CN116854867B - Hydrophobic association type hyperbranched papermaking wet strength agent and preparation method thereof - Google Patents
Hydrophobic association type hyperbranched papermaking wet strength agent and preparation method thereof Download PDFInfo
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- CN116854867B CN116854867B CN202310951486.6A CN202310951486A CN116854867B CN 116854867 B CN116854867 B CN 116854867B CN 202310951486 A CN202310951486 A CN 202310951486A CN 116854867 B CN116854867 B CN 116854867B
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- Prior art keywords
- monomer
- boron trifluoride
- parts
- trifluoride diethyl
- wet strength
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- 230000002209 hydrophobic effect Effects 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000000178 monomer Substances 0.000 claims abstract description 95
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 claims abstract description 84
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 63
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 50
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000003999 initiator Substances 0.000 claims abstract description 25
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 25
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 21
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims abstract description 18
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000001301 oxygen Substances 0.000 claims abstract description 15
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 15
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 claims abstract description 14
- 125000002091 cationic group Chemical group 0.000 claims abstract description 14
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical group CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000012986 chain transfer agent Substances 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 12
- 238000004321 preservation Methods 0.000 claims abstract description 9
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 claims abstract description 8
- -1 acrylic ester Chemical class 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 238000007142 ring opening reaction Methods 0.000 claims abstract description 5
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000002994 raw material Substances 0.000 claims description 23
- 238000006116 polymerization reaction Methods 0.000 claims description 22
- 239000011259 mixed solution Substances 0.000 claims description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical group [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 14
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 13
- 239000012966 redox initiator Substances 0.000 claims description 13
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 13
- FZGFBJMPSHGTRQ-UHFFFAOYSA-M trimethyl(2-prop-2-enoyloxyethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CCOC(=O)C=C FZGFBJMPSHGTRQ-UHFFFAOYSA-M 0.000 claims description 11
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical group [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 10
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 9
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 8
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- 239000003638 chemical reducing agent Substances 0.000 claims description 6
- 239000007800 oxidant agent Substances 0.000 claims description 6
- 230000001590 oxidative effect Effects 0.000 claims description 6
- 239000004289 sodium hydrogen sulphite Substances 0.000 claims description 5
- RRHXZLALVWBDKH-UHFFFAOYSA-M trimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]azanium;chloride Chemical compound [Cl-].CC(=C)C(=O)OCC[N+](C)(C)C RRHXZLALVWBDKH-UHFFFAOYSA-M 0.000 claims description 5
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 4
- ZWAPMFBHEQZLGK-UHFFFAOYSA-N 5-(dimethylamino)-2-methylidenepentanamide Chemical compound CN(C)CCCC(=C)C(N)=O ZWAPMFBHEQZLGK-UHFFFAOYSA-N 0.000 claims description 3
- 239000004280 Sodium formate Substances 0.000 claims description 3
- NJSSICCENMLTKO-HRCBOCMUSA-N [(1r,2s,4r,5r)-3-hydroxy-4-(4-methylphenyl)sulfonyloxy-6,8-dioxabicyclo[3.2.1]octan-2-yl] 4-methylbenzenesulfonate Chemical compound C1=CC(C)=CC=C1S(=O)(=O)O[C@H]1C(O)[C@@H](OS(=O)(=O)C=2C=CC(C)=CC=2)[C@@H]2OC[C@H]1O2 NJSSICCENMLTKO-HRCBOCMUSA-N 0.000 claims description 3
- ZGCZDEVLEULNLJ-UHFFFAOYSA-M benzyl-dimethyl-(2-prop-2-enoyloxyethyl)azanium;chloride Chemical compound [Cl-].C=CC(=O)OCC[N+](C)(C)CC1=CC=CC=C1 ZGCZDEVLEULNLJ-UHFFFAOYSA-M 0.000 claims description 3
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 claims description 3
- 235000019254 sodium formate Nutrition 0.000 claims description 3
- 239000000835 fiber Substances 0.000 abstract description 42
- 238000006243 chemical reaction Methods 0.000 description 29
- 230000000052 comparative effect Effects 0.000 description 11
- 239000008367 deionised water Substances 0.000 description 11
- 229910021641 deionized water Inorganic materials 0.000 description 11
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 9
- VHSCQANAKTXZTG-UHFFFAOYSA-N 1,1,1-trifluoro-2-(trifluoromethyl)pent-4-en-2-ol Chemical compound FC(F)(F)C(C(F)(F)F)(O)CC=C VHSCQANAKTXZTG-UHFFFAOYSA-N 0.000 description 8
- 238000004132 cross linking Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- 230000009286 beneficial effect Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 125000003700 epoxy group Chemical group 0.000 description 6
- 238000007664 blowing Methods 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 230000001105 regulatory effect Effects 0.000 description 5
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 description 5
- 229910000342 sodium bisulfate Inorganic materials 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 230000002708 enhancing effect Effects 0.000 description 4
- 125000001165 hydrophobic group Chemical group 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 230000008961 swelling Effects 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 208000002430 Multiple chemical sensitivity Diseases 0.000 description 2
- 238000005411 Van der Waals force Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical group FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- GJOWSEBTWQNKPC-UHFFFAOYSA-N 3-methyloxiran-2-ol Chemical compound CC1OC1O GJOWSEBTWQNKPC-UHFFFAOYSA-N 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 238000010009 beating Methods 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000011121 hardwood Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000011534 incubation Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 239000011122 softwood Substances 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
-
- 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
-
- 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
- D21H21/20—Wet strength agents
-
- 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
- Y02W30/64—Paper recycling
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention relates to a hydrophobic association hyperbranched papermaking wet strength agent and a preparation method thereof. The method comprises the following steps: making glycidol carry out ring-opening homopolymerization under the action of boron trifluoride diethyl ether to obtain a branched monomer; uniformly mixing acrylamide, cationic monomer, functional monomer, branched monomer, hydrophobic monomer and water, introducing nitrogen to remove oxygen, adding a chain transfer agent and an initiator to react, and then carrying out heat preservation to prepare the hydrophobic association hyperbranched papermaking wet strength agent; the functional monomer is glycidyl methacrylate and/or allyl glycidyl ether; the hydrophobic monomer is one or more of acrylic ester, methyl methacrylate and N-vinyl pyrrolidone. According to the papermaking wet strength agent, the hyperbranched molecular structure enables molecular chains to be stretched more and more fiber pulp fibers to be attached, so that the binding force among paper fibers is improved, the stretching and stretching actions among the fibers are obviously enhanced, and the tensile strength and the wet strength index of paper can be effectively improved.
