CN114773540B - High molecular weight amphoteric polyacrylamide and preparation method thereof - Google Patents
High molecular weight amphoteric polyacrylamide and preparation method thereof Download PDFInfo
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- 229920002401 polyacrylamide Polymers 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 239000000178 monomer Substances 0.000 claims abstract description 154
- 239000007864 aqueous solution Substances 0.000 claims abstract description 107
- 239000003999 initiator Substances 0.000 claims abstract description 51
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 37
- 239000000243 solution Substances 0.000 claims abstract description 32
- 229920000642 polymer Polymers 0.000 claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000012986 chain transfer agent Substances 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims description 40
- 125000002091 cationic group Chemical group 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 125000000129 anionic group Chemical group 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- 230000001105 regulatory effect Effects 0.000 claims description 12
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 9
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical group [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 8
- UMSVPCYSAUKCAZ-UHFFFAOYSA-N propane;hydrochloride Chemical compound Cl.CCC UMSVPCYSAUKCAZ-UHFFFAOYSA-N 0.000 claims description 7
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical group CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 claims description 6
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 6
- 238000007664 blowing Methods 0.000 claims description 6
- 230000001276 controlling effect Effects 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 6
- SJIXRGNQPBQWMK-UHFFFAOYSA-N 2-(diethylamino)ethyl 2-methylprop-2-enoate Chemical compound CCN(CC)CCOC(=O)C(C)=C SJIXRGNQPBQWMK-UHFFFAOYSA-N 0.000 claims description 5
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical group [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 5
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 claims description 5
- 238000012544 monitoring process Methods 0.000 claims description 5
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 5
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 5
- JHUFGBSGINLPOW-UHFFFAOYSA-N 3-chloro-4-(trifluoromethoxy)benzoyl cyanide Chemical compound FC(F)(F)OC1=CC=C(C(=O)C#N)C=C1Cl JHUFGBSGINLPOW-UHFFFAOYSA-N 0.000 claims description 4
- ZWAPMFBHEQZLGK-UHFFFAOYSA-N 5-(dimethylamino)-2-methylidenepentanamide Chemical compound CN(C)CCCC(=C)C(N)=O ZWAPMFBHEQZLGK-UHFFFAOYSA-N 0.000 claims description 4
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 4
- 239000003638 chemical reducing agent Substances 0.000 claims description 4
- 239000007800 oxidant agent Substances 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims description 4
- 239000012966 redox initiator Substances 0.000 claims description 4
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 4
- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 3
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 claims description 3
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- -1 dimethylaminomethyl propyl acrylamide Chemical compound 0.000 claims description 3
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 claims description 3
- SZHIIIPPJJXYRY-UHFFFAOYSA-M sodium;2-methylprop-2-ene-1-sulfonate Chemical compound [Na+].CC(=C)CS([O-])(=O)=O SZHIIIPPJJXYRY-UHFFFAOYSA-M 0.000 claims description 3
- YPHQUSNPXDGUHL-UHFFFAOYSA-N n-methylprop-2-enamide Chemical compound CNC(=O)C=C YPHQUSNPXDGUHL-UHFFFAOYSA-N 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 9
- 239000002002 slurry Substances 0.000 abstract description 8
- 230000009172 bursting Effects 0.000 abstract description 7
- 238000001914 filtration Methods 0.000 abstract description 5
- 230000000052 comparative effect Effects 0.000 description 13
- 239000002994 raw material Substances 0.000 description 9
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 5
- 239000000835 fiber Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 150000001450 anions Chemical class 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 229940088644 n,n-dimethylacrylamide Drugs 0.000 description 2
- YLGYACDQVQQZSW-UHFFFAOYSA-N n,n-dimethylprop-2-enamide Chemical compound CN(C)C(=O)C=C YLGYACDQVQQZSW-UHFFFAOYSA-N 0.000 description 2
- 239000010893 paper waste Substances 0.000 description 2
