CN1152068C - Continuous bulk process and plant for preparing ABS via stirring from outside reactor - Google Patents
Continuous bulk process and plant for preparing ABS via stirring from outside reactor Download PDFInfo
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- CN1152068C CN1152068C CNB021209707A CN02120970A CN1152068C CN 1152068 C CN1152068 C CN 1152068C CN B021209707 A CNB021209707 A CN B021209707A CN 02120970 A CN02120970 A CN 02120970A CN 1152068 C CN1152068 C CN 1152068C
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Abstract
The present invention relates to a method for producing ABS resin out of a kettle with a continuous main body stirring method, and more specially, the present invention relates to a method for producing ABS resin products. The method comprises: in the technology of producing ABS resin with a traditional continuous main body method, an intense stirring system is added in first kettles of a plurality of polymerization kettles which can realize continuous polymerization; thus, the phase planes of materials are converted, and the rubber granules are controlled within a suitable range; then, the materials are conveyed in a subsequent polymerization kettle for polymerization reaction and devolatilization. Thus, a final ABS resin product is produced. The present invention also relates to a device for realizing the method. By adopting the method and the device of the present invention, the produced ABS resin has good performance. Compared with traditional ABS resin products, the size and the distribution of the rubber granules are obviously improved, and the impact strength and the tensile strength are increased. Thus, the application range of the ABS resin is widened, and the quality of the ABS resin products is enhanced.
Description
The present invention relates to a kind of still and stir continous way substance law ABS resin production method outward, specifically in the technology of traditional continous way substance law production ABS resin, after the first still of a plurality of polymeric kettles of realizing successive polymerization, add after a powerful stirring system realizes the transformation mutually of its material, again its material is sent into follow-up polymeric kettle and continued polyreaction, through devolatilization, produce final ABS resin product again.The invention still further relates to the device of realizing aforesaid method.
ABS resin is a kind of engineering plastics of having many uses, it has very high shock strength and resistance toheat to be fit to be used in household electrical appliances, as inner bag, kitchen utensils, automobile component and the toy etc. of the shell of TV, receiving set, computer, commercial parts, huge tanks, refrigerator.It is the product that close association is arranged with high-level standard of living.The use of ABS resin is very surprising in the growth rate of China, thereby causes gap very big between demand and the turnout, and 80% of about domestic consumption needs import, in order to reach self-supporting, must greatly develop production technology and increase output.
ABS resin product and manufacturing processed have very big differentiation at nearly many decades, in the latter stage fifties, the business-like production technology of ABS resin is an emulsion polymerization method, the suspension polymerization technology also is used subsequently, up to the end of the sixties substance law just be used industrial, its principal advantages is that the fund of founding the factory is few, the product quality unanimity that continuous processing is produced.Compare with emulsion process technology, product is finished in a step.And there is not an environmental issue of waste disposal.After the eighties, United States Government effluxes the strict standard of having stipulated to environmental protection and waste water, and substance law technology more and more obtains people's attention.
Body-solution polymerization and successive polymerization belong to known method and are described in for example US3, and 903,200, US4,598,124, US5,166,261, US5,414,045, US5,569,709, US5, in 807,928 United States Patent (USP)s such as grade;
U.S. Pat 5,404,045 by people such as Chen-Youn Sue invention; US5,569,709; Disclose and a kind ofly be used to prepare the grafting of ABS resin graft copolymer, change and the multi-stage bulk process of crosslinked control mutually, comprise that the liquid feeding that will contain vinylidene aromatic monomer, unsaturated nitrile and butadiene polymer joins the graft reaction device, make it pre-reaction and generate graft rubber external phase polymerisate.Subsequently graft reaction device product is joined the phase shift reactor.The second section polymerisate that comes out from the phase shift reactor joins the end reaction device, and further polymerization generates the three stage polymerization product.And then produce final thermoplastic compounds through devolatilization.
By the US5 of people such as Davide Preti invention, 807,928; It discloses a kind of " preparation method of acrylonitrile/butadiene/styrene copolymer resin ".Comprising: a) preparation is by being dissolved in the solution that the two block line style rubber of the 5-B type that contains in vinylbenzene and the acrylonitrile monemer mixture are formed; B) in the solution of step a), add and at least aly have the average-volume diameter greater than 1.5 μ m and be comprised in rubber grain preliminary shaping ABS resin in the polymer matrix; C) this preliminary shaping ABS resin is dissolved in the solution of step (a); The solution that d) will so obtain continuously imports in the polyreaction of ABS resin; E) make the final solution polymerization reaction take place so that preparation has the ABS resin of polymorphic shape.
