CN102516460B - 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 a kind of carboxy styrene-butadiene latex special for coating paper and preparation method thereof, the carboxylic styrene butadiene latex making can be used for the end, the face coating of all kinds of paper products such as medium/high shelves enamelled paper, white board, gives White Board with higher pigment bonding strength, moisture-resistant frictional strength and good printing adaptability.
Background technology
Along with socioeconomic fast development, China per capita paper using amount is increasing.According to Chinese papermaking association statistics, 2000～2010 years, paper and production amount are average annual increased 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, compared with increasing by 7.05% last year, a year consumption is 68 kilograms per capita, increases by 4 kilograms than 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.
As can be seen here, along with the increase of top grade packing demand, White Board is by the trend that is Future Development.Latex is as one of topmost starting material of Paper Coating, and paper industry is also more and more higher to its specification of quality.In White Board production process, very high to the requirement of latex performance, should there is good rheological property, to obtain suitable working viscosity, improve the glossiness on White Board surface, there is again good cohesive strength, to improve the surface strength of White Board; Meanwhile, also require latex to there is good Technological adaptability, especially high stability (comprising mechanical stability and chemical stability).
Carboxylic styrene butadiene latex is the current 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 formerly on paper feeder application also less, be mainly because cohesive strength and stability aspect can not meet the demands.
Chinese invention patent CN 1208736A and ZL200510082910.X disclose the preparation method of relevant White Board carboxylic styrene butadiene latex.But these patents are in the time of synthetic carboxylate latex, or use unsaturated acyl amine monomers, or add emulsifying agent after in latex, are all difficult to prepare high stability, particularly the latex of chemical stability excellence.
Japanese Patent J P94-173198 provides with 22～55 parts of divinyl, unsaturated carboxylic acid (toxilic acid and vinylformic acid, methylene-succinic acid (formal name used at school is methene succsinic acid or methylene-succinic acid), at least one in fumaric acid shares) consumption is 0.4～4 part, other comonomer (vinylbenzene, vinyl cyanide, methyl methacrylate etc.) 38～74.5 parts be principal monomer, alkylbenzene sulfonate, alkyl-sulphate, the anionic emulsifiers such as alkylsulfonate and alkyl phenylate type, in alkyl ether type nonionic surfactant at least three kinds are compound, total emulsifiers consumption is 5 parts of monomer total amount, carry out emulsion copolymerization by conventional emulsion polymerisation process and obtain this type of latex.But total emulsifiers large usage quantity in the technology that this patent provides, certainly will affect wet surface strength and the resistance to 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, first stage is under acid Conditions of Emulsion Polymerization, to prepare carboxylated seed latex, subordinate phase is to have continued polyreaction under alkaline Conditions of Emulsion Polymerization (PH is 7～10), prepares the carboxylic styrene butadiene latex of low emulsifier content.But it is unstable that the weak point of this patent is polymerization system, in polymerization process, easily produce blob of viscose, and the styrene-butadiene latex of preparing by carboxylated emulsifier-free emulsion polymerization method is difficult to meet the strict demand of paper coating to chemical stability.
Summary of the invention
The object of the present invention is to provide a kind of carboxy styrene-butadiene latex special for coating paper, use this latex can improve dry, wet surface strength and the glossiness of White Board, improve its printing adaptability.
For achieving the above object, the present invention adopts following technical scheme:
A kind of carboxy styrene-butadiene latex special for coating paper, 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 conditioning agent and 100～150 parts of deionized waters;
Wherein, described 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 described unsaturated carboxylic acid function monomer is one or more in vinylformic acid, methacrylic acid and methylene-succinic acid;
Described compound emulsifying agent by anionic emulsifier and nonionic emulsifying agent with (1～2): the mass ratio of (1～3) is composited; Described anionic emulsifier is one or more in alkylbenzene sulfonate, alkyl-sulphate and alkyl phenol ether sulphonate; Described nonionic emulsifying agent is alkyl phenylate type or alkyl ether type;
Described polymer protection glue is selected from guar gum or Viscogum BE;
Described initiator adopts water-soluble thermolysis type persulfuric acid salt;
Described molecular weight regulator is sulfur alcohol compound;
Described PH conditioning agent is sodium hydroxide or potassium hydroxide;
Described sequestrant is disodium ethylene diamine tetraacetate or tetrasodium ethylenediamine tetraacetate;
When preparation, polymeric kettle through nitrogen replacement, vacuumize after, drop into respectively in composition of raw materials 30～90% deionized water, 10～50% emulsifying agent, 10～50% unsaturated carboxylic acid function monomer, polymer protection glue and sequestrant; Be warming up to after 80～90 ℃, in 1～6 hour, at the uniform velocity drip in divinyl and vinylbenzene, molecular weight regulator, remaining unsaturated carboxylic acid function monomer, composition of raw materials 60～90% initiator, 1～10% PH conditioning agent and remaining emulsifying agent; After monomer dropping, improve temperature of reaction to 90～100 ℃, continue reaction 1～3 hour; When participating in the total conversion rate of polymerization, monomer reaches 98.0% when above of monomer total mass, be cooled to 60～80 ℃, turn and expect to stripping vessel, add in remaining initiator and composition of raw materials 40～80% PH conditioning agent, controlling stripping vessel vacuum tightness is-0.07～-0.09MPa, and then degassed 3～5 hours of vacuum flashing continues to adjust pH value to 7～9 with remaining PH conditioning agent, cool to 30～50 ℃, the packing of discharging after filtering.
