BE591575A - - Google Patents

Info

Publication number
BE591575A
BE591575A BE591575DA BE591575A BE 591575 A BE591575 A BE 591575A BE 591575D A BE591575D A BE 591575DA BE 591575 A BE591575 A BE 591575A
Authority
BE
Belgium
Prior art keywords
emi
vulcanization
weight
parts
copolymer
Prior art date
Application number
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.)
Publication of BE591575A publication Critical patent/BE591575A/fr

Links

Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01K—ANIMAL HUSBANDRY; AVICULTURE; APICULTURE; PISCICULTURE; FISHING; REARING OR BREEDING ANIMALS, NOT OTHERWISE PROVIDED FOR; NEW BREEDS OF ANIMALS
    • A01K9/00—Sucking apparatus for young stock ; Devices for mixing solid food with liquids
    • A01K9/005—Teats or nipples
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • 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
    • C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
    • C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
    • C08F255/026—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms on to ethylene-vinylester copolymers
    • 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
    • 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
    • C08F291/00—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds according to more than one of the groups C08F251/00 - C08F289/00
    • 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
    • C08F291/00—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds according to more than one of the groups C08F251/00 - C08F289/00
    • C08F291/02—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds according to more than one of the groups C08F251/00 - C08F289/00 on to elastomers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L11/00—Compositions of homopolymers or copolymers of chloroprene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L21/00—Compositions of unspecified rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C08L23/0853—Vinylacetate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L31/00—Compositions of homopolymers or 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 acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid; Compositions of derivatives of such polymers
    • C08L31/02—Homopolymers or copolymers of esters of monocarboxylic acids
    • C08L31/04—Homopolymers or copolymers of vinyl acetate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
    • C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L7/00—Compositions of natural rubber
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08L9/02—Copolymers with acrylonitrile
    • C08L9/04—Latex
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C08L23/0869—Acids or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08L9/02—Copolymers with acrylonitrile

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Animal Husbandry (AREA)
  • Biodiversity & Conservation Biology (AREA)
  • Textile Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Description

       

  Compositions de copolymères d'éthylène et de polymères

  
 <EMI ID=1.1> 

  
La présente invention a pour objet des compositions de copolymères d'éthylène normalement

  
 <EMI ID=2.1> 

  
insaturés ainsi qu'un procédé de durcissement de ces compositions. 

  
On a trouvé que l'on peut obtenir de nouvelles compositions ayant des propriétés remarquables

  
 <EMI ID=3.1> 

  
 <EMI ID=4.1>   <EMI ID=5.1> 

  
au moins un atone de carbone tertiaire avec un

  
 <EMI ID=6.1> 

  
Selon une caractéristique de l'in-

  
 <EMI ID=7.1> 

  
mélangés les uns aux autres et peuvent être utilisés

  
 <EMI ID=8.1> 

  
nisées, tandis que selon une autre caractéristique de l'invention les dits polymères peuvent être amenés en contact les uns avec les autres à l'état façonné, et peuvent être soumis ensuite à un procédé de vulcanisation.

  
 <EMI ID=9.1> 

  
d'éthylène précités sont par exemple les esters de l'acide acrylique et des aonoalcools saturés ayant de

  
 <EMI ID=10.1> 

  
Ces copolymères peuvent être produits par des procédés connus en soi. Les produits de vulcanisation ayant des propriétés mécaniques particulièrement bonnes sont

  
 <EMI ID=11.1>  et des esters vinyliques organiques sont utilisés, 

  
 <EMI ID=12.1> 

  
sation formateur de radical libre, dans une phase liquide contenant en prédominance du butanol tertiaire,

  
 <EMI ID=13.1> 

  
 <EMI ID=14.1> 

  
 <EMI ID=15.1> 

  
 <EMI ID=16.1> 

  
 <EMI ID=17.1> 

  
cités sont caractérises &#65533;n ce qu'ils contiennent un

  
 <EMI ID=18.1> 

  
carbone dont une seule valence est saturée par un

  
 <EMI ID=19.1> 

  
 <EMI ID=20.1> 

  
aliphatiques singles ou doubles. La teneur en compo-

  
 <EMI ID=21.1> 

  
 <EMI ID=22.1> 

  
 <EMI ID=23.1> 

  
 <EMI ID=24.1> 

  
 <EMI ID=25.1> 

  
 <EMI ID=26.1> 

  
 <EMI ID=27.1>   <EMI ID=28.1>  monoalcools saturés ayant de 1 à 8 atomes de carbone

  
 <EMI ID=29.1> 

  
 <EMI ID=30.1> 

  
cyclohexanol, et en outre le caoutchouc butyle.

  
 <EMI ID=31.1> 

  
 <EMI ID=32.1> 

  
 <EMI ID=33.1> 

  
 <EMI ID=34.1> 

  
 <EMI ID=35.1> 

  
mère caoutchouteux. Il est préférable d'utiliser des <EMI ID=36.1>  mère d'éthylène.