By the US3 of people such as David L invention, 903,200 patent disclosures a kind of continous way mass polymerization technology of ABS resin polymkeric substance; Wherein, proposed to disperse described first section grafted elastoprene monomer phase by first section partially polymerized mixture of shear agitation, described rubber monomer particulate mean sizes is about 0.7-1.0 μ m, this rubber grain is mixed in the mixture and be grafted on the polymkeric substance.
Invent by people such as Vincent A, in disclosed US4 on July 1st, 1986,598,124 patents, a kind of mass polymerization technology of ABS resin polymerization mixture is shown, by polymeric vinylbenzene and acrylonitrile grafting are hanged down on the gel elastoprene to first beginning and end grafted, form graft copolymer comprising (A); (B) with described by being disperseed in the grafted monomer multipolymer by graft copolymer; The particle size of the described elastoprene in the wherein said polymkeric substance is 0.1-10 μ m, preferred 0.8-10 μ m.
By people such as Wan C.WU invention, in disclosed US5 on November 24th, 1992,166,261 patents have disclosed a kind of continous way mass polymerization prepared high gloss ABS resin.Wherein Fig. 1 illustrates a kind of preferred embodiment that is used for method and apparatus of the present invention.Wherein, two polymerization container R1 and R2 are shown, devolatilization device DV;
The ABS resin product of above-mentioned patent preparation, though its advantage is respectively arranged, can be used for different occasions, but all have the common deficiency, be exactly abundant inadequately in the transformation mutually of graftomer, cause final ABS resin product shock strength, it is lower to draw Zhang Qiangdu, thereby to ABS resin plastic working performance, the life-span of goods etc. exerts an influence.
In addition, the technology of producing high impact polystyrene (the cinnamic multipolymer of grafting rubbers) is long, and production equipment is very general; Can the such problem of the long-term thinking of the inventor in order to solve the ABS resin product that meets market in urgent need, utilize original production high impact polystyrene device, through transforming a little, and can production ABS resin product.
The inventor is through the years of researches practice, from high impact polystyrene (the cinnamic multipolymer of grafting rubbers) production technology research, it is diverted to and produces the ABS resin finished product that meets market demand the most at last, comprises the various products of producing the ejection formation class and the extrusion type trade mark.Finally explore and utilize original production high impact polystyrene device to transform the optimal path of producing the ABS resin product that meets market demand a little.
Below, prove the feasibility of the theory and practice that realizes the inventive method in conjunction with the defective of production process of producing high impact polystyrene at present and existence.
1. the high impact polystyrene production process tentatively is rubber to be dissolved in become the charging of polyreaction rubber liquid in styrene monomer and the solvent, enter after the reactor, temperature of reaction rises, polyreaction makes monomer (vinylbenzene) aggregate into polystyrene (ps), because different solubility, polystyrene will form another and practise physiognomy, and main practising physiognomy be rubber and monomeric solution or be called for short rubber and practise physiognomy, and be called and will disperse to practise physiognomy and be dispersed in the polystyrene of rubber in practising physiognomy; When polyreaction is carried out gradually, when the content volume of polystyrene has surpassed the content volume that rubber practises physiognomy, under abundant stirring state, practise physiognomy very big transformation can take place, be called the conversion of practising physiognomy.After conversion, mainly practising physiognomy will be for polystyrene, and original rubber is practised physiognomy to be transformed into and disperseed to practise physiognomy.Impel the conversion of practising physiognomy to need enough shearings.Practise physiognomy the conversion after; whole viscosity can significantly descend; rubber is practised physiognomy and is begun to form the dispersive rubber grain simultaneously; but the rubber grain size is also unstable; contrary phenomenon of mixing usually can increase the difficulty of control and operation in the production process of working continuously; such as the bottom, below that begins to occur in first reactor of the conversion of practising physiognomy is based on finishing in first reactor against the existence that mixes phenomenon.When polymeric solution enters the upper end of second reactor, just finish the conversion of practising physiognomy gradually.But the stir speed (S.S.) difference of two reactors, the viscosity of polymerization colloidal sol is very not high before the conversion of practising physiognomy is finished, increased the load of reactor stirring system, practise physiognomy the conversion after, though viscosity can descend, but the solid content of polymerization colloidal sol (PS) is along with the continuation meeting of polyreaction constantly increases, whole viscosity in the reactor also constantly increases, the running of stirring system becomes the problem of a difficulty, the size of especially wishing to control by faster rotational speed rubber grain is an operational bottleneck, the rerum natura of the size of rubber grain and distribution thereof and product has substantial connection, and the rubber grain in the high impact polystyrene product is greatly about 1.0-5 μ m.
