CN102516460A - Carboxy styrene-butadiene latex special for coating paper - Google Patents
Carboxy styrene-butadiene latex special for coating paper Download PDFInfo
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Abstract
The invention discloses polymer emulsion special for coating paper. The polymer emulsion comprises the following raw materials in part by weight: 100 parts of monomer, 0.4 to 2 parts of composite emulsifier, 0.4 to 2 parts of macromolecular protective glue, 0.4 to 2 parts of initiator, 0.2 to 1.2 parts of molecular weight regulator, 0.02 to 0.1 part of chelating agent, 0.2 to 1 part of pH regulator and 100 to 150 parts of deionized water. Butadiene and styrene are used as main monomers and added with an unsaturated carboxylic acid functional monomer, the emulsifier is compounded by adopting an anionic emulsifier and a nonionic emulsifier, and the reaction stability is improved by using the water-soluble macromolecular protective glue; and the polymer emulsion is synthesized by feeding in a continuous dripping mode for high-temperature emulsion polymerization and adopting a reduced pressure flash degassing technology. The prepared carboxy styrene-butadiene latex can be used for bottom and surface coating of various paper products such as coated paper, white board paper and the like, and endows the coated paper with high glossiness, pigment bonding strength, surface water resistance and good printing adaptability.
Description
Technical field
The present invention relates to a kind of White Board specialty polymer emulsion; Particularly relate to special-purpose carboxylic styrene butadiene latex of a kind of White Board and preparation method thereof; During the carboxylic styrene butadiene latex that makes can be used for/and the end of all kinds of paper products such as high-grade enamelled paper, white board, face coating, give White Board with higher pigment bonding strength, moisture-resistant frictional strength and good printing adaptability.
Background technology
Along with socioeconomic fast development, China's paper using amount per capita is increasing.The Chinese papermaking of certificate association statistics, 2000～2010 years, paper and production amount are average annual to increase by 11.76%, and consumption increases by 9.88% every year; Wherein, 9,173 ten thousand tons of national paper in 2010 and cardboard consumptions, than increasing by 7.05% last year, a year consumption is 68 kilograms per capita, increases by 4 kilograms than the last year.In main products, 1,590 ten thousand tons of uncoated writing and printing paper consumptions account for paper and cardboard aggregate consumption 17.33%, increase by 6.21% on a year-on-year basis; And 5,490,000 tons of the consumptions of coated printing paper (comprising enamelled paper, white board etc.) account for paper and cardboard aggregate consumption 5.98%, increase by 18.57% on a year-on-year basis.
This shows that along with the increase of top grade packing demand, White Board will be the trend of Future Development.Latex is coated with one of topmost starting material as paper, and paper industry is also increasingly high to its specification of quality.In the White Board production process, very high to the latex performance demands, should have good rheological property, with the working viscosity that obtains to suit, improve the glossiness on White Board surface, have good cohesive strength again, to improve the surface strength of White Board; Simultaneously, also require latex to have good Technological adaptability, especially high stability (comprising mechanical stability and chemicalstability).
Carboxylic styrene butadiene latex is the present the widest latex of range of application on White Board is produced, but these latex are mainly by productions such as German BASF, LG-DOW, Korea S LG.At present, the latex of domestic production is formerly used on the paper feeder also less, mainly is because cohesive strength and stable aspect can not meet the demands.
Chinese invention patent CN 1208736A discloses the preparation method of relevant White Board with carboxylic styrene butadiene latex with ZL200510082910.X.Yet these patents are when synthesizing carboxylate latex, or use unsaturated acyl amine monomers, or emulsifying agent is added in the back in latex, all is difficult to prepare high stability, particularly the excellent latex of chemicalstability.
Japanese Patent J P94-173198 provides with 22～55 parts of divinyl; Unsaturated carboxylic acid (in toxilic acid and vinylformic acid, methylene-succinic acid (formal name used at school is methene succsinic acid or methylene-succinic acid), the fumaric acid at least a shared) consumption is 0.4～4 part; Other comonomers (vinylbenzene, vinyl cyanide, TEB 3K etc.) are principal monomer for 38～74.5 parts; In anionic emulsifiers such as sulfonated alkylbenzene, alkyl-sulphate, AS and alkyl phenylate type, the alkyl ether type nonionic surfactant at least three kinds are compound; The total emulsifiers consumption is 5 parts of monomer total amount, carries out emulsion copolymerization through emulsion polymerisation process commonly used and obtains this type of latex.But total emulsifiers large usage quantity in the technology that this patent provided certainly will influence the wet surface strength and the anti-whipability of White Board.U.S. Pat 3784498 discloses a kind of two stage polymerization process of carboxylic styrene butadiene latex; The consumption of emulsifying agent is 0～0.1% in the method; Fs is the carboxylated seed latex of preparation under the acid letex polymerization condition; Subordinate phase is to continue under the alkaline letex polymerization condition (PH is 7～10) to accomplish polyreaction, prepares the carboxylic styrene butadiene latex of low emulsifier content.But it is unstable that the weak point of this patent is a polymerization system, is prone to produce blob of viscose in the polymerization process, and be difficult to satisfy the strict demand of paper coating to chemicalstability through the styrene-butadiene latex of carboxylated emulsifier-free emulsion polymerization method preparation.
Summary of the invention
The object of the present invention is to provide the special-purpose carboxylic styrene butadiene latex of a kind of White Board, use this latex can improve dried, the wet surface strength and the glossiness of White Board, improve its printing adaptability.
