CN103554337A - Bulk and suspension composite polymerization method for self-granulation solid acrylic resin - Google Patents
Bulk and suspension composite polymerization method for self-granulation solid acrylic resin Download PDFInfo
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- CN103554337A CN103554337A CN201310493693.8A CN201310493693A CN103554337A CN 103554337 A CN103554337 A CN 103554337A CN 201310493693 A CN201310493693 A CN 201310493693A CN 103554337 A CN103554337 A CN 103554337A
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Abstract
The invention discloses a bulk and suspension composite polymerization method for self-granulation solid acrylic resin. Irregular columnar solid acrylic resin is obtained by a two-step polymerization method; in the first step, a prepolymer with polymerization conversion rate of 10-40% is obtained by a bulk prepolymerization method, and the prepolymer is used as a raw material for the second step of suspension polymerization; in the second step, the irregular columnar solid acrylic resin is obtained by a suspension polymerization method of continuously and dropwise adding the prepolymer at a high-temperature and single-temperature section in a reaction kettle with a metal blade-shaped self-granulation cutting device synchronously rotating with a reaction kettle shaft and coated with a polytetrafluoroethylene anti-sticking coating. The method disclosed by the invention overcomes the problems that the existing way of merely adopting the bulk polymerization method cannot obtain the solid acrylic resin with moderate weight-average molecular weight and relatively narrow molecular weight distribution, the implosion phenomenon is easily caused by the polymerization and the polymerization temperature is difficult to control; the cost is reduced.
Description
Technical field
The present invention relates to the polymerization process of solid propenoic acid resin for a kind of coating and ink class industry, especially a kind of solid propenoic acid resin body suspension composite polymeric method realizing from granulation.
Background technology
Conventionally coating and ink class industry have two kinds by the synthetic method of solid propenoic acid resin, i.e. bulk polymerization and suspension polymerization.The production method present situation of current solid propenoic acid resin is in the industry or adopts separately mass polymerization production method synthesis of solid acrylic resin, or adopting separately suspension polymerization production method synthesis of solid acrylic resin.
Mass polymerization production method is in polymerization process, only to adopt mix monomer and initiator and the polyreaction that do not adopt other medium to participate in.The product that mass polymerization production method obtains is blocks of solid acrylic resin and this blocks of solid acrylic resin is sold after by granulating equipment granulation through heating and melting.The shortcoming of mass polymerization production method is that the weight-average molecular weight of the solid propenoic acid resin that obtains after polymerization is about 20000 left and right or slightly high, and the weight-average molecular weight overwhelming majority of coating or the needed solid propenoic acid resin of ink class industry is advisable between 30000---100000, so limited the range of application of the solid propenoic acid resin that mass polymerization production method produces.Because the polymerization autoacceleration effect of middle and later periods of mass polymerization production method polymerization will cause resulting solid propenoic acid resin molecular weight distribution wide, its molecular weight distribution coefficient is greatly between 3---5, the coating or the ink storage stability that use the wide solid propenoic acid resin of molecular weight distribution to manufacture are poor, it shows as and between the shelf lives, easily produces precipitation, layering and grow diming phenomenon.Polymerization autoacceleration effect due to the mass polymerization production method polymerization middle and later periods also can cause easily producing implode phenomenon and the unmanageable phenomenon of polymerization temperature in addition.
