CN102786608B - Interface free radical emulsion polymerization method - Google Patents
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Abstract
The invention discloses an interface free radical emulsion polymerization method. A long-carbon-chain alkylamine polyoxyethyl ether oxide having the function of an emulsifier is adopted as an initiator for free radical emulsion polymerization, and is positioned on the surface of a reaction micelle to initiate monomers to polymerize on the interface. The method is suitable for the preparation of high-molecular-weight and narrow-distribution polymers from all monomers which can be polymerized through the free radical emulsion polymerization method.
Description
Technical field
The invention belongs to polyreaction implementation method field, relate to free-radical emulsion polymerization field, particularly a kind of interface free-radical emulsion polymerization method.The present invention adopts the initiator that long alkyl chain length amine polyoxyethylene ether oxide compound is radical polymerization, also be the emulsifying agent of letex polymerization simultaneously, the feature of this reagent is to have both the dual-use function of radical polymerization initiator and letex polymerization emulsifying agent, because long alkyl chain length amine polyoxyethylene ether oxide compound is positioned at the surface of reacting micella, at interface trigger monomer, carry out polyreaction.Nitroxyl free radical is given the feature that polyreaction has active free radical polymerization, and interface initiation is given active centre the taxis of polymkeric substance is had to certain regulating and controlling effect.
Background technology
Controlled or Living Radical Emulsion Polymerization is the focus of current letex polymerization research, nitroxyl free radical is first stability free radical, concentration of active center in can stabilized radical emulsion polymerization systems, weakens chain termination reaction, thereby reaches the object of controlled or living polymerization.2,2,6,6-tetramethyl--1-oxygen phenylpiperidines (TEMPO) and derivative thereof are the representatives of living free radical polymerization, can be used as free radical scavenger, be easy to Propagating Radical covalent attachment and become dormancy kind, under comparatively high temps (120 ℃), dormancy kind can contraryly all be cleaved into Propagating Radical again, participate in again initiated polymerization [Pan Zuren chief editor, polymer chemistry (the 5th edition), 109-113 page, Chemical Industry Press, 2011].The nitroxyl free radical emulsion polymerization systems of reporting at present, due to 2,2,6,6-tetramethyl--1-oxygen phenylpiperidines (TEMPO) and derivative thereof, without surfactivity, all need to add independently a certain amount of emulsifying agent [Macromolecules, 1998,31 (12), 4041-4044].
The present invention adopts the initiator that long alkyl chain length amine polyoxyethylene ether oxide compound is radical polymerization, also be the emulsifying agent of letex polymerization simultaneously, because long alkyl chain length amine polyoxyethylene ether oxide compound is positioned at the surface of reacting micella, at interface trigger monomer, carry out polyreaction.
Summary of the invention
The method that the object of this invention is to provide a kind of interface free-radical emulsion polymerization, it is characterized in that adopting having the initiator that the long alkyl chain length amine polyoxyethylene ether oxide compound of emulsification function is free-radical emulsion polymerization, this method is applicable to prepare the polymkeric substance of high molecular, narrow distribution.
Technical scheme of the present invention is as follows: a kind of interface provided by the present invention free-radical emulsion polymerization method, it is characterized in that adding deionized water in polymerization reactor, the consumption of water is 1.5-2.5 times (in mass) of monomer total amount, add a kind of long alkyl chain length amine Soxylat A 25-7 oxide compound or several long alkyl chain length amine Soxylat A 25-7 hopcalite, the consumption of long alkyl chain length amine Soxylat A 25-7 oxide compound is the 4%-6%(mass percent of monomer total amount), add again monomer, by the atmosphere in nitrogen replacement polymerization reactor for several times, open stirring, after stirring certain hour, form monomer emulsion, be warming up to temperature of reaction, polymerization temperature regulates and controls by circulatory mediator, polymeric reaction temperature general control is 30 ℃ of-130 ℃ of left and right, preferably between 50 ℃-80 ℃, polymerization reaction time was controlled between 7-40 hour, polymerization reaction time is determined according to the requirement of final monomer conversion, monomer conversion general control is between 50%-80%, optimum control is between 60%-70%, add the ethanolic soln containing 5% hydrochloric acid to stop polymerization, terminator consumption is the 0.05%-0.15%(mass percent of monomer total amount), flocculation, precipitation polymers, with after washing with alcohol several, product polystyrene is dried to constant weight in the vacuum drying oven of 50 ℃-60 ℃, adopts classical way test sample structure and performance.