For realizing above-mentioned purpose, the present invention adopts following technical scheme:
The special-purpose carboxylic styrene butadiene latex of a kind of White Board; In parts by weight; Its composition of raw materials comprises: 100 parts of monomers, 0.4～2 part of compound emulsifying agent, 0.4～2 part of polymer protection glue, 0.4～2 part of initiator, 0.2～1.2 part of molecular weight regulator, 0.02～0.1 part of sequestrant, 0.2～1 part of PH regulator and 100～150 parts of deionized waters;
Wherein, said 100 parts of monomers are made up of 30～55 parts of divinyl, 40～65 parts of vinylbenzene and 1～5 part of unsaturated carboxylic acid function monomer, and said unsaturated carboxylic acid function monomer is one or more in vinylformic acid, methylacrylic acid and the methylene-succinic acid;
Said compound emulsifying agent by anionic emulsifier and nonionic emulsifying agent with (1～2): the mass ratio of (1～3) is composited; Said anionic emulsifier is one or more in sulfonated alkylbenzene, alkyl-sulphate and the alkyl phenol ether sulphonate; Said nonionic emulsifying agent is alkyl phenylate type or alkyl ether type;
Said polymer protection glue is selected from guar gum or Viscogum BE;
Said initiator adopts water-soluble thermolysis type persulfuric acid salt;
Said molecular weight regulator is a sulfur alcohol compound;
Said PH regulator is sodium hydroxide or Pottasium Hydroxide;
Said sequestrant is EDTA Disodium or tetrasodium ethylenediamine tetraacetate;
During preparation, polymeric kettle through nitrogen replacement, vacuumize after, drop in the composition of raw materials 30～90% deionized water, 10～50% emulsifying agent, 10～50% unsaturated carboxylic acid function monomer, polymer protection glue and sequestrant respectively; After being warming up to 80～90 ℃, in 1～6 hour, at the uniform velocity drip in divinyl and vinylbenzene, molecular weight regulator, remaining unsaturated carboxylic acid function monomer, the composition of raw materials 60～90% initiator, 1～10% PH regulator and remaining emulsifying agent; After monomer dropping finishes, improve temperature of reaction to 90～100 ℃, continue reaction 1～3 hour; Participate in the polymeric total conversion rate when monomer and reach 98.0% when above of monomer total mass, be cooled to 60～80 ℃, commentaries on classics is expected to stripping vessel; Add in remaining initiator and the composition of raw materials 40～80% PH regulator; Control stripping vessel vacuum tightness be-0.07～-0.09MPa, the vacuum flashing degassing 3～5 hours continues with remaining PH regulator accent pH value to 7～9 then; Cool to 30～50 ℃, the packing of discharging after filtering.
For further realizing the object of the invention, said sulfur alcohol compound is preferably n-dodecyl mercaptan or uncle's lauryl mercaptan.
Said anionic emulsifier is preferably one or more in C8～C18 sodium alkyl benzene sulfonate, C8～C18 sodium alkyl sulfate, the C8～C18 alkyl two phenolic ether sodium disulfonates.
Said nonionic emulsifying agent optimization ethylene oxide adduct number is that 5～20 C8～C 12 TX10s, oxyethane adduct number are that 5～20 C8～C 12 AEOs and propylene oxide adduct number are one or more in C4～C8 fatty alcohol polyoxypropylene ether of 2～10.
Said polymer protection glue is preferably the non-ionic type guar gum, and 25 ℃, viscosity is 500～5000m Pa.s during 1% solid content.
The content of said carboxylic styrene butadiene latex residual styrene after the vacuum flashing degassing is 0～500ppm.
Divinyl, styrene monomer, molecular weight regulator and remaining unsaturated carboxylic acid function monomer at the uniform velocity dropwised in 1～5 hour; 60～90% initiator and 1～10% PH regulator at the uniform velocity dropwised in 2～6 hours; Remaining emulsifying agent dripped at the uniform velocity to add in 1～4 hour and finishes.
The present invention adopts the compound emulsifying agent system; Be composited by anionic emulsifier and nonionic emulsifying agent; Described anionic emulsifier is sulfonated alkylbenzene, alkyl-sulphate or alkyl phenol ether sulphonate; Be preferably C8～C18 sodium alkyl benzene sulfonate, C8～C18 sodium alkyl sulfate, C8～C18 alkyl two phenolic ether sodium disulfonates or their mixture; Wherein different alkyl carbon chain length and different anionic hydrophilic segmented structure are determining hydrophile-lipophile balance value (HLB value) size of respective anionic emulsifying agent and each other compatibleness, in the alkyl phenol ether type emulsifying agent molecule-C
6H
5Structure can increase its emulsifying stability, adopts anionic emulsifier that the reaction stability of letex polymerization and the size of emulsion particle are had direct influence.
Described nonionic emulsifying agent is alkyl phenylate type or alkyl ether type; Be preferably C8～C 12 TX10s (the oxyethane adduct number is 5～20), C8～C12 AEO (the oxyethane adduct number is 5～20), C4～C8 fatty alcohol polyoxypropylene ether (the propylene oxide adduct number is 2～10) or their mixture, wherein different alkyl carbon chain length and different hydrophilic ethylene oxide or propylene oxide adduct number are determining hydrophile-lipophile balance value (HLB value) size of nonionic emulsifying agent and each other compatibleness.In described nonionic emulsifying agent, in the alkyl phenol ether type emulsifying agent molecule-C
6H
5Structure can increase its emulsifying stability; Fatty alcohol-ether type emulsifying agent is not then because of containing APEO (alkyl phenol ether structure) oxious component; Have more the environmental friendliness characteristic; Select the wherein nonionic emulsifying agent and the composite use of anionic emulsifier of one or more different structures and HLB value, can improve the chemicalstability and the anti-polyvalent ion interference performance of carboxylic styrene butadiene latex.