2. the polyreaction of production ABS resin has similarity with production high impact polystyrene (PS), the switching process etc. of practising physiognomy of its rubber for example, but many different places are arranged also, except used monomer difference, the viscosity of polymerization colloidal sol much bigger (1-3 doubly) when polyreaction, the heat that reaction is simultaneously produced also higher (increasing more than 30%), more different from the texture ratio of practising physiognomy of product, though ABS resin and PS are the plastics system of two-phase face structure, rubber in the PS structure granular size of practising physiognomy is about 1-5 μ m, and the particle of practising physiognomy of the rubber and ABS resin is practised physiognomy in the structure is about 0.3-0.65 μ m; Based on above difference, in the process of especially production ABS resin, the high viscosity of polymerization colloidal sol makes that general high impact polystyrene factory can't the production ABS resin, and its major cause is that stirring system can't be born the stirring load that high viscosity produces.If can overcome this operational bottleneck, but high impact polystyrene device production ABS resin just, and this also is a problem to be solved by this invention.
3. abovely can bring difficulty for running from analyzing PS process description contrary phenomenon of mixing the production process of working continuously, the enough stirrings of changing of process need of practising physiognomy just can be finished, for ABS resin production, also there are the problems referred to above, owing in first reactor, can not fully finish the conversion of practising physiognomy, when this ABS resin polymerization colloidal sol of not finishing the conversion of practising physiognomy arrives the upper end of second reactor, PS is higher for its ratio of viscosities, general stirring system (for example producing second reactor of PS) can not be born the load that such viscosity produces, and can't in time finish the conversion of practising physiognomy; In this case, even produce ABS resin, wherein the rubber grain skewness can not reach ideal size such as 0.3-0.5 μ m, causes the product rerum natura bad, shock strength and to draw Zhang Qiangdu lower.Thereby, limited the end-use of product.
4. because causing, the contrary mixed phenomenon in the production process practises physiognomy conversion not exclusively in order to overcome, thereby the stirring system that the material viscosity that enters second reactor is raise to reactor has increased the great number of issues that load is brought, the present invention is provided with a kind of external class pipeline high speed strong mixer system and (is suitable for the PS production equipment is changed into the ABS resin production equipment between first reactor and second reactor, at a high speed, small-sized, it is little more favourable to take up room).Powerful stirring system outside first reactor is not practised physiognomy the material elder generation input still of changing fully, import second reactor again after finishing the transformation of practising physiognomy, use device production ABS resin product of the present invention, excellent property, rubber grain size and distribution all can reach requirement.
Based on above-mentioned, purpose of the present invention aims to provide a kind of production and has premium properties, shock strength and to draw Zhang Qiangdu all high, the method for the ABS resin product that the purposes scope is wide.
Another object of the present invention provides a kind of device that adopts aforesaid method to produce above-mentioned ABS resin product, and this device can be by now widely distributed PS production equipment reconstruction, its less investment, and the time is fast.Find more than one for solving market high quality ABS resin in short supply product, fast, good, the road of province.
