CN104761682B - A kind of ontology ABS resin production method - Google Patents
A kind of ontology ABS resin production method Download PDFInfo
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- CN104761682B CN104761682B CN201410839115.XA CN201410839115A CN104761682B CN 104761682 B CN104761682 B CN 104761682B CN 201410839115 A CN201410839115 A CN 201410839115A CN 104761682 B CN104761682 B CN 104761682B
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Abstract
A kind of ontology ABS resin production method, specifically in the technique of traditional continuous bulk production ABS resin, after the second reactor of four series connection piston flow reactors of continuous polymerization, increase a returning charge pump, the material a part returning charge pump come out from second reactor is returned into strong mixer, this is more than phase transition point and the higher material of viscosity completes phase transition under high shear with the rubber in the material from first reactor in strong mixer, the control to rubber grain particle size in ontology ABS resin is realized by adjusting agitator speed and material viscosity, its material is sent into subsequent piston flow reactor again and continues polymerization reaction, devolatilization, produce final ABS resin product.
Description
Technical field
The present invention relates to a kind of production methods of ontology ABS resin, especially by effective control ontology ABS reaction mass
The rubber phase changing condition of middle dissolution obtains the ontology ABS production method of suitable particle diameter rubber grain, belongs to organic polymer
Polymeric material technical field.
Background technique
Traditional substance law ABS production main process is that polybutadiene rubber is dissolved in acrylonitrile and styrene forms
Mixed solution in, form a kind of mixed solution, then with feed pump with certain flow velocity by this miscible fluid be sent into raw material it is pre-
Hot systems, after pre-heating system, raw material reaches reaction temperature, and the material come out from pre-heating system is pumped into charging by 4 again
In the concatenated piston flow reactor with stirring and heat exchange coil of platform, composition of raw materials different according to the product grade of production
Appropriate initiator is added in difference, reaction process, and every reactor control carries out polymerization reaction in different temperature.Ordinary circumstance, 4
The concatenated reactor of platform is successively increased from First to the 4th reaction temperature, and polymerization conversion successively rises in reactor
Height, the viscosity of material also successively increases in reactor.In the first polymer reactor, just start when reaction only one in reactor
A liquid phase produces the copolymer of styrene and acrylonitrile, this copolymerization with the progress that styrene, acrylonitrile compolymer react
Object is also dissolved in unreacted styrene and acrylonitrile solution, has both been dissolved in the solution being at this moment made of styrene and acrylonitrile
Rubber, and acrylonitrile and styrol copolymer have been dissolved, until the conversion ratio of acrylonitrile and styrene is close to 20%, it is at this moment molten
Liquid begins to decline the solubility of rubber, and as conversion ratio further increases, rubber starts to be precipitated from solution, forms rubber
Phase, this process are known as phase transition in ABS production process, open when conversion ratio reaches 20% in ontology ABS resin reaction process
Beginning phase transition takes place the 20% of phase transition this conversion ratio and is known as phase transition point.The phase of conventional bulk ABS production technology turns
Becoming is usually to occur in second reactor, i.e., meets and exceeds 20% in second reactor conversion ratio, be precipitated during phase transition
Effect of the rubber under blender effect by shearing force, forms rubber grain, forms the size and rubber of rubber grain partial size
In phase transition, suffered shearing force is related, also related with material properties.If the viscosity of used rubber itself is smaller, instead
Answer the viscosity of material bigger, the revolving speed of blender is higher, and the shearing force that rubber is subject to is bigger, and obtained rubber grain partial size is just
Small, whereas if the viscosity of used rubber itself is larger, the viscosity of material is smaller when phase transition, and stirring intensity is smaller, rubber
Suffered shearing force is smaller, and the rubber grain of formation is bigger.
Three patents reflect existing ontology ABS resin production technology below.
