BE821433A - PROCESS FOR PREPARING STYRENE-ACRYLONITRILE COPOLYMERS. - Google Patents

PROCESS FOR PREPARING STYRENE-ACRYLONITRILE COPOLYMERS.

Info

Publication number
BE821433A
BE821433A BE149843A BE149843A BE821433A BE 821433 A BE821433 A BE 821433A BE 149843 A BE149843 A BE 149843A BE 149843 A BE149843 A BE 149843A BE 821433 A BE821433 A BE 821433A
Authority
BE
Belgium
Prior art keywords
emi
styrene
acrylonitrile
acrylonitrile copolymers
preparing styrene
Prior art date
Application number
BE149843A
Other languages
French (fr)
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
Priority to BE149843A priority Critical patent/BE821433A/en
Application filed filed Critical
Publication of BE821433A publication Critical patent/BE821433A/en
Priority to CS125375A priority patent/CS188939B2/en
Priority to IT2062175A priority patent/IT1033162B/en
Priority to CA220,840A priority patent/CA1033892A/en
Priority to GB827275A priority patent/GB1475449A/en
Priority to NL7502394A priority patent/NL7502394A/en
Priority to FR7506245A priority patent/FR2262674B1/fr
Priority to AT156375A priority patent/AT334624B/en
Priority to JP2406675A priority patent/JPS50124982A/ja
Priority to ES435205A priority patent/ES435205A1/en
Priority to AU78703/75A priority patent/AU7870375A/en
Priority to DE19752508996 priority patent/DE2508996C2/en
Priority to SU752170161A priority patent/SU663311A3/en

Links

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
    • C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
    • C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
    • C08F279/04—Vinyl aromatic monomers and nitriles as the only monomers
    • 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
    • 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

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)
  • Polymerisation Methods In General (AREA)
  • Graft Or Block Polymers (AREA)

Description

       

  Procédé de préparation de copolymères styrène-acrylonitrile

  
La présente invention ae rapporte à un procédé de préparation de copolymères de styrène et d'acrylonitrile, ces copolymères étant généralement désignés par les termes "résines SAN".

  
Par rapport aux homopolymères de styrène, les résines SAN présentent de nombreux avantages, dont une moindre déformation thermique, une résistance accrue  <EMI ID=1.1> 

  
par l'une quelconque des méthodes connues, c'est-à-dire, en suspension, en émulsion ou en masse. La copolymérisation est du type radicalaire. Au lieu de styrène ou en mélange avec le styrène, on peut utiliser un autre hydrocarbure

  
 <EMI ID=2.1> 

  
alpha-méthylstyrène, p-chlorostyrène, etc. A titre de simplification de l'exposé,ces composés ou leurs mélanges sont désignés par le terme "styrène". De même, l'acrylonitrile peut être remplacé par du méthacrylonitrile ou être utilisé en mélange avec ce dernier.

  
Afin de contrôler la longueur de chaînes des polymères obtenus par voie radicalaire, sans trop influencer la vitesse de polymérisation, on introduit dans le mélange réactionnel, des agents régulateurs ou des agents de transfert de chaînes. Le choix de cet agent régulateur dépend du type de monomère mis en oeuvre. Dans le cas de polymères styréniques, les agents de transfert de chaînes les plus couramment utilisés sont les mercaptans, dont notamment le tert-dodécylmercaptan. Pour la polymérisation de l'acrylonitrile, on peut utiliser la triéthylamine comme agent de transfert de chaînes.

  
Cependant, dans le cas de préparation de copolymères de styrène et d'acrylonitrile, les agents de transfert cités ci-dessus présentent certains inconvénients. Les mercaptans réagissent avec l'acrylonitrile et donnent des résultats peu reproductibles. D'autre part, la triéthylamine est peu efficace et agit défavorablement sur le taux de polymérisation.

  
La présente invention permet de remédier à ces inconvénients et elle

  
a pour objet un procédé de préparation de copolymères de styrène et d'acrylonitrile en présence d'un agent de transfert ou agent régulateur qui est inerte vis-à-vis des monomères et qui permet de contrôler la longueur des chaînes des  <EMI ID=3.1> 

  
A cet effet, le procédé de la présente invention pour la copolymérisation de styrène et d'acrylonitrile est caractérisé en ce que la copolymérisation est effectuée en présence de dithiobis-(benzothiazole) en tant qu'agent de transfert de chaînée.

  
 <EMI ID=4.1> 

  
élevée quand on utilise du dithiobis-(benzothiazole) ou, en abrégé TBT, au lieu d'un autre agent de transfert, ce qui démontre un meilleur contrôle de la longueur des chaînes de SAN.