A kind of still of the present invention stirs the method that the continous way substance law prepares ABS resin outward, comprising:
A kind of rubber is dissolved in vinylbenzene, the acrylonitrile monemer and in solvent, tranquilizer, chain transfer auxiliary agent, initiator through mixing the step of establishing the 1st reactor of agitating member in adding;
In first reactor, carry out polyreaction and generate any step of first section polymerisate certain to the inversion of phases;
The outer powerful stirring system of material input still that contains first section polymerisate that to discharge from first reactor, through this brute force stirring system stir realize practising physiognomy change after and be controlled at rubber grain in the optimum range after enter the step of second reactor;
In a follow-up N reactor, proceed polyreaction, generate the step of polymerisate;
To separate through devolatilization again from the material that final reactor is discharged, remove unreacted residual monomer and solvent, obtain the step of thermoplasticity polymerization product A BS resin of the present invention;
It is characterized in that outside the still of the first reactor postposition powerful stirring system comprises the material that includes first section polymerisate that will discharge from first reactor is established agitating member in sending into after one is suitable for carrying the pump pressurization of high-viscosity material strong mixer, the setting of this strong mixer agitating member and rotating speed should be able to be guaranteed to finish through the material that strong mixer stirs and change promptly wherein rubber mutually and be transformed into disperse phase by external phase and control rubber particle size and send into follow-up reactor after in optimum range and continue reaction.
Described N=1,2 or 3; Promptly 3,4 or 5 still continuous polymerizations prepare ABS resin.
Described strong mixer is a propeller agitator, and the gap between its rotating vane and the stator blades is 3.175-6.35mm (a 1/8-1/4 inch).
The service temperature of described strong mixer is 120-124 ℃.
The finished product ABS resin rubber grain is distributed as 0.4-0.8 μ m.
Described rubber is polybutadiene rubber.
Can use corresponding to the raw material for preparing high impact polystyrene with reference to method of the present invention, process operation parameter prepares high impact polystyrene.
The present invention also provides the device of realizing above-mentioned preparation ABS resin method, comprises
A kind of rubber is dissolved in vinylbenzene, the acrylonitrile monemer and in solvent, tranquilizer, chain transfer auxiliary agent, initiator through mixing the system that establishes the 1st reactor of agitating member in adding;
In first reactor, carry out polyreaction and generate any system of first section polymerisate certain to the inversion of phases;
The outer powerful stirring system of material input still that contains first section polymerisate that to discharge from first reactor stirs to realize practising physiognomy through this brute force stirring system and changes the back and control the system that rubber grain enters second reactor after in the scope that suits;
In a follow-up N reactor, proceed polyreaction, generate the system of polymerisate;
To separate through devolatilization again from the material that final reactor is discharged, remove unreacted residual monomer and solvent, obtain the system of thermoplasticity polymerization product A BS resin of the present invention;
It is characterized in that outside the still of the first reactor postposition powerful stirring system comprises the material that includes first section polymerisate that will discharge from first reactor is established agitating member in sending into after one is suitable for carrying the pump pressurization of high-viscosity material strong mixer, the setting of this strong mixer agitating member and rotating speed should be able to be guaranteed to finish through the material that strong mixer stirs and change promptly wherein rubber mutually and be transformed into disperse phase by external phase and control the rubber size and send into follow-up reactor after in suitable scope and continue reaction.
List preferred embodiment below and describe the present invention in conjunction with the accompanying drawings.
Fig. 1 is traditional ABS resin (or PS) continous way mass polymerization process flow sheet.
Fig. 2 is that ABS resin still of the present invention forces to stir the mass polymerization process flow sheet outward.
Referring to Fig. 1, Fig. 1 is traditional continous way substance law solution polymerization ABS resin (or PS) process flow sheet.A is a styrene monomer among the figure; B is acrylonitrile monemer (AN); C is a solvent ethylbenzene; D is the rubber grain slurry; Auxiliary agents such as E initiator; 1 circulation storage tank; 2 feed sump; 3 feed preheaters; 4 adjuvant systems; 5 the 1st reactors; 6 the 2nd reactors; 7 the 3rd reactors; 8 devolatilization grooves; 9 product pelletizings; 10 finished product packings.
