EP1285009A1 - Polymers with hydroxy functions on the side-chains - Google Patents

Polymers with hydroxy functions on the side-chains

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Publication number
EP1285009A1
EP1285009A1 EP01936523A EP01936523A EP1285009A1 EP 1285009 A1 EP1285009 A1 EP 1285009A1 EP 01936523 A EP01936523 A EP 01936523A EP 01936523 A EP01936523 A EP 01936523A EP 1285009 A1 EP1285009 A1 EP 1285009A1
Authority
EP
European Patent Office
Prior art keywords
acrylate
ethylene
meth
cooh
copolymer
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.)
Withdrawn
Application number
EP01936523A
Other languages
German (de)
French (fr)
Inventor
Patrice Robert
Jean-Jacques Flat
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.)
Arkema SA
Original Assignee
Atofina SA
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Filing date
Publication date
Application filed by Atofina SA filed Critical Atofina SA
Publication of EP1285009A1 publication Critical patent/EP1285009A1/en
Withdrawn legal-status Critical Current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
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/08—Epoxidation
    • 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
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/14—Esterification

Definitions

  • the present invention relates to polymers having hydroxyl functions on the side chains and more particularly those which result from the reaction (i) of a copolymer comprising an unsaturated epoxide on a side chain with (ii) a reagent carrying a carboxylic acid function and optionally one or more hydroxyl functions.
  • the reaction can be written as follows, R-j denoting a group which can carry one or more hydroxyl functions:
  • Patent EP 600767 describes compositions consisting of the reaction product of an ethylene-vinyl acetate- (meth) hydroxyethyl acrylate copolymer with an excess polyisocyanate. These compositions are moisture crosslinkable adhesives.
  • Patent EP 810247 describes compositions consisting of the reaction product of an ethylene- (meth) alkyl acrylate- (meth) acrylate of hydroxyethyl copolymer with an excess polyisocyanate. These compositions are moisture crosslinkable adhesives.
  • Patent EP 538033 describes copolymers of ethylene and hydroxyethyl (meth) acrylate. These polymers can be transformed into films which have properties of permeability to water vapor and impermeability to liquid water (breathable).
  • copolymers which can contain many more hydroxyl functions but above all which can contain other functions in addition to the hydroxyl functions. It suffices for example to start from a copolymer of ethylene and an unsaturated epoxide and to react a product carrying a carboxylic acid function and optionally one or more hydroxyl functions.
  • the unsaturated epoxide functions are used, provided that they are in sufficient number, to fix other functions on the copolymer.
  • the present invention relates to a polymer of formula (1) below in which R1 denotes an alkyl, cycloalkyl or aromatic radical which can carry one or more hydroxyl functions.
  • This polymer of general formula (1) can be obtained by reacting the copolymer of general formula (2) with a reagent R1-COOH
  • the copolymer (2) is a copolymer of ethylene and of an unsaturated epoxide.
  • the reagent R1 COOH is a carboxylic acid comprising at least one alcohol function on its radical R1.
  • the polymer (1) can carry groups R1 and groups R2 different from R1, the groups R2 being branched in the same way as the groups R1 described above.
  • R2 denotes a quinone.
  • These products are useful as proton-donating polymers, for making breathable films or products crosslinkable with polyisocyanates, in particular adhesives crosslinkable with moisture.
  • copolymer (2) By way of example of copolymer (2), mention may be made of polyolefins, polystyrene, P MA, polyamides, fluorinated polymers, polycarbonate, saturated polyesters such as PET or PBT, thermoplastic polyurethanes (TPU ) and polyketones, all of these polymers being grafted with an unsaturated epoxide such as for example glycidyl (meth) acrylate.
  • the copolymer (2) is chosen from copolymers of ethylene and of an unsaturated epoxide. These copolymers can be polyethylenes grafted with an unsaturated epoxide or copolymers of ethylene and of an unsaturated epoxide, copolymerized, which are obtained, for example, by radical polymerization.
  • unsaturated epoxides there may be mentioned: - aliphatic glycidyl esters and ethers such as allyl glycidylether, vinyl glycidylether, maleate and glycidyl itaconate, glycidyl (meth) acrylate, and alicyclic glycidyl esters and ethers such as 2-cyclohexene-1-glycidyl ether, cyclohexene-4,5-diglycidyl carboxylate, cyclohexene-4-glycidyl carboxylate, 5-norbornene-2-methyl-2-glycidyl carboxylate and endo cis-bicyclo (2,2,1) -5-heptene-2,3-diglycidyl dicarboxylate.
  • polyethylene means homo- or copolymers.
  • alpha-olefins advantageously those having from 3 to 30 carbon atoms
  • alpha olefins that may be mentioned include propylene, 1-butene, 1-pentene, 3-methyl-1 -butene, 1-hexene, 4-methyl-1-pentene, 3 -methyl-1 -pentene, 1-octene, 1-dececene, 1-dodecene, 1- tetradecene, 1-hexadecene, 1-octadecene, 1 - eicocene, 1-dococene, 1- tetracocene, 1-hexacocene, 1 - octacocene, and 1 -triacontene; these alpha-olefins can be used alone or as a mixture of two or more " of two,
  • esters of unsaturated carboxylic acids such as, for example, alkyl (meth) acrylates, the alkyls possibly having up to 24 carbon atoms, examples of alkyl acrylate or methacrylate are in particular methyl methacrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate,
  • the polyethylene can comprise several of the preceding comonomers.
