CN105294947A - Preparing method for high-performance styrene-butadiene latex for papermaking - Google Patents
Preparing method for high-performance styrene-butadiene latex for papermaking Download PDFInfo
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- CN105294947A CN105294947A CN201510679768.0A CN201510679768A CN105294947A CN 105294947 A CN105294947 A CN 105294947A CN 201510679768 A CN201510679768 A CN 201510679768A CN 105294947 A CN105294947 A CN 105294947A
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Abstract
The invention discloses a preparing method for high-performance styrene-butadiene latex for papermaking. The nucleocapsid emulsion polymerization technology is adopted for the latex, seed latex A with the particle size ranging from 40 to 60 nm and seed latex B with the particle size ranging from 80 to 100 nm serve as seed latex, auxiliaries such as a dispersing agent (such as AMP, DMAE, KTPP and a polyatomic acid homopolymer) and an environment-friendly cross-linking agent (such as AAEM, DAAM and ADH) are added, deionized water serves as a dispersing medium, butadiene and styrene serve as main monomers, a composite emulsification system of a reaction type emulsifier (such as allyl ether sulfonate, acrylamido sulfonate and maleic acid derivatives) and an anionic emulsifier (lauryl sodium sulfate) is adopted, and the doublet feature of the particle size of styrene-butadiene latex obtained through polymerization is achieved. Styrene-butadiene latex obtained through the method is good in water tolerance and weather fastness, has good mechanical stability and chemical stability, is good in smoothness and is improved in bonding strength when used for coating in papermaking and has remarkable advantages on the aspects of covering power and ink absorbing performance.
Description
Technical field
The present invention relates to a kind of preparation method of paper grade (stock) high-performance styrene-butadiene latex, be mainly used in the face of the paper products such as decorating base paper, abrasion-proof paper, medium-to-high grade art paper, white board, paperboard, boxboard, primary coat cloth.Also can be used for the tackiness agent etc. of other field, belong to the technical field of emulsion polymerization in macromolecular material.
Background technology
Styrene-butadiene latex is widely used in paper coating, play the effect of bonding, common styrene-butadiene latex, after emulsion film forming, is difficult to compatible with polymer body, the surface easily moving to film or the interface be connected with base material, and the water tolerance of film is deteriorated, and and sticking power between base material be deteriorated, oil suction ink is poor, styrene-butadiene latex prepared by existing technology can have higher stability, but the water tolerance of emulsion film forming, adhesion property, oil suction ink, and cohesive strength is not ideal enough.
The method of current domestic synthesis styrene-butadiene latex, general use unsaturated acyl amine monomers, adopt the compound system of anionic emulsification system or nonionic and anionic emulsifier, emulsifying power is low, consumption is large, also affect simultaneously latex use properties (such as: the stability of latex admixtion, water resisting property, time degree of becoming sticky, wet adhesive bonding intensity, ink absorption and slickness etc.).Some adopts a large amount of vinyl unsaturated carboxylic acids, and unsaturated amides improves its stability, but the latex prepared so often occurs some problems in Paper Coating process, and as the thermo-responsive reduction of latex, latex is in paper making and cloth coating medium viscosity increase etc.
In recent years, along with the requirement of printing industry to paper is more and more higher, the development of paper industry is more and more faster, and compete also more and more fierce, latex is one of topmost raw material as paper making additive, and the qualitative performance requirements of paper industry to latex is more and more higher.For many years, the research of latex quality improvement aspect is constantly carried out in countries in the world, have developed a series of high-performance styrene-butadiene latex for paper industry, has delivered a large amount of related articles and patent.The domestic mechanism that carries out the research that styrene-butadiene latex is correlated with is also few, and the correlative theses delivered and patent number few, the synthesis technique of latex control and formula all fairly simple.For the situation of current domestic styrene-butadiene latex capability and performance relative deficiency, our company, through research and development in recent years and technological accumulation, have developed a kind of paper grade (stock) high-performance styrene-butadiene latex.
