CN102115506A - Preparation method of large-grain size latex particles - Google Patents
Preparation method of large-grain size latex particles Download PDFInfo
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- CN102115506A CN102115506A CN2009102443925A CN200910244392A CN102115506A CN 102115506 A CN102115506 A CN 102115506A CN 2009102443925 A CN2009102443925 A CN 2009102443925A CN 200910244392 A CN200910244392 A CN 200910244392A CN 102115506 A CN102115506 A CN 102115506A
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Abstract
The invention relates to a preparation method of latex particles with grain sizes from 500nm to 1000nm. Agglomerating agent is copolymer of alkyl acrylate and carboxyl monomer, wherein the weight percentage of the carboxyl monomer is 3-60%, and the weight percentage of the alkyl acrylate is 97-40%; mixed emulsifying agent is fatty acid soap and alkane sulfonate, ferrous sulfate, rongalit, ethylenediaminetetraacetic acid tetrasodium salt and sodium hydrogensulfite are reducing agent, the reaction temperature is 75 DEG C, a first section of initiating agent is water-soluble initiating agent, a second section of initiating agent is oil-soluble initiating agent, and the average grain diameters are adjusted by cross-linking agent from 50 to 250nm to obtain the agglomerating agent; and the large-grain size latex comprises the components based on the parts by weight: 100 parts of the primary latex, 0.5-4 parts of the agglomerating agent, and 0.05-0.8 part of KOH solution under the agglomerating temperature of 20-80 DEG C. The method is used for preparing the large-grain size latex of synthetic resin, so that the low-temperature shock resistance of the resin can be improved, and the processed large-grain size latex can be used for producing the high-grade automobile lamp.
Description
Technical field:
The present invention relates to the latex particle preparation method of a kind of particle diameter 500nm～1000nm.
Background technology:
Usually less than 150nm, we are referred to as elementary latex with it with the latex polymer particles particle diameter of ordinary method preparation.The latex of this particle diameter can not satisfy the application requiring of many aspects, and the grafting trunk latex particle size of using as preparation ABS has required between 250～450nm, therefore, needs to adopt agglomeration method that small particle size is become large grain size latex.
The method for preparing large grain size latex is a lot, and freezing agglomeration technique, chemical agglomeration method, pressure agglomeration technique, polymer latex agglomeration technique are arranged.
Freezing agglomeration technique agglomeration particle diameter is uncontrollable, and big energy-consuming.
The chemical agglomeration method is difficult to prepare the latex of the above particle diameter of 400nm.
The pressure agglomeration technique also is difficult for the above latex of preparation 400nm.
Arbitrary target grain size latex in preparation 500～800nm scope.Need to solve two aspect problems, the one, the associated problem of the special-purpose agglomerant that solution preparation super-size latex is used, comprise agglomerant building-up reactions stability problem, reach stable reaction, heat release is easily controlled, analyse the few purpose of glue, solve the control of agglomerant particle diameter simultaneously, molecular weight control, and the agglomerant Synthesis conversion is low excessively, problems such as molecular structure control, solve agglomeration problem, comprise the agglomeration effect, the agglomeration speed issue, seek to improve the method for agglomeration rate, also will solve the particle diameter of large grain size latex, the viscosity controller problem solves agglomerating latex to the storage time, temperature, monomer, the stability problem of pH, solve large grain size latex blending stability, heat-resistant stability, alkaline-resisting stability problem, the 2nd, solve agglomerating latex grafting stability and the problems such as application in ABS makes.
Summary of the invention:
The large grain size latex particulate preparation method who the purpose of this invention is to provide a kind of particle diameter 500nm～1000nm.
The selected agglomerant of a kind of large grain size latex particulate preparation method of the present invention is the multipolymer of alkyl acrylate and carboxylic monomer, is emulsion state.
Carboxylic monomer is the monomer or the mix monomer of vinylformic acid, methacrylic acid, methylene-succinic acid.
Alkyl acrylate monomer is that the carbonatoms of alkyl is 2～12 monomer or mix monomer.
