CN102268115B - Heating-free technology for producing polymer emulsion - Google Patents
Heating-free technology for producing polymer emulsion Download PDFInfo
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- CN102268115B CN102268115B CN201010192444.1A CN201010192444A CN102268115B CN 102268115 B CN102268115 B CN 102268115B CN 201010192444 A CN201010192444 A CN 201010192444A CN 102268115 B CN102268115 B CN 102268115B
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Abstract
The invention relates to a heating-free technology for producing a polymer emulsion, comprising the steps of: conducting resistance removal to methyl methacrylate (MMA) and methyl acrylate (MA) monomers with an alumina column respectively for standby application; supplying nitrogen into a polymerization reaction vessel for 10min so as to get rid of oxygen, adding sodium sulfite, the monomers and (NH4)2S2O8, with nitrogen supply and stirring maintained, and when the temperature rises to 30-33DEG C, starting to introduce cooling water for controlling the temperature ranging from 34-36DEG C for 4-5h and then synchronously adding in a dropwise manner and in equal ratio, (1) a mixture of monomers, (2) a Na2SO3\emulsifier water solution and (3) a (NH4)2S2O3\emulsifier water solution, when the above materials are added to 85-90%, stopping adding (2) and (3), and doubling the adding speed so as to add all of (1) fastly, and simultaneously leaving the temperature to rise to 40-45DEG C, and after a one-hour reaction, continuing to adding the remaining (2) and (3), and leaving another one hour for reaction. With solid content of 70%, the obtained polymer emulsion in the invention can be used as base materials of high grade coatings and adhesives.
Description
Technical field
This project relates to exempts from heating energy-saving method or Technology in polymer production, exactly relates to the heat management problems prepared in polyacrylate dispersion.
Background technology
Emulsion polymerization is the common method of a large amount of multiple free radical polyalcohol product of production adopted at present, because the monomer adopted in breast polymerization is that a large class contains carbon-carbon double bond
the free yl polymerizating monomer of (except stupid ring), wherein modal have ethene, propylene, butene-1, divinyl, vinylchlorid, tetrafluoroethylene, acetylene, (methyl) acrylate, acrylamide, vinylbenzene, vinyl acetate, (methyl) vinylformic acid, toxilic acid (acid anhydride) etc., these monomers can add water, after emulsifying agent and initiator, be heated to a certain degree, letex polymerization can be there is, production emulsion products or aqueous polymer emulsion, if adopt single peroxide initiator in polymerization, then usually need system to be heated to comparatively high temps such as more than 50 DEG C initiated polymerizations, if adding initiator is by highly active oxidation/reduction system, then can cause emulsion polymerization under much lower temperature, theoretically, initiated polymerization temperature is minimum can close to the freezing point of water that is 0 DEG C, and for the letex polymerization of free radical monomer, once initiated polymerization, a large amount of heat will be released, the redox initiator activity added is higher, the activity of monomer is higher, temperature needed for initial initiation is lower, as long as the relative rate of heat release and heat absorption in control polymerization system, that heat release is greater than heat absorption, system will from heating up, the speed adding monomer and initiator is faster, what pass into is slower for the medium (Chang Weishui) cooled, certainly heating up of polymerization system is faster or higher, even can be raised to 100 degree, this illustrates that above-mentioned polymerization process does not need other heating completely.
About employing redox initiation system at low temperatures initiated polymerization prepare being reported in of polymer emulsion and just occurred many years ago very much, such as have in Teaching Materials at College level " polymer chemistry " second edition 110 ~ 111 pages of Pan Zuren chief editor: at 5 ~ 10 DEG C, adopt K
2s
2o
8, H
2o
2, isopropyl benzene hydroperoxide and redox initiation system is formed with ferrous salt respectively to alkane hydrogen peroxide in the Meng cause the industrial production example that vinylbenzene and butadiene emulsions copolymerization prepare styrene-butadiene rubber(SBR).
