CN119331173B - Self-crosslinking type multicomponent graft copolymerization paper reinforcing agent and preparation method thereof - Google Patents

Self-crosslinking type multicomponent graft copolymerization paper reinforcing agent and preparation method thereof

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CN119331173B
CN119331173B CN202411728706.XA CN202411728706A CN119331173B CN 119331173 B CN119331173 B CN 119331173B CN 202411728706 A CN202411728706 A CN 202411728706A CN 119331173 B CN119331173 B CN 119331173B
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self
acrylamide
graft copolymer
paper
deionized water
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CN119331173A (en
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费贵强
李志银
解攀
杨晨榕
于鑫波
李实�
陈国�
宁钰钰
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Shaanxi University of Science and Technology
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Shaanxi University of Science and Technology
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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
    • C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
    • C08F251/02—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof on to cellulose or derivatives thereof
    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
    • 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
    • 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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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Paper (AREA)
  • Graft Or Block Polymers (AREA)

Abstract

The invention discloses a self-crosslinking type multicomponent graft copolymer paper reinforcing agent and a preparation method thereof, which belong to the technical field of papermaking, wherein carboxymethyl cellulose is used as a dispersing agent, isopropanol is used as a chain transfer agent, deionized water is used as a solvent, methyl acryloyloxyethyl trimethyl ammonium chloride, acrylamide, acrylic acid and 2-acrylamide-2-methylpropanesulfonic acid are subjected to polymerization reaction under the action of an initiator at 50-80 ℃, the mass ratio of the carboxymethyl cellulose to the methyl acryloyloxyethyl trimethyl ammonium chloride to the acrylamide is (1-10), the mass ratio of the acrylic acid to the 2-acrylamide-2-methylpropanesulfonic acid is (1-5), the mass ratio of the methyl cellulose to the methacrylic acid is (10-30), the mass ratio of the acrylic acid to the 2-acrylamide-2-methylpropanesulfonic acid is (1-5), and the pH value of the obtained reaction solution is regulated to 4.5-5.5, so that the self-crosslinking type multicomponent graft copolymer paper reinforcing agent is obtained. The invention increases the stability of the cross-linking structure of the reinforcing agent, increases the binding force and can obviously improve the strength and the water resistance of the paper.

Description

Self-crosslinking type multicomponent graft copolymerization paper reinforcing agent and preparation method thereof
Technical Field
The invention belongs to the technical field of papermaking, and particularly relates to a self-crosslinking type multicomponent graft copolymerization paper reinforcing agent and a preparation method thereof.
Background
With the rapid development of the paper industry, the demands on paper quality and performance are increasing, and therefore paper reinforcing techniques are required. The paper reinforcing technology is to raise the physical performance, chemical performance, printability, etc. of paper through one series of technological process to meet the requirement of different fields on paper quality, and the paper reinforcing agent is one kind of chemical additive for raising paper physical performance, and is one kind of liquid paint and consists of several kinds of chemical product. In the paper making process, the paper reinforcing agent is added into paper pulp or coated on the surface of paper, and can obviously improve the performance indexes of the paper such as tensile strength, tear strength, folding endurance, bursting strength and the like, so that the paper reinforcing agent is widely focused on development and application as a key auxiliary agent for improving the physical properties of the paper.
In the existing paper reinforcing technology, the commonly used reinforcing agents have various limitations. For example, the effect of a single-component reinforcing agent is limited, and it is difficult to comprehensively improve various performance indexes of paper. Some reinforcing agents only improve certain specific properties of the paper, while improving other important properties only weakly. And the preparation process of part of the reinforcing agent is complex and complicated, has higher cost and is not beneficial to large-scale production and wide application. Other traditional reinforcing agents also have adverse effects on the environment, which is not in accordance with the current green environmental protection concept.
In recent years, polymer-based paper reinforcing agents have been attracting attention due to their unique properties. However, the existing polymer reinforcing agent often has the problems of complex process, higher cost and unstable performance in the preparation process.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides the self-crosslinking type multicomponent graft copolymerization paper reinforcing agent and the preparation method thereof, which have the advantages of simple preparation process, lower cost and environmental protection, and graft the monomers of each component with carboxymethyl cellulose while copolymerizing to form a crosslinked network structure, thereby increasing the stability of the crosslinked structure, increasing the cohesive force and remarkably improving the strength and the water resistance of the paper.
