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WO2018167699A1 - Procédé d'obtention de matériaux polymères à trois composants présentant une composition variable orientée, synthétisés par des copolymérisation séquentielle dans un réacteur semi-continu avec un gradient d'alimentation - Google Patents

Procédé d'obtention de matériaux polymères à trois composants présentant une composition variable orientée, synthétisés par des copolymérisation séquentielle dans un réacteur semi-continu avec un gradient d'alimentation Download PDF

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Publication number
WO2018167699A1
WO2018167699A1 PCT/IB2018/051722 IB2018051722W WO2018167699A1 WO 2018167699 A1 WO2018167699 A1 WO 2018167699A1 IB 2018051722 W IB2018051722 W IB 2018051722W WO 2018167699 A1 WO2018167699 A1 WO 2018167699A1
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chains
comonomers
gradient
semi
composition
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PCT/IB2018/051722
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English (en)
Spanish (es)
Inventor
Carlos Federico Jasso Gastinel