CN112194743B - Preparation method and application of modified polyacrylamide based on Hofmann degradation reaction - Google Patents
Preparation method and application of modified polyacrylamide based on Hofmann degradation reaction Download PDFInfo
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- CN112194743B CN112194743B CN202011072176.XA CN202011072176A CN112194743B CN 112194743 B CN112194743 B CN 112194743B CN 202011072176 A CN202011072176 A CN 202011072176A CN 112194743 B CN112194743 B CN 112194743B
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- 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
- C08F8/00—Chemical modification by after-treatment
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- 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
- C08F4/00—Polymerisation catalysts
- C08F4/40—Redox systems
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- 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
- D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/41—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups
- D21H17/44—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups cationic
- D21H17/45—Nitrogen-containing groups
- D21H17/455—Nitrogen-containing groups comprising tertiary amine or being at least partially quaternised
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- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
Abstract
The invention discloses a preparation method and application of modified polyacrylamide based on Hofmann degradation reaction, wherein the preparation method comprises the following steps: carrying out Hoffman degradation reaction on the copolymer solution under the temperature gradient change condition that the temperature is increased from 0 ℃ to 25 ℃; the method specifically comprises the following steps: s1: synthesis of the terpolymer: s2: a hofmann degradation reaction occurs: a. cooling a certain volume of copolymer solution to 25 ℃ room temperature, carrying out ice-water bath to 0 ℃, adding NaOH solution and NaClO solution, and controlling-CONH in a reaction system 2 OH-, clO-in a molar ratio of 1: (0.6-2.4): (0.25-0.95), sealing and shaking, continuing ice-water bath for 20min, naturally recovering to 25 ℃, and carrying out Hofmann degradation reaction in the temperature rising process; b. and (5) drying. The ternary polymerization product after Hofmann degradation is prepared by a two-step method for the first time and is used as a papermaking dry strength agent, so that the tear strength, bursting strength, scratch resistance and wear resistance of paper are obviously improved, and the dirt resistance and water resistance of the paper are improved.
Description
Technical Field
The invention belongs to the technical field of high molecular polymer synthesis, and particularly relates to a preparation method and application of modified polyacrylamide based on Hofmann degradation reaction.
Background
The hofmann degradation reaction or hofmann rearrangement reaction is an organic reaction in which the first-order amide is rearranged into a primary amine and one carbon atom is reduced. The preparation of polyvinylamine by vinylamine polymerization is not possible due to the instability of vinylamine with respect to its isomer glyoxylimine and its condensates, whereas the preparation of polyvinylamine by hofmann reaction of polyacrylamide is an important process. The polyvinylamine contains strong polar basic group-NH in molecular chain 2 And the copolymer is easy to react with other functional groups, so that the copolymer has wide application prospect as a reactive polymer.
Since The 40's OF The 20 th century, after Jones et al first performed Hofmann reactions on polyacrylamides, such reactions were studied extensively [ JONES G D, ZOMLEFER J, HAWKINS K. ATTEMPTED PREPARATION OF POLYVINYLAMINE (1) [ J ]. The Journal OF Organic Chemistry,1944,9 (6): 500-512 ]. Jones and Arcus et al first tried to convert polyacrylamide and polymethacrylamide into their vinylamine derivatives by Hofmann reaction. However, since the Hofmann reaction is carried out at a temperature of a steam bath, a large number of side reactions occur, and the final product contains only a small amount of amine groups [ STEGALL T A. Analysis, chromatography, and Optimization of Polyvinylamide Conversion to the Hofmann reaction [ J ].2013]. Subsequently, schiller et al performed a Hofmann reaction on polyacrylamide at room temperature, and the degree of amination reached 61%, which is still not very desirable [ SCHILLER A, SUEN T. Ionic derivatives of polyacrylamides [ J ]. Industrial & Engineering Chemistry,1956,48 (12): 2132-2137].