  
La quantité de TBT à mettre en oeuvre peut varier dans de larges limites et elle peut être aussi faible que 0,001 X du poids des monomères mis en oeuvre.

  
 <EMI ID=5.1> 

  
amélioration des résultats. Généralement, la quantité de TBT est comprise entre environ 0,05 et 1 X du poids des monomères mis en oeuvre.

  
Pour démontrer l'activité particulière du TBT en tant qu'agent régulateur, on a effectué des essais comparatifs. On a utilisé différents mélanges de styrène et d'acrylonitrile et on les a introduits dans des tubes à pression. On

  
a ensuite soumis ces mélanges à une polymérisation thermique, sous azote, pendant 1 heure et avec agitation.

  
le série d'essais : <EMI ID=6.1> 
- température de polymérisation : 105[deg.]C.

TABLEAU I.

  

 <EMI ID=7.1> 
 

  
(1) : Pourcentage calculé sur le poids des monomères

  
(2) : Viscosité intrinsèque (1 g. de résine dans 100 ml. de méthyléthylcétone;

  
30'C).

  
2e série d'essais : <EMI ID=8.1> 

  

 <EMI ID=9.1> 


  
(1) Pourcentage calculé sur le poids des monomères

  
 <EMI ID=10.1> 

  

 <EMI ID=11.1> 


  
 <EMI ID=12.1>  

  
4e série d'essais : <EMI ID=13.1> 
- température de polymérisation : 100[deg.]C.

TABLEAU IV.

  

 <EMI ID=14.1> 


  
(1) : Pourcentage calculé sur le poids des monomères

  
(2) : Viscosité intrinsèque.

REVENDICATIONS

  
1) Procédé de préparation de copolymères de styrène et d'acrylonitrile,

  
 <EMI ID=15.1> 



  Process for the preparation of styrene-acrylonitrile copolymers

  
The present invention relates to a process for the preparation of copolymers of styrene and of acrylonitrile, these copolymers being generally designated by the terms “SAN resins”.

  
Compared to styrene homopolymers, SAN resins have many advantages, including less thermal deformation, increased strength <EMI ID = 1.1>

  
by any of the known methods, that is to say, in suspension, in emulsion or in bulk. The copolymerization is of the radical type. Instead of styrene or mixed with styrene, another hydrocarbon can be used

  
 <EMI ID = 2.1>

  
alpha-methylstyrene, p-chlorostyrene, etc. By way of simplification of the description, these compounds or their mixtures are designated by the term “styrene”. Likewise, acrylonitrile can be replaced by methacrylonitrile or be used in admixture with the latter.

  
In order to control the chain length of the polymers obtained by the radical route, without influencing the polymerization rate too much, regulating agents or chain transfer agents are introduced into the reaction mixture. The choice of this regulating agent depends on the type of monomer used. In the case of styrenic polymers, the most commonly used chain transfer agents are mercaptans, including tert-dodecylmercaptan in particular. For the polymerization of acrylonitrile, triethylamine can be used as a chain transfer agent.

  
However, in the case of the preparation of copolymers of styrene and of acrylonitrile, the transfer agents mentioned above have certain drawbacks. Mercaptans react with acrylonitrile and give poorly reproducible results. On the other hand, triethylamine is not very effective and acts unfavorably on the rate of polymerization.

  
The present invention overcomes these drawbacks and it

  
relates to a process for preparing copolymers of styrene and acrylonitrile in the presence of a transfer agent or regulating agent which is inert with respect to the monomers and which makes it possible to control the length of the chains of <EMI ID = 3.1>

  
To this end, the process of the present invention for the copolymerization of styrene and acrylonitrile is characterized in that the copolymerization is carried out in the presence of dithiobis- (benzothiazole) as a chain transfer agent.

  
 <EMI ID = 4.1>

  
High when using dithiobis- (benzothiazole) or, abbreviated TBT, instead of another transfer agent, which demonstrates better control of SAN chain length.

  
The quantity of TBT to be used can vary within wide limits and it can be as low as 0.001% of the weight of the monomers used.

  
 <EMI ID = 5.1>

  
improved results. Generally, the amount of TBT is between approximately 0.05 and 1 X of the weight of the monomers used.

  
To demonstrate the particular activity of TBT as a regulatory agent, comparative tests were carried out. Different mixtures of styrene and acrylonitrile were used and filled into pressure tubes. We

  
then subjected these mixtures to thermal polymerization, under nitrogen, for 1 hour and with stirring.

  
the test series: <EMI ID = 6.1>
- polymerization temperature: 105 [deg.] C.