For further realizing the object of the invention, described sulfur alcohol compound is preferably n-dodecyl mercaptan or tertiary lauryl mercaptan.
Described anionic emulsifier is preferably one or more in C8～C18 sodium alkyl benzene sulfonate, C8～C18 sodium alkyl sulfate, C8～C18 alkyl two phenolic ether sodium disulfonates.
One or more in C4～C8 fatty alcohol polyoxypropylene ether that C8～C 12 alkylphenol polyoxyethylene that described nonionic emulsifying agent optimization ethylene oxide adduct number is 5～20, C8～C 12 fatty alcohol-polyoxyethylene ether that ethoxymer distribution is 5～20 and propylene oxide adduct number are 2～10.
Described polymer protection glue is preferably non-ionic type guar gum, and 25 ℃, when 1% solid content, viscosity is 500～5000m Pa.s.
The content of described carboxylic styrene butadiene latex residual styrene after vacuum flashing is degassed 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 conditioning agent at the uniform velocity dropwised in 2～6 hours; Remaining emulsifying agent in 1～4 hour drip at the uniform velocity add complete.
The present invention adopts complex emulsifier, be composited by anionic emulsifier and nonionic emulsifying agent, described anionic emulsifier is alkylbenzene sulfonate, 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 and the compatibleness each other of respective anionic emulsifying agent, in alkyl phenol ether type emulsifying agent molecule-C
6h
5structure can increase its emulsifying stability, adopts the reaction stability of anionic emulsifier on letex polymerization and the size of emulsion particle to have direct impact.
Described nonionic emulsifying agent is alkyl phenylate type or alkyl ether type, be preferably C8～C 12 alkylphenol polyoxyethylene (ethoxymer distribution is 5～20), C8～C12 fatty alcohol-polyoxyethylene ether (ethoxymer distribution is 5～20), C4～C8 fatty alcohol polyoxypropylene ether (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 and the compatibleness each other of nonionic emulsifying agent.In described nonionic emulsifying agent, in alkyl phenol ether type emulsifying agent molecule-C
6h
5structure can increase its emulsifying stability, fatty alcohol-ether type emulsifying agent is not because containing APEO (alkyl phenol ether structure) oxious component, have more environmental friendliness characteristic, select wherein nonionic emulsifying agent and the composite use of anionic emulsifier of one or more different structures and HLB value, can improve chemical stability 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, further to improve polymerization stability; The present invention, in the time of synthetic latex, uses sequestrant to prevent the disadvantageous effect of metal ion to polyreaction; Synthetic latex solid content prepared by the present invention is 50 ± 2%.
Be 0～500ppm by the content of the synthetic carboxylic styrene butadiene latex residual styrene after stripping vessel vacuum flashing is degassed of the present invention.
With respect to prior art, tool of the present invention has the following advantages:
(1) in polymeric kettle bed material of the present invention, dropping in advance part unsaturated carboxylic acid function monomer can generate and have surface-active macromolecule emulsifier at the polymerization initial stage, greatly reduce the usage quantity of small-molecular emulsifier, reduce the whipability of latex, improve the water resisting property of White Board.
(2) technique difference of the present invention.Part initiator and neutralizing agent turn and expect to add to stripping vessel at latex, can further improve the monomer conversion of latex, and improve the system stability of latex in the time that vacuum flashing is degassed.
(3) emulsifying agent that the present invention adopts is far below prior art, and kind is different from prior art.At least one nonionic emulsifying agent at least one anionic emulsifier in composite emulsifying system employing alkylbenzene sulfonate, alkyl-sulphate, 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, 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 the derivatives thereof such as guar gum, Viscogum BE; be preferably the non-ionic type guar gum being derived by polygalactomannan; its viscosity in the time of 1% solid content is 500～5000mPa.s (25 ℃); its formula ratio is 0.4～2 part of monomer total amount; the usage quantity of conventional polymer protection glue in synthetic far below latex; both improve polymerization stability and the chemical stability of latex, do not affected again the water resisting property of White Board.
