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WO2001029099A1 - Process for the manufacture of styrene-acrylonitrile copolymers - Google Patents

Process for the manufacture of styrene-acrylonitrile copolymers Download PDF

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Publication number
WO2001029099A1
WO2001029099A1 PCT/US2000/028722 US0028722W WO0129099A1 WO 2001029099 A1 WO2001029099 A1 WO 2001029099A1 US 0028722 W US0028722 W US 0028722W WO 0129099 A1 WO0129099 A1 WO 0129099A1
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WIPO (PCT)
Prior art keywords
styrene
reaction mixture
acrylonitrile
temperature
addition
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Ceased
Application number
PCT/US2000/028722
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French (fr)
Inventor
Bahar Azimipour
Philippe Delbecq
Hendricus Franciscus Zirkzee
Gilles Bodineau
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General Electric Co
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General Electric Co
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Publication date
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Publication of WO2001029099A1 publication Critical patent/WO2001029099A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/42—Nitriles
    • C08F220/44—Acrylonitrile
    • 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
    • C08F212/10—Styrene with nitriles

Definitions

  • the present invention generally relates to a process for the manufacture of a styrene-acrylonitrile copolymer (SAN copolymer) and in particular an SAN copolymer comprising a level of acrylonitrile (AN) of 40% by weight or more and preferably of 45% by weight or more and generally of 45 to 50% by weight.
  • SAN copolymer styrene-acrylonitrile copolymer
  • AN acrylonitrile
  • SAN copolymers are among the most widely used thermoplastic materials because of their excellent resistance to solvents and their excellent tensile strength, for example in comparison with polystyrene. Thus, SAN copolymers are widely employed, alone or in the form of alloys with other polymers and copolymers, in the domestic appliance industry, packaging, electronics and the automobile industry.
  • SAN copolymers are conventionally manufactured by suspension copolymerization in the following way:
  • the reactor is initially charged with all the water and acrylonitrile, which is the least reactive monomer, and a portion of the styrene, which is the most reactive monomer.
  • the temperature of the reaction mixture is then increased with stirring to 120°C and, 30 minutes after having reached this temperature, the remainder of the styrene is added to the reactor with a constant rate of introduction.
  • the temperature of the reaction mixture is increased to 140°C, this stage generally being known as "cooking stage".
  • This cooking stage generally has a duration of the order of 3 to 3 hours 45 minutes for the SAN suspension.
  • the SAN copolymer is recovered conventionally by centrifuging, in order to separate the pearls from the aqueous liquid, and drying on a fluidized bed.
  • the conventional process gives good results for the manufacture of SAN copolymers with a low level of acrylonitrile but, for levels of acrylonitrile > 30% by weight, the copolymers obtained result in moulded products having a high yellow index.
  • the process comprises the following stages:
  • reaction mixture comprising all the water, acrylonitrile, initiator or initiators, chain-transfer agent or agents and suspending agent or agents and optionally a predetermined fraction of the total amount of the styrene;
  • the addition of the remaining amount of styrene can be carried out continuously or noncontinuously .
  • the duration of the addition of the remaining amount of styrene generally lasts from 400 to 500 minutes .
  • the addition of styrene comprises a first phase, during which the amount of styrene added is increased to a maximum, and then a second phase, during which the amount of styrene added is decreased until all the total amount of styrene has been added.