- 239000004289 sodium hydrogen sulphite Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229920001131 Pulp (paper) Polymers 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000004808 allyl alcohols Chemical group 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000012792 core layer Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000010813 municipal solid waste Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- RAJUSMULYYBNSJ-UHFFFAOYSA-N prop-1-ene-1-sulfonic acid Chemical compound CC=CS(O)(=O)=O RAJUSMULYYBNSJ-UHFFFAOYSA-N 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F285/00—Macromolecular compounds obtained by polymerising monomers on to preformed graft polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/56—Acrylamide; Methacrylamide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/10—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of amides or imides
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/54—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen
- D21H17/55—Polyamides; Polyaminoamides; Polyester-amides
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
- D21H21/18—Reinforcing agents
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Paper (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerisation Methods In General (AREA)
Abstract
The invention provides a preparation method of high molecular weight amphoteric polyacrylamide, which comprises the following steps: step 1, primary polymerization: reacting the first mixed monomer aqueous solution under the action of an initiator to form a primary polymer solution; step 2, secondary polymerization: the second mixed monomer aqueous solution and the primary polymer react under the action of a chain transfer agent and an initiator to form a secondary polymer solution; step 3, three polymerization: and the third monomer aqueous solution and the secondary polymer solution react under the action of an initiator to prepare the high molecular weight amphoteric polyacrylamide. When the amphoteric polyacrylamide prepared by the preparation method is used for paper making, the water filtering effect of the slurry can be effectively enhanced, and the bursting strength of finished paper is improved.
Description
Technical Field
The invention belongs to the technical field of amphoteric polymers, and particularly relates to high molecular weight amphoteric polyacrylamide and a preparation method thereof.
Background
The varieties of polyacrylamide reinforcing agents used for papermaking in the current market are various and can be roughly summarized into anionic polyacrylamide, cationic polyacrylamide and amphoteric polyacrylamide. However, with the rapid development of paper making technology, the papermaking wet end system is changed from acid to alkaline, the speed of a paper machine is continuously increased, and papermaking white water is recycled in a closed mode, so that the conductivity of the papermaking system is greatly increased, and the trend of increasing anion garbage is accompanied. The problems of slow water filtering, low fine fiber retention rate, poor paper strength and the like are increasingly worsened in papermaking production due to the influence of a series of factors such as increasingly-increased recycling ratio of waste paper raw materials in China, so that the effect of the traditional polyacrylamide product can not be fully exerted.
Disclosure of Invention
The invention aims to provide a preparation method of high molecular weight amphoteric polyacrylamide, when the amphoteric polyacrylamide prepared by the preparation method is used for paper making, the water filtering effect of slurry can be effectively enhanced, the retention rate of fine fibers can be effectively improved, and the bursting strength of finished paper can be improved.
In order to solve the technical problems, the invention adopts the following technical scheme: the preparation method of the high-component amphoteric polyacrylamide comprises the following steps:
step 1, primary polymerization: adding the first mixed monomer aqueous solution into a reaction kettle, regulating the pH to 3-4, blowing nitrogen into the reaction kettle, heating to 80-85 ℃, adding an initiator to react for 0.5-1h, and then heating to 95 ℃ to continue to react for 2-3h to form a primary polymer solution;
step 2, secondary polymerization: continuously adding a second mixed monomer aqueous solution into the primary polymer solution in the reaction kettle, regulating the pH to 3-4, then adding a chain transfer agent and an initiator, controlling the reaction temperature to be 85-90 ℃, and reacting for 2-3 hours to form a secondary polymer solution;
step 3, three polymerization: adding a third monomer aqueous solution into the secondary polymer solution in the reaction kettle, regulating the pH to 3-4, adding an initiator again, continuing the reaction at 85-90 ℃, monitoring the viscosity in the solution, and ending the reaction when the viscosity is 10000-15000cps, thus obtaining the high molecular weight amphoteric polyacrylamide.