Description
Technical Field
The invention relates to the technical field of pulp aids, in particular to a hydrophobic association hyperbranched papermaking wet strength agent and a preparation method thereof.
Background
In the modern paper industry, advances and developments in paper technology are increasingly dependent on the use of paper chemicals. In order to improve the production efficiency of paper machines, improve the quality of paper products, reduce the consumption of raw materials and energy sources, reduce environmental pollution and other important links, the paper industry must fully use novel, efficient and pollution-free papermaking chemicals.
Paper is a writing material formed by cross-linking various fiber raw materials in a staggered and complex net shape, and the strength performance of the writing material is mainly determined by the strength of the fibers and the bonding strength among the fibers. Since the hydrogen bonding in the sheet is susceptible to water and is very susceptible to water damage, the fiber-to-fiber bonding in the sheet will be replaced by water-to-fiber bonding when the dry sheet is contacted with water, and the sheet will lose its original strength properties. In general, after the paper is completely wet out with water, almost all of its strength properties are lost, with the unsized paper generally retaining only 2% to 7% of the dry strength of the base paper and even highly sized paper retaining only 10% to 12% of the dry strength of the base paper. However, in practical use, some paper types (such as towel paper, photographic base paper, paper bag paper, floor paper, etc.) with certain wet strength are often required, and all the paper types are required to retain certain strength performance after being fully soaked by water. Thus, it is often desirable to add chemical aids to the pulp to increase the retention of the wet sheet, a particular class of chemical aids being known in the paper industry as "wet strength agents".
In practice, various methods are almost used up in order to achieve the wet strength properties required for paper. Long ago, people treated the base paper with sulfuric acid to make it sheepskin, after sulfuric acid treatment, part of cellulose on the paper surface is gelled, so that a compact structure is formed, and the paper still maintains high strength performance in a wet state. In addition, people have also been sprayed with waterproof paint, metal foil or plastic film, covering the paper surface; or contacting the surface sized sheet with formaldehyde; even under the condition of high temperature and high acidity, formaldehyde is directly used for treatment to improve the wet strength of paper. However, these methods are costly, have low production efficiency, and only exert the water-resistant effect of the reinforcing agent, and do not substantially improve the wet strength properties of the paper. And toxic substances are released in the use process, the application is limited, and for this reason, the paper industry is seeking papermaking auxiliary agents capable of fundamentally improving the wet strength performance of paper sheets.
In summary, it is very necessary to provide a hydrophobic association hyperbranched papermaking wet strength agent and a preparation method thereof.
Disclosure of Invention
In order to solve one or more technical problems in the prior art, the invention provides a hydrophobic association hyperbranched papermaking wet strength agent and a preparation method thereof.
The invention provides a preparation method of a hydrophobic association hyperbranched papermaking wet strength agent in a first aspect, which comprises the following steps:
(1) Making glycidol carry out ring-opening homopolymerization under the action of boron trifluoride diethyl ether to obtain a branched monomer;
(2) Uniformly mixing acrylamide, cationic monomer, functional monomer, branched monomer, hydrophobic monomer and water to obtain a mixed solution, introducing nitrogen into the mixed solution to remove oxygen, adding a chain transfer agent and an initiator to perform polymerization reaction, and performing heat preservation treatment to obtain the hydrophobic association hyperbranched papermaking wet strength agent;
The functional monomer is glycidyl methacrylate and/or allyl glycidyl ether; the hydrophobic monomer is one or more of acrylic ester, methyl methacrylate and N-vinyl pyrrolidone.
Preferably, step (1) is: under the protection of inert gas, adding a first part of boron trifluoride diethyl etherate into glycidol to react for 0.5-1.5 h at 40-45 ℃, then adding a second part of boron trifluoride diethyl etherate to react for 1.5-2.5 h at 45-50 ℃, and finally adding a third part of boron trifluoride diethyl etherate to react for 4-6 h at 50-55 ℃ to obtain the branched monomer.
Preferably, the mass ratio of the first part of boron trifluoride diethyl etherate, the second part of boron trifluoride diethyl etherate and the third part of boron trifluoride diethyl etherate is 1: (1-3): (1-3), preferably 1:2:2; the mass ratio of the sum of the mass dosages of the first part of boron trifluoride diethyl etherate, the second part of boron trifluoride diethyl etherate and the third part of boron trifluoride diethyl etherate to the glycidol is (1-1.2): 100.
