CN113831439A - A kind of carboxylated nitrile latex for papermaking and preparation method thereof - Google Patents
A kind of carboxylated nitrile latex for papermaking and preparation method thereof Download PDFInfo
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- CN113831439A CN113831439A CN202111287600.7A CN202111287600A CN113831439A CN 113831439 A CN113831439 A CN 113831439A CN 202111287600 A CN202111287600 A CN 202111287600A CN 113831439 A CN113831439 A CN 113831439A
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- CN
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- Prior art keywords
- emulsion
- carboxylated nitrile
- emulsifier
- sodium alkyl
- carboxylated
- Prior art date
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- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 229920000126 latex Polymers 0.000 title claims abstract description 14
- 150000002825 nitriles Chemical class 0.000 title claims abstract description 14
- 239000004816 latex Substances 0.000 title claims abstract description 13
- 239000000839 emulsion Substances 0.000 claims abstract description 40
- 239000000178 monomer Substances 0.000 claims abstract description 17
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 11
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 9
- 150000003254 radicals Chemical class 0.000 claims abstract description 9
- 238000007720 emulsion polymerization reaction Methods 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 8
- 238000001914 filtration Methods 0.000 claims abstract description 7
- 239000003999 initiator Substances 0.000 claims abstract description 5
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 20
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 14
- 229910052708 sodium Inorganic materials 0.000 claims description 14
- 239000011734 sodium Substances 0.000 claims description 14
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 claims description 13
- 239000000126 substance Substances 0.000 claims description 13
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 9
- 238000006116 polymerization reaction Methods 0.000 claims description 9
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 9
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 8
- 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
- -1 sodium alkyl sulfate Chemical class 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 6
- LRMHFDNWKCSEQU-UHFFFAOYSA-N ethoxyethane;phenol Chemical compound CCOCC.OC1=CC=CC=C1 LRMHFDNWKCSEQU-UHFFFAOYSA-N 0.000 claims description 6
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 5
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 5
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 5
- 239000011976 maleic acid Substances 0.000 claims description 5
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 5
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 4
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical compound OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 claims description 4
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 4
- 239000001530 fumaric acid Substances 0.000 claims description 4
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 4
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 3
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 3
- 229940077388 benzenesulfonate Drugs 0.000 claims description 3
- 238000007334 copolymerization reaction Methods 0.000 claims description 3
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 3
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- 150000008052 alkyl sulfonates Chemical class 0.000 claims description 2
- 239000012874 anionic emulsifier Substances 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 150000004679 hydroxides Chemical class 0.000 claims description 2
- 239000012875 nonionic emulsifier Substances 0.000 claims description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- CSVRUJBOWHSVMA-UHFFFAOYSA-N oxolan-2-yl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCO1 CSVRUJBOWHSVMA-UHFFFAOYSA-N 0.000 claims 1
- 230000001070 adhesive effect Effects 0.000 abstract description 5
- 239000000853 adhesive Substances 0.000 abstract description 4
- 239000007864 aqueous solution Substances 0.000 abstract 1
- XNINAOUGJUYOQX-UHFFFAOYSA-N 2-cyanobutanoic acid Chemical compound CCC(C#N)C(O)=O XNINAOUGJUYOQX-UHFFFAOYSA-N 0.000 description 12
- 229940051841 polyoxyethylene ether Drugs 0.000 description 7
- 229920000056 polyoxyethylene ether Polymers 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 6
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- FZSHSWCZYDDOCK-UHFFFAOYSA-N 2-methylprop-2-enoic acid;oxolane Chemical compound C1CCOC1.CC(=C)C(O)=O FZSHSWCZYDDOCK-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- CCJAYIGMMRQRAO-UHFFFAOYSA-N 2-[4-[(2-hydroxyphenyl)methylideneamino]butyliminomethyl]phenol Chemical compound OC1=CC=CC=C1C=NCCCCN=CC1=CC=CC=C1O CCJAYIGMMRQRAO-UHFFFAOYSA-N 0.000 description 1
- UBESITQVAPQMMN-UHFFFAOYSA-N 2-dodecylphenol;sodium Chemical compound [Na].CCCCCCCCCCCCC1=CC=CC=C1O UBESITQVAPQMMN-UHFFFAOYSA-N 0.000 description 1
