CN1112381C - Novel environment protection acrylonitrile emulsion, preparation process and use thereof - Google Patents
Novel environment protection acrylonitrile emulsion, preparation process and use thereof Download PDFInfo
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- CN1112381C CN1112381C CN 99123833 CN99123833A CN1112381C CN 1112381 C CN1112381 C CN 1112381C CN 99123833 CN99123833 CN 99123833 CN 99123833 A CN99123833 A CN 99123833A CN 1112381 C CN1112381 C CN 1112381C
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Abstract
The present invention relates to a method of polymerizing emulsion, which is used for preparing a novel environment-protection acrylonitrile emulsion. In a preparing process, a method of adding monomers and initiator in a reaction process step by step is adopted; a method of emulsifying monomers in a water solution and then adding initiator for initiating polymerization is also adopted; the obtained polymerization emulsion can be also used as the base material of emulsion print, adhesive for adhering wood, paper and fiber products, cement replacing polyvinyl alcohol and EVA glue and an interfacial agent of concrete; furthermore, the obtained polymerization emulsion can be also used as slush-coating imitation porcelain, whitewash, cement putty, etc.; the obtained polymerization emulsion is remarkably superior to various emulsions of the prior art, polyvinyl alcohol and 107 glue in properties.
Description
The present invention relates to a kind of polymer emulsion, particularly the preparation method of polyacrylonitrile emulsion and purposes belong to field of polymer technology.
In the prior art, polymer emulsion mainly be other unsaturated monomer copolymerization such as polyvinyl acetate emulsion, acrylic ester emulsion, styrene-butadiene emulsion, vinyl acetate between to for plastic and acrylate or ethene etc. and and the emulsion of urethane, above-mentioned polymer latex all adopts method of emulsion polymerization to obtain, and reaction is an initiator with persulphate or hydrogen peroxide generally.Carry out in order to make stable polymerization reaction, can adopt the method that in reaction process, progressively adds monomer and initiator, also can be earlier with monomer emulsification in the presence of emulsifying agent, the method that adds the initiator initiated polymerization again, the former can fine control heat balance, reacting balance is carried out, but operate loaded down with trivial details, the latter is owing in the inductive phase of reaction fierceness later, be difficult to obtain high-quality emulsion; The said products has peculiar smell and the high problem of cost in addition, easily environment is polluted.Polymer emulsion mainly is used as the base-material of emulsion paint, but by the emulsion paint of polymer emulsion preparation owing to be subjected to the restriction of base-material, have shortcoming water-fast, fast light, the alkali resistance difference.Therefore seek that the preparation method is simple, cost is low, excellent performance, nontoxic, free of contamination polymer emulsion be a very significant problem.
Polyacrylonitrile mainly is used as fiber, adopts the method polymerization of body or suspension usually.Disclose among CN85102368 and the CN85104179 by the poly-method of emulsion and prepared monomeric multipolymers such as chloroprene, vinylformic acid, acrylate, vinylbenzene and vinyl cyanide, the finishing composition, building, fiber, the textile printing and dyeing tamanori that are used for leather, but the polyacrylonitrile emulsion that letex polymerization obtains is not appeared in the newspapers as yet.
The object of the present invention is to provide a kind of polymer emulsion, particularly the polyacrylonitrile emulsion.
Another object of the present invention is to provide a kind of polymer emulsion, particularly the preparation method of polyacrylonitrile emulsion.
A further object of the present invention is to provide a kind of polymer emulsion, particularly the purposes of polyacrylonitrile emulsion aspect tamanori, coating.
To achieve these goals, the technical solution used in the present invention be with acrylonitrile monemer in the aqueous solution, there are letex polymerization down in emulsifying agent and initiator, obtain the polyacrylonitrile emulsion.
The technology of above-mentioned reaction can adopt the method that progressively adds monomer and initiator in the reaction process, also can adopt elder generation with monomer emulsification in the aqueous solution, adds the method for initiator initiated polymerization again.
The ratio of above-mentioned monomer and water is 1: 2-8,
The consumption of above-mentioned initiator is monomeric 0.05-2%.
The temperature of above-mentioned reaction is controlled at 40-95 ℃.
The initiator of above-mentioned reaction can be selected over cure acids initiator for use, as Potassium Persulphate, hydrogen persulfate; Also can select hydrogen peroxide for use, and be fit to other water-soluble peroxide initiators of the present invention; Can also select redox initiator such as persulphate-Sodium Metabisulphate 65 for use and be fit to other redox initiation system of the present invention; The redox initiation system that particularly adds Sodium Silicofluoride, reaction is control easily.