Summary of the invention
The object of this invention is to provide the preparation method preparing a kind of paper grade (stock) high-performance styrene-butadiene latex, this particle diameter distribution of latex is bimodal distribution, modest viscosity, preparation coating out, flowing property is excellent, is very suitable for the coating preparing high-content, is mainly used in the primary coat of all kinds of paper product such as enamelled paper, white board, face is coated with coating, smoothness is good, and gives White Board with higher glossiness, pigment bonding strength, surperficial water resisting property and good printing adaptability (as ink absorption).Styrene-butadiene latex prepared by this technology except can having higher stability, the water tolerance of emulsion film forming, adhesion property, and cohesive strength has good raising.
For realizing object of the present invention, the technical scheme of employing is:
A preparation method for paper grade (stock) high-performance styrene-butadiene latex, raw material (parts by weight) composed as follows:
Deionized water: 90 ~ 110 parts;
Divinyl: 50 ~ 70 parts;
Vinylbenzene: 30 ~ 50 parts;
Seed latex A:3 ~ 5 part;
Seed latex B:3 ~ 5 part;
Environment-friendly type linking agent: 2 ~ 5 parts;
Dispersion agent: 1 ~ 3 part;
Anionic emulsifier: 1 ~ 3 part;
Reactive emulsifier: 1 ~ 3 part;
Initiator: 0.2 ~ 0.8 part;
Molecular weight regulator: 0.2 ~ 0.6 part;
Ionogen needed for letex polymerization, sequestrant, PH buffer reagent;
Production process is as follows:
(1) seed latex A: polymeric kettle vacuumizes rear input soft water, whole emulsifying agents, molecular weight regulator, PH buffer reagent, and whole monomer, after being warmed up to 60 ~ 80 DEG C, drip initiator 3 ~ 4 hours, 80 DEG C are incubated 2 ~ 3 hours, and transformation efficiency reaches after more than 98%, cool to 30 DEG C with bottom discharge, obtained seed latex A;
(2) seed latex B: polymeric kettle vacuumizes rear input soft water, whole emulsifying agent, molecular weight regulator, PH buffer reagent, and whole monomer, after being warmed up to 40 ~ 60 DEG C, add whole initiators, react 10 ~ 15 hours, transformation efficiency reaches after more than 98%, cool to 30 DEG C with bottom discharge, obtained seed latex B;
(3) paper grade (stock) styrene-butadiene latex:
1. in material-compound tank, drop into 30 ~ 50 parts of deionized waters, whole anionic emulsifiers, reactive emulsifier, molecular weight regulator, PH buffer reagent, ionogen, sequestrant, dispersion agent and environment-friendly type linking agent, stir 1 ~ 2 hour, be mixed with the pre-emulsion of aqueous phase;
2., after polymeric kettle vacuumizes, drop into the deionized water of 50 ~ 70 parts, account for the pre-emulsion of whole aqueous phase 20 ~ 30%, account for 10 ~ 30% divinyl and the vinylbenzene of whole monomer total amount, be warmed up to 70 ~ 80 DEG C, add the initiator accounting for total amount 20 ~ 40%, react 1 hour;
3. drip residual monomer and pre-emulsion, initiator, control temperature is at 90 ~ 95 DEG C, and the time is 2 ~ 4 hours, drips off simultaneously simultaneously;
4. be warming up to 95 DEG C, insulation reaction, after 2 ~ 3 hours, adds terminator;
5. temperature drops to less than 40 DEG C, adds liquid caustic soda, regulates between pH value to 7 ~ 9, discharging, filters, packaging, obtained paper grade (stock) styrene-butadiene latex.
In one embodiment, seed latex A used is the styrene-butadiene latex of 40 ~ 60nm, and mass fraction is 3%-5%, the raw material used by seed latex A and massfraction as follows:
In one embodiment, seed latex B used is the styrene-butadiene latex of 80 ~ 100nm, and mass fraction is 3%-5%, the raw material used by seed latex B and massfraction as follows:
In one embodiment, dispersion agent is AMP (2-amino-2-methyl-1-propanol), DMAE (dimethyl-1-amino-1-ethanol), KTPP (Potassium tripolyphosphate), and polyprotonic acid homopolymer one or more mixtures wherein.