Preferably, the cationic monomer is one or more of methacryloxyethyl trimethyl ammonium chloride, acryloxyethyl trimethyl ammonium chloride, (meth) acryloxyethyl dimethyl benzyl ammonium chloride, diallyl dimethyl ammonium chloride and dimethylaminopropyl acrylamide; and/or the chain transfer agent is one or more of dodecyl mercaptan, isopropanol, sodium hypophosphite and sodium formate.
Preferably, the initiator includes a redox initiator and an azo-type initiator; the oxidant in the redox initiator is potassium persulfate and/or ammonium persulfate, and the reducing agent in the redox initiator is sodium bisulphite; the azo initiator is azo diisobutylamidine hydrochloride, azo diiso Ding Mi hydrochloride azo-diisoheptonitrile one or more of azobisisobutyronitrile; preferably, the mass ratio of the azo initiator to the redox initiator is 10: (1-1.5); the mass ratio of the oxidant to the reducing agent is (1-3): 1.
Preferably, in the polymerization reaction, each raw material used comprises, by weight, 120-160 parts of acrylamide, 40-80 parts of a cationic monomer, 5-10 parts of a functional monomer, 2-3 parts of a branched monomer, 20-30 parts of a hydrophobic monomer, 700-800 parts of water, 1-3 parts of a chain transfer agent and 0.25-0.6 part of an initiator.
Preferably, the time for introducing nitrogen and removing oxygen is 40-80 min; and/or adding an initiator at a temperature of 20 to 25 ℃.
Preferably, the temperature of the polymerization reaction is 60-80 ℃, and the time of the polymerization reaction is 4-5 h.
Preferably, the heat preservation treatment is heat preservation treatment for 8-12 hours at 60-80 ℃.
The invention provides in a second aspect the hydrophobic association hyperbranched papermaking wet strength agent prepared by the preparation method according to the first aspect.
Compared with the prior art, the invention has at least the following beneficial effects:
(1) The hydrophobic association hyperbranched papermaking wet strength agent prepared by the invention has the advantages that as the preparation raw materials contain branched monomers, the papermaking wet strength agent is of a hyperbranched molecular structure, the hyperbranched molecular structure enables a molecular chain to be more stretched, the hyperbranched molecular structure has larger space relative to a linear molecular structure, more fiber pulp fibers are attached, the binding force among paper fibers is improved, the stretching and stretching actions among the fibers are obviously enhanced, the bonding among the fibers is more compact, the retention of fine fibers is improved, and the tensile strength and the wet strength index of paper can be effectively improved.
(2) Epoxy groups are introduced into the molecules of the hydrophobic association hyperbranched papermaking wet strength agent, and can react with amino, carboxyl, hydroxyl and other active groups. As the pulp fiber raw material has active groups such as amino, carboxyl, hydroxyl and the like, epoxy groups can react with certain groups to form a netlike cross-linking structure in the forming and drying processes of paper sheets, and the papermaking wet strength agent and the fibers form new bonding bonds, the strength of the formed new bonding bonds is generally several times or even tens of times of Van der Waals force, and the bonding bonds are particularly critical for enhancing the wet strength of the paper sheets, thereby playing a role in enhancing. In addition, the papermaking wet strength agent also has amino and hydroxyl groups, so that intermolecular crosslinking can possibly occur, the existing combination between fibers can be protected after the intermolecular crosslinking of the papermaking wet strength agent, the water absorption swelling of the fibers is prevented by generating a staggered network structure around the fibers, and a crosslinked network formed by the existing epoxy groups between the fibers and hydroxyl groups, carboxyl groups and other groups carried on the surfaces of the fibers is protected, so that the effect of improving the strength performance of paper sheets in a wet state is achieved.
(3) The hydrophobic group is introduced into the hydrophobic association hyperbranched papermaking wet strength agent molecule, so that the polymer can reflect excellent water resistance. The hydrophobic groups are attached to the surface and the inside of the paper pages to delay the time of water penetration into the paper pages, prevent the water absorption swelling of the fibers, and protect the existing inter-fiber hydrogen bonding to a certain extent, thereby being beneficial to improving the wet strength index of the paper.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be clearly and completely described below in connection with the embodiments of the present invention. It will be apparent that the described embodiments are some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention provides a preparation method of a hydrophobic association hyperbranched papermaking wet strength agent (abbreviated as papermaking wet strength agent) in a first aspect, which comprises the following steps:
(1) Making glycidol (alias: epoxypropanol) undergo the process of ring-opening homopolymerization under the action of boron trifluoride diethyl ether (alias: boron trifluoride-diethyl ether complex) so as to obtain branched monomer; in the invention, the glycidol can carry out ring-opening homopolymerization under the action of boron trifluoride diethyl ether serving as an initiator to form a branched monomer (hyperbranched monomer);
(2) Uniformly mixing acrylamide, cationic monomer, functional monomer, branched monomer, hydrophobic monomer and water to obtain a mixed solution, introducing nitrogen into the mixed solution to remove oxygen, adding a chain transfer agent and an initiator to perform polymerization reaction, and performing heat preservation treatment to obtain the hydrophobic association hyperbranched papermaking wet strength agent; the functional monomer is glycidyl methacrylate and/or allyl glycidyl ether; the hydrophobic monomer is one or more of acrylic ester, methyl methacrylate and N-vinyl pyrrolidone.