At present, the precursors of Hofmann degradation mainly comprise polyacrylamide and derivatives thereof, and Hofmann degradation methods for polyacrylamide or acrylamide-dimethyl diallyl ammonium chloride-vinyl triacetoxysilane terpolymers modified by a cationic monomer dimethyl diallyl ammonium chloride and an organosilicon monomer vinyl triacetoxysilane are not disclosed by the existing documents or patent reports, and are blank in the technical field of polyacrylamide synthesis at home. Compared with the copolymer of acrylamide monomer and water-soluble cationic monomer, the organosilicon monomer has low surface energy, hydrophobicity and weather resistance, so that the instability of a polymerization reaction system and polymer precipitation are easily caused, and the terpolymer of the organosilicon monomer, acrylamide and dimethyl diallyl ammonium chloride exists in a solid solution state and does not present a uniform liquid state; in addition, due to the introduction of a large amount of organic silicon monomers (Si-O bonds and Si-C bonds) and cationic monomers (N-C bonds) in the molecular chain of the modified polyacrylamide, hofmann degradation reaction is difficult to occur, and the amination degree is low.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a preparation method and application of modified polyacrylamide based on Hofmann degradation reaction.
The technical scheme of the invention is summarized as follows:
a preparation method of modified polyacrylamide based on Hofmann degradation reaction comprises the following steps: carrying out Hoffman degradation reaction on the copolymer solution under the temperature gradient change condition that the temperature is increased from 0 ℃ to 25 ℃; the method specifically comprises the following steps:
s1: synthesis of the terpolymer:
a. according to the formula (1-2): (0.5-1): (0.3-0.8): (0.04-0.1) mixing an acrylamide monomer, a dimethyl diallyl ammonium chloride monomer, a vinyl triacetoxy silane monomer and sodium dodecyl benzene sulfonate according to the mass ratio, adding a certain amount of deionized water, and performing ultrasonic dispersion for 0.5-1 h to prepare a mixed solution with the total solute content of 30%;
b. (NH) was added to the resulting mixed solution 4 ) 2 S 2 O 8 And Na 2 SO 3 The initiator accounts for 0.1 to 0.3 percent of the mass of the mixed solution, and the mixture is stirred and mixed evenly to obtain reactant solution;
c. introducing nitrogen into the reactant solution for 0.5-1 h, and reacting for 4-6 h under the water bath condition of 40 ℃ to obtain a copolymer solution;
s2: a hofmann degradation reaction occurs:
a. cooling a certain volume of copolymer solution to 25 ℃ room temperature, carrying out ice-water bath to 0 ℃, adding NaOH solution and NaClO solution, and controlling-CONH in a reaction system 2 、OH - 、ClO - In a molar ratio of 1: (0.6-2.4): (0.25-0.95), sealing and shaking, continuing ice-water bath for 20min, naturally recovering to 25 ℃, and in the process of heating, performing Hofmann degradation reaction to gradually change the solution from colorless and transparent to brown yellow;
b. and dropwise adding the reacted solution onto a silicon wafer, and drying for 2-3 h at 60 ℃ to obtain the silicon wafer.
Preferably, the (NH) 4 ) 2 S 2 O 8 And NaSO 3 The mixing mass ratio of (1.5-3): 1.
preferably, the concentration of the NaOH solution is 4 to 6M.
Preferably, the concentration of the NaClO solution is 1.5-2M.
Preferably, the volume ratio of the copolymer solution to the NaOH solution to the NaClO solution is 2:1:1.
the invention also provides application of the modified polyacrylamide based on the Hofmann degradation reaction in a papermaking dry strength agent.
The invention has the beneficial effects that:
1. according to the invention, a ternary copolymer product of acrylamide-dimethyl diallyl ammonium chloride monomer-vinyl triacetoxysilane monomer after Hofmann degradation is prepared by a two-step method for the first time, firstly, an acrylamide monomer, a dimethyl diallyl ammonium chloride monomer and a vinyl triacetoxysilane monomer are used according to a certain proportion under a redox initiator system, an emulsion polymerization method is adopted to prepare a ternary copolymer precursor existing in a uniform liquid form, then NaClO is added into a precursor solution under a strong alkaline condition, hofmann degradation is carried out under a specific temperature rise gradient condition of 0-25 ℃, a degradation product with high amination degree is obtained, meanwhile, in the research process, the Hofmann degradation reaction of the ternary copolymer can be carried out only under the temperature rise process condition of 0-25 ℃, no matter the temperature rise can not be carried out in any one of the temperature ranges of 0 ℃,25 ℃ or 0-25 ℃, therefore, the gradient temperature change is a key factor for realizing the Hofmann degradation of the ternary copolymer.