Above-mentioned interface free-radical emulsion polymerization process can select other letex polymerization conventional additives such as appropriate chain-transfer agent, emulsifying agent and/or assistant for emulsifying agent, ionogen etc. to optimize emulsion polymerization process according to actual needs.In order to regulate and control the molecular weight of polymkeric substance, can select chain-transfer agent as required, chain-transfer agent is selected from mercaptan, be selected from the mixture of one or more mercaptan in tert-dodecyl mercaptan, uncle's ten carbon mercaptan, uncle's 14 carbon mercaptan, uncle's 16 carbon mercaptan, preferred tertiary DDM dodecyl mercaptan, chain-transfer agent consumption is determined according to the requirement of final polymericular weight.In order to optimize, reduce the consumption of long alkyl chain length amine Soxylat A 25-7 oxide compound, can select as required emulsifying agent to be selected from the mixture of one or more emulsifying agents in RA rosin acid, soap, preferred fatty acid sodium, emulsifier is optimized definite according to kind and the consumption of long alkyl chain length amine Soxylat A 25-7 oxide compound in system; In order to improve emulsifying power and latex stability, minimizing emulsifier, can select appropriate assistant for emulsifying agent as required, assistant for emulsifying agent is selected from the sodium salt (sodiumβ-naphthalenesulfonate formaldehyde condensation products) of naphthene sulfonic acid and formaldehyde condensation products.In order to reduce micelle-forming concentration, improve rate of polymerization, reduce surface tension of latex and viscosity, buffer pH value, is easy to derive heat of polymerization, and after raising polymerization process and polymerization, the stability of latex, can select appropriate ionogen as required, and ionogen is selected from K
3pO
4, KCl.
The radical polymerization initiator of interface provided by the present invention free-radical emulsion polymerization method is generally selected from one or more the long alkyl chain length amine polyoxyethylene ether hopcalites in long alkyl chain length amine polyoxyethylene ether oxide compound, and long alkyl chain length amine polyoxyethylene ether oxide compound has following constitutional features:
Wherein: R
1generally be selected from the alkane that carbonatoms is 6-24, the alkane that is preferably 12-18 from carbonatoms; Alkane can be straight-chain paraffin and isomers thereof, can be also naphthenic hydrocarbon; M, n are the polymerization degree, and m, n are all not less than 1, m conventionally, n sum is mean polymerisation degree (m+n), and mean polymerisation degree is generally selected between 2-20, preferably between 5-15.The lauryl amine Soxylat A 25-7 oxide compound that long alkyl chain length amine Soxylat A 25-7 oxide compound is preferably 5 from mean polymerisation degree, the lauryl amine Soxylat A 25-7 oxide compound that mean polymerisation degree is 10, the octadecylamine Soxylat A 25-7 oxide compound that mean polymerisation degree is 5, the octadecylamine Soxylat A 25-7 oxide compound that mean polymerisation degree is 10, the octadecylamine Soxylat A 25-7 oxide compound that mean polymerisation degree is 15.Long alkyl chain length amine polyoxyethylene ether oxide compound also can be selected from Rosin Amine Polyoxyethylene Ether ether oxide compound, conventionally the mean polymerisation degree that requires the mean polymerisation degree of Soxylat A 25-7 to be less than 15(Soxylat A 25-7 is greater than at 15 o'clock, Rosin Amine Polyoxyethylene Ether ether oxide compound is solid, does not advise adopting).The present invention adopts the initiator that long alkyl chain length amine polyoxyethylene ether oxide compound is radical polymerization, is also the emulsifying agent of letex polymerization simultaneously, and the feature of this reagent is to have both the dual-use function of radical polymerization initiator and letex polymerization emulsifying agent.Because the nitroxyl free radical in long alkyl chain length amine polyoxyethylene ether oxide compound has the function of Mulberry Extract, therefore interface provided by the present invention free-radical emulsion polymerization method has the feature of controlled or living polymerization.