  
On prépare les compositions de l'inven-

  
 <EMI ID=37.1> 

  
 <EMI ID=38.1> 

  
broyeur à cylindre. Si l'on applique une quantité rela-;,.

  
 <EMI ID=39.1> 

  
généralement sur le broyeur d'abord et l'on y ajoute 

  
 <EMI ID=40.1>   <EMI ID=41.1> 

  
 <EMI ID=42.1> 

  
 <EMI ID=43.1> 

  
 <EMI ID=44.1> 

  
 <EMI ID=45.1> 

  
 <EMI ID=46.1> 

  
 <EMI ID=47.1>   <EMI ID=48.1> 

  
comparer avec le brevet Français n[deg.] 1.225.715 du  5 Février 1959). Dans le cas où les compositions

  
 <EMI ID=49.1> 

  
on peut utiliser comme agents de durcissement les

  
 <EMI ID=50.1> 

  
 <EMI ID=51.1> 

  
 <EMI ID=52.1> 

  
ou les polyamines primaires et secondaires ou leurs sels (à comparer avec les breveta anglais n[deg.] 707.425 du 25 Octobre 1951, n[deg.] 723.456 du 5 Juillet 1952, et n[deg.] 741.654 du 13 Novembre 1951).

  
 <EMI ID=53.1> 

  
comme agents de vulcanisation des substances qui se décomposent aux températures élevées avec formation de radicaux libres, telles que les composés azoïques facilement décomposables par exemple l'azodiisobutyronitrile, les esters d'acide azodicarbo::ylique ou les composés peroxy tels que les peroxydes, par exemple

  
 <EMI ID=54.1> 

  
le peroxyde de cyclohexanone, le perbenzoate de tertiobutyle, les peroxydes polyfonctionnels tels que par

  
 <EMI ID=55.1> 

  
 <EMI ID=56.1> 

  
que de tertiobutyle, les persulfates, les perborates.  Toutefois, les peroxydes qui ont une vitesse de , 

  
 <EMI ID=57.1> 

  
px-dcëderment .

  
 <EMI ID=58.1> 

  
 <EMI ID=59.1> 

  
 <EMI ID=60.1> 

  
 <EMI ID=61.1> 

  
2, et avantageusement au noins 3 doubles liaisons

  
 <EMI ID=62.1> 

  
ont de préférence un point d'ébullition supérieur à ,100[deg.]C.. 

  
 <EMI ID=63.1>   <EMI ID=64.1> 

  
 <EMI ID=65.1> 

  
 <EMI ID=66.1> 

  
ques ou hexaallyliques de la triuéthylol- ou

  
 <EMI ID=67.1> 

  
 <EMI ID=68.1> 

  
 <EMI ID=69.1> 

  
 <EMI ID=70.1> 

  
 <EMI ID=71.1> 

  
cyanuratc de triallyle, le phosphate de triallyle. Ces composés sont utilisés avantajeusenent en quantités de

  
 <EMI ID=72.1> 

  
 <EMI ID=73.1> 

  
Outre les agents de durcissement cités, 

  
 <EMI ID=74.1> 

  
 <EMI ID=75.1> 

  
carbone, la silice, le silicate de calcium, le

  
 <EMI ID=76.1>  

  
bioxyde de titane, le sulfure de zinc, l'oxyde de zinc, l'alumine hydratée, le carbonate de calcium, 

  
 <EMI ID=77.1> 

  
 <EMI ID=78.1> 

  
phénoliques, les agents assouplissants, les antioxydants.

  
Les compositions de l'invention conviennent à la fabrication des articles façonnés, par exemple à la production de revêtements de fils et câbles métalliques, de flancs blancs de pneumatiques pour automobiles, de joints, scellements et profilés résistants à l'ozone, d'apprêts pour matières textiles tels que Matières pour tentes et tissus imperméables, de cuir artificiel, de tuyaux, de tubes flexibles, de récipients pour liquides et d'autres articles moulés. Les produits ainsi obtenus se distinguent par une bonne résistance aux ajouts

  
 <EMI ID=79.1> 

  
 <EMI ID=80.1> 

  
sentes compositions dans la production des matières plastiques composites, des structuras stratifiées par stratification des feuilles préformées des présentas compositions sur les métaux, les étoffes, le verre, et autres matières. Pour améliorer la force de liaison

  
 <EMI ID=81.1> 

  
adjuvants tels que par exemple les polyisocyanates.

  
Selon un autre mode do réalisation

  
 <EMI ID=82.1> 

  
tures stratifiées en mettant en contact le polymère caoutchouteux oléfiniquement insaturé sous forme ,  préfaçonnée, avec ,une couche de copolymère d'éthylène  cité et en vulcanisant ensuite les structures stratifiées pendant qu'elles sont au contact d'un. agent vulcanisant, de préférence un composé formateur de radicaux libres. Le polymère caoutchouteux peut contenir des agents vulcanisants ordinaires et en outre, les ingrédients de mélange cités précédemment, tandis

  
 <EMI ID=83.1> 

  
agents de durcissement les composants formateurs de radicaux libres cités, de préférence en combinaison avec les monomères organiques polymérisables cités

  
 <EMI ID=84.1> 

  
oléfiniques.