  • the first phase of the addition during which the amount of styrene added is increased, generally lasts from 90 to 120 minutes from the beginning of the rise in temperature to 120°C, that is to say that the addition of styrene is a maximum 90 to 120 minutes after the beginning of the rise in temperature.
  • This rise in temperature generally lasts of the order of 90 minutes .
  • the increase in the amount of styrene added lasts 90 to 120 minutes and, when it is added after reaching the temperature of 120°C, this increase lasts of the order to 30 minutes.
  • the maximum for addition of the styrene generally corresponds to a total amount of styrene added of 10% by weight approximately of the total remaining amount of styrene.
  • the second phase of addition of the remaining amount of styrene, in which the amount [lacuna] styrene added is gradually decreased, has a duration generally of 300 to 350 minutes.
  • the copolymerization is brought to completion by raising the temperature of the reaction mixture to 140°C and by maintaining the reaction mixture at this temperature for a sufficient duration.
  • the rise in temperature to 140°C can be carried out after the complete addition of the remaining amount of styrene or slightly before the end of this addition.
  • the duration of heating at 140°C, including the rise in temperature, is generally of the order of 200 to 250 minutes.
  • the suspending agents, the initiators and the chain-transfer agents used in the process of the invention are conventional and they are used in the usual proportions .
  • suspending agents of tricalcium phosphates, poly (vinyl alcohol) s and acrylic acid/alkyl acrylate copolymers.
  • a recommended suspending agent is Ethapol ® , which is a copolymer of acrylic acid and of 2-ethylhexyl acrylate sold by the Company CIRS .
  • alkyl peroxides such as di-t-butyl peroxide (DTBP), t-butyl cumyl peroxide (BCUP) and 2, 5-dimethyl-2, 5- di ( tert-butylperoxy) hexane .
  • n- (C ⁇ -Ci ⁇ ) alkyl mercaptans such as n-tert- decyl [sic] mercaptan (TTDM) .
  • TTDM n-tert- decyl [sic] mercaptan
  • An SAN copolymer having a level of acrylonitrile of 45% by weight is manufactured by the process of the invention using the temperature profile and the profile for addition of acrylonitrile of Figure
  • the initial reaction mixture has the following composition :
  • the initial reaction mixture is brought to a temperature of 120°C. Once the temperature of 120°C has been reached (time to) , the addition of the remaining 50 parts of styrene is begun.
  • the total duration of the addition of the styrene is 405 minutes. Shortly before the end of the addition, the temperature of the reaction mixture was raised in order to reach the temperature of 140°C at the end of the addition. This temperature was maintained for 135 minutes in order to bring the copolymerization to completion.
  • the total duration of the copolymerization from the beginning of the addition of the remaining amount of styrene is 540 minutes.
  • An SAN copolymer having a level of acrylonitrile of 45% by weight is manufactured by the process of the invention using the temperature profile and the profile for addition of acrylonitrile of Figure
  • the initial reaction mixture has the following composition :
  • the initial reaction mixture is heated to 60°C and then 120°C.
  • an SAN copolymer comprises 45% by weight of acrylonitrile is conventionally recovered.
  • lacuna was prepared without keeping constant the styrene monomer/acrylonitrile monomer ratio in the reaction mixture, that is to say by adding the remaining styrene fraction with a constant flow rate.
  • Test specimens made of copolymer of Examples 1 and 2 and of Comparative Example A were moulded under the same conditions and the yellow index of the test specimens was determined by means of a Spectroflash ® 300 device for measuring the yellow index .