A kind of interface provided by the present invention free-radical emulsion polymerization method is applicable to adopt free radical polymerization, can adopt emulsion polymerisation process to carry out all monomers of polymerization, polymerization single polymerization monomer is at least selected from the mixture of following a kind of monomer or several monomers: ethene and derivative thereof, Styrene and its derivatives, conjugated diolefine hydrocarbons and their derivates, vinylformic acid and salt thereof, acrylate and derivative thereof, methacrylic acid and salt thereof, methacrylic ester and derivative thereof, acrylamide and derivative thereof, Methacrylamide and derivative thereof, toxilic acid and salt thereof, maleic anhydride and derivative thereof, maleic acid ester and derivative thereof, vinyl pyridine and derivative thereof, vinyl pyrrolidone and derivative thereof, vinyl ether and derivative thereof, fluorinated ethylene and derivative thereof, chloroethylenes and derivative thereof, preferably from the mixture of following a kind of monomer or several monomers: vinylbenzene, alpha-methyl styrene, divinyl, isoprene, chloroprene, methyl acrylate, methyl methacrylate, vinyl pyridine, vinyl cyanide, vinylchlorid, vinyl fluoride, tetrafluoroethylene, R 1216, vinylidene chloride, vinyl-acetic ester.
Effect of the present invention and benefit are: interface provided by the present invention free-radical emulsion polymerization method, the long alkyl chain length amine polyoxyethylene ether oxide compound that emulsification function is had both in employing is radical polymerization initiator, technique is simple, cost is low, polymerizing condition is gentle, polyreaction has the feature of controlled or living polymerization, prepared polymkeric substance has the feature of high molecular, narrow distribution, can realize the Effective Regulation of traditional free-radical emulsion polymerization method to polymer architecture.
Polymer architecture and method for analyzing performance are as follows: adopt
1microcosmic and the sequential structure of H-NMR nuclear magnetic resonance spectrometer analyzing polymers, with CDCl
3for solvent, tetramethylsilane (TMS) is interior mark.Adopt molecular weight and the distribution thereof of gel permeation chromatograph analyzing polymers, take tetrahydrofuran (THF) as solvent, measuring temperature is 30 ℃.Adopt glass transition temperature Tg and the fusing point Tm of differential scanning calorimeter dsc analysis polymkeric substance, 10 ℃/min of temperature rise rate.
Embodiment
The present invention proposes following examples as further instruction, but and the scope of unrestricted the claims in the present invention protection.
Embodiment 1
The synthetic method of long carbon chain aliphatic amine Soxylat A 25-7 oxide compound: add a certain amount of long carbon chain aliphatic amine Soxylat A 25-7, deionized water in reactor, be warming up to 55 ℃, control the concentration of long carbon chain aliphatic amine Soxylat A 25-7 between 10-50%, hydrogen peroxide is 1.15 with the mol ratio of long carbon chain aliphatic amine Soxylat A 25-7, open stirring, in 0.5-1.0 hour, be added dropwise to 30% hydrogen peroxide solution, after dropwising, be warming up to 75 ℃, continue reaction 5 hours, coolingly must grow carbon chain aliphatic amine Soxylat A 25-7 oxide compound.Lauryl amine Soxylat A 25-7 1205(mean polymerisation degree is 5), lauryl amine Soxylat A 25-7 1210(mean polymerisation degree is 10) transformation efficiency be respectively 98.74%, 90.60%, octadecylamine Soxylat A 25-7 1805(mean polymerisation degree is 5), octadecylamine Soxylat A 25-7 1810(mean polymerisation degree is 10), octadecylamine Soxylat A 25-7 1815(mean polymerisation degree is 15) transformation efficiency be respectively 95.40%, 92.03%, 90.93%.Long carbon chain aliphatic amine Soxylat A 25-7 is that the Zhangjiagang Chemical Co., Ltd. of circling in the air produces, product grade is lauryl amine Soxylat A 25-7 1205, lauryl amine Soxylat A 25-7 1210, octadecylamine Soxylat A 25-7 1805, octadecylamine Soxylat A 25-7 1810, octadecylamine Soxylat A 25-7 1815, is technical grade product.