  • polyethylene which may be a mixture of several polymers, comprises at least 50% and preferably 75% (in moles) of ethylene, its density may be between 0.86 and 0.98 g / cm 3 .
  • LDPE low density polyethylene
  • HDPE high density polyethylene
  • LLDPE linear low density polyethylene
  • VLDPE very low density polyethylene
  • metallocene catalysis that is to say the polymers obtained by copolymerization of ethylene and of alphaolefin such as propylene, butene, hexene or octene in the presence of a monosite catalyst generally consisting of an atom of zirconium or titanium and two cyclic alkyl molecules linked to the metal. More specifically, metallocene catalysts are usually composed of two cyclopentadienic rings linked to the metal. These catalysts are frequently used with aluminoxanes as cocatalysts or activators, preferably methylaluminoxane (MAO). Hafnium can also be used as the metal to which cyclopentadiene is attached. Other metallocenes can include transition metals from groups IV A, V A, and VI A. Metals of the lanthamide series can also be used. - EPR elastomers (ethylene - propylene - rubber)
  • copolymers of ethylene and of the unsaturated epoxide that is to say those in which the unsaturated epoxide is not grafted
  • these are: copolymers of ethylene, of the unsaturated epoxide and optionally of another monomer which can be chosen from the comonomers which have been mentioned above for the ethylene copolymers intended to be grafted.
  • the copolymers of ethylene and of an unsaturated epoxide are advantageously ethylene / alkyl (meth) acrylate / unsaturated epoxide copolymers obtained by copolymerization of the monomers and not by grafting of the unsaturated epoxide onto the polyethylene, they contain 0 to 40% by weight of alkyl (meth) acrylate, preferably 5 to 35% and up to 10% by weight of unsaturated epoxide, preferably 0.1 to 8%.
  • the epoxide is advantageously glycidyl (meth) acrylate.
  • the alkyl (meth) acrylate is chosen from methyl (meth) acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate.
  • the amount of alkyl (meth) acrylate is advantageously from 20 to 35%.
  • the MFI is advantageously between 5 and 100 (in g / 10 min at 190 ° C. under 2.16 kg), the melting temperature is between 60 and 110 ° C. This copolymer can be obtained by radical polymerization of the monomers.
  • the trunk is made up of glycidyl (meth) acrylate, ethylene and alkyl (meth) acrylate units.
  • the trunk of formula (2-1) only represents a glycidyl (meth) acrylate unit, the ethylene and alkyl (meth) acrylate units not being represented.
  • a polymer according to the invention of formula (1-1) is therefore obtained, where, as before, only a glycidyl (meth) acrylate unit of the trunk is represented , the ethylene and alkyl (meth) acrylate units not being represented:
  • the reagent R1-COOH is a carboxylic acid comprising at least one alcohol function on its radical R1.
  • the reagent R1-COOH is the product of the following formula: HO 2 CC (CH 2 OH) 2 -CH 3
  • DMPA Acid Di Methylol Propionic
  • the reagent can be added to the copolymers (2) in the molten state by carrying out an intimate mixture.
  • the device in which this intimate mixing is made can be any device used for mixing thermoplastics such as a single or twin screw extruder, a kneader or a BUSS® kneader knockout.
  • the reagent, solid or liquid it is introduced as such into these mixing devices using hoppers or any device for introducing powders or liquids.
  • the particle size of these possible powders can be very variable, the finer it is, the more homogeneously its incorporation in the molten polymer is advantageously at most 200 ⁇ m and preferably between 10 and 150 ⁇ m.
  • the copolymer (1) containing the hydroxyl functions is in the molten state, it can be sent to a device for filming or injecting or cooling and recovering it in the form of granules like most thermoplastics and then transform later.
  • the proportion of reagent R1-COOH to be used is one molecule per epoxide function. However, it is possible not to use all of the available epoxy functions and therefore to use fewer reagent molecules R1 COOH than the number of epoxy functions.
  • epoxy functions which are not consumed in the reaction by R1-COOH are used to subsequently graft an R2-COOH reagent in the same manner as for R1 COOH. It is also possible to graft simultaneously R1 COOH and R2COOH by reacting the copolymer (2) with a mixture of R1-COOH and R2-COOH.
  • the invention therefore also relates to polymers of general formula (1-2) below:
  • R2-COOH is a carboxylated quinone.
  • quinone mention may be made of benzoquinone, naphthoquinone and anthraquinone.
  • the reaction of R2-COOH on the epoxy groups takes place under the same conditions as for R1-COOH.
  • DMPA Dimethylolpropionigue acid
  • LOTADER AX8840® is a random ethylene / glycidyl methacrylate (GMA) copolymer, containing 8% by weight of GMA and having an MFI equal to 4 g / 10 min (at 190 ° C under 2.16 kg).
  • the grafting is carried out in the molten state in a mixer, internal BRABENDER laboratory mixer. The mixer body temperature was set at
  • the LOTADER AX8840® and the DMPA are introduced into the mixer chamber and the reagents are mixed for 4 min.