Acrylic ester aquosity copolymer emulsion comprises pure third, vinegar third, phenylpropyl alcohol, organosilicon crylic acid latex a large series products, and be widely used in coating, tackiness agent and sealing tape, Gross World Product reaches millions of tons, all adopts heated polymerizable method.Such as methyl acrylate is that the polymerized emulsion product of main body is commonly used for vinylformic acid specialty elastomer again, but up to the present, although adopt the research report of low-temperature oxidation reduction initiated polymerization a lot, although that is theoretically, initiated polymerization temperature is minimum can close to the freezing point of water that is 0 DEG C, but exempts to add thermal-initiated polymerization for employing and produce (methyl) acrylic ester copolymerization thing emulsion technology or method has no report always.
Summary of the invention:
Known from above-mentioned theory, initiated polymerization temperature is minimum can close to the freezing point of water that is 0 DEG C, and for the letex polymerization of free radical monomer, once initiated polymerization, a large amount of heat will be released, the redox initiator activity added is higher, the activity of monomer is higher, temperature needed for initial initiation is lower, as long as the relative rate of heat release and heat absorption in control polymerization system, that heat release is greater than heat absorption, system will from heating up, the speed adding monomer and initiator is faster, what pass into is slower for the medium (Chang Weishui) cooled, certainly heating up of polymerization system is faster or higher, but be raised to how many degree as well? on the one hand in order to make the activity of initiator moderate, on the other hand in order to cooling water temperature can be made with the water under normal temperature to facilitate control polymerization temperature, through calculating, testing us thinks at 30-45 DEG C better, preferably at 34-36 DEG C, after making system cause, control temperature is stabilized in 35 DEG C, add all the other monomers and initiator, can realize exempting from heated polymerizable.
In the reactor that thermometer, reflux exchanger, feeding device, whipping appts are housed, nitrogen is passed into after 5 ~ 10 minutes from bottom, add water, emulsifying agent, first monomer, make emulsifier concentration reach water 0.5 ~ 5%, make monomer reach 5 ~ 20% of water, keep logical nitrogen, stir half an hour, add first reductive agent, its consumption consumption is 3/1 to four/3rds of oxygenant mole number used, preferably 2/3rds.Add first oxygenant after 10 ~ 20 minutes, its consumption is 0.2 ~ 2% of added amount of monomer, is preferably 0.3 ~ 0.5%, continues to keep logical N
2and stirring, note observing temperature, when having in time heating up, initiation reaction is described, when it is warmed up to 30-33 DEG C, the water coolant passing into any natural temperature makes temperature control at 35 DEG C ± 1 DEG C, when after temperature-stable, synchronously mix monomer is added respectively from header tank, the solution of Oxidizing and Reducing Agents, control the flow of feed rate and logical water coolant, the temperature controlled in reactor makes it to remain on 35 ± 1 DEG C, to raw material monomer used only remaining total amount about 5 ~ 10% time, start to add monomer with the feed rate more fast again than usual dispatch, and stop adding initiator while adding monomer fast, the initiator etc. of remaining about 5-10% added after 1 hour, above-mentioned whole process keep always 100-150 liter (volumes at 35 DEG C)/hour flow velocity pass into nitrogen, to add after remaining initiator again stirring reaction 1-2 hour up to residual monomer concentration below 0.01%, add auxiliary agent and namely obtain polymer emulsion product.
The present invention the monomer that is suitable for: vinylformic acid, methacrylic acid, acrylamide, N hydroxymethyl acrylamide, vinylbenzene, vinyl cyanide, vinyl acetate, methyl acrylate, ethyl propenoate, butyl acrylate, Octyl acrylate, methyl methacrylate, butyl methacrylate, can be single monomer, also can be its two kinds and two or more mix monomers.Monomer adopts vacuum 40 DEG C of distilations or for subsequent use after removing stopper with multistage activated alumina adsorption column.
Oxygenant in initiator of the present invention has K
2s
2o
8, (NH
4)
2s
2o
8, Na
2s
2o
8, cyclohexanone peroxide, benzoyl peroxide, hydrogen phosphide cumene, for subsequent use after monomer should being dissolved in for oil-soluble initiator; The reductive agent adopted is NaHSO
3, Na
2sO
3, sodium hydrosulfite 90min, sodium hypophosphite, Sodium Nitrite etc., all water miscible, redox initiation system can be formed by a kind of oxygenant and a kind of reductive agent, also can form combined oxidation reduction initiating system by two or more Oxidizing and Reducing Agents, but component can complicate the issue too much.