- NKEQIYNYTHZJRN-UHFFFAOYSA-N CCCCCCCCCCCCC(C=CC=C1)=C1O.N Chemical compound CCCCCCCCCCCCC(C=CC=C1)=C1O.N NKEQIYNYTHZJRN-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- ZIWRUEGECALFST-UHFFFAOYSA-M sodium 4-(4-dodecoxysulfonylphenoxy)benzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCOS(=O)(=O)c1ccc(Oc2ccc(cc2)S([O-])(=O)=O)cc1 ZIWRUEGECALFST-UHFFFAOYSA-M 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 239000007787 solid 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
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
-
- 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
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/26—Emulsion polymerisation with the aid of emulsifying agents anionic
-
- 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
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/30—Emulsion polymerisation with the aid of emulsifying agents non-ionic
-
- 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
- D21H19/00—Coated paper; Coating material
- D21H19/10—Coatings without pigments
- D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
- D21H19/20—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H19/22—Polyalkenes, e.g. polystyrene
-
- 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
- D21H19/00—Coated paper; Coating material
- D21H19/36—Coatings with pigments
- D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
- D21H19/56—Macromolecular organic compounds or oligomers thereof obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H19/58—Polymers or oligomers of diolefins, aromatic vinyl monomers or unsaturated acids or derivatives thereof
-
- 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
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
- D21H21/18—Reinforcing agents
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Paper (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
本发明提供一种造纸用羧基丁腈胶乳及其制备方法，属于乳液聚合技术领域，涉及胶黏剂领域，其制备方法包括以下步骤：聚合釜抽真空后，将丁二烯单体、苯乙烯、丙烯腈、羧酸单体、功能单体、乳化剂和引发剂的混合物的水溶液进行自由基乳液聚合，70‑90℃下滴加时间为3‑6小时，升温至80‑90℃保温2小时，将反应产物用碱性物质调节PH＝5‑9，经过滤后，制得羧基丁腈乳液；羧酸单体的加入，能够提高乳液的稳定性，丙烯腈单体的加入，可提高纸张的耐油性及印刷适性，可使印刷纸张色彩鲜明艳丽。The invention provides a carboxylated nitrile latex for papermaking and a preparation method thereof, belonging to the technical field of emulsion polymerization and to the field of adhesives. , the aqueous solution of the mixture of acrylonitrile, carboxylic acid monomer, functional monomer, emulsifier and initiator is subjected to free radical emulsion polymerization, and the dripping time is 3-6 hours at 70-90 ℃, and the temperature is raised to 80-90 ℃ and kept for 2 After filtration, the carboxynitrile emulsion was prepared; the addition of carboxylic acid monomers can improve the stability of the emulsion, and the addition of acrylonitrile monomers can improve the stability of the emulsion. The oil resistance and printability of the paper can make the printed paper bright and colorful.
Description
Technical Field
The invention relates to the field of adhesives, and particularly relates to a carboxylated butyronitrile latex for papermaking and a preparation method thereof.
Background
The nitrile latex is a water-based emulsion system prepared by emulsion copolymerization of butadiene, styrene, a proper amount of acrylonitrile and carboxylic acid monomers. Carboxyl is introduced into the molecular chain of the carboxyl butyronitrile latex, so that the cohesive force of the polymer is increased, and because the carboxyl has hydrophilicity, the carboxyl tends to be distributed on the surface of particles more and forms a hydration layer on the surface of latex particles in the polymerization process, so that the latex particles are effectively prevented from colliding under the action of high shear force to cause coagulation. Thus endowing the nitrile latex with excellent mechanical and chemical stability, good rheological property and adhesive property. The molecular chain is introduced with the acrylonitrile monomer and applied to the coating paper, so that the printing paper has excellent printability and is bright in color.
Disclosure of Invention
The invention aims to provide an adhesive for papermaking, namely carboxylated butyronitrile latex with stronger adhesive force, mechanical stability, chemical stability and printing adaptability.
In order to achieve the purpose, the invention adopts the following technical scheme:
the carboxyl butyronitrile emulsion comprises the following components in parts by weight:
the preparation method of the carboxyl butyronitrile emulsion comprises the following steps:
vacuumizing a polymerization kettle, adding deionized water, an emulsifier 1, an emulsifier 2 and an initiator, heating to 70-90 ℃, dropwise adding a mixture solution of butadiene, styrene, acrylonitrile, carboxylic acid monomers and functional monomers to carry out free radical emulsion polymerization, wherein the dropwise adding time is 3-6 hours, heating to 80-90 ℃, keeping the temperature for 2 hours, cooling, adjusting the pH to 5-9 by using an alkaline substance, and filtering to obtain the carboxylated butyronitrile emulsion.
Preferably, the method of preparing an acrylic emulsion according to claim 1, wherein said emulsifier 1 is an anionic emulsifier, preferably at least one of sodium alkyl sulfate, sodium alkyl sulfonate, sodium alkyl benzene sulfonate, sodium alkyl diphenyl ether disulfonate, ammonium alkyl phenol ether sulfate, and sodium alkyl phenol ether sulfosuccinate.