According to the hydrophobic association hyperbranched papermaking wet strength agent, a branching monomer is added in the polymerization process, and the branching monomer contains hydroxyl groups, so that the papermaking wet strength agent can participate in graft copolymerization in the acrylamide polymerization process, the hyperbranched molecular structure enables a molecular chain to be more extended, more fiber pulp fibers are attached, the binding force among paper fibers is improved, the extension and stretching effects among the fibers are obviously enhanced, the adhesion among the fibers is more compact, the retention of fine fibers is improved, and the tensile strength and the wet strength index of paper can be effectively improved. Epoxy groups (introduced by functional monomers) are introduced into molecules of the hydrophobic association hyperbranched papermaking wet strength agent, and can react with active groups such as amino, carboxyl, hydroxyl and the like. As the pulp fiber raw material has active groups such as amino, carboxyl, hydroxyl and the like, the epoxy groups can react with certain groups to form a netlike cross-linking structure in the forming and drying processes of paper sheets, and the papermaking wet strength agent and the fibers form new bonding bonds, the strength of the formed new bonding bonds is generally several times or even tens of times of Van der Waals force, and the bonding bonds are particularly critical for enhancing the wet strength of the paper sheets, thereby playing a role in enhancing. In addition, the papermaking wet strength agent also has amino and hydroxyl groups, so that intermolecular crosslinking can possibly occur, the existing combination between fibers can be protected after the intermolecular crosslinking of the papermaking wet strength agent, the water absorption swelling of the fibers is prevented by generating a staggered network structure around the fibers, and a crosslinked network formed by the existing epoxy groups between the fibers and hydroxyl groups, carboxyl groups and other groups carried on the surfaces of the fibers is protected, so that the effect of improving the strength performance of paper sheets in a wet state is achieved. The hydrophobic group is introduced into the hydrophobic association hyperbranched papermaking wet strength agent molecule, so that the polymer can reflect excellent water resistance. The hydrophobic groups are attached to the surface and the inside of the paper pages to delay the time of water penetration into the paper pages, prevent the water absorption swelling of the fibers, and protect the existing inter-fiber hydrogen bonding to a certain extent, thereby being beneficial to improving the wet strength index of the paper.
According to some preferred embodiments, step (1) is: under the protection of inert gas, adding a first part of boron trifluoride diethyl ether into glycidol to react for 0.5-1.5 h (for example, 0.5, 1 or 1.5 h) at 40-45 ℃, then adding a second part of boron trifluoride diethyl ether to react for 1.5-2.5 h (for example, 1.5, 2 or 2.5 h) at 45-50 ℃ and preferably 2h, and finally adding a third part of boron trifluoride diethyl ether to react for 4-6 h (for example, 4, 4.5, 5, 5.5 or 6 h) at 50-55 ℃ and obtaining the branched monomer.
In the invention, boron trifluoride diethyl etherate is preferably divided into three parts and respectively added into a reaction system, and gradual heating reaction is carried out, so that compared with the process of directly adding all boron trifluoride diethyl etherate at a constant temperature, the reaction can be controlled more accurately, the purity and yield of the product are improved, and more ideal branched monomer products can be obtained.
According to some specific embodiments, the preparation of the branching monomer is: adding glycidol into equipment provided with an electric stirrer, a thermometer, a constant-pressure dropping funnel and a nitrogen protection device, introducing nitrogen for 30min to remove oxygen, slowly dripping boron trifluoride diethyl ether under the protection of nitrogen, controlling the temperature to be 40-45 ℃, performing constant-temperature reaction for 1 hour after dripping, slowly dripping boron trifluoride diethyl ether after heating to 45-50 ℃, performing constant-temperature reaction for 2 hours after dripping, slowly dripping boron trifluoride diethyl ether after heating to 50-55 ℃, performing constant-temperature reaction for 5 hours after dripping, taking out a product, washing with acetone, and drying (for example, drying for 8-12 hours) at 60 ℃ to obtain a branched monomer; the speed of adding boron trifluoride diethyl etherate dropwise is not particularly limited, and may be, for example, 10 to 20 drops/min.
According to some preferred embodiments, the mass ratio of the first part of boron trifluoride diethyl etherate, the second part of boron trifluoride diethyl etherate, the third part of boron trifluoride diethyl etherate is 1: (1-3): (1-3) (e.g., 1:1:1, 1:2:2, 1:3:3, 1:1:2, 1:1:3, 1:2:1, 1:2:3, 1:3:1, or 1:3:2), preferably 1:2:2; the mass ratio of the sum of the mass dosages of the first part of boron trifluoride diethyl etherate, the second part of boron trifluoride diethyl etherate and the third part of boron trifluoride diethyl etherate to the glycidol is (1-1.2): 100 (e.g., 1:100, 1.1:100, or 1.2:100).
According to some preferred embodiments, the cationic monomer is one or more of methacryloxyethyl trimethyl ammonium chloride, acryloxyethyl trimethyl ammonium chloride, (meth) acryloxyethyl dimethyl benzyl ammonium chloride, diallyl dimethyl ammonium chloride, dimethylaminopropyl acrylamide; and/or the chain transfer agent is one or more of dodecyl mercaptan, isopropanol, sodium hypophosphite and sodium formate.