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

The process comprises: (a) the introduction, into a reactor, [lacuna] a reaction mixture comprising all the water, acrylonitrile, initiator or initiators, chain-transfer agent or agents and suspending agent or agents and optionally a predetermined fraction of the total amount of the styrene; (b) stirring the reaction mixture and increasing the temperature of this reaction mixture to 60 °C and then to 120 °C; (c) when the temperature of the reaction mixture has reached 60 °C or 120 °C, the addition of the remaining amount of styrene, so as to keep constant the styrene monomer/acrylonitrile monomer ratio in the reaction mixture throughout the duration of the addition; (d) raising the temperature of the reaction mixture to 140 °C and the maintenance at this temperature for a sufficient duration to bring the copolymerization to completion; and (e) cooling the reaction mixture and the recovery of the styrene/acrylonitrile copolymer. Application to the manufacture of SAN copolymers having a level of acrylonitrile of at least 40 % by weight.

Description

Process for the manufacture of styrene-acrylonitrile copolymers
The present invention generally relates to a process for the manufacture of a styrene-acrylonitrile copolymer (SAN copolymer) and in particular an SAN copolymer comprising a level of acrylonitrile (AN) of 40% by weight or more and preferably of 45% by weight or more and generally of 45 to 50% by weight.
SAN copolymers are among the most widely used thermoplastic materials because of their excellent resistance to solvents and their excellent tensile strength, for example in comparison with polystyrene. Thus, SAN copolymers are widely employed, alone or in the form of alloys with other polymers and copolymers, in the domestic appliance industry, packaging, electronics and the automobile industry.
SAN copolymers are conventionally manufactured by suspension copolymerization in the following way:
The reactor is initially charged with all the water and acrylonitrile, which is the least reactive monomer, and a portion of the styrene, which is the most reactive monomer. The temperature of the reaction mixture is then increased with stirring to 120°C and, 30 minutes after having reached this temperature, the remainder of the styrene is added to the reactor with a constant rate of introduction. After the addition of the styrene, the temperature of the reaction mixture is increased to 140°C, this stage generally being known as "cooking stage". This cooking stage generally has a duration of the order of 3 to 3 hours 45 minutes for the SAN suspension. After degassing, the SAN copolymer is recovered conventionally by centrifuging, in order to separate the pearls from the aqueous liquid, and drying on a fluidized bed.
The conventional process gives good results for the manufacture of SAN copolymers with a low level of acrylonitrile but, for levels of acrylonitrile > 30% by weight, the copolymers obtained result in moulded products having a high yellow index.
Moreover, it is known that the chemical resistance of SAN copolymers is mainly due to the presence of acrylonitrile units, this resistance increasing with the increase in the level of acrylonitrile in the copolymer.
Consequently, it would be desirable to have available a process for the manufacture of SAN copolymers which makes it possible to obtain copolymers resulting in moulded articles with a low yellow index, in particular for high levels of acrylonitrile of 40% by weight of more and preferably of 45% by weight or more . It has now been found, according to the invention, that it is possible to manufacture a styrene-acrylonitrile copolymer, in particular a copolymer which has a high level of acrylonitrile units and which results in moulded articles exhibiting a low yellow index, by exerting precise control over the profile for addition of the styrene during the polymerization reaction and over the temperature profile .
According to the invention, the process comprises the following stages:
(a) introducing, into a reactor, a reaction mixture comprising all the water, acrylonitrile, initiator or initiators, chain-transfer agent or agents and suspending agent or agents and optionally a predetermined fraction of the total amount of the styrene;
(b) while stirring the reaction mixture, increasing the temperature of the reaction mixture to 60°C and then to 120°C; (c) when the temperature of the reaction mixture has reached 60°C or 120°C, adding the remaining amount of styrene, so as to keep constant the styrene monomer/acrylonitrile monomer ratio by weight in the reaction mixture throughout the duration of the addition;
(d) raising the temperature of the reaction mixture to 140°C and maintaining at this temperature in order to bring the copolymerization to completion; and
(e) allowing the mixture to cool and recovering the SAN copolymer.
The addition of the remaining amount of styrene can be carried out continuously or noncontinuously . The duration of the addition of the remaining amount of styrene generally lasts from 400 to 500 minutes .
In order to keep constant the styrene monomer/acrylonitrile monomer ratio by weight in the reaction mixture and taking into account the kinetics of copolymerization, the addition of styrene comprises a first phase, during which the amount of styrene added is increased to a maximum, and then a second phase, during which the amount of styrene added is decreased until all the total amount of styrene has been added.
The first phase of the addition, during which the amount of styrene added is increased, generally lasts from 90 to 120 minutes from the beginning of the rise in temperature to 120°C, that is to say that the addition of styrene is a maximum 90 to 120 minutes after the beginning of the rise in temperature. This rise in temperature generally lasts of the order of 90 minutes .
Thus, when the styrene is added from the beginning of the rise, the increase in the amount of styrene added lasts 90 to 120 minutes and, when it is added after reaching the temperature of 120°C, this increase lasts of the order to 30 minutes.
