CN108948253A - A kind of low viscosity, AS particle of high fluidity and preparation method thereof - Google Patents
A kind of low viscosity, AS particle of high fluidity and preparation method thereof Download PDFInfo
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- CN108948253A CN108948253A CN201810656701.9A CN201810656701A CN108948253A CN 108948253 A CN108948253 A CN 108948253A CN 201810656701 A CN201810656701 A CN 201810656701A CN 108948253 A CN108948253 A CN 108948253A
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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
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- Chemical Kinetics & Catalysis (AREA)
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Abstract
The invention discloses a kind of low viscosities, the AS particle of high fluidity and preparation method thereof, can influence to provide a kind of preparation method of AS particle easy to process, high fluidity in lesser situation to ABS resin.Belong to plastic applications, resulting materials are made by containing the following parts by weight: styrene is 75 parts, and acrylonitrile is 25 parts, and recycle monomer is 73 parts, and chain-transferring agent is 0-18 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 low viscosity, high fluidity
Son, while a kind of preparation method of the AS particle of the low viscosity, high fluidity being provided.
In order to realize above-mentioned task, the present invention is realised by adopting the following technical scheme:
A kind of low viscosity, high fluidity AS particle be made of following raw material by weight percentage: styrene 75
Part, acrylonitrile is 25 parts, and recycle monomer is 73 parts, and chain-transferring agent is 0-18 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).
The preparation method of the AN particle of low viscosity, high fluidity described in more than one, 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 75 parts, and acrylonitrile is 25 parts, is followed
Ring monomer is 73 parts, and chain-transferring agent is 0-18 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 low viscosity, high fluidity
AN 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 invention has the advantages that products obtained therefrom is the AN particle of a kind of low viscosity, high fluidity, 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-109) 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 AN particle (AS-109) of low viscosity as described above, high fluidity being produced, with weight percent
Meter, is made of following raw material: styrene is 81 parts, and acrylonitrile is 27 parts, and recycle monomer is 79 parts, and chain-transferring agent is 15.5 parts,
Chain initiator is 2 parts, speed of agitator 30r/min;
The AS particle (AS-109) 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 AN particle (AS-109) of low viscosity as described above, high fluidity being produced, with weight percent
Meter, is made of following raw material: styrene is 75 parts, and acrylonitrile is 25 parts, and recycle monomer is 73 parts, and chain-transferring agent is 14 parts, chain
Initiator is 1.7 parts, speed of agitator 30r/min;
The AS particle (AS-109) 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 AN particle (AS-109) of low viscosity as described above, high fluidity being produced, with weight percent
Meter, is made of following raw material: styrene is 69 parts, and acrylonitrile is 23 parts, and recycle monomer is 68 parts, and chain-transferring agent is 13 parts, chain
Initiator is 1.5 parts, speed of agitator 30r/min;
The AS particle (AS-109) 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 AN particle (AS-109) of low viscosity as described above, high fluidity being produced, with weight percent
Meter, is made of following raw material: styrene is 62 parts, and acrylonitrile is 21 parts, and recycle monomer is 61 parts, and chain-transferring agent is 12.5 parts,
Chain initiator is 1.2 parts, speed of agitator 30r/min;
The AS particle (AS-109) 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 AN particle (AS-109) of low viscosity as described above, high fluidity being produced, with weight percent
Meter, is made of following raw material: styrene is 56 parts, and acrylonitrile is 29 parts, and recycle monomer is 55 parts, and chain-transferring agent is 11 parts, chain
Initiator is 1 part, speed of agitator 30r/min;
The AS particle (AS-109) 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-109) of 1 embodiment of table
From the comparison of embodiment 1-5 in table 1 it is found that under different feeds flow, fed according to following example 6 formula, institute
The AS-109 data stabilization of production, and every product index reaches criterion of acceptability.