The patent of invention of northern Hua Jin Chemical Industry Group Co., Ltd and Dalian University of Technology's joint application " is used to prepare
The continuous pipe type plug flow Flexible reactor and preparation method of ontology ABS resin or SAN resin ", the applying date: 2012-12-21,
Publication number: CN103030743A, publication date: 2013-04-10.Disclosure abstract: the present invention relates to one kind to be used to prepare ontology
The continuous pipe type plug flow Flexible reactor and preparation method of ABS resin or SAN resin, process flow is by following four part group
At: raw material compounding system, polymerization reaction system, pumped vacuum systems and extruding pelletization system.Reaction system includes four plug flows
Reactor and different material circuits.It is controlled by different material circuits, the series connection of four piston flow reactors may be implemented
Connection carries out the production of continuous bulk ABS resin.It can also realize that one or two two-in-series plug flow with return-flow system is anti-
The parallel polymerization system of device group is answered, the production of continuous bulk SAN resin is carried out.When preparing SAN resin, control two-in-series is flat
The reflux ratio of the return-flow system of plug-flow reactor group, to control the depth of cure of SAN resin polymerization reaction.It can carry out continuous sheet
The flexible apparatus and production technology of body ABS resin or SAN production of resins, ABS the or SAN naval stores of preparation, molecular weight is controllable,
Molecular weight distribution is relatively narrow, and properties of product are excellent, and device technique stability is good.In this patent application, hence it is evident that in phase transition point
Any technical measures are not taken, that is, phase transition point is as the progress nature of reaction reaches.
The patent of invention proposed by applicant Shanghai Huayi Polymer Co., Ltd. is " a kind of to prepare high-impact abs polymer
The technique of mixture " application, notification number: CN103450405A.Clip Text are as follows: the invention discloses poly- by continuous bulk
The method that conjunction prepares compound body of ABS polymer in high shock resistant.Its step includes: to be dissolved in monoalkyl vinyl aromatic monomer, vinyl
The polybutadiene rubber solutions of unsaturated nitrile monomer mixture are added to the first continuous stirred tank reactor, in certain temperature
Lower progress grafting rubbers reaction.Second continuous stirred tank reactor receive the reaction mixture from the first grafting reactor into
Row graft rubber phase transition controls the partial size of rubber particles under thermal polymerization temperature operating condition.Third and fourth reactor then
Two reactors convert more monomers, and adjust final copolymer molecular weight.Polymer after reaction is using multistage, multi-functional de-
Device and rubber cross are waved, the ABS product with low remaining fugitive constituent and rubber cross is obtained.Present invention use continuously stirs slot
Formula reactor carries out grafting rubbers reaction and rubber phase transition, and product ontology ABS resin has excellent impact resistance.
In this patent application, any technical measures are not obviously equally taken in phase transition point, the phase of rubber turns
Change process is completed in second reactor, and the viscosity of phase transition has been glued corresponding to conversion ratio when just having entered phase transition point
Degree.
" kettle stirs the method and apparatus that continous way substance law prepares ABS outside " the patent Shen proposed by applicant Cui Guixin
Please, open on 2 26th, 2003, publication number: CN1398907A, related abstract content are as follows: the present invention relates to stir outside a kind of kettle
Mix continous way substance law ABS resin production method, the specifically technique in traditional continous way substance law production ABS resin
In, after realizing the first kettle of multiple polymeric kettles of continuous polymerization, the strong stirring system of addition realizes that practising physiognomy for its material turns
Become and control rubber grain in an optimum range, then its material is sent into subsequent polymeric kettle and continues polymerization reaction, devolatilization is raw
The final ABS resin product of output.
It is different from technology disclosed in preceding two patents, in the technology of this patent application publication, phase transition point is taken
The technical measures for reinforcing stirring, increase a strong mixer, but still be in phase between first and second reactor
Biggish shearing force is provided for phase transition simply by reinforcement stirring under conditions of transition point initial viscosity is constant, to rubber
The control of grain particle size can have certain positive effect, but without the viscosity of change phase transition point, it can not achieve to rubber
The larger range of adjustment of glue grain diameter.
It is the key that ontology ABS resin production technology and technological difficulties that rubber size, which is controlled in ideal range,.?