In one embodiment, environment-friendly type linking agent uses AAEM (methacrylic acid acetoxyethyl), DAAM (diacetone-acryloamide(DAA)), and ADH (adipic dihydrazide), one or more mixtures wherein.
In one embodiment, reactive emulsifier comprises allyl ether series sulfonate, acrylamido sulfonate, and one or more mixtures of maleic acid derivatives.
In one embodiment, the composite emulsifying system of reactive emulsifier and anionic emulsifier is used.
Beneficial effect of the present invention: prior art is compared, the present invention adopts two particle diameter seed glue, and prepared styrene-butadiene latex is bimodal distribution, during for paper making and cloth coating, good fluidity, strong covering power, ink absorption is moderate, good with the mixed stability of pigment; Dispersion agent used in the present invention, improve the dispersion stabilization of seed latex and improve reactive polymeric stability, in latex, particulate matter is few, and the mobility under mechanical stability and high-shear is outstanding; Environment-friendly type linking agent used in the present invention, not only increases the cohesive strength after styrene-butadiene latex coating, and formaldehydeless releasing in drying process, has the feature of environmental protection; The present invention also uses the compound system of reactive emulsifier and anionic emulsifier, not only ensure that the stable of polymerization reaction system, and greatly reduces the residual of emulsifying agent in styrene-butadiene latex product, and after making coating, paper has good water resistance.
Embodiment
Seed latex A: formula following (weight part), polymeric kettle vacuumizes rear input soft water, whole emulsifying agents, molecular weight regulator, PH buffer reagent, with whole monomer, after being warmed up to 72 DEG C, drip initiator 3 hours, 80 DEG C are incubated 3 hours, transformation efficiency reaches after more than 98%, cools to 30 DEG C with bottom discharge.
Seed latex B: formula following (weight part), polymeric kettle vacuumizes rear input soft water, whole emulsifying agent, molecular weight regulator, PH buffer reagent, with whole monomer, after being warmed up to 40 ~ 60 DEG C, add whole initiators, react 10 ~ 15 hours, transformation efficiency reaches after more than 98%, cools to 30 DEG C with bottom discharge.
The preparation I of pre-emulsion: feed intake according to following formula:
A small amount of ionogen, sequestrant, PH buffer reagent, adds material-compound tank and stirs 1 hour, for subsequent use.
The preparation II of pre-emulsion: feed intake according to following formula:
A small amount of ionogen, sequestrant, PH buffer reagent, adds material-compound tank and stirs 1.5 hours, for subsequent use.
The preparation III of pre-emulsion: feed intake according to following formula:
A small amount of ionogen, sequestrant, PH buffer reagent, adds material-compound tank and stirs 1.5 hours, for subsequent use.
Embodiment 1:
The polymeric kettle of 300L first vacuumizes, vacuum tightness reaches-0.1MPa, according to dropping into soft water 64KG, pre-emulsion I12KG, 5.0KG divinyl, 5.0KG vinylbenzene, heat up, when temperature reaches 85 DEG C, add the initiator of 20%-30%, react 1 hours, then drip the component of following formula ratio simultaneously:
Time for adding 2.5 hours, during dropping, control temperature is at about 92 DEG C.Temperature is raised to 92 DEG C of insulation reaction 3 hours, when transformation efficiency reaches more than 99%, carry out degassed process, remove unreacted monomer, add terminator, cool to less than 40 DEG C, add alkali lye and regulate between pH value to 7 ~ 9, discharging is packed, the i.e. paper grade (stock) high-performance styrene-butadiene latex of obtained a kind of excellent performance, solid content 49.2%, viscosity 215cps, its physical property measurement the results are shown in subordinate list.
Embodiment 2:
The polymeric kettle of 300L first vacuumizes, vacuum tightness reaches-0.1MPa, according to dropping into soft water 65KG, pre-emulsion II14KG, 8.0KG divinyl, 8.0KG vinylbenzene, heat up, when temperature reaches 85 DEG C, add the initiator of 20%-30%, react 1 hours, then drip the component of following formula ratio simultaneously:
Time for adding 3 hours, during dropping, control temperature is at about 95 DEG C.95 DEG C of insulation reaction 2 hours, when transformation efficiency reaches more than 99%, carry out degassed process, remove unreacted monomer, add terminator, be cooled to less than 40 DEG C, add alkali lye and regulate between pH value to 7 ~ 9, discharging is packed, the i.e. paper grade (stock) high-performance styrene-butadiene latex of obtained a kind of excellent performance, solid content 50.1%, viscosity 195cps, its physical property measurement the results are shown in subordinate list.
