CN104119480A - High-branch type polyvinyl alcohol-acrylamide graft copolymer, preparing method thereof and applications of the copolymer - Google Patents
High-branch type polyvinyl alcohol-acrylamide graft copolymer, preparing method thereof and applications of the copolymer Download PDFInfo
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Abstract
The invention relates to a preparing method of a high-branch type polyvinyl alcohol-acrylamide graft copolymer. The preparing method includes: dissolving polyvinyl alcohol with water, feeding nitrogen, cooling, adding a catalyst, reacting for 10-30 min, adding dropwise a monomer mixture solution with the adding time being controlled to be 30-90 min and the reaction temperature during addition being controlled to be 65-95 DEG C, reacting at 85-95 DEG C for 20-30 min after the addition is finished, adding the catalyst, reacting at 80-95 DEG C for 15-25 min, adding the catalyst, sampling in the reaction process and measuring viscosity, adding a terminating agent when the viscosity at 25 DEG C reaches 1500-15000 mPa*s to stop the reaction, and adjusting the solid content. The graft copolymer has characteristics of high molecular weight, more branches, low viscosity, less gel, good retention property, and high interference resistance to hetero-ion, and can achieve satisfied enhancing effects even when being used as a papermaking dry strength agent in a bad high-temperature high-conductivity environment for manufacturing paper with pulp.
Description
Technical field
The present invention relates to Polymer Synthesizing and Dry Strength Resin field, be specifically related to a kind of high branched chain type polyvinyl alcohol-acrylamide grafted copolymer, its preparation method and its application as Dry Strength Resin.
Background technology
For China's paper making raw material, mainly adopt the present situation of paper waste; add by energy-saving and emission-reduction and environment protection state basic policy and force; papermaking enterprise has to carry forward vigorously cleaner production; cause in whitewater closure circulation, system rubbish and impurities accumulation serious, the high electricity of high temperature leads that under the system of manufacturing paper with pulp, auxiliary dosage is large, retention is low, paper strength is poor.In order improving, to keep, to improve paper quality, paper plant is used Dry Strength Resin in a large number.
Dry Strength Resin is a class important chemical that increases paper strength, and modal Dry Strength Resin comprises natural polymer, as starch, melon glue, Mierocrystalline cellulose etc., and synthetic polymer, as polyvinyl alcohol, polymine, polyacrylamide etc.
With starch as Dry Strength Resin, need to be with steam by its gelatinization redilution during use, technical process is complicated, and has increased equipment, steam energy consumption and personnel's input; Larger shortcoming is that starch based Dry Strength Resin retention is low, consumption is large, paper machine white water is seriously polluted; In addition, for take state, give up as the paper kind of raw material, even if increase consumption, ring crush intensity and pop strength do not reach index request yet.Guar gum and Mierocrystalline cellulose price are high, and retention is low, generally only for speciality paper industry.
Polyvinyl alcohol is a kind of polyhydric high molecular weight water soluble polymer, nontoxic, there is excellent adhesive property and film-forming properties, by the long-term top sizing for paper, can increase surface strength, friction intensity and inner tension stress, pop strength, the folding endurance of paper product, increase gloss and the smoothness of paper, improve paper oil-proofness and organic solvent resistance, improve printing adaptability.But polyvinyl alcohol is directly added in slurry, and because it is nonionic, retention is low, does not reach the result of use of expection.
The open CN101215807A of Chinese patent discloses a kind of preparation method of cationic polyvinyl alcohol paper intensifier, it is first by the polyvinyl alcohol having dissolved and cationic etherifying agent reaction, synthesizing cationic polyvinyl alcohol, and then and aldehydes cross-linking modified reaction under acidic conditions, in alkali and after cationic polyvinyl alcohol paper strengthening agent, this toughener is amide-containing, carboxyl isoreactivity group not, few with the reaction bonded point of paper fibre.
The open CN103333352A of Chinese patent discloses a kind of preparation method of cross-linked graft modified polyvinyl alcohol surface reinforcing agent, and it is that polyvinyl alcohol is mixed and obtains polyvinyl alcohol water solution with water; This aqueous solution is heated up, add the vinyl monomer, cationic monomer of ketocarbonyl-containing, containing the vinyl monomer of vinyl monomer, self-cross linking monomer and the other types of long side-chain radical, then drip initiator solution, after completing, polymerization regulates pH value with alkali, add hydrazine or derivatives thereof to stir, can make cross-linked graft modified polyvinyl alcohol surface reinforcing agent; This patent gained toughener and fiber binding site are few, and retention is low, are not suitable for starching interior interpolation and use.And polymine price is high, be generally used for anion garbage capturing agent and retention aid, for paper, strengthen, cost performance is low.