Embodiment 2
In polymerization reactor, add successively 0.3g octadecylamine Soxylat A 25-7 (mean polymerisation degree is 5) oxide compound, 14g ionized water and 13.5g vinylbenzene, open stirring, controlling polymerization temperature is 50 ℃, after polyreaction 21 hours, add the ethanolic soln containing 5% hydrochloric acid to stop polymerization, terminator consumption is the 0.05%-0.15%(mass percent of monomer total amount), flocculation, precipitation polymers, with after washing with alcohol several, product polystyrene is dried to constant weight in the vacuum drying oven of 50 ℃-60 ℃, adopts classical way test sample structure and performance.Monomer styrene transformation efficiency is 76.8%, and polystyrene number-average molecular weight is 191.23 ten thousand, and weight-average molecular weight is 217.01 ten thousand, and molecular weight distribution is 1.13.
Embodiment 3
In polymerization reactor, add successively 0.3g lauryl amine Soxylat A 25-7 (mean polymerisation degree is 5) oxide compound, 14g ionized water and 13.5g vinylbenzene, open stirring, controlling polymerization temperature is 50 ℃, after polyreaction 16 hours, add the ethanolic soln containing 5% hydrochloric acid to stop polymerization, terminator consumption is the 0.05%-0.15%(mass percent of monomer total amount), flocculation, precipitation polymers, with after washing with alcohol several, product polystyrene is dried to constant weight in the vacuum drying oven of 50 ℃-60 ℃, adopts classical way test sample structure and performance.Monomer styrene transformation efficiency is 29.1%, and polystyrene number-average molecular weight is 112.11 ten thousand, and weight-average molecular weight is 158.30 ten thousand, and molecular weight distribution is 1.41.
Embodiment 4
In polymerization reactor, add successively 0.3g octadecylamine Soxylat A 25-7 (mean polymerisation degree is 5) oxide compound, 14g ionized water and 13.5g methyl acrylate, open stirring, controlling polymerization temperature is 50 ℃, after polyreaction 16 hours, add the ethanolic soln containing 5% hydrochloric acid to stop polymerization, terminator consumption is the 0.05%-0.15%(mass percent of monomer total amount), flocculation, precipitation polymers, with after washing with alcohol several, product polystyrene is dried to constant weight in the vacuum drying oven of 50 ℃-60 ℃, adopts classical way test sample structure and performance.Monomer methyl acrylate transformation efficiency is 62.3%, and polymethyl acrylate number-average molecular weight is 57.62 ten thousand, and weight-average molecular weight is 74.33 ten thousand, and molecular weight distribution is 1.29.
Embodiment 5
In polymerization reactor, add successively 0.3g octadecylamine Soxylat A 25-7 (mean polymerisation degree is 10) oxide compound, 14g deionized water and 13.5g alpha-methyl styrene, open stirring, controlling polymerization temperature is 50 ℃, after polyreaction 16 hours, add the ethanolic soln containing 5% hydrochloric acid to stop polymerization, terminator consumption is the 0.05%-0.15%(mass percent of monomer total amount), flocculation, precipitation polymers, with after washing with alcohol several, product polystyrene is dried to constant weight in the vacuum drying oven of 50 ℃-60 ℃, adopt classical way test sample structure and performance.Monomer alpha-methyl styrene transformation efficiency is 35.3%, and poly alpha methylstyrene number-average molecular weight is 108.12 ten thousand, and weight-average molecular weight is 145.90 ten thousand, and molecular weight distribution is 1.35.