Rubber grain size influences the surface gloss of material and impact strength property very big in ABS resin, and the prior art can only
Small limited adjustment is carried out to rubber size by adjusting agitator speed realization.It will be to ontology ABS resin rubber grain
Partial size carries out biggish adjustment, is the rubber clone changed in ingredient under the conditions of the prior art.
Existing ontology ABS resin technology is entered naturally when progressivelying reach 20% with the carry out rate to be transformed of polymerization reaction
Phase transition point, the material viscosity of phase transition point is exactly conversion ratio 20% or slightly larger than 20% when corresponding material viscosity, thus is passed
System technology can not change the viscosity of phase transition point, so when producing the ABS product of the high glaze trade mark, in technique to obtain compared with
The problem of small rubber grain partial size can only be forced to use the rubber of low viscosity, and such technology is brought is the rubber of low viscosity
It is not the universal product, and the amount for producing rubber used in ABS is little, the producer for producing this low viscosity rubber is seldom, so adopting
Purchase is difficult, and price also remains high, and not only increases production cost but also manufacturer cannot change the trade mark in time.If energy
The material viscosity of phase transition point is artificially adjusted by technological means realization, and it is corresponding to be more than 20% fixed conversion ratio
Viscosity, the product of larger rubber grain can have both been produced with General Purpose Rubber or has produced the ABS tree compared with small particle rubber grain
Fat prod, so that it may when realizing transformation ABS resin product grade, not have to change rubber clone, no longer be limited by rubber clone.
Summary of the invention
The shortcomings that in order to overcome above-mentioned technique, the purpose of the present invention is artificially manufacture a kind of adjustable by technique adjustment
Rubber phase transition point condition, the viscosity of phase transition point is adjusted especially by technological means, is made close to phase transition point
Reaction mass is rapidly reached and is more than phase transition point, makes the conversion ratio of reaction mass rapidly more than 20%, from less than 20%
Reaction mass, which has, enters the higher viscosity of phase transition point than natural reaction, and the rubber in phase transition process is allowed to receive enough
Shearing force, and then by adjusting agitator speed and adjustment material viscosity realize to rubber grain partial size in ontology ABS resin
The control of size meets requirement of the different product to rubber grain particle size, rather than is changed by changing rubber clone
Rubber grain particle size.
A kind of ontology ABS resin production method of the invention, mainly by control phase transition point conversion ratio and viscosity come
The method for adjusting rubber size size, comprising:
Polybutadiene rubber is dissolved in the mixed solution of acrylonitrile and styrene, initiator, chain-transferring agent, molten is added
Agent etc. is driven into 4 concatenated piston flow reactors with stirring and heat exchange coil by pump then after pre-heating system
Step；
The reaction step before polymerization reaction generates first segment polymerizate to phase transition point is carried out in first reactor；
By the material for having been approached phase transition point come out from first reactor and the return object from second reactor outlet
Material enters in the strong mixer among first reactor and second reactor together, and it is anti-that phase transition occurs under high shear
It answers, the material after phase transition reaction enters in second reactor the step of continuing polymerization reaction；
Continue the step of polymerization reaction generates polymerizate in third, the 4th reactor；
The material being discharged from the 4th reactor is separated using deliming, unreacted residual monomer and solvent is removed, obtains
To ABS product of the invention；
It is characterized by: have a returning charge pump in second reactor outlet, the material a part come out from second reactor
It is returned in strong mixer with returning charge pump, this is more than phase transition point and the higher material of viscosity is in strong mixer and next
Complete phase transition under high shear from the rubber in the material of first reactor, make the conversion ratio of reaction mass from less than
20% rapidly more than 20%, makes reaction mass with the higher viscosity of phase transition point is entered than natural reaction, allows in phase transition mistake
The rubber of journey receives enough shearing forces, and then realizes by adjusting agitator speed and adjustment material viscosity to ontology ABS
The control of rubber grain particle size in resin.
The returning charge pump is mounted on the outlet line branch road between second reactor and third reactor, and returning charge pumps out
Mouth pipeline is connected to the entrance of strong mixer, and returning charge pump uses speed regulating motor, keeps returning charge flow adjustable.