At present, polyacrylamide Dry Strength Resin is most widely used general, and particularly amphiprotic polyacrylamide net effect is better.Such as Chinese patent is announced preparation method and the additive for papermaking that CN101062963B discloses water-soluble polymers, it adopts different zwitterion monomers, acrylamide, molecular weight regulator and linking agent copolymerization, preparation has the high molecular polymer of specific ion and crosslinking structure, and is applied to the toughener of paper industry.The open CN103772603A of Chinese patent discloses preparation method and the application thereof of the narrow distribution crosslinked polyacrylamide of high molecular, a kind of toughener when having higher weight-average molecular weight with lower molecular weight distribution has been proposed, it is good that this toughener has reinforced effects, in plain boiled water, run off few, it is good to determine, the advantages such as jello is few, environmental protection.The open CN102720094A of Chinese patent discloses branched chain type Dry Strength Resin and preparation method thereof, it is in inert atmosphere, by acrylamide, anionic monomer, cationic monomer and cross-linkable monomer, under light trigger effect, initiated polymerization, prepares the Dry Strength Resin with branched structure.The open CN103421147A of Chinese patent discloses the preparation method of graftomer type both sexes Dry Strength Resins, it mixes cationic starch and water, heating gelatinization, add successively again water, acrylamide, anionic monomer, cross-linkable monomer, chain-transfer agent, other functional monomers and photoinitiator, under oxygen-free environment, temperature is risen to 70-95 ℃, to reaction system irradiating ultraviolet light reaction 1-2 hour, viscosity stops irradiating ultraviolet light after reaching 4000-9000mPa.s, add pH adjusting agent to regulate pH to 4-6, and add free radical scavenger, obtain Dry Strength Resin.These above patents all adopt and add the method for linking agent to make branched chain type or cross-linking type Dry Strength Resin, there is a common problem: add the difficult control of linking agent post polymerization, side chain degree is generally done not high, because linking agent has been added the easy cross linked gel of molecular chain, water-soluble variation; And linking agent adds that to have lacked side chain few, does not reach the object of high side chain, reinforced effects is poor.
Prior art generally adopts the method for adding linking agent to prepare branched chain type or cross-linking type Dry Strength Resin, has the difficult control of reaction, easily the problem of gel.For this reason, the present invention proposes a kind of preparation method of high branched chain type polyvinyl alcohol-acrylamide grafted copolymer, catalysis graft acrylamide on polyvinyl alcohol main chain, cationic monomer and anionic monomer, in the situation that not adding linking agent, the both sexes Dry Strength Resin that synthesizes high side chain degree, produce easily control, it is high that product has molecular weight, side chain is many, viscosity is little, gel is few, keep, the advantages such as anti-hetero-ion interference is strong, give full play to the synergistic enhancing effect of polyvinyl alcohol and amphoteric polyacrylamide Dry Strength Resin, even under the environment of badly manufacturing paper with pulp that graft copolymer of the present invention is led at the high electricity of high temperature, also can reach satisfied reinforced effects, and good water solubility, easy to use.
Below in conjunction with specific embodiment, the present invention is described in further details.Should be understood that these embodiment are for ultimate principle of the present invention, principal character and advantage are described, and the present invention is not limited by the following examples.The implementation condition adopting in embodiment can be done further adjustment according to specific requirement, and not marked implementation condition is generally the condition in normal experiment.In addition, while there is no specified otherwise, the consumption of component is weight in grams (g) and % by weight.
Summary of the invention
Technical problem to be solved by this invention is to overcome the deficiencies in the prior art, and a kind of preparation method of improved high branched chain type polyvinyl alcohol-acrylamide grafted copolymer is provided.
For overcoming the above problems, the present invention takes following technical scheme:
A kind of preparation method of high branched chain type polyvinyl alcohol-acrylamide grafted copolymer, it is implemented as follows: by polyvinyl alcohol (PVA) and water, be the ratio mixing of 10-20:100 in mass ratio, being heated to 75 ℃-95 ℃ insulations dissolves, after polyvinyl alcohol dissolves completely, logical nitrogen is more than 30 minutes, and be cooled to 60 ℃～80 ℃, add catalyzer, reaction 10-30 minute, make the activation of polyvinyl alcohol molecule chain produce free radical, then drip monomer mixture solution, control monomer mixture solution time for adding between 30～90 minutes, temperature of reaction is controlled between 65 ℃-95 ℃ during this time, after monomer mixture solution drips, control temperature reacts after 20～30 minutes between 85 ℃-95 ℃, add catalyzer, continuation is reacted after 15～25 minutes at 80 ℃-95 ℃, add again catalyzer, in reaction process, sample viscosimetric, at 25 ℃, viscosity reaches after 1500～15000mPa.s, add terminator, stopped reaction, and add water adjustment product solid content to 10wt%～30wt%, obtain described high branched chain type polyvinyl alcohol-acrylamide grafted copolymer, wherein:
Monomer mixture solution be take water as solvent, and mass concentration is between 20%～40%, and pH, between 2～5, wherein contains the first monomer, the second monomer, the 3rd monomer, molecular weight regulator, sequestrant, and pH adjusting agent and selectable, the 4th monomer, wherein:
The first monomer is acrylamide, Methacrylamide or the combination of the two;
The second monomer is for being selected from dimethyl diallyl ammonium chloride, (methyl) vinylformic acid dimethylin ethyl ester, (methyl) vinylformic acid diethylin ethyl ester, dimethylamino-propyl (methyl) acrylamide and their methyl chloride, benzyl chloride quaternary ammonium salt (MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride for example, acrylyl oxy-ethyl-trimethyl salmiac, methylacryloxyethyldimethyl benzyl ammonium chloride, acrylyl oxy-ethyl dimethyl benzyl ammonium chloride, (3-acrylamide propyl) trimethyl ammonium chloride, the combination of one or more (3-methacryloyl amido propyl group) trimethyl ammonium chloride),
The 3rd monomer is for being selected from (methyl) vinylformic acid, methylene-succinic acid, fumaric acid (acid anhydride), toxilic acid (acid anhydride), sodium vinyl sulfonate, vinylbenzenesulfonic acid sodium, 2-acrylamido-2 methyl propane sulfonic acid, the combination of one or more in styrene sulfonic acid and their salt;
The 4th monomer is for being selected from one or more the combination in n-methylolacrylamide, glycidyl methacrylate, (methyl) Hydroxyethyl acrylate, (methyl) Propylene glycol monoacrylate, (methyl) vinyl cyanide, (methyl) vinylbenzene and (methyl) alkyl acrylate;
The mass ratio that feeds intake of described polyvinyl alcohol, the first monomer, the second monomer, the 3rd monomer, the 4th monomer is: 5～30:30～90:0.2～20:0.2～20:0～20,
In aforesaid method, total catalyst consumption is 0.02%～1.5% of described high branched chain type polyvinyl alcohol-acrylamide grafted copolymer weight, the amount of the catalyzer wherein adding for the first time accounts for 5%～60% of total catalyst consumption, the amount of the catalyzer adding for the second time accounts for 10%～60% of total catalyst consumption, and the amount of the catalyzer adding for the third time accounts for 10%～60% of total catalyst consumption.
As a preferred aspect of the present invention, the mass ratio that feeds intake of polyvinyl alcohol, the first monomer, the second monomer, the 3rd monomer, the 4th monomer is 1:2～10:0.1～1:0.1～1:0～0.5.
According to the present invention, described catalyzer can be persulphate, ceric ammonium nitrate, ceric ammonium nitrate/tetramethylolmethane, superoxide, water-soluble azo class, persulphate/sulfurous acid (hydrogen) salt, persulphate/thiosulphate, the combination of one or more in potassium permanganate.As preferably, catalyzer is for being selected from ammonium persulphate, Potassium Persulphate, ceric ammonium nitrate, hydrogen peroxide, azo-bis-isobutyrate hydrochloride, azo di-isopropyl imidazoline salt hydrochlorate, the combination of one or more arbitrary proportions in ammonium persulphate/sodium bisulfite.
According to the present invention, described molecular weight regulator can, for conventional those in this area, be not particularly limited.Be specifically as follows selected from mercapto compounds as mercaptoethanol, Thiovanic acid, mercapto glycerol etc., lauryl mercaptan, Virahol, sodium hypophosphite, sodium formiate, thanomin, vinyl carbinol, sodium allyl sulfonate, methallylsulfonic acid sodium, 2, the combination of one or more of 4-phenylbenzene-4-methyl-1-pentene etc.
The charging capacity of molecular weight regulator is generally 0.01%～3.5% of high branched chain type polyvinyl alcohol-acrylamide grafted copolymer weight.
According to the present invention, described sequestrant can be selected from aminocarboxylic acid and salt series thereof, comprises nitrilotriacetic acid(NTA) (NTA), nitrilotriacetic acid(NTA) salt, ethylenediamine tetraacetic acid (EDTA) (EDTA), EDTA-2Na, EDTA-4Na, diethylenetriamine pentacarboxylic acid (DTPA), diethylenetriamine pentacarboxylic acid salt etc.; Organic phospho acid and salt series thereof, comprise ethylene diamine tetra methylene phosphonic acid (EDTMPA), ethylene diamine tetra methylene phosphonic acid sodium (EDTMPS), diethylene triamine pentamethylene phosphonic (DETPMP), diethylene triamine pentamethylene phosphonic salt (DETPMPS), amine three methylenephosphonic acids (ATMP), amine three methene phosphonates, phytinic acid etc.; Hydroxycarboxylic acid salt, comprises one or more in tartrate, heptose hydrochlorate, Sunmorl N 60S, sodium alginate etc.
The charging capacity of sequestrant is generally 0.01%～0.5% of high branched chain type polyvinyl alcohol-acrylamide grafted copolymer weight.
According to the present invention, polyvinyl alcohol can and be preferably one or more the combination being selected from the following polyvinyl alcohol trade mark: 0388,0399,0588,0599,1088,1099,1750,1788,1799,2088,2099,2488,2497,2499,2688 and 2699.