  
Parmi les types de structures qui peuvent être produits par le présent procédé, se trouvent les enduits protecteurs pour pneumatiques pour automobiles, pour étoffes qui sont enduites de polymères caoutchouteux cités et pour les structures produites à partir de caoutchouc mousse naturel,

  
de sorte que ces dernières structures peuvent être produites en une seule étape de travail. Les structures pourvues d'enduits protecteurs de copolymères

  
*

  
d'éthylène durcis se distinguent par une grande résistance à l'oxygène, à la lumière et à l'ozone.

  
En vue d'éviter le durcissement pendant le mélange des compositions précitées, les températures pendant le mélange doivent être maintenues de préférence au-dessous de 100[deg.]C. Après le façonnage, la réticulation ou la vulcanisation des compositions est effectuée par chauffage de celles-ci à des températures  <EMI ID=85.1> 

  
et de préférence de 100[deg.] à 200[deg.]C&#65533; pendant environ

  
 <EMI ID=86.1> 

  
structures composites à partir des présentes composi-

  
 <EMI ID=87.1> 

  
vont entrer en contact les unes avec les autres au

  
 <EMI ID=88.1> 

  
 <EMI ID=89.1> 

  
des parties de ces structures com&#65533;o&#65533;ites.

  
 <EMI ID=90.1> 

  
ties indiquées sont des parties en poids .

EXEMPLE 1 .

  
 <EMI ID=91.1> 

  
 <EMI ID=92.1> 

  

 <EMI ID=93.1> 


  
 <EMI ID=94.1>  

  
 <EMI ID=95.1> 

  
d'essai sont examines au bout de différentes périodes

  
 <EMI ID=96.1>  celle-ci étant notée suivant une échelle empirique 
(0=sans craquelure, 1 =traces de craquelures, 

  
2 = formation de craquelures distinctes, 3 formation de craquelures fortes, 4 = formation de craquelures très fortes, 5 = rupture). 

  

 <EMI ID=97.1> 


  
 <EMI ID=98.1> 

  
Dans un broyeur à cylindre, on prépaie

  
 <EMI ID=99.1>  

  

 <EMI ID=100.1> 


  
 <EMI ID=101.1> 

  
 <EMI ID=102.1> 

  
40 mn , à 151[deg.]C (4 atmosphères) et les échantillons

  
d'essai obtenus sont ensuite soumis à une concentration

  
 <EMI ID=103.1> 

  
sats présentent des caractéristiques similaires à celles des mélanges de l'exemple 1.

  
 <EMI ID=104.1> 

  
On prépare les mélanges suivants dans un malaxeur à cylindre.

  

 <EMI ID=105.1> 
 

  

 <EMI ID=106.1> 


  
 <EMI ID=107.1> 

  
 <EMI ID=108.1> 

  

 <EMI ID=109.1> 


  
Dans tous les cas, l'addition du copo-

  
 <EMI ID=110.1> 

  
ration de la résistance à l'ozone.

  
 <EMI ID=111.1> 

  
 <EMI ID=112.1> 

  
malaxeur Banbury 
 <EMI ID=113.1> 
 Des plaques d'essai provenant dos mélanges sont vulcanisées dans la presse de vulcani-;

  
 <EMI ID=114.1> 

  
à l'ozone sont les suivantes.

  

 <EMI ID=115.1> 


  
 <EMI ID=116.1> 

  
 <EMI ID=117.1> 

  
un broyeur à cylindre :

  

 <EMI ID=118.1> 


  
Les autres additifs sont les cernes qu'à l'exemple 4 (acide stéarique 0,5, oxyde de

  
 <EMI ID=119.1> 

  
thiazylsulfénamide 1 partie). 

  
La vulcanisation et les tests des )laques sont conduits de façon indiquée à l'exemple 4. Les valeurs illustrant la résistance à l'ozone sont les suivantes : 

  

 <EMI ID=120.1> 


  
 <EMI ID=121.1> 

  
 <EMI ID=122.1> 

  
un broyeur à cylindre :

  

 <EMI ID=123.1> 


  
On conduit la vulcanisation et les tests des plaques de façon décrite à l'exemple 4. Les valeurs illustrant la résistance à l'ozone sont les suivantes :

  

 <EMI ID=124.1> 


  
EXEMPLE 7.

  
 <EMI ID=125.1> 

  
un broyeur à cylindre  
 <EMI ID=126.1> 
 On conduit la vulcanisation et les tests des plaques de façon décrite à l'exemple 4. Les valeurs illustrant la résistance à l'ozone sont les suivantes :

  

 <EMI ID=127.1> 


  
EXEMPLE 8.

