CN101519471A - Emulsion polymerization preparation method of chlorinated polyether resin - Google Patents

Emulsion polymerization preparation method of chlorinated polyether resin Download PDF

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Publication number
CN101519471A
CN101519471A CN200810020771A CN200810020771A CN101519471A CN 101519471 A CN101519471 A CN 101519471A CN 200810020771 A CN200810020771 A CN 200810020771A CN 200810020771 A CN200810020771 A CN 200810020771A CN 101519471 A CN101519471 A CN 101519471A
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emulsion
chlorinated polyether
emulsification
water
preparation
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CN200810020771A
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李金忠
周存林
吴德兵
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Jiangsu Liside Chemical Plant Co ltd
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Jiangsu Liside Chemical Plant Co ltd
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Abstract

The invention discloses an emulsion polymerization preparation method of chlorinated polyether resin, which comprises the steps of pre-emulsifying vinyl chloride and vinyl isobutyl ether, and continuously carrying out polymerization reaction. As a further improvement, the pre-emulsification treatment process comprises the steps of uniformly mixing 75-80 parts of chloroethylene and 20-25 parts of vinyl isobutyl ether, and then adding the mixture into deionized water containing a composite emulsifier and a buffering agent for high-speed stirring and emulsification. The polymerization reaction is that chloroethylene and vinyl isobutyl ether are pre-emulsified and then polymerized with water containing a composite emulsifier, a buffering agent and an initiator for 4.5 to 6 hours under the stirring condition, and the polymerization temperature is 45 to 60 ℃. The preparation method has the advantages of suitability for industrial production, simple and safe operation and stable product quality and performance.