Finally obtained ABS resin product rubber grain partial size is 1-3 microns.
The strong mixer temperature controls the conversion ratio in 105-115 DEG C, strong mixer and controls in 20-30%.
The inventory that the returning charge pump is returned from second reactor to strong mixer is the 5-300% of inlet amount.
Detailed description of the invention
Fig. 1 is ontology ABS resin production technological process of the invention.R1, R2, R3, R4 respectively indicate first, second,
Third, the 4th reactor, PR indicate that returning charge pump, AT indicate strong mixer.
Specific embodiment
In ontology ABS resin reaction system, four tandem reactors are shared, the from first to the 4th reactor is each to export
Conversion ratio successively increase, corresponding material viscosity also successively increases, by taking the MABS276 trade mark as an example, first reactor outlet
Conversion ratio close to 20%, reaction mass enters conversion ratio after second reactor and progressively reaches and slowly more than 20%, reaches phase and turns
After height, the rubber being dissolved in material starts phase transition, and rubber is precipitated from solution, completes phase transition in the second reactor
Material the reaction was continued, reach second reactor outlet when, conversion ratio reaches 40%.Third reactor outlet conversion ratio is 55%,
4th reactor outlet conversion ratio is 65%.The technical scheme is that increase a returning charge pump in second reactor outlet, it will
A part in material that second reactor comes out is returned in the strong mixer being mounted between the first and second reactors,
Mix the material that return is exported from second reactor in strong mixer with the material exported from first reactor, if
The mass flow of return is equal with the flow from first reactor, and mixed materials conversion rate is close to 30%, in strong stirring
Jumping mode has been more than phase transition point to materials conversion rate in device, and the viscosity of material has also been more than phase transition with jumping mode at this time
The corresponding viscosity of 20% conversion ratio of point, has reached viscosity corresponding to 30% conversion ratio.At this moment in first reactor material
Rubber has phase transition condition completely, and high-viscosity material at this time can expeditiously pass the shearing force that strong mixer manufactures
It leads and is on the rubber of phase transition process, rubber can receive stronger shearing force, and the rubber with same viscosity is anti-
It answers in device viscosity less than normal to be formed by rubber grain with low sheraing stirring to compare, under the conditions of strong mixer and high-viscosity material
Rubber is formed by that grain diameter is smaller, can obtain the mixed of different viscosities by changing returning charge amount and second reactor conversion ratio
Close reaction mass, change strong mixer revolving speed also can the rubber grain particle size to ABS resin have an impact, thus can
To obtain the rubber grain of different-grain diameter.The viscosity and stirring intensity that this technical solution passes through adjusting phase transition point reaction mass
Etc. operating conditions, to realize the purpose of rubber size size in control ontology ABS resin, rather than by conventional method by changing
The rubber clone become in formula achievees the purpose that change rubber grain size in turn to change rubber viscosity.
Using the styrene-acrylonitrile reaction solution prepared dissolved with common polybutadiene rubber, feed rate is 13 ton/hours,
80 DEG C of first reactor inlet temperature, 100 DEG C of outlet temperature, first reactor conversion rate at tube exit is close to 20%；Second reactor enters
110 DEG C of temperature of mouth, 120 DEG C of outlet temperature, second reactor conversion rate at tube exit 40%；120 DEG C of third reactor inlet temperature, out
140 DEG C of temperature of mouth, third reactor outlet conversion ratio 55%；4th 140 DEG C of reactor inlet temperature, 160 DEG C of outlet temperature, the
Four reactor outlet conversion ratios 60%.Strong mixer is returned with a part of material that returning charge pump exports second reactor to enter
Mouthful, the mass flow of return is 13 tons/when, 110 DEG C of strong mixer temperature, conversion ratio is 30% in strong mixer.From the 4th
It is that 1-3 is micro- that the material that reactor comes out, which obtains its rubber grain partial size of ABS resin product into subsequent devolatilization and granulating system,
Rice.The mass flow of return is 2 tons/when, the conversion ratio in strong mixer is 23%, obtained ABS resin product rubber grain
Partial size is 6-9 microns.