Operating process is as follows, a kind of rubber is dissolved in part vinylbenzene (A), form slurry in vinyl cyanide (B) monomer, and in remaining styrene monomer (A), acrylonitrile monemer (B), solvent ethylbenzene (C), charging feed basin (2) proportionally, mixing, after feed preheater (3) preheating, will be in the way of above-mentioned raw materials being sent into first reactor (5) at auxiliary agent (initiator, tranquilizer, the chain transfer auxiliary agent) the various auxiliary agents in the basin add in the above-mentioned raw material, material in first reactor is in certain temperature, under the pressure condition, carry out polyreaction certain before the phase transformation a bit, generate first section polymerisate, the monomer whose transformation efficiency reaches a certain value, send into second reactor (6) from bottom discharge material and proceed polyreaction, generate second section polymerisate, the switching process of practising physiognomy under the effect of the agitating member of in reactor, establishing simultaneously, after monomer conversion reaches a certain value, discharge by second reactor (6) bottom and to send into the 3rd reactor (7) and proceed polyreaction and generate the three stage polymerization product and reach required monomer conversion, the reacted material of the 3rd reactor (7) is sent into devolatilization poor (8), remove residual volatile matter, obtain ABS resin, recovered solvent ethylbenzene returns circulation storage tank (1), again as the solvent in the polyreaction.
Fig. 2 is that the outer powerful continous way substance law that stirs of still of the present invention prepares the ABS resin schema, among the figure, and preheater (H); The 1st reactor (R1); The 2nd reactor (R2); The 3rd reactor (R3); On-line mixing device (M1); Recycle pump (B); Intensive mixer (S1); On-line mixing device (M1), recycle pump (B) are referred to as the outer powerful stirring system of still with intensive mixer (S1).
Flow process of the present invention is different with Fig. 1 tradition continous way substance law solution polymerization ABS resin, after first reactor, the powerful stirring system of one reactor outside is set, this system comprises that reception from the practise physiognomy on-line mixing device (M1) of material of conversion of not realizing fully of discharging of first reactor lower part, sends into the recycle pump (B) of intensive mixer (S1) to the material pressurization and with it.Be subjected to contrary mix up enter on-line mixing device (M1) with the first section reaction product material that generates by first reactor (R1) that influencing the conversion of not practising physiognomy fully after, through recycle pump pressurization back by the vane-type machine,massing (about 100-200 rev/min) is powerful at a high speed stir under, finishing practises physiognomy switching process and control rubber grain enters second reactor after in a scope that suits and proceeds polyreaction.
Testing apparatus such as Fig. 2 comprise preparation of raw material groove C, preheater H; continuous measurement fresh feed pump B1, B2; establish tower polymerization reactor R1, R2, the R3 of the rotating speed variable-ratio of agitator in three series connection, vacuum devolatilization groove is set, equipment such as finished product tablets press behind the 3rd reactor R3.The S1 of strong mixer system outside a variable-ratio (0-450RPM) the vane-type still is installed between the first reactor R1 and the second reactor R2, therebetween, switch valve is set, material can be discharged from the first reactor R1 and directly be entered the second reactor R2, also can switch material and enter the S1 of strong mixer system outside the still, enter the second reactor R2 again from first reactor R1 discharge by valve;
Outside still among the powerful stirring system S1, material at first passes through on-line mixing device M1, reach the conversion of practising physiognomy fully through sending into machine,massing S1 after toothed gear pump B1 (B2) pressurization after joining with the polymerization colloidal sol of recycle system backflow again, simultaneously, also can utilize the powerful size of controlling rubber grain that stirs, by the polymerization colloidal sol after the brute force stirring, part continues to be fed into the second reactor R2, and the part circulation is met with the polymeric solution of first reactor R1 discharge and entered follow-up technological process.The about 30KG/hr of total flux of toothed gear pump B1 (B2).
Test type mainly is divided into two classes, does not contain the outer powerful stirring system S1 of still in a kind of flow process, corresponding to prior art, is called Comparative Examples, and test number is 1,2,7.Contain the outer powerful stirring system S1 of still in a kind of flow process, reflection inventive concept and technical characterictic are called experimental example, and test number is 3,4,5,6,8,9.The variation (test 1-6 is one group, and 7-9 is one group) that adds rubber content in addition, rotation speed change (in testing 1,2 group, reactor R2 rotating speed difference) etc.Have to observe in the flow process, no powerful stirring system S1, and rubber content, difference such as rotating speed is to the influences of finished product rerum natura.
The rotating speed of the first reactor R1, the second reactor R2 and the 3rd reactor R3 adopts the rotating speed of continuous bulk ABS resin (or PS) reactor R1, R2, R3 in the prior art usually, is respectively 60 rev/mins, 30 rev/mins, 15 rev/mins.It is to be increased gradually by monomer conversion that speed is successively decreased gradually, the viscosity of reaction product raise gradually the decision.