Description

The emulsion-polymerizing preparation method of chlorinated polyether resin
Technical field
The present invention relates to the preparation method of vinyl chloride emulsion copolymer resin, relate in particular to the method for the emulsion polymerization prepared chlorinated polyether resin of vinylchlorid and VINYL ISOBUTYL ETHER.
Background technology
Chlorinated polyether resin is the multipolymer of a kind of vinylchlorid and VINYL ISOBUTYL ETHER, can be used for the base-material of the coating of air drying type coating and other physical dryness method.Germany, the U.S. and Japan and domestic a few manufacturer production are only arranged at present in the world.Chlorinated polyether resin can adopt and suspend and emulsion polymerisation process production.
Produce chlorinated polyether resin about suspension method, the preparation method that Jiangyin Correspondent fine chemistry industry company applies for a kind of chlorinated polyether resin on September 28th, 2002 (open day: on March 12nd, 2003, the patent No.: 02138359.6), consisting of of its prescription: vinylchlorid 65~98%, vinyl isobutyl ether 2~35%, the 3rd monomer is a vinylformic acid, unsaturated organic acids such as maleic anhydride, the 3rd monomeric weight is 0.03~5% of above-mentioned total monomer weight, polymerization in water, the weight of water is 1~5 times of above-mentioned total monomer weight, drop into dispersion agent, emulsifying agent, initiator etc., polymerization temperature: 40~80 ℃, constantly stir polymerization reaction time during polymerization: 3~10 hours.The advantage of this method is: reaction conditions is easy to control, polymerization yield height, and resin quality is good.But also there is an apparent in view shortcoming in this method, that is: remaining a large amount of unreacted nearly 30% vinylchlorid, VINYL ISOBUTYL ETHER monomer in the polymerization process system, polymkeric substance must be through removing monomer again, and the ether of recovery will use through the dry back of the distillation that relaunders, dewaters.And reclaim vinylchlorid and want compressed processing, finishing apparatus is more, the operating process lengthening.In addition, this method also exists reaction pressure in the polymerization process excessive (0.7~1.2MPa), particle size analysis is difficult to control in the not good and polymerization process of security, and particle diameter is excessive, and resin is difficult to shortcomings such as oven dry.
Prepare about emulsion copolymerization in the early stage patent (as USP3741946) of chlorinated polyether resin, proposed to adopt substep to add the synthetic technology of forming even chlorinated polyether resin of VC, adopt low temperature (30~40 ℃) polymerization to improve the molecular weight and the coating performance of multipolymer simultaneously, but owing to only adopt active very low ammonium persulfate initiator under temperature of reaction, initiator amount is big, polymerization time long nearly 30 hours.For shortening polymerization reaction time, Hangzhou Electrochemical Group Co., Ltd. has applied for emulsion-polymerizing preparation method (the open day: on March 16th, 2005 of a kind of vinylchlorid/IVE copolymer resins on June 25th, 2004, the patent No. is 200410025656.5), that is: 65~85 parts of vinylchlorid and 15~35 parts of IVE monomers are carried out polymerization at the water that contains emulsifying agent, water soluble oxidized-reduction initiating system, pH regulator agent, polymerization is 2~12 hours under agitation condition, and polymerization temperature is 35~65 ℃.Wherein, vinyl chloride monomer can be once or the gradation input.This preparation method's advantage is: the reaction times is short, and the emulsion-stabilizing that obtains, copolymer resins are formed evenly, and solvability and Heat stability is good are good with the cementability of various metals.This preparation method's shortcoming is: if take disposablely to advance vinylchlorid and have the reaction pressure height, speed of response is fast but polymerization reaction heat is difficult to timely derivation, and potential safety hazard is big in the reaction process, and the reactive polymeric degree is difficult to control, unstable product quality; If adopt the method that adds vinylchlorid in batches, to occur reacting more violent if before pressure descends, add vinylchlorid, polymerization temperature control is unstable, even the danger of overtemperature, superpressure, implode can appear, production is in unsafe condition, as when significantly pressure drop is arranged, adding, extend reaction time again, the performance of resin is affected again, and monomer to occur in the polymerization of aqueous phase more, sticking still is more serious, the polymerization kiss-coating accounts for 0.5%~2% of the amount of monomer that always feeds intake more, every production one still is all wanted clear still, and labour intensity is big, and safety and Health hazardness is big.Therefore this preparation method often only suits to carry out under laboratory condition, is not suitable for suitability for industrialized production.
Summary of the invention
Problem to be solved by this invention provides a kind of chlorinated polyether resin manufacture method that is suitable for suitability for industrialized production, and is easy to operate and safe, and the quality product stable performance through present method is produced has solved
For solving the problems of the technologies described above, the technical solution adopted in the present invention is: a kind of emulsion-polymerizing preparation method of chlorinated polyether resin, earlier vinylchlorid and VINYL ISOBUTYL ETHER are carried out pre-emulsification, and carry out polyreaction more continuously.