The raw materials in the preparation method are easy to obtain, and the preparation method can finally obtain a high molecular weight product by adopting a special polymerization means to carry out multi-part polymerization, is very suitable for industrial production and has excellent reinforcing effect when the prepared amphoteric polyacrylamide is applied to pulp manufacture, and can enhance the water filtering effect of the slurry. In addition, by controlling the local existence of anions and cations in a molecular chain, in one polymerization, a nonionic monomer A and an anionic monomer are polymerized under the action of an initiator, wherein a plurality of active points are excited, so that the nonionic monomer A and the anionic monomer react to form a plurality of branched chains, and most of the end parts of the branched chains are the anionic monomer; in the secondary polymerization, a nonionic monomer B and a cationic monomer are polymerized under the action of an initiator and a chain transfer agent, wherein a plurality of active points of the nonionic monomer B are excited to polymerize the cationic monomer and the nonionic monomer B, in addition, the step further excites a product obtained in the primary polymerization to further polymerize the product obtained by the reaction of the cationic monomer and the nonionic monomer B with the product obtained in the primary polymerization, and simultaneously, the cationic monomer and the nonionic monomer B are polymerized with the product obtained in the primary polymerization respectively, so that a polymer with multiple branched chains and grid shape is prepared, and the grid density and the molecular weight of the polymer are improved; only cationic monomers are used in the third polymerization, and the product of the second polymerization is further subjected to edge sealing, so that a special structure in which anions and cations exist in the polymer in different regions is finally obtained, and the use effect of the amphoteric polyacrylamide is further improved.
Further, the preparation method of the first mixed monomer aqueous solution comprises the following steps: mixing the nonionic monomer A and the anionic monomer according to the mass ratio of 8-15:1 to prepare a first mixed monomer, and uniformly mixing the first mixed monomer with water to form a first mixed monomer aqueous solution, wherein the mass concentration of the first mixed monomer aqueous solution is 10-30%.
Further, the preparation method of the second mixed monomer aqueous solution comprises the following steps: mixing the nonionic monomer B and the cationic monomer according to the mass ratio of 7-12:1 to prepare a second mixed monomer, and uniformly mixing the second mixed monomer with water to form a second mixed monomer aqueous solution, wherein the mass concentration of the second mixed monomer aqueous solution is 20-45%.
Further, the preparation method of the third monomer aqueous solution comprises the following steps: uniformly mixing the cationic monomer with water to form a third monomer aqueous solution, wherein the mass concentration of the third monomer aqueous solution is 40-50%.
Further, the adding mass ratio of the first mixed monomer aqueous solution to the second mixed monomer aqueous solution to the third monomer aqueous solution is 1:1:0.1-0.2.
Further, in the step 4, the amount of the initiator is 0.01% -0.1% of the weight of the first mixed monomer aqueous solution; in the step 5, the dosage of the initiator is 0.01-0.1% of the weight of the second mixed monomer aqueous solution; in the step 5, the using amount of the chain transfer agent is 0.05-0.1% of the weight of the second mixed monomer aqueous solution; in the step 6, the amount of the initiator is 0.01% -0.1% of the weight of the third monomer aqueous solution.
Further, the nonionic monomer A is acrylamide or methacrylamide, and the anionic monomer is acrylic acid, methacrylic acid or acrylic sulfonic acid.
Further, the nonionic monomer B is one or a mixture of a plurality of N-methyl acrylamide, N-dimethyl acrylamide, N-methylol acrylamide and N-vinyl pyrrolidone, and the cationic monomer is dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, dimethylaminopropyl acrylamide or dimethylaminomethyl propyl acrylamide.
Further, the chain transfer agent is one or more of sodium allylsulfonate, sodium methallylsulfonate, allyl alcohol or thiourea.
Further, the initiator is prepared by mixing a redox initiator and a photoinitiator according to a weight ratio of 4:3, and the redox initiator is prepared by mixing an oxidant and a reducing agent according to a weight ratio of 1:1; wherein the oxidant is ammonium persulfate or potassium persulfate, and the reducing agent is sodium bisulfite or sodium thiosulfate; the photoinitiator is azo diether propane hydrochloride.
The invention also discloses high molecular weight polyacrylamide which is prepared by adopting the preparation method.
The invention also discloses application of the high molecular weight polyacrylamide in the papermaking industry.