(5) the present invention adopts water-soluble persulfate initiator, does not need reductive agent, has avoided the environmental pollution that uses organic peroxide evocating agent to cause; At high temperature stage feeding polymerization of this initiator, 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 greatly reduced recovery amount of monomer, has reduced energy expenditure.
(6) the present invention adopts vacuum flashing Degassing Technology residual styrene content can be reduced to 0～500ppm, has farthest eliminated the destruction of residual monomer to system stability and the pollution to environment, has improved the over-all properties of White Board.
(7) the present invention adopts monomer and molecular weight regulator gradation to add technology, not only can improve transformation efficiency, and makes the even chain of monomer; The latex that uses the present invention to produce, in the time carrying out coating, the consistency of the auxiliary agents such as latex and pigment is good, and the coating of preparation has excellent mobility, water-retentivity and mechanical stability under shear conditions.
(8) unsaturated carboxylic acid that the present invention adopts is not selected expensive fumaric acid or toxilic acid, vinylformic acid, methacrylic acid, methylene-succinic acid or their mixture are only used, be conducive to reduce costs, 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 thering is 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 paper and white board with its preparation paper coating, can improve dry, wet surface strength and the pigment bonding strength of paper, improve its printing adaptability, and there is the effect of resistance to whipability.
Embodiment
Below in conjunction with embodiment, the invention will be further described, it should be noted that, embodiments of the present invention are not limited to this.
Part in embodiment is all weight part below, and wherein monomer total mass is 100 parts, and monomer is made up of divinyl, vinylbenzene and unsaturated carboxylic acid function monomer, and unsaturated carboxylic acid function monomer is one or more in vinylformic acid, methacrylic acid and methylene-succinic acid.
In the present invention, the testing method of latex physical index and implication thereof are:
Total solid content test adopts SH/T1154-99 standard, refer to latex sample under defined terms heat drying to constant-quality, weigh the quality of heating front and back latex sample to determine total solid content, its numerical values recited depends on the theoretical solid content of latex sample and the transformation efficiency of monomer;
Viscosity test adopts SH/T1152-92 standard, refers to that its numerical values recited is relevant with the pH value of solid content, size, carboxyl-content and the system of latex sample by the viscosity of rotary viscosity design determining latex sample;
PH value test adopts SH/T1150-99 standard, refers to determine with PH instrumentation the pH value of latex sample, and its numerical values recited and initiator amount, carboxyl-content are relevant with alkali lye add-on;
Surface tension test adopts SH/T1156-99 standard, refer to that the wire rings that a level on tensiometer is suspended immerses in latex sample, then slowly extract, needed maximum, force in a flash before ring leaves 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;
Mechanical stability test adopts SH/T1151-92 standard, refer to by 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;
Chemical stability test adopts SH/T1608-95 standard, refer at the uniform velocity add at the appointed time a certain amount of calcium chloride solution by certain stirring velocity in 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 test of macroscopic view gel fraction adopts SH/T1153-92 standard; refer to latex sample to filter with the stainless (steel) wire that aperture is 180 ± 10 μ m; 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 is produced
1) process that feeds intake: stir at a band, import and export of nitrogen, material import and export, in the 10L polymeric kettle of thermometric pressure tap and chuck, (first polymeric kettle vacuumizes, use again nitrogen replacement, when reach-0.10MPa of vacuum tightness) drop into respectively 60 parts of deionized waters, (deionized water is 10 parts to emulsifier solution, sodium lauryl sulphate is 0.1 part, polyoxyethylene octylphenol ether-10 (ethoxymer distribution is 10) are 0.1 part, 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), then start to be warming up to 85 ℃.
2) reaction is controlled and is added: control 85 ± 2 ℃ of temperature, in polymeric kettle, add continuously monomer mixture (55 parts of divinyl, 40 parts of vinylbenzene, 2.8 parts, 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, sodium hydroxide) and emulsifier solution, sodium lauryl sulphate is 0.1 part, and polyoxyethylene octylphenol ether-10 are 0.1 part).Controlling monomer and emulsifier solution time for adding is 4 hours, and initiator solution time for adding is 5 hours.After treating monomer dropping, be warming up to 95 ± 2 ℃, continue to maintain reaction until transformation efficiency is greater than 98%.