As further improvement, described pre-emulsification process is to drop in the deionized water that contains compound emulsifying agent, buffer reagent after 75~80 parts of vinylchlorid and 20~25 parts of VINYL ISOBUTYL ETHERs mix to carry out high-speed stirring emulsification.Described polyreaction be vinylchlorid and VINYL ISOBUTYL ETHER after pre-emulsification, with the water that contains compound emulsifying agent, buffer reagent, initiator polymerization 5~6 hours under agitation condition, polymerization temperature is 45~60 ℃ again.
As further improving, described compound emulsifying agent is reactive anionic emulsifier and nonionic emulsifier compound emulsification system, and the compound emulsifying agent add-on is 1.5~2.5% of a monomer total amount.Described buffer reagent is water miscible carbonate, supercarbonate, hydrophosphate or phosphoric acid salt, and the buffer reagent add-on is 1~1.3% of a monomer total amount.Described initiator is water miscible persulphate, and the add-on of initiator is 0.5~0.8% of a monomer total amount.Described water is deionized water, and water and monomeric weight ratio are 1.5~2:1.
Adopt above technical scheme, compare with common in the past preparation method, remarkable advantage of the present invention is: the present invention adopts the earlier pre-emulsification of monomer to add the method for carrying out polyreaction more continuously, having reduced solubilising micellar new in the polymerization process forms, the mix monomer ratio of components that is solubilized in the micella is relatively stable, and polymerization process is steady, and heat release is even, reaction pressure is in 0.3~0.5MPa, easy control of reaction system.And the present invention reduces at the aqueous phase monomer polymerization, can in time replenish the adsorption surface promoting agent in the continuous propagation process of polymer latex bundle of particle and be protected, and reduced the gel and the kiss-coating phenomenon of polymerization process generation, reduced the number of times of clear still.Produce 28~30 stills (14m3) in now every month and only need clear still 1~2 time and easy cleaning, gel and kiss-coating amount only account for 0.2%~0.3% of the amount of monomer that always feeds intake during each clear still, the labour intensity and the potential safety hazard of clear still have been reduced, greatly reduce production cost, and the resin whiteness of taking this kind method to make improves, accumulation between resin particle is few, resin flow is good, the exsiccant time shortens, production efficiency and output also further improve, technology, product performance are also highly stable, adapt to very much large-scale industrial production.
Embodiment
Further specify the present invention below by embodiment.
Embodiment 1: with compound emulsifying agent 45Kg, buffer reagent 10Kg, deionized water 2000Kg puts in the pre-emulsification still, after the stirring and dissolving, pump into the mixed solution that contains monomer vinylchlorid 2640Kg, VINYL ISOBUTYL ETHER 660Kg, high-speed stirring emulsification after volume pump pump in the polymeric kettle, the pre-throwing has compound emulsifying agent 21Kg, buffer reagent 24.32Kg, deionized water 3280Kg in the polymeric kettle, metering simultaneously pumps into the 21.12Kg initiator, and temperature of reaction is controlled at 60 ℃, reacts end in 4.5 hours.Get viscosity 45mpa.s resin after the breakdown of emulsion drying.
Viscosity measurement: resinous 20% (m/m) toluene solution, NDJ-79 rotary viscosity design determining in the time of 23 ℃.
Embodiment 2: with compound emulsifying agent 28Kg, buffer reagent 6Kg, deionized water 1500Kg puts in the pre-emulsification still, after the stirring and dissolving, pump into the mixed solution that contains monomer vinylchlorid 2400Kg, VINYL ISOBUTYL ETHER 800Kg, high-speed stirring emulsification after volume pump pump in the polymeric kettle, the pre-throwing has compound emulsifying agent 8Kg, buffer reagent 18Kg, deionized water 3100Kg in the polymeric kettle, metering simultaneously pumps into the 12Kg initiator, and temperature of reaction is controlled at 45 ℃, reacts end in 6 hours.Get viscosity 36mpa.s resin after the breakdown of emulsion drying.(the resin viscosity measuring method is the same)
Embodiment 3: with compound emulsifying agent 35Kg, buffer reagent 8Kg, chain regulator 12Kg, deionized water 1600Kg put in the emulsification still after the stirring and dissolving, pump into the mixed solution that contains monomer vinylchlorid 2400Kg, VINYL ISOBUTYL ETHER 800, high-speed stirring emulsification is after volume pump pumps in the polymeric kettle, and pre-throwing of polymeric kettle has compound emulsifying agent 13Kg, buffer reagent 20.8Kg, deionized water 2730Kg, and metering simultaneously pumps into the 16.8Kg initiator, temperature of reaction is controlled at 55 ℃, reacts end in 5 hours.Get viscosity 25mpa.s resin after the breakdown of emulsion drying.(the resin viscosity measuring method is the same)
Embodiment 4: with compound emulsifying agent 35Kg, buffer reagent 8Kg, deionized water 1800Kg puts in the pre-emulsification still, after the stirring and dissolving, pump into the mixed solution that contains monomer vinylchlorid 2400Kg, VINYL ISOBUTYL ETHER 600Kg, high-speed stirring emulsification after volume pump pump in the polymeric kettle, the pre-throwing has compound emulsifying agent 13Kg, buffer reagent 18.4Kg, deionized water 1575Kg in the polymeric kettle, metering simultaneously pumps into the 14.4Kg initiator, and temperature of reaction is controlled at 50 ℃, reacts end in 5 hours.Get viscosity 60mpa.s resin after the breakdown of emulsion drying.(the resin viscosity measuring method is the same)

