CN109111542A - A kind of high flowing, the AS particle of long chain and preparation method thereof - Google Patents
A kind of high flowing, the AS particle of long chain and preparation method thereof Download PDFInfo
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- CN109111542A CN109111542A CN201810656697.6A CN201810656697A CN109111542A CN 109111542 A CN109111542 A CN 109111542A CN 201810656697 A CN201810656697 A CN 201810656697A CN 109111542 A CN109111542 A CN 109111542A
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- parts
- particle
- chain
- long chain
- acrylonitrile
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
Abstract
The invention discloses a kind of high flowings, the AS particle of long chain and preparation method thereof, can influence to provide a kind of preparation method of easy to process, high fluidity, long chain AS particle in lesser situation to ABS resin.Belong to plastic applications, resulting materials are made by containing the following parts by weight: styrene is 74 parts, and acrylonitrile is 26 parts, and recycle monomer is 73 parts, and chain-transferring agent is 0-10 parts, and chain initiator is 0-2 parts.Compared with prior art, present invention process is reasonable, and product viscosity is small, mobility is high, few containing residual monomer, transparency is good, the product for the production new grades that original device can be stable, and product characteristic is stablized, the ABS of corresponding production is in mobility, drawing force, bending, it is able to satisfy customer demand in terms of hardness and hot torsion characteristic, obtains downstream extensive use.
Description
Technical field
The present invention relates to chemical production field more particularly to a kind of produce AS particle used in ABS product.
Background technique
ABS resin refers to that acrylonitrile-butadiene-styrene copolymer, ABS are Acrylonitrile Butadiene
The acronym of Styrene is a kind of intensity height, good toughness, thermoplastics type's high molecular material easily processed into type.According to
The difference of each component in finished product can produce the production of the different applications such as injection grade, extrusion grade, flame retardant grade, plating grade, tubing grade
Product.
SAN (being AS as product) is second of principal goods material for producing ABS product.It is a kind of solid particles of light.SAN
Mobility, drawing force, bending, hardness and hot torsion characteristic are provided.The variation of the ratio of its molecular weight and styrene and acrylonitrile
The characteristic of final products can be changed slightly.
Summary of the invention
According to the few disadvantage of the existing SAN trade mark, present invention aims at provide the AS grain of a kind of high flowing, long chain
Son, while in a kind of system for the AS particle that can influence to provide the high fluidity, long chain in lesser situation on ABS resin
Preparation Method.
In order to realize above-mentioned task, the present invention is realised by adopting the following technical scheme:
It is a kind of it is high flowing, long chain AS particle be made of following raw material by weight percentage: styrene 74
Part, acrylonitrile is 26 parts, and recycle monomer is 73 parts, and chain-transferring agent is 0-12 parts, and chain initiator is 0-2 parts.
The styrene is product after ethylbenzene dehydrogenation.
The acrylonitrile is that propylene, ammonia, air and water are that raw material is made.
The recycle monomer is the mixed solution that acrylonitrile and styrene are formed according to 1:3 ratio.
The chain-transferring agent is n-octyl mercaptan (NOM).
The chain initiator is 1,1 cyclohexane peroxides (THP).
A kind of high flowing as described above, long chain AS particle preparation method, this method according to the following steps into
Row:
(1) raw material is premixed according to formula rate, so that each raw material is tentatively uniformly mixed, obtains premix, in which:
The formula by weight percentage, is made of following raw material: styrene is 74 parts, and acrylonitrile is 26 parts, is followed
Ring monomer is 73 parts, and chain-transferring agent is 0-12 parts, and chain initiator is 0-2 parts.
(2) volume is added in premix obtained in step (1) is 40m3Jacket reactor carry out polymerization reaction,
In:
The collet is divided into 4 sections, and 1st area is conduction oil, and 2,3,4 areas are recirculated cooling water；
The reaction kettle is stirred using double helix, speed of agitator 30r/min；
(3) molten polymer come out from reaction kettle carries out devolatilization, granulation, drying, obtains high flowing, long chain
AS particle, in which:
The devolatilization is to be removed the unreacting material contained in polymer by vacuumizing；
Described be granulated is BKG pelletizer underwater cutpellet；
The drying is centrifugal dehydration, is evaporated aqueous vapor by self heat.
The beneficial effects of the present invention are: products obtained therefrom is the AS particle of a kind of high flowing, long chain, there is high flowing
Property, the features such as lacking containing residual monomer.