According to some preferred embodiments, the initiator comprises a redox initiator and an azo initiator; the oxidant in the redox initiator is potassium persulfate and/or ammonium persulfate, the reducing agent in the redox initiator is sodium bisulphite, and preferably, the redox initiator is a combination of potassium persulfate and sodium bisulphite or a combination of ammonium persulfate and sodium bisulphite; the azo initiator is azo diisobutylamidine hydrochloride, azo diiso Ding Mi hydrochloride azo-diisoheptonitrile one or more of azobisisobutyronitrile; preferably, the mass ratio of the azo initiator to the redox initiator is 10: (1-1.5); the mass ratio of the oxidant to the reducing agent is (1-3): 1, preferably 2:1.
According to some preferred embodiments, each feedstock employed in the polymerization reaction comprises, in parts by weight, 120-160 parts (e.g., 120, 125, 130, 135, 140, 145, 150, 155, or 160 parts) of acrylamide, 40-80 parts (e.g., 40, 45, 50, 55, 60, 65, 70, 75, or 80 parts) of cationic monomer, 5-10 parts (e.g., 5,6, 7, 8, 9, or 10 parts) of functional monomer, 2-3 parts (e.g., 2, 2.5, or 3 parts) of branched monomer, 20-30 parts (e.g., 20, 25, or 30 parts) of hydrophobic monomer, 700-800 parts (e.g., 700, 710, 720, 730, 740, 750, 760, 770, 780, 790, or 800 parts) of chain transfer agent, 1-3 parts (e.g., 1, 1.5, 2, 2.5, or 3 parts), and 0.25-0.6 parts (e.g., 0.25, 0.3, 0.4, 0.5, or 0.6 parts) of initiator; in the present invention, "parts" refers to "parts by weight", and in the specific examples and comparative examples, the unit of parts by weight may be unified as, for example, the unit of weight such as "g" or "kg"; in the present invention, it is preferable that the mass ratio of the acrylamide, the cationic monomer, the functional monomer, the branched monomer to the amount of the hydrophobic monomer is (120 to 160): (40-80): (5-10): (2-3): (20-30), thus being more beneficial to obtaining the hydrophobic association hyperbranched papermaking wet strength agent with better tensile strength and wet strength index effect of the paper.
According to some preferred embodiments, the time to remove oxygen by nitrogen is 40-80 minutes (e.g., 40, 45, 50, 55, 60, 65, 70, 75, or 80 minutes); and/or adding an initiator at a temperature of 20 to 25 ℃.
According to some preferred embodiments, the polymerization reaction is carried out at a temperature of 60 to 80 ℃ for a time of 4 to 5 hours.
According to some preferred embodiments, the incubation is for 8 to 12 hours (e.g., 8, 9, 10, 11, or 12 hours) at 60 to 80 ℃. In the invention, the heat preservation treatment is preferably continued for 8-12 hours at 60-80 ℃ after the polymerization reaction is finished, so that the performance and purity of the product are ensured, and the obtained product has good quality and good stability.
According to some specific embodiments, the preparation of the hydrophobically associating hyperbranched papermaking wet strength agent is: preparing an aqueous solution by taking acrylamide, a cationic monomer, a functional monomer, a branched monomer, a hydrophobic monomer and deionized water as main raw materials, introducing nitrogen to remove oxygen for 60min, adding a chain transfer agent and an initiator under the condition of constant-temperature water bath at 20-25 ℃ to polymerize, slowly adjusting and stirring along with the increase of viscosity in the reaction process, continuously increasing the reaction temperature, keeping the constant-temperature reaction at 60-80 ℃ for 4-5h without increasing the viscosity, keeping the temperature for 8-12 h after the reaction is finished, and obtaining a colorless transparent aqueous solution, namely the hydrophobic association hyperbranched papermaking wet strength agent; the rotational speed of the stirring is not particularly limited, and can be routinely selected by those skilled in the art, for example, can be adjusted in the range of 100 to 400 r/min.
According to some preferred embodiments, in step (2), 2-allylhexafluoroisopropanol is also added to the mixture; the addition amount of the 2-allylhexafluoroisopropanol is 20-30 parts; namely, the step (2) is as follows: uniformly mixing acrylamide, cationic monomer, functional monomer, branching monomer, hydrophobic monomer, 2-allylhexafluoroisopropanol and water to obtain a mixed solution, introducing nitrogen into the mixed solution to remove oxygen, adding a chain transfer agent and an initiator to perform polymerization reaction, and performing heat preservation treatment to obtain a hydrophobic association hyperbranched papermaking wet strength agent; when 2-allylhexafluoroisopropanol is also added to the mixture, each of the raw materials used in the polymerization reaction comprises, in parts by weight, 120 to 160 parts (e.g., 120, 125, 130, 135, 140, 145, 150, 155 or 160 parts), 40 to 80 parts (e.g., 40, 45, 50, 55, 60, 65, 70, 75 or 80 parts) of a cationic monomer, 5 to 10 parts (e.g., 5, 6, 7, 8, 9 or 10 parts) of a functional monomer, 2 to 3 parts (e.g., 2, 2.5 or 3 parts) of a branched monomer, 20 to 30 parts (e.g., 20, 25 or 30 parts) of a hydrophobic monomer, 20 to 30 parts (e.g., 20, 25 or 30 parts) of 2-allylhexafluoroisopropanol, 700 to 800 parts (e.g., 700, 710, 720, 730, 740, 750, 760, 770, 780, 790 or 800 parts), 1 to 3 parts (e.g., 1, 1.5, 2, 2.5 or 3 parts) of a chain transfer agent, and 0.25 to 0.6 part (e.g., 0.25, 0.4, 0.5 or 0).