  
On prépare les saisies suivants dans un broyeur à cylindre :

  

 <EMI ID=128.1> 
 

  
On conduit la vulcanisation et les 

  
 <EMI ID=129.1> 

  
 <EMI ID=130.1> 

  
sont les suivantes :

  

 <EMI ID=131.1> 


  
 <EMI ID=132.1> 

  
Sur une feuille produite à partir d'un

  
 <EMI ID=133.1> 

  
100 parties de copolymère butadiène-styrène (72 : 28)

  
 <EMI ID=134.1> 

  
 <EMI ID=135.1> 

  
5 parties d'oxyde de zinc

  
 <EMI ID=136.1> 

  
 <EMI ID=137.1> 

  
sition suivante :

  
 <EMI ID=138.1> 

  
45 parties d'acétate de vinyle

  
30 parties d'acide silicique précipité très actif 1 partie d'antioxydant non décolorant

  
5 parties de phtalate de dioctyle

  
 <EMI ID=139.1> 

  
 <EMI ID=140.1> 

  
 <EMI ID=141.1> 

  
et les deux feuilles sont vulcanisées dans une presse  pendant qu'elles sont en contact l'une avec l'autre à

  
 <EMI ID=142.1>  

  
On obtient un stratifié dont les couches adhèrent 

  
 <EMI ID=143.1> 

  
forte :ent l'une à l'autre. 

  
EXEMPLE 10

  
 <EMI ID=144.1> 

  
suivante : 

  
 <EMI ID=145.1> 

  
 <EMI ID=146.1> 

  
 <EMI ID=147.1> 

  
30 parties d'acide silicique précipita très actif

  
 <EMI ID=148.1> 

  
 <EMI ID=149.1> 

  
 <EMI ID=150.1> 

  
 <EMI ID=151.1> 

  
 <EMI ID=152.1> 

  
 <EMI ID=153.1> 

  
 <EMI ID=154.1> 

  
5 parties d'o;:yde de sine (actif)

  
 <EMI ID=155.1> 

  
 <EMI ID=156.1> 

  
 <EMI ID=157.1> 

  
 <EMI ID=158.1> 

  
éthane sulfuricue

  
2,5 parties d'hydrazide d'acide benzène sulfurique.

  
L'ensemble est ensuite vulcanise dans un moule à caoutchouc Gousse et l'on obtient un caout-

  
 <EMI ID=159.1> 

  
 <EMI ID=160.1> 



  Compositions of ethylene copolymers and polymers

  
 <EMI ID = 1.1>

  
The present invention relates to compositions of ethylene copolymers normally

  
 <EMI ID = 2.1>

  
unsaturated as well as a method of curing these compositions.

  
It has been found that it is possible to obtain new compositions having remarkable properties.

  
 <EMI ID = 3.1>

  
 <EMI ID = 4.1> <EMI ID = 5.1>

  
at least one tertiary carbon atom with a

  
 <EMI ID = 6.1>

  
According to a characteristic of the in-

  
 <EMI ID = 7.1>

  
mixed with each other and can be used

  
 <EMI ID = 8.1>

  
nized, while according to another characteristic of the invention said polymers can be brought into contact with each other in the shaped state, and can then be subjected to a vulcanization process.

  
 <EMI ID = 9.1>

  
of the aforementioned ethylene are, for example, esters of acrylic acid and saturated aonoalcohols having

  
 <EMI ID = 10.1>

  
These copolymers can be produced by methods known per se. Vulcanization products with particularly good mechanical properties are

  
 <EMI ID = 11.1> and organic vinyl esters are used,

  
 <EMI ID = 12.1>

  
free radical-forming system, in a liquid phase predominantly containing tertiary butanol,

  
 <EMI ID = 13.1>

  
 <EMI ID = 14.1>

  
 <EMI ID = 15.1>

  
 <EMI ID = 16.1>

  
 <EMI ID = 17.1>

  
cited are characterized &#65533; n what they contain a

  
 <EMI ID = 18.1>

  
carbon of which only one valence is saturated by a

  
 <EMI ID = 19.1>

  
 <EMI ID = 20.1>

  
aliphatic singles or doubles. The compound content

  
 <EMI ID = 21.1>

  
 <EMI ID = 22.1>

  
 <EMI ID = 23.1>

  
 <EMI ID = 24.1>

  
 <EMI ID = 25.1>

  
 <EMI ID = 26.1>

  
 <EMI ID = 27.1> <EMI ID = 28.1> saturated monoalcohols having 1 to 8 carbon atoms

  
 <EMI ID = 29.1>

  
 <EMI ID = 30.1>

  
cyclohexanol, and additionally butyl rubber.

  
 <EMI ID = 31.1>

  
 <EMI ID = 32.1>

  
 <EMI ID = 33.1>

  
 <EMI ID = 34.1>

  
 <EMI ID = 35.1>

  
rubbery mother. It is preferable to use <EMI ID = 36.1> ethylene mother.