The present invention uses a kind of novel high polymer protection glue as co-emulsifier, with further raising polymerization stability; The present invention uses sequestrant to prevent the disadvantageous effect of metals ion to polyreaction when synthetic latex; The synthetic latex solid content of the present invention's preparation is 50 ± 2%.
Content by synthetic carboxylic styrene butadiene latex of the present invention residual styrene after the stripping vessel vacuum flashing degassing is 0～500ppm.
With respect to prior art, the present invention has following advantage:
(1) drops into part unsaturated carboxylic acid function monomer in the polymeric kettle bed material of the present invention in advance and can have surface-active macromolecule emulsifier in the generation of polymerization initial stage; Reduce the usage quantity of small-molecular emulsifier greatly; Reduce the whipability of latex, improve the water resisting property of White Board.
(2) technology that the present invention adopted is different.Part initiator and neutralizing agent change at latex expects to stripping vessel, to add, and can further improve the monomer conversion of latex, and improves the system stability of latex when vacuum flashing outgases.
(3) emulsifying agent that adopts of the present invention is far below prior art, and kind is different from prior art.At least a nonionic emulsifying agent at least a anionic emulsifier in composite emulsifying system employing sulfonated alkylbenzene, alkyl-sulphate, the alkyl two phenolic ether stilbene-4,4'-bis-(1-azo-3, 4-dihydroxy-benzene)-2,2'-disulfonates and alkyl phenol ether, polyoxyethylene aliphatic alcohol ether, the polyoxypropylene fatty alcohol-ether carries out composite, and its formula ratio is 0.4～2 part of monomer total amount.
(4) the present invention also adopts a kind of novel water-soluble polymer protection glue that auxiliary emulsifying effect is provided.Described polymer protection glue is water-soluble seed glue and verivates thereof such as guar gum, Viscogum BE; Be preferably by polygalactomannan deutero-non-ionic type guar gum; Its viscosity when 1% solid content is 500～5000mPa.s (25 ℃), and its formula ratio is 0.4～2 part of monomer total amount, the usage quantity of polymer protection glue commonly used in synthesizing far below latex; Both improve the polymerization stability and the chemicalstability of latex, do not influenced the water resisting property of White Board again.
(5) the present invention adopts water-soluble persulfate initiator, does not need reductive agent, has avoided using the environmental pollution that organic peroxide evocating agent caused; This initiator is stage feeding polymerization at high temperature, has improved polymerization rate greatly, and monomer conversion can be increased to more than 98%, and the reaction times can shorten to 5～8 hours, has significantly reduced the recovery amount of monomer, has reduced energy expenditure.
(6) the present invention adopts vacuum flashing degassing technology can residual styrene content be reduced to 0～500ppm, has farthest eliminated residual monomer to the destruction of system stability with to the pollution of environment, has improved the over-all properties of White Board.
(7) the present invention adopts monomer and molecular weight regulator gradation adding technology, not only can improve transformation efficiency, and make monomer evenly increase chain; The latex that uses the present invention to produce, when carrying out the coating preparation, the consistency of auxiliary agents such as latex and pigment is good, and coatings formulated has excellent flowability, water-retentivity and mechanical stability under shear conditions.
(8) unsaturated carboxylic acid of the present invention's employing is not selected expensive fumaric acid or toxilic acid for use; Vinylformic acid, methylacrylic acid, methylene-succinic acid or their mixture have only been used; Help reducing cost; And the cooperation of two kinds or above unsaturated carboxylic acid function monomer has improved the polymerization stability of latex.
The invention has the beneficial effects as follows: owing to have above plurality of advantages; Adopt the present invention can produce novel high-stability carboxylic butadiene-styrene latex; Carry out the end, the face coating of all kinds of enamelled papers and white board with its preparation paper coating; Can improve dried, the wet surface strength and the pigment bonding strength of paper, improve its printing adaptability, and have the effect of anti-whipability.
Embodiment
Below in conjunction with embodiment the present invention is further described, need to prove, embodiment of the present invention is not limited thereto.
Part among the following embodiment all is a weight part, and wherein the monomer total mass is 100 parts, and monomer is made up of divinyl, vinylbenzene and unsaturated carboxylic acid function monomer, and the unsaturated carboxylic acid function monomer is one or more in vinylformic acid, methylacrylic acid and the methylene-succinic acid.