The invention has the advantages and positive effects that:
1. the high molecular weight amphoteric polyacrylamide prepared by the preparation method is suitable for paper manufacture, can effectively improve the water filtering effect of slurry during use, can improve the retention rate of fine fibers, and improves the bursting strength of finished paper.
2. In the preparation method, during one-time polymerization, a nonionic monomer A and an anionic monomer are polymerized under the action of an initiator, wherein a plurality of active points of the nonionic monomer A and the anionic monomer are excited, so that the nonionic monomer A and the anionic monomer react to form a plurality of branched chains, and most of the end parts of the branched chains are the anionic monomer; in the secondary polymerization, a nonionic monomer B and a cationic monomer are polymerized under the action of an initiator and a chain transfer agent, wherein a plurality of active points of the nonionic monomer B are excited to polymerize the cationic monomer and the nonionic monomer B, in addition, the step further excites a product obtained in the primary polymerization to further polymerize the product obtained by the reaction of the cationic monomer and the nonionic monomer B with the product obtained in the primary polymerization, and simultaneously, the cationic monomer and the nonionic monomer B are polymerized with the product obtained in the primary polymerization respectively, so that a polymer with multiple branched chains and grid shape is prepared, and the grid density and the molecular weight of the polymer are improved; and only the cationic monomer is used in the third polymerization, and the edge of the product of the second polymerization is further sealed, so that the final polymerization product has stable performance, and a stable structure and use are maintained conveniently.
3. The preparation method provided by the invention is simple to operate, is convenient for realizing industrial production, is easy to obtain raw materials, and can enable the raw materials to fully react through three times of polymerization to prepare the high molecular weight amphoteric polyacrylamide with good performance.
Detailed Description
The present invention will be described in detail with reference to the following embodiments.
Example 1:
the high molecular weight amphoteric polyacrylamide is prepared by the following steps:
step 1, primary polymerization: adding the first mixed monomer aqueous solution into a reaction kettle, adjusting the pH to 3-4, blowing nitrogen into the reaction kettle, heating to 85 ℃, adding an initiator to react for 1h, and then heating to 95 ℃ to continue to react for 3h to form a primary polymer solution;
step 2, secondary polymerization: continuously adding a second mixed monomer aqueous solution into the primary polymer solution in the reaction kettle, regulating the pH to 3-4, then adding a chain transfer agent and an initiator, controlling the reaction temperature to 90 ℃, and reacting for 3 hours to form a secondary polymer solution;
step 3, three polymerization: adding a third monomer aqueous solution into the secondary polymer solution in the reaction kettle, regulating the pH to 3-4, adding an initiator again, continuing the reaction at 90 ℃, monitoring the viscosity in the solution, and ending the reaction when the viscosity is 10000-15000cps, thus obtaining the high molecular weight amphoteric polyacrylamide.
In this embodiment, the first mixed monomer aqueous solution is an aqueous solution with a mass concentration of 30% prepared by mixing acrylamide and acrylic acid according to a mass ratio of 8:1 and then mixing the mixed solution with water; the second mixed monomer aqueous solution is an aqueous solution with the mass concentration of 20% which is prepared by mixing N, N-dimethylacrylamide and diethylaminoethyl methacrylate according to the mass ratio of 7:1 and then mixing the mixture with water; the third monomer aqueous solution is a dimethylaminopropyl acrylamide aqueous solution with the weight concentration of 40 percent; the initiator is a mixture of ammonium persulfate, sodium bisulphite and azo diether propane hydrochloride according to the mass ratio of 2:2:3; the chain transfer agent is sodium allylsulfonate.
In this embodiment, the mass ratio of the first mixed monomer aqueous solution, the second mixed monomer aqueous solution, and the third mixed monomer aqueous solution is 1:1:0.1; in the step 1, the amount of the initiator is 0.01% of the weight of the first mixed monomer aqueous solution; in the step 2, the amount of the initiator is 0.01% of the weight of the second mixed monomer aqueous solution, and the amount of the chain transfer agent is 0.05% of the weight of the second mixed monomer aqueous solution; in step 3, the initiator was used in an amount of 0.01% by weight of the aqueous third monomer solution.