  
The compositions of the invention are prepared

  
 <EMI ID = 37.1>

  
 <EMI ID = 38.1>

  
cylinder crusher. If we apply a rela -;,.

  
 <EMI ID = 39.1>

  
usually on the grinder first and we add

  
 <EMI ID = 40.1> <EMI ID = 41.1>

  
 <EMI ID = 42.1>

  
 <EMI ID = 43.1>

  
 <EMI ID = 44.1>

  
 <EMI ID = 45.1>

  
 <EMI ID = 46.1>

  
 <EMI ID = 47.1> <EMI ID = 48.1>

  
compare with French patent n [deg.] 1.225.715 of February 5, 1959). In the event that the compositions

  
 <EMI ID = 49.1>

  
the hardening agents can be used

  
 <EMI ID = 50.1>

  
 <EMI ID = 51.1>

  
 <EMI ID = 52.1>

  
or the primary and secondary polyamines or their salts (to be compared with the English patents n [deg.] 707,425 of October 25, 1951, n [deg.] 723,456 of July 5, 1952, and n [deg.] 741,654 of November 13, 1951) .

  
 <EMI ID = 53.1>

  
as vulcanizing agents of substances which decompose at high temperatures with the formation of free radicals, such as easily decomposable azo compounds, for example azodiisobutyronitrile, esters of azodicarb :: ylic acid or peroxy compounds such as peroxides, for example example

  
 <EMI ID = 54.1>

  
cyclohexanone peroxide, tert-butyl perbenzoate, polyfunctional peroxides such as by

  
 <EMI ID = 55.1>

  
 <EMI ID = 56.1>

  
than tert-butyl, persulphates, perborates. However, peroxides which have a rate of,

  
 <EMI ID = 57.1>

  
px-dully.

  
 <EMI ID = 58.1>

  
 <EMI ID = 59.1>

  
 <EMI ID = 60.1>

  
 <EMI ID = 61.1>

  
2, and advantageously at number 3 double bonds

  
 <EMI ID = 62.1>

  
preferably have a boiling point greater than .100 [deg.] C ..

  
 <EMI ID = 63.1> <EMI ID = 64.1>

  
 <EMI ID = 65.1>

  
 <EMI ID = 66.1>

  
ques or hexaallyliques of triuethylol- or

  
 <EMI ID = 67.1>

  
 <EMI ID = 68.1>

  
 <EMI ID = 69.1>

  
 <EMI ID = 70.1>

  
 <EMI ID = 71.1>

  
triallyl cyanurate, triallyl phosphate. These compounds are used advantageously in amounts of

  
 <EMI ID = 72.1>

  
 <EMI ID = 73.1>

  
In addition to the hardening agents mentioned,

  
 <EMI ID = 74.1>

  
 <EMI ID = 75.1>

  
carbon, silica, calcium silicate,

  
 <EMI ID = 76.1>

  
titanium dioxide, zinc sulphide, zinc oxide, hydrated alumina, calcium carbonate,

  
 <EMI ID = 77.1>

  
 <EMI ID = 78.1>

  
phenolics, softening agents, antioxidants.

  
The compositions of the invention are suitable for the manufacture of shaped articles, for example, for the production of coatings for metal wires and cables, white sidewalls of automotive tires, ozone resistant gaskets, seals and profiles, primers. for textile materials such as materials for tents and waterproof fabrics, artificial leather, hoses, flexible tubes, containers for liquids and other molded articles. The products thus obtained are distinguished by good resistance to additions

  
 <EMI ID = 79.1>

  
 <EMI ID = 80.1>

  
These compositions are used in the production of composite plastics, laminated structures by laminating the preformed sheets, and the compositions present on metals, fabrics, glass, and other materials. To improve bond strength

  
 <EMI ID = 81.1>

  
adjuvants such as, for example, polyisocyanates.

  
According to another embodiment

  
 <EMI ID = 82.1>

  
Laminated structures by contacting the olefinically unsaturated rubbery polymer in preformed form with a layer of the said ethylene copolymer and then vulcanizing the laminate structures while in contact with a. vulcanizing agent, preferably a free radical forming compound. The rubbery polymer may contain ordinary vulcanizing agents and in addition the aforementioned blend ingredients, while

  
 <EMI ID = 83.1>

  
curing agents the named free radical-forming components, preferably in combination with the named polymerizable organic monomers

  
 <EMI ID = 84.1>

  
olefins.

  
Among the types of structures which can be produced by the present process are protective coatings for automotive tires, for fabrics which are coated with the cited rubbery polymers and for structures produced from natural foam rubber,

  
so that these latter structures can be produced in a single working step. Structures provided with protective coatings of copolymers

  
*

  
hardened ethylene are distinguished by high resistance to oxygen, light and ozone.