According to the present invention, pH adjusting agent and terminator are all not particularly limited, wherein pH adjusting agent can be for being selected from sulfuric acid, hydrochloric acid, phosphoric acid, acetic acid, sodium hydroxide, potassium hydroxide, ammoniacal liquor, triethylamine, the combination of one or more in trolamine and strong acid weak base salt or strong base-weak acid salt.The consumption of pH adjusting agent is to make to regulate needed amount between pH to 2～5 of monomer mixture solution.Terminator can be selected from one or more the combination in benzoquinones, S-WAT, sodium bisulfite, potassium sulfite, Potassium hydrogen sulfite, Sulfothiorine etc.The consumption of terminator is generally the 0.05%-2% of product gross weight.
The present invention is also particularly related to a kind of high branched chain type polyvinyl alcohol-acrylamide grafted copolymer, and its preparation method by above-mentioned high branched chain type polyvinyl alcohol-acrylamide grafted copolymer makes.
The prepared high branched chain type polyvinyl alcohol-acrylamide grafted copolymer of the present invention has the advantages such as molecular weight is high, side chain is many, viscosity is little, gel is few, keep, anti-hetero-ion interference is strong, give full play to the synergistic enhancing effect of polyvinyl alcohol and amphoteric polyacrylamide Dry Strength Resin, even under the environment of badly manufacturing paper with pulp of leading at the high electricity of high temperature, also can reach satisfied reinforced effects, and good water solubility, easy to use, for this reason, the present invention is also particularly related to this high branched chain type polyvinyl alcohol-acrylamide grafted copolymer as the purposes of papermaking dry-strengthening agent.
Due to the employing of above technical scheme, the present invention compared with prior art tool has the following advantages:
The present invention is usingd high-molecular polyvinyl alcohol chain as main skeleton structure, through catalyst activation, make to produce on polyvinyl alcohol molecule chain a large amount of free radicals, then adopt the mode dripping, by acrylamide, cationic monomer and anionic monomer progressively graft polymerization to the macromolecular chain of polyvinyl alcohol, form the macromolecular grafted multipolymer of higly branched chain.Because monomer mixture has adopted dropping technique, reduced initial stage monomer concentration and free radical quantity, reduced the homopolymerization of acrylamide, make it be more prone to graft copolymerization.Later stage is added catalyzer at twice, has delayed polymerization rate, and molecular chain length is progressively increased, and easy control of reaction finally makes the polyvinyl alcohol-acrylamide grafted copolymer of high molecular, high side chain degree.
High branched chain type polyvinyl alcohol-acrylamide grafted copolymer provided by the invention has the advantages such as molecular weight is high, side chain is many, viscosity is little, gel is few, keep, anti-hetero-ion interference is strong, give full play to the synergistic enhancing effect of polyvinyl alcohol and amphoteric polyacrylamide Dry Strength Resin, as papermaking dry-strengthening agent, even under the environment of badly manufacturing paper with pulp of leading at the high electricity of high temperature, also can reach satisfied reinforced effects, and good water solubility, easy to use.
Embodiment
Embodiment 1
This example provides a kind of preparation method of high branched chain type polyvinyl alcohol-acrylamide grafted copolymer, and main raw material used and charging capacity see table:
Described method is specifically implemented as follows:
To with stirrer, thermometer, in 1 liter of four-hole boiling flask of reflux condensing tube and nitrogen ingress pipe, add deionized water 200g, under whipped state, slowly add PVA1799 20.0g, be warming up to 95 ℃ and be incubated 30 minutes, after PVA dissolves completely, logical nitrogen 30 minutes, be cooled to 70 ℃, add 5% ammonium persulfate aqueous solution 6.0g, react 20 minutes, then drip monomer mixed solution, monomer mixed solution is by acrylamide 110g, dimethylaminoethyl methacrylate 4.2g, MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride (effective constituent 78%) 5.5g, methylacryloxyethyldimethyl benzyl ammonium chloride (effective constituent 60%) 1.8g, vinylformic acid 3.0g, n-methylolacrylamide 0.5g, methyl methacrylate 5g, methallylsulfonic acid sodium 0.38g, sodium formiate 0.12g, EDTA0.07g, deionized water 360g, and adjust pH value to 3.0 compositions with 50% sulfuric acid, within 60 minutes, drip off, after dripping off, between 88 ℃-92 ℃, react 25 minutes, add 5% ammonium persulfate aqueous solution 3.0g, between 87 ℃-90 ℃, react 20 minutes, add 5% ammonium persulfate aqueous solution 3.0g, continue reaction 20 minutes, viscosity rises gradually, reach after expection viscosity, add 5% sodium sulfite aqueous solution 24g termination reaction, obtaining solid content is 20.3%, at 25 ℃, viscosity is 8800mPa.s, pH value is 4.6 the graft copolymer aqueous solution.