  • the proportions used are: 93% of LOTADER AX8840® / 7% of DMPA.
  • the speed of rotation of the blades is fixed at 50 rpm.
  • the product was characterized by infrared and NMR analysis.
  • the product is then shaped in a press to give a film of 200 ⁇ m.

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  • Chemical & Material Sciences (AREA)
  • General 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)
  • Compositions Of Macromolecular Compounds (AREA)
  • Epoxy Resins (AREA)

Abstract

The invention concerns polymers of formula (1) wherein: R1 represents an alkyl, cycloalkyl or aromatic radical capable of bearing one or several hydroxyl functions. They can be obtained by reacting a copolymer bearing an epoxy function on a side-chain with a product of formula R1-COOH.

Description

POLYMÈRES AYANT DES FONCTIONS HYDROXYLES SUR LES CHAÎNESPOLYMERS HAVING HYDROXYL FUNCTIONS ON CHAINS
LATÉRALESSIDE
[Domaine de l'invention][Field of the invention]
La présente invention concerne des polymères ayant des fonctions hydroxyles sur les chaînes latérales et plus particulièrement ceux qui résultent de la réaction (i) d'un copolymère comprenant un époxyde insaturé sur une chaîne latérale avec (ii) un réactif portant une fonction acide carboxylique et éventuellement une ou plusieurs fonctions hydroxyles. La réaction peut s'écrire de la façon suivante, R-j désignant un groupement pouvant porter une ou plusieurs fonctions hydroxyles:The present invention relates to polymers having hydroxyl functions on the side chains and more particularly those which result from the reaction (i) of a copolymer comprising an unsaturated epoxide on a side chain with (ii) a reagent carrying a carboxylic acid function and optionally one or more hydroxyl functions. The reaction can be written as follows, R-j denoting a group which can carry one or more hydroxyl functions:
OO
Ces polymères sont utiles comme donneurs de protons par exemple dans des mélanges avec d'autres polymères. Ces polymères peuvent aussi être transformés en films qui ont des propriétés de perméabilité à la vapeur d'eau et d'imperméabilité à l'eau liquide (imperrespirants). Ces polymères peuvent être aussi utilisés pour leur réactivité avec des poiyisocyanates par exemple pour faire des adhésifs réticulables à l'humidité, [l'art antérieur et le problème technique] Le brevet EP 600767 décrit des compositions constituées du produit de réaction d'un copolymère éthylène-acétate de vinyle-(meth)acrylate d'hydroxyethyle avec un polyisocyanate en excès. Ces compositions sont des adhésifs réticulables à l'humidité. Le brevet EP 810247 décrit des compositions constituées du produit de réaction d'un copolymère éthylène-(meth)acrylate d'alkyle-(meth)acrylate d'hydroxyethyle avec un polyisocyanate en excès. Ces compositions sont des adhésifs réticulables à l'humidité.These polymers are useful as proton donors, for example in blends with other polymers. These polymers can also be transformed into films which have properties of permeability to water vapor and impermeability to liquid water (breathable). These polymers can also be used for their reactivity with polyisocyanates for example to make adhesives crosslinkable with humidity, [the prior art and the technical problem] Patent EP 600767 describes compositions consisting of the reaction product of an ethylene-vinyl acetate- (meth) hydroxyethyl acrylate copolymer with an excess polyisocyanate. These compositions are moisture crosslinkable adhesives. Patent EP 810247 describes compositions consisting of the reaction product of an ethylene- (meth) alkyl acrylate- (meth) acrylate of hydroxyethyl copolymer with an excess polyisocyanate. These compositions are moisture crosslinkable adhesives.
Le brevet EP 538033 décrit des copolymères de l'éthylène et du (meth)acrylate d'hydroxyethyle. Ces polymères peuvent être transformés en films qui ont des propriétés de perméabilité à la vapeur d'eau et d'imperméabilité à l'eau liquide (imperrespirants).Patent EP 538033 describes copolymers of ethylene and hydroxyethyl (meth) acrylate. These polymers can be transformed into films which have properties of permeability to water vapor and impermeability to liquid water (breathable).
On a maintenant trouvé des copolymères qui peuvent contenir beaucoup plus de fonctions hydroxyles mais surtout qui peuvent contenir d'autres fonctions en plus des fonctions hydroxyles. Il suffit de partir par exemple d'un copolymère de l'éthylène et d'un époxyde insaturé et de faire réagir un produit portant une fonction acide carboxylique et éventuellement une ou plusieurs fonctions hydroxyles. On utilise les fonctions époxyde insaturé, pourvu qu'elles soient en nombre suffisant, pour fixer d'autres fonctions sur le copolymère.We have now found copolymers which can contain many more hydroxyl functions but above all which can contain other functions in addition to the hydroxyl functions. It suffices for example to start from a copolymer of ethylene and an unsaturated epoxide and to react a product carrying a carboxylic acid function and optionally one or more hydroxyl functions. The unsaturated epoxide functions are used, provided that they are in sufficient number, to fix other functions on the copolymer.