Embodiment 3:
The polymeric kettle of 300L first vacuumizes, and vacuum tightness reaches-0.1MPa, according to dropping into soft water 67KG, pre-emulsion III15KG, 12KG divinyl, 4KG vinylbenzene, heats up, when temperature reaches 85 DEG C, add the initiator of 20%-30%, react 1 hours, then drip the component of following formula ratio simultaneously:
Time for adding 3 hours, during dropping, control temperature is at about 92 DEG C.Temperature rises to 92 DEG C of insulation reaction 3 hours, when transformation efficiency reaches more than 99%, carry out degassed process, remove unreacted monomer, add terminator, be cooled to less than 40 DEG C, add alkali lye and regulate between pH value to 7 ~ 9, discharging is packed, the i.e. paper grade (stock) high-performance styrene-butadiene latex of obtained a kind of excellent performance, solid content 49.8%, viscosity 210cps, its physical property measurement the results are shown in subordinate list.
Embodiment 4 ~ 5 sees attached list.
The testing method accepted standard of latex is as follows:
Table 1
Table 2
Claims (7)
1. a preparation method for paper grade (stock) high-performance styrene-butadiene latex, is characterized in that:
Raw material (parts by weight) composed as follows:
Deionized water: 90 ~ 110 parts;
Divinyl: 50 ~ 70 parts;
Vinylbenzene: 30 ~ 50 parts;
Seed latex A:3 ~ 5 part;
Seed latex B:3 ~ 5 part;
Environment-friendly type linking agent: 2 ~ 5 parts;
Dispersion agent: 1 ~ 3 part;
Anionic emulsifier: 1 ~ 3 part;
Reactive emulsifier: 1 ~ 3 part;
Initiator: 0.2 ~ 0.8 part;
Molecular weight regulator: 0.2 ~ 0.6 part;
Ionogen needed for letex polymerization, sequestrant, PH buffer reagent;
Production process is as follows:
(1) seed latex A: polymeric kettle vacuumizes rear input soft water, whole emulsifying agents, molecular weight regulator, PH buffer reagent, and whole monomer, after being warmed up to 60 ~ 80 DEG C, drip initiator 3 ~ 4 hours, 80 DEG C are incubated 2 ~ 3 hours, and transformation efficiency reaches after more than 98%, cool to 30 DEG C with bottom discharge, obtained seed latex A;
(2) seed latex B: polymeric kettle vacuumizes rear input soft water, whole emulsifying agent, molecular weight regulator, PH buffer reagent, and whole monomer, after being warmed up to 40 ~ 60 DEG C, add whole initiators, react 10 ~ 15 hours, transformation efficiency reaches after more than 98%, cool to 30 DEG C with bottom discharge, obtained seed latex B;
(3) paper grade (stock) styrene-butadiene latex:
1. in material-compound tank, drop into 30 ~ 50 parts of deionized waters, whole anionic emulsifiers, reactive emulsifier, molecular weight regulator, PH buffer reagent, ionogen, sequestrant, dispersion agent and environment-friendly type linking agent, stir 1 ~ 2 hour, be mixed with the pre-emulsion of aqueous phase;
2., after polymeric kettle vacuumizes, drop into the deionized water of 50 ~ 70 parts, account for the pre-emulsion of whole aqueous phase 20 ~ 30%, account for 10 ~ 30% divinyl and the vinylbenzene of whole monomer total amount, be warmed up to 70 ~ 80 DEG C, add the initiator accounting for total amount 20 ~ 40%, react 1 hour;
3. drip residual monomer and pre-emulsion, initiator, control temperature is at 90 ~ 95 DEG C, and the time is 2 ~ 4 hours, drips off simultaneously simultaneously;
4. be warming up to 95 DEG C, insulation reaction, after 2 ~ 3 hours, adds terminator;
5. temperature drops to less than 40 DEG C, adds liquid caustic soda, regulates between pH value to 7 ~ 9, discharging, filters, packaging, obtained paper grade (stock) styrene-butadiene latex.