The invention is realized by the following technical scheme:
The preparation method of the self-crosslinking type multicomponent grafted copolymer paper reinforcing agent comprises the steps of taking carboxymethyl cellulose as a dispersing agent, isopropanol as a chain transfer agent and deionized water as a solvent, initiating polymerization reaction of methacryloxyethyl trimethyl ammonium chloride, acrylamide, acrylic acid and 2-acrylamide-2-methylpropanesulfonic acid under the action of an initiator at 50-80 ℃, wherein the mass ratio of the carboxymethyl cellulose to the methacryloxyethyl trimethyl ammonium chloride to the acrylamide to the acrylic acid to the 2-acrylamide-2-methylpropanesulfonic acid is (1-10): (1-5): (10-30): (1-10): (1-5), and then regulating the pH value of the obtained reaction solution to 4.5-5.5, thereby obtaining the self-crosslinking type multicomponent grafted copolymer paper reinforcing agent.
The invention further improves that:
The method specifically comprises the following steps:
S1, dissolving carboxymethyl cellulose in deionized water, and then adding isopropanol to stir to obtain a first mixed solution;
s2, dissolving methacryloyloxyethyl trimethyl ammonium chloride, acrylamide, acrylic acid and 2-acrylamide-2-methylpropanesulfonic acid in deionized water to obtain a second mixed solution;
dissolving an initiator in deionized water to obtain an aqueous solution;
S3, adding the second mixed solution and the aqueous solution into the first mixed solution at 50-80 ℃ at the same time and at a constant speed, then preserving heat at 50-80 ℃, and then regulating the pH value of the obtained reaction solution to 4.5-5.5 to obtain the self-crosslinking multicomponent graft copolymer paper reinforcing agent.
And S1, wherein the carboxymethyl cellulose is 1-5% of the total mass of the methacryloyloxyethyl trimethyl ammonium chloride, the acrylamide, the acrylic acid and the 2-acrylamide-2-methylpropanesulfonic acid.
And S2, the initiator is ammonium persulfate or potassium persulfate.
The ammonium persulfate or the potassium persulfate is 0.1-3% of the total mass of the methacryloxyethyl trimethyl ammonium chloride, the acrylamide, the acrylic acid and the 2-acrylamide-2-methylpropanesulfonic acid.
In the first mixed solution of S1, the mass ratio of the carboxymethyl cellulose to the deionized water is (1-5) 100.
And S2, in the second mixed solution, the mass ratio of the acrylamide to the deionized water is (1-3): 1-5, and in the aqueous solution, the mass ratio of the initiator to the deionized water is (0.1-1): 1-20.
And S3, adding the second mixed solution and the aqueous solution for 1-3h.
And S3, the heat preservation time is 1-3h.
A self-crosslinking type multicomponent graft copolymer paper reinforcing agent obtained by the method of preparing a self-crosslinking type multicomponent graft copolymer paper reinforcing agent according to any one of the above.
Compared with the prior art, the invention has the following beneficial technical effects:
the preparation method of the self-crosslinking type multicomponent graft copolymerization paper reinforcing agent has the advantages that CMC has good dispersion performance and water solubility, so that a reaction system is more stable, and the consistency and reliability of the quality of the reinforcing agent are ensured. The method has the advantages of reducing performance fluctuation caused by unstable reaction, improving controllability of the preparation process, taking isopropanol as a chain transfer agent, initiating polymerization reaction by an initiator, grafting monomer methacryloyloxyethyl trimethyl ammonium chloride, acrylamide, acrylic acid and 2-acrylamide-2-methylpropanesulfonic acid with carboxymethyl cellulose while copolymerizing, and decomposing the initiator to generate free radicals under the condition of 50-80 ℃. These radicals attack the above monomers containing carbon-carbon double bonds, for example AM, the radicals attack the double bonds of AM and open the double bonds, forming a monomer radical with a reactive monomer radical (CH-CH (CONH 2)) that reacts rapidly with the double bonds of other monomer molecules, they compete with each other in systems where multiple monomers are present to participate in chain extension, the extended polymer chain reacts with the carboxymethyl cellulose (CMC) backbone, the CMC backbone has many reactive groups such as hydroxyl (-OH), when the polymer chain radical approaches the CMC backbone, it abstracts the hydrogen atoms on the CMC hydroxyl groups to form water molecules, and the polymer chain radical is linked to the CMC backbone by forming new chemical bonds, the extended polymer chain radical is from AMPS, which encounters a hydroxyl group on the CMC backbone, the reaction formula is: CMC-O-CH 2-CH(CONHCH2C(CH3)2SO3 H), the grafting of AMPS chain segments on CMC main chain is