[Brève description de l'invention][Brief description of the invention]
La présente invention concerne un polymère de formule (1 ) suivante dans laquelle R1 désigne un radical alkyle, cycloalkyle ou aromatique pouvant porter une ou plusieurs fonctions hydroxyles.The present invention relates to a polymer of formula (1) below in which R1 denotes an alkyl, cycloalkyl or aromatic radical which can carry one or more hydroxyl functions.
OHOH
(1)(1)
CH CH2 O C RiCH CH 2 OC Ri
O On peut obtenir ce polymère de formule générale (1) par réaction du copolymère de formule générale (2) avec un réactif R1-COOHO This polymer of general formula (1) can be obtained by reacting the copolymer of general formula (2) with a reagent R1-COOH
™™
Selon une première forme avantageuse de l'invention, le copolymère (2) est un copolymère de l'éthylène et d'un époxyde insaturé.According to a first advantageous form of the invention, the copolymer (2) is a copolymer of ethylene and of an unsaturated epoxide.
Selon une deuxième forme avantageuse de l'invention, le réactif R1 COOH est un acide carboxylique comprenant au moins une fonction alcool sur son radical R1.According to a second advantageous form of the invention, the reagent R1 COOH is a carboxylic acid comprising at least one alcohol function on its radical R1.
Selon une troisième forme avantageuse de l'invention, le polymère (1 ) peut porter des groupes R1 et des groupes R2 différents de R1 , les groupes R2 étant branchés de la même manière que les groupes R1 décrits précédemment. R2 désigne une quinone.According to a third advantageous form of the invention, the polymer (1) can carry groups R1 and groups R2 different from R1, the groups R2 being branched in the same way as the groups R1 described above. R2 denotes a quinone.
Ces produits sont utiles comme polymères donneurs de protons, pour faire des films imperrespirants ou des produits réticulables par des poiyisocyanates en particulier des adhésifs réticulables à l'humidité.These products are useful as proton-donating polymers, for making breathable films or products crosslinkable with polyisocyanates, in particular adhesives crosslinkable with moisture.
[Description détaillée de l'invention][Detailed description of the invention]
A titre d'exemple de copolymère (2), on peut citer les polyoléfines, le polystyrène, le P MA, les polyamides, les polymères fluorés, le polycarbonate, les polyesters saturés tels que le PET ou le PBT, les polyuréthanes thermoplastiques (TPU) et les polycétones, tous ces polymères étant greffés par un époxyde insaturé tel que par exemple le (méth)acrylate de glycidyle.By way of example of copolymer (2), mention may be made of polyolefins, polystyrene, P MA, polyamides, fluorinated polymers, polycarbonate, saturated polyesters such as PET or PBT, thermoplastic polyurethanes (TPU ) and polyketones, all of these polymers being grafted with an unsaturated epoxide such as for example glycidyl (meth) acrylate.
Selon une première forme avantageuse de l'invention, le copolymère (2) est choisi parmi les copolymères de l'éthylène et d'un époxyde insaturé. Ces copolymères peuvent être des polyéthylènes greffés par un époxyde insaturé ou des copolymères de l'éthylène et d'un époxyde insaturé, copolymérisés, que l'on obtient, par exemple, par polymérisation radicalaire. A titre d'exemple d'époxydes insaturés, on peut citer : - les esters et éthers de glycidyle aliphatiques tels que l'allyl glycidyléther, le vinyle glycidyléther, le maléate et l'itaconate de glycidyle, le (méth)acrylate de glycidyle, et les esters et éthers de glycidyle alicycliques tels que le 2- cyclohexène-1 -glycidyléther, le cyclohexène-4,5-diglycidyl carboxylate, le cyclohexène-4-glycidyl carboxylate, le 5-norbornène-2-méthyl-2-gIycidyl carboxylate et l'endo cis-bicyclo(2,2,1)-5-heptène-2,3-diglycidyl dicarboxylate. S'agissant des polyéthylènes sur lesquels on vient greffer I'époxyde insaturé, on entend par polyéthylène des homo- ou copolymères. A titre de comonomères, on peut citer :According to a first advantageous form of the invention, the copolymer (2) is chosen from copolymers of ethylene and of an unsaturated epoxide. These copolymers can be polyethylenes grafted with an unsaturated epoxide or copolymers of ethylene and of an unsaturated epoxide, copolymerized, which are obtained, for example, by radical polymerization. As examples of unsaturated epoxides, there may be mentioned: - aliphatic glycidyl esters and ethers such as allyl glycidylether, vinyl glycidylether, maleate and glycidyl itaconate, glycidyl (meth) acrylate, and alicyclic glycidyl esters and ethers such as 2-cyclohexene-1-glycidyl ether, cyclohexene-4,5-diglycidyl carboxylate, cyclohexene-4-glycidyl carboxylate, 5-norbornene-2-methyl-2-glycidyl carboxylate and endo cis-bicyclo (2,2,1) -5-heptene-2,3-diglycidyl dicarboxylate. As regards the polyethylenes to which the unsaturated epoxide is grafted, the term “polyethylene” means homo- or copolymers. As comonomers, we can cite:
- les alpha-oléfines, avantageusement celles ayant de 3 à 30 atomes de carbone; à titre d'exemples d'alpha oléfines on peut citer le propylène, le 1- butène, le 1-pentène, le 3-méthyl-1 -butène, le 1-hexène, Ie 4-méthyl-1-pentène, le 3-méthyl-1 -pentène, le 1-octène, le 1 -décène, le 1-dodécène, le 1- tetradécène, le 1 -hexadécène, le 1-octadécène, le 1 — eicocene, le 1-dococène, le 1-tétracocène, le 1 -hexacocène, le 1 — octacocène, et le 1 -triacontène; ces alpha-oléfines peuvent être utilisées seules ou en mélange de deux ou de plus "de deux,- alpha-olefins, advantageously those having from 3 to 30 carbon atoms; examples of alpha olefins that may be mentioned include propylene, 1-butene, 1-pentene, 3-methyl-1 -butene, 1-hexene, 4-methyl-1-pentene, 3 -methyl-1 -pentene, 1-octene, 1-dececene, 1-dodecene, 1- tetradecene, 1-hexadecene, 1-octadecene, 1 - eicocene, 1-dococene, 1- tetracocene, 1-hexacocene, 1 - octacocene, and 1 -triacontene; these alpha-olefins can be used alone or as a mixture of two or more " of two,
- les esters d'acides carboxyliques insaturés tels que par exemple les (méth)acrylates d'alkyle, les alkyles pouvant avoir jusqu'à 24 atomes de carbone, des exemples d'acrylate ou methacrylate d'alkyle sont notamment le methacrylate de méthyle, l'acrylate d'éthyle, l'acrylate de n-butyle, l'acrylate d'isobutyle, l'acrylate de 2-éthylhexyle,esters of unsaturated carboxylic acids such as, for example, alkyl (meth) acrylates, the alkyls possibly having up to 24 carbon atoms, examples of alkyl acrylate or methacrylate are in particular methyl methacrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate,
- les esters vinyliques d'acides carboxyliques saturés tels que par exemple l'acétate ou le propionate de vinyle.- vinyl esters of saturated carboxylic acids such as, for example, vinyl acetate or propionate.
- les diènes tels que par exemple le 1 ,4-hexadiène. - le polyethylene peut comprendre plusieurs des comonomères précédents.- dienes such as, for example, 1,4-hexadiene. the polyethylene can comprise several of the preceding comonomers.
Avantageusement le polyethylene qui peut être un mélange de plusieurs polymères, comprend au moins 50% et de préférence 75% (en moles) d'éthylène, sa densité peut être comprise entre 0,86 et 0,98 g/cm3. Le MFIAdvantageously, polyethylene, which may be a mixture of several polymers, comprises at least 50% and preferably 75% (in moles) of ethylene, its density may be between 0.86 and 0.98 g / cm 3 . The MFI
(indice de viscosité à 190°C, 2,16 kg) est compris avantageusement entre 0,1 et 1000 g/10 min.(viscosity index at 190 ° C, 2.16 kg) is advantageously between 0.1 and 1000 g / 10 min.
A titre d'exemple de polyéthylènes on peut citer :Examples of polyethylenes that may be mentioned:
- le polyethylene basse densité (LDPE) - le polyethylene haute densité (HDPE)- low density polyethylene (LDPE) - high density polyethylene (HDPE)
- le polyethylene linéaire basse densité (LLDPE)- linear low density polyethylene (LLDPE)
- le polyethylene très basse densité (VLDPE)- very low density polyethylene (VLDPE)
- le polyethylene obtenu par catalyse métallocène, c'est-à-dire les polymères obtenus par copolymérisation d'éthylène et d'alphaoléfine telle que propylene, butène, héxène ou octène en présence d'un catalyseur monosite constitué généralement d'un atome de zirconium ou de titane et de deux molécules cycliques alkyles liées au métal. Plus spécifiquement, les catalyseurs métallocènes sont habituellement composés de deux cycles cyclopentadiéniques liés au métal. Ces catalyseurs sont fréquemment utilisés avec des aluminoxanes comme cocatalyseurs ou activateurs, de préférence le méthylaluminoxane (MAO). Le hafnium peut aussi être utilisé comme métal auquel le cyclopentadiène est fixé. D'autres métallocènes peuvent inclure des métaux de transition des groupes IV A, V A, et VI A. Des métaux de la série des lanthamides peuvent aussi être utilisés. - les élastomères EPR (éthylène - propylene - rubber)the polyethylene obtained by metallocene catalysis, that is to say the polymers obtained by copolymerization of ethylene and of alphaolefin such as propylene, butene, hexene or octene in the presence of a monosite catalyst generally consisting of an atom of zirconium or titanium and two cyclic alkyl molecules linked to the metal. More specifically, metallocene catalysts are usually composed of two cyclopentadienic rings linked to the metal. These catalysts are frequently used with aluminoxanes as cocatalysts or activators, preferably methylaluminoxane (MAO). Hafnium can also be used as the metal to which cyclopentadiene is attached. Other metallocenes can include transition metals from groups IV A, V A, and VI A. Metals of the lanthamide series can also be used. - EPR elastomers (ethylene - propylene - rubber)
- les élastomères EPDM (éthylène - propylene - diène)- EPDM elastomers (ethylene - propylene - diene)
- les mélanges de polyethylene avec un EPR ou un EPDM- mixtures of polyethylene with an EPR or an EPDM
- les copolymères éthylène-(méth)acrylate d'alkyle pouvant contenir jusqu'à 60% en poids de (méth)acrylate et de préférence 2 à 40%. Le greffage est une opération connue en soi.- ethylene- (meth) acrylate copolymers which may contain up to 60% by weight of (meth) acrylate and preferably 2 to 40%. Grafting is an operation known in itself.
