BE903354A - COPOLYMERS OF OLEFINICALLY UNSATURATED CARBOXYLIC ACIDS AND THEIR PREPARATION PROCESS - Google Patents
COPOLYMERS OF OLEFINICALLY UNSATURATED CARBOXYLIC ACIDS AND THEIR PREPARATION PROCESS Download PDFInfo
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- BE903354A BE903354A BE0/215666A BE215666A BE903354A BE 903354 A BE903354 A BE 903354A BE 0/215666 A BE0/215666 A BE 0/215666A BE 215666 A BE215666 A BE 215666A BE 903354 A BE903354 A BE 903354A
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- Prior art keywords
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- copolymers
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- 229920001577 copolymer Polymers 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims description 4
- 150000001735 carboxylic acids Chemical class 0.000 title abstract description 5
- 239000000178 monomer Substances 0.000 claims abstract description 14
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 8
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229920001567 vinyl ester resin Polymers 0.000 claims abstract description 7
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical group ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- BEQKKZICTDFVMG-UHFFFAOYSA-N 1,2,3,4,6-pentaoxepane-5,7-dione Chemical compound O=C1OOOOC(=O)O1 BEQKKZICTDFVMG-UHFFFAOYSA-N 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- 239000003505 polymerization initiator Substances 0.000 claims description 3
- 150000002432 hydroperoxides Chemical class 0.000 claims description 2
- 239000003999 initiator Substances 0.000 claims description 2
- 150000004967 organic peroxy acids Chemical class 0.000 claims description 2
- 150000002978 peroxides Chemical class 0.000 claims description 2
- 239000002253 acid Substances 0.000 abstract description 8
- 239000002562 thickening agent Substances 0.000 abstract description 7
- 150000007513 acids Chemical class 0.000 abstract description 6
- -1 acrylic acid Chemical class 0.000 abstract description 5
- 239000000203 mixture Substances 0.000 abstract description 3
- 239000003381 stabilizer Substances 0.000 abstract description 3
- 239000000375 suspending agent Substances 0.000 abstract description 3
- 239000004753 textile Substances 0.000 abstract description 3
- 239000002537 cosmetic Substances 0.000 abstract description 2
- 239000003599 detergent Substances 0.000 abstract description 2
- 239000003814 drug Substances 0.000 abstract description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 5
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000002170 ethers Chemical class 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- NSGQRLUGQNBHLD-UHFFFAOYSA-N butan-2-yl butan-2-yloxycarbonyloxy carbonate Chemical compound CCC(C)OC(=O)OOC(=O)OC(C)CC NSGQRLUGQNBHLD-UHFFFAOYSA-N 0.000 description 1
- ZGPBOPXFOJBLIV-UHFFFAOYSA-N butoxycarbonyloxy butyl carbonate Chemical compound CCCCOC(=O)OOC(=O)OCCCC ZGPBOPXFOJBLIV-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- 150000002016 disaccharides Chemical class 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- PYGSKMBEVAICCR-UHFFFAOYSA-N hexa-1,5-diene Chemical group C=CCCC=C PYGSKMBEVAICCR-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- WCYWZMWISLQXQU-UHFFFAOYSA-N methyl Chemical compound [CH3] WCYWZMWISLQXQU-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 150000002772 monosaccharides Chemical class 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
-
- 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
- C08F218/00—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 acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
- C08F218/02—Esters of monocarboxylic acids
- C08F218/04—Vinyl esters
- C08F218/10—Vinyl esters of monocarboxylic acids containing three or more carbon atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Copolymères d'un ou plusieurs acides carboxyliques insatures tels que l'acide acrylique, d'un ou plusieurs esters vinyliques d'acides trialkylacétiques à structure fortement ramifiée, tels que des esters vinyliques, et d'un ou plusieurs monomères polyinsaturés tels qu'un ether polyallylique de pentacrytritol. Ces compositions sont utilisés comme épaississants, agents de suspension ou stabilisateurs dans le domaine des textiles, des cosmétiques, des produits pharmaceutiques, des détergents, etc.Copolymers of one or more unsaturated carboxylic acids such as acrylic acid, of one or more vinyl esters of highly branched trialkylacetic acids, such as vinyl esters, and of one or more polyunsaturated monomers such as polyallylic ether of pentacrytritol. These compositions are used as thickeners, suspending agents or stabilizers in the field of textiles, cosmetics, pharmaceuticals, detergents, etc.