  
In order to avoid hardening during mixing of the above compositions, temperatures during mixing should preferably be kept below 100 [deg.] C. After shaping, crosslinking or vulcanization of the compositions is carried out by heating them to temperatures <EMI ID = 85.1>

  
and preferably from 100 [deg.] to 200 [deg.] C &#65533; during about

  
 <EMI ID = 86.1>

  
composite structures from the present composi-

  
 <EMI ID = 87.1>

  
will come into contact with each other at

  
 <EMI ID = 88.1>

  
 <EMI ID = 89.1>

  
parts of these structures are known as o &#65533; ites.

  
 <EMI ID = 90.1>

  
Parts shown are parts by weight.

EXAMPLE 1.

  
 <EMI ID = 91.1>

  
 <EMI ID = 92.1>

  

 <EMI ID = 93.1>


  
 <EMI ID = 94.1>

  
 <EMI ID = 95.1>

  
test are examined after different periods

  
 <EMI ID = 96.1> this being noted according to an empirical scale
(0 = without cracking, 1 = traces of cracking,

  
2 = formation of distinct cracks, 3 formation of strong cracks, 4 = formation of very strong cracks, 5 = rupture).

  

 <EMI ID = 97.1>


  
 <EMI ID = 98.1>

  
In a cylinder mill, we prepay

  
 <EMI ID = 99.1>

  

 <EMI ID = 100.1>


  
 <EMI ID = 101.1>

  
 <EMI ID = 102.1>

  
40 min, at 151 [deg.] C (4 atmospheres) and the samples

  
test obtained are then subjected to a concentration

  
 <EMI ID = 103.1>

  
sats have characteristics similar to those of the mixtures of Example 1.

  
 <EMI ID = 104.1>

  
The following mixtures are prepared in a roller mixer.

  

 <EMI ID = 105.1>
 

  

 <EMI ID = 106.1>


  
 <EMI ID = 107.1>

  
 <EMI ID = 108.1>

  

 <EMI ID = 109.1>


  
In all cases, the addition of the copo-

  
 <EMI ID = 110.1>

  
ozone resistance ration.

  
 <EMI ID = 111.1>

  
 <EMI ID = 112.1>

  
Banbury mixer
 <EMI ID = 113.1>
 Test plates from the mixtures are vulcanized in the vulcanization press;

  
 <EMI ID = 114.1>

  
ozone are as follows.

  

 <EMI ID = 115.1>


  
 <EMI ID = 116.1>

  
 <EMI ID = 117.1>

  
a roller mill:

  

 <EMI ID = 118.1>


  
The other additives are dark circles as in Example 4 (stearic acid 0.5, oxide of

  
 <EMI ID = 119.1>

  
thiazylsulfenamide 1 part).

  
The vulcanization and the tests of the lacquers are carried out as indicated in Example 4. The values illustrating the resistance to ozone are as follows:

  

 <EMI ID = 120.1>


  
 <EMI ID = 121.1>

  
 <EMI ID = 122.1>

  
a roller mill:

  

 <EMI ID = 123.1>


  
The vulcanization and the tests of the plates are carried out as described in Example 4. The values illustrating the resistance to ozone are as follows:

  

 <EMI ID = 124.1>


  
EXAMPLE 7.

  
 <EMI ID = 125.1>

  
a cylinder crusher
 <EMI ID = 126.1>
 The vulcanization and the tests of the plates are carried out as described in Example 4. The values illustrating the resistance to ozone are as follows:

  

 <EMI ID = 127.1>


  
EXAMPLE 8.

  
The following seizures are prepared in a roller mill:

  

 <EMI ID = 128.1>
 

  
The vulcanization and

  
 <EMI ID = 129.1>

  
 <EMI ID = 130.1>

  
are the following :

  

 <EMI ID = 131.1>


  
 <EMI ID = 132.1>

  
On a sheet produced from a

  
 <EMI ID = 133.1>

  
100 parts of butadiene-styrene copolymer (72: 28)

  
 <EMI ID = 134.1>

  
 <EMI ID = 135.1>

  
5 parts of zinc oxide

  
 <EMI ID = 136.1>

  
 <EMI ID = 137.1>

  
next sition:

  
 <EMI ID = 138.1>

  
45 parts of vinyl acetate

  
30 parts of very active precipitated silicic acid 1 part of non-bleaching antioxidant

  
5 parts dioctyl phthalate

  
 <EMI ID = 139.1>

  
 <EMI ID = 140.1>

  
 <EMI ID = 141.1>

  
and the two sheets are vulcanized in a press while they are in contact with each other to

  
 <EMI ID = 142.1>

  
A laminate is obtained, the layers of which adhere

  
 <EMI ID = 143.1>

  
strong: ent to each other.