S'agissant des copolymères de l'éthylène et de l'époxyde insaturé c'est- à-dire ceux dans lesquels l'époxyde insaturé n'est pas greffé il s'agit des copolymères de l'éthylène, de l'époxyde insaturé et éventuellement d'un autre monomère pouvant être choisi parmi les comonomères qu'on a cité plus haut pour les copolymères de l'éthylène destinés à être greffés.As regards the copolymers of ethylene and of the unsaturated epoxide, that is to say those in which the unsaturated epoxide is not grafted, these are: copolymers of ethylene, of the unsaturated epoxide and optionally of another monomer which can be chosen from the comonomers which have been mentioned above for the ethylene copolymers intended to be grafted.
Les copolymères de l'éthylène et d'un époxyde insaturé sont avantageusement des copolymères éthylène/(méth)acrylate d'alkyle/époxyde insaturé obtenus par copolymérisation des monomères et non pas par greffage de l'époxyde insaturé sur le polyethylene, ils contiennent de 0 à 40% en poids de (méth)acrylate d'alkyle, de préférence 5 à 35% et jusqu'à 10% en poids d'époxyde insaturé, de préférence 0,1 à 8%. L'époxyde est avantageusement le (méth)acrylate de glycidyle.The copolymers of ethylene and of an unsaturated epoxide are advantageously ethylene / alkyl (meth) acrylate / unsaturated epoxide copolymers obtained by copolymerization of the monomers and not by grafting of the unsaturated epoxide onto the polyethylene, they contain 0 to 40% by weight of alkyl (meth) acrylate, preferably 5 to 35% and up to 10% by weight of unsaturated epoxide, preferably 0.1 to 8%. The epoxide is advantageously glycidyl (meth) acrylate.
Avantageusement le (méth)acrylate d'alkyle est choisi parmi le (méth)acrylate de méthyle, l'acrylate d'éthyle, l'acrylate de n-butyle, l'acrylate d'isobutyle, l'acrylate de 2-éthylhexyle. La quantité de (méth)acrylate d'alkyle est avantageusement de 20 à 35%. Le MFI est avantageusement compris entre 5 et 100 (en g/10 min à 190°C sous 2,16 kg), la température de fusion est comprise entre 60 et 110°C. Ce copolymère peut être obtenu par polymérisation radicalaire des monomères.Advantageously, the alkyl (meth) acrylate is chosen from methyl (meth) acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate. The amount of alkyl (meth) acrylate is advantageously from 20 to 35%. The MFI is advantageously between 5 and 100 (in g / 10 min at 190 ° C. under 2.16 kg), the melting temperature is between 60 and 110 ° C. This copolymer can be obtained by radical polymerization of the monomers.
Les formules (1-1) et (2-1 ), ci-dessous, sont des formules plus détaillées des formules générales respectivement (1 ) et (2) précédentes. Avantageusement le copolymère (2) est celui de formule (2-1 ) suivante :The formulas (1-1) and (2-1), below, are more detailed formulas of the general formulas respectively (1) and (2) above. Advantageously, the copolymer (2) is that of formula (2-1) below:
| (2-1)| (2-1)
Le tronc est constitué de motifs (méth)acrylate de glycidyle, éthylène et (méth)acrylate d'alkyle. Le tronc de la formule (2-1) représente uniquement un motif (méth)acrylate de glycidyle, les motifs éthylène et (méth)acrylate d'alkyle n'étant pas représentés. Après réaction de R1 COOH sur le polymère de formule (2-1 ), on obtient donc un polymère selon l'invention de formule (1-1 ) suivante, où comme précédemment seul un motif (méth)acrylate de glycidyle du tronc est représenté, les motifs éthylène et (méth)acrylate d'alkyle n'étant pas représentés :The trunk is made up of glycidyl (meth) acrylate, ethylene and alkyl (meth) acrylate units. The trunk of formula (2-1) only represents a glycidyl (meth) acrylate unit, the ethylene and alkyl (meth) acrylate units not being represented. After reaction of R1 COOH on the polymer of formula (2-1), a polymer according to the invention of formula (1-1) is therefore obtained, where, as before, only a glycidyl (meth) acrylate unit of the trunk is represented , the ethylene and alkyl (meth) acrylate units not being represented:
CH2 OCH 2 O
(1-1)(1-1)
Quant au réactif R1-COOH, on peut citer à titre d'exemple l'acide acétique, l'acide propionique et l'acide benzoïque. Selon une deuxième forme avantageuse de l'invention c'est un acide carboxylique comprenant au moins une fonction alcool sur son radical R1.As for the reagent R1-COOH, mention may be made, for example, of acetic acid, propionic acid and benzoic acid. According to a second advantageous form of the invention, it is a carboxylic acid comprising at least one alcohol function on its radical R1.