3) remove residual monomer and aftertreatment: when monomer mass transformation efficiency reaches 98% when above, stopped reaction, latex is turned and expected to stripping vessel, add appropriate initiator mixing solutions (10 parts of deionized waters, 0.05 part of Potassium Persulphate, 0.6 part, sodium hydroxide), be-0.70MPa, to carry out vacuum flashing under the condition of 65 ℃ of still temperature degassed that the degassed time is 3 hours in degassed still vacuum tightness.Latex is after vacuum flashing is degassed, and unreacted divinyl removes completely, and when residual styrene content < 500ppm, slowly adding 20% sodium hydroxide solution to regulate pH value is 8.40.Finally be cooled to 40 ℃, the packing of discharging after filtering.
(2) the physical index test case of latex is as table 1:
Table 1
Table 1 can be found out, the polymerization single polymerization monomer transformation efficiency very high (being greater than 98%) in the present embodiment, modest viscosity (100～300mPa.s), particle diameter fine evenly (100～300nm).Due to this embodiment adopt 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, reaction stability, mechanical stability and the chemical stability of styrene-butadiene latex are all better.
The carboxylic styrene butadiene latex that adopts the present embodiment to produce, during for the preparation of paper coating, the consistency of the auxiliary agents such as latex and pigment is good, and the coating of preparation has excellent mobility, water-retentivity and mechanical stability under shear conditions.This latex, after two kinds of carboxyl functions are monomer copolymerization modified, has higher activity of cross-linking reaction and preferably shear flow sex change, can improve dry, wet surface strength and the pigment bonding strength of White Board, improves its printing adaptability.Owing to using extremely low emulsifier (0.4 part) in 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 polymerization stability and the chemical stability of synthetic latex had been improved; do not affect again the water resisting property of White Board; also there is good resistance to whipability; can reduce the usage quantity of defoamer, improve the surface quality of White Board.
Embodiment 2:
(1) latex is produced
1) process that feeds intake: stir at a band, import and export of nitrogen, material import and export, in the 10L polymeric kettle of thermometric pressure tap and chuck, (first polymeric kettle vacuumizes, use again nitrogen replacement, when reach-0.10MPa of vacuum tightness) drop into respectively 60 parts of deionized waters, (deionized water is 10 parts to emulsifier solution, Sodium dodecylbenzene sulfonate is 0.2 part, polyoxyethylene octylphenol ether-10 are 0.2 part, butyl fatty alcohol polyoxypropylene ether-2 (propylene oxide adduct number is 2) are 0.1 part, non-ionic type guar gum is 1.5 parts), 0.06 part of tetrasodium ethylenediamine tetraacetate, 1.5 parts of methylene-succinic acids, then start to be warming up to 85 ℃.
2) reaction is controlled and is added: control 85 ± 2 ℃ of temperature, in polymeric kettle, add continuously monomer mixture (30 parts of divinyl, 65 parts of vinylbenzene, 3.5 parts, vinylformic acid, n-dodecyl mercaptan is 0.6 part), initiator mixing solutions (10 parts of deionized waters, 1.2 parts of Potassium Persulphates, 0.05 part, sodium hydroxide) and emulsifier solution (deionized water is 10 parts, Sodium dodecylbenzene sulfonate is 0.2 part, polyoxyethylene octylphenol ether-10 are 0.2 part, and butyl fatty alcohol polyoxypropylene ether-2 are 0.1 part).Controlling monomer and emulsifier solution time for adding is 3.5 hours, and initiator solution time for adding is 5 hours.After treating monomer dropping, be warming up to 95 ± 2 ℃, continue to maintain reaction until transformation efficiency is greater than 98%.
3) remove residual monomer and aftertreatment: transformation efficiency reaches 98% when above, stopped reaction, latex is turned and expected to stripping vessel, add appropriate initiator mixing solutions (10 parts of deionized waters, 0.2 part of Potassium Persulphate, 0.75 part, sodium hydroxide), be-0.70MPa, to carry out vacuum flashing under the condition of 65 ℃ of still temperature degassed that the degassed time is 5 hours in degassed still vacuum tightness.Latex is after vacuum flashing is degassed, and unreacted divinyl removes completely, and when residual styrene content < 500ppm, slowly adding 20% sodium hydroxide solution to regulate pH value is 8.0.Finally be cooled to 40 ℃, the packing of discharging after filtering.
(2) the physical index test case of latex is as table 2:
Table 2
Embodiment 3:
(1) latex is produced
1) process that feeds intake: stir at a band, import and export of nitrogen, material import and export, in the 10L polymeric kettle of thermometric pressure tap and chuck, (first polymeric kettle vacuumizes, use again nitrogen replacement, when reach-0.10MPa of vacuum tightness) drop into respectively 60 parts of deionized waters, (deionized water is 10 parts to emulsifier solution, disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate is 0.4 part, polyoxyethylene nonylphenol ether-20 (ethoxymer distribution is 20) are 0.2 part, butyl fatty alcohol polyoxypropylene ether-2 are 0.2 part, non-ionic type guar gum is 0.4 part), 0.02 part of tetrasodium ethylenediamine tetraacetate, 1.2 parts of methylene-succinic acids, then start to be warming up to 85 ℃.