realized, thus forming a cross-linked network structure, increasing the stability of the cross-linked structure, increasing the cohesive force, and the prepared paper reinforcing agent has excellent performance, moderate cost, environmental protection, easy operation, good reinforcing effect, stable performance, convenient use and low cost, can obviously improve the strength and water resistance of paper, can be used for producing high-quality packaging paper, printing paper, special paper and the like, meets the high requirement of different application scenes on the quality of the paper, and can better meet the continuous development requirement of the paper industry. Compared with the reinforcing agent with single component, the reinforcing agent prepared by the invention has more comprehensive and remarkable improvement on the paper performance. The raw materials used in the preparation process of the invention are relatively environment-friendly, and fewer pollutants are produced in the reaction process. Compared with some traditional reinforcing agents, the environment-friendly reinforcing agent has smaller influence on the environment and accords with the current development concept of green and environment protection. The paper strength and durability are improved, so that the paper usage amount can be reduced, natural resources such as wood are saved, and the requirement of sustainable development is met.
Furthermore, isopropanol is used as a chain transfer agent and ammonium persulfate is used as an initiator, sulfate radical (SO 4 - DEG) is generated by the ammonium persulfate, the reaction conditions are mild and easy to control, the requirements and the safety risks of severe reaction conditions such as high temperature, high pressure and the like on equipment are avoided, the production cost and the production difficulty are reduced, and the method is favorable for large-scale production, popularization and application.
Drawings
FIG. 1 is an infrared spectrum of the self-crosslinking type multicomponent graft copolymer paper reinforcing agent of the present invention.
FIG. 2 is a graph showing the stability test of the self-crosslinking type multicomponent graft copolymer paper reinforcing agent according to the present invention.
FIG. 3 is a graph showing the effect of AMPS content on the dry and wet tensile of paper according to the present invention.
FIG. 4 is a graph showing the effect of AMPS content on paper break and tear strength according to the present invention.
Detailed Description
The following detailed description of the invention is of the embodiments, and is intended to be exemplary and explanatory only and should not be construed as limiting the scope of the invention.
The invention relates to a self-crosslinking type multicomponent graft copolymerization paper reinforcing agent, which comprises the raw materials of dispersing agent CMC (carboxymethyl cellulose), chain transfer agent isopropanol, initiator persulfate (ammonium persulfate or potassium persulfate), comonomer DMC (methacryloxyethyl trimethyl ammonium chloride), AM (acrylamide), AA (acrylic acid) and AMPS (2-acrylamide-2-methylpropanesulfonic acid), wherein the mass ratio of CMC, DMC, AM, AA to AMPS is (1-10), 1-5, 10-30, 1-10, 1-5, isopropanol is 1-5 percent of the total mass of CMC, DMC, AM, AA and AMPS, and the addition amount of the initiator is CMC, DMC, AM, AA and 0.1-3 percent of the total mass of AMPS.
The invention relates to a preparation method of a self-crosslinking type multicomponent graft copolymerization paper reinforcing agent, which comprises the following steps:
step one, dissolution of CMC
Dissolving CMC in deionized water at 60-80 deg.c to prepare 1-5 wt% solution, adding isopropanol and stirring for 2-10min to obtain transparent viscous mixed solution.
Step two, preparation of reinforcing agent
(1) AM, AA, AMPS, DMC is dissolved in deionized water and stirred uniformly to prepare a mixed solution, wherein the mass ratio of AM to deionized water is (1-3): 1-5.
(2) And dissolving an initiator in deionized water to prepare an aqueous initiator solution, wherein the mass ratio of the initiator to the deionized water is (0.1-1) (1-20).
(3) Slowly dripping the solution prepared in the step (1) and the step (2) into the mixed solution of CMC and isopropanol at 50-80 ℃, controlling the dripping time to be 60-180min, preserving the temperature for 1-3h after the dripping is finished, then cooling to room temperature, adjusting the pH to 4.5-5.5 by using ammonia water with the mass percent of 25-28%, and obtaining the self-crosslinking multi-component graft copolymer paper reinforcing agent sol, wherein the self-crosslinking multi-component graft copolymer paper reinforcing agent sol is used for improving the strength performance of paper, including tensile index, folding strength, tearing strength and bursting strength.