Anionic emulsifier of the present invention is: the acid of sodium stearate, nilox resin sodium, sodium lauryl sulphate, sodium laurylsulfonate, Sodium dodecylbenzene sulfonate, Sodium palmityl sulfate, sodium oleate; The nonionic emulsifier adopted has octyl group or polyoxyethylene nonylphenol ether such as OP-10, OP-15, OP-25.It can be the mixture that single emulsifying agent may also be them.Usual employing be anionic emulsifier/nonionic emulsifying agent=1/1 ~ 5, be preferably 1/2 ~ 3.The maleylation vitriol of non-ionic type anionic emulsifier such as octyl group or polyoxyethylene nonylphenol ether OP-10 or OP-15 can also be adopted, can be used alone.The water that the present invention adopts is deionized water or the distilled water of the common arbitrary temp of 0 DEG C ~ 30 DEG C.Nitrogen gas purity 99.99%.
Add-on and raw water, monomer and the climate temperature at that time of first above-mentioned monomer and first initiator are closely related, if temperature is higher, first monomer or first initiator add-on can add in right amount less, if temperature is lower, should add in right amount, usually with 35 DEG C of temperature for benchmark, temperature often declines 1 DEG C, and initiator amount increases the 1-3% of its benchmark consumption, and vice versa.
Embodiment 1
When temperature, monomer temperature and water temperature are all close to 5 DEG C, employing is exempted from heating method and is prepared pure acrylate copolymer emulsion.Butyl acrylate (BA), methyl methacrylate (MMA) go resistance for subsequent use respectively by alumina column.In 1000L enamel polymerization reaction kettle, logical nitrogen drives away oxygen in 10 minutes, keep logical nitrogen later always, add 250 ~ 280kg to anhydrate, Sodium dodecylbenzene sulfonate 1 ~ 2kg, OP-15 emulsifying agent 5 ~ 10kg stirs, and adds S-WAT 0.6 ~ 1kg, adds MMA50 ~ 80kg, AA1 ~ 3kg, adds (NH
4)
2s
2o
81 ~ 1.5kg, logical nitrogen is kept to stir, when temperature is raised to 30-33 DEG C, start to pass into cooling water control temperature in reacting kettle jacketing, temperature is finally made to control 35 ± 1 DEG C, remain on 4 ~ 5 hours synchronous equal proportions in this temperature range inherence and drip the mix monomer be 1. made up of 380 ~ 500kgBA, 180 ~ 250kgMMA, 10 ~ 15kgAA, 2. by 0.8 ~ 1kg Na
2sO
3, 1 ~ 2kg Sodium dodecylbenzene sulfonate and 20kg water composition reductant solution, 3. by 1.2-1.6kg (NH
4)
2s
2o
3with 8 ~ 12kgOP-15 add water 30kg composition oxidizing agent solution, when above-mentioned raw materials adds 85 ~ 90%, stop adding 2. and 3., and 1. feed rate is doubled to add fast, after allowing temperature slowly rise to 40 ~ 45 DEG C of reaction 1h simultaneously, add again above-mentioned remainder 2. and 3., then react 1 hour.Add 5 ~ 8kg ammonia neutralization and make PH=6 ~ 6.5, product is obtained with 100 order nylon net filters, resulting polymers emulsion solid content can reach 70%, can be used as high-grade quick-drying waterproof paint, the anti-stone of automobile hits damping paint and the base-material of tackiness agent on automatic paper composite packaging flow production line.