2. The ternary polymerization product after Hofmann degradation is used for the papermaking dry strength agent, and due to the introduction of the organic silicon monomer, the papermaking dry strength agent has the effect of covalently crosslinking inorganic filler and lignocellulose in paper, so that the bonding strength between inorganic particles and cellulose molecules is higher, and the tear strength and the bursting strength of the paper are further obviously improved; meanwhile, the introduction of the organic silicon monomer endows the papermaking dry strength agent with low surface performance and hydrophobicity, so that the surface of paper is smoother and smoother, the scratch resistance and the wear resistance of the paper are improved, and the stain resistance and the water resistance of the paper are improved.
Drawings
FIG. 1 is a flow chart of a preparation method of modified polyacrylamide based on Hofmann degradation reaction according to the invention;
FIG. 2 is a schematic view of the apparatus for synthesizing the terpolymer according to examples 1 to 2;
FIG. 3 is a schematic view of a Hofmann degradation reaction generating apparatus for the terpolymers of examples 1-2 and comparative examples 1-3;
FIG. 4 is an infrared spectrum of a Huffman degradation product prepared in examples 1 to 2 and a product prepared in comparative example 1;
FIG. 5 is a scanning electron microscope image of the Hoffman degradation product prepared in examples 1-2;
wherein H-PAD-1 and H-PAD-2 represent the Hofmann degradation products prepared in examples 1 and 2, respectively, and PAD represents the product prepared in comparative example 1.
Detailed Description
The present invention is further described in detail below with reference to examples so that those skilled in the art can practice the invention with reference to the description.
Example 1
Mixing 20g of acrylamide, 5g of dimethyl diallyl ammonium chloride, 4.5g of vinyl triacetoxy silane and 0.5g of sodium dodecyl benzene sulfonate, adding 70g of deionized water, ultrasonically dispersing for 0.5h, continuously adding 0.10g of ammonium persulfate and 0.05g of sodium sulfite into the obtained solution, sealing a three-neck flask, fully stirring, and reacting for 4h under the condition of water bath at 40 ℃ to obtain a terpolymer solution for later use;
and (II) measuring 10mL of terpolymer solution, placing the terpolymer solution in another three-neck flask, cooling to the room temperature of 25 ℃, carrying out ice-water bath to 0 ℃, adding 5mL of 4M NaOH solution and 5mL of 1.5M NaClO solution, sealing, shaking, continuing the ice-water bath for 20min, taking the three-neck flask out of the ice-water bath device, naturally recovering the reaction system to 25 ℃, gradually changing the solution from colorless transparency to brown during the temperature rise process, dropwise adding the reacted solution onto a silicon wafer, drying for 3H at the temperature of 60 ℃, and obtaining a Hofmann degraded product, wherein the sample is marked as an H-PAD-1 sample, carrying out infrared spectroscopic analysis, and carrying out scanning electron microscope shooting.
Example 2
Mixing 15g of acrylamide, 8.5g of dimethyldiallylammonium chloride, 6g of vinyltriacetoxysilane and 0.5g of sodium dodecyl benzene sulfonate, adding 70g of deionized water, ultrasonically dispersing for 0.5h, continuously adding 0.05g of ammonium persulfate and 0.025 g of sodium sulfite into the obtained solution, sealing a three-neck flask, fully stirring, and reacting for 4h under the condition of water bath at 40 ℃ to obtain a terpolymer solution for later use;
and (II) measuring 10mL of terpolymer solution, placing the terpolymer solution in another three-neck flask, cooling to the room temperature of 25 ℃, carrying out ice-water bath to 0 ℃, adding 5mL of 4M NaOH solution and 5mL of 1.5M NaClO solution, sealing, shaking, continuing the ice-water bath for 20min, taking the three-neck flask out of the ice-water bath device, naturally recovering the reaction system to 25 ℃, gradually changing the solution from colorless transparency to brown during the temperature rise process, dropwise adding the reacted solution onto a silicon wafer, drying for 3H at the temperature of 60 ℃, and obtaining a Hofmann degraded product, marking the product as an H-PAD-2 sample, carrying out infrared spectroscopic analysis, and carrying out scanning electron microscope shooting.