Example 2:
the high molecular weight amphoteric polyacrylamide is prepared by the following steps:
step 1, primary polymerization: adding the first mixed monomer aqueous solution into a reaction kettle, adjusting the pH to 3-4, blowing nitrogen into the reaction kettle, heating to 80 ℃, adding an initiator to react for 1h, and then heating to 95 ℃ to continue to react for 2h to form a primary polymer solution;
step 2, secondary polymerization: continuously adding a second mixed monomer aqueous solution into the primary polymer solution in the reaction kettle, regulating the pH to 3-4, then adding a chain transfer agent and an initiator, controlling the reaction temperature to be 85 ℃, and reacting for 2 hours to form a secondary polymer solution;
step 3, three polymerization: adding a third monomer aqueous solution into the secondary polymer solution in the reaction kettle, regulating the pH to 3-4, adding an initiator again, continuing the reaction at 85 ℃, monitoring the viscosity in the solution, and ending the reaction when the viscosity is 10000-15000cps, thus obtaining the high molecular weight amphoteric polyacrylamide.
The raw materials and proportions in this example were the same as in example 1.
Example 3:
the high molecular weight amphoteric polyacrylamide is prepared by the following steps:
step 1, primary polymerization: adding the first mixed monomer aqueous solution into a reaction kettle, adjusting the pH to 3-4, blowing nitrogen into the reaction kettle, heating to 85 ℃, adding an initiator to react for 0.5h, and then heating to 95 ℃ to continue to react for 2h to form a primary polymer solution;
step 2, secondary polymerization: continuously adding a second mixed monomer aqueous solution into the primary polymer solution in the reaction kettle, regulating the pH to 3-4, then adding a chain transfer agent and an initiator, controlling the reaction temperature to 90 ℃, and reacting for 2 hours to form a secondary polymer solution;
step 3, three polymerization: adding a third monomer aqueous solution into the secondary polymer solution in the reaction kettle, regulating the pH to 3-4, adding an initiator again, continuing the reaction at 90 ℃, monitoring the viscosity in the solution, and ending the reaction when the viscosity is 10000-15000cps, thus obtaining the high molecular weight amphoteric polyacrylamide.
The raw materials and proportions in this example were the same as in example 1.
Example 4:
the preparation method and the process parameters of the embodiment are the same as those of embodiment 1, and the difference is only that the raw materials and the proportions are different, specifically as follows:
in this embodiment, the first mixed monomer aqueous solution is an aqueous solution with a mass concentration of 10% prepared by mixing methacrylamide and propenesulfonic acid according to a mass ratio of 15:1 and then mixing the mixture with water; the second mixed monomer aqueous solution is an aqueous solution with the mass concentration of 20% which is prepared by mixing N-methacrylamide and dimethylaminoethyl methacrylate according to the mass ratio of 12:1 and then mixing the mixture with water; the third monomer aqueous solution is a dimethylaminoethyl methacrylate aqueous solution with the weight concentration of 40%; the initiator is a mixture of potassium persulfate, sodium bisulfite and azo diether propane hydrochloride according to the mass ratio of 2:2:3; the chain transfer agent is sodium methallyl sulfonate.
In this embodiment, the mass ratio of the first mixed monomer aqueous solution, the second mixed monomer aqueous solution, and the third mixed monomer aqueous solution is 1:1:0.2; in the step 1, the amount of the initiator is 0.1% of the weight of the first mixed monomer aqueous solution; in the step 2, the amount of the initiator is 0.1% of the weight of the second mixed monomer aqueous solution, and the amount of the chain transfer agent is 0.5% of the weight of the second mixed monomer aqueous solution; in step 3, the initiator was used in an amount of 0.1% by weight of the aqueous third monomer solution.