Now with Comparative Examples 1,2,7; The data of experimental example 3,4,5,6,8,9 are listed in table 1.
Table 1 Comparative Examples, the experimental example data summary table
| Parameter | Comparative Examples 1 | Comparative Examples 2 | Experimental example 3 | Experimental example 4 | Experimental example 5 | Experimental example 6 | Comparative Examples 7 | Experimental example 8 | Experimental example 9 | ||
| Composition of raw materials | Vinylbenzene | ％WT | 48.0 | 48.0 | 48.0 | 48.0 | 48.0 | 48.0 | 45.6 | 45.6 | 45.6 |
| Vinyl cyanide | ％WT | 21.8 | 21.8 | 21.8 | 21.8 | 21.8 | 21.8 | 20.7 | 20.7 | 20.7 | |
| Ethylbenzene | ％WT | 20.0 | 20.0 | 20.0 | 20.0 | 20.0 | 20.0 | 20.0 | 20.0 | 20.0 | |
| Rubber | ％WT | 10.0 | 10.0 | 10.0 | 10.0 | 10.0 | 10.0 | 13.5 | 13.5 | 13.5 | |
| Tranquilizer | ％WT | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | |
| The chain transfer auxiliary agent | PPM | 300 | 300 | 300 | 300 | 300 | 300 | 300 | 300 | 300 | |
| Initiator | PPM | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | |
| The charging parameter | Inlet amount | KG/hr | 9.7 | 9.7 | 9.7 | 9.7 | 9.7 | 9.7 | 9.7 | 9.7 | 9.7 |
| Feeding temperature | ℃ | 75 | 75 | 75 | 75 | 75 | 75 | 75 | 75 | 75 | |
| Reactor | Reactor R1 | Polymerization temperature ℃ | 110-120 | 110-120 | 110-120 | 110-120 | 110-120 | 110-120 | 110-120 | 110-120 | 110-120 |
| Stir speed (S.S.) RPM | 65 | 65 | 65 | 65 | 65 | 65 | 65 | 65 | 65 | ||
| The outer machine,massing S1 of still | Polymerization temperature ℃ | Do not have | Do not have | 120-124 | 120-124 | 120-124 | 120-124 | Do not have | 120-124 | 120-124 | |
| Stir speed (S.S.) RPM | Do not have | Do not have | 50 | 100 | 150 | 250 | Do not have | 150 | 200 | ||
| Reactor R2 | Polymerization temperature ℃ | 126-132 | 126-132 | 126-132 | 126-132 | 126-132 | 126-132 | 126-132 | 126-132 | 126-132 | |
| Stir speed (S.S.) RPM | 30 | 60 | 30 | 30 | 30 | 30 | 30 | 30 | 30 | ||
| Reactor R3 | Polymerization temperature ℃ | 138-160 | 138-160 | 138-160 | 138-160 | 138-160 | 138-160 | 138-160 | 138-160 | 138-160 | |
| Stir speed (S.S.) RPM | 15 | 15 | 15 | 15 | 15 | 15 | 15 | 15 | 15 | ||
| The product rerum natura | Shock strength | KG-CM/CM | 11.0 | 12.3 | 10.2 | 14.0 | 18.0 | 8.2 | 12 | 21 | 23 |
| Testing method D256 | |||||||||||
| Draw Zhang Qiangdu | KG/CM | ?310 | 326 | 310 | 340 | 460 | 430 | 280 | 440 | 450 | |
| Testing method D638 | |||||||||||
| Unit elongation | ％ | ?38 | 32 | 40 | 38 | 25 | 10 | 33 | 30 | 25 | |
| Testing method D638 | |||||||||||
| Softening temperature | ℃ | ?102 | 102 | 102 | 102 | 102 | 102 | 102 | 102 | 102 | |
| Testing method D1525 | |||||||||||
| Proportion | ?1.04 | 1.04 | 1.04 | 1.04 | 1.04 | 1.04 | 1.04 | 1.04 | 1.04 | ||
| Testing method D792 | |||||||||||
| Rubber particle size distributes | μm | ?0.8-2.5 | 0.7-2.0 | 0.8-1.8 | 0.6-1.4 | 0.4-0.8 | 0.3-0.5 | 1.2-2.3 | 0.5-0.7 | 0.4-0.7 |
By above-mentioned experiment, from Comparative Examples, experimental example, observe following phenomenon:
1. Comparative Examples 1 adopts routine techniques production ABS resin, and its finished product rerum natura shock strength, the intensity of extending are all lower, the size of rubber grain and distribute all extensivelyr, and average particle size particle size is bigger.