Detailed description of the invention
Fig. 1 is SAN device flow diagram of the present invention.
Specific embodiment
The present invention is on the basis of original AS product (hereinafter referred to as AS-103), according to pair of melt index and component
Than changing SAN particle properties by the additional amount and the proportion of styrene and acrylonitrile that change chain-transferring agent NOM, thus raw
The AS product (hereinafter referred to as AS-105) of output new grades.The specific implementation process is as follows:
Specific embodiments of the present invention are given below, it should be noted that the invention is not limited to implement in detail below
Example, all equivalent transformations made on the basis of the technical solutions of the present application each fall within protection scope of the present invention.
Embodiment 1
A method of the AS particle (AS-105) of high flowing as described above, long chain being produced, with weight percent
Meter, is made of following raw material: styrene is 84 parts, and acrylonitrile is 30 parts, and recycle monomer is 83 parts, and chain-transferring agent is 12 parts, chain
Initiator is 1.3 parts, speed of agitator 30r/min；
The AS particle (AS-105) that above-mentioned preparation method prepares the present embodiment is deferred to, preparation forms and carries out performance test,
Its test result is as shown in table 1.
Embodiment 2
A method of the AS particle (AS-105) of high flowing as described above, long chain being produced, with weight percent
Meter, is made of following raw material: styrene is 78 parts, and acrylonitrile is 27 parts, and recycle monomer is 77 parts, and chain-transferring agent is 10 parts, chain
Initiator is 1.1 parts, speed of agitator 30r/min；
The AS particle (AS-105) that above-mentioned preparation method prepares the present embodiment is deferred to, preparation forms and carries out performance test,
Its test result is as shown in table 1.
Embodiment 3
A method of the AS particle (AS-105) of high flowing as described above, long chain being produced, with weight percent
Meter, is made of following raw material: styrene is 73 parts, and acrylonitrile is 26 parts, and recycle monomer is 72 parts, and chain-transferring agent is 9 parts, and chain draws
Sending out agent is 1 part, speed of agitator 30r/min；
The AS particle (AS-105) that above-mentioned preparation method prepares the present embodiment is deferred to, preparation forms and carries out performance test,
Its test result is as shown in table 1.
Embodiment 4
A method of the AS particle (AS-105) of high flowing as described above, long chain being produced, with weight percent
Meter, is made of following raw material: styrene is 67 parts, and acrylonitrile is 24 parts, and recycle monomer is 66 parts, and chain-transferring agent is 9 parts, and chain draws
Sending out agent is 0.5 part, speed of agitator 30r/min；
The AS particle (AS-105) that above-mentioned preparation method prepares the present embodiment is deferred to, preparation forms and carries out performance test,
Its test result is as shown in table 1.
Embodiment 5
A method of the AS particle (AS-105) of high flowing as described above, long chain being produced, with weight percent
Meter, is made of following raw material: styrene is 56 parts, and acrylonitrile is 20 parts, and recycle monomer is 55 parts, and chain-transferring agent is 7 parts, and chain draws
Sending out agent is 0.2 part, speed of agitator 30r/min；
The AS particle (AS-105) that above-mentioned preparation method prepares the present embodiment is deferred to, preparation forms and carries out performance test,
Its test result is as shown in table 1.
The performance data of the AS particle (AS-105) of 1 embodiment of table
From the comparison of embodiment 1-5 in table 1 it is found that under different feeds flow, according to formula, (styrene is 74 parts, propylene
Nitrile is 26 parts, and recycle monomer is 73 parts, and chain-transferring agent is 0-12 parts, and chain initiator is 0-2 parts) charging, AS-105 produced
Data stabilization, and every product index reaches criterion of acceptability.It is fed according to following example 6 formula, AS-109 produced
Data stabilization, and every product index reaches criterion of acceptability.
Embodiment 6
A kind of high flowing as described in claim 1, long chain AS particle preparation method, referring also to attached drawing 1
Shown in SAN device flow chart, this method follows the steps below:
During SAN continuous production AS-103, by adjusting styrene, acrylonitrile, chain-transferring agent, initiator and circulation
The charge proportion of monomer, adjustment reaction kettle, flash tank technology controlling and process transition to AS-105.After transition, AS-105 is according to such as
Lower scheme continues to produce:
(1) raw material is premixed according to formula rate, so that each raw material is tentatively uniformly mixed, obtains premix, in which:
The formula rate by weight percentage, is made of following raw material: styrene is 74 parts, acrylonitrile 26
Part, recycle monomer is 73 parts, and chain-transferring agent is 0-12 parts, and chain initiator is 0-2 parts；
(2) volume is added in premix obtained in step (1) is 40m3Jacket reactor carry out polymerization reaction；
Wherein the collet is divided into 4 sections, and 1st area is conduction oil, and 2,3,4 areas are recirculated cooling water；
The reaction kettle is stirred using double helix, speed of agitator 30r/min.