Embodiment 2
When temperature, monomer temperature and water temperature are all close to 0 DEG C, adopt and exempt from heating method and prepare polyacrylic ester and imitate natural rubber latex or vinylformic acid arctic rubber.Methyl acrylate (MA) goes resistance for subsequent use by alumina column.In 1000L enamel polymerization reaction kettle, logical nitrogen drives away oxygen in 10 minutes, keep logical nitrogen later always, add 250 ~ 270kg to anhydrate, Sodium dodecylbenzene sulfonate 1 ~ 2kg, OP-15 emulsifying agent 5 ~ 10kg stirs, and adds S-WAT 0.6 ~ 1kg, adds MA60 ~ 80kg, AA0.5 ~ 1.5kg, adds (NH
4)
2s
2o
81 ~ 1.5kg, logical nitrogen is kept to stir, when temperature is raised to 30-33 DEG C, start to pass into cooling water control temperature in reacting kettle jacketing, temperature is finally made to control 35 ± 1 DEG C, remain on 4 ~ 5 hours synchronous equal proportions in this temperature range inherence and drip the mix monomer be 1. made up of 450 ~ 500kgMA, 100 ~ 150kgBA, 3 ~ 5kgAA, 30 ~ 50kg isoprene, 2. by 0.8 ~ 1kg Na
2sO
3, 5 ~ 7kg polyoxyethylene octylphenol ether maleylation sodium sulfate and 20kg water composition reductant solution, 3. by 1.2-1.6kg (NH
4)
2s
2o
3, the oxidizing agent solution that forms of 6 ~ 9kg polyoxyethylene octylphenol ether maleylation sodium sulfate and water 30kg; when above-mentioned raw materials adds 85 ~ 90%; stop adding 2. and 3.; and 1. feed rate is doubled to add fast; after allowing temperature slowly rise to 40 ~ 45 DEG C of reaction 1h simultaneously; add again above-mentioned remainder 2. and 3., then react 1 hour.Add 3 ~ 5kg ammonia neutralization and make PH=7, obtain product with 100 order nylon net filters, resulting polymers emulsion solid content can reach 60%, natural rubber latex can be replaced to make coating glue stick and use.Also arctic rubber can be used as with after hydrochloric acid coagulation after washing, drying.
Claims (7)
1. exempt to heat the method for producing polymer emulsion for one kind, it is characterized in that: (methyl) acrylate, go resistance for subsequent use, logical nitrogen in polymerization reaction kettle, add water, emulsifying agent, stir, add monomer, redox initiator, when temperature is in time being raised to 30-33 DEG C, passing into water coolant makes temperature control 35 ± 1 DEG C, at 4 ~ 5 hours, synchronous equal proportion dripped 1. mix monomer, 2. reductive agent and emulsifier aqueous solution, 3. oxygenant and emulsifier aqueous solution, when above-mentioned raw materials adds 85 ~ 90%, stop adding 2. and 3., double to add 1. fast, temperature is made to rise to 40 DEG C of reaction 1h, add remaining 2. and 3., react 1 hour again, resulting polymers emulsion solid content reaches 70%, as quick drying paint, the base-material of tackiness agent.
2. exempt from according to claim 1 to heat the method for producing polymer emulsion, described monomer is vinylformic acid, methacrylic acid, acrylamide, N hydroxymethyl acrylamide, vinylbenzene, vinyl cyanide, vinyl acetate, methyl acrylate, ethyl propenoate, butyl acrylate, Octyl acrylate, methyl methacrylate, butyl methacrylate or two or more mix monomer above-mentioned, and monomer adopts vacuum 40 DEG C of distilations or hinders with the removing of activated alumina adsorption column.
3. exempt from according to claim 1 to heat the method for producing polymer emulsion, the oxygenant in described initiator has K
2s
2o
8, (NH
4)
2s
2o
8, Na
2s
2o
8, cyclohexanone peroxide, benzoyl peroxide, hydrogen phosphide cumene, for subsequent use after should being dissolved in monomer for oil-soluble initiator, the reductive agent adopted is NaHSO
3, Na
2sO
3, sodium hydrosulfite 90min, sodium hypophosphite, Sodium Nitrite, ferrous salt, or form redox initiation system by two or more oxygenants and two or more reductive agents.
4. exempt from according to claim 1 to heat the method for producing polymer emulsion, described emulsifying agent is sodium stearate, nilox resin acid sodium, sodium lauryl sulphate, sodium laurylsulfonate, Sodium dodecylbenzene sulfonate, Sodium palmityl sulfate, one in the maleylation vitriol of a kind of in sodium oleate or multiple and nonionic emulsifier octyl group wherein or polyoxyethylene nonylphenol ether OP-10 or OP-15 or OP-25 or octyl group or polyoxyethylene nonylphenol ether OP-10 or OP-15 forms blending emulsifiers, or in these emulsifying agent above-mentioned two or multiple mixture, anionic/nonionic emulsifying agent=1/1 ~ 5.
5. exempt from according to claim 1 to heat the method for producing polymer emulsion, described water is deionized water or the distilled water of common any natural temperature of 0 DEG C ~ 33 DEG C, and said nitrogen gas purity is 99.99%.