In the invention, preferably, 2-allyl hexafluoroisopropanol monomer is also added to participate in the reaction in the polymerization process, so that the mechanical strength and water resistance of the papermaking wet strength agent can be further enhanced, the dry tensile index, wet tensile index and wet/dry tensile index ratio of the papermaking wet strength agent are improved, and a fluorocarbon structure with strong adsorptivity can be introduced into a polymer molecular chain, thereby being beneficial to attaching more fiber pulp fibers, improving the bonding force among the paper fibers, and the introduction of the fluorocarbon structure can improve the hydrophobicity of the polymer, thereby being beneficial to improving the water resistance and the tensile strength of the papermaking wet strength agent.
The present invention provides in a second aspect a hydrophobically associating hyperbranched papermaking wet strength agent obtainable by the process according to the first aspect of the invention.
The invention will be further illustrated by way of example, but the scope of the invention is not limited to these examples.
In the present invention, the preparation of the branching monomers in the following examples and comparative examples is:
Adding glycidol into equipment provided with an electric stirrer, a thermometer, a constant-pressure dropping funnel and a nitrogen protection device, introducing nitrogen for 30min to remove oxygen, slowly dripping a first part of boron trifluoride diethyl ether under the protection of nitrogen, controlling the temperature at 40 ℃, carrying out constant-temperature reaction for 1 hour after dripping, heating to 48 ℃, slowly dripping a second part of boron trifluoride diethyl ether, carrying out constant-temperature reaction for 2 hours after dripping, heating to 50 ℃, slowly dripping a third part of boron trifluoride diethyl ether, carrying out constant-temperature reaction for 5 hours after dripping, taking out a product, washing with acetone, and drying at 60 ℃ to obtain a branched monomer; wherein the mass ratio of the first part of boron trifluoride diethyl etherate to the second part of boron trifluoride diethyl etherate to the third part of boron trifluoride diethyl etherate is 1:2:2; the mass ratio of the sum of the mass dosages of the first part of boron trifluoride diethyl etherate, the second part of boron trifluoride diethyl etherate and the third part of boron trifluoride diethyl etherate to glycidol is 1.2:100.
Example 1
The preparation of the hydrophobic association hyperbranched papermaking wet strength agent adopts the following raw materials: 150 parts of acrylamide, 50 parts of acryloyloxyethyl trimethyl ammonium chloride, 7 parts of glycidyl methacrylate, 2 parts of a branched monomer, 25 parts of methyl methacrylate, 760 parts of deionized water, 1 part of sodium hypophosphite, 0.02 part of potassium persulfate, 0.01 part of sodium bisulfite and 0.3 part of azodiisobutylamidine hydrochloride; the preparation method comprises the following steps: sequentially adding acrylamide, acryloyloxyethyl trimethyl ammonium chloride, glycidyl methacrylate, a branching monomer, methyl methacrylate and deionized water into a reactor, and stirring for 40min to uniformly mix the raw materials to obtain a mixed solution; blowing nitrogen into the mixed solution to remove oxygen for 60min, regulating the temperature to 20 ℃ under the protection of nitrogen, sequentially adding sodium hypophosphite, azodiisobutylamidine hydrochloride, potassium persulfate and sodium bisulfate to perform polymerization reaction, and continuously increasing the reaction temperature to 70 ℃ to perform constant-temperature reaction for 4.5h along with the increase of the viscosity of the system in the reaction process; then preserving heat for 10 hours at 70 ℃ to obtain the hydrophobic association hyperbranched papermaking wet strength agent.
Example 2
The preparation of the hydrophobic association hyperbranched papermaking wet strength agent adopts the following raw materials: 140 parts of acrylamide, 60 parts of methacryloxyethyl trimethyl ammonium chloride, 8 parts of glycidyl methacrylate, 3 parts of a branched monomer, 28 parts of methyl methacrylate, 770 parts of deionized water, 1.5 parts of sodium hypophosphite, 0.018 part of potassium persulfate, 0.009 part of sodium bisulfite and 0.25 part of azobisisobutyrimidine hydrochloride; the preparation method comprises the following steps: sequentially adding acrylamide, methacryloxyethyl trimethyl ammonium chloride, glycidyl methacrylate, a branching monomer, methyl methacrylate and deionized water into a reactor, and stirring for 40min to uniformly mix the raw materials to obtain a mixed solution; blowing nitrogen into the mixed solution to remove oxygen for 60min, regulating the temperature to 20 ℃ under the protection of nitrogen, sequentially adding sodium hypophosphite, azodiisobutylamidine hydrochloride, potassium persulfate and sodium bisulfate to perform polymerization reaction, and continuously increasing the reaction temperature to 80 ℃ to perform constant-temperature reaction for 4h along with the increase of the viscosity of the system in the reaction process; then preserving heat for 10 hours at 80 ℃ to obtain the hydrophobic association hyperbranched papermaking wet strength agent.