The testing method of latex physical index and implication thereof are among the present invention:
The SH/T1154-99 standard is adopted in the total solid content test; Refer to the latex sample under defined terms heat drying to constant-quality; The quality of latex sample is to confirm total solid content before and after the weighing heating, and its numerical values recited depends on the theoretical solid content and the monomeric transformation efficiency of latex sample;
Viscosity test adopts the SH/T1152-92 standard, refers to the viscosity with rotary viscosity design determining latex sample, and its numerical values recited is relevant with the pH value of solid content, size, carboxyl-content and the system of latex sample;
The SH/T1150-99 standard is adopted in pH value test, refers to decide with the PH instrumentation pH value of latex sample, and its numerical values recited and initiator amount, carboxyl-content are relevant with the alkali lye add-on;
The SH/T1156-99 standard is adopted in the surface tension test; The wire rings that finger suspends a level on the tensiometer immerses in the latex sample; Slowly extract then; Needed in a flash maximum, force before ring leaves the latex specimen surface is the surface tension of latex sample, and its numerical values recited is relevant with emulsifier type and consumption, carboxyl-content and pH value;
Latex particle size adopts LB-550V type laser particle analyzer to test, and refers to utilize the latex particle size size of laser light scattering principle test latex sample, and its numerical values recited is relevant with emulsifier type and consumption, protection glue consumption, carboxyl-content and pH value;
The mechanically stable property testing adopts the SH/T1151-92 standard; Refer to through high-speed stirring latex sample; Detect the coagulum content of its formation, weigh the high speed shear stability of latex sample, its numerical values recited is relevant with consumption, protection glue consumption, carboxyl-content and pH value with emulsifier type;
The chemically stable property testing adopts the SH/T1608-95 standard; Finger at the uniform velocity adds a certain amount of calcium chloride solution by certain stirring velocity at the appointed time in the latex sample; Detect the coagulum content of its generation; Weigh the polyvalent ion stability of latex sample, its numerical values recited is relevant with consumption, protection glue consumption, carboxyl-content and pH value with emulsifier type;
The SH/T1153-92 standard is adopted in the test of macroscopic view gel fraction; It is that the stainless (steel) wire of 180 ± 10 μ m filters that finger uses the aperture with the latex sample; Detect its coagulum content; Weigh the reaction stability of latex sample, consumption, system pH value and the polymerization technique etc. of its numerical values recited and emulsifier type and consumption, protection glue consumption, carboxyl-content, initiator and sequestrant all have relation.
Embodiment 1
(1) latex production
1) process that feeds intake: (polymeric kettle at first vacuumizes in the 10L polymeric kettle of a band stirring, import and export of nitrogen, material import and export, thermometric pressure taps and chuck; Use nitrogen replacement again, vacuum tightness reaches-during 0.10MPa) and dropping into 60 parts of deionized waters respectively, (deionized water is 10 parts to emulsifier solution; Sodium lauryl sulphate is 0.1 part; Polyoxyethylene octylphenol ether-10 (the oxyethane adduct number is 10) is 0.1 part, and the non-ionic type guar gum is 2 parts), 0.1 part of tetrasodium ethylenediamine tetraacetate; 2.2 parts of methylene-succinic acids (formal name used at school is methene succsinic acid or methylene-succinic acid) begin to be warming up to 85 ℃ then.
2) reaction is controlled and added: 85 ± 2 ℃ of controlled temperature add monomer mixture (55 parts of divinyl, 40 parts of vinylbenzene continuously in polymeric kettle; 2.8 parts in vinylformic acid; N-dodecyl mercaptan is 1.2 parts), (deionized water is 10 parts for initiator mixing solutions (10 parts of deionized waters, 0.35 part of Potassium Persulphate, 0.04 part in sodium hydroxide) and emulsifier solution; Sodium lauryl sulphate is 0.1 part, and polyoxyethylene octylphenol ether-10 is 0.1 part).Control monomer and emulsifier solution dropping time are 4 hours, and the initiator solution dropping time is 5 hours.After treating that monomer dropping finishes, be warming up to 95 ± 2 ℃, continue to keep reaction up to transformation efficiency greater than 98%.
3) remove residual monomer and aftertreatment: when the monomer mass transformation efficiency reaches 98% when above; Stopped reaction expects the latex commentaries on classics to stripping vessel, adds an amount of initiator mixing solutions (10 parts of deionized waters; 0.05 part of Potassium Persulphate; 0.6 part in sodium hydroxide), under the condition of degassing still vacuum tightness for 65 ℃ of-0.70MPa, still temperature, carry out vacuum flashing and outgas, the degassing time is 3 hours.Latex is through after the vacuum flashing degassing, and unreacted divinyl removes fully, and during residual styrene content＜500ppm, slowly adding 20% sodium hydroxide solution, to regulate pH value be 8.40.Be cooled to 40 ℃ at last, the packing of discharging after filtering.
(2) the physical index test case such as the table 1 of latex:
Table 1
Table 1 can be found out, the polymerization single polymerization monomer transformation efficiency in the present embodiment very high (greater than 98%), modest viscosity (100～300mPa.s), particle diameter fine even (100～300nm).Because this embodiment adopts anionic emulsifier and nonionic emulsifying agent composite; And use the further stable polymerization of non-ionic type protection glue to react; Under the auxiliary stabilization of methylene-succinic acid and two kinds of carboxylic acid functional monomers of vinylformic acid, the reaction stability of styrene-butadiene latex, mechanical stability and chemicalstability are all better.
The carboxylic styrene butadiene latex that adopts present embodiment to produce, when being used to prepare paper coating, the consistency of auxiliary agents such as latex and pigment is good, and coatings formulated has excellent flowability, water-retentivity and mechanical stability under shear conditions.This latex has higher activity of cross-linking reaction and preferable shear flow sex change after two kinds of carboxyl functions are monomer copolymerization modified, can improve dried, the wet surface strength and the pigment bonding strength of White Board, improves its printing adaptability.Owing to use extremely low emulsifying agent consumption (0.4 part) among this embodiment; And use a kind of novel water-soluble polymer protection glue (2 parts of non-ionic type guar gums) that auxiliary emulsifying effect is provided; Both improve the polymerization stability and the chemicalstability of synthetic latex, do not influenced the water resisting property of White Board again, also had anti-preferably whipability; Can reduce the usage quantity of skimmer, improve the surface quality of White Board.