Suspension polymerization, by mix monomer, initiator, water and suspension agent and molecular weight regulator form and with stirring, in the polymerization reaction kettle of heating and cooling device and condensation reflux unit, after multistage temperature is controlled, obtain median size and be less than the weight-average molecular weight of 1 millimeter between 20000---100000, the pearl solid propenoic acid resin of molecular weight distribution coefficient between 1.6---2.5.Conventional suspension polymerization is then disposable all the putting in reactor and at about 50 ℃ of the mix monomer that is mixed with initiator and molecular weight regulator to be started to timing by first dropping into water and suspension agent in reactor, is divided into that a plurality of temperature sections are controlled and approximately with 5 ℃ of intensifications per hour---the heat-up rate of 8 ℃ carries out polyreaction.Final polymeric reaction temperature is warming up to approximately 100 ℃ and keep this temperature within about 1 hour, be then cooled to 30 ℃ with interior discharging and after dehydrating, obtain pearl solid propenoic acid resin.Whole polymerization times approximately needs 10---12 hour.The advantage of suspension polymerization be can obtain molecular weight distribution coefficient between 1.6---2.5 compared with narrow molecular weight distributions and weight-average molecular weight the solid propenoic acid resin between 20000---100000.The shortcoming of suspension polymerization is: because be carries out polyreaction can to cause the functional monomer that contains carboxyl or hydroxyl in mix monomer be not finally to change solid propenoic acid resin into other monomer formation copolyreaction completely in polymerization process in large water gaging, but above-mentioned functional monomer has significant proportion in the polymerization initial stage is dissolved in water and along with the autohemagglutination that carries out of polymerization is during water soluble resin is dissolved in water until polymerization finishes finally to fall as wastewater treatment.The reason that produces above-mentioned functions monomer wasted problem is that above-mentioned functions monomer all has the characteristic miscible with the unlimited ratio of water and most coating or ink and all wishes to add above-mentioned functions monomer with solid propenoic acid resin in solid propenoic acid resin production process, so that containing carboxyl or hydroxyl, the solid propenoic acid resin obtaining after polymerization make color stuffing in the process of manufacturing coating or ink be easy to disperse, the good and effect that has good sticking power to being similar to plastic product surface of stability in storage.Because having and above-mentioned functions monomer miscible with the unlimited ratio of water, above-mentioned functions monomer there is higher reactivity ratio with respect to other polymerization single polymerization monomers, also there is the feature of higher reactive behavior, adopt traditional suspension polymerization to be difficult to synthesize some coating or the needed solid propenoic acid resin with high acid value or high hydroxyl value of ink.While adopting traditional suspension polymerization to contain above-mentioned functional monomer in mix monomer, the COD value that reaction finishes the polymerization waste water of rear generation can reach between 10000---100000, and the follow-up water treatment need of work of high COD value waste water like this drops into compared with large wealth force-summing device and in the flocculation process stage of water treatment, produced again a lot of solid waste and caused secondary refuse to produce simultaneously.Adopt conventional suspension polymerization to comprise disposable the putting in polymerization reaction kettle of whole raw materials of water, therefore need to start timing from approximately 50 ℃, adopt the temperature controlled polymerization methods of multistage, all polymerization time approximately needs complete for 10---12 hour, and polymerization time long production efficiency is low relatively.
Summary of the invention
The defect that the present invention exists in order to overcome the operational path of the traditional suspension polymerization synthesis of solid acrylic resin of at present simple employing bulk polymerization or simple employing, and further bring into play the advantage separately of above-mentioned two kinds of polymerization processs, provide a kind of and can and from the suspension polymerization still of prilling granulator, obtain irregular column solid propenoic acid resin body suspension composite polymeric method by band from the solid propenoic acid resin body suspension composite polymeric method of granulation.
For achieving the above object, the technical solution used in the present invention is: can be from the solid propenoic acid resin body suspension composite polymeric method of granulation, adopt two-stage polymerization method to obtain irregular column solid propenoic acid resin, the first step adopts bulk prepolymerization method to obtain the prepolymer of polymerisation conversion between 10%--40%, and using this prepolymer as second step suspension polymerization raw material; Second step adopt with synchronize with reactor axle rotation metal blade shape and scribble tetrafluoroethylene anti-stick coating in the suspension polymerization still of granulation cutting unit, at high-temperature list temperature section, drip continuously the suspension polymerization of prepolymer as previously mentioned and obtain irregular column solid propenoic acid resin.Described second step, with synchronize the metal blade shape that rotates and scribble tetrafluoroethylene anti-stick coating in the suspension polymerization still of granulation cutting unit with reactor axle, the prepolymer being dripped after blade cuts becomes the solid propenoic acid resin of interrupted irregular column from continuous column, the water that is about reactor 1/2nd volumes by pumping enters reactor and adds the dispersion agent of the corresponding conventional suspension polymerization usage quantity of the water yield therewith, water is warmed up to 90 ℃ simultaneously---and 100 ℃ are standby; The prepolymer that the mass polymerization that is about reactor 1/3rd volumes is obtained is with being pumped to dropping tank; In reactor, water temperature reaches 90 ℃---100 ℃, start to drip continuously aforesaid prepolymer in reactor; Because making current in reactor, the effect of stirring in reactor to Polycondensation Reactor and Esterification Reactor, flows in the middle of thering is autoreaction still top, what then by Polycondensation Reactor and Esterification Reactor, along reactor wall, upwards flowed flows, and the prepolymer being dripped continuously is cut into interrupted irregular column form object; Be cut into irregular column prepolymer and be about 90 ℃ in water temperature---100 ℃, and in containing the current of dispersion agent, carrying out in reactor with water same stream to flow; After whole prepolymer droppings finishes, continue to keep approximately 100 ℃ of slakings of material in reactor temperature approximately 1 hour, be then cooled to 30 ℃ with interior discharging, and after dehydrating, obtain irregular column solid propenoic acid resin.