2. Comparative Examples 2 is as Comparative Examples 1, also is to adopt routine techniques production ABS resin, and different is doubles the rotating speed of the second reactor R2, is 60 rev/mins, and the product rerum natura comprises shock strength, the intensity of extending, and rubber grain size distribution etc. are improved not obvious.
3. experimental example 3 adopts the technology of the present invention, but the outer strong mixer S1 rotating speed lower (50 rev/mins) of still, the product rerum natura is similar to Comparative Examples 1, does not have very and improves.
4. experimental example 4 adopts the technology of the present invention, and the outer strong mixer rotating speed of still is brought up to 150 rev/mins, and the product rerum natura is improved, and shock strength increases by 27%.
5. experimental example 5 adopts the technology of the present invention, and the outer strong mixer rotating speed of still is brought up to 200 rev/mins, and the product rerum natura is improved greatly, and shock strength increases by 65%.
6. experimental example 6 adopts the technology of the present invention, the outer strong mixer rotating speed of still is brought up to 250 rev/mins, rubber grain mean value is reduced to 0.3-0.5 μ m, the rubber grain size can be effectively controlled in the outer powerful stirring of product rerum natura explicit declaration still, just too small-particle has negative impact to the product rerum natura, shock strength has reduced 54.5% than experimental example 5 on the contrary, can recognize that from this point moderate stirring can control the size of rubber grain, just can obtain best product rerum natura.
7. Comparative Examples 7 still adopts routine techniques, only has been to use the higher composition of raw materials of rubber content (rubber content 13.5wt%), and the product rerum natura is similar to Comparative Examples 1 as a result, and a small amount of variation of rubber content is described, the product rerum natura is not had very influence.
8. experimental example 8,9 shows, after employing Comparative Examples prescription and the technology of the present invention, under the rotating speed of 150-200RPM, the product rerum natura is significantly improved, and shock strength is increased to 75%, and the rubber grain size is reduced to 0.4-0.7 μ m.
Conclusion
We think from above-mentioned experimental phenomena, in adopting continous way substance law solution polymerization ABS resin technology:
1. adopt the outer strong mixer S1 of still of the present invention to stir the material that the first reactor R1 discharges and can improve the final rerum natura of product, for example rubber grain size and distribution, shock strength and the intensity of extending all can improve etc.
2. the outer strong mixer S1 stirring extent of still directly influences the final rerum natura of product, and stirring extent is low, and is to little purpose; Stirring extent is too high, causes the final rubber grain of product too small, and shock strength descends on the contrary, and the final rerum natura of product is produced adverse influence.Therefore stirring extent must be moderate.
3. a little variation of rubber content is very little to the final rerum natura influence of product in the composition of raw materials.
The above embodiments and accompanying drawing only are special cases of the present invention, and they do not limit the present invention, and one of skill in the art can make amendment as the case may be not breaking away under the spirit of the present invention, and all such modifications all are within the scope of the present invention; The spirit and scope of the present invention are defined by the claims.
Claims (6)
1. a still stirs the method that the continous way substance law prepares ABS resin outward, comprising:
A kind of rubber is dissolved in vinylbenzene, the acrylonitrile monemer and in solvent, tranquilizer, chain transfer auxiliary agent, initiator through mixing the step of establishing the 1st reactor of agitating member in adding;
In first reactor, carry out polyreaction and generate any step of first section polymerisate certain to the inversion of phases;
The outer powerful stirring system of material input still that contains first section polymerisate that to discharge from first reactor stirs to realize practising physiognomy through this brute force stirring system and changes the back and control the step that rubber grain enters second reactor continuation polyreaction after in an optimum range;
In a follow-up 1-3 reactor (being the 3-5 still), proceed polyreaction, generate the step of polymerisate;
To separate through devolatilization again from the material that final reactor is discharged, remove unreacted residual monomer and solvent, obtain the step of thermoplasticity polymerization product A BS resin of the present invention;
It is characterized in that behind first reactor increasing the strong mixer that the outer powerful stirring system of a still comprises that the material that includes first section polymerisate that will discharge from first reactor is established agitating member in sending into after is suitable for carrying the pump pressurization of high-viscosity material, the setting of this strong mixer agitating member and rotating speed should be able to be guaranteed to finish through the material that strong mixer stirs and change promptly wherein rubber mutually and be transformed into disperse phase by external phase and control rubber particle size and send into follow-up reactor after in an optimum range and continue to react;
Described strong mixer is a propeller agitator, and the gap between its rotating vane and the stator blades is 3.175-6.35mm (a 1/8-1/4 inch).