The alkyl group is preferably C8-C18, more preferably C8-C16, most preferably at least one of C8-C14 sodium alkyl sulfate, C8-C14 sodium alkyl sulfonate, C8-C14 sodium alkyl benzene sulfonate, C8-C14 sodium alkyl diphenyl ether disulfonate, C8-C14 ammonium alkyl phenol ether sulfate, and C8-C14 sodium alkyl phenol ether sulfosuccinate. As a further preferable scheme, the emulsifier 1 selected by the invention is dodecyl series.
Preferably, the emulsifier 2 is a nonionic emulsifier, preferably fatty alcohol-polyoxyethylene ether with alkyl group of C10-C18, and most preferably fatty alcohol-polyoxyethylene ether with alkyl group of C12-C18, and as a further preferable scheme, the emulsifier 2 is dodecyl fatty alcohol-polyoxyethylene ether.
Preferably, the initiator is selected from at least one of sodium persulfate, ammonium persulfate and potassium persulfate;
preferably, the carboxylic acid monomer is selected from at least one of acrylic acid, methacrylic acid, maleic acid, fumaric acid, or itaconic acid.
Preferably, the functional monomer is at least one selected from the group consisting of hydroxyethyl methacrylate, hydroxypropyl methacrylate, tetrahydrofuran methacrylate, glycidyl methacrylate and N-methylol acrylamide, and the basic substance is selected from the group consisting of hydroxides of alkali metals.
Preferably, the reaction temperature of the free radical emulsion copolymerization is 70 ℃ to 90 ℃.
In another aspect, the invention provides a carboxylated nitrile emulsion prepared by the preparation method.
The invention has the following beneficial effects:
the inventor finds that the emulsion prepared by using a certain amount of carboxylic acid monomer in the invention has better mechanical stability and chemical stability than the butyronitrile emulsion with a smaller amount or no added carboxylic acid monomer. The addition of an appropriate amount of acrylonitrile can improve the printing adaptability of the printing paper. The use of the functional monomer can increase the crosslinking degree of the latex particles properly, and the water retention and strength of the paper can be improved when the functional monomer is applied to coated paper.
Detailed Description
The invention is illustrated below by means of specific examples, without being restricted thereto.
Example 1
The preparation of the carboxylic butyronitrile emulsion comprises the following components in parts by weight:
the carboxyl butyronitrile emulsion comprises the following components in parts by weight:
the preparation method of the carboxyl butyronitrile emulsion comprises the following steps:
and (2) vacuumizing a polymerization kettle, adding deionized water, sodium dodecyl diphenyl ether disulfonate, dodecyl fatty alcohol-polyoxyethylene ether and sodium persulfate, starting stirring, heating to 70 ℃, dropwise adding a mixture solution of butadiene, styrene, acrylonitrile, acrylic acid and hydroxyethyl methacrylate for free radical emulsion polymerization, wherein the dropwise adding time is 3 hours, heating to 80 ℃, keeping the temperature for 2 hours, cooling, adjusting the pH to 5-9 by using a sodium hydroxide alkaline substance, and filtering to obtain the carboxylated butyronitrile emulsion.
Example 2
The preparation of the carboxylic butyronitrile emulsion comprises the following components in parts by weight:
the carboxyl butyronitrile emulsion comprises the following components in parts by weight:
the preparation method of the carboxyl butyronitrile emulsion comprises the following steps:
and (2) vacuumizing a polymerization kettle, adding deionized water, sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, dodecyl fatty alcohol-polyoxyethylene ether and ammonium persulfate, stirring, heating to 90 ℃, dropwise adding a mixture solution of butadiene, styrene, acrylonitrile, maleic acid, itaconic acid and hydroxypropyl methacrylate for free radical emulsion polymerization, heating to 90 ℃, keeping the temperature for 2 hours, cooling, adjusting the pH value to 5-9 by using a potassium hydroxide alkaline substance, and filtering to obtain the carboxyl butyronitrile emulsion.
Example 3
The preparation of the carboxylic butyronitrile emulsion comprises the following components in parts by weight:
the carboxyl butyronitrile emulsion comprises the following components in parts by weight:
the preparation method of the carboxyl butyronitrile emulsion comprises the following steps:
and (2) after the polymerization kettle is vacuumized, adding deionized water, sodium dodecyl sulfate, sodium dodecyl phenol ether sulfosuccinate, dodecyl fatty alcohol-polyoxyethylene ether and potassium persulfate, starting stirring, heating to 80 ℃, dropwise adding a mixture solution of butadiene, styrene, acrylonitrile, methacrylic acid, fumaric acid, glycidyl methacrylate and N-hydroxymethyl acrylamide to perform free radical emulsion polymerization, wherein the dropwise adding time is 4.5 hours, heating to 85 ℃, keeping the temperature for 2 hours, cooling, adjusting the pH to 5-9 by using a sodium hydroxide alkaline substance, and filtering to obtain the carboxylated butyronitrile emulsion.
