with the vinylformic acid of concentration 30～70% and the Hydroxyethyl acrylate mix monomer aqueous solution, concentration 5～15% is added drop-wise in the reactor simultaneously then.Used ammonium persulphate oven dry weight is 0.8～2.5% of vinylformic acid and a Hydroxyethyl acrylate mix monomer oven dry weight, and the dropping time is 3～5 hours, is warming up to 96～98 ℃ then, is incubated 0.5～1 hour, is cooled to below 50 ℃.
Described N, N-dimethyl-1, the add-on of 3-propylene diamine is 30～80% of a vinylformic acid oven dry weight.
The add-on of described hydrochloric acid is: HCl and N in the hydrochloric acid, and N-dimethyl-1, the mol ratio of 3-propylene diamine is 1: 1.
The add-on of described sodium bisulfite is 1～3% of vinylformic acid and a Hydroxyethyl acrylate mix monomer over dry gross weight.
In described vinylformic acid and the Hydroxyethyl acrylate mix monomer, the weight ratio of vinylformic acid and Hydroxyethyl acrylate is 1: 5 to 2: 1.
Polyhydroxy cation polymkeric substance with present method preparation can improve the dispersiveness of coal ash fiber in water, can increase the bonding force between coal ash fiber and wood pulp or the straw pulp fiber, improves to be mixed with the coal ash fiber strength of paper.
The innovative point of present technique is: on the copolymer chain of water-soluble acrylic and Hydroxyethyl acrylate, connect cation group by amidate action, a lot of carboxyls and hydroxyl are arranged on the copolymer chain of water-soluble acrylic and Hydroxyethyl acrylate, the ability that good wetting ability and formation hydrogen bond are arranged, the cation group that connects on the copolymer chain easily and on the coal ash fiber with the negative charge effect, and receive on the coal ash fiber, reach to each other and wood pulp or straw pulp fiber combining power thereby improve coal ash fiber.
Embodiment
Embodiment 1
In the reactor that 100 liters of bands stir, heat, add 20kg water, open and stir, the sodium bisulfite of 0.9kg is joined in the reactor, it is fully dissolved, open heating and make reactor be warmed up to 90 ℃, then the vinylformic acid of weight content 10% and the mix monomer aqueous solution 50kg of 50% Hydroxyethyl acrylate and the ammonium persulfate aqueous solution 1.6kg of concentration 15% are added drop-wise in the reactor simultaneously.The dropping time is 5 hours, is warming up to 96 ℃ then, is incubated 30 minutes, is cooled to below 50 ℃.In reactor, add N again, N-dimethyl-1,3-propylene diamine 3.5kg adds concentration and is 37% hydrochloric acid 3.4kg then, transfers to pH 6.5, obtains weight concentration and be 46.7% polyhydroxy cation polymkeric substance 75kg.
Embodiment 2
In the reactor that 100 liters of bands stir, heat, add 30kg water, open and stir, the sodium bisulfite of 0.18kg is joined in the reactor, it is fully dissolved, open heating and make reactor be warmed up to 90 ℃, then the vinylformic acid of weight content 40% and the ammonium persulfate aqueous solution 1.5kg of 20% Hydroxyethyl acrylate mix monomer aqueous solution 30kg and concentration 10% are added drop-wise in the reactor simultaneously.The dropping time is 3 hours, is warming up to 98 ℃ then, is incubated 1 hour, is cooled to below 50 ℃.In reactor, add N again, N-dimethyl-1,3-propylene diamine 3.6kg adds concentration and is 37% hydrochloric acid 3.5kg then, transfers to pH 6.9, obtains weight concentration and be 34.9% polyhydroxy cation polymkeric substance 63kg.
Embodiment 3
In the reactor that 100 liters of bands stir, heat, add 10kg water, open and stir, the sodium bisulfite of 0.21kg is joined in the reactor, it is fully dissolved, open heating and make reactor be warmed up to 90 ℃, then the vinylformic acid of weight content 15% and the ammonium persulfate aqueous solution 2.6kg of 20% Hydroxyethyl acrylate mix monomer aqueous solution 60kg and concentration 8% are added drop-wise in the reactor simultaneously.The dropping time is 3.5 hours, is warming up to 97 ℃ then, is incubated 45 minutes, is cooled to below 50 ℃.In reactor, add N again, N-dimethyl-1,3-propylene diamine 4.5kg adds concentration and is 37% hydrochloric acid 4.4kg then, transfers to pH 7.5, obtains weight concentration and be 35.1% polyhydroxy cation polymkeric substance 74kg.