Embodiment 6
A kind of preparation method of the AS particle of low viscosity, high fluidity, referring also to attached SAN device process shown in FIG. 1
Figure, this method follow 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-109.After transition, AS-109 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 75 parts, acrylonitrile 25
Part, recycle monomer is 73 parts, and chain-transferring agent is 0-18 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 low viscosity, high fluidity
AS particle (AS-109), 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.
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-109) of new grades.
The product quality data of AS-103 are as follows:
The product quality data of AS-109 are as follows:
During AS-103 makes the transition AS-109 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 6350kg/h yield
NOM additional amount is 13kg/h;AS-109 melt index target value is 7g/10min, corresponding when stablizing under 6350kg/h yield
NOM additional amount is 14.6kg/h;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, need to be first high by NOM additional amount when transition starts according to equilibrium principle
Corresponding NOM additional amount 14.6kg/h when AS-109 stablizes under 6350kg/h yield, is set as 17.3kg/h, when react into
After row 60min, NOM is set as 14.6kg/h, continues to add 60min, the melt index of the 3rd hour product is already close to target
Value, can finely tune NOM near 14.6kg/h, so that production be made to reach stable state.
2, polymers compositions (AN): refer to AN proportion in the polymer;The target components of AS-103 are 28%, AS-
109 target components are 25%, 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 13.6% (AN) by 28% (AN), is adjusted to 21.8% (AN) after reaction carries out 60min, then by setting value,
Continue plus 60min, the component (AN) of the 3rd hour product are then fed according to 25% (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 raising of AS-109 will cause line pressure drop after transition
It is low, temperature can be suitably reduced, heater is dodged by one and cools down 3 DEG C, heater is dodged by two and cools down 2 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-109 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.AS-109 transition AS-103 process is with above-mentioned transformation process on the contrary, thinking phase
Together, it no longer repeats herein, transformation process is to be applicable according to repeatedly making the transition obtained by data-optimized summary different production lines.
The unqualified material that transformation process generates is few, and transformation process is on product quality after transition without influence, and the dynamic for not influencing system is flat
Weighing apparatus can guarantee that production safety is stablized in whole process.
Claims (9)
1. the AS particle of a kind of low viscosity, high fluidity, which is characterized in that by weight percentage, be made of following raw material: benzene
Ethylene is 75 parts, and acrylonitrile is 25 parts, and recycle monomer is 73 parts, and chain-transferring agent is 0-18 parts, and chain initiator is 0-2 parts.
2. the AS particle of low viscosity as described in claim 1, high fluidity, it is characterised in that: styrene is after ethylbenzene dehydrogenation
Product contains a small amount of ethylbenzene.
3. the AS particle of low viscosity as described in claim 1, high fluidity, 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 low viscosity as described in claim 1, high fluidity, 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 low viscosity as described in claim 1, high fluidity, it is characterised in that: chain-transferring agent is n-octyl mercaptan.
6. the AS particle of low viscosity as described in claim 1, high fluidity, it is characterised in that: 1,1 peroxidating of chain initiator
Hexamethylene.
7. a kind of preparation method of the AS particle of low viscosity as described in claim 1, high fluidity, 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 75 parts, and acrylonitrile is 25 parts, is followed
Ring monomer is 73 parts, and chain-transferring agent is 0-18 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 low viscosity, high fluidity
Particle.
8. the preparation method of the AS particle of low viscosity according to claim 7, high fluidity, which is characterized 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. the preparation method of the AS particle of low viscosity according to claim 7, high fluidity, which is characterized 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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- 2018-06-24 CN CN201810656701.9A patent/CN108948253A/en active Pending
Non-Patent Citations (3)
Title |
---|
丁浩: "《塑料工业使用手册 上》", 31 December 2000, 化学工业出版社 * |
刘金龙: "《SAN树脂工艺技术浅析》", 《橡胶资源利用》 * |
张晔辉等: "《天津大沽ABS产品牌号的改进及研发》", 《橡胶资源利用》 * |
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