Example 1
2G CMC is dissolved in deionized water at 60 ℃ to prepare a solution with the mass percent of 5 percent, 0.5g isopropanol is added, and the solution is stirred for 10 minutes to obtain a transparent viscous mixed solution.
Heating the mixed solution of CMC and isopropanol to 80 ℃, dissolving 10g of AM, 3g of AA, 0.5g of AMPS and 2g of DMC in 50g of deionized water, and uniformly stirring to prepare an aqueous solution;
dissolving 0.2g of ammonium persulfate in 10g of deionized water to prepare an aqueous solution;
And respectively and simultaneously adding the two aqueous solutions into a mixed solution of CMC and isopropanol through a constant pressure funnel, ensuring that the simultaneous dripping is completed, controlling the dripping time to be 60min, preserving the heat for 2h after the dripping is completed, then cooling to room temperature, and regulating the pH value to be 5 by using 26 mass percent of ammonia water to obtain the cross-linked multi-component graft copolymerization paper reinforcing agent sol.
Example 2
2GCMC is dissolved in deionized water at 60 ℃ to prepare a solution with the mass percent of 5 percent, 0.5g of isopropanol is added, and the solution is stirred for 10 minutes to obtain a transparent viscous mixed solution.
Heating the mixed solution of CMC and isopropanol to 80 ℃, dissolving 10g of AM, 3g of AA, 1g of AMPS and 2g of DMC in 50g of deionized water, and uniformly stirring to prepare an aqueous solution;
dissolving 0.2g of ammonium persulfate in 10g of deionized water to prepare an aqueous solution;
And respectively and simultaneously adding the two aqueous solutions into a mixed solution of CMC and isopropanol through a constant pressure funnel, ensuring that the simultaneous dripping is completed, controlling the dripping time to be 60min, preserving the heat for 2h after the dripping is completed, then cooling to room temperature, and regulating the pH value to be 5 by using ammonia water with the mass percent of 26%, thereby obtaining the cross-linking type multi-component graft copolymerization paper reinforcing agent sol.
Example 3
2GCMC is dissolved in deionized water at 60 ℃ to prepare a solution with the mass percent of 5 percent, 0.5g of isopropanol is added, and the solution is stirred for 10 minutes to obtain a transparent viscous mixed solution.
Heating the mixed solution of CMC and isopropanol to 80 ℃, dissolving 10g of AM, 3g of AA, 1.5g of AMPS and 2g of DMC in 50g of deionized water, and uniformly stirring to prepare an aqueous solution;
dissolving 0.2g of ammonium persulfate in 10g of deionized water to prepare an aqueous solution;
And respectively and simultaneously adding the two aqueous solutions into a mixed solution of CMC and isopropanol through a constant pressure funnel, ensuring that the simultaneous dripping is completed, controlling the dripping time to be 60min, preserving the heat for 2h after the dripping is completed, then cooling to room temperature, and regulating the pH value to be 5 by using ammonia water with the mass percent of 26%, thereby obtaining the cross-linking type multi-component graft copolymerization paper reinforcing agent sol.
Example 4
2GCMC is dissolved in deionized water at 60 ℃ to prepare a solution with the mass percent of 5 percent, 0.5g of isopropanol is added, and the solution is stirred for 10 minutes to obtain a transparent viscous mixed solution.
Heating the mixed solution of CMC and isopropanol to 80 ℃, dissolving 10g of AM, 3g of AA, 2.5g of AMPS and 2g of DMC in 50g of deionized water, and uniformly stirring to prepare an aqueous solution;
dissolving 0.2g of ammonium persulfate in 10g of deionized water to prepare an aqueous solution;
and respectively and simultaneously adding the two aqueous solutions into a mixed solution of CMC and isopropanol through a constant pressure funnel, ensuring that the simultaneous dripping is completed, controlling the dripping time to be 60min, preserving the heat for 2h after the dripping is completed, then cooling to room temperature, and regulating the pH value to be 5 by 28 mass percent of ammonia water to obtain the cross-linked multi-component graft copolymerization paper reinforcing agent sol.
