CN102977255B - Preparation method of BMA (Butyl Methacrylate)-MMA (Methl Methacrylate) solid bead copolymer resin - Google Patents
Preparation method of BMA (Butyl Methacrylate)-MMA (Methl Methacrylate) solid bead copolymer resin Download PDFInfo
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- CN102977255B CN102977255B CN201210505726.1A CN201210505726A CN102977255B CN 102977255 B CN102977255 B CN 102977255B CN 201210505726 A CN201210505726 A CN 201210505726A CN 102977255 B CN102977255 B CN 102977255B
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Abstract
The invention relates to a preparation method of BMA (Butyl Methacrylate)-MMA (Methl Methacrylate) solid bead copolymer resin, and belongs to the technical field of industrial resin. The method comprises the following steps of: adding deionized water and an auxiliary dispersing agent into a reaction kettle, starting stirring, and heating; adding an initiator, a molecular weight regulator, BMA and MMA into the reaction kettle, stirring and heating; adding a dispersing agent into the reaction kettle and continuing the reaction; and washing and sieving to obtain the product solid bead copolymer resin. According to the method provided by the invention, by adopting a water suspension polymerization method, a monomer is dispersed into water for reaction, the heat transfer of the system is uniform, the reaction is relatively moderate and controllable, and the final product BMA-MMA solid bead copolymer resin does not need further processing.
Description
Technical field
The present invention relates to a kind of preparation method of BMA-MMA solid bead copolymer resin, be used to the method preparing solid bead n-BMA-methyl methacrylate copolymer resin specifically, belong to technical field of industrial resin.
Background technology
In prior art, the homopolymerization of methacrylate-based monomer and copolymer resins many employings substance law, solution method are synthesized.
Use substance law synthesizes, and the mixture of monomer and initiator is disposable to be put in reactor, need through prepolymerization, polymerization, high-temperature post-treatment obtains bulk or sheet-like resin, but makes ink, during the purposes such as varnish, also need to carry out pulverizing granulation to it, can the finished product be obtained.
Polymerization process is a strong exothermic process, and in mass polymerization, along with the carrying out of polymerization-filling, system viscosity increases, and heat radiation difficulty, very easily implode occurs.Therefore mass polymerization complex process, reaction time consumption is long, and equipment investment is large.Use solution method is synthesized, and monomer and initiator are put in suitable solution and reacted, and finally obtains the liquid acrylic containing solution, to obtain solid resin, also needs to distill to it the solvent that removes in resin.This process high energy consumption and also need to carry out recovery aftertreatment to solution.
Suspension polymerization refer to monomer small droplets stir and the effect low suspension of dispersion agent in water in monomer small droplets a kind of polymerization process of polymerization reaction take place.Whole reaction system viscosity is low, and good heat dissipation is easy to control.Finally obtain as solid bead resin, aftertreatment is relatively simple.In suspension polymerization, the selection of dispersion agent is particularly important, suspension polymerization many uses inorganic dispersant of current acrylic resin, such as magnesiumcarbonate, calcium phosphate powder etc.Use inorganic dispersion machine, need in last handling process with acid or alkali, dispersion agent to be removed, a large amount of waste water can be produced.Use water-soluble polymer to make dispersion agent, save acid cleaning process, direct clear water washs, and simplifies technique, also environmental protection more.
Summary of the invention
The object of the invention is to overcome above-mentioned weak point, provide a kind of preparation method of BMA-MMA solid bead copolymer resin, adopt in this way, can obtain BMA-MMA solid bead copolymer resin, technique is relatively simple, and reaction process is easy to control, convenient post-treatment.And the solvability of the product obtained is good, transparency is high.
According to technical scheme provided by the invention, the preparation method of BMA-MMA solid bead copolymer resin, step is by weight:
(1) prepare burden: 40-80 part n-BMA (BMA), 20-50 part methyl methacrylate (MMA), 0.1-0.8 part molecular weight regulator, 0.3-2 part initiator, 4-10 part dispersion agent, the deionized water of 0.5-3 part dispersion aids and 150-250 part, for subsequent use;
(2) react: the deionized water first step (1) prepared and dispersion aids join in reactor, open and stir, and be warming up to 35-50 DEG C; Then initiator, molecular weight regulator, BMA and MMA are all put in reactor, stir 30-60 minute at 35-50 DEG C after, be warming up to 65-80 DEG C; After reacting 60-90min at the temperature disclosed above, dispersion agent is joined in reaction, continue reaction 9-12h;
(3) wash: get step (2) reacted reaction solution and dewater in centrifuges; Centrifuge dewatering is used again after washing one time with the clear water of 150-250 part again; Finally dry up with the hot blast of 80-100 DEG C;
(4) sieve: step (3) 40-60 object sieve sieves, and obtains product B MA-MMA solid bead copolymer resin.