Embodiment 2:
(1) latex production
1) process that feeds intake: in the 10L polymeric kettle of a band stirring, import and export of nitrogen, material import and export, thermometric pressure taps and chuck (polymeric kettle at first vacuumizes, use again nitrogen replacement, vacuum tightness reach-during 0.10MPa) drop into 60 parts of deionized waters respectively; (deionized water is 10 parts to emulsifier solution; X 2073 is 0.2 part, and polyoxyethylene octylphenol ether-10 is 0.2 part, and butyl fatty alcohol polyoxypropylene ether-2 (the propylene oxide adduct number is 2) is 0.1 part; The non-ionic type guar gum is 1.5 parts); 0.06 part of tetrasodium ethylenediamine tetraacetate, 1.5 parts of methylene-succinic acids begin to be warming up to 85 ℃ then.
2) reaction is controlled and added: 85 ± 2 ℃ of controlled temperature add monomer mixture (30 parts of divinyl, 65 parts of vinylbenzene continuously in polymeric kettle; 3.5 parts in vinylformic acid, n-dodecyl mercaptan are 0.6 part), initiator mixing solutions (10 parts of deionized waters, 1.2 parts of Potassium Persulphates; 0.05 part in sodium hydroxide) and emulsifier solution (deionized water is 10 parts; X 2073 is 0.2 part, and polyoxyethylene octylphenol ether-10 is 0.2 part, and butyl fatty alcohol polyoxypropylene ether-2 is 0.1 part).Control monomer and emulsifier solution dropping time are 3.5 hours, and the initiator solution dropping time is 5 hours.After treating that monomer dropping finishes, be warming up to 95 ± 2 ℃, continue to keep reaction up to transformation efficiency greater than 98%.
3) remove residual monomer and aftertreatment: transformation efficiency reaches 98% when above; Stopped reaction expects the latex commentaries on classics to stripping vessel, adds an amount of initiator mixing solutions (10 parts of deionized waters; 0.2 part of Potassium Persulphate; 0.75 part in sodium hydroxide), under the condition of degassing still vacuum tightness for 65 ℃ of-0.70MPa, still temperature, carry out vacuum flashing and outgas, the degassing time is 5 hours.Latex is through after the vacuum flashing degassing, and unreacted divinyl removes fully, and during residual styrene content＜500ppm, slowly adding 20% sodium hydroxide solution, to regulate pH value be 8.0.Be cooled to 40 ℃ at last, the packing of discharging after filtering.
(2) the physical index test case such as the table 2 of latex:
Table 2
Embodiment 3:
(1) latex production
1) process that feeds intake: in the 10L polymeric kettle of a band stirring, import and export of nitrogen, material import and export, thermometric pressure taps and chuck (polymeric kettle at first vacuumizes, use again nitrogen replacement, vacuum tightness reach-during 0.10MPa) drop into 60 parts of deionized waters respectively; (deionized water is 10 parts to emulsifier solution; Disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate is 0.4 part, and polyoxyethylene nonylphenol-20 (the oxyethane adduct number is 20) is 0.2 part, and butyl fatty alcohol polyoxypropylene ether-2 is 0.2 part; The non-ionic type guar gum is 0.4 part); 0.02 part of tetrasodium ethylenediamine tetraacetate, 1.2 parts of methylene-succinic acids begin to be warming up to 85 ℃ then.
2) reaction is controlled and added: 85 ± 2 ℃ of controlled temperature add monomer mixture (42 parts of divinyl, 54 parts of vinylbenzene continuously in polymeric kettle; 2.8 parts in vinylformic acid, uncle's lauryl mercaptan are 0.2 part), initiator mixing solutions (10 parts of deionized waters, 1.6 parts of Potassium Persulphates; 0.05 part in Pottasium Hydroxide) and emulsifier solution (deionized water is 10 parts; Disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate is 0.6 part, and polyoxyethylene nonylphenol-20 is 0.3 part, and butyl fatty alcohol polyoxypropylene ether-2 is 0.3 part).Control monomer and emulsifier solution dropping time are 3.5 hours, and the initiator solution dropping time is 5 hours.After treating that monomer dropping finishes, be warming up to 95 ± 2 ℃, continue to keep reaction up to transformation efficiency greater than 98%.
3) remove residual monomer and aftertreatment: transformation efficiency reaches 98% when above; Stopped reaction expects the latex commentaries on classics to stripping vessel, adds an amount of initiator mixing solutions (10 parts of deionized waters; 0.4 part of Potassium Persulphate; 0.75 part in Pottasium Hydroxide), under the condition of degassing still vacuum tightness for 65 ℃ of-0.70MPa, still temperature, carry out vacuum flashing and outgas, the degassing time is 3 hours.Latex is through after the vacuum flashing degassing, and unreacted divinyl removes fully, and during residual styrene content＜500ppm, slowly adding 20% potassium hydroxide solution, to regulate pH value be 7.8.Be cooled to 40 ℃ at last, the packing of discharging after filtering.