Comparative example 1
2GCMC is dissolved in deionized water at 60 ℃ to prepare a solution with the mass percent of 5 percent, 0.5g of isopropanol is added, and the solution is stirred for 10 minutes to obtain a transparent viscous mixed solution.
Heating the mixed solution of CMC and isopropanol to 80 ℃, dissolving 10g of AM, 3g of AA and 2g of DMC in 50g of deionized water, and uniformly stirring to prepare an aqueous solution;
dissolving 0.2g of ammonium persulfate in 10g of deionized water to prepare an aqueous solution;
And (3) respectively and simultaneously adding the two aqueous solutions into a mixed solution of CMC and isopropanol through a constant pressure funnel, ensuring that the two aqueous solutions are completely dripped at the same time, controlling the dripping time to be 60min, preserving the heat for 2h after the dripping is completed, then cooling to room temperature, and regulating the pH value to be 5 by using ammonia water with the mass percent of 26% to obtain the paper reinforcing agent sol.
Structure and performance analysis of synthetic paper reinforcing agent
FT-IR analysis of self-crosslinking multicomponent graft copolymer paper reinforcing agent
In FIG. 1, the wide strong absorption peak appears in 3308cm-1 is a hydroxyl (-OH) stretching vibration absorption peak, the weak absorption peak appears in 2113cm-1 is a sulfur-oxygen double bond (S=O) stretching vibration absorption peak, the stronger absorption peak appears in 1641cm-1 is an amide carbonyl (C=O) stretching vibration peak, 1563cm-1 is a COO-symmetrical stretching vibration peak, which indicates that CMC and monomer grafting is successful, the absorption peak in 1456cm-1 is an N+ (CH 3) 3 bending vibration absorption peak, 1041cm-1 is a C-O stretching vibration absorption peak, no characteristic absorption peak with a carbon-carbon double bond (C=C) in the polymer is found in the spectrogram, and the monomer is completely reacted in the reaction, thereby conforming to the structural characteristics of the self-crosslinking multi-component grafting copolymerization paper reinforcing agent.
Stability analysis of self-crosslinking type multicomponent graft copolymer paper reinforcing agent
As can be seen from fig. 2, the TSI values of all sol samples showed an increasing trend in the 60min test. TSI is an index for evaluating the stability of a liquid dispersion, the smaller the TSI index, the more stable the sol over a fixed aging time. When the addition amount of AMPS reaches 8.1%, the TSI value of the sol is minimum, and the stability of the sol is best. This is because AMPS carries sulfonate groups that are strongly anionic, which can be used to make polymer chains less prone to entanglement and aggregation by charge repulsion. When the AMPS is added at 2.85%, the charge repulsion is weak due to the small number of sulfonate groups, there is some entanglement between polymer chains, and slight flocculation of the sol occurs over time, resulting in reduced sol stability. When the addition amount of AMPS reaches 8.1%, enough sulfonate groups can effectively spread the polymer chains, so that the polymer chains can be uniformly dispersed in the aqueous solution, and the stability of the sol is good. When AMPS is added in excess, excessive AMPS can cause too high a charge density on the polymer chain, causing excessive electrostatic repulsion, causing the polymer chain to stretch too loosely, and AMPS itself has a certain spatial structure, and the increase in the added amount can produce steric hindrance, which effects hinder movement and reaction of other molecules in the system, resulting in reduced stability of the system.
Performance test
The self-crosslinking type multi-component graft copolymer paper reinforcing agent prepared in the above way is subjected to sheet making according to the following way, bleached refined cotton pulp with a certain mass is weighed according to the ration of 95g/m 2, the self-crosslinking type multi-component graft copolymer paper reinforcing agent with an addition amount of 0.6 percent (mass ratio of the self-crosslinking type multi-component graft copolymer paper reinforcing agent to the absolute dry pulp) and PAE with a mass ratio of 1.6 percent (mass ratio of the self-crosslinking type multi-component graft copolymer paper reinforcing agent to the absolute dry pulp) are sequentially added, the self-crosslinking type multi-component graft copolymer paper reinforcing agent and PAE are fluffed in a standard fluffer, the self-crosslinking type multi-component graft copolymer paper reinforcing agent rotates 6000 times per minute, so that the self-crosslinking type multi-component graft copolymer paper reinforcing agent is adsorbed on fibers through hydrogen bonding and electrostatic interaction, the paper with the ration of 95g/m 2 is obtained by the paper sample sheet machine, and finally the paper is dried in vacuum for 10 minutes at 105 ℃, and the physical properties of the finished paper are tested.