Embodiment 2
This example provides a kind of preparation method of high branched chain type polyvinyl alcohol-acrylamide grafted copolymer, and main raw material used and charging capacity see table:
Described method is specifically implemented as follows:
To with stirrer, thermometer, in 1 liter of four-hole boiling flask of reflux condensing tube and nitrogen ingress pipe, add deionized water 200g, under whipped state, slowly add PVA0599 30.0g, be warming up to 95 ℃ and be incubated 30 minutes, after PVA dissolves completely, logical nitrogen 30 minutes, be cooled to 75 ℃, add 5% ceric ammonium nitrate aqueous solution 2.0g, react 30 minutes, then drip monomer mixed solution, monomer mixed solution is by acrylamide 98g, dimethylaminoethyl methacrylate 3.2g, N, N-dimethylamino propyl acrylamide 2.1g, MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride (effective constituent 78%) 5.5g, methylene-succinic acid 2g, fumaric acid 0.5g, Hydroxyethyl acrylate 3.3g, vinylbenzene 6g, methallylsulfonic acid sodium 0.25g, Virahol 3g, EDTA-2Na0.1g, deionized water 360g, and adjust pH value to 2.5 compositions with 50% sulfuric acid, within 60 minutes, drip off, after dripping off, between 88 ℃-92 ℃, react 25 minutes, add 5% ceric ammonium nitrate aqueous solution 3g, between 87 ℃-90 ℃, react 20 minutes, add 5% ceric ammonium nitrate aqueous solution 3g, continue reaction 20 minutes, viscosity rises gradually, reach after expection viscosity, add 5% aqueous solution of sodium bisulfite 24g termination reaction, obtaining solid content is 20.7%, at 25 ℃, viscosity is 6750mPa.s, pH value is 3.8 the graft copolymer aqueous solution.
Embodiment 3
This example provides a kind of preparation method of high branched chain type polyvinyl alcohol-acrylamide grafted copolymer, and main raw material used and charging capacity see table:
Described method is specifically implemented as follows:
To with stirrer, thermometer, in 1 liter of four-hole boiling flask of reflux condensing tube and nitrogen ingress pipe, add deionized water 150g, under whipped state, slowly add PVA1788 15.0g, be warming up to 90 ℃ and be incubated 30 minutes, after PVA dissolves completely, logical nitrogen 30 minutes, be cooled to 68 ℃, add 5% ammonium persulfate aqueous solution 4g, react 15 minutes, then drip monomer mixed solution, monomer mixed solution is by acrylamide 113g, N, N-dimethylamino propyl acrylamide 5.1g, acrylyl oxy-ethyl-trimethyl salmiac (effective constituent 78%) 5.0g, methylacryloxyethyldimethyl benzyl ammonium chloride (effective constituent 60%) 2.8g, methacrylic acid 1.5g, fumaric acid 2.0g, glycidyl methacrylate 1.1g, vinyl cyanide 8g, methallylsulfonic acid sodium 0.3g, sodium hypophosphite 0.1g, diethylenetriamine pentacarboxylic acid (DTPA) 0.05g, deionized water 400g, and adjust pH value to 2.8 compositions with 50% sulfuric acid, within 60 minutes, drip off, after dripping off, between 89 ℃-93 ℃, react 20 minutes, add 5% ammonium persulfate aqueous solution 4g, between 87 ℃-90 ℃, react 20 minutes, add 5% azo-bis-isobutyrate hydrochloride aqueous solution 1g, continue reaction 20 minutes, viscosity rises gradually, reach after expection viscosity, add 5% potassium sulfite aqueous solution 24g termination reaction, obtaining solid content is 21.3%, at 25 ℃, viscosity is 9200mPa.s, pH value is 4.1 the graft copolymer aqueous solution.
Embodiment 4
This example provides a kind of preparation method of high branched chain type polyvinyl alcohol-acrylamide grafted copolymer, and main raw material used and charging capacity see table:
Described method is specifically implemented as follows:
To with stirrer, thermometer, in 1 liter of four-hole boiling flask of reflux condensing tube and nitrogen ingress pipe, add deionized water 150g, under whipped state, slowly add PVA2088 15.0g, be warming up to 95 ℃ and be incubated 30 minutes, after PVA dissolves completely, logical nitrogen 30 minutes, be cooled to 68 ℃, add 5% persulfate aqueous solution 2g, react 20 minutes, then drip monomer mixed solution, monomer mixed solution is by acrylamide 113g, dimethylaminoethyl methacrylate 4.2g, MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride (effective constituent 78%) 4.0g, methylacryloxyethyldimethyl benzyl ammonium chloride (effective constituent 60%) 4.8g, methylene-succinic acid 1.6g, 2-acrylamide-2-methylpro panesulfonic acid 2.0g, hydroxyethyl methylacrylate 1.1g, n-methylolacrylamide 1.8g, mercaptoethanol 0.5g, sodium hypophosphite 0.15g, ethylenediamine tetraacetic methene phosphoric acid (EDTMPA) 0.1g, deionized water 400g, and adjust pH value to 2.6 compositions with 50% sulfuric acid, within 60 minutes, drip off, after dripping off, between 85 ℃-92 ℃, react 20 minutes, add 5% persulfate aqueous solution 2g, between 87 ℃-90 ℃, react 20 minutes, add 5% persulfate aqueous solution 4g, continue reaction 20 minutes, viscosity rises gradually, reach after expection viscosity, add 5% sodium sulfite aqueous solution 16g termination reaction, obtaining solid content is 20.9%, at 25 ℃, viscosity is 8200mPa.s, pH value is 3.9 the graft copolymer aqueous solution.