The invention has the beneficial effects as follows: owing to having adopted the solid propenoic acid resin body suspension composite polymeric method having from granulation function of the present invention, overcome simple employing bulk polymerization and can not obtain weight-average molecular weight between 20000---100000, the coating that the use face of molecular weight distribution coefficient between 1.6---2.5 is wider or ink class industry solid propenoic acid resin.Thereby also overcome easy generation implode phenomenon and the unmanageable problem of polymerization temperature that simple employing bulk polymerization causes due to polymerization middle and later periods polymerization autoacceleration effect in polymerization process simultaneously and saved melting granulating technology and reduced production cost.Due to adopted of the present invention have from granulation work can solid propenoic acid resin body suspension composite polymeric method, when having overcome the conventional suspension polymerization of simple employing having contained carboxyl or hydroxy kind functional monomer in mix monomer because above-mentioned functions row monomer has the problem that the character miscible with the unlimited ratio of water causes synthesizing the solid propenoic acid resin of high acid value or high hydroxyl value.When having overcome the problems referred to above, also solved and contained in functional monomer participation polymerization situation, the COD value of polymerization waste water is up between 10000---100000, the large and wasting of resources problem that is discharged as waste water from the functional monomer obtaining after oil deep processing of wastewater treatment difficulty.
The present invention has utilized the body suspension composite polymeric method that technological process as shown in Figure 1 forms can prepare weight-average molecular weight between 20000～100000, and molecular weight distribution is between 1.6～2.5 and can have the irregular column solid propenoic acid resin of high hydroxyl value or high acid value.
Accompanying drawing explanation
Fig. 1 is the first step bulk prepolymerization reactor of realizing two steps of the present invention and second step with synchronize the connection diagram of the suspension polymerization still from granulation cutting unit of the metal blade shape that rotates with reactor axle, in figure:
1 is bulk prepolymerization reactor; 2 is suspension polymerization still; 3 for dripping tank; 4 is that metal blade shape is from granulation cutting unit.
embodiment
The first step is the bulk prepolymerization stage: the mix monomer that is mixed with initiator and molecular weight regulator is all pumped to stirring, the bulk prepolymerization reactor 1 of heating and cooling device and condensation reflux unit is warming up to reactor and between 50 ℃ to 65 ℃, carries out prepolymerization under whipped state.Actual temp is looked the kind of the mix monomer that participates in reaction and is determined.Mix monomer in reactor becomes viscosity from watery viscosity and is cooled to 30 ℃ with the interior prepolymerization that stops between 100mPa.s---300mPa.s time, and now prepolymerized transformation efficiency is between 10%---40%.Keep 30 ℃ to using the raw material of interior temperature as the improved suspension polymerization of the second step stage this prepolymer.
Second step is the suspension polymerization stage after improving: on its suspension polymerization still 2 tops, be provided with and drip tank 3, in reactor lower than between 10 centimetres to 20 centimetres of polymerization water liquid levels, install additional that 4---8 sheet scribbles tetrafluoroethylene anti-stick coating and synchronize with stir shaft rotate from granulation metal blade 4 as to the prepolymer being dripped continuously by high temperature from granulation cutting unit, thereby the prepolymer being dripped after this blade cuts from continuous column become interrupted irregular column realized resin after polymerization from granulation function.Aforesaid device just can carry out after having transformed the suspension polymerization stage after second step of the present invention also improves.First the water that pumping quantity is about reactor 1/2nd volumes enters reactor and adds the dispersion agent of the corresponding conventional suspension polymerization usage quantity of the water yield therewith water to be warmed up to 90 ℃ simultaneously---and 100 ℃ are standby.The prepolymer that the aforesaid mass polymerization that is about reactor 1/3rd volumes is obtained is pumped to dropping tank, and in reactor, water temperature reaches 90 ℃---100 ℃ and in reactor scribbling under the cutting unit operating condition that tetrafluoroethylene is coated with anti-stick coating described in original stirring and the present invention start to drip continuously aforesaid prepolymer in reactor.Due to the effect of the original stirring of reactor, making in reactor current have in the middle of autoreaction still top to flow then to Polycondensation Reactor and Esterification Reactor is that the prepolymer being dripped the continuously described by the present invention cutting unit that scribbles tetrafluoroethylene anti-stick coating is cut into interrupted irregular column form object and has reached of the present invention from granulation function along the reactor wall mobile mobility that makes progress by Polycondensation Reactor and Esterification Reactor.Be cut into irregular column prepolymer and be about 90 ℃ in water temperature---in 100 ℃ and the current that contain dispersion agent, carrying out in reactor with water same stream to flow behavior.Because polymerization water temperature is about 90 ℃---100 ℃ and to be dripped thing be not original mix monomer but polymerisation conversion is about the prepolymer of 10%---40%, therefore do not wait until that when granulation prepolymer reaches the extreme higher position of polywater, polymerization has become the solid propenoic acid resin of irregular column.After whole prepolymer droppings finishes, continuation keeps approximately 100 ℃ of slakings of material in reactor temperature approximately 1 hour, is then cooled to 30 ℃ with interior discharging, and after dehydrating, obtains irregular column solid propenoic acid resin of the present invention.