In the agglomerant, carboxylic monomer accounts for 3～60% of agglomerant weight, and when it was lower than 3%, the agglomeration ability drop was higher than 60%, and agglomeration power also descends.
In the agglomerant, alkyl acrylate accounts for 97～40% of agglomerant weight.
Agglomerant the best is the multipolymer of butyl acrylate and acrylic or methacrylic acid.
Use the synthetic agglomerant of fatty acid soaps and alkylsulfonate.Fatty acid soaps is sodium stearate, potassium stearate, sodium oleate or potassium oleate, sodium fat synthesis or potassium, and alkylsulfonate is Sodium dodecylbenzene sulfonate, sodium lauryl sulphate or dodecyl sulphate potassium, also can mix the use nonionogenic tenside.
Synthetic agglomerant can adopt various emulsion polymerisation process commonly used such as batch method, continuous processing.
Agglomerant latex particle size size is big to the influence of agglomeration ability.When agglomerant latex particle size during less than 50nm, agglomeration power is lower, when median size during greater than 250nm, and the latex instability of hole enlargement.The present invention regulates median size at 50～250nm with linking agent.
Linking agent is Vinylstyrene or allyl methacrylate(AMA) or O-phthalic allyl propionate, adds umber 0.3-1.5 part by weight.
The agglomerant that use makes carries out hole enlargement to polybutadiene latex, styrene-butadiene latex, nitrile rubber, can make the latex of any particle diameter in 500～1000nm scope, and average deviation is about ± 50nm.
Agglomeration prescription by weight: 100 parts in elementary latex, 0.5～4 part of agglomerant, 0.05～0.8 part of potassium hydroxide solution; 17～80 ℃ of agglomeration temperature.
A kind of large grain size latex particulate preparation method of the present invention utilizes the agglomeration of elementary small grain size latex particle to prepare the super-size latex of median size 500～1000nm, and preparation process is as follows:
(a) the agglomeration preparation of agglomerant
(1) agglomerant is the multipolymer of alkyl acrylate and carboxylic monomer, is emulsion state;
In the agglomerant, carboxylic monomer accounts for 3～60% of agglomerant weight, and alkyl acrylate accounts for 97～40% of agglomerant weight;
(2) mixing with emulsifying agent is fatty acid soaps and alkylsulfonate, and the two weight ratio is 2/ (0.3～1.5); Fatty acid soaps adds by weight, and 1.5-2.5 part, alkylsulfonate add 0.3-1.5 part by weight;
(3) use ferrous sulfate, Diao Bai piece, tetrasodium ethylenediamine tetraacetate, sodium bisulfite to be reductive agent; Add by weight: ferrous sulfate 0.001-0.01 part, Diao Bai piece 0.2-1.0 part, tetrasodium ethylenediamine tetraacetate 0.01-0.1 part, sodium bisulfite 0.1-0.7 part;
(4) temperature of reaction 60-90 ℃, one section initiator is a water soluble starter, adds 0.08-0.4 part by weight; Two sections initiators are oil-soluble initiator, add 0.02-0.2 part by weight;
(5) regulate median size at 50～250nm with linking agent, linking agent adds 0.3-1.5 part by weight;
(b) 500～1000nm super-size latex preparation method
(1) 20～80 ℃ of agglomeration temperature;
(2) agglomeration prescription by weight: 100 parts in elementary latex, 0.5～4 part of agglomerant, 0.05～0.8 part of potassium hydroxide solution.
Can carry out graft polymerization separately with 500～1000nm latex, also can with single stage method large grain size latex mixed grafting, the also large grain size latex mixed grafting that can make with the chemical agglomeration method, also can with small-particle latex mixed grafting.When being used to make ABS resin,, can in the latex of 240～260nm, add 10～15% 600nm latex particle in order to improve impact resistance.
The invention provides the preparation method of the super-size latex of a kind of particle diameter 500nm～1000nm.This method can be applicable to the synthetic production of synthetic resins industry large grain size latex, help the particle size growth control of latex particle, range of application is very extensive, can improve resin low temperature impact resistance, and the product that uses present method to produce can be used for the manufacturing of battle wagon light fixture after processing.