The physical properties of the paper are detected and calculated according to the national standard, the tensile index is measured by referring to the tensile strength of GB/T12914-2008 paper and paperboard, the tearing strength is measured by referring to the tearing strength of GB/T455-2002 paper and paperboard, and the folding strength is measured by referring to the folding resistance of GB/T457-2008 paper and paperboard.
Effect of AMPS content on paper strength properties
To determine the optimum content of AMPS, the strength properties of the paper were tested at 0.6% add-on of the self-crosslinking multicomponent graft copolymer paper reinforcing agent, and the results are shown in fig. 3 and 4. When the content of AMPS is 0%, the dry tensile index of the prepared sizing paper is 65.5 N.m/g, the wet tensile index is 15.1 N.m/g, the folding strength is 130 times, and the tearing strength is 13.4 N.m2/g. As can be seen from fig. 3 and 4, the dry and wet tensile indices of the sized paper first show an increasing trend with increasing AMPS content. This is because the self-crosslinking type multicomponent graft copolymer paper reinforcing agent itself carries positive charges that are attracted to negative charges on the cotton pulp fibers, adsorbing the self-crosslinking type multicomponent graft copolymer paper reinforcing agent to the fiber surfaces. In addition, the amino, carbonyl and carboxyl functional groups on the polymer chain segments can react with the hydroxyl groups on the cotton pulp fibers to form a crosslinked structure, so that the toughness and strength among the fibers are improved. When the AMPS content is 8.1%, the dry tensile index of the paper reaches 68.4 N.m/g, the wet tensile index reaches 18.8 N.m/g, the folding strength reaches 121 times, the tearing strength reaches 14.2 N.m 2/g, and compared with paper without internal sizing, the paper is respectively improved by 32%, 487.5%, 348% and 5.2%. However, as AMPS content increases, the dry and wet strength index of the paper decreases because the degree of self-polymerization of the polymer segments is excessive, resulting in flocculation. In summary, the AMPS content of 8.1% is the optimum.

Claims (9)

1.一种自交联型多组分接枝共聚纸张增强剂的制备方法，其特征在于，以羧甲基纤维素为分散剂、异丙醇为链转移剂、去离子水为溶剂，将甲基丙烯酰氧乙基三甲基氯化铵、丙烯酰胺、丙烯酸和2-丙烯酰胺-2-甲基丙磺酸在引发剂的作用下，在50-80℃下进行反应，羧甲基纤维素、甲基丙烯酰氧乙基三甲基氯化铵、丙烯酰胺、丙烯酸和2-丙烯酰胺-2-甲基丙磺酸的质量比为（1-10）：（1-5）：（10-30）：（1-10）：1，之后调节所得反应液的pH至4.5-5.5，得到自交联型多组分接枝共聚纸张增强剂。1. A method for preparing a self-crosslinking multi-component graft copolymer paper strengthening agent, characterized in that, with carboxymethyl cellulose as a dispersant, isopropyl alcohol as a chain transfer agent, and deionized water as a solvent, methacryloyloxyethyltrimethylammonium chloride, acrylamide, acrylic acid, and 2-acrylamide-2-methylpropanesulfonic acid are reacted at 50-80° C. under the action of an initiator, wherein the mass ratio of carboxymethyl cellulose, methacryloyloxyethyltrimethylammonium chloride, acrylamide, acrylic acid, and 2-acrylamide-2-methylpropanesulfonic acid is (1-10): (1-5): (10-30): (1-10): 1, and then the pH of the resulting reaction solution is adjusted to 4.5-5.5 to obtain a self-crosslinking multi-component graft copolymer paper strengthening agent. 2.