2. according to the method for preparing ABS resin of claim 1, the service temperature that it is characterized in that described strong mixer is 120-124 ℃.
3. according to 1 the method for preparing ABS resin of claim 1-2, it is characterized in that the finished product ABS resin rubber grain is distributed as 0.4-0.8 μ m.
4. according to 1 the method for preparing ABS resin of claim 1-2, it is characterized in that described rubber is polybutadiene rubber.
5. the purposes of any method of claim 1-4 is characterized in that available raw material corresponding to the preparation high impact polystyrene, and process operation parameter prepares high impact polystyrene.
6. realize that any method of aforesaid right requirement 1-4 prepares the device of ABS resin, comprises for one kind
A kind of rubber is dissolved in vinylbenzene, the acrylonitrile monemer and with solvent, tranquilizer, chain transfer auxiliary agent, initiator through mixing the system that establishes the 1st reactor of agitating member in adding;
In first reactor, carry out polyreaction and generate any system of first section polymerisate certain to the inversion of phases;
The outer powerful stirring system of material input still that contains first section polymerisate that to discharge from first reactor stirs to realize practising physiognomy through this brute force stirring system and changes the back and control the system that rubber grain enters second reactor continuation polyreaction after in a suitable scope;
In a follow-up 1-3 reactor (being the 3-5 still), proceed polyreaction, generate the system of polymerisate;
To separate through devolatilization again from the material that final reactor is discharged, remove unreacted residual monomer and solvent, obtain the system of thermoplasticity polymerization product A BS resin of the present invention;
It is characterized in that outside the still of the first reactor postposition powerful stirring system comprises the material that includes first section polymerisate that will discharge from first reactor is established agitating member in sending into after one is suitable for carrying the pump pressurization of high-viscosity material strong mixer, the setting of this strong mixer agitating member and rotating speed should be able to be guaranteed to finish through the material that strong mixer stirs and change promptly rubber wherein mutually and be transformed into disperse phase by external phase and control rubber particle size and send into follow-up reactor after in a suitable scope and continue reaction;
Described strong mixer is a propeller agitator, and the gap between its rotating vane and the stator blades is 3.175-6.35mm (a 1/8-1/4 inch).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021209707A CN1152068C (en) | 2002-06-06 | 2002-06-06 | Continuous bulk process and plant for preparing ABS via stirring from outside reactor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021209707A CN1152068C (en) | 2002-06-06 | 2002-06-06 | Continuous bulk process and plant for preparing ABS via stirring from outside reactor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1398907A CN1398907A (en) | 2003-02-26 |
| CN1152068C true CN1152068C (en) | 2004-06-02 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB021209707A Expired - Lifetime CN1152068C (en) | 2002-06-06 | 2002-06-06 | Continuous bulk process and plant for preparing ABS via stirring from outside reactor |
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| Country | Link |
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| CN (1) | CN1152068C (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100671135B1 (en) * | 2004-09-08 | 2007-01-17 | 주식회사 엘지화학 | Method for Preparing Styrenic Resin Having High Impact Strength and Gloss |
| CN103406056A (en) * | 2013-05-30 | 2013-11-27 | 防城港盛农磷化有限公司 | Calcium superphosphate size mixing, stirring and curing method and production device thereof |
| CN104761682B (en) * | 2014-12-30 | 2019-06-11 | 北方华锦化学工业股份有限公司 | A kind of ontology ABS resin production method |
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2002
- 2002-06-06 CN CNB021209707A patent/CN1152068C/en not_active Expired - Lifetime
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