Selon une forme préférée de l'invention, le réactif R1-COOH est le produit de formule suivante : HO2C-C(CH2OH)2-CH3 According to a preferred form of the invention, the reagent R1-COOH is the product of the following formula: HO 2 CC (CH 2 OH) 2 -CH 3
qu'on appelle DMPA (abréviation de Acide Di Methylol Propionique) dans lacalled DMPA (abbreviation of Acid Di Methylol Propionic) in the
•suite du texte.• continuation of the text.
S'agissant de la réaction du copolymère (2) avec le réactif R1-COOH, on peut ajouter le réactif dans les copolymères (2) à l'état fondu en effectuant un mélange intime. Le dispositif dans lequel on fait ce mélange intime peut être tout appareil utilisé pour le mélange des thermoplastiques tel qu'une extrudeuse mono ou double vis, un malaxeur ou un KO malaxeur BUSS®.As regards the reaction of the copolymer (2) with the reagent R1-COOH, the reagent can be added to the copolymers (2) in the molten state by carrying out an intimate mixture. The device in which this intimate mixing is made can be any device used for mixing thermoplastics such as a single or twin screw extruder, a kneader or a BUSS® kneader knockout.
Selon la nature du réactif, solide ou liquide, on l'introduit tel quel dans ces dispositifs mélangeurs à l'aide de trémies ou tout dispositif d'introduction de poudres ou de liquides. La granulométrie de ces poudres éventuelles peut être très variable, plus elle est fine plus son incorporation dans le polymère fondu est homogène avantageusement elle est d'au plus 200 μm et de préférence comprise entre 10 et 150 μm. Le copolymère (1) contenant les fonctions hydroxyles est à l'état fondu, on peut l'envoyer dans un dispositif pour le mettre en film ou l'injecter ou le refroidir et le récupérer sous forme de granulés comme la plupart des thermoplastiques puis le transformer ultérieurement.Depending on the nature of the reagent, solid or liquid, it is introduced as such into these mixing devices using hoppers or any device for introducing powders or liquids. The particle size of these possible powders can be very variable, the finer it is, the more homogeneously its incorporation in the molten polymer is advantageously at most 200 μm and preferably between 10 and 150 μm. The copolymer (1) containing the hydroxyl functions is in the molten state, it can be sent to a device for filming or injecting or cooling and recovering it in the form of granules like most thermoplastics and then transform later.
La proportion de réactif R1-COOH à utiliser est d'une molécule par fonction époxyde. Cependant on peut ne pas utiliser toutes les fonctions époxydes disponibles et donc utiliser moins de molécules de réactif R1 COOH que le nombre de fonctions époxy.The proportion of reagent R1-COOH to be used is one molecule per epoxide function. However, it is possible not to use all of the available epoxy functions and therefore to use fewer reagent molecules R1 COOH than the number of epoxy functions.
Selon une troisième forme avantageuse de l'invention, on utilise des fonctions époxy non consommées dans la réaction par R1-COOH pour greffer ultérieurement un réactif R2-COOH de la même manière que pour R1 COOH. On peut aussi greffer simultanément R1 COOH et R2COOH en faisant réagir le copolymère (2) avec un mélange de R1-COOH et R2-COOH. L'invention concerne donc aussi des polymères de formule générale (1-2) suivante :According to a third advantageous form of the invention, epoxy functions which are not consumed in the reaction by R1-COOH are used to subsequently graft an R2-COOH reagent in the same manner as for R1 COOH. It is also possible to graft simultaneously R1 COOH and R2COOH by reacting the copolymer (2) with a mixture of R1-COOH and R2-COOH. The invention therefore also relates to polymers of general formula (1-2) below:
OHOH
C ΛΛΛ CH CH2 O RiC ΛΛΛ CH CH 2 O Ri
OH (1-2)OH (1-2)
OO
C VΛΛΛ CH CH2 O R2 C VΛΛΛ CH CH 2 OR 2
OO
Avantageusement R2-COOH est une quinone carboxylée. A titre d'exemple de quinone, on peut citer la benzoquinone, la naphtoquinone et l'anthraquinone. La réaction de R2-COOH sur les groupes époxy se fait dans les mêmes conditions que pour R1-COOH. [Exemple]Advantageously R2-COOH is a carboxylated quinone. As an example of quinone, mention may be made of benzoquinone, naphthoquinone and anthraquinone. The reaction of R2-COOH on the epoxy groups takes place under the same conditions as for R1-COOH. [Example]
Greffage du DMPA (acide Diméthylolpropionigue) sur le LOTADER AX8840®. Le DMPA se présente sous la forme d'une poudre blanche et a un point de fusion de 190°C.Grafting of DMPA (Dimethylolpropionigue acid) on the LOTADER AX8840®. DMPA comes in the form of a white powder and has a melting point of 190 ° C.