2) reaction is controlled and is added: control 85 ± 2 ℃ of temperature, in polymeric kettle, add continuously monomer mixture (42 parts of divinyl, 54 parts of vinylbenzene, 2.8 parts, vinylformic acid, tertiary lauryl mercaptan is 0.2 part), initiator mixing solutions (10 parts of deionized waters, 1.6 parts of Potassium Persulphates, 0.05 part, potassium hydroxide) and emulsifier solution (deionized water is 10 parts, disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate is 0.6 part, polyoxyethylene nonylphenol ether-20 are 0.3 part, and butyl fatty alcohol polyoxypropylene ether-2 are 0.3 part).Controlling monomer and emulsifier solution time for adding is 3.5 hours, and initiator solution time for adding is 5 hours.After treating monomer dropping, be warming up to 95 ± 2 ℃, continue to maintain reaction until transformation efficiency is greater than 98%.
3) remove residual monomer and aftertreatment: transformation efficiency reaches 98% when above, stopped reaction, latex is turned and expected to stripping vessel, add appropriate initiator mixing solutions (10 parts of deionized waters, 0.4 part of Potassium Persulphate, 0.75 part, potassium hydroxide), be-0.70MPa, to carry out vacuum flashing under the condition of 65 ℃ of still temperature degassed that the degassed time is 3 hours in degassed still vacuum tightness.Latex is after vacuum flashing is degassed, and unreacted divinyl removes completely, and when residual styrene content < 500ppm, slowly adding 20% potassium hydroxide solution to regulate pH value is 7.8.Finally be cooled to 40 ℃, the packing of discharging after filtering.
(2) the physical index test case of latex is as table 3:
Table 3
Embodiment 4:
(1) latex is produced
1) process that feeds intake: (first polymeric kettle vacuumizes in the 10L polymeric kettle of a band stirring, import and export of nitrogen, material import and export, thermometric pressure tap and chuck, use again nitrogen replacement, when reach-0.10MPa of vacuum tightness) drop into respectively 60 parts of deionized waters, (deionized water is 10 parts to emulsifier solution, disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate is 0.2 part, butyl fatty alcohol polyoxypropylene ether-2 are 0.2 part, non-ionic type guar gum is 1.5 parts), 0.06 part of disodium ethylene diamine tetraacetate, 1.2 parts of methylene-succinic acids, then start to be warming up to 85 ℃.
2) reaction is controlled and is added: control 85 ± 2 ℃ of temperature, in polymeric kettle, add continuously monomer mixture (42 parts of divinyl, 54 parts of vinylbenzene, 2.8 parts, vinylformic acid, tertiary 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, potassium hydroxide) and emulsifier solution, disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate is 0.4 part, and butyl fatty alcohol polyoxypropylene ether-2 are 0.4 part).Controlling monomer and emulsifier solution time for adding is 4.5 hours, and initiator solution time for adding is 6 hours.After treating monomer dropping, be warming up to 95 ± 2 ℃, continue to maintain reaction until transformation efficiency is greater than 98%.
3) remove residual monomer and aftertreatment: transformation efficiency reaches 98% when above, stopped reaction, latex is turned and expected to stripping vessel, add appropriate initiator mixing solutions (10 parts of deionized waters, 0.2 part of ammonium persulphate, 0.75 part, potassium hydroxide), be-0.70MPa, to carry out vacuum flashing under the condition of 65 ℃ of still temperature degassed that the degassed time is 3 hours in degassed still vacuum tightness.Latex is after vacuum flashing is degassed, and unreacted divinyl removes completely, and when residual styrene content < 500ppm, slowly adding 20% potassium hydroxide solution to regulate pH value is 8.1.Finally be cooled to 40 ℃, the packing of discharging after filtering.
(2) the physical index test case of latex is as table 4:
Table 4
Embodiment 5:
(1) latex is produced
1) process that feeds intake: stir at a band, import and export of nitrogen, material import and export, in the 10L polymeric kettle of thermometric pressure tap and chuck, (first polymeric kettle vacuumizes, use again nitrogen replacement, when reach-0.10MPa of vacuum tightness) drop into respectively 60 parts of deionized waters, (deionized water is 10 parts to emulsifier solution, disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate is 0.2 part, isomery tridecyl fatty alcohol-polyoxyethylene ether-10 (ethoxymer distribution is 10) are 0.3 part, non-ionic type guar gum is 1.2 parts), 0.06 part of disodium ethylene diamine tetraacetate, 1.2 parts of methylene-succinic acids, then start to be warming up to 85 ℃.