Embodiment 5
This example provides a kind of preparation method of high branched chain type polyvinyl alcohol-acrylamide grafted copolymer, and main raw material used and charging capacity see table:
Described method is specifically implemented as follows:
To with stirrer, thermometer, in 1 liter of four-hole boiling flask of reflux condensing tube and nitrogen ingress pipe, add deionized water 200g, under whipped state, slowly add PVA2499 5.0g, PVA1099 10.0g, be warming up to 95 ℃ and be incubated 60 minutes, after PVA dissolves completely, logical nitrogen 30 minutes, be cooled to 75 ℃, add 5% ammonium persulfate aqueous solution 2.5g, react 20 minutes, then drip monomer mixed solution, monomer mixed solution is by acrylamide 80.5g, dimethylaminoethyl methacrylate 6.0g, MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride (effective constituent 78%) 9.5g, methylene-succinic acid 1.6g, sodium vinyl sulfonate 2.8g, methallylsulfonic acid sodium 0.25g, EDTA-4Na0.1g, deionized water 430g, and adjust pH value to 2.5 compositions with 50% sulfuric acid, within 60 minutes, drip off, after dripping off, between 88 ℃-95 ℃, react 20 minutes, add 5% ammonium persulfate aqueous solution 1.5g, between 87 ℃-90 ℃, react 20 minutes, add 5% ammonium persulfate aqueous solution 1.5g, continue reaction 20 minutes, viscosity rises gradually, reach after expection viscosity, add 5% sodium thiosulfate solution 15g termination reaction, obtaining solid content is 15.5%, at 25 ℃, viscosity is 7700mPa.s, pH value is 3.7 the graft copolymer aqueous solution.
Embodiment 6
This example provides a kind of preparation method of high branched chain type polyvinyl alcohol-acrylamide grafted copolymer, and main raw material used and charging capacity see table:
Described method is specifically implemented as follows:
To with stirrer, thermometer, in 1 liter of four-hole boiling flask of reflux condensing tube and nitrogen ingress pipe, add deionized water 200g, under whipped state, slowly add PVA2688 10.0g, be warming up to 95 ℃ and be incubated 60 minutes, after PVA dissolves completely, logical nitrogen 30 minutes, be cooled to 60 ℃, add 5% aqueous solution of sodium bisulfite 1.0g, 5% ammonium persulfate aqueous solution 2.0g, react 20 minutes, then drip monomer mixed solution, monomer mixed solution is by acrylamide 85.0g, dimethylaminoethyl methacrylate 4.5g, MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride (effective constituent 78%) 5.5g, methylacryloxyethyldimethyl benzyl ammonium chloride (effective constituent 60%) 4.8g, methylene-succinic acid 3.5g, sodium allyl sulfonate 0.1g, methallylsulfonic acid sodium 0.3g, diethylene triamine pentamethylene phosphonic salt (DETPMPS) 0.1g, deionized water 440g, and adjust pH value to 2.7 compositions with 50% sulfuric acid, within 60 minutes, drip off, after dripping off, between 88 ℃-93 ℃, react 20 minutes, add 5% ammonium persulfate aqueous solution 2.0g, between 87 ℃-90 ℃, react 20 minutes, add 5% ammonium persulfate aqueous solution 2.0g, continue reaction 15 minutes, viscosity rises gradually, reach after expection viscosity, add 5% aqueous solution of sodium bisulfite 15g termination reaction, obtaining solid content is 15.1%, at 25 ℃, viscosity is 8300mPa.s, pH value is 4.0 the graft copolymer aqueous solution.
Comparative example 1
To with stirrer, thermometer, in 1 liter of four-hole boiling flask of reflux condensing tube and nitrogen ingress pipe, add deionized water 200g, under whipped state, slowly add PVA1799 15.0g, be warming up to 95 ℃ and be incubated 30 minutes, after PVA dissolves completely, logical nitrogen 30 minutes, be cooled to 70 ℃, the ammonium persulfate aqueous solution 4g that adds a catalyzer 5%, react 20 minutes, then drip monomer mixed solution, monomer mixed solution is by acrylamide 115g, dimethylaminoethyl methacrylate 4.2g, MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride (effective constituent 78%) 5.5g, methylacryloxyethyldimethyl benzyl ammonium chloride (effective constituent 60%) 1.5g, vinylformic acid 2g, methylene-succinic acid 3g, methylene-bisacrylamide 0.05g, methallylsulfonic acid sodium 0.40g, sodium hypophosphite 0.12g, EDTA0.08g, deionized water 360g, and adjust pH value to 2.8 compositions with 50% sulfuric acid, within 60 minutes, drip off, after dripping off, between 88 ℃-92 ℃, react 20 minutes, the ammonium persulfate aqueous solution 4g that adds quadric catalysis agent 5%, between 87 ℃-90 ℃, react 20 minutes, the ammonium persulfate aqueous solution 4g that adds three catalyzer 5%, continue reaction 10 minutes, viscosity rises gradually, reach after expection viscosity, add 5% sodium sulfite aqueous solution 20g termination reaction, obtaining solid content is 20.6%, at 25 ℃, viscosity is 18500mPa.s, pH value is 4.3 the graft copolymer aqueous solution.