2. paper grade (stock) high-performance styrene-butadiene latex preparation method according to claim 1, is characterized in that: seed latex A used is the styrene-butadiene latex of 40 ~ 60nm, and mass fraction is 3%-5%, the raw material used by seed latex A and massfraction as follows:
3. paper grade (stock) high-performance styrene-butadiene latex preparation method according to claim 1, is characterized in that: seed latex B used is the styrene-butadiene latex of 80 ~ 100nm, and mass fraction is 3%-5%, the raw material used by seed latex B and massfraction as follows:
4. paper grade (stock) high-performance styrene-butadiene latex preparation method according to claim 1, is characterized in that: dispersion agent is AMP, DMAE, KTPP, and polyprotonic acid homopolymer one or more mixtures wherein.
5. paper grade (stock) high-performance styrene-butadiene latex preparation method according to claim 1, is characterized in that: environment-friendly type linking agent uses AAEM, DAAM, and ADH, one or more mixtures wherein.
6. paper grade (stock) high-performance styrene-butadiene latex preparation method according to claim 1, is characterized in that: reactive emulsifier comprises allyl ether series sulfonate, acrylamido sulfonate, and one or more mixtures of maleic acid derivatives.
7. paper grade (stock) high-performance styrene-butadiene latex preparation method according to claim 1, is characterized in that: the composite emulsifying system using reactive emulsifier and anionic emulsifier.
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| CN106699968A (en) * | 2016-11-23 | 2017-05-24 | 厦门大学 | Method for preparing nanosilicon dioxide modified styrene-butadiene latex |
| CN106699969A (en) * | 2016-11-23 | 2017-05-24 | 厦门大学 | Preparation method of styrene-butadiene latex with controlled particle size |
| CN106749822A (en) * | 2016-11-30 | 2017-05-31 | 杭州蓝诚新材料有限公司 | Modified butadiene-styrene latex and preparation method thereof |
| CN108440701A (en) * | 2018-02-26 | 2018-08-24 | 江苏共创人造草坪有限公司 | A kind of chinampa high-performance carboxyl styrene emulsion |
| CN108440719A (en) * | 2018-03-26 | 2018-08-24 | 杭州蓝励新材料有限公司 | Styrene-butadiene latex for paper coating, seed latex and preparation method thereof |
| CN110698592A (en) * | 2019-10-25 | 2020-01-17 | 安庆华兰科技有限公司 | Styrene-butadiene latex for latex foaming and preparation method thereof |
| CN112574358A (en) * | 2020-12-09 | 2021-03-30 | 湖北分聚新材料有限公司 | Preparation method of bimodal distribution high-solid-content styrene-butadiene latex |
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| CN106699968A (en) * | 2016-11-23 | 2017-05-24 | 厦门大学 | Method for preparing nanosilicon dioxide modified styrene-butadiene latex |
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| CN108440701B (en) * | 2018-02-26 | 2020-11-24 | 江苏共创人造草坪股份有限公司 | High-performance carboxylic styrene-butadiene emulsion for artificial lawn |
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| CN108440719B (en) * | 2018-03-26 | 2020-06-05 | 杭州蓝励新材料有限公司 | Styrene-butadiene latex for paper coating, seed latex and preparation method thereof |
| CN110698592A (en) * | 2019-10-25 | 2020-01-17 | 安庆华兰科技有限公司 | Styrene-butadiene latex for latex foaming and preparation method thereof |
| CN112574358A (en) * | 2020-12-09 | 2021-03-30 | 湖北分聚新材料有限公司 | Preparation method of bimodal distribution high-solid-content styrene-butadiene latex |
| CN113999573A (en) * | 2021-11-25 | 2022-02-01 | 亚士防水科技(滁州)有限公司 | Water-based paint and preparation method and application thereof |
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Application publication date: 20160203 |