2) reaction is controlled and is added: control 85 ± 2 ℃ of temperature, in polymeric kettle, add continuously monomer mixture (42 parts of divinyl, 54 parts of vinylbenzene, 2.8 parts of methacrylic acids, tertiary lauryl mercaptan is 0.8 part), initiator mixing solutions (10 parts of deionized waters, 1.2 parts of ammonium persulphates, 0.05 part, potassium hydroxide) and emulsifier solution (deionized water is 10 parts, disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate is 0.2 part, and isomery tridecyl fatty alcohol-polyoxyethylene ether-10 are 0.3 part).Controlling monomer and emulsifier solution time for adding is 4.5 hours, and initiator solution time for adding is 6 hours.After treating monomer dropping, be warming up to 95 ± 2 ℃, continue to maintain reaction until transformation efficiency is greater than 98%.
3) remove residual monomer and aftertreatment: transformation efficiency reaches 98% when above, stopped reaction, latex is turned and expected to stripping vessel, add appropriate initiator mixing solutions (10 parts of deionized waters, 0.2 part of ammonium persulphate, 0.75 part, potassium hydroxide), be-0.70MPa, to carry out vacuum flashing under the condition of 65 ℃ of still temperature degassed that the degassed time is 3 hours in degassed still vacuum tightness.Latex is after vacuum flashing is degassed, and unreacted divinyl removes completely, and when residual styrene content < 500ppm, slowly adding 20% potassium hydroxide solution to regulate pH value is 8.5.Finally be cooled to 40 ℃, the packing of discharging after filtering.
(2) the physical index test case of latex is as table 5:
Table 5
Embodiment 6:
(1) latex is produced
1) process that feeds intake: stir at a band, import and export of nitrogen, material import and export, in the 10L polymeric kettle of thermometric pressure tap and chuck, (first polymeric kettle vacuumizes, use again nitrogen replacement, when reach-0.10MPa of vacuum tightness) drop into respectively 60 parts of deionized waters, (deionized water is 10 parts to emulsifier solution, disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate is 0.1 part, isomery decyl fatty alcohol-polyoxyethylene ether-10 (ethoxymer distribution is 10) are 0.1 part), non-ionic type guar gum is 1.5 parts, 0.1 part of disodium ethylene diamine tetraacetate, 1.2 parts of methylene-succinic acids, then start to be warming up to 85 ℃.
2) reaction is controlled and is added: control 85 ± 2 ℃ of temperature, in polymeric kettle, add continuously monomer mixture (42 parts of divinyl, 54 parts of vinylbenzene, 2.8 parts of methacrylic acids, tertiary lauryl mercaptan is 0.8 part), initiator mixing solutions (10 parts of deionized waters, 1.2 parts of ammonium persulphates, 0.05 part, potassium hydroxide) and emulsifier solution (deionized water is 10 parts, disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate is 0.1 part, and isomery decyl fatty alcohol-polyoxyethylene ether-10 are 0.1 part).Controlling monomer and emulsifier solution time for adding is 4.5 hours, and initiator solution time for adding is 6 hours.After treating monomer dropping, be warming up to 95 ± 2 ℃, continue to maintain reaction until transformation efficiency is greater than 98%.
3) remove residual monomer and aftertreatment: transformation efficiency reaches 98% when above, stopped reaction, latex is turned and expected to stripping vessel, add appropriate initiator mixing solutions (10 parts of deionized waters, 0.2 part of ammonium persulphate, 0.75 part, potassium hydroxide), be-0.70MPa, to carry out vacuum flashing under the condition of 65 ℃ of still temperature degassed that the degassed time is 3 hours in degassed still vacuum tightness.Latex is after vacuum flashing is degassed, and unreacted divinyl removes completely, and when residual styrene content < 500ppm, slowly adding 20% potassium hydroxide solution to regulate pH value is 8.2.Finally be cooled to 40 ℃, the packing of discharging after filtering.
(2) the physical index test case of latex is as table 6:
Table 6
Embodiment 7:
(1) latex is produced
1) process that feeds intake: stir at a band, import and export of nitrogen, material import and export, in the 10L polymeric kettle of thermometric pressure tap and chuck, (first polymeric kettle vacuumizes, use again nitrogen replacement, when reach-0.10MPa of vacuum tightness) drop into respectively 60 parts of deionized waters, (deionized water is 10 parts to emulsifier solution, disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate is 0.1 part, isomery decyl fatty alcohol-polyoxyethylene ether-10 are 0.1 part, butyl fatty alcohol polyoxypropylene ether-2 are 0.1 part, non-ionic type guar gum is 2.0 parts), 0.06 part of tetrasodium ethylenediamine tetraacetate, 0.5 part of methylene-succinic acid, then start to be warming up to 85 ℃.