Embodiment
Embodiment 1
Agglomerant (F
1) preparation
Initial deionized water 1. 150
Potassium oleate 2.0
Sodium lauryl sulphate 1.0
Reductive agent deionized water 2. 10
Ferrous sulfate 0.005
Tetrasodium ethylenediamine tetraacetate 0.01
Diao Bai piece 0.32
Potassium Persulphate 1. 0.005
Deionized water 3. 40
Potassium Persulphate 2. 0.15
Mix monomer butyl acrylate 80
Methacrylic acid 20
Tert-dodecyl mercaptan 0.08
Dicumyl peroxide 0.1
75 ℃ of temperature of reaction, one section initiator is a Potassium Persulphate, two sections initiators are dicumyl peroxide, transformation efficiency 〉=95%, pH:5.4.
The large grain size latex preparation
Small grain size latex particle diameter 100nm 100
Agglomerant F
13.0
Stirring at room 0.5 hour makes 605nm latex.
The grafting of 605nm large grain size latex
Large grain size latex 60
St 30
AN 10
Tert-dodecyl mercaptan 0.3
Potassium oleate 0.5
Dicumyl peroxide 0.3
FeSO
4 0.004
Diao Bai piece 0.3
Tetrasodium ethylenediamine tetraacetate 0.02
Deionized water 3. 200
Grafting powder 28
Styrene-acrylonitrile copolymer 72
Make the ABS rerum natura
Melting index 20g/10min
Resistance to impact shock 184J/m
Tensile strength 43MPa
Rockwell hardness 103
84 ℃ of heat-drawn wires
Comparative Examples 1
Agglomerant (F
d) preparation
Deionized water 1. 150
Potassium oleate 2.0
Sodium lauryl sulphate 1.0
Deionized water 2. 10
FeSO
4 0.005
Tetrasodium ethylenediamine tetraacetate 0.01
Diao Bai piece 0.32
Dicumyl peroxide 0.4
Potassium Persulphate 0.2
75 ℃ of temperature of reaction, one section initiator is a dicumyl peroxide, two sections initiators are Potassium Persulphate, transformation efficiency 94%, pH:5.45.
The large grain size latex preparation
Small grain size latex particle diameter 100nm 100
Agglomerant F
D13.0
Stirring at room 1 hour makes the bimodal latex of 438nm macroparticle.
438nm latex grafting prescription is with 605nm latex
Blending granulation gained ABS rerum natura result
Melting index 23g/10min
Resistance to impact shock 200J/m
Tensile strength 44MPa
Rockwell hardness 104
85 ℃ of heat-drawn wires
Embodiment 2
Agglomerant (F
2) preparation
Deionized water 1. 150
Potassium oleate 2.0
Sodium lauryl sulphate 1.0
Deionized water 2. 10
Ferrous sulfate 0.005
Tetrasodium ethylenediamine tetraacetate 0.01
Diao Bai piece 0.32
Potassium Persulphate 0.15
Linking agent O-phthalic allyl propionate 1.0
Obtain the latex of pH 4.56, solid content 34.34%.
The large grain size latex preparation
Small grain size latex particle diameter 100nm 100
Agglomerant F
23.0
Stirring at room 1 hour makes 515nm macroparticle latex.
Comparative Examples 2C F
D2
1 one sections initiation dicumyl peroxides of embodiment are used Potassium Persulphate for two sections
PH5.45 as a result, solid content 33%
The agglomeration result
Small grain size latex particle diameter 100nm 100
Agglomerant F
D23.0
Stirring at room 1 hour makes 373nm latex, and size distribution is three peaks,
970nm/49.4％，178nm/44.8％，5200nm/5.8％。
600nm macroparticle latex is used
600nm latex (butt) 15
Common 240nm latex 85
Above-mentioned latex gained grafting powder and vinylbenzene-blending of acrylon multipolymer 28: 72
Rerum natura result
Melting index 9.0g/10min
Resistance to impact shock 415J/m
Tensile strength 45MPa
Rockwell hardness 106
89 ℃ of heat-drawn wires.