Embodiment 6
In polymerization reactor, add successively 0.3g octadecylamine Soxylat A 25-7 (mean polymerisation degree is 15) oxide compound, 14g ionized water and 13.5g methyl methacrylate, open stirring, controlling polymerization temperature is 55 ℃, after polyreaction 16 hours, add the ethanolic soln containing 5% hydrochloric acid to stop polymerization, terminator consumption is the 0.05%-0.15%(mass percent of monomer total amount), flocculation, precipitation polymers, with after washing with alcohol several, product polystyrene is dried to constant weight in the vacuum drying oven of 50 ℃-60 ℃, adopt classical way test sample structure and performance.Monomers methyl methacrylate transformation efficiency is 72.6%, and polymethylmethacrylate number-average molecular weight is 75.32 ten thousand, and weight-average molecular weight is 111.49 ten thousand, and molecular weight distribution is 1.48.
Embodiment 7
In polymerization reactor, add successively 0.3g lauryl amine Soxylat A 25-7 (mean polymerisation degree is 10) oxide compound, 14g ionized water and 13.5g vinyl pyridine, open stirring, controlling polymerization temperature is 50 ℃, after polyreaction 16 hours, add the ethanolic soln containing 5% hydrochloric acid to stop polymerization, terminator consumption is the 0.05%-0.15%(mass percent of monomer total amount), flocculation, precipitation polymers, with after washing with alcohol several, product polystyrene is dried to constant weight in the vacuum drying oven of 50 ℃-60 ℃, adopts classical way test sample structure and performance.Monomer ethylene yl pyridines transformation efficiency is 49.8%, and polyvinylpyridine number-average molecular weight is 64.97 ten thousand, and weight-average molecular weight is 86.41 ten thousand, and molecular weight distribution is 1.33.
Embodiment 8
In polymerization reactor, add successively 0.6g lauryl amine Soxylat A 25-7 (mean polymerisation degree is 10) oxide compound, 14g ionized water and 13.5g vinyl cyanide, open stirring, controlling polymerization temperature is 50 ℃, after polyreaction 16 hours, add the ethanolic soln containing 5% hydrochloric acid to stop polymerization, terminator consumption is the 0.05%-0.15%(mass percent of monomer total amount), flocculation, precipitation polymers, with after washing with alcohol several, product polystyrene is dried to constant weight in the vacuum drying oven of 50 ℃-60 ℃, adopts classical way test sample structure and performance.Monomer vinyl cyanide transformation efficiency is 62.7%, and polyacrylonitrile number-average molecular weight is 66.12 ten thousand, and weight-average molecular weight is 99.84 ten thousand, and molecular weight distribution is 1.51.
Embodiment 9
In polymerization reactor, add successively 0.3g octadecylamine Soxylat A 25-7 (mean polymerisation degree is 15) oxide compound, 14g ionized water and 13.5g vinylchlorid, open stirring, controlling polymerization temperature is 45 ℃, after polyreaction 16 hours, add the ethanolic soln containing 5% hydrochloric acid to stop polymerization, terminator consumption is the 0.05%-0.15%(mass percent of monomer total amount), flocculation, precipitation polymers, with after washing with alcohol several, product polystyrene is dried to constant weight in the vacuum drying oven of 50 ℃-60 ℃, adopts classical way test sample structure and performance.Monomer conversion rate of vinyl chloride is 55.1%, and polyvinyl chloride number-average molecular weight is 53.22 ten thousand, and weight-average molecular weight is 75.57 ten thousand, and molecular weight distribution is 1.42.