Description
<EMI ID=1.1>
procédé de préparation".
La présente invention est relative à des copoiymères d'acides carboxyliques oléfiniquement insaturés et à leur procédé de préparation.
On connaît, dans la pratique industrielle, des polymères et des copolymères de l'acide acrylique ou d'autres acides oléfiniquement insaturés, généralement réticulés avec un monomère polyinsaturé, ces produits étant utilisés comme épaississants, agents de suspension ou stabilisateurs, dans une ambiance aqueuse ou de solvants polaires, et ce dans le domaine des textiles, des cosmétiques, des produits pharmaceutiques, des détergents ou dans d'autres domaines encore. Ces polymères ou copolymères se caractérisent par le fait qu'ils donnent une viscosité extrêmement élevée quand ils sont dispersés dans l'eau et neutralisés.
Une caractéristique commune à ces épaississants
<EMI ID=2.1>
vent en présence d'électrolytes comme par exemple de chlorure de sodium. Cette sensibilité aux électrolytes est indésirable, d'une façon générale, dans divers secteurs d'application.
Dans la littérature récente des brevets, la description d'épaississants synthétiques ayant des caractéristiques améliorées de résistance aux électrolytes est apparue. C'est ainsi que dans les brevets des Etats-Unis d'Amérique nos. 3.915.921 et 3.943.151, on revendique des copolymères obtenus en faisant réagir un acide
<EMI ID=3.1> res, sous forme de latex, obtenus en copolymérisant (a) un acide acrylique ou méthacrylique avec (b) un ester de la formule générale :
<EMI ID=4.1>
dans laquelle R représente l'hydrogène ou le radical méthyle, n est égal à au moins 2 et R' est un groupe hydrophobe comportant de préférence de 12 à 24 atomes de carbone, et (c) un ester acrylique
<EMI ID=5.1>
un monomère polyfonctionnei.
Enfin, le brève: des Etats-Unis d'Amérique n[deg.]
4.268.641 revendique des copolymères entre un acide oléfiniquernent insaturé et un ester acrylique ou méthacrylique pour des tension-actifs non ioniques à longue ou très longue chaîne, sans l'utilisation de monomères polyfonctionnels.
Il apparaît des brevets mentionnés ci-dessus que l'amélioration à la résistance aux électrolytes dans des épaississsants synthétiques s'obtient en copolymérisant un acide carboxylique oléfiniquement insaturé avec un ester acrylique ou méthacrylique caractérisé par un reste d'alcooi à longue ou très longue chaîne linéaire. Cependant, aucun des épaississants de ce type que l'on a proposé jusqu'à présent ne présente, pour l'un ou l'autre motif, des propriétés totalement satisfaisantes.
On a maintenant trouvé qu'en copolymérisant :
(a) un ou plusieurs acides carboxyliques oléfiniquement insaturés,
(b) un ou plusieurs esters vinyliques d'acides trialkylacétiques à structure fortement ramifiée, représentés par la formule générale 1 :
<EMI ID=6.1>
<EMI ID=7.1>
de carbone du reste alkylique pouvant atteindre 10, (c) un ou plusieurs monomères polyinsaturés, on obtient des copolymères dont les solutions aqueuses, après neutralisation, présentent une viscosité élevée et une résistance aux électrolytes, qui est nettement meilleure que celle des copolymères connus.
Les copolymères suivant l'invention peuvent de ce fait être avantageusement utilisés comme épaississants, agents de suspension, stabilisateurs, dans les domaines des textiles. des cosmé-
<EMI ID=8.1>
domaines encore.