  
EXAMPLE 10

  
 <EMI ID = 144.1>

  
next :

  
 <EMI ID = 145.1>

  
 <EMI ID = 146.1>

  
 <EMI ID = 147.1>

  
30 parts of silicic acid precipitated very active

  
 <EMI ID = 148.1>

  
 <EMI ID = 149.1>

  
 <EMI ID = 150.1>

  
 <EMI ID = 151.1>

  
 <EMI ID = 152.1>

  
 <EMI ID = 153.1>

  
 <EMI ID = 154.1>

  
5 parts o;: sine yde (active)

  
 <EMI ID = 155.1>

  
 <EMI ID = 156.1>

  
 <EMI ID = 157.1>

  
 <EMI ID = 158.1>

  
sulfuric ethane

  
2.5 parts of benzene sulfuric acid hydrazide.

  
The whole is then vulcanized in a rubber pod mold and a rubber is obtained.

  
 <EMI ID = 159.1>

  
 <EMI ID = 160.1>

Claims (1)

<EMI ID=161.1> <EMI ID = 161.1> <EMI ID=162.1> <EMI ID = 162.1> <EMI ID=163.1> <EMI ID = 163.1> <EMI ID=164.1> <EMI ID = 164.1> est un copolymère de 40 à 90 parties en poids is a copolymer of 40 to 90 parts by weight <EMI ID=165.1> <EMI ID = 165.1> <EMI ID=166.1> <EMI ID = 166.1> <EMI ID=167.1> <EMI ID = 167.1> <EMI ID=168.1> <EMI ID = 168.1> en poids de copolymère et 95 à 5 parties en poids de polymère caoutchouteux. by weight of copolymer and 95 to 5 parts by weight of rubbery polymer. <EMI ID=169.1> <EMI ID = 169.1> <EMI ID=170.1> <EMI ID = 170.1> carbone. carbon. 5[deg.]) La composition contient, outre le 5 [deg.]) The composition contains, in addition to <EMI ID=171.1> <EMI ID = 171.1> vulcanisation. vulcanization. <EMI ID=172.1> <EMI ID = 172.1> substance qui libère des libres aux taupe- substance that releases free to mole- <EMI ID=173.1> <EMI ID = 173.1> <EMI ID=174.1> <EMI ID = 174.1> libres est un compose peroxy orjanique. <EMI ID=175.1> free is an orjanic peroxy compound. <EMI ID = 175.1> <EMI ID=176.1> <EMI ID = 176.1> <EMI ID=177.1> <EMI ID = 177.1> totale de copolymère et de polymère caoutchouteux, total of copolymer and rubbery polymer, 12[deg.]) Le monomère polymérisable est présent en quantités de 0,5 à 20 parties en poids, calcu- 12 [deg.]) The polymerizable monomer is present in amounts of 0.5 to 20 parts by weight, calculated <EMI ID=178.1> <EMI ID = 178.1> caoutchouteux , rubbery, 13[deg.]) L'agent de vulcanisation est choi- 13 [deg.]) The vulcanizing agent is chosen <EMI ID=179.1> <EMI ID = 179.1> <EMI ID=180.1> <EMI ID = 180.1> ratures élevées, les oxydes et hydroxydes de létaux polyvalents, les polyamines. high erasures, oxides and hydroxides of polyvalent lethals, polyamines. <EMI ID=181.1> <EMI ID = 181.1> de vulcanisation, des charges choisies dans le groupe comprenant le noir de carbone, la silice, le silicate de calcium, le carbonate de calcium, la magnésie calcinée, les argiles, l'alumine hydratée. <EMI ID=182.1> vulcanization, fillers chosen from the group comprising carbon black, silica, calcium silicate, calcium carbonate, calcined magnesia, clays and hydrated alumina. <EMI ID = 182.1> <EMI ID=183.1> <EMI ID = 183.1> <EMI ID=184.1> <EMI ID = 184.1> férence de 100 à 200[deg.]C jusqu'à réticulation de la composition. from 100 to 200 [deg.] C until crosslinking of the composition. III - Un procédé de production des structures composites caractérisé par les points suivants pris isolénen't ou en combinaison : III - A process for the production of composite structures characterized by the following points taken alone or in combination: 1[deg.]) Il consiste à nettre en contact 1 [deg.]) It consists in making contact <EMI ID=185.1> <EMI ID = 185.1> <EMI ID=186.1> <EMI ID = 186.1> <EMI ID=187.1> <EMI ID = 187.1> au moins l'un de ces polymères contenant un a&#65533;ent de vulcanisation, pour obtenir une structure composite, at least one of these polymers containing a vulcanization agent, to obtain a composite structure, <EMI ID=188.1> <EMI ID = 188.1> rature de 100 à 200[deg.]C jusqu'à réticulation de ces polymères. rature from 100 to 200 [deg.] C until crosslinking of these polymers. <EMI ID=189.1> <EMI ID = 189.1> <EMI ID=190.1> <EMI ID = 190.1> d'un ester vinylique choisi dans le .groupe comprenant of a vinyl ester chosen from the group comprising <EMI ID=191.1> <EMI ID = 191.1> <EMI ID=192.1> <EMI ID = 192.1> eaux libres en quantités nécessaires pour produire la open water in quantities necessary to produce the <EMI ID=193.1> <EMI ID = 193.1> <EMI ID=194.1> <EMI ID = 194.1> libres est un composé peroxy organique. <EMI ID=195.1> free is an organic peroxy compound. <EMI ID = 195.1> <EMI ID=196.1> <EMI ID = 196.1> <EMI ID=197.1> <EMI ID = 197.1> <EMI ID=198.1> <EMI ID = 198.1> <EMI ID=199.1> <EMI ID = 199.1> <EMI ID=200.1> <EMI ID = 200.1> <EMI ID=201.1> <EMI ID = 201.1> caoutchouteuse préfaçonné. preformed rubbery. <EMI ID=202.1> <EMI ID = 202.1>
BE591575D 1959-06-03 BE591575A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DEF0028598 1959-06-03