6. exempt from according to claim 1 to heat the method for producing polymer emulsion, described polymerization reaction kettle and preparation technology are: thermometer is being housed, reflux exchanger, feeding device, in the reactor of whipping appts, pass into nitrogen after 5 ~ 10 minutes, add water, emulsifying agent, monomer, emulsifier concentration is made to reach 0.5 ~ 5% of water, monomer is made to reach 5 ~ 20% of water, keep logical nitrogen, stir half an hour, add reductive agent, the consumption of reductive agent is 3/1 to four/3rds of oxygenant mole number used, oxygenant is added after 10 ~ 20 minutes, its consumption is 0.2 ~ 2% of added amount of monomer, continue to keep logical N
2and stirring, note observing temperature, when having in time heating up, initiation reaction is described, when it is warmed up to 30-33 DEG C, the water coolant passing into any natural temperature makes temperature control at 35 DEG C ± 1 DEG C, when after temperature-stable, synchronously mix monomer is added respectively from header tank, the solution of Oxidizing and Reducing Agents, control the flow of feed rate and logical water coolant, the temperature controlled in reactor makes it to remain on 35 ± 1 DEG C, to raw material monomer used only remaining total amount about 5 ~ 10% time, start to add monomer with the feed rate more fast again than usual dispatch, and stop adding initiator while adding monomer fast, the initiator etc. of remaining about 5-10% added after 1 hour, above-mentioned whole process keeps the flow velocity of 100-150 liter/h to pass into nitrogen always, to add after remaining initiator again stirring reaction 1-2 hour up to residual monomer concentration below 0.01%, add auxiliary agent and namely obtain polymer emulsion product.
7. exempt from according to claim 1 to heat the method for producing polymer emulsion, described monomer or initiator first add-on and raw water, monomer and climate temperature at that time closely related, if temperature is higher, monomer or initiator first add-on suitably add less, if temperature is lower, should add, with 35 DEG C of temperature for benchmark, temperature often declines 1 DEG C, and initiator amount increases the 1-3% of its benchmark consumption.
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| CN201010192444.1A CN102268115B (en) | 2010-06-02 | 2010-06-02 | Heating-free technology for producing polymer emulsion |
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| CN102268115B true CN102268115B (en) | 2015-04-22 |
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| CN107034729A (en) * | 2017-02-22 | 2017-08-11 | 镇江市天亿化工研究设计院有限公司 | A kind of cation colophony size |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1563117A (en) * | 2004-03-30 | 2005-01-12 | 复旦大学 | Method for preparing polymethacrylates in high glass-transition temperature |
| CN1667002A (en) * | 1997-12-20 | 2005-09-14 | 帝国化学工业公司 | Polymerisation method |
| CN101041706A (en) * | 2006-03-25 | 2007-09-26 | 赛拉尼斯乳胶有限公司 | Polymer dispersions, process for the preparation thereof and the use thereof |
| CN101100589A (en) * | 2007-07-23 | 2008-01-09 | 中山宝立得高分子材料有限公司 | Modified propylene ester adhesive and producing method thereof |
| CN101365732A (en) * | 2005-08-09 | 2009-02-11 | 阿肯马法国公司 | Method for preparing a polymeric material including a multiblock copolymer prepared by controlled free-radical polymerisation |
-
2010
- 2010-06-02 CN CN201010192444.1A patent/CN102268115B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1667002A (en) * | 1997-12-20 | 2005-09-14 | 帝国化学工业公司 | Polymerisation method |
| CN1563117A (en) * | 2004-03-30 | 2005-01-12 | 复旦大学 | Method for preparing polymethacrylates in high glass-transition temperature |
| CN101365732A (en) * | 2005-08-09 | 2009-02-11 | 阿肯马法国公司 | Method for preparing a polymeric material including a multiblock copolymer prepared by controlled free-radical polymerisation |
| CN101041706A (en) * | 2006-03-25 | 2007-09-26 | 赛拉尼斯乳胶有限公司 | Polymer dispersions, process for the preparation thereof and the use thereof |
| CN101100589A (en) * | 2007-07-23 | 2008-01-09 | 中山宝立得高分子材料有限公司 | Modified propylene ester adhesive and producing method thereof |
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