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WO2001029099A1 - Procede de fabrication de copolymeres styrene/acrylonitrile - Google Patents

Procede de fabrication de copolymeres styrene/acrylonitrile 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
Authority
WO
WIPO (PCT)
Prior art keywords
styrene
reaction mixture
acrylonitrile
temperature
addition
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/US2000/028722
Other languages
English (en)
Inventor
Bahar Azimipour
Philippe Delbecq
Hendricus Franciscus Zirkzee
Gilles Bodineau
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
General Electric Co
Original Assignee
General Electric Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by General Electric Co filed Critical General Electric Co
Publication of WO2001029099A1 publication Critical patent/WO2001029099A1/fr
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 .

Landscapes

  • 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

Le procédé de la présente invention consiste : (a) à introduire, dans un réacteur, un mélange de réaction comprenant eau, acrylonitrile, un ou plusieurs initiateur, un ou plusieurs agent de migration de chaîne, un ou plusieurs agent de suspension et éventuellement une fraction déterminée de la quantité totale de styrène, (b) à mélanger le mélange de réaction et à augmenter la température de ce mélange à 60 °C et ensuite à 120 °C, (c) lorsque la température du mélange de réaction a atteint 60 °C ou 120 °C, à ajouter la quantité restante du styrène, de manière à conserver le ration monomère acrylonitrile/monomère styrène constant dans le mélange de réaction lors de l'ajout, (d) à élever la température du mélange de réaction à 140 °C et à le maintenir à cette température suffisamment longtemps pour que pour la copolymérisation puisse avoir lieu, et (e) à refroidir le mélange de réaction et à récupérer le copolymère styrène/acrylonitrile. L'invention s'applique aux copolymères styrène/acrylonitrile présentant un niveau d'acrylonitrile d'au moins 40 % en poids.
PCT/US2000/028722 1999-10-20 2000-10-17 Procede de fabrication de copolymeres styrene/acrylonitrile Ceased WO2001029099A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR9913087A FR2800079A1 (fr) 1999-10-20 1999-10-20 Procede de fabrication de copolymeres styrene-acrylonitrile
FR99/13087 1999-10-20

Publications (1)

Publication Number Publication Date
WO2001029099A1 true WO2001029099A1 (fr) 2001-04-26

Family

ID=9551136

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2000/028722 Ceased WO2001029099A1 (fr) 1999-10-20 2000-10-17 Procede de fabrication de copolymeres styrene/acrylonitrile

Country Status (2)

Country Link
FR (1) FR2800079A1 (fr)
WO (1) WO2001029099A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106084111A (zh) * 2016-07-28 2016-11-09 淄博华星助剂有限公司 超低分子量as树脂的制备方法
CN113436688A (zh) * 2021-06-26 2021-09-24 浙江智英石化技术有限公司 一种san反应进料控制方法、系统及其存储介质

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 (zh) * 2016-07-28 2016-11-09 淄博华星助剂有限公司 超低分子量as树脂的制备方法
CN106084111B (zh) * 2016-07-28 2018-03-27 淄博华星助剂有限公司 超低分子量as树脂的制备方法
CN113436688A (zh) * 2021-06-26 2021-09-24 浙江智英石化技术有限公司 一种san反应进料控制方法、系统及其存储介质

Also Published As

Publication number Publication date
FR2800079A1 (fr) 2001-04-27

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