Comparative example 2
To adding one time monomer in 1 liter of four-hole boiling flask with stirrer, thermometer, reflux condensing tube and nitrogen ingress pipe: deionized water 500g, acrylamide 90.5g, dimethylaminoethyl methacrylate 3.2g, MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride (effective constituent 78%) 2.5g, methylacryloxyethyldimethyl benzyl ammonium chloride (effective constituent 60%) 2.5g, vinylformic acid 2.0g, N, N-DMAA 0.25g, methallylsulfonic acid sodium 0.50g, EDTA0.08g, 50% sulfuric acid is adjusted pH value to 2.8.Logical nitrogen, is warmed up to 70 ℃, adds the ammonium persulfate aqueous solution 2.0g of a catalyzer 5%, reacts 20 minutes.Then drip secondary monomer mixed solution, secondary monomer mixed solution is by acrylamide 10g, dimethylaminoethyl methacrylate 1.5g, MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride (effective constituent 78%) 2.5g, methylene-succinic acid 2.0g, methylene-bisacrylamide 0.05g, methallylsulfonic acid sodium 0.20g, deionized water 170g, and adjust pH value to 2.8 compositions with 50% sulfuric acid.Within 30 minutes, drip off, after dripping off, between 90 ℃-95 ℃, react 20 minutes, add the ammonium persulfate aqueous solution 2g of quadric catalysis agent 5%, between 87 ℃-90 ℃, react 20 minutes, the ammonium persulfate aqueous solution 2g that adds three catalyzer 5%, continue reaction 30 minutes, viscosity rises gradually, reaches after expection viscosity, add 5% sodium sulfite aqueous solution 20g termination reaction, obtaining solid content is that at 15.3%, 25 ℃, viscosity is 9300mPa.s, the amphiprotic polyacrylamide aqueous solution that pH value is 3.6.
Application examples
Adopt reclaimed waste paper case to discongest, pull an oar as raw material, beating degree reaches after 37 ° of SR, add 1.0% Tai-Ace S 150 and adjust pH value in 6 left and right, add 1.5 ‰-7.5 ‰ Dry Strength Resin (over dry/oven dry stock) to stir 5 minutes, with the machine-processed handsheet that obtains quantitative 110g/m2 of handsheet, adopt the squeezing of standard page squeezing machine, after rotary dryer is dried, under standard atmosphere condition, balance is 24 hours, measures its ring crush intensity, bursting strength and folding endurance.Experimental result is listed in table 1:
Table 1. adds the handsheet intensity index (dry/oven dry stock) of Dry Strength Resin
From above-described embodiment, comparative example and application examples, it is good that the present invention adopts the synthetic side chain Dry Strength Resin of the method for polyvinyl alcohol-acrylamide graft polymerization to have the easily control of good polymerization stability, viscosity, good water solubility, application performance, and reinforced effects is obviously better than adding Dry Strength Resin prepared by linking agent.
Above the present invention is described in detail; its object is to allow the personage who is familiar with this art can understand content of the present invention and be implemented; can not limit the scope of the invention with this; the equivalence that all spirit according to the present invention are done changes or modifies, and all should be encompassed in protection scope of the present invention.
Claims (10)
1. the preparation method of a high branched chain type polyvinyl alcohol-acrylamide grafted copolymer, it is characterized in that, described preparation method is implemented as follows: the ratio that is 10-20:100 in mass ratio by polyethylene alcohol and water is mixed, being heated to 75 ℃-95 ℃ insulations dissolves, after polyvinyl alcohol dissolves completely, logical nitrogen is more than 30 minutes, and be cooled to 60 ℃～80 ℃, add catalyzer, reaction 10-30 minute, make the activation of polyvinyl alcohol molecule chain produce free radical, then drip monomer mixture solution, control monomer mixture solution time for adding between 30～90 minutes, temperature of reaction is controlled between 65 ℃-95 ℃ during this time, after monomer mixture solution drips, control temperature reacts after 20～30 minutes between 85 ℃-95 ℃, add catalyzer, continuation is reacted after 15～25 minutes at 80 ℃-95 ℃, add again catalyzer, in reaction process, sample viscosimetric, at 25 ℃, viscosity reaches after 1500～15000mPa.s, add terminator, stopped reaction, and add water adjustment product solid content to 10wt%～30wt%, obtain described high branched chain type polyvinyl alcohol-acrylamide grafted copolymer, wherein:
Described monomer mixture solution be take water as solvent, and mass concentration is between 20%～40%, and pH is between 2～5, wherein contain the first monomer, the second monomer, the 3rd monomer, molecular weight regulator, sequestrant, pH adjusting agent and selectable, the 4th monomer, wherein:
Described the first monomer is acrylamide, Methacrylamide or the combination of the two;