The maximum for addition of the styrene generally corresponds to a total amount of styrene added of 10% by weight approximately of the total remaining amount of styrene.
The second phase of addition of the remaining amount of styrene, in which the amount [lacuna] styrene added is gradually decreased, has a duration generally of 300 to 350 minutes.
The copolymerization is brought to completion by raising the temperature of the reaction mixture to 140°C and by maintaining the reaction mixture at this temperature for a sufficient duration.
The rise in temperature to 140°C can be carried out after the complete addition of the remaining amount of styrene or slightly before the end of this addition. The duration of heating at 140°C, including the rise in temperature, is generally of the order of 200 to 250 minutes.
The suspending agents, the initiators and the chain-transfer agents used in the process of the invention are conventional and they are used in the usual proportions .
Mention may be made, among suspending agents, of tricalcium phosphates, poly (vinyl alcohol) s and acrylic acid/alkyl acrylate copolymers. A recommended suspending agent is Ethapol®, which is a copolymer of acrylic acid and of 2-ethylhexyl acrylate sold by the Company CIRS .
Mention may be made, among radical initiators, of alkyl peroxides, such as di-t-butyl peroxide (DTBP), t-butyl cumyl peroxide (BCUP) and 2, 5-dimethyl-2, 5- di ( tert-butylperoxy) hexane .
Mention may be made among chain-transfer agents, of n- (Cβ-Ciδ) alkyl mercaptans, such as n-tert- decyl [sic] mercaptan (TTDM) . The continuation of the description refers to the appended figures, which respectively represent:
Figure 1 - temperature profile and profile for the continuous addition of styrene as a function of the time of an implementation of the process of the invention; and
Figure 2 - temperature profile and profile for the noncontinuous addition of styrene as a function of the time of another implementation of the process of the invention. Example 1
An SAN copolymer having a level of acrylonitrile of 45% by weight is manufactured by the process of the invention using the temperature profile and the profile for addition of acrylonitrile of Figure
1.
The initial reaction mixture has the following composition :
Parts by weight
Styrene 5
Acrylonitrile 45
BCUP 0.028 DTBP 0.04
TDDM 0.7
Poly (vinyl alcohol) (colloid) 0.1
Demineralized water 100
The initial reaction mixture is brought to a temperature of 120°C. Once the temperature of 120°C has been reached (time to) , the addition of the remaining 50 parts of styrene is begun.
During the first phase of the addition (to to tm) , which lasts 60 minutes, the flow rate for introduction of the styrene was continuously increased, so as to keep constant the styrene monomer/acrylonitrile monomer ratio of the reaction mixture. The maximum flow rate at time tm is 14.81 parts/hour.
At this point tm, the second phase of the addition of remaining styrene was initiated by decreasing the feed flow rate in order to still keep constant the styrene monomer/acrylonitrile monomer ratio in the reaction mixture.
The total duration of the addition of the styrene is 405 minutes. Shortly before the end of the addition, the temperature of the reaction mixture was raised in order to reach the temperature of 140°C at the end of the addition. This temperature was maintained for 135 minutes in order to bring the copolymerization to completion.
The total duration of the copolymerization from the beginning of the addition of the remaining amount of styrene is 540 minutes.
An SAN copolymer having a level of acrylonitrile of 45% by weight was then recovered conventionally,
Example 2
An SAN copolymer having a level of acrylonitrile of 45% by weight is manufactured by the process of the invention using the temperature profile and the profile for addition of acrylonitrile of Figure
2.
The initial reaction mixture has the following composition :
Parts by weight
Styrene 4.44 Acrylonitrile 45
Poly (vinyl alcohol) 0.1
DTBP 0.04 BCUP 0.028
TDDM 0.56 Demineralized water 150
The initial reaction mixture is heated to 60°C and then 120°C.
The addition of the remaining 50.55 parts of styrene is begun as soon as the reaction mixture reaches the temperature of 60°C. This addition is carried out in separate portions but still while keeping constant the styrene monomer/acrylonitrile monomer ratio in the reaction mixture.
The conditions of the addition of the remaining amount of styrene are given in the table below. Time Temperature Rate or flow rate of addition of (minute) (C) [sic] acrylonitrile
(parts by weight per hour)
0 room 0
36 60°C 2.22 Beginning AN [sic] addition
70 10
90 120°C 17.73 Maximum level of addition
120 120°C 10
180 120°C 6.66
240 120C [sic] 5.2
420 4.44 Beginning rise in temperature
465 140°C
540 140°C End of copolymerization
After cooling, an SAN copolymer comprises 45% by weight of acrylonitrile is conventionally recovered.
Comparative Example A
An SAN copolymer comprising 45% by weight
[lacuna] was prepared without keeping constant the styrene monomer/acrylonitrile monomer ratio in the reaction mixture, that is to say by adding the remaining styrene fraction with a constant flow rate.
The operating conditions are shown below.
Initial reaction mixture
Parts by weight Styrene 22
Acrylonitrile 45
BCUP 0.028
DTBP 0.04
TDDM 0.557 Poly (vinyl alcohol) 0.1
Demineralized water 100 Addition of the remaining 33 parts of styrene
Time Temperature Styrene addition
(minutes) (beginning rise in temperature) 0 120°C End rise in temperature
30 120°C Beginning addition of the styrene 270 120°C End styrene addition
Beginning rise in temperature [sic] 315 140°C
540 140°C End of the copolymerization
After cooling, an SAN copolymer (45% AN) is conventionally recovered.
Test specimens made of copolymer of Examples 1 and 2 and of Comparative Example A were moulded under the same conditions and the yellow index of the test specimens was determined by means of a Spectroflash® 300 device for measuring the yellow index .
The results are given in the table below.
Yellow index Example 1 15.70
Example 2 14.41
Comparative Example A 29.51
The results show that, with the process of the invention, the yellow index is reduced by virtually half.