(2) the physical index test case such as the table 3 of latex:
Table 3
Embodiment 4:
(1) latex production
1) process that feeds intake: (polymeric kettle at first vacuumizes in the 10L polymeric kettle of a band stirring, import and export of nitrogen, material import and export, thermometric pressure taps and chuck; Use nitrogen replacement again, vacuum tightness reaches-during 0.10MPa) and dropping into 60 parts of deionized waters respectively, (deionized water is 10 parts to emulsifier solution; Disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate is 0.2 part; Butyl fatty alcohol polyoxypropylene ether-2 is 0.2 part, and the non-ionic type guar gum is 1.5 parts), 0.06 part of EDTA Disodium; 1.2 parts of methylene-succinic acids begin to be warming up to 85 ℃ then.
2) reaction is controlled and added: 85 ± 2 ℃ of controlled temperature add monomer mixture (42 parts of divinyl, 54 parts of vinylbenzene continuously in polymeric kettle; 2.8 parts in vinylformic acid; Uncle's lauryl mercaptan is 0.8 part), (deionized water is 10 parts for initiator mixing solutions (10 parts of deionized waters, 1.0 parts of ammonium persulphates, 0.05 part in Pottasium Hydroxide) and emulsifier solution; Disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate is 0.4 part, and butyl fatty alcohol polyoxypropylene ether-2 is 0.4 part).Control monomer and emulsifier solution dropping time are 4.5 hours, and the initiator solution dropping time is 6 hours.After treating that monomer dropping finishes, be warming up to 95 ± 2 ℃, continue to keep reaction up to transformation efficiency greater than 98%.
3) remove residual monomer and aftertreatment: transformation efficiency reaches 98% when above; Stopped reaction expects the latex commentaries on classics to stripping vessel, adds an amount of initiator mixing solutions (10 parts of deionized waters; 0.2 part of ammonium persulphate; 0.75 part in Pottasium Hydroxide), under the condition of degassing still vacuum tightness for 65 ℃ of-0.70MPa, still temperature, carry out vacuum flashing and outgas, the degassing time is 3 hours.Latex is through after the vacuum flashing degassing, and unreacted divinyl removes fully, and during residual styrene content＜500ppm, slowly adding 20% potassium hydroxide solution, to regulate pH value be 8.1.Be cooled to 40 ℃ at last, the packing of discharging after filtering.
(2) the physical index test case such as the table 4 of latex:
Table 4
Embodiment 5:
(1) latex production
1) process that feeds intake: (polymeric kettle at first vacuumizes in the 10L polymeric kettle of a band stirring, import and export of nitrogen, material import and export, thermometric pressure taps and chuck; Use nitrogen replacement again, vacuum tightness reaches-during 0.10MPa) and dropping into 60 parts of deionized waters respectively, (deionized water is 10 parts to emulsifier solution; Disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate is 0.2 part; Isomery tridecyl AEO-10 (the oxyethane adduct number is 10) is 0.3 part, and the non-ionic type guar gum is 1.2 parts), 0.06 part of EDTA Disodium; 1.2 parts of methylene-succinic acids begin to be warming up to 85 ℃ then.
2) reaction is controlled and added: 85 ± 2 ℃ of controlled temperature add monomer mixture (42 parts of divinyl, 54 parts of vinylbenzene continuously in polymeric kettle; 2.8 parts of methylacrylic acids; Uncle's lauryl mercaptan is 0.8 part), (deionized water is 10 parts for initiator mixing solutions (10 parts of deionized waters, 1.2 parts of ammonium persulphates, 0.05 part in Pottasium Hydroxide) and emulsifier solution; Disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate is 0.2 part, and isomery tridecyl AEO-10 is 0.3 part).Control monomer and emulsifier solution dropping time are 4.5 hours, and the initiator solution dropping time is 6 hours.After treating that monomer dropping finishes, be warming up to 95 ± 2 ℃, continue to keep reaction up to transformation efficiency greater than 98%.
3) remove residual monomer and aftertreatment: transformation efficiency reaches 98% when above; Stopped reaction expects the latex commentaries on classics to stripping vessel, adds an amount of initiator mixing solutions (10 parts of deionized waters; 0.2 part of ammonium persulphate; 0.75 part in Pottasium Hydroxide), under the condition of degassing still vacuum tightness for 65 ℃ of-0.70MPa, still temperature, carry out vacuum flashing and outgas, the degassing time is 3 hours.Latex is through after the vacuum flashing degassing, and unreacted divinyl removes fully, and during residual styrene content＜500ppm, slowly adding 20% potassium hydroxide solution, to regulate pH value be 8.5.Be cooled to 40 ℃ at last, the packing of discharging after filtering.
(2) the physical index test case such as the table 5 of latex:
Table 5
Embodiment 6:
(1) latex production
1) process that feeds intake: (polymeric kettle at first vacuumizes in the 10L polymeric kettle of a band stirring, import and export of nitrogen, material import and export, thermometric pressure taps and chuck; Use nitrogen replacement again, vacuum tightness reaches-during 0.10MPa) and dropping into 60 parts of deionized waters respectively, (deionized water is 10 parts to emulsifier solution; Disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate is 0.1 part; Isomery decyl AEO-10 (the oxyethane adduct number is 10) is 0.1 part), the non-ionic type guar gum is 1.5 parts, 0.1 part of EDTA Disodium; 1.2 parts of methylene-succinic acids begin to be warming up to 85 ℃ then.