Embodiment 4
In the reactor that 100 liters of bands stir, heat, add 28kg water, open and stir, the sodium bisulfite of 0.63kg is joined in the reactor, it is fully dissolved, open heating and make reactor be warmed up to 90 ℃, then the vinylformic acid of weight content 30% and the ammonium persulfate aqueous solution 2.8kg of 40% Hydroxyethyl acrylate mix monomer aqueous solution 30kg and concentration 15% are added drop-wise in the reactor simultaneously.The dropping time is 4.5 hours, is warming up to 98 ℃ then, is incubated 50 minutes, is cooled to below 50 ℃.In reactor, add N again, N-dimethyl-1,3-propylene diamine 6.3kg adds concentration and is 37% hydrochloric acid 6.1kg then, transfers to pH 7.0, obtains weight concentration and be 40.8% polyhydroxy cation polymkeric substance 69kg.
Embodiment 5
In the reactor that 100 liters of bands stir, heat, add 20kg water, open and stir, the sodium bisulfite of 0.32kg is joined in the reactor, it is fully dissolved, open heating and make reactor be warmed up to 90 ℃, then the vinylformic acid of weight content 20% and the ammonium persulfate aqueous solution 3.2kg of 20% Hydroxyethyl acrylate mix monomer aqueous solution 40kg and concentration 10% are added drop-wise in the reactor simultaneously.The dropping time is 4.0 hours, is warming up to 97 ℃ then, is incubated 40 minutes, is cooled to below 50 ℃.In reactor, add N again, N-dimethyl-1,3-propylene diamine 9.6kg adds concentration and is 37% hydrochloric acid 9.3kg then, transfers to pH 7.2, obtains weight concentration and be 37.7% polyhydroxy cation polymkeric substance 77kg.
Claims (5)
1. the preparation method of a fly ash fiber reinforced modifier, it is characterized in that: earlier vinylformic acid and Hydroxyethyl acrylate mix monomer are carried out copolymerization in aqueous solution of sodium bisulfite, under the initiation of ammonium persulphate, obtain the multipolymer of vinylformic acid and Hydroxyethyl acrylate, again toward wherein adding N, N-dimethyl-1, the 3-propylene diamine carries out amidation, adds hydrochloric acid then and is neutralized to pH 6.5～7.5, obtains the polyhydroxy cation polymkeric substance.
The method that described vinylformic acid and Hydroxyethyl acrylate carry out copolymerization is: add entry and sodium bisulfite earlier in reactor, be warming up to 90 ℃, the ammonium persulfate aqueous solution with the vinylformic acid of concentration 30～70% and the Hydroxyethyl acrylate mix monomer aqueous solution, concentration 5～15% is added drop-wise in the reactor simultaneously then.Used ammonium persulphate oven dry weight is 0.8～2.5% of vinylformic acid and a Hydroxyethyl acrylate mix monomer oven dry weight, and the dropping time is 3～5 hours, is warming up to 96～98 ℃ then, is incubated 0.5～1 hour, is cooled to below 50 ℃.
2. the described N of claim 1, N-dimethyl-1, the add-on of 3-propylene diamine is 30～80% of a vinylformic acid oven dry weight.
3. the add-on of the described hydrochloric acid of claim 1 is: HCl and N in the hydrochloric acid, and N-dimethyl-1, the mol ratio of 3-propylene diamine is 1: 1.
4. the add-on of the described sodium bisulfite of claim 1 is 1～3% of vinylformic acid and a Hydroxyethyl acrylate mix monomer over dry gross weight.
5.