Described the second monomer is for being selected from dimethyl diallyl ammonium chloride, (methyl) vinylformic acid dimethylin ethyl ester, (methyl) vinylformic acid diethylin ethyl ester, the combination of one or more in dimethylamino-propyl (methyl) acrylamide and their methyl chloride, benzyl chloride quaternary ammonium salt;
Described the 3rd monomer is for being selected from (methyl) vinylformic acid, methylene-succinic acid, fumaric acid (acid anhydride), toxilic acid (acid anhydride), sodium vinyl sulfonate, vinylbenzenesulfonic acid sodium, 2-acrylamido-2 methyl propane sulfonic acid, the combination of one or more in styrene sulfonic acid and their salt;
Described the 4th monomer is for being selected from one or more the combination in n-methylolacrylamide, glycidyl methacrylate, (methyl) Hydroxyethyl acrylate, (methyl) Propylene glycol monoacrylate, (methyl) vinyl cyanide, (methyl) vinylbenzene and (methyl) alkyl acrylate;
The mass ratio that feeds intake of described polyvinyl alcohol, the first monomer, the second monomer, the 3rd monomer, the 4th monomer is: 5～30:30～90:0.2～20:0.2～20:0～20,
In aforesaid method, total catalyst consumption is 0.02%～1.5% of described high branched chain type polyvinyl alcohol-acrylamide grafted copolymer weight, the amount of the catalyzer wherein adding for the first time accounts for 5%～60% of total catalyst consumption, the amount of the catalyzer adding for the second time accounts for 10%～60% of total catalyst consumption, and the amount of the catalyzer adding for the third time accounts for 10%～60% of total catalyst consumption.
2. the preparation method of high branched chain type polyvinyl alcohol-acrylamide grafted copolymer according to claim 1, it is characterized in that, described catalyzer is persulphate, ceric ammonium nitrate, ceric ammonium nitrate/tetramethylolmethane, superoxide, water-soluble azo class, persulphate/sulfurous acid (hydrogen) salt, persulphate/thiosulphate, the combination of one or more in potassium permanganate.
3. the preparation method of high branched chain type polyvinyl alcohol-acrylamide grafted copolymer according to claim 2, it is characterized in that, described catalyzer is for being selected from ammonium persulphate, Potassium Persulphate, ceric ammonium nitrate, hydrogen peroxide, azo-bis-isobutyrate hydrochloride, azo di-isopropyl imidazoline salt hydrochlorate, the combination of one or more in ammonium persulphate/sodium bisulfite.
4. the preparation method of high branched chain type polyvinyl alcohol-acrylamide grafted copolymer according to claim 1, it is characterized in that, described molecular weight regulator is selected from mercapto compounds, lauryl mercaptan, Virahol, sodium hypophosphite, sodium formiate, thanomin, vinyl carbinol, sodium allyl sulfonate, methallylsulfonic acid sodium, 2, the combination of one or more of 4-phenylbenzene-4-methyl-1-pentene etc.
5. according to the preparation method of the high branched chain type polyvinyl alcohol-acrylamide grafted copolymer described in claim 1 or 4, it is characterized in that, the charging capacity of described molecular weight regulator is 0.01%～3.5% of described high branched chain type polyvinyl alcohol-acrylamide grafted copolymer weight.
6. the preparation method of high branched chain type polyvinyl alcohol-acrylamide grafted copolymer according to claim 1, it is characterized in that, described sequestrant is for being selected from nitrilotriacetic acid(NTA), nitrilotriacetic acid(NTA) salt, EDTA, EDTA-2Na, EDTA-4Na, diethylenetriamine pentacarboxylic acid, diethylenetriamine pentacarboxylic acid salt, ethylene diamine tetra methylene phosphonic acid, ethylene diamine tetra methylene phosphonic acid sodium, diethylene triamine pentamethylene phosphonic, diethylene triamine pentamethylene phosphonic salt, amine three methylenephosphonic acids, amine three methene phosphonates, phytinic acid, tartrate, heptose hydrochlorate, Sunmorl N 60S, the combination of one or more in sodium alginate.
7. according to the preparation method of the high branched chain type polyvinyl alcohol-acrylamide grafted copolymer described in claim 1 or 6, it is characterized in that, the charging capacity of described sequestrant is 0.01%～0.5% of described high branched chain type polyvinyl alcohol-acrylamide grafted copolymer weight.
8. the preparation method of high branched chain type polyvinyl alcohol-acrylamide grafted copolymer according to claim 1, is characterized in that, described polyvinyl alcohol is one or more the combination being selected from the following polyvinyl alcohol trade mark: 0388,0399,0588,0599,1088,1099,1750,1788,1799,2088,2099,2488,2497,2499,2688 and 2699.
9. high branched chain type polyvinyl alcohol-acrylamide grafted copolymer, is characterized in that: the preparation method by the high branched chain type polyvinyl alcohol-acrylamide grafted copolymer described in any one claim in claim 1 to 8 makes.
10. high branched chain type polyvinyl alcohol-acrylamide grafted copolymer claimed in claim 9 is as papermaking dry-strengthening agent purposes.
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