Example 5:
the preparation method and the process parameters of the embodiment are the same as those of embodiment 1, and the difference is only that the raw materials and the proportions are different, specifically as follows:
in this embodiment, the first mixed monomer aqueous solution is an aqueous solution with a mass concentration of 25% prepared by mixing acrylamide and methacrylic acid in a mass ratio of 10:1 and then mixing the mixed solution with water; the second mixed monomer aqueous solution is an aqueous solution with the mass concentration of 45% which is prepared by mixing N-vinyl pyrrolidone and dimethylaminomethyl propyl acrylamide according to the mass ratio of 8:1 and then mixing the mixed solution with water; the third monomer aqueous solution is 50% by weight of dimethylaminoethyl methacrylate aqueous solution; the initiator is a mixture of potassium persulfate, sodium thiosulfate and azo diether propane hydrochloride according to the mass ratio of 2:2:3; the chain transfer agent is allyl alcohol.
In this embodiment, the mass ratio of the first mixed monomer aqueous solution, the second mixed monomer aqueous solution, and the third mixed monomer aqueous solution is 1:1:0.2; in the step 1, the amount of the initiator is 0.05% of the weight of the first mixed monomer aqueous solution; in the step 2, the amount of the initiator is 0.05% of the weight of the second mixed monomer aqueous solution, and the amount of the chain transfer agent is 0.1% of the weight of the second mixed monomer aqueous solution; in step 3, the initiator was used in an amount of 0.05% by weight of the aqueous third monomer solution.
Example 6:
the preparation method and the process parameters of the embodiment are the same as those of embodiment 1, and the difference is only that the raw materials and the proportions are different, specifically as follows:
in the embodiment, the first mixed monomer aqueous solution is an aqueous solution with a mass concentration of 20% which is prepared by mixing acrylamide and acrylic sulfonic acid according to a mass ratio of 12:1 and then mixing the mixture with water; the second mixed monomer aqueous solution is an aqueous solution with the mass concentration of 20% which is prepared by mixing N-methylolacrylamide and dimethylaminoethyl methacrylate according to the mass ratio of 12:1 and then mixing the mixture with water; the third monomer aqueous solution is a 50% by weight aqueous solution of diethylaminoethyl methacrylate; the initiator is a mixture of potassium persulfate, sodium thiosulfate and azo diether propane hydrochloride according to the mass ratio of 2:2:3; the chain transfer agent is thiourea.
In this embodiment, the mass ratio of the first mixed monomer aqueous solution, the second mixed monomer aqueous solution, and the third mixed monomer aqueous solution is 1:1:0.1; in the step 1, the amount of the initiator is 0.1% of the weight of the first mixed monomer aqueous solution; in the step 2, the amount of the initiator is 0.05% of the weight of the second mixed monomer aqueous solution, and the amount of the chain transfer agent is 0.1% of the weight of the second mixed monomer aqueous solution; in step 3, the initiator was used in an amount of 0.05% by weight of the aqueous third monomer solution.
Comparative example 1:
this comparative example was prepared using the method of example 1 in publication CN108794685a to give an amphoteric polyacrylamide.
Comparative example 2:
this comparative example was prepared using the method of example 1 in publication CN111848863B to give an amphoteric polyacrylamide.
Comparative example 3:
this comparative example uses a one-step reaction to prepare amphoteric polyacrylamide, the preparation process of which is as follows:
adding the first mixed monomer aqueous solution, the second mixed monomer aqueous solution and the third monomer aqueous solution into a reaction kettle according to the mass ratio of 1:1:0.1, adjusting the pH value to 3-4, blowing nitrogen into the reaction kettle, heating to 85 ℃, adding an initiator to react for 1h, heating to 95 ℃, continuing to react, and ending the reaction when the viscosity is 10000-15000cps, thus obtaining the high molecular weight amphoteric polyacrylamide.
Wherein the first mixed monomer aqueous solution is an aqueous solution with the mass concentration of 30% which is prepared by mixing acrylamide and acrylic acid according to the mass ratio of 8:1 and then mixing the mixture with water; the second mixed monomer aqueous solution is an aqueous solution with the mass concentration of 20% which is prepared by mixing N, N-dimethylacrylamide and diethylaminoethyl methacrylate according to the mass ratio of 7:1 and then mixing the mixture with water; the third monomer aqueous solution is a dimethylaminopropyl acrylamide aqueous solution with the weight concentration of 40 percent; the initiator is a mixture of ammonium persulfate, sodium bisulphite and azo diether propane hydrochloride according to the mass ratio of 2:2:3; the chain transfer agent is sodium allylsulfonate.