Les acides oléfiniquement insaturés que l'on peut employer sont l'acide acrylique et l'acide méthacrylique, avec une préférence pour l'acide acrylique. Comme composant (b), on utilise de façon appropriée, comme déjà mentionné, des esters vinyliques de plusieurs acides trialkylacétiques, comportant au moins 10 atomes de carbone dans le reste alkylique. La quantité de ces esters vinyliques varie de préférence de 1 à 30% en poids par rapport à la quantité totale des monomères.
Les monomères polyinsaturés que l'on peut employer sont par exemple, les éthers polyallyliques de monosaccharides, les éthers polyallyliques de disaccharides, les éthers di-, tri- et tétra allyliques de pentaérythritol, les éthers diallyliques et triallyliques de triméthylolpropane, l'acrylate et le méthacrylate d'allyle, l'adipate
<EMI ID=9.1>
varier de 0,1 à 5% en poids par rapport à la quantité totale des monomères.
La polymérisation se fait dans un milieu organique qui est solvant pour les monomères et non solvant pour le polymère se formant, en présence d'un initiateur de polymérisation et dans une ambiance inerte.
Le milieu organique de polymérisation est choisi parmi les hydrocarbures aliphatiques, aromatiques ou chlorurés comme par exemple l'hexane, l'heptane, l'octane, le toluène, le xylène, le
<EMI ID=10.1>
On utilise de préférence le chlorure de méthylène.
Les initiateurs de polymérisation sont des peroxydes, des hydroperoxydes et des peracides organiques, comme par exemple le peroxyde de benzoyle, le peroxyde de lauroyle, le peroxydicarbonate de di-n-butyle, le peroxydicarbonate de di-sec-butyle, le peroxydicar-
<EMI ID=11.1>
ou leurs mélanges. On préfère en particulier utiliser le peroxydicarbonate de dicétyle.
La polymérisation peut se faire de façon discontinue, de façon semi-continue ou en continu à une température de 0 à 100[deg.]C sous une pression atmosphérique, sous une pression inférieure à ia pression atmosphérique ou sous pression, et dans une ambiance inerte. On opère de préférence à la pression atmosphérique.
Les exemples suivants sont donnés à titre d'illustration sans intention de limitation quelconque du cadre de l'invention.
Exemple 1.
Une série d'essais ont été faits dans du chlorure de méthylène en employant (a) de l'acide acrylique, (b) un mélange technique d'esters vinyliques d'acides trialkylacétiques ayant les caractéristiques suivantes :
<EMI ID=12.1>
et (c) du polyallylpentaérytritol.
Comme initiateur, on a utilisé du peroxydicarbonate de dicétyle en opérant à la température de reflux des réactifs sous une atmosphère d'azote.
Le polymère, insoluble dans le chlorure de méthylè-
<EMI ID=13.1>
polymère dans l'eau, avec neutralisation à pH 7 en utilisant de l'hydro-xyde de sodium, sans et avec addition de quantités croissantes de chlorure de sodium.
Pour la mesure de la viscosité, on a utilisé l'appareil
<EMI ID=14.1>
<EMI ID=15.1>
<EMI ID=16.1>
<EMI ID=17.1>
Une seconde série d'essais ont été réalisés suivant
<EMI ID=18.1>
poids des monomères employés et la viscosité de solutions à 1% de polymère dans de l'eau, avec neutralisation au pH 7 avec de l'hydroxyde de sodium, sans et avec addition de quantités croissantes de chlorure de sodium.
<EMI ID=19.1>
<EMI ID=20.1>
REVENDICATIONS.
1. Copolymères de :
(a) un ou plusieurs acides carboxyliques oléfiniquement insaturés; <EMI ID=21.1> re fortement ramifiée, répondant à la formule 1 :
<EMI ID=22.1>
<EMI ID=23.1>
l'un au moins est toujours un méthyle, la somme totale des atomes de carbone du reste alkylique pouvant atteindre dix, et
(c) un ou plusieurs monomères polyinsaturés.
<EMI ID=24.1>
<EMI ID = 1.1>
preparation process ".