Comparative example 1
The step (one) is the same as the example 1;
and (II) measuring 10mL of terpolymer solution, placing the terpolymer solution in another three-neck flask, cooling to the room temperature of 25 ℃, adding 5mL of 4M NaOH solution and 5mL of 1.5M NaClO solution, sealing, fully oscillating for 20min, standing for 72h at the temperature of 25 ℃, observing that the solution is still colorless and transparent and has no color change, dropwise adding the solution onto a silicon chip, drying for 3h at the temperature of 60 ℃, and obtaining a product in the comparative example 1, wherein the product is marked as a PAD sample, and infrared spectrum analysis is carried out.
Comparative example 2
The step (one) is the same as the example 1;
and (II) measuring 10mL of terpolymer solution, placing the terpolymer solution in another three-neck flask, cooling to the room temperature of 25 ℃, carrying out ice-water bath to 0 ℃, adding 5mL of 4M NaOH solution and 5mL of 1.5M NaClO solution, sealing, fully shaking for 20min, and observing that the solution is colorless and transparent without any color change.
Comparative example 3
The step (one) is the same as the example 1;
and (II) measuring 10mL of terpolymer solution, placing the terpolymer solution in another three-neck flask, cooling to the room temperature of 25 ℃, then adding 5mL of 4M NaOH solution and 5mL of 1.5M NaClO solution, sealing, fully shaking for 2 min, standing at 15 ℃ for 72h, and observing that the solution is colorless and transparent without any color change.
FIG. 4 is an infrared spectrum of the Hofmann degradation product prepared in examples 1 to 2 and the product prepared in comparative example 1: as shown in FIG. 4 and the test phenomena of examples 1 to 2 and comparative examples 1 to 3, the amide groups in the polymer products prepared in examples 1 to 2 were converted into primary amines, while the amide groups in the polymer product in comparative example 1 were not rearranged, and it was found that the Hofmann degradation reaction did not occur in the terpolymers in examples 1 to 2 and comparative examples 1 to 3 at a constant temperature of 25 ℃, 0 ℃ and 15 ℃. Therefore, the Hofmann degradation reaction of the terpolymer can only be carried out under the condition of a temperature rise process of 0-25 ℃, and the reaction can not be carried out at any temperature of 0 ℃,25 ℃ or 0-25 ℃, so that the gradient temperature change is a key factor for realizing the Hofmann degradation of the terpolymer.
Comparative example 4 Hofmann degradation product of acrylamide-dimethyldiallylammonium chloride bipolymer
Mixing 20g of acrylamide and 10g of dimethyldiallylammonium chloride, adding 70g of deionized water, ultrasonically dispersing for 0.5h, continuously adding 0.10g of ammonium persulfate and 0.05g of sodium sulfite into the obtained solution, sealing a three-neck flask, fully stirring, and reacting for 4h under the condition of water bath at 40 ℃ to obtain a terpolymer solution for later use;
the procedure in step (II) is the same as in example 1.
Comparative example 5 commercially available Polyacrylamide product
The products of examples 1-2 and comparative examples 4-5 are applied to a papermaking dry strength agent, added to paper pulp with a beating degree of 35 DEG SR, added in an amount of 0.5% (5 kg/t paper pulp), and uniformly stirred, and then the weight of the paper sheet is controlled to be 60g/m 2 After drying, the paper produced was tested according to GB/T24323-2009 "determination of physical properties of paper sheets in pulp laboratories", the test results are shown in the following table:
| example 1 | Example 2 | Comparison ofExample 4 | Comparative example 5 | |
| Burst index/kPa m 2 /g | 3.95 | 4.52 | 2.74 | 2.41 |
| Tear index/mN. M 2 /g | 4.91 | 5.84 | 3.36 | 3.08 |
| Folding strength/time | 76 | 92 | 40 | 32 |
As can be seen from the table above, the ternary polymerization product after Hofmann degradation is used as the papermaking dry strength agent, and due to the introduction of the organic silicon monomer, the papermaking dry strength agent has the function of covalently crosslinking the inorganic filler and the lignocellulose in the paper, so that the bonding strength between inorganic particles and cellulose molecules is higher, and the tear strength and the bursting strength of the paper are further remarkably improved. In addition, the introduction of the organic silicon monomer body endows the papermaking dry strength agent with low surface energy and hydrophobicity, so that the surface of paper is smoother and smoother, the scratch resistance and the wear resistance are improved, and the dirt resistance and the water resistance of the paper are improved.