2) reaction is controlled and added: 85 ± 2 ℃ of controlled temperature add monomer mixture (42 parts of divinyl, 54 parts of vinylbenzene continuously in polymeric kettle; 2.8 parts of methylacrylic acids; Uncle's lauryl mercaptan is 0.8 part), (deionized water is 10 parts for initiator mixing solutions (10 parts of deionized waters, 1.2 parts of ammonium persulphates, 0.05 part in Pottasium Hydroxide) and emulsifier solution; Disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate is 0.1 part, and isomery decyl AEO-10 is 0.1 part).Control monomer and emulsifier solution dropping time are 4.5 hours, and the initiator solution dropping time is 6 hours.After treating that monomer dropping finishes, be warming up to 95 ± 2 ℃, continue to keep reaction up to transformation efficiency greater than 98%.
3) remove residual monomer and aftertreatment: transformation efficiency reaches 98% when above; Stopped reaction expects the latex commentaries on classics to stripping vessel, adds an amount of initiator mixing solutions (10 parts of deionized waters; 0.2 part of ammonium persulphate; 0.75 part in Pottasium Hydroxide), under the condition of degassing still vacuum tightness for 65 ℃ of-0.70MPa, still temperature, carry out vacuum flashing and outgas, the degassing time is 3 hours.Latex is through after the vacuum flashing degassing, and unreacted divinyl removes fully, and during residual styrene content＜500ppm, slowly adding 20% potassium hydroxide solution, to regulate pH value be 8.2.Be cooled to 40 ℃ at last, the packing of discharging after filtering.
(2) the physical index test case such as the table 6 of latex:
Table 6
Embodiment 7:
(1) latex production
1) process that feeds intake: in the 10L polymeric kettle of a band stirring, import and export of nitrogen, material import and export, thermometric pressure taps and chuck (polymeric kettle at first vacuumizes, use again nitrogen replacement, vacuum tightness reach-during 0.10MPa) drop into 60 parts of deionized waters respectively; (deionized water is 10 parts to emulsifier solution; Disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate is 0.1 part, and isomery decyl AEO-10 is 0.1 part, and butyl fatty alcohol polyoxypropylene ether-2 is 0.1 part; The non-ionic type guar gum is 2.0 parts); 0.06 part of tetrasodium ethylenediamine tetraacetate, 0.5 part of methylene-succinic acid begins to be warming up to 85 ℃ then.
2) reaction is controlled and is added: 85 ± 2 ℃ of controlled temperature; In polymeric kettle, add monomer mixture (40 parts of divinyl, 59 parts of vinylbenzene, 0.5 part in vinylformic acid continuously; Uncle's lauryl mercaptan is 0.8 part), initiator mixing solutions (10 parts of deionized waters; 1.2 parts of ammonium persulphates, 0.01 part in sodium hydroxide) and emulsifier solution (deionized water is 10 parts, and disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate is 0.1 part; Isomery decyl AEO-10 is 0.1 part, and butyl fatty alcohol polyoxypropylene ether-2 is 0.1 part).Control monomer and emulsifier solution dropping time are 4.5 hours, and the initiator solution dropping time is 6 hours.After treating that monomer dropping finishes, be warming up to 95 ± 2 ℃, continue to keep reaction up to transformation efficiency greater than 98%.
3) remove residual monomer and aftertreatment: transformation efficiency reaches 98% when above; Stopped reaction expects the latex commentaries on classics to stripping vessel, adds an amount of initiator mixing solutions (10 parts of deionized waters; 0.2 part of ammonium persulphate; 0.16 part in sodium hydroxide), under the condition of degassing still vacuum tightness for 65 ℃ of-0.70MPa, still temperature, carry out vacuum flashing and outgas, the degassing time is 3 hours.Latex is through after the vacuum flashing degassing, and unreacted divinyl removes fully, and during residual styrene content＜500ppm, slowly adding 20% sodium hydroxide solution, to regulate pH value be 8.7.Be cooled to 40 ℃ at last, the packing of discharging after filtering.
(2) the physical index test case such as the table 7 of latex:
Table 7
Comparative Examples 1:
Adopt the method for embodiment 6, in step 1, do not use the non-ionic type guar gum, other raw material consumption and processing condition are identical, the physical index such as the table 8 of gained latex:
Table 8
Table 8 can be found out; In this Comparative Examples, owing to do not use the non-ionic type guar gum, only rely on methylene-succinic acid and the emulsifying agent of less consumption in the step 1 to be difficult to the stable emulsifying effect that provides enough; Cause the polyreaction stability decreases; Have more condensation prod to occur, and the particle diameter of gained latex is thick, the also obvious variation of mechanical stability and chemicalstability.
Comparative Examples 2:
Adopt the method for embodiment 6; In step 1 and step 2, do not use the anionic emulsifier disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate; Nonionic emulsifying agent isomery decyl AEO-10 consumption in step 1 and the step 2 is increased to 0.2 part respectively; Other raw material consumption and processing condition are identical, the physical index such as the table 9 of gained latex:
Table 9
Table 9 can be found out; In this Comparative Examples,, and only depend on nonionic emulsifying agent and the non-ionic type guar gum of same consumption to be difficult to the stable emulsifying effect that provides enough if do not use anionic emulsifier; Cause polyreaction stability obviously to descend; Have more condensation prod to occur, and the particle diameter of gained latex is thick, the also obvious variation of mechanical stability and chemicalstability.