The present invention relates to copolymers of olefinically unsaturated carboxylic acids and to their process of preparation.
Polymers and copolymers of acrylic acid or of other olefinically unsaturated acids, generally crosslinked with a polyunsaturated monomer, are known in industrial practice, these products being used as thickeners, suspending agents or stabilizers, in an aqueous environment or polar solvents, and this in the field of textiles, cosmetics, pharmaceuticals, detergents or in other fields as well. These polymers or copolymers are characterized by the fact that they give an extremely high viscosity when they are dispersed in water and neutralized.
A characteristic common to these thickeners
<EMI ID = 2.1>
wind in the presence of electrolytes such as sodium chloride for example. This sensitivity to electrolytes is generally undesirable in various application sectors.
In recent patent literature, the description of synthetic thickeners with improved characteristics of resistance to electrolytes has appeared. This is how in the patents of the United States of America nos. 3,915,921 and 3,943,151, we claim copolymers obtained by reacting an acid
<EMI ID = 3.1> res, in the form of latex, obtained by copolymerizing (a) an acrylic or methacrylic acid with (b) an ester of the general formula:
<EMI ID = 4.1>
in which R represents hydrogen or the methyl radical, n is equal to at least 2 and R 'is a hydrophobic group preferably comprising from 12 to 24 carbon atoms, and (c) an acrylic ester
<EMI ID = 5.1>
a polyfunctional monomer.
Finally, the short: from the United States of America n [deg.]
4,268,641 claims copolymers between an olefinically unsaturated acid and an acrylic or methacrylic ester for long or very long chain nonionic tension-active agents, without the use of polyfunctional monomers.
It appears from the patents mentioned above that the improvement in resistance to electrolytes in synthetic thickeners is obtained by copolymerizing an olefinically unsaturated carboxylic acid with an acrylic or methacrylic ester characterized by a long or very long chain alcohol residue. linear. However, none of the thickeners of this type that has been proposed so far has, for one or the other reason, completely satisfactory properties.
We have now found that by copolymerizing:
(a) one or more olefinically unsaturated carboxylic acids,
(b) one or more vinyl esters of trialkylacetic acids with a highly branched structure, represented by the general formula 1:
<EMI ID = 6.1>
<EMI ID = 7.1>
carbon of the alkyl residue up to 10, (c) one or more polyunsaturated monomers, copolymers are obtained whose aqueous solutions, after neutralization, have a high viscosity and resistance to electrolytes, which is significantly better than that of known copolymers.
The copolymers according to the invention can therefore advantageously be used as thickeners, suspending agents, stabilizers, in the fields of textiles. cosmé-
<EMI ID = 8.1>
areas again.
The olefinically unsaturated acids which can be used are acrylic acid and methacrylic acid, with preference for acrylic acid. As component (b), suitable use is made, as already mentioned, of vinyl esters of several trialkylacetic acids, having at least 10 carbon atoms in the alkyl residue. The amount of these vinyl esters preferably varies from 1 to 30% by weight relative to the total amount of the monomers.
Polyunsaturated monomers which can be used are, for example, polyallyl ethers of monosaccharides, polyallyl ethers of disaccharides, di-, tri- and tetra allyl ethers of pentaerythritol, diallyl and triallyl ethers of trimethylolpropane, acrylate and allyl methacrylate, adipate
<EMI ID = 9.1>
vary from 0.1 to 5% by weight relative to the total amount of the monomers.
The polymerization takes place in an organic medium which is solvent for the monomers and non-solvent for the polymer forming, in the presence of a polymerization initiator and in an inert atmosphere.
The organic polymerization medium is chosen from aliphatic, aromatic or chlorinated hydrocarbons such as, for example, hexane, heptane, octane, toluene, xylene,
<EMI ID = 10.1>
Preferably methylene chloride is used.
The polymerization initiators are peroxides, hydroperoxides and organic peracids, such as for example benzoyl peroxide, lauroyl peroxide, di-n-butyl peroxydicarbonate, di-sec-butyl peroxydicarbonate, peroxydicar-
<EMI ID = 11.1>
or their mixtures. It is particularly preferred to use diketyl peroxydicarbonate.