While embodiments of the invention have been disclosed above, it is not limited to the applications listed in the description and the embodiments, which are fully applicable in all kinds of fields of application of the invention, and further modifications may readily be effected by those skilled in the art, so that the invention is not limited to the specific details without departing from the general concept defined by the claims and the scope of equivalents.
Claims (6)
1. A preparation method of modified polyacrylamide based on Hofmann degradation reaction is characterized by comprising the following steps: carrying out Hoffman degradation reaction on the copolymer solution under the temperature gradient change condition that the temperature is increased from 0 ℃ to 25 ℃; the method specifically comprises the following steps:
s1: synthesis of the terpolymer:
a. according to the formula (1-2): (0.5-1): (0.3-0.8): (0.04-0.1) mixing an acrylamide monomer, a dimethyl diallyl ammonium chloride monomer, a vinyl triacetoxy silane monomer and sodium dodecyl benzene sulfonate according to the mass ratio, adding a certain amount of deionized water, and performing ultrasonic dispersion for 0.5-1 h to prepare a mixed solution with the total solute content of 30%;
b. (NH) was added to the resulting mixed solution 4 ) 2 S 2 O 8 And Na 2 SO 3 The initiator accounts for 0.1-0.3% of the mixed solution by mass, and is stirred and mixed uniformly to obtain a reactant solution;
c. introducing nitrogen into the reactant solution for 0.5-1 h, and reacting for 4-6 h under the water bath condition of 40 ℃ to obtain a copolymer solution;
s2: a hofmann degradation reaction occurs:
a. cooling a certain volume of copolymer solution to 25 ℃ room temperature, carrying out ice-water bath to 0 ℃, adding NaOH solution and NaClO solution, and controlling-CONH in a reaction system 2 、OH - 、ClO - In a molar ratio of 1: (0.6-2.4): (0.25-0.95), sealing and shaking, continuing ice-water bath for 20min, naturally recovering to 25 ℃, and carrying out Hofmann degradation reaction in the temperature rising process to gradually change the solution from colorless and transparent to brown yellow;
b. and dropwise adding the reacted solution onto a silicon wafer, and drying at 60 ℃ for 2-3 h to obtain the silicon wafer.
2. Hoffmann degradation reaction based on the method according to claim 1The preparation method of the modified polyacrylamide is characterized in that (NH) 4 ) 2 S 2 O 8 And NaSO 3 The mixing mass ratio of (1.5-3): 1.
3. the preparation method of modified polyacrylamide based on Hofmann degradation reaction according to claim 1, wherein the concentration of the NaOH solution is 4-6M.
4. The preparation method of the modified polyacrylamide based on the Hofmann degradation reaction according to claim 1, wherein the concentration of the NaClO solution is 1.5-2M.
5. The preparation method of the modified polyacrylamide based on the Hofmann degradation reaction according to claim 1, wherein the volume ratio of the copolymer solution to the NaOH solution to the NaClO solution is 2:1:1.
6. the application of the modified polyacrylamide based on the Hofmann degradation reaction prepared by the preparation method of any one of claims 1-5 in a papermaking dry strength agent.
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| CN102216340A (en) * | 2008-11-27 | 2011-10-12 | S.P.C.M.股份公司 | Novel method for preparing acrylamide copolymers by hofmann degradation reaction |
| CN104395525A (en) * | 2012-07-09 | 2015-03-04 | S.P.C.M.公司 | Improved method for manufacturing paper using a cationic polymer obtained by hofmann degradation |
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| CN102216340A (en) * | 2008-11-27 | 2011-10-12 | S.P.C.M.股份公司 | Novel method for preparing acrylamide copolymers by hofmann degradation reaction |
| CN104395525A (en) * | 2012-07-09 | 2015-03-04 | S.P.C.M.公司 | Improved method for manufacturing paper using a cationic polymer obtained by hofmann degradation |
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