Described dispersion agent is polyvinyl alcohol or cellulose family, or the graft copolymer of Polyvinylpyrolidone (PVP) and methylcellulose gum.
Described molecular weight regulator is n-dodecyl mereaptan.
Described dispersion aids is the mixture of one or more materials in the higher alcohols of C6-C14.
Described initiator is dibenzoyl peroxide.
Tool of the present invention has the following advantages: the present invention adopts aqueous suspension polymerization method, and monomer dispersion is reacted in water, and system heat transfer evenly, is reacted comparatively gentle controlled, finally obtained BMA-MMA solid bead copolymer resin, without the need to other processing.And the dispersion agent used in formula is a kind of compound organic dispersing agent, because the polymkeric substance of methyl acrylic ester can be dissolved in methacrylate-based monomer, this just needs dispersion agent to have very strong protective capability and suitable surface tension.The present invention uses Polyvinylpyrolidone (PVP) and methylcellulose gum graft copolymer compound, dispersive ability is strong, and can not with monomer and polymkeric substance generation side reaction, react rear water to clean, eliminate the process of pickling, saved cost, decrease the discharge of waste water, the product solvability simultaneously obtained is good, and transparency is high.
Embodiment
Embodiment 1
(1) prepare burden: get 30 parts of MMA, 70 parts of BMA, 1.2 parts of initiators, 0.4 part of molecular weight regulator, 1 part of dispersion aids, 8 parts of dispersion agents and 180 parts of deionized waters, for subsequent use;
Wherein, described dispersion agent is polyvinyl alcohol dispersion agent, and dispersion aids is one or more in the higher alcohols of C6-C14, and molecular weight regulator is n-dodecyl mereaptan, and initiator is benzoyl peroxide.
(2) react: first by the deionized water that step (1) prepares, dispersion aids is all put in still, open and stir, and temperature is raised to 35 DEG C.By BMA, MMA, molecular weight regulator, initiator all joins in reactor, makes reactor temperature be 35 DEG C, stirs 50 minutes; Be warmed up to 65 DEG C afterwards, and dispersion agent was put in still after 60 minutes by reaction at this temperature, continue reaction 11 hours.
(3) wash: get after the reacted reaction solution centrifuge of step (2) dewaters, then put into and to wash in hopper by 200 parts of clean water after 1 hour, then use centrifuge dewatering; In addition, after, dry up under the hot-air flow of 100 DEG C with cyclone drying tower, then carry out drying treatment;
(4) sieve: finally carrying out sieving with 40 object sieves obtains product B MA-MMA solid bead copolymer resin.
Embodiment 2
(1) prepare burden: get 45 parts of MMA, 55 parts of BMA, 0.8 part of initiator, 0.8 part of molecular weight regulator, 1.8 parts of dispersion aidss, 7 parts of dispersion agents and 200 parts of deionized waters, for subsequent use
Wherein, described dispersion agent is methylcellulose gum, and dispersion aids is one or more in the higher alcohols of C6-C14, and molecular weight regulator is n-dodecyl mereaptan, and initiator is benzoyl peroxide.
(2) react: first by the deionized water that step (1) prepares, dispersion aids is all put in still, open and stir, and temperature is raised to 50 DEG C.By BMA, MMA, molecular weight regulator, initiator all joins in reactor, makes reactor temperature be 50 DEG C, stirs 40 minutes.Be warmed up to 75 DEG C afterwards, and dispersion agent was put in still after 40 minutes by reaction at this temperature, continue reaction 10 hours.
(3) wash: get step (2) reacted reaction solution and dewater in centrifuges; Put into again and to wash in hopper by 180 parts of clean water after 1 hour, then use centrifuge dewatering.Finally dry up under the hot-air flow of 90 DEG C with cyclone drying tower, then carry out drying treatment.