2) reaction is controlled and is added: control 85 ± 2 ℃ of temperature, in polymeric kettle, add continuously monomer mixture (40 parts of divinyl, 59 parts of vinylbenzene, 0.5 part, vinylformic acid, tertiary lauryl mercaptan is 0.8 part), initiator mixing solutions (10 parts of deionized waters, 1.2 parts of ammonium persulphates, 0.01 part, sodium hydroxide) and emulsifier solution (deionized water is 10 parts, disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate is 0.1 part, isomery decyl fatty alcohol-polyoxyethylene ether-10 are 0.1 part, and butyl fatty alcohol polyoxypropylene ether-2 are 0.1 part).Controlling monomer and emulsifier solution time for adding is 4.5 hours, and initiator solution time for adding is 6 hours.After treating monomer dropping, be warming up to 95 ± 2 ℃, continue to maintain reaction until transformation efficiency is greater than 98%.
3) remove residual monomer and aftertreatment: transformation efficiency reaches 98% when above, stopped reaction, latex is turned and expected to stripping vessel, add appropriate initiator mixing solutions (10 parts of deionized waters, 0.2 part of ammonium persulphate, 0.16 part, sodium hydroxide), be-0.70MPa, to carry out vacuum flashing under the condition of 65 ℃ of still temperature degassed that the degassed time is 3 hours in degassed still vacuum tightness.Latex is after vacuum flashing is degassed, and unreacted divinyl removes completely, and when residual styrene content < 500ppm, slowly adding 20% sodium hydroxide solution to regulate pH value is 8.7.Finally be cooled to 40 ℃, the packing of discharging after filtering.
(2) the physical index test case of latex is as table 7:
Table 7
Comparative example 1:
Adopt the method for embodiment 6, do not use non-ionic type guar gum in step 1, other raw material consumption and processing condition are identical, and the physical index of gained latex is as table 8:
Table 8
Table 8 can be found out, in this comparative example, owing to not using non-ionic type guar gum, only rely on methylene-succinic acid and the emulsifying agent of less consumption in step 1 to be difficult to the stable emulsifying effect that provides enough, cause polyreaction stability decreases, have more condensation product to occur, and the particle diameter of gained latex is thick, mechanical stability and chemical stability be obvious variation also.
Comparative example 2:
Adopt the method for embodiment 6, in step 1 and step 2, do not use anionic emulsifier disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate, nonionic emulsifying agent isomery decyl fatty alcohol-polyoxyethylene ether-10 consumption in step 1 and step 2 is increased to respectively to 0.2 part, other raw material consumption and processing condition are identical, and the physical index of gained latex is as table 9:
Table 9
Table 9 can be found out, in this comparative example, if do not use anionic emulsifier, and only depend on the nonionic emulsifying agent of same consumption and non-ionic type guar gum to be difficult to the stable emulsifying effect that provides enough, cause polyreaction stability obviously to decline, have more condensation product to occur, and the particle diameter of gained latex is thick, mechanical stability and chemical stability be obvious variation also.
Latex indices from above-mentioned comparative example can find out, its solid content is on the low side, and particle diameter is thick, and reaction stability, mechanical stability and chemical stability are all obviously worse than embodiment.Compared with embodiment, when the latex of being prepared by above-mentioned comparative example is applied to Paper Coating, because of the consistency of other components in itself and coating poor, mechanical stability and rheological are not good enough, in coating allotment and high-speed coating process, easily produce condensation product 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 White Board requirement, and then have affected the printing adaptability of White Board.
In order more clearly to express the raw material consumption of 7 embodiment and 2 comparative examples and the product performance that obtain, list with tabulated form below, in table 10.