Claims (4)
1. a kind of ontology ABS resin production method, the method that rubber size size is mainly adjusted by control phase transition point,
Include:
Polybutadiene rubber is dissolved in the mixed solution of acrylonitrile and styrene, initiator, chain-transferring agent, solvent is added,
Then after pre-heating system, 4 concatenated the step of having stirring and the piston flow reactor of heat exchange coil, are driven by pump；
The reaction step before polymerization reaction generates first segment polymerizate to phase transition point is carried out in first reactor；
By the material for having been approached phase transition point come out from first reactor and the return material one from second reactor outlet
It rises into the strong mixer among first reactor and second reactor, completes phase transition under high shear, complete phase
The material of transformation enters in second reactor the step of continuing polymerization reaction；
Continue the step of polymerization reaction generates polymerizate in third, the 4th reactor；
The material being discharged from the 4th reactor is separated using deliming, unreacted residual monomer and solvent is removed, obtains ABS
Product；
It is characterized by: have returning charge pump in second reactor outlet, the material a part come out from second reactor is with returning
Material pump is returned in strong mixer, and this is more than phase transition point and the higher material of viscosity in strong mixer and from the
The rubber dissolved in the material of one reactor completes phase transition under high shear, make the conversion ratio of reaction mass from less than
20% rapidly more than 20%, makes reaction mass with the higher viscosity of phase transition point is entered than natural reaction, allows in phase transition
The rubber of process receives enough shearing forces, realizes by adjusting agitator speed and material viscosity in ontology ABS resin
The control of rubber grain particle size.
2. according to the ABS resin production method of claim 1, it is characterised in that returning charge pump is mounted on second reactor and third is anti-
The outlet line branch road between device is answered, returning charge pump discharge pipeline is connected to the entrance of strong mixer, and returning charge pump uses speed regulation
Motor keeps returning charge flow adjustable.
3. according to the ABS resin production method of claim 1, it is characterised in that finally obtained ABS resin product rubber grain
Partial size is 1-3 microns.
4. according to the ABS resin production method of claim 1, it is characterised in that strong mixer temperature is controlled at 105-115 DEG C,
Conversion ratio control is in 20-30% in strong mixer.
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| CN111499804B (en) * | 2020-04-09 | 2022-09-13 | 北方华锦化学工业股份有限公司 | Method for preparing high impact resistance and high gloss ABS resin by using high viscosity rubber |
| CN115055145B (en) * | 2022-06-10 | 2024-03-19 | 大连理工大学 | HIPS resin production process system and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1398907A (en) * | 2002-06-06 | 2003-02-26 | 崔贵心 | Continuous bulk process and plant for preparing ABS via stirring from outside reactor |
| CN102977279A (en) * | 2012-12-21 | 2013-03-20 | 北方华锦化学工业集团有限公司 | Tubular plug flow reactor with material internal circulation and preparation method for preparing continuous bulk ABS (Acrylonitrile-Butadiene-Styrene) resin |
| CN103030743A (en) * | 2012-12-21 | 2013-04-10 | 北方华锦化学工业集团有限公司 | Continuous pipe type flexible plug flow reactor and method for preparing mass ABS resin or SAN resin |
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- 2014-12-30 CN CN201410839115.XA patent/CN104761682B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1398907A (en) * | 2002-06-06 | 2003-02-26 | 崔贵心 | Continuous bulk process and plant for preparing ABS via stirring from outside reactor |
| CN102977279A (en) * | 2012-12-21 | 2013-03-20 | 北方华锦化学工业集团有限公司 | Tubular plug flow reactor with material internal circulation and preparation method for preparing continuous bulk ABS (Acrylonitrile-Butadiene-Styrene) resin |
| CN103030743A (en) * | 2012-12-21 | 2013-04-10 | 北方华锦化学工业集团有限公司 | Continuous pipe type flexible plug flow reactor and method for preparing mass ABS resin or SAN resin |
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