Claims (4)
1. a large grain size latex particulate preparation method utilizes the agglomeration of elementary small grain size latex particle to prepare the large grain size latex of median size 500～1000nm, it is characterized in that:
(a) preparation of the agglomerant used of agglomeration
(1) agglomerant is the multipolymer of alkyl acrylate and carboxylic monomer, is emulsion state;
In the agglomerant, carboxylic monomer accounts for 3～60% of agglomerant weight, and alkyl acrylate accounts for 97～40% of agglomerant weight;
(2) mixing with emulsifying agent is fatty acid soaps and alkylsulfonate, and the two weight ratio is 2/ (0.3～1.5); Fatty acid soaps adds by weight, and 1.5-2.5 part, alkylsulfonate add 0.3-1.5 part by weight;
(3) use ferrous sulfate, Diao Bai piece, tetrasodium ethylenediamine tetraacetate, sodium bisulfite to be reductive agent; Add by weight: ferrous sulfate 0.001-0.01 part, Diao Bai piece 0.2-1.0 part, tetrasodium ethylenediamine tetraacetate 0.01-0.1 part, sodium bisulfite 0.1-0.7 part;
(4) temperature of reaction is 75 ℃, and one section initiator is a water soluble starter, adds 0.08-0.4 part by weight; Two sections initiators are oil-soluble initiator, add 0.02-0.2 part by weight;
(5) regulate median size at 50～250nm with linking agent, linking agent adds 0.3-1.5 part by weight;
(b) 500～1000nm super-size latex preparation method
(1) 20～80 ℃ of agglomeration temperature;
(2) agglomeration prescription by weight: 100 parts in elementary latex, 0.5～4 part of agglomerant, 0.05～0.8 part of KOH solution.
2. a kind of large grain size latex particulate preparation method according to claim 1 is characterized in that: carboxylic monomer is the monomer or the mix monomer of vinylformic acid, methacrylic acid, methylene-succinic acid;
3. a kind of large grain size latex particulate preparation method according to claim 1 is characterized in that: alkyl acrylate monomer is that the carbonatoms of alkyl is 2～12 monomer or mix monomer.
4. a kind of large grain size latex particulate preparation method according to claim 1, it is characterized in that: agglomerant is the multipolymer of butyl acrylate and methacrylic acid.
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103497282B (en) * | 2013-09-27 | 2016-02-10 | 安庆华兰科技有限公司 | A kind of preparation method of agglomeration graft modification Powdered acrylonitrile-butadiene rubber |
| CN106029772A (en) * | 2013-12-23 | 2016-10-12 | 阿朗新科新加坡私人有限公司 | Novel anti-agglomerants for the rubber industry |
| CN106632814A (en) * | 2016-10-10 | 2017-05-10 | 长春工业大学 | Preparation method of polymer emulsion with large particle size, narrow distribution range and high solid content |
| US10385200B2 (en) | 2014-06-30 | 2019-08-20 | Arlanxeo Singapore Pte. Ltd. | Anti-agglomerants for the rubber industry |
| CN110183576A (en) * | 2019-06-04 | 2019-08-30 | 万华化学集团股份有限公司 | A kind of emulsifier, preparation method and the application of the production polybutadiene latex can be used for agglomeration |
| CN110770268A (en) * | 2018-05-16 | 2020-02-07 | 株式会社Lg化学 | Method for producing conjugated diene polymer and method for producing graft copolymer comprising the conjugated diene polymer |
| US10584195B2 (en) | 2013-12-23 | 2020-03-10 | Arlanxeo Singapore Pte. Ltd. | Ultra pure rubber |
| US10647842B2 (en) | 2013-12-23 | 2020-05-12 | Arlanxeo Singapore Pte. Ltd. | Anti-agglomerants for elastomeric ethylene/A-olefin copolymers |