Embodiment 10
In polymerization reactor, add successively 0.3g octadecylamine Soxylat A 25-7 (mean polymerisation degree is 15) oxide compound, 14g ionized water and 13.5g tetrafluoroethylene, open stirring, controlling polymerization temperature is 65 ℃, after polyreaction 16 hours, add the ethanolic soln containing 5% hydrochloric acid to stop polymerization, terminator consumption is the 0.05%-0.15%(mass percent of monomer total amount), flocculation, precipitation polymers, with after washing with alcohol several, product polystyrene is dried to constant weight in the vacuum drying oven of 50 ℃-60 ℃, adopts classical way test sample structure and performance.Monomer tetrafluoroethylene transformation efficiency is 56.7%, and tetrafluoroethylene number-average molecular weight is 91.12 ten thousand, and weight-average molecular weight is 128.48 ten thousand, and molecular weight distribution is 1.41.
Embodiment 11
In polymerization reactor, add successively 0.3g Rosin Amine Polyoxyethylene Ether ether oxide compound (R
1for naphthenic hydrocarbon, synthetic method is referring to embodiment 1: Rosin Amine Polyoxyethylene Ether ether makes through hydrogen peroxide oxidation, Rosin Amine Polyoxyethylene Ether Mi Wei Wuhan Hezhong Bio-chemical Manufature Co., Ltd. produces, product grade is Rosin Amine Polyoxyethylene Ether (8) ether, the mean polymerisation degree of Soxylat A 25-7 is 8), 14g ionized water and 13.5g vinylbenzene, open stirring, controlling polymerization temperature is 50 ℃, after polyreaction 21 hours, add the ethanolic soln containing 5% hydrochloric acid to stop polymerization, terminator consumption is the 0.05%-0.15%(mass percent of monomer total amount), flocculation, precipitation polymers, with after washing with alcohol several, product polystyrene is dried to constant weight in the vacuum drying oven of 50 ℃-60 ℃, adopt classical way test sample structure and performance.Monomer styrene transformation efficiency is 66.9%, and polystyrene number-average molecular weight is 131.26 ten thousand, and weight-average molecular weight is 174.57 ten thousand, and molecular weight distribution is 1.33.
Embodiment 12
In polymerization reactor, add successively 0.3g octadecylamine Soxylat A 25-7 (mean polymerisation degree is 5) oxide compound, 14g ionized water and 13.5g vinylbenzene, 0.046g tert-dodecyl mercaptan (chain-transfer agent), open stirring, controlling polymerization temperature is 50 ℃, after polyreaction 21 hours, add the ethanolic soln containing 5% hydrochloric acid to stop polymerization, terminator consumption is the 0.05%-0.15%(mass percent of monomer total amount), flocculation, precipitation polymers, with after washing with alcohol several, product polystyrene is dried to constant weight in the vacuum drying oven of 50 ℃-60 ℃, adopt classical way test sample structure and performance.Monomer styrene transformation efficiency is 70.1%, and polystyrene number-average molecular weight is 89.12 ten thousand, and weight-average molecular weight is 145.26 ten thousand, and molecular weight distribution is 1.63.
Embodiment 13
In polymerization reactor, add successively 0.2g octadecylamine Soxylat A 25-7 (mean polymerisation degree is 5) oxide compound, 0.26g sodium soap (emulsifying agent), 14g ionized water and 13.5g vinylbenzene, open stirring, controlling polymerization temperature is 50 ℃, after polyreaction 21 hours, add the ethanolic soln containing 5% hydrochloric acid to stop polymerization, terminator consumption is the 0.05%-0.15%(mass percent of monomer total amount), flocculation, precipitation polymers, with after washing with alcohol several, product polystyrene is dried to constant weight in the vacuum drying oven of 50 ℃-60 ℃, adopt classical way test sample structure and performance.Monomer styrene transformation efficiency is 68.1%, and polystyrene number-average molecular weight is 101.12 ten thousand, and weight-average molecular weight is 114.26 ten thousand, and molecular weight distribution is 1.13.