(4) sieve: finally carrying out sieving with 40 object sieves obtains BMA-MMA solid bead copolymer resin.
Embodiment 3
(1) prepare burden: 80 parts of BMA, 50 parts of MMA, 0.8 part of molecular weight regulator, 2 parts of initiators, 10 parts of dispersion agents, the deionized water of 3 parts of dispersion aidss and 250 parts, for subsequent use;
Described dispersion agent is the graft copolymer of Polyvinylpyrolidone (PVP) and methylcellulose gum; Molecular weight regulator is n-dodecyl mereaptan; Dispersion aids is the mixture of one or more materials in the higher alcohols of C6-C14; Initiator is dibenzoyl peroxide.
(2) react: the deionized water first step (1) prepared and dispersion aids join in reactor, open and stir, and be warming up to 40 DEG C; Then initiator, molecular weight regulator, BMA and MMA are all put in reactor, stir at 40 DEG C after 50 minutes and be warming up to 80 DEG C; After reacting 60min at the temperature disclosed above, dispersion agent is joined in reaction, continue reaction 9h;
(3) wash: get step (2) reacted reaction solution and dewater in centrifuges; Centrifuge dewatering is used again after washing one time with the clear water of 250 parts again; Finally dry up with the hot blast of 80-100 DEG C;
(4) sieve: step (3) 60 object sieves sieve, and obtain product solid bead copolymer resin.
Claims (1)
1. a preparation method for BMA-MMA solid bead copolymer resin, is characterized in that step is by weight:
(1) prepare burden: 40-80 part n-BMA, 20-50 part methyl methacrylate, 0.1-0.8 part molecular weight regulator, 1.2-2 part initiator, 7-10 part dispersion agent, the deionized water of 0.5-3 part dispersion aids and 150-250 part, for subsequent use;
(2) react: the deionized water first step (1) prepared and dispersion aids join in reactor, open and stir, and be warming up to 35-50 DEG C; Then initiator, molecular weight regulator, n-BMA and methyl methacrylate are all put in reactor, stir 30-60 minute at 35-50 DEG C after, be warming up to 65-80 DEG C; After reacting 60-90min at the temperature disclosed above, dispersion agent is joined in reaction, continue reaction 9-12h;
(3) wash: get step (2) reacted reaction solution and dewater in centrifuges; Centrifuge dewatering is used again after washing one time with the clear water of 150-250 part again; Finally dry up with the hot blast of 80-100 DEG C;
(4) sieve: step (3) 40-60 object sieve sieves, and obtains product solid bead copolymer resin;
Described dispersion agent is the graft copolymer of Polyvinylpyrolidone (PVP) and methylcellulose gum; Described molecular weight regulator is n-dodecyl mereaptan; Described dispersion aids is the mixture of one or more materials in the higher alcohols of C6-C14; Described initiator is dibenzoyl peroxide.
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| CN201210505726.1A CN102977255B (en) | 2012-12-03 | 2012-12-03 | Preparation method of BMA (Butyl Methacrylate)-MMA (Methl Methacrylate) solid bead copolymer resin |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102090983A (en) * | 2010-12-02 | 2011-06-15 | 天津大学 | Butyl acrylate-methyl methacrylate copolymer based denture base material as well as preparation method and application thereof |
| TW201233689A (en) * | 2011-01-06 | 2012-08-16 | Kaneka Corp | Methyl methacrylate polymer production method |
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| RU2486211C1 (en) * | 2009-10-22 | 2013-06-27 | Асахи Касеи Кемикалз Корпорейшн | Methacrylic resin, article moulded therefrom and method of producing methacrylic resin |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102090983A (en) * | 2010-12-02 | 2011-06-15 | 天津大学 | Butyl acrylate-methyl methacrylate copolymer based denture base material as well as preparation method and application thereof |
| TW201233689A (en) * | 2011-01-06 | 2012-08-16 | Kaneka Corp | Methyl methacrylate polymer production method |
Non-Patent Citations (1)
| Title |
|---|
| 潘祖仁等.4.3 分散剂和分散液界面化学基础.《悬浮聚合》.化学工业出版社,1997,(第1版),第112页. * |
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