Le LOTADER AX8840® est un copolymère statistique éthylène/méthacrylate de glycidyle (GMA), contenant 8% en poids de GMA et ayant un MFI égal à 4 g/10min (à 190°C sous 2,16kg). Le greffage est effectué à l'état fondu dans un malaxeur, mélangeur interne de laboratoire BRABENDER. La température du corps du malaxeur a été fixée àLOTADER AX8840® is a random ethylene / glycidyl methacrylate (GMA) copolymer, containing 8% by weight of GMA and having an MFI equal to 4 g / 10 min (at 190 ° C under 2.16 kg). The grafting is carried out in the molten state in a mixer, internal BRABENDER laboratory mixer. The mixer body temperature was set at
220°C.220 ° C.
Le LOTADER AX8840® et le DMPA sont introduits dans la chambre du malaxeur et les réactifs sont malaxés pendant 4 min. Les proportions utilisées sont : 93% de LOTADER AX8840® / 7% de DMPA. La vitesse de rotation des pales est fixée à 50 tr/min.The LOTADER AX8840® and the DMPA are introduced into the mixer chamber and the reagents are mixed for 4 min. The proportions used are: 93% of LOTADER AX8840® / 7% of DMPA. The speed of rotation of the blades is fixed at 50 rpm.
Le produit a été caractérisé par analyse infra rouge et RMN.The product was characterized by infrared and NMR analysis.
Le produit est ensuite mis en forme sous presse pour donner un film de 200 μm. The product is then shaped in a press to give a film of 200 μm.

Claims

REVENDICATIONS
1. Polymère de formule (1)1. Polymer of formula (1)
OH d)OH d)
CH CH2 O C RiCH CH 2 OC Ri
OO
obtenu par réaction d'un acide carboxylique de formule R1-COOH ouobtained by reaction of a carboxylic acid of formula R1-COOH or
CH CH2 (2)CH CH 2 (2)
O'O '
ses dérivés avec un copolymère (2) de l'éthylène et d'un époxyde insaturé greffé ou copolymérisé.its derivatives with a copolymer (2) of ethylene and of an unsaturated epoxide grafted or copolymerized.
2. Polymère selon la revendication 1 dans lequel R1 désigne un radical alkyle, cycloalkyle ou aromatique comprenant au moins une fonction hydroxyle.2. Polymer according to claim 1 wherein R1 denotes an alkyl, cycloalkyl or aromatic radical comprising at least one hydroxyl function.
3. Polymère selon l'une des revendications 1 ou 2 dans lequel le copolymère (2) de l'éthylène et d'un époxyde insaturé, greffé ou copolymérisé, est un copolymère éthylène/(méth)acrylate de glycidyle/ (méth)acrylate d'alkyle.3. Polymer according to one of claims 1 or 2 in which the copolymer (2) of ethylene and of an unsaturated, grafted or copolymerized epoxide is an ethylene / (meth) glycidyl acrylate / (meth) acrylate copolymer alkyl.
4. Polymère selon l'une quelconque des revendications précédentes dans lequel R1 -COOH est l'acide propionique diméthylol ou DMPA de formule suivante : HO2C-C(CH2OH)2-CH3 5 Polymère selon l'une quelconque des revendications précédentes de formule (1-2) :4. Polymer according to any one of the preceding claims, in which R1 -COOH is propionic acid dimethylol or DMPA of the following formula: HO 2 CC (CH 2 OH) 2 -CH 3 5 Polymer according to any one of the preceding claims of formula (1-2):
OHOH
C ww CH CH2 O RiC ww CH CH 2 O Ri
OH (1-2)OH (1-2)
OO
C .ΛΛΛΛΛ CH CH7 O RaC .ΛΛΛΛΛ CH CH 7 O Ra
OO
R2 étant une quinone. R2 being a quinone.
EP01936523A 2000-05-17 2001-05-15 Polymers with hydroxy functions on the side-chains Withdrawn EP1285009A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR0006285 2000-05-17
FR0006285A FR2809109B1 (en) 2000-05-17 2000-05-17 POLYMERS HAVING HYDROXYL FUNCTIONS ON THE SIDE CHAINS
PCT/FR2001/001473 WO2001087995A1 (en) 2000-05-17 2001-05-15 Polymers with hydroxy functions on the side-chains

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EP (1) EP1285009A1 (en)
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AU (1) AU2001262410A1 (en)
CA (1) CA2408865A1 (en)
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WO2006048708A2 (en) * 2004-10-08 2006-05-11 Basf Coatings Japan Ltd. Resin composition having hydroxyl group for coatings, coating composition, method of finish coating and coated article
FR2906535A1 (en) * 2006-10-03 2008-04-04 Arkema France Hot-melting adhesive composition based on a copolymer, comprising ethylene unit and polyisocyanate, resulting from reaction of ethylene copolymer and grafted/copolymerized unsaturated epoxy with carboxylic acid
PL2125947T3 (en) * 2007-02-23 2019-06-28 Basf Se Composite materials and method for production thereof
JP5857788B2 (en) * 2012-02-22 2016-02-10 旭硝子株式会社 Fluorine-containing elastomer composition and crosslinked article thereof
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AU2001262410A1 (en) 2001-11-26
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CA2408865A1 (en) 2001-11-22
WO2001087995A1 (en) 2001-11-22
CN1429237A (en) 2003-07-09
FR2809109B1 (en) 2003-10-03
KR20030003289A (en) 2003-01-09
FR2809109A1 (en) 2001-11-23

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