Example 3
The preparation of the hydrophobic association hyperbranched papermaking wet strength agent adopts the following raw materials: 160 parts of acrylamide, 45 parts of acryloyloxyethyl trimethyl ammonium chloride, 10 parts of allyl glycidyl ether, 2.5 parts of branched monomer, 25 parts of methyl methacrylate, 750 parts of deionized water, 2 parts of sodium hypophosphite, 0.02 part of potassium persulfate, 0.01 part of sodium bisulfite and 0.25 part of azodiisobutylamidine hydrochloride; the preparation method comprises the following steps: sequentially adding acrylamide, acryloyloxyethyl trimethyl ammonium chloride, allyl glycidyl ether, a branching monomer, methyl methacrylate and deionized water into a reactor, and stirring for 40min to uniformly mix the raw materials to obtain a mixed solution; blowing nitrogen into the mixed solution to remove oxygen for 60min, regulating the temperature to 20 ℃ under the protection of nitrogen, sequentially adding sodium hypophosphite, azodiisobutylamidine hydrochloride, potassium persulfate and sodium bisulfate to perform polymerization reaction, and continuously increasing the reaction temperature to 75 ℃ to perform constant-temperature reaction for 4.5h along with the increase of the viscosity of the system in the reaction process; then preserving heat for 10 hours at 75 ℃ to obtain the hydrophobic association hyperbranched papermaking wet strength agent.
Example 4
The preparation of the hydrophobic association hyperbranched papermaking wet strength agent adopts the following raw materials: 150 parts of acrylamide, 50 parts of acryloyloxyethyl trimethyl ammonium chloride, 7 parts of glycidyl methacrylate, 2 parts of a branching monomer, 25 parts of methyl methacrylate, 25 parts of 2-allylhexafluoroisopropanol, 760 parts of deionized water, 1 part of sodium hypophosphite, 0.02 part of potassium persulfate, 0.01 part of sodium bisulfite and 0.3 part of azodiisobutylamidine hydrochloride; the preparation method comprises the following steps: sequentially adding acrylamide, acryloyloxyethyl trimethyl ammonium chloride, glycidyl methacrylate, a branching monomer, methyl methacrylate, 2-allylhexafluoroisopropanol and deionized water into a reactor, and stirring for 40min to uniformly mix the raw materials to obtain a mixed solution; blowing nitrogen into the mixed solution to remove oxygen for 60min, regulating the temperature to 20 ℃ under the protection of nitrogen, sequentially adding sodium hypophosphite, azodiisobutylamidine hydrochloride, potassium persulfate and sodium bisulfate to perform polymerization reaction, and continuously increasing the reaction temperature to 70 ℃ to perform constant-temperature reaction for 4.5h along with the increase of the viscosity of the system in the reaction process; then preserving heat for 10 hours at 70 ℃ to obtain the hydrophobic association hyperbranched papermaking wet strength agent.
Example 5
The preparation of the hydrophobic association hyperbranched papermaking wet strength agent adopts the following raw materials: 160 parts of acrylamide, 45 parts of acryloyloxyethyl trimethyl ammonium chloride, 15 parts of allyl glycidyl ether, 5 parts of a branching monomer, 40 parts of methyl methacrylate, 750 parts of deionized water, 2 parts of sodium hypophosphite, 0.02 part of potassium persulfate, 0.01 part of sodium bisulfite and 0.25 part of azodiisobutylamidine hydrochloride; the preparation method comprises the following steps: sequentially adding acrylamide, acryloyloxyethyl trimethyl ammonium chloride, allyl glycidyl ether, a branching monomer, methyl methacrylate and deionized water into a reactor, and stirring for 40min to uniformly mix the raw materials to obtain a mixed solution; blowing nitrogen into the mixed solution to remove oxygen for 60min, regulating the temperature to 20 ℃ under the protection of nitrogen, sequentially adding sodium hypophosphite, azodiisobutylamidine hydrochloride, potassium persulfate and sodium bisulfate to perform polymerization reaction, and continuously increasing the reaction temperature to 75 ℃ to perform constant-temperature reaction for 4.5h along with the increase of the viscosity of the system in the reaction process; then preserving heat for 10 hours at 75 ℃ to obtain the hydrophobic association hyperbranched papermaking wet strength agent.
Comparative example 1
Comparative example 1 is substantially the same as example 1 except that:
the raw materials for preparing the papermaking wet strength agent do not contain branching monomers, and the branching monomers are not added in the process of preparing the papermaking wet strength agent.
Comparative example 2
Comparative example 2 is substantially the same as example 1 except that:
the raw materials for preparing the papermaking wet strength agent do not contain functional monomers (glycidyl methacrylate), and the functional monomers (glycidyl methacrylate) are not added in the process of preparing the papermaking wet strength agent.
Comparative example 3
Comparative example 3 is substantially the same as example 1 except that:
The raw material for preparing the papermaking wet strength agent does not contain a hydrophobic monomer (methyl methacrylate), and the hydrophobic monomer (methyl methacrylate) is not added in the process of preparing the papermaking wet strength agent.
Comparative example 4
Comparative example 4 is substantially the same as example 1 except that:
The raw materials for preparing the papermaking wet strength agent do not contain functional monomers (glycidyl methacrylate), branching monomers and hydrophobic monomers (methyl methacrylate), and the functional monomers (glycidyl methacrylate), branching monomers and hydrophobic monomers (methyl methacrylate) are not added in the process of preparing the papermaking wet strength agent.