Embodiment 14
In polymerization reactor, add successively 0.3g octadecylamine Soxylat A 25-7 (mean polymerisation degree is 15) oxide compound, 14g ionized water and 13.5g divinyl, open stirring, controlling polymerization temperature is 50 ℃, after polyreaction 18 hours, add the ethanolic soln containing 5% hydrochloric acid to stop polymerization, terminator consumption is the 0.05%-0.15%(mass percent of monomer total amount), flocculation, precipitation polymers, with after washing with alcohol several, product polystyrene is dried to constant weight in the vacuum drying oven of 50 ℃-60 ℃, adopts classical way test sample structure and performance.Monomer butadiene conversion is 71.6%, and polyhutadiene number-average molecular weight is 75.46 ten thousand, and weight-average molecular weight is 107.91 ten thousand, and molecular weight distribution is 1.43.
Embodiment 15
In polymerization reactor, add successively 0.3g octadecylamine Soxylat A 25-7 (mean polymerisation degree is 15) oxide compound, 14g ionized water and 13.5g isoprene, open stirring, controlling polymerization temperature is 50 ℃, after polyreaction 18 hours, add the ethanolic soln containing 5% hydrochloric acid to stop polymerization, terminator consumption is the 0.05%-0.15%(mass percent of monomer total amount), flocculation, precipitation polymers, with after washing with alcohol several, product polystyrene is dried to constant weight in the vacuum drying oven of 50 ℃-60 ℃, adopts classical way test sample structure and performance.Monomer isoprene transformation efficiency is 68.5%, and polyisoprene number-average molecular weight is 90.32 ten thousand, and weight-average molecular weight is 121.93 ten thousand, and molecular weight distribution is 1.35.
Embodiment 16
In polymerization reactor, add successively 0.3g octadecylamine Soxylat A 25-7 (mean polymerisation degree is 15) oxide compound, 14g ionized water and 13.5g chloroprene, open stirring, controlling polymerization temperature is 55 ℃, after polyreaction 20 hours, add the ethanolic soln containing 5% hydrochloric acid to stop polymerization, terminator consumption is the 0.05%-0.15%(mass percent of monomer total amount), flocculation, precipitation polymers, with after washing with alcohol several, product polystyrene is dried to constant weight in the vacuum drying oven of 50 ℃-60 ℃, adopts classical way test sample structure and performance.Monomer chloroprene transformation efficiency is 61.3%, and sovprene number-average molecular weight is 80.02 ten thousand, and weight-average molecular weight is 117.63 ten thousand, and molecular weight distribution is 1.47.
Claims (13)
1. an interface free-radical emulsion polymerization method, it is characterized in that: in polymerization reactor, add deionized water, the consumption of water is 1.5-2.5 times of monomer total amount in mass, add a kind of long alkyl chain length amine Soxylat A 25-7 oxide compound or several long alkyl chain length amine Soxylat A 25-7 hopcalite, the consumption mass percent of long alkyl chain length amine Soxylat A 25-7 oxide compound is the 4%-6% of monomer total amount, add again polymerization single polymerization monomer, by the atmosphere in nitrogen replacement polymerization reactor for several times, open stirring, after stirring, form monomer emulsion, be warming up to temperature of reaction, polymerization temperature regulates and controls by circulatory mediator, polymeric reaction temperature is controlled at 30 ℃-130 ℃, polymerization reaction time was controlled between 7-40 hour, polymerization reaction time is determined according to the requirement of final monomer conversion, monomer conversion is controlled between 50%-80%, add the ethanolic soln containing 5% hydrochloric acid to stop polymerization, terminator consumption mass percent is the 0.05%-0.15% of monomer total amount, and flocculation, precipitation polymers, with after washing with alcohol several, in the vacuum drying oven of 50 ℃-60 ℃, be dried to constant weight, adopt classical way test sample structure and performance, wherein long alkyl chain length amine Soxylat A 25-7 oxide compound has following constitutional features:
Wherein: R
1be selected from the alkyl that carbonatoms is 6-24, m, n are all not less than 1, m, n sum is mean polymerisation degree, and mean polymerisation degree is selected between 2-20.