For technology contents of the present invention is made to specific descriptions, hereby for embodiment, be illustrated, embodiment Raw all represents it with weight.
Embodiment 1:
The first step: by 78 ㎏ methyl methacrylates, 18 ㎏ butyl acrylates, 4 ㎏ vinylformic acid and 1.5 ㎏ Diisopropyl azodicarboxylates and 0.5 ㎏ normal-butyl thiol molecule amount conditioning agent add in reactor, are warming up to 60 ℃ and keep this temperature to carry out bulk prepolymerization under whipped state.When material in reactor is cooled to below 30 ℃ when about watery viscosity becomes similar edible oil viscosity state, now polymerisation conversion is about 25%.This polymerisation conversion is about to 25% prepolymer, and to maintain 30 ℃ of following temperature standby.
Second step: above-mentioned prepolymer is pumped in the dropping tank of modified version suspension polymerization still, more than water is warming up to 90 degree in 200 ㎏ water and 0.2 ㎏ dispersion agent are pumped in reactor and under whipped state reactor.Now the prepolymer dripping in tank is dripped continuously and in dropping process, maintains all the time water temperature more than 90 ℃ in reactor.The prepolymer being dripped continuously in water, in dropping process, meet scribble tetrafluoroethylene anti-stick coating after granulation cutting unit, be cut into interrupted irregular column, the very fast polymerization in more than 90 ℃ high-temperature water of this irregular column prepolymer becomes rigid irregular column solid propenoic acid resin.After whole prepolymers are added dropwise to complete, keep said temperature after one hour, to be cooled to 30 ℃ with bottom discharge, after dehydrating, obtain: non-volatile part; >=99%, acid number: 22mgKOH/g, weight-average molecular weight: 45000, molecular weight distribution coefficient: 1.9 irregular column solid propenoic acid resin.
Embodiment 2:
The first step: by 60 ㎏ vinylbenzene, 10 ㎏ methyl methacrylates, 22 ㎏ butyl acrylates, 8 ㎏ vinylformic acid and 1.5 ㎏ Diisopropyl azodicarboxylates and 0.5 ㎏ normal-butyl thiol molecule amount conditioning agent add in reactor, are warming up to 55 ℃ and keep this temperature to carry out bulk prepolymerization under whipped state.When material in reactor is cooled to below 30 ℃ when 1 watery viscosity becomes similar edible oil viscosity, now polymerisation conversion is about 35%.This polymerisation conversion is about to 35% prepolymer, and to maintain 30 ℃ of following temperature standby.
Second step: above-mentioned prepolymer is pumped in the dropping tank of modified version suspension polymerization still, more than water is warming up to 90 degree in 200 ㎏ water and 0.2 ㎏ dispersion agent are pumped in reactor and under whipped state reactor.Now the prepolymer dripping in tank is dripped continuously and in dropping process, maintains all the time water temperature more than 90 ℃ in reactor.The prepolymer being dripped continuously in water, in dropping process, meet scribble tetrafluoroethylene anti-stick coating after granulation cutting unit, be cut into interrupted irregular column, the very fast polymerization in more than 90 ℃ high-temperature water of this irregular column prepolymer becomes rigid irregular column solid propenoic acid resin.After being added dropwise to complete, whole prepolymers keep said temperature after one hour, to be cooled to 30 ℃ with bottom discharge.After dehydrating, obtain: non-volatile part; >=99%, acid number: 48mgKOH/g, weight-average molecular weight: 36000, molecular weight distribution coefficient: 2.1 irregular column solid propenoic acid resin.