When the invention is applied, the used pulp is hardwood pulp and softwood pulp, the mass percentage of the pulp is 85:15, and the pulp is mixed and pulped, and the beating degree is 37 DEG SR. The filler addition was 10%, the slurry concentration was diluted to 1.0% by mass with tap water, the wet strength agent addition was 3% by mass (wet strength agent absolute/slurry absolute percentage), the wet strength agents for papermaking prepared in each of the above examples and each comparative example were added and stirred for 1min, a round sheet of 0.03m 2 was manufactured according to the national standard method for papermaking, the basis weight of the sheet was 80g/m 2, and then the dry tensile index and the wet tensile index (wet tensile index was measured after 1h immersion) were measured according to GB/T12914-2018, GB/T465.2-2008, respectively, and the wet/dry tensile index ratio (i.e., the ratio of wet tensile index to dry tensile index) was calculated, and the results are shown in Table 1.
TABLE 1
As can be seen from the data in table 1, the hydrophobic association hyperbranched papermaking wet strength agent prepared by the invention has remarkable effect of improving the wet tensile index of paper, and has high dry tensile index of paper; when the hydrophobic association hyperbranched papermaking wet strength agent prepared in some preferred embodiments of the invention is applied, the dry tensile index of the paper can be up to more than 47.9N.m/g, and the ratio of the wet/dry tensile index is up to more than 30%; in the present invention, the higher the dry tensile index of the paper, the higher the dry tensile strength of the corresponding paper, and the higher the wet tensile index of the paper, the higher the wet tensile strength of the corresponding paper.
The invention is not described in detail in a manner known to those skilled in the art. Finally, it should be noted that: although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme recorded in the foregoing embodiments can be modified or some technical features of the technical scheme can be replaced equivalently; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. The preparation method of the hydrophobic association hyperbranched papermaking wet strength agent is characterized by comprising the following steps of:
(1) Under the protection of inert gas, adding a first part of boron trifluoride diethyl ether into glycidol to react for 0.5-1.5 h at the temperature of 40-45 ℃, then adding a second part of boron trifluoride diethyl ether to react for 1.5-2.5 h at the temperature of 45-50 ℃, and finally adding a third part of boron trifluoride diethyl ether to react for 4-6 h at the temperature of 50-55 ℃ so that the glycidol is subjected to ring-opening homopolymerization under the action of the boron trifluoride diethyl ether to obtain a branched monomer;
(2) Uniformly mixing acrylamide, cationic monomer, functional monomer, branched monomer, hydrophobic monomer and water to obtain a mixed solution, introducing nitrogen into the mixed solution to remove oxygen, adding a chain transfer agent and an initiator to perform polymerization reaction, and performing heat preservation treatment to obtain the hydrophobic association hyperbranched papermaking wet strength agent;
the cationic monomer is one or more of methacryloyloxyethyl trimethyl ammonium chloride, acryloyloxyethyl trimethyl ammonium chloride, (meth) acryloyloxyethyl dimethyl benzyl ammonium chloride, diallyl dimethyl ammonium chloride and dimethylaminopropyl acrylamide; the functional monomer is glycidyl methacrylate and/or allyl glycidyl ether; the hydrophobic monomer is one or more of acrylic ester, methyl methacrylate and N-vinyl pyrrolidone;
in the polymerization reaction, the raw materials comprise, by weight, 120-160 parts of acrylamide, 40-80 parts of cationic monomers, 5-10 parts of functional monomers, 2-3 parts of branched monomers, 20-30 parts of hydrophobic monomers, 700-800 parts of water, 1-3 parts of chain transfer agents and 0.25-0.6 part of initiators.
2. The method of manufacturing according to claim 1, characterized in that:
The mass ratio of the first part of boron trifluoride diethyl etherate to the second part of boron trifluoride diethyl etherate to the third part of boron trifluoride diethyl etherate is 1: (1-3): (1-3);
The mass ratio of the sum of the mass dosages of the first part of boron trifluoride diethyl etherate, the second part of boron trifluoride diethyl etherate and the third part of boron trifluoride diethyl etherate to the glycidol is (1-1.2): 100.
3. The preparation method according to claim 2, characterized in that:
The mass ratio of the first part of boron trifluoride diethyl etherate to the second part of boron trifluoride diethyl etherate to the third part of boron trifluoride diethyl etherate is 1:2:2.
4. The method of manufacturing according to claim 1, characterized in that:
the chain transfer agent is one or more of dodecyl mercaptan, isopropanol, sodium hypophosphite and sodium formate.
5. The method of manufacturing according to claim 1, characterized in that:
the initiator comprises a redox initiator and an azo initiator;
The oxidant in the redox initiator is potassium persulfate and/or ammonium persulfate, and the reducing agent in the redox initiator is sodium bisulphite;
the azo initiator is azo diisobutylamidine hydrochloride, azo diiso Ding Mi hydrochloride azo-diisoheptonitrile one or more of azobisisobutyronitrile;
The mass ratio of the oxidant to the reducing agent is (1-3): 1.
6. The method of manufacturing according to claim 5, wherein:
The mass ratio of the azo initiator to the redox initiator is 10: (1-1.5).
7. The method of manufacturing according to claim 1, characterized in that:
The time for introducing nitrogen and deoxidizing is 40-80 min; and/or
And adding an initiator at the temperature of 20-25 ℃.
8. The method of manufacturing according to claim 1, characterized in that:
the temperature of the polymerization reaction is 60-80 ℃, and the time of the polymerization reaction is 4-5 h.
9. The method of manufacturing according to claim 1, characterized in that:
the heat preservation treatment is carried out for 8-12 hours at the temperature of 60-80 ℃.
10. A hydrophobically associating hyperbranched papermaking wet strength agent obtainable by the process according to any one of claims 1 to 9.
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