(3) molten polymer come out from reaction kettle carries out devolatilization, granulation, drying, obtains high flowing, long chain
AS particle；
Wherein the devolatilization is to be removed the unreacting material contained in polymer by vacuumizing；
Described be granulated is BKG pelletizer underwater cutpellet；
The drying is centrifugal dehydration, is evaporated aqueous vapor by self heat.
Comparative analysis
As described above, the present invention be on the basis of original AS product, now by change chain-transferring agent NOM additional amount and
The proportion of styrene and acrylonitrile changes SAN particle properties, to produce the AS product (AS-105) of new grades.
The product quality data of AS-103 are as follows:
The product quality data of AS-105 are as follows:
During AS-103 makes the transition AS-105 it can be seen from table, need to change has melt index, polymers compositions
(AN), yellow colour index, decantation tank component.Data transformation process decomposes as follows:
1, melt index: AS-103 melt index target value is 5g/10min, corresponding when stablizing under 5900kg/h yield
NOM additional amount is 14.6kg/h；AS-105 melt index target value is 3g/10min,
Corresponding NOM additional amount is 9.5kg/h when stablizing under 5900kg/h yield；Since SAN technique is continuous production, it is
The system moment is in homeostasis process, and to minimize rejected product yield, transformation process is limited to 3 hours, according to flat
Weigh principle, and NOM additional amount need to be first lower than corresponding NOM when AS-105 stablizes under 5900kg/h yield and is added by transition when starting
9.5kg/h is measured, 8kg/h is set as, after reaction carries out 60min, then NOM setting value is close toward 9.5kg/h, setting value 9,
Continue plus 60min, the melt index of the 3rd hour product can finely tune NOM already close to target value near 9.5kg/h,
To make production reach stable state.
2, polymers compositions (AN): refer to AN proportion in the polymer；The target components of AS-103 are 28%, AS-
105 target components are 26%, and since SAN technique is continuous production, system time is in homeostasis process, unqualified to make
Product yield minimizes, and transformation process is limited to 3 hours, and according to equilibrium principle, the charging of AN and SM is adjusted when transition starts
Ratio is adjusted to 15% (AN) by 28% (AN), is adjusted to 24% (AN) after reaction carries out 60min, then by setting value, continues
Add 60min, the component (AN) of the 3rd hour product is then fed according to 26% (AN) ratio already close to target value.
3, yellow colour index: being the detection to product colour, it is only necessary to according to material characteristic regulating system temperature in reasonable model
It can guarantee that yellow colour index is qualified in enclosing.Due to, containing acrylonitrile (AN), encountering high temperature in AS product and being easy that polymer is made to turn yellow,
In process of production to guarantee that polymer is in molten state and remaining content of monomer is minimum, need to keep the temperature polymer and risen
Warm devolatilization, temperature-rise period be easy to cause product to turn yellow, and the melt index reduction of AS-105 will cause line pressure liter after transition
Height needs to improve the mobility of polymer by heating up, and in order to make yellow colour index control in qualified range, one is dodged and is added
Hot device heats up 3 DEG C, dodges heater for two and heats up 3 DEG C.
4, tank component is decanted: main material includes AN and SM in clear filling, and normally unreacted material can recycle when charging
Into decantation tank.Decantation tank component refers to AN proportion in decantation tank material；The decantation tank target components of AS-103 are
The decantation tank target components of 27%, AS-105 are 25%, and since SAN technique is continuous production, system time is in dynamic equilibrium
Process need to only change charging when component reduces since the change of AN and SM component in transformation process will affect decantation tank component
Component can realize the change of decantation tank component.
Transformation process is to be applicable according to repeatedly making the transition obtained by data-optimized summary different production lines.Transformation process
The unqualified material generated is few, and transformation process, without influence, and does not influence the dynamic equilibrium of system, Neng Goubao to product quality after transition
Production safety in whole process is demonstrate,proved to stablize.