Wherein the amount of initiator is the weight of the initiator in each step of example 1 and the amount of chain initiator is the same as that of example 1.
Experimental example 1:
the amphoteric polyacrylamides prepared in examples 1 to 6 and comparative examples 1 and 2 were used in papermaking to conduct experiments on the influence of the drainage properties of the slurry, and the experimental results are shown in table 1;
the experimental environment for papermaking is as follows: the system conductivity was 6000. Mu.s/cm, the positive charge demand was 710. Mu. Eq/L, and the system temperature was 50 ℃.
Table 1 slurry drainage effect of examples and comparative examples
As can be seen from the experimental data in table 1, compared with the blank control and the comparative example, the amphoteric polyacrylamide prepared by the preparation method of the present invention has good drainage effect when being used in slurry; as can be seen from the data of comparative example 3 and examples, the amphoteric polyacrylamide prepared by the three-step polymerization method of the present invention has a remarkable drainage effect when applied to slurry.
Experimental example 2:
the amphoteric polyacrylamides obtained in the experimental examples and comparative examples were sheet-formed, and the basis weight and bursting strength of the finished paper were measured, and the measurement results thereof are shown in table 3.
The testing method comprises the following steps: selecting core layer waste paper pulp, and setting the quantitative of paper to 120g/m 2 The whole sheet making process uses a KFR semiautomatic sheet making device, 3kg of cationic starch and 3kg of AKD neutral sizing agent are sequentially added in the sheet making process, 1.2kg of aluminum sulfate (the dosage is equal to that of absolute dry fiber) is diluted by using the mesh water according to the amounts of 20kg and 40kg of the product, paper sheets are manufactured, then the paper sheets are dried on a drum dryer at 105 ℃, and the basis weight and the bursting strength of the paper sheets are tested after being dried for 24 hours at constant temperature and humidity. The test method of the bursting strength and the basis weight is disclosed in GB/T13024-2003.
Table 2 basis weight, burst test data for papers prepared from examples and comparative products
Wherein, the usage kg/t in the table means the mass ratio of the sample to the finished paper; the burst average index is the average of two sets of data.
From the experimental data in table 2, it can be seen that when the amphoteric polyacrylamide prepared by the preparation method is used for making paper, the prepared paper has good bursting strength, and the paper strength is effectively improved; the product produced by the production method of the present invention is more effective than the blank and the comparative example of the prior art.
The foregoing describes the embodiments of the present invention in detail, but the description is merely a preferred embodiment of the present invention and should not be construed as limiting the scope of the invention. All equivalent changes and modifications within the scope of the present invention are intended to be covered by the present invention.
Claims (8)
1. A method for preparing high molecular weight amphoteric polyacrylamide, which is characterized by comprising the following steps:
step 1, primary polymerization: adding the first mixed monomer aqueous solution into a reaction kettle, regulating the pH to 3-4, blowing nitrogen into the reaction kettle, heating to 80-85 ℃, adding an initiator to react for 0.5-1h, and then heating to 95 ℃ to continue to react for 2-3h to form a primary polymer solution;
step 2, secondary polymerization: continuously adding a second mixed monomer aqueous solution into the primary polymer solution in the reaction kettle, regulating the pH to 3-4, then adding a chain transfer agent and an initiator, controlling the reaction temperature to be 85-90 ℃, and reacting for 2-3 hours to form a secondary polymer solution;
step 3, three polymerization: adding a third monomer aqueous solution into the secondary polymer solution in the reaction kettle, regulating the pH to 3-4, adding an initiator again, continuing the reaction at 85-90 ℃, monitoring the viscosity in the solution, and ending the reaction when the viscosity is 10000-15000cps to prepare the high molecular weight amphoteric polyacrylamide;
the preparation method of the first mixed monomer aqueous solution comprises the following steps: mixing a nonionic monomer A and an anionic monomer according to a mass ratio of 8-15:1 to prepare a first mixed monomer, and uniformly mixing the first mixed monomer with water to form a first mixed monomer aqueous solution, wherein the mass concentration of the first mixed monomer aqueous solution is 10-30%;
the preparation method of the second mixed monomer aqueous solution comprises the following steps: mixing the nonionic monomer B and the cationic monomer according to the mass ratio of 7-12:1 to prepare a second mixed monomer, and uniformly mixing the second mixed monomer with water to form a second mixed monomer aqueous solution, wherein the mass concentration of the second mixed monomer aqueous solution is 20-45%;
the preparation method of the third monomer aqueous solution comprises the following steps: uniformly mixing the cationic monomer with water to form a third monomer aqueous solution, wherein the mass concentration of the third monomer aqueous solution is 40-50%;
the nonionic monomer A is acrylamide or methacrylamide, and the anionic monomer is acrylic acid, methacrylic acid or acrylic sulfonic acid.