The polymerization can be carried out discontinuously, semi-continuously or continuously at a temperature of 0 to 100 [deg.] C under atmospheric pressure, under pressure below atmospheric pressure or under pressure, and in an ambient inert. It is preferably carried out at atmospheric pressure.
The following examples are given by way of illustration without any intention of limiting the scope of the invention.
Example 1.
A series of tests were carried out in methylene chloride using (a) acrylic acid, (b) a technical mixture of vinyl esters of trialkylacetic acids having the following characteristics:
<EMI ID = 12.1>
and (c) polyallylpentaérytritol.
As initiator, diketyl peroxydicarbonate was used, operating at the reflux temperature of the reactants under a nitrogen atmosphere.
The polymer, insoluble in methylene chloride-
<EMI ID = 13.1>
polymer in water, with neutralization at pH 7 using sodium hydroxide, without and with the addition of increasing amounts of sodium chloride.
For the viscosity measurement, the apparatus was used
<EMI ID = 14.1>
<EMI ID = 15.1>
<EMI ID = 16.1>
<EMI ID = 17.1>
A second series of tests was carried out according to
<EMI ID = 18.1>
weight of the monomers used and the viscosity of solutions at 1% of polymer in water, with neutralization at pH 7 with sodium hydroxide, without and with the addition of increasing amounts of sodium chloride.
<EMI ID = 19.1>
<EMI ID = 20.1>
CLAIMS.
1. Copolymers of:
(a) one or more olefinically unsaturated carboxylic acids; <EMI ID = 21.1> re highly branched, corresponding to formula 1:
<EMI ID = 22.1>
<EMI ID = 23.1>
at least one is always methyl, the total sum of the carbon atoms of the alkyl residue being up to ten, and
(c) one or more polyunsaturated monomers.
<EMI ID = 24.1>
Claims (1)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IT48535/85A IT1200111B (en) | 1985-09-06 | 1985-09-06 | Acrylic! copolymers contg. tri:alkyl:acetic acid vinyl! ester! monomer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| BE903354A true BE903354A (en) | 1986-02-03 |
Family
ID=11267155
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| BE0/215666A BE903354A (en) | 1985-09-06 | 1985-10-01 | COPOLYMERS OF OLEFINICALLY UNSATURATED CARBOXYLIC ACIDS AND THEIR PREPARATION PROCESS |
Country Status (2)
| Country | Link |
|---|---|
| BE (1) | BE903354A (en) |
| IT (1) | IT1200111B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0724875A1 (en) * | 1995-02-01 | 1996-08-07 | 3V SIGMA S.p.A | Emulsifying agents for cosmetic compositions |
| EP1431380A1 (en) * | 2002-12-18 | 2004-06-23 | 3V SIGMA S.p.A | Detergent compositions for cleaning |
| EP1767568A1 (en) | 2005-09-27 | 2007-03-28 | 3V SIGMA S.p.A | Easily wettable polycarboxylic thickeners |
-
1985
- 1985-09-06 IT IT48535/85A patent/IT1200111B/en active
- 1985-10-01 BE BE0/215666A patent/BE903354A/en not_active IP Right Cessation
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0724875A1 (en) * | 1995-02-01 | 1996-08-07 | 3V SIGMA S.p.A | Emulsifying agents for cosmetic compositions |
| EP1431380A1 (en) * | 2002-12-18 | 2004-06-23 | 3V SIGMA S.p.A | Detergent compositions for cleaning |
| EP1767568A1 (en) | 2005-09-27 | 2007-03-28 | 3V SIGMA S.p.A | Easily wettable polycarboxylic thickeners |
Also Published As
| Publication number | Publication date |
|---|---|
| IT1200111B (en) | 1989-01-05 |
| IT8548535A0 (en) | 1985-09-06 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| RE | Patent lapsed |
Owner name: 3V PARTICIPAZIONI INDUSTRIALI S.P.A. Effective date: 19981031 |