Claims (9)
1. the AS particle of a kind of high flowing, long chain, which is characterized in that by weight percentage, be made of following raw material: benzene
Ethylene is 74 parts, and acrylonitrile is 26 parts, and recycle monomer is 73 parts, and chain-transferring agent is 0-12 parts, and chain initiator is 0-2 parts.
2. the AS particle of high flowing as described in claim 1, long chain, it is characterised in that: styrene is after ethylbenzene dehydrogenation
Product contains a small amount of ethylbenzene.
3. the AS particle of high flowing as described in claim 1, long chain, it is characterised in that: acrylonitrile is propylene, ammonia, sky
Gas and water are made for raw material, contain a small amount of water.
4. the AS particle of flowing as described in claim 1 high, long chain, it is characterised in that: recycle monomer be acrylonitrile and
The mixed solution that styrene is formed according to 1:3 ratio.
5. the AS particle of high flowing as described in claim 1, long chain, it is characterised in that: chain-transferring agent is n-octyl mercaptan.
6. the AS particle of high flowing as described in claim 1, long chain, it is characterised in that: 1,1 peroxidating of chain initiator
Hexamethylene.
7. a kind of height as described in claim 1 flows, the preparation method of the AS particle of long chain, which is characterized in that the party
Method follows the steps below:
(1) raw material is premixed according to formula rate, so that each raw material is tentatively uniformly mixed, obtains premix, in which:
The formula rate by weight percentage, is made of following raw material: styrene is 74 parts, and acrylonitrile is 26 parts, is followed
Ring monomer is 73 parts, and chain-transferring agent is 0-12 parts, and chain initiator is 0-2 parts；
(2) volume is added in premix obtained in step (1) is 40m3Jacket reactor carry out polymerization reaction；
(3) molten polymer come out from reaction kettle carries out devolatilization, granulation, drying, obtains the AS of high flowing, long chain
Particle.
8. height according to claim 7 flows, the preparation method of the AS particle of long chain, it is characterised in that step (2)
Described in collet be divided into 4 sections, 1st area is conduction oil, and 2,3,4 areas are recirculated cooling water；
The reaction kettle is stirred using double helix, speed of agitator 30r/min.
9. height according to claim 7 flows, the preparation method of the AS particle of long chain, it is characterised in that step (3)
Described in devolatilization be by vacuumize by the unreacting material contained in polymer remove；
Described be granulated is BKG pelletizer underwater cutpellet；
The drying is centrifugal dehydration, is evaporated aqueous vapor by self heat.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810656697.6A CN109111542A (en) | 2018-06-24 | 2018-06-24 | A kind of high flowing, the AS particle of long chain and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201810656697.6A CN109111542A (en) | 2018-06-24 | 2018-06-24 | A kind of high flowing, the AS particle of long chain and preparation method thereof |
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| CN109111542A true CN109111542A (en) | 2019-01-01 |
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| CN201810656697.6A Pending CN109111542A (en) | 2018-06-24 | 2018-06-24 | A kind of high flowing, the AS particle of long chain and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114573744A (en) * | 2022-03-14 | 2022-06-03 | 万华化学(四川)有限公司 | Method for reducing residual styrene-acrylonitrile copolymer resin and application |
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|---|---|---|---|---|
| US4542196A (en) * | 1982-09-24 | 1985-09-17 | Cosden Technology, Inc. | Process for producing styrenic/alkenylnitrile copolymers |
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2018
- 2018-06-24 CN CN201810656697.6A patent/CN109111542A/en active Pending
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|---|---|---|---|---|
| US4542196A (en) * | 1982-09-24 | 1985-09-17 | Cosden Technology, Inc. | Process for producing styrenic/alkenylnitrile copolymers |
| CN85106459A (en) * | 1983-09-21 | 1987-02-18 | 考斯顿技术公司 | Make the method for styrenic-alkenylnitrile copolymers |
| CN85106458A (en) * | 1983-09-21 | 1987-04-15 | 科斯登技术公司 | Produce the method for vinylbenzene-olefin nitrile copolymer |
| JP2003105147A (en) * | 2002-09-24 | 2003-04-09 | Denki Kagaku Kogyo Kk | Thermoplastic copolymer composition |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114573744A (en) * | 2022-03-14 | 2022-06-03 | 万华化学(四川)有限公司 | Method for reducing residual styrene-acrylonitrile copolymer resin and application |
| CN114573744B (en) * | 2022-03-14 | 2024-02-27 | 万华化学(四川)有限公司 | Method for reducing residual styrene-acrylonitrile copolymer resin and application thereof |
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