2. method according to claim 1, is characterized in that: R wherein
1be selected from the alkyl that carbonatoms is 12-18.
3. method according to claim 1, is characterized in that: wherein mean polymerisation degree is selected between 5-15.
4. according to the method described in claim 1 or 2 or 3, it is characterized in that: to be wherein selected from mean polymerisation degree be 5 lauryl amine Soxylat A 25-7 oxide compound, the lauryl amine Soxylat A 25-7 oxide compound that mean polymerisation degree is 10, the octadecylamine Soxylat A 25-7 oxide compound that mean polymerisation degree is 5, the octadecylamine Soxylat A 25-7 oxide compound that mean polymerisation degree is 10, the octadecylamine Soxylat A 25-7 oxide compound that mean polymerisation degree is 15 to long alkyl chain length amine Soxylat A 25-7 oxide compound.
5. method according to claim 1, is characterized in that: wherein long alkyl chain length amine Soxylat A 25-7 oxide compound is selected from the Rosin Amine Polyoxyethylene Ether ether oxide compound that Soxylat A 25-7 mean polymerisation degree is less than 15.
6. method according to claim 1, is characterized in that: wherein polymeric reaction temperature is controlled between 50 ℃-80 ℃.
7. method according to claim 1, is characterized in that: wherein monomer conversion is controlled between 60%-70%.
8. method according to claim 1, is characterized in that: wherein polymerization process is selected chain-transfer agent, and chain-transfer agent is the mixture of one or more mercaptan in mercaptan.
9. method according to claim 1, is characterized in that: wherein polymerization process is selected emulsifying agent, and emulsifying agent is the mixture of one or more emulsifying agents in RA rosin acid, soap.
10. method according to claim 1, is characterized in that: wherein polymerization process is selected ionogen, and ionogen is K
3pO
4, one or more the electrolytical mixtures in KCl.
11. methods according to claim 1, is characterized in that polymerization single polymerization monomer is selected from one or more the mixture in following compounds: ethene and derivative thereof.
12. methods according to claim 1, it is characterized in that polymerization single polymerization monomer is selected from Styrene and its derivatives, conjugated diolefine hydrocarbons and their derivates, acrylate and derivative thereof, methacrylic acid and salt thereof, methacrylic ester and derivative thereof, acrylamide and derivative thereof, Methacrylamide and derivative thereof, toxilic acid and salt thereof, maleic anhydride and derivative thereof, maleic acid ester and derivative thereof, vinyl pyridine and derivative thereof, vinyl pyrrolidone and derivative thereof, vinyl ether and derivative thereof, fluorinated ethylene and derivative thereof, chloroethylenes and derivative thereof.
13. methods according to claim 1, is characterized in that polymerization single polymerization monomer is selected from one or more the mixture in following compounds: vinylbenzene, alpha-methyl styrene, divinyl, isoprene, chloroprene, methyl acrylate, methyl methacrylate, vinyl pyridine, vinyl cyanide, vinylchlorid, vinyl fluoride, tetrafluoroethylene, R 1216, vinylidene chloride, vinyl-acetic ester.
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| DE3237574A1 (en) * | 1982-10-09 | 1984-04-12 | Hoechst Ag, 6230 Frankfurt | Use of amine oxides in the pulp and paper manufacture |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| DE3237574A1 (en) * | 1982-10-09 | 1984-04-12 | Hoechst Ag, 6230 Frankfurt | Use of amine oxides in the pulp and paper manufacture |
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| JP特开昭52-63250 1975.11.20 |
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