Claims (7)

1, a kind of emulsion-polymerizing preparation method of chlorinated polyether resin is characterized in that earlier vinylchlorid and VINYL ISOBUTYL ETHER being carried out pre-emulsification, carries out polyreaction more continuously.
2, the emulsion-polymerizing preparation method of a kind of chlorinated polyether resin according to claim 1 is characterized in that described pre-emulsification process is to drop in the water that contains compound emulsifying agent, buffer reagent after 75~80 parts of vinylchlorid and 20~25 parts of VINYL ISOBUTYL ETHERs mix to carry out high-speed stirring emulsification.
3, the emulsion-polymerizing preparation method of a kind of chlorinated polyether resin according to claim 1, it is characterized in that described polyreaction is that vinylchlorid and VINYL ISOBUTYL ETHER are after pre-emulsification, with the water that contains compound emulsifying agent, buffer reagent, initiator polymerization 4.5~6 hours under agitation condition, polymerization temperature is 45~60 ℃ again.
4, the emulsion-polymerizing preparation method of a kind of chlorinated polyether resin according to claim 3 is characterized in that described initiator is water miscible persulphate, and the add-on of initiator is 0.5~0.8% of a vinyl chloride monomer total amount.
5, according to the emulsion-polymerizing preparation method of claim 2 or 3 described a kind of chlorinated polyether resins, it is characterized in that described compound emulsifying agent is reactive anionic emulsifier and nonionic emulsifier compound emulsification system, the total add-on of compound emulsifying agent is 1.5~2.5% of a vinyl chloride monomer total amount.
6, according to the emulsion-polymerizing preparation method of claim 2 or 3 described a kind of chlorinated polyether resins, it is characterized in that described buffer reagent is water miscible carbonate, supercarbonate, hydrophosphate or phosphoric acid salt, the total add-on of buffer reagent is 1~1.3% of a vinyl chloride monomer total amount.
7, according to the emulsion-polymerizing preparation method of claim 2 or 3 described a kind of chlorinated polyether resins, it is characterized in that described water is deionized water, water and monomeric weight ratio are 1.5~2:1.
CN200810020771A 2008-02-26 2008-02-26 Emulsion polymerization preparation method of chlorinated polyether resin Pending CN101519471A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102382229A (en) * 2011-08-09 2012-03-21 安徽省化工研究院 Chlorinated polyether resin with core-shell structure and preparation method thereof
CN102492077A (en) * 2011-11-14 2012-06-13 江苏利思德化工有限公司 Preparation method for modified chlorinated polyether resin
CN110078854A (en) * 2019-04-30 2019-08-02 杭州电化集团有限公司 A kind of preparation method of graphene chlorinated polyether resin

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102382229A (en) * 2011-08-09 2012-03-21 安徽省化工研究院 Chlorinated polyether resin with core-shell structure and preparation method thereof
CN102382229B (en) * 2011-08-09 2013-04-24 安徽省化工研究院 Preparation method of chlorinated polyether resin with core-shell structure
CN102492077A (en) * 2011-11-14 2012-06-13 江苏利思德化工有限公司 Preparation method for modified chlorinated polyether resin
CN110078854A (en) * 2019-04-30 2019-08-02 杭州电化集团有限公司 A kind of preparation method of graphene chlorinated polyether resin
CN110078854B (en) * 2019-04-30 2021-05-18 杭州电化集团有限公司 Preparation method of graphene epichlorohydrin resin

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Open date: 20090902