Profit requires in 1 described vinylformic acid and the Hydroxyethyl acrylate mix monomer, and the weight ratio of vinylformic acid and Hydroxyethyl acrylate is 1: 5 to 2: 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200910201320 CN101747471B (en) | 2009-12-17 | 2009-12-17 | Method for preparing fly ash fiber reinforced modifier |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200910201320 CN101747471B (en) | 2009-12-17 | 2009-12-17 | Method for preparing fly ash fiber reinforced modifier |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101747471A true CN101747471A (en) | 2010-06-23 |
| CN101747471B CN101747471B (en) | 2012-05-23 |
Family
ID=42475139
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200910201320 Expired - Fee Related CN101747471B (en) | 2009-12-17 | 2009-12-17 | Method for preparing fly ash fiber reinforced modifier |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101747471B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102086610A (en) * | 2010-11-23 | 2011-06-08 | 华东理工大学 | Reinforced modification method for applying fly ash fiber to paper making process |
| CN110331619A (en) * | 2019-06-18 | 2019-10-15 | 宁波市嘉化新材料科技有限公司 | A kind of coal ash fiber is used to substitute the enhancing modified technique of part waste paper |
-
2009
- 2009-12-17 CN CN 200910201320 patent/CN101747471B/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102086610A (en) * | 2010-11-23 | 2011-06-08 | 华东理工大学 | Reinforced modification method for applying fly ash fiber to paper making process |
| CN110331619A (en) * | 2019-06-18 | 2019-10-15 | 宁波市嘉化新材料科技有限公司 | A kind of coal ash fiber is used to substitute the enhancing modified technique of part waste paper |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101747471B (en) | 2012-05-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101240101B (en) | Method for preparing ketohydrazine cross-linked acrylic ester-polyurethane composite weaving emulsion and use thereof | |
| CN101649583B (en) | Cation surface sizing agent and preparation method thereof | |
| CN102127191B (en) | Preparation method of graft copolymer for surface sizing | |
| CN106968132B (en) | A kind of Study of Paper-Strengthening Agent Based | |
| CN108341912B (en) | Preparation method of sizing reinforcing agent | |
| CN102115551A (en) | Starch-based nano biological latex and preparation method thereof | |
| CN102086610B (en) | Reinforced modification method for applying fly ash fiber to paper making process | |
| CN102732186A (en) | Modified starch adhesive and method for preparing same | |
| CN103866618B (en) | Cypres and preparation method thereof, glue application solution and sized paper | |
| CN104086709A (en) | High-branch-chain water-soluble cellulose-acrylamide grafted copolymer and preparation method and application thereof | |
| CN110079270A (en) | A kind of fibre modification soybean protein base adhesive of wood-based plate and preparation method thereof | |
| CN101747471B (en) | Method for preparing fly ash fiber reinforced modifier | |
| CN110305604A (en) | A kind of bond for corrugated board and preparation method thereof | |
| Yin et al. | An environmentally-friendly soybean based resin as an alternative to formaldehyde-based counterpart for biomass composites | |
| CN102230301B (en) | Preparation method of cationic styrene acrylic surface sizing agent | |
| CN101357970A (en) | Carboxymethyl wood flour water absorbent and preparation method thereof | |
| CN104532663A (en) | Composite-fiber flame-retardant paper and preparation method thereof | |
| CN103103878A (en) | Cation modified sesbania gum surface sizing agent and preparation method thereof | |
| CN101003957B (en) | Dispersion liquid of polymer in use for papermaking, preparation method and application | |
| CN103012692B (en) | Method for preparing soybean protein copolymer emulsion | |
| CN110330592B (en) | Preparation method of polyacrylamide for fragrant adhesive | |
| CN102627737B (en) | Preparation method of high-dispersion alkyl ketene dimer (AKD) neutral/alkaline sizing agent | |
| CN101492519B (en) | Impact modifier MBS resin of polyvinyl chloride | |
| CN104861213A (en) | Method for preparing complex starch | |
| CN101532266B (en) | Synthesis and production method for star polymer for paper making dispersant |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| ASS | Succession or assignment of patent right |
Owner name: SHANGHAI HUAMING HI-TECH. (GROUP) CO., LTD. Free format text: FORMER OWNER: EAST CHINA UNIVERSITY OF SCIENCE Effective date: 20110822 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| COR | Change of bibliographic data |
Free format text: CORRECT: ADDRESS; FROM: 200237 XUHUI, SHANGHAI TO: 200231 XUHUI, SHANGHAI |
|
| TA01 | Transfer of patent application right |
Effective date of registration: 20110822 Address after: 200231 No. 1305, Lane 18, Huajing Road, Shanghai, China Applicant after: Huaming High Technology (Group) Co., Ltd., Shanghai Address before: 200237 Meilong Road, Shanghai, No. 130, No. Applicant before: East China University of Science and Technology |
|
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20120523 Termination date: 20181217 |