The emulsifying agent of above-mentioned reaction can be selected negatively charged ion, positively charged ion and nonionic surface active agent for use, as alkylphenol polyoxyethylene, OP/TX-10, peregal, sodium lauryl sulphate, Sodium dodecylbenzene sulfonate, penetrant t, polyvinyl alcohol etc.Wherein, OP/TX-10 is the ethylene oxide condensate of alkylphenol.
The reaction times of above-mentioned reaction is 2-8 hour.
If desired, can add defoamer and anticorrosion and bactericidal agent in the above-mentioned reaction.
The viscosity of products therefrom is 1000-10000CPS.
Because in the aqueous solution, vinyl cyanide and low-molecular-weight polypropylene nitrile are easy to hydrolysis under acidic conditions, thus the polyacrylonitrile emulsion that obtains by above-mentioned reaction method actual be polyacrylonitrile and polyacrylic copolymer emulsion, structure can be schematically as follows:
This polyacrylonitrile emulsion with vinyl cyanide and acrylic acid copolymer structure has the advantage of the two performance concurrently, is used as the base-material of emulsion paint, the performance of prepared emulsion paint obviously is better than the various emulsion paints of prior art, product is nonpoisonous and tasteless, and the preparation method is simple, and cost is lower than existing emulsion paint.
Polyacrylonitrile emulsion of the present invention can also replace Virgin's milk liquid or polyvinyl alcohol to be used for bonding timber, paper and fibre product; Can also be as cement, concrete interfacial agents; The imitative magnetic of blade coating, Da Bai, cement plaster etc. can also be used for, the electronic industry tamanori can be used as in addition.
In a word, the present invention adopts method of emulsion polymerization, prepared a kind of novel environment friendly polyacrylonitrile emulsion, in preparation process, promptly can adopt the method that in reaction process, progressively adds monomer and initiator, also can adopt elder generation with monomer emulsification in the aqueous solution, add the method for initiator initiated polymerization again; The polymer emulsion that obtains can be used as the base-material of emulsion paint; The tamanori of bonding timber, paper and fibre product; Can also replace polyvinyl alcohol, EVA glue as cement, concrete interfacial agents; Can be used for the imitative magnetic of blade coating, Da Bai, cement plaster etc. in addition, performance obviously is better than the various emulsions and the tamanori of prior art.
Describe the present invention in detail below in conjunction with embodiment.
Embodiment one
With purity is that 99% polyacrylonitrile 100kg adds in the reactor, add 200kg water, stir down and heat up, to 40 ℃, add ammonium persulfate 0.05kg, S-WAT 0.05kg, polyoxyethylene octylphenol ether 2kg, reacted 8 hours, and adjusted PH to neutral with sodium hydroxide, obtaining viscosity is the polyacrylonitrile emulsion of 9000CPS.
Embodiment two
With purity is that 99% polyacrylonitrile 100kg adds in the reactor, adds 400kg water, stirs down and heats up, to 95 ℃, add Sodium Persulfate 0.5kg, Sodium Metabisulfite 0.5kg, polyvinyl alcohol 5kg reacted 2 hours, and obtaining viscosity is the polyacrylonitrile emulsion of 3000CPS.
Embodiment three
With purity is that 99% polyacrylonitrile 100kg adds in the reactor, add 600kg water, stir down and heat up,, add Potassium Persulphate 1kg to 60 ℃, S-WAT 1kg, OP-10 2kg, peregal 0.5kg reacted 4 hours, adjust PH to neutral with sodium hydroxide, obtaining viscosity is the polyacrylonitrile emulsion of 2000CPS.
Embodiment four
With purity is that 99% polyacrylonitrile 100kg adds in the reactor, adds 800kg water, stirs down and heats up, and to 80 ℃, adds hydrogen peroxide 1kg, and sodium dodecylbenzene 2kg reacted 2 hours, and obtaining viscosity is the polyacrylonitrile emulsion of 1000CPS.
Embodiment five
With purity is that 99% polyacrylonitrile 100kg adds in the reactor, add 300kg water, stir down and heat up, to 60 ℃, add ethyl acetate 70kg, Sodium Metabisulfite 1kg, Sodium Silicofluoride 0.5kg, polyoxyethylene octylphenol ether 2kg reacted 4 hours, and obtaining viscosity is the polyacrylonitrile emulsion of 3000CPS.