根据权利要求1所述的自交联型多组分接枝共聚纸张增强剂的制备方法，其特征在于，具体包括以下步骤：2. The method for preparing the self-crosslinking multi-component graft copolymer paper strengthening agent according to claim 1, characterized in that it specifically comprises the following steps: S1，将羧甲基纤维素溶解在去离子水中，之后加入异丙醇进行搅拌，得到第一混合溶液；S1, dissolving carboxymethyl cellulose in deionized water, then adding isopropyl alcohol and stirring to obtain a first mixed solution; S2，将甲基丙烯酰氧乙基三甲基氯化铵、丙烯酰胺、丙烯酸和2-丙烯酰胺-2-甲基丙磺酸溶解在去离子水中，得到第二混合溶液；S2, dissolving methacryloyloxyethyltrimethylammonium chloride, acrylamide, acrylic acid and 2-acrylamide-2-methylpropanesulfonic acid in deionized water to obtain a second mixed solution; 将引发剂溶解在去离子水，得到水溶液；dissolving the initiator in deionized water to obtain an aqueous solution; S3，在50-80℃的第一混合溶液中同时且匀速加入第二混合溶液和水溶液，之后在50-80℃下保温，再调节所得反应液的pH至4.5-5.5，得到自交联型多组分接枝共聚纸张增强剂。S3, simultaneously and uniformly adding the second mixed solution and the aqueous solution to the first mixed solution at 50-80° C., then keeping the temperature at 50-80° C., and adjusting the pH of the resulting reaction solution to 4.5-5.5 to obtain a self-crosslinking multi-component graft copolymer paper strengthening agent. 3.根据权利要求2所述的自交联型多组分接枝共聚纸张增强剂的制备方法，其特征在于，S2所述的引发剂为过硫酸铵或过硫酸钾。3. The method for preparing a self-crosslinking multi-component graft copolymer paper strengthening agent according to claim 2, wherein the initiator described in S2 is ammonium persulfate or potassium persulfate. 4.根据权利要求3所述的自交联型多组分接枝共聚纸张增强剂的制备方法，其特征在于，所述过硫酸铵或过硫酸钾为甲基丙烯酰氧乙基三甲基氯化铵、丙烯酰胺、丙烯酸和2-丙烯酰胺-2-甲基丙磺酸总质量的0.1%-3%。4. The method for preparing a self-crosslinking multi-component graft copolymer paper strengthening agent according to claim 3, wherein the ammonium persulfate or potassium persulfate is 0.1% to 3% of the total mass of methacryloyloxyethyltrimethylammonium chloride, acrylamide, acrylic acid, and 2-acrylamide-2-methylpropanesulfonic acid. 5.根据权利要求2所述的自交联型多组分接枝共聚纸张增强剂的制备方法，其特征在于，S1所述第一混合溶液中，羧甲基纤维素和去离子水的质量比为（1-5）:100。5. The method for preparing a self-crosslinking multi-component graft copolymer paper strengthening agent according to claim 2, wherein in S1, the mass ratio of carboxymethyl cellulose to deionized water in the first mixed solution is (1-5):100. 6.根据权利要求2所述的自交联型多组分接枝共聚纸张增强剂的制备方法，其特征在于，S2所述第二混合溶液中，丙烯酰胺和去离子水的质量比为（1-3）：（1-5），水溶液中，引发剂和去离子水的质量比为（0.1-1）：（1-20）。6. The method for preparing a self-crosslinking multi-component graft copolymer paper strengthening agent according to claim 2, characterized in that in the second mixed solution S2, the mass ratio of acrylamide to deionized water is (1-3): (1-5), and in the aqueous solution, the mass ratio of initiator to deionized water is (0.1-1): (1-20). 7.根据权利要求2所述的自交联型多组分接枝共聚纸张增强剂的制备方法，其特征在于，S3中第二混合溶液和水溶液的加入时间为1-3h。7. The method for preparing a self-crosslinking multi-component graft copolymer paper strengthening agent according to claim 2, characterized in that the time for adding the second mixed solution and the aqueous solution in S3 is 1-3 hours. 8.根据权利要求2所述的自交联型多组分接枝共聚纸张增强剂的制备方法，其特征在于，S3所述保温的时间为1-3h。8. The method for preparing a self-crosslinking multi-component graft copolymer paper strengthening agent according to claim 2, wherein the heat preservation time in S3 is 1-3 hours. 9.一种由权利要求1-8中任一项所述的自交联型多组分接枝共聚纸张增强剂的制备方法得到的自交联型多组分接枝共聚纸张增强剂。9. A self-crosslinking multi-component graft copolymer paper strengthening agent obtained by the preparation method of the self-crosslinking multi-component graft copolymer paper strengthening agent according to any one of claims 1 to 8.
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