The performance index of table 10 carboxylic styrene butadiene latex
Claims (7)
1. a carboxy styrene-butadiene latex special for coating paper, 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 adjusting agent and 100～150 parts of deionized waters;
Wherein, described 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 described unsaturated carboxylic acid function monomer is one or more in vinylformic acid, methacrylic acid and methylene-succinic acid;
Described compound emulsifying agent by anionic emulsifier and nonionic emulsifying agent with (1～2): the mass ratio of (1～3) is composited; Described anionic emulsifier is one or more in alkylbenzene sulfonate, alkyl-sulphate and alkyl phenol ether sulphonate; Described nonionic emulsifying agent is alkyl phenylate type or alkyl ether type;
Described polymer protection glue is selected from guar gum or Viscogum BE;
Described initiator adopts water-soluble thermolysis type persulfuric acid salt;
Described molecular weight regulator is sulfur alcohol compound;
Described pH adjusting agent is sodium hydroxide or potassium hydroxide;
Described sequestrant is disodium ethylene diamine tetraacetate or tetrasodium ethylenediamine tetraacetate;
When preparation, polymeric kettle through nitrogen replacement, vacuumize after, drop into respectively in composition of raw materials 30～90% deionized water, 10～50% emulsifying agent, 10～50% unsaturated carboxylic acid function monomer, polymer protection glue and sequestrant; Be warming up to after 80～90 ℃, in 1～6 hour, at the uniform velocity drip in divinyl and vinylbenzene, molecular weight regulator, remaining unsaturated carboxylic acid function monomer, composition of raw materials 60～90% initiator, 1～10% pH adjusting agent and remaining emulsifying agent; After monomer dropping, improve temperature of reaction to 90～100 ℃, continue reaction 1～3 hour; When participating in the total conversion rate of polymerization, monomer reaches 98.0% when above of monomer total mass, be cooled to 60～80 ℃, turn and expect to stripping vessel, add in remaining initiator and composition of raw materials 40～80% pH adjusting agent, controlling stripping vessel vacuum tightness is-0.07～-0.09MPa, and then degassed 3～5 hours of vacuum flashing continues with remaining pH adjusting agent adjust pH to 7～9, cool to 30～50 ℃, the packing of discharging after filtering.
2. carboxy styrene-butadiene latex special for coating paper according to claim 1, is characterized in that: described sulfur alcohol compound is n-dodecyl mercaptan or tertiary lauryl mercaptan.
3. carboxy styrene-butadiene latex special for coating paper according to claim 1, is characterized in that: described anionic emulsifier is one or more in C8～C18 sodium alkyl benzene sulfonate, C8～C18 sodium alkyl sulfate, C8～C18 alkyl two phenolic ether sodium disulfonates.
4. carboxy styrene-butadiene latex special for coating paper according to claim 1, is characterized in that: one or more in C4～C8 fatty alcohol polyoxypropylene ether that C8～C12 alkylphenol polyoxyethylene that described nonionic emulsifying agent selection ethoxymer distribution is 5～20, C8～C12 fatty alcohol-polyoxyethylene ether that ethoxymer distribution is 5～20 and propylene oxide adduct number are 2～10.
5. carboxy styrene-butadiene latex special for coating paper according to claim 1, is characterized in that: described polymer protection glue is non-ionic type guar gum, and 25 ℃, when 1% solid content, viscosity is 500～5000mPas.
6. carboxy styrene-butadiene latex special for coating paper according to claim 1, is characterized in that: the content of described carboxylic styrene butadiene latex residual styrene after vacuum flashing is degassed is 0～500ppm.
7. carboxy styrene-butadiene latex special for coating paper according to claim 1, 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 adjusting agent at the uniform velocity dropwised in 2～6 hours; Remaining emulsifying agent in 1～4 hour drip at the uniform velocity add complete.
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| CN103074802B (en) * | 2013-01-24 | 2015-03-18 | 陕西科技大学 | Preparation method for ultraviolet curing water-based paper varnish |
| CN106320068A (en) * | 2016-08-26 | 2017-01-11 | 枣阳市恒泰化工有限公司 | Carboxylic butadiene-styrene latex special for white paperboards |
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| CN107236081A (en) * | 2017-06-29 | 2017-10-10 | 襄阳福源兴盛科技有限公司 | A kind of carboxylic acid styrene-butadiene latex |
| CN107254020A (en) * | 2017-06-29 | 2017-10-17 | 襄阳福源兴盛科技有限公司 | A kind of carboxylic acid styrene-butadiene latex and its production method |
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| CN110483674B (en) * | 2019-07-18 | 2022-04-15 | 广东腾龙化工科技有限公司 | Butadiene-styrene copolymer latex for paper coating and preparation method and application thereof |
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| CN113388063A (en) * | 2021-08-04 | 2021-09-14 | 福建亮晶晶新材料有限公司 | Preparation method of polymer latex for papermaking |
| CN114957548A (en) * | 2022-07-07 | 2022-08-30 | 华东理工大学 | Preparation method of styrene-butadiene latex for coating synthetic paper |
| CN115260374B (en) * | 2022-09-14 | 2023-11-03 | 广东巴德富新材料有限公司 | High-water-resistance styrene-butadiene latex and rigid waterproof mortar coating using same |
| CN117004344A (en) * | 2023-10-07 | 2023-11-07 | 淄博奥固特科技有限公司 | Carboxyl styrene-butadiene latex for lithium battery cathode and preparation method thereof |
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