TABLE I.

  

 <EMI ID = 7.1>
 

  
(1): Percentage calculated on the weight of the monomers

  
(2): Intrinsic viscosity (1 g. Of resin in 100 ml. Of methyl ethyl ketone;

  
30'C).

  
2nd series of tests: <EMI ID = 8.1>

  

 <EMI ID = 9.1>


  
(1) Percentage calculated on the weight of the monomers

  
 <EMI ID = 10.1>

  

 <EMI ID = 11.1>


  
 <EMI ID = 12.1>

  
4th series of tests: <EMI ID = 13.1>
- polymerization temperature: 100 [deg.] C.

TABLE IV.

  

 <EMI ID = 14.1>


  
(1): Percentage calculated on the weight of the monomers

  
(2): Intrinsic viscosity.

CLAIMS

  
1) Process for preparing copolymers of styrene and acrylonitrile,

  
 <EMI ID = 15.1>

Claims (1)

2) Procédé suivant revendication 1, caractérisé en ce qu'on utilise le dithiobis- <EMI ID=16.1> 2) Method according to claim 1, characterized in that the dithiobis- <EMI ID = 16.1> is used
BE149843A 1974-03-01 1974-10-24 PROCESS FOR PREPARING STYRENE-ACRYLONITRILE COPOLYMERS. BE821433A (en)

Priority Applications (13)

Application Number Priority Date Filing Date Title
BE149843A BE821433A (en) 1974-10-24 1974-10-24 PROCESS FOR PREPARING STYRENE-ACRYLONITRILE COPOLYMERS.
CS125375A CS188939B2 (en) 1974-10-24 1975-02-25 Process of copolymerisation of styrene and acrylonitrile
IT2062175A IT1033162B (en) 1974-03-01 1975-02-25 PROCEDURE OF COPOLYMERIZATION OF STIROLD AND ACRYLONITRULE AND COPOLYMERS OBTAINED WITH THIS PROCEDURE
CA220,840A CA1033892A (en) 1974-03-01 1975-02-26 Process for copolymerizing styrene and acrylonitrile
GB827275A GB1475449A (en) 1974-03-01 1975-02-27 Process for copolymerizing styrene and acrylonitrile
NL7502394A NL7502394A (en) 1974-03-01 1975-02-28 PROCEDURE FOR THE COPOLYMERIZATION OF STYRENE AND ACRYLONITRILE AND PRODUCTS FOUND CONSISTING WHOLLY OR IN PART OF THE COPOLYMERS THEREFORE PREPARED.
AU78703/75A AU7870375A (en) 1974-03-01 1975-02-28 Copolymerization process
FR7506245A FR2262674B1 (en) 1974-03-01 1975-02-28
AT156375A AT334624B (en) 1974-03-01 1975-02-28 PROCESS FOR THE COPOLYMERIZATION OF STYRENE AND ACRYLONITRILE
JP2406675A JPS50124982A (en) 1974-03-01 1975-02-28
ES435205A ES435205A1 (en) 1974-03-01 1975-02-28 Process for copolymerizing styrene and acrylonitrile
DE19752508996 DE2508996C2 (en) 1974-03-01 1975-03-01 Process for the preparation of copolymers
SU752170161A SU663311A3 (en) 1974-10-24 1975-09-04 Method of obtaining polymer resins

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
BE149843A BE821433A (en) 1974-10-24 1974-10-24 PROCESS FOR PREPARING STYRENE-ACRYLONITRILE COPOLYMERS.

Publications (1)

Publication Number Publication Date
BE821433A true BE821433A (en) 1975-02-17

Family

ID=3842709

Family Applications (1)

Application Number Title Priority Date Filing Date
BE149843A BE821433A (en) 1974-03-01 1974-10-24 PROCESS FOR PREPARING STYRENE-ACRYLONITRILE COPOLYMERS.

Country Status (3)

Country Link
BE (1) BE821433A (en)
CS (1) CS188939B2 (en)
SU (1) SU663311A3 (en)

Also Published As

Publication number Publication date
SU663311A3 (en) 1979-05-15
CS188939B2 (en) 1979-03-30

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Legal Events

Date Code Title Description
RE Patent lapsed

Owner name: LABOFINA S.A.

Effective date: 19861031

RR Patent reestablished after lapse

Free format text: 871026 *LABOFINA S.A.

RE20 Patent expired

Owner name: S.A. FINA RESEARCH

Effective date: 19941024