Publications (1)

Publication Number Publication Date
BE591575A true BE591575A (en)

Family

ID=7092942

Family Applications (1)

Application Number Title Priority Date Filing Date
BE591575D BE591575A (en) 1959-06-03

Country Status (5)

Country Link
BE (1) BE591575A (en)
DE (1) DE1420148B2 (en)
FR (1) FR1258665A (en)
IT (1) IT630983A (en)
NL (1) NL252240A (en)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AR204831A1 (en) * 1973-05-08 1976-03-05 Du Pont SUITABLE CURABLE BLENDS TO BE USED IN VULCANIZABLE COMPOSITIONS VULCANIZABLE COMPOSITIONS AND VULCANIZED PRODUCTS
GB1603205A (en) * 1977-04-12 1981-11-18 Raychem Ltd Polymer compositions
JPS5556143A (en) * 1978-10-19 1980-04-24 Asahi Chem Ind Co Ltd Polyethylene composition for rotational molding with high gloss releasability and impact resistance
NL8005229A (en) * 1980-09-19 1982-04-16 Stamicarbon PROCESS FOR PREPARING AN ENTCOPOLYMER
DE3339385A1 (en) * 1983-10-29 1985-05-09 Bayer Ag, 5090 Leverkusen POLYMER MIXTURES AND COVULCANISES MADE THEREOF
WO1989005331A1 (en) * 1987-12-04 1989-06-15 Shell Internationale Research Maatschappij B.V. Cross-linked polymers
ES2019755A6 (en) * 1989-12-14 1991-07-01 Repsol Quimica Sa Procedure for the obtention of thermoplastic elastomer mixtures.

Also Published As

Publication number Publication date
NL252240A (en)
FR1258665A (en) 1961-04-14
IT630983A (en)
DE1420148B2 (en) 1970-03-05
DE1420148A1 (en) 1969-02-13

Similar Documents

Publication Publication Date Title
US4134927A (en) Production of thermoplastic olefin elastomers
TWI439476B (en) Polymers modified by silanes
JP6824936B2 (en) Compositions, thermoplastic vulcanized products produced from compositions and products produced from compositions
US20090306246A1 (en) Crosslinked composition comprising a core/shell copolymer, method of obtaining same and uses thereof
EP0008143B1 (en) Process for the manufacture of objects from compositions containing polyethylene modified with polar monomers and cellulosic fibres
TW201008963A (en) Modified polyolefins
JP2009510250A (en) Peroxide-cured thermoplastic vulcanizate and process for producing the same
US5643997A (en) Polyethylenic resin composition
KR20070012643A (en) Cross-linked composition comprising a triblock sequenced copolymer, method for the production thereof, and uses of the same
JPH03131639A (en) Plastic article with affinitive barrier resin
FR2522331A1 (en) MODIFIED POLYOLEFIN COMPOSITION AND PROCESS FOR PRODUCING THE SAME
JPH08505181A (en) Polyolefin functionalization method
CN116333408A (en) Curable composition comprising ethylene polymer, monoperoxycarbonate and tertiary alkyl hydroperoxide
EP0469693B1 (en) Impact resistent molding materials of polyamide
BE591575A (en)
US5037891A (en) Modified ethylene-α-olefin copolymer rubber and a process for producing the same
JP7221280B2 (en) Compositions containing tin-based catalysts and titanium dioxide for moisture curing of silane-functionalized ethylene-based polymers
KR100700328B1 (en) Polyolefin compositions, method for the production and use thereof
EP0495996B1 (en) Polyethylene resin composition
US3531455A (en) Peroxide-cured chlorinated polyethylene
JPH0198649A (en) Chlorinated polyethylene elastomer composition enhanced in resistance against ozone inducing decomposition
JP2002273838A (en) Laminate
KR101135699B1 (en) Resin composition including high melt strength polyolefin
KR100920513B1 (en) Polyethylene Composite for High- Pressure Pipes
KR100236489B1 (en) Polypropylene-based resin composition having releasability