Latex each item index from above-mentioned Comparative Examples can find out that its solid content is on the low side, and particle diameter is thick, and reaction stability, mechanical stability and chemicalstability all obviously are worse than embodiment.Compare with embodiment, when being applied to the paper coating by the latex of above-mentioned Comparative Examples preparation, because of the consistency of other components in itself and the coating relatively poor; Mechanical stability and rheological are not good enough; In coating allotment and high-speed coating process, be easy to generate the condensation prod particle, cause the surface gloss of White Board low, quality of forming film is poor; Pigment bonding strength and surperficial water resisting property do not reach the White Board requirement, and then have influenced the printing adaptability of White Board.
For the raw material consumption of more clearly expressing 7 embodiment and 2 Comparative Examples and the product performance that obtained, list with tabulated form below, see table 10.
The performance index of table 10 carboxylic styrene butadiene latex
Claims (7)
1. the special-purpose carboxylic styrene butadiene latex of a White Board; It is characterized in that: in parts by weight; Its composition of raw materials comprises: 100 parts of monomers, 0.4～2 part of compound emulsifying agent, 0.4～2 part of polymer protection glue, 0.4～2 part of initiator, 0.2～1.2 part of molecular weight regulator, 0.02～0.1 part of sequestrant, 0.2～1 part of PH regulator and 100～150 parts of deionized waters;
Wherein, said 100 parts of monomers are made up of 30～55 parts of divinyl, 40～65 parts of vinylbenzene and 1～5 part of unsaturated carboxylic acid function monomer, and said unsaturated carboxylic acid function monomer is one or more in vinylformic acid, methylacrylic acid and the methylene-succinic acid;
Said compound emulsifying agent by anionic emulsifier and nonionic emulsifying agent with (1～2): the mass ratio of (1～3) is composited; Said anionic emulsifier is one or more in sulfonated alkylbenzene, alkyl-sulphate and the alkyl phenol ether sulphonate; Said nonionic emulsifying agent is alkyl phenylate type or alkyl ether type;
Said polymer protection glue is selected from guar gum or Viscogum BE;
Said initiator adopts water-soluble thermolysis type persulfuric acid salt;
Said molecular weight regulator is a sulfur alcohol compound;
Said PH regulator is sodium hydroxide or Pottasium Hydroxide;
Said sequestrant is EDTA Disodium or tetrasodium ethylenediamine tetraacetate;
During preparation, polymeric kettle through nitrogen replacement, vacuumize after, drop in the composition of raw materials 30～90% deionized water, 10～50% emulsifying agent, 10～50% unsaturated carboxylic acid function monomer, polymer protection glue and sequestrant respectively; After being warming up to 80～90 ℃, in 1～6 hour, at the uniform velocity drip in divinyl and vinylbenzene, molecular weight regulator, remaining unsaturated carboxylic acid function monomer, the composition of raw materials 60～90% initiator, 1～10% PH regulator and remaining emulsifying agent; After monomer dropping finishes, improve temperature of reaction to 90～100 ℃, continue reaction 1～3 hour; Participate in the polymeric total conversion rate when monomer and reach 98.0% when above of monomer total mass, be cooled to 60～80 ℃, commentaries on classics is expected to stripping vessel; Add in remaining initiator and the composition of raw materials 40～80% PH regulator; Control stripping vessel vacuum tightness be-0.07～-0.09MPa, the vacuum flashing degassing 3～5 hours continues with remaining PH regulator accent pH value to 7～9 then; Cool to 30～50 ℃, the packing of discharging after filtering.
2. the special-purpose carboxylic styrene butadiene latex of White Board according to claim 1, it is characterized in that: said sulfur alcohol compound is n-dodecyl mercaptan or uncle's lauryl mercaptan.
3. the special-purpose carboxylic styrene butadiene latex of White Board according to claim 1, it is characterized in that: said anionic emulsifier is one or more in C8～C18 sodium alkyl benzene sulfonate, C8～C18 sodium alkyl sulfate, the C8～C18 alkyl two phenolic ether sodium disulfonates.
4. the special-purpose carboxylic styrene butadiene latex of White Board according to claim 1 is characterized in that: it is that 5～20 C8～C12 TX10, oxyethane adduct number are that 5～20 C8～C12 AEO and propylene oxide adduct number are one or more in C4～C8 fatty alcohol polyoxypropylene ether of 2～10 that said nonionic emulsifying agent is selected the oxyethane adduct number.
5. the special-purpose carboxylic styrene butadiene latex of White Board according to claim 1, it is characterized in that: said polymer protection glue is the non-ionic type guar gum, 25 ℃, viscosity is 500～5000mPa.s during 1% solid content.
6. the special-purpose carboxylic styrene butadiene latex of White Board according to claim 1 is characterized in that: the content of said carboxylic styrene butadiene latex residual styrene after the vacuum flashing degassing is 0～500ppm.
7. the special-purpose carboxylic styrene butadiene latex of White Board according to claim 1, it is characterized in that: divinyl, styrene monomer, molecular weight regulator and remaining unsaturated carboxylic acid function monomer at the uniform velocity dropwised in 1～5 hour; 60～90% initiator and 1～10% PH regulator at the uniform velocity dropwised in 2～6 hours; Remaining emulsifying agent dripped at the uniform velocity to add in 1～4 hour and finishes.
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| CN101649025A (en) * | 2009-06-06 | 2010-02-17 | 中国石油兰州石油化工公司 | Preparation method of carboxylic styrene butadiene latex |
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