Claims

1. Process for the manufacture of a styrene/acrylonitrile copolymer, characterized in that it comprises:
(a) the introduction, into a reactor, of a reaction mixture comprising all the water, acrylonitrile, initiator or initiators, chain-transfer agent or agents and suspending agent or agents and optionally a predetermined fraction of the total amount of the styrene;
(b) stirring the reaction mixture and increasing the temperature of this reaction mixture to 60°C and then to 120°C; (c) when the temperature of the reaction mixture has reached 60°C or 120°C, the addition of the remaining amount of styrene, so as to keep constant the styrene monomer/acrylonitrile monomer ratio in the reaction mixture throughout the duration of the addition;
(d) raising the temperature of the reaction mixture to 140°C and the maintenance at this temperature for a sufficient duration to bring the copolymerization to completion; and (e) cooling the reaction mixture and the recovery of the styrene/acrylonitrile copolymer.
2. Process according to Claim 1, characterized in that the addition of the remaining amount of styrene is carried out continuously or noncontinuously .
3. Process according to Claim 1 or 2, characterized in that the addition of the remaining amount of styrene comprises a first phase, during which the amount of styrene added is increased as a function of the time up to a maximum, and then a second phase, during which the amount of styrene added is decreased.
4. Process according to Claim 3, characterized in that the maximum for addition of styrene corresponds to a total amount added of 10% by weight approximately of the total remaining amount of styrene.
5. Process according to any one of the preceding claims, characterized in that the SAN copolymer obtained has a level of acrylonitrile of at least 40% by weight.
6. Process according to any one of Claims 1 to 4, characterized in that the SAN copolymer obtained has a level of acrylonitrile of at least 45% by weight.
7. Process according to Claim 6, characterized in that the SAN copolymer has a level of acrylonitrile of 45 to 50% by weight.
PCT/US2000/028722 1999-10-20 2000-10-17 Process for the manufacture of styrene-acrylonitrile copolymers Ceased WO2001029099A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR9913087A FR2800079A1 (en) 1999-10-20 1999-10-20 Manufacture of a styrene/acrylonitrile copolymer useful in e.g. domestic appliance industry, involves reaction of acrylonitrile and styrene and adding remaining amount of styrene to keep the copolymer ratio constant
FR99/13087 1999-10-20

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106084111A (en) * 2016-07-28 2016-11-09 淄博华星助剂有限公司 The preparation method of Ultra-low molecular weight AS resin
CN113436688A (en) * 2021-06-26 2021-09-24 浙江智英石化技术有限公司 SAN reaction feeding control method, system and storage medium thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3931128A (en) * 1972-10-31 1976-01-06 Denki Kagaku Kogyo Kabushiki Kaisha Process for preparing copolymer of acrylonitrile and aromatic vinyl compound
US4039734A (en) * 1966-03-24 1977-08-02 Imperial Chemical Industries Limited Production of random or homogeneous copolymers
US4551309A (en) * 1982-09-24 1985-11-05 Cosden Technology, Inc. Apparatus for producing styrenic/alkenylnitrile copolymers
US4677171A (en) * 1982-09-24 1987-06-30 Cosden Technology, Inc. Process for producing styrenic/alkenylnitrile copolymers

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4039734A (en) * 1966-03-24 1977-08-02 Imperial Chemical Industries Limited Production of random or homogeneous copolymers
US3931128A (en) * 1972-10-31 1976-01-06 Denki Kagaku Kogyo Kabushiki Kaisha Process for preparing copolymer of acrylonitrile and aromatic vinyl compound
US4551309A (en) * 1982-09-24 1985-11-05 Cosden Technology, Inc. Apparatus for producing styrenic/alkenylnitrile copolymers
US4677171A (en) * 1982-09-24 1987-06-30 Cosden Technology, Inc. Process for producing styrenic/alkenylnitrile copolymers

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106084111A (en) * 2016-07-28 2016-11-09 淄博华星助剂有限公司 The preparation method of Ultra-low molecular weight AS resin
CN106084111B (en) * 2016-07-28 2018-03-27 淄博华星助剂有限公司 The preparation method of Ultra-low molecular weight AS resins
CN113436688A (en) * 2021-06-26 2021-09-24 浙江智英石化技术有限公司 SAN reaction feeding control method, system and storage medium thereof

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