2. The method for preparing the high molecular weight amphoteric polyacrylamide according to claim 1, wherein: the mass ratio of the first mixed monomer aqueous solution to the second mixed monomer aqueous solution to the third mixed monomer aqueous solution is 1:1:0.1-0.2.
3. The method for preparing the high molecular weight amphoteric polyacrylamide according to claim 1 or 2, wherein: in the step 1, the dosage of the initiator is 0.01% -0.1% of the weight of the first mixed monomer aqueous solution;
in the step 2, the dosage of the initiator is 0.01-0.1% of the weight of the second mixed monomer aqueous solution;
in the step 2, the using amount of the chain transfer agent is 0.05-0.1% of the weight of the second mixed monomer aqueous solution;
in the step 3, the amount of the initiator is 0.01% -0.1% of the weight of the third monomer aqueous solution.
4. A method for preparing a high molecular weight amphoteric polyacrylamide according to claim 3, wherein: the nonionic monomer B is one or a mixture of a plurality of N-methyl acrylamide, N-dimethyl acrylamide, N-methylol acrylamide and N-vinyl pyrrolidone, and the cationic monomer is dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, dimethylaminopropyl acrylamide or dimethylaminomethyl propyl acrylamide.
5. The method for preparing the high molecular weight amphoteric polyacrylamide according to claim 4, wherein: the chain transfer agent is one or more of sodium allylsulfonate, sodium methallylsulfonate, allyl alcohol or thiourea.
6. The method for preparing the high molecular weight amphoteric polyacrylamide according to claim 5, wherein: the initiator is prepared by mixing a redox initiator and a photoinitiator according to a weight ratio of 4:3, and the redox initiator is prepared by mixing an oxidant and a reducer according to a weight ratio of 1:1; wherein the oxidant is ammonium persulfate or potassium persulfate, and the reducing agent is sodium bisulfite or sodium thiosulfate; the photoinitiator is azo diamidino propane hydrochloride.
7. A high molecular weight amphoteric polyacrylamide prepared by the method of any one of claims 1-6.
8. Use of the high molecular weight amphoteric polyacrylamide according to claim 7 in the paper industry.
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| JP2000239326A (en) * | 1999-02-19 | 2000-09-05 | Japan Pmc Corp | Polymer of acrylamide-based copolymer, additive for papermaking and paper |
| CN104672376A (en) * | 2015-02-02 | 2015-06-03 | 天津市浩宇助剂有限公司 | Preparation process of water-in-water emulsion type retention and drainage agent |
| CN108794685A (en) * | 2018-06-01 | 2018-11-13 | 苏州派凯姆新能源科技股份有限公司 | A kind of molecular weight amphoteric high polyacrylamide and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000239326A (en) * | 1999-02-19 | 2000-09-05 | Japan Pmc Corp | Polymer of acrylamide-based copolymer, additive for papermaking and paper |
| CN104672376A (en) * | 2015-02-02 | 2015-06-03 | 天津市浩宇助剂有限公司 | Preparation process of water-in-water emulsion type retention and drainage agent |
| CN108794685A (en) * | 2018-06-01 | 2018-11-13 | 苏州派凯姆新能源科技股份有限公司 | A kind of molecular weight amphoteric high polyacrylamide and preparation method thereof |
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