Embodiment 3:
The first step: by 80 ㎏ methyl methacrylates, the positive fourth fat of 15 ㎏ methacrylic acid, 5 ㎏ vinylformic acid and 1.5 ㎏ Diisopropyl azodicarboxylates and 1 ㎏ normal-butyl thiol molecule amount conditioning agent add in reactor, are warming up to 55 ℃ and keep this temperature to carry out bulk prepolymerization under whipped state.When material in reactor is cooled to below 30 ℃ when 1 watery viscosity becomes similar edible oil viscosity, now polymerisation conversion is about 30%.This polymerisation conversion is about to 30% prepolymer, and to maintain 30 ℃ of following temperature standby.
Second step: above-mentioned prepolymer is pumped in the dropping tank of modified version suspension polymerization still, more than water is warming up to 90 degree in 200 ㎏ water and 0.2 ㎏ dispersion agent are pumped in reactor and under whipped state reactor.Now the prepolymer dripping in tank is dripped continuously and in dropping process, maintains all the time water temperature more than 90 ℃ in reactor.The prepolymer being dripped continuously in water, in dropping process, meet scribble tetrafluoroethylene anti-stick coating after granulation cutting unit, be cut into interrupted irregular column, the very fast polymerization in more than 90 ℃ high-temperature water of this irregular column prepolymer becomes rigid irregular column solid propenoic acid resin.After whole prepolymers are added dropwise to complete, keeping said temperature after one hour, to be cooled to 30 ℃ obtains after dehydrating with bottom discharge: non-volatile part; >=99%, acid number: 26mgKOH/g, weight-average molecular weight: 75000 molecular weight distribution coefficients: 2.3 irregular column solid propenoic acid resin.
Claims (2)
- One kind can be from the solid propenoic acid resin body suspension composite polymeric method of granulation, it is characterized in that: adopt two-stage polymerization method to obtain irregular column solid propenoic acid resin, the first step adopts bulk prepolymerization method to obtain the prepolymer of polymerisation conversion between 10%--40%, and using this prepolymer as second step suspension polymerization raw material; Second step adopt with synchronize with reactor axle rotation metal blade shape and scribble tetrafluoroethylene anti-stick coating in the suspension polymerization still of granulation cutting unit, at high-temperature list temperature section, drip continuously the suspension polymerization of prepolymer as previously mentioned and obtain irregular column solid propenoic acid resin.
- According to claim 1 a kind of can be from the solid propenoic acid resin body suspension composite polymeric method of granulation, it is characterized in that: described second step, with synchronize the metal blade shape that rotates and scribble tetrafluoroethylene anti-stick coating in the suspension polymerization still of granulation cutting unit with reactor axle, the prepolymer being dripped after blade cuts becomes the solid propenoic acid resin of interrupted irregular column from continuous column, by the dispersion agent that is pumped to the water that is about reactor 1/2nd volumes and enters reactor and add the corresponding conventional suspension polymerization usage quantity of the water yield therewith, water is warmed up to 90 ℃ simultaneously---100 ℃ are standby, the prepolymer that the mass polymerization that is about reactor 1/3rd volumes is obtained is with being pumped to dropping tank, in this reactor, water temperature reaches 90 ℃---100 ℃, start to drip continuously aforesaid prepolymer in reactor, the prepolymer being dripped continuously is cut into interrupted irregular column form object, be cut into irregular column prepolymer and be about 90 ℃ in water temperature---100 ℃, and in containing the current of dispersion agent, carrying out in reactor with water same stream to flow, after whole prepolymer droppings finishes, continue to keep approximately 100 ℃ of slakings of material in reactor temperature approximately 1 hour, be then cooled to 30 ℃ with interior discharging, after dehydrating, obtain irregular column solid propenoic acid resin.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104031202A (en) * | 2014-06-17 | 2014-09-10 | 中国科学院化学研究所 | Polyacrylic acid printing ink resin and preparation method thereof |
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2013
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| CN1265336A (en) * | 1998-03-17 | 2000-09-06 | Basf公司 | Reactor for chemical reaction |
| CN101558078A (en) * | 2006-12-12 | 2009-10-14 | 萨宝公司 | Macrolide compounds endowed with antiinflammatory activity |
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| CN104031202A (en) * | 2014-06-17 | 2014-09-10 | 中国科学院化学研究所 | Polyacrylic acid printing ink resin and preparation method thereof |
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Application publication date: 20140205 |