Embodiment six
With purity is that 99% polyacrylonitrile 100kg adds in the reactor, add 400kg water, stir down and heat up, to 65 ℃, add ethyl acetate 50kg, Sodium Metabisulfite 0.5kg, Sodium Silicofluoride 0.5kg, polyoxyethylene octylphenol ether 3kg reacted 6 hours, added defoamer 0.5kg and anticorrosion and bactericidal agent 0.5kg and obtained the polyacrylonitrile emulsion that viscosity is 4000CPS.
Embodiment seven
In reactor, add 400kg water and 4kg polyvinyl alcohol, stir down and heat up, to 65 ℃, with 20kg purity is that 99% polyacrylonitrile and 0.2kg ammonium persulfate add reactor, react after 0.5 hour 80kg polyacrylonitrile and 0.2kg ammonium persulfate were added reactor continuously in 2 hours, react adding 0.1kg ammonium persulfate after 0.5 hour, reacted 0.5 hour, adjustment PH extremely neutrality obtains the polyacrylonitrile emulsion that viscosity is 10000CPS.
Embodiment eight
The polyacrylonitrile emulsion is used as tamanori, bonding leather, fabric, paper etc., and adhesive property is as follows:
Shearing resistance (MPa)
Do wet
Embodiment 2 6.9 2.0
Embodiment 4 6.1.0 1.9
Embodiment 5 8.0 3.5
Embodiment 6 8.7 3.6
Embodiment 7 7.2 3.1
Embodiment nine
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Claims (8)
1, a kind of preparation method of polyacrylonitrile emulsion, it is characterized in that adopting method of emulsion polymerization polypropylene nitrile monomer, earlier with unisexuality emulsification in the aqueous solution, add the initiator initiated polymerization again in the polymerization process, perhaps in reaction process, add monomer and initiator polymerization continuously; Wherein the ratio of monomer and water is 1: 2-8, the consumption of initiator are monomeric 0.05%-2wt%, and the temperature of reaction is 40-95 ℃.
2, preparation method according to claim 1 is characterized in that initiator is persulfuric acid initiator, water-soluble peroxide initiator or redox initiator.
3, preparation method according to claim 2 is characterized in that initiator is vitriolate of tartar, ammonium persulfate, hydrogen peroxide, persulphate-Sodium Metabisulphate 65 or the redox initiation system that adds Sodium Silicofluoride.
4, preparation method according to claim 1 is characterized in that the polymeric emulsifying agent is negatively charged ion, positively charged ion or nonionic surface active agent.
5. preparation method according to claim 4 is characterized in that emulsifying agent is ethylene oxide condensate, peregal, sodium lauryl sulphate, Sodium dodecylbenzene sulfonate, penetrant t or the polyvinyl alcohol of alkylphenol polyoxyethylene, alkylphenol.
6, preparation method according to claim 1 is characterized in that the reaction times is 2-8 hour.
7, a kind of polyacrylonitrile emulsion is characterized in that adopting method of emulsion polymerization polypropylene nitrile monomer, obtains the polymer emulsion that viscosity is 1000-10000CPS.
8, the purposes of polyacrylonitrile emulsion in tamanori and paint binder for preparing according to any one described method of claim 1-6.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 99123833 CN1112381C (en) | 1999-11-15 | 1999-11-15 | Novel environment protection acrylonitrile emulsion, preparation process and use thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 99123833 CN1112381C (en) | 1999-11-15 | 1999-11-15 | Novel environment protection acrylonitrile emulsion, preparation process and use thereof |
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| CN1296021A CN1296021A (en) | 2001-05-23 |
| CN1112381C true CN1112381C (en) | 2003-06-25 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN 99123833 Expired - Fee Related CN1112381C (en) | 1999-11-15 | 1999-11-15 | Novel environment protection acrylonitrile emulsion, preparation process and use thereof |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100497469C (en) * | 2007-09-24 | 2009-06-10 | 林玉珠 | Environment-friendly type macromolecule surfacant |
| CN100537618C (en) * | 2007-11-29 | 2009-09-09 | 鲁东大学 | Method for preparing loosening porous type polyacrylonitrile resin |
| CN104558391B (en) * | 2013-10-22 | 2018-03-02 | 中国石油化工集团公司 | A kind of preparation method of polyacrylonitrile emulsion |
| CN104151982B (en) * | 2014-08-21 | 2016-08-17 | 苏州靖羽新材料有限公司 | A kind of polyacrylonitrile interior wall coating |
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