Example 4
The preparation of the carboxylic butyronitrile emulsion comprises the following components in parts by weight:
the carboxyl butyronitrile emulsion comprises the following components in parts by weight:
the preparation method of the carboxyl butyronitrile emulsion comprises the following steps:
and (2) vacuumizing a polymerization kettle, adding deionized water, sodium dodecyl sulfate, ammonium dodecyl phenol ether sulfate, dodecyl fatty alcohol-polyoxyethylene ether, ammonium persulfate and sodium persulfate, starting stirring, heating to 85 ℃, dropwise adding a mixture solution of butadiene, styrene, acrylonitrile, fumaric acid, acrylic acid and tetrahydrofuran methacrylate for free radical emulsion polymerization, wherein the dropwise adding time is 5 hours, heating to 90 ℃, keeping the temperature for 2 hours, cooling, adjusting the pH to 5-9 by using a potassium hydroxide alkaline substance, and filtering to obtain the carboxylated butyronitrile emulsion.
Comparative example 1:
by adopting the method of the embodiment 2, the dosage of the maleic acid and the itaconic acid in the scheme is respectively 1 part, and the dosages of other raw materials and the process conditions are completely the same.
Comparative example 2:
by adopting the method of example 2, maleic acid and itaconic acid are not used in the scheme, and the amounts of other raw materials and process conditions are completely the same.
The emulsions prepared according to the above examples and comparative examples were tested using the following criteria:
total solid content: SH/T1154-92
Viscosity: SH/T1152-92
pH value: SH/T1150-92
Macroscopic gel fraction: SH/T1153-92
Mechanical stability: SH/T1151-92
Chemical stability: SH/T1608-95
The results are shown in Table 1:
TABLE 1
As can be seen from the results of the tests in the tables, the carboxylated nitrile latices prepared in examples 1 to 4 according to the invention have better stability and better mechanical and chemical stability. Compared with the examples, when the emulsion prepared by the comparative example is applied to paper coating, the emulsion has poor self-stability and poor compatibility with the coating, so that the increase of coagulated polymer particles in the coating can be caused, and the smoothness, the glossiness, the binding power and the printing performance of the coated paper are influenced.
The foregoing description of the examples is provided to facilitate understanding and application of the invention by one of ordinary skill in the art. The invention is not limited to the above examples, and those skilled in the art will appreciate that various modifications and changes can be made in the present invention without departing from the scope of the invention.
Claims (8)
1. The carboxylated nitrile latex for papermaking is characterized by comprising the following steps: the composition comprises the following components in parts by weight:
2. the process for the preparation of carboxylated nitrile latex according to claim 1, characterized in that it comprises the following steps:
the method comprises the following steps: vacuumizing the polymerization kettle;
step two: adding deionized water, an emulsifier 1, an emulsifier 2 and an initiator into a polymerization kettle, and heating to 70-90 ℃;
step three: and (2) dropwise adding a mixture solution of butadiene, acrylonitrile, styrene, carboxylic acid monomers and functional monomers into a polymerization kettle for free radical emulsion polymerization, wherein the dropwise adding time is 3-6 hours, heating to 80-90 ℃, keeping the temperature for 2 hours, cooling, adjusting the pH to 5-9 by using an alkaline substance, and filtering to obtain the carboxylated butyronitrile emulsion.
3. The carboxylated nitrile emulsion according to claim 1, wherein the emulsifier 1 is an anionic emulsifier, preferably at least one of sodium alkyl sulfate, sodium alkyl sulfonate, sodium alkyl benzene sulfonate, sodium alkyl diphenyl ether disulfonate, ammonium alkyl phenol ether sulfate, sodium alkyl phenol ether sulfosuccinate.
4. The carboxylated nitrile emulsion according to claim 1, wherein the emulsifier 2 is a non-ionic emulsifier.
5. The carboxylated nitrile emulsion according to claim 1, wherein the initiator is at least one selected from the group consisting of sodium persulfate, ammonium persulfate, and potassium persulfate.
6. The method for preparing a carboxylated nitrile butadiene emulsion according to claim 1, wherein the carboxylic acid monomer is at least one selected from the group consisting of acrylic acid, methacrylic acid, maleic acid, fumaric acid and itaconic acid.
7. The method for preparing carboxylated nitrile butadiene emulsion according to claim 1, wherein said functional monomer is at least one selected from the group consisting of hydroxyethyl methacrylate, hydroxypropyl methacrylate, tetrahydrofuryl methacrylate, glycidyl methacrylate and N-methylol acrylamide, and said basic substance is selected from the group consisting of hydroxides of alkali metals.
8. The process for preparing a carboxylated nitrile butadiene emulsion according to claim 2, wherein the reaction temperature for the copolymerization of the free radical emulsion is between 70 ℃ and 90 ℃.
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