| US10703865B2 (en) | 2013-12-23 | 2020-07-07 | Arlanxeo Singapore Pte. Ltd. | Highly pure halogenated rubbers |
| CN115057956A (en) * | 2022-06-28 | 2022-09-16 | 万华化学集团股份有限公司 | Agglomeration method of polybutadiene latex with high solid content and narrow distribution and application thereof |
| CN117024659A (en) * | 2023-09-11 | 2023-11-10 | 河南大树实业有限公司 | Preparation method of large-particle-size high-solid-content styrene-butadiene latex |
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| CN103497282B (en) * | 2013-09-27 | 2016-02-10 | 安庆华兰科技有限公司 | A kind of preparation method of agglomeration graft modification Powdered acrylonitrile-butadiene rubber |
| US10647842B2 (en) | 2013-12-23 | 2020-05-12 | Arlanxeo Singapore Pte. Ltd. | Anti-agglomerants for elastomeric ethylene/A-olefin copolymers |
| US10889671B2 (en) | 2013-12-23 | 2021-01-12 | Arlanxeo Singapore Pte. Ltd. | Ultra pure rubber and method thereof |
| US11827753B2 (en) | 2013-12-23 | 2023-11-28 | Arlanxeo Singapore Pte. Ltd. | Highly pure halogenated rubbers |
| CN106029772A (en) * | 2013-12-23 | 2016-10-12 | 阿朗新科新加坡私人有限公司 | Novel anti-agglomerants for the rubber industry |
| US10703865B2 (en) | 2013-12-23 | 2020-07-07 | Arlanxeo Singapore Pte. Ltd. | Highly pure halogenated rubbers |
| US10584195B2 (en) | 2013-12-23 | 2020-03-10 | Arlanxeo Singapore Pte. Ltd. | Ultra pure rubber |
| CN106029772B (en) * | 2013-12-23 | 2020-03-24 | 阿朗新科新加坡私人有限公司 | Novel anti-agglomerants for the rubber industry |
| US10611886B2 (en) | 2013-12-23 | 2020-04-07 | Arlanxeo Singapore Pte. Ltd. | Anti-agglomerants for the rubber industry |
| US11584815B2 (en) | 2013-12-23 | 2023-02-21 | Arlanxeo Singapore Pte. Ltd. | Sealant comprising a polymeric composition including a lower critical solution temperature compound |
| US10385200B2 (en) | 2014-06-30 | 2019-08-20 | Arlanxeo Singapore Pte. Ltd. | Anti-agglomerants for the rubber industry |
| CN106632814A (en) * | 2016-10-10 | 2017-05-10 | 长春工业大学 | Preparation method of polymer emulsion with large particle size, narrow distribution range and high solid content |
| CN110770268A (en) * | 2018-05-16 | 2020-02-07 | 株式会社Lg化学 | Method for producing conjugated diene polymer and method for producing graft copolymer comprising the conjugated diene polymer |
| US11286314B2 (en) | 2018-05-16 | 2022-03-29 | Lg Chem, Ltd. | Method for preparing conjugated diene-based polymer and method for preparing graft copolymer including the same |
| CN110770268B (en) * | 2018-05-16 | 2022-05-13 | 株式会社Lg化学 | Method for producing conjugated diene polymer and method for producing graft copolymer comprising the conjugated diene polymer |
| CN110183576A (en) * | 2019-06-04 | 2019-08-30 | 万华化学集团股份有限公司 | A kind of emulsifier, preparation method and the application of the production polybutadiene latex can be used for agglomeration |
| CN110183576B (en) * | 2019-06-04 | 2021-10-22 | 万华化学(四川)有限公司 | Emulsifying agent for producing polybutadiene latex capable of being used for agglomeration, preparation method and application thereof |
| CN115057956A (en) * | 2022-06-28 | 2022-09-16 | 万华化学集团股份有限公司 | Agglomeration method of polybutadiene latex with high solid content and narrow distribution and application thereof |
| CN117024659A (en) * | 2023-09-11 | 2023-11-10 | 河南大树实业有限公司 | Preparation method of large-particle-size high-solid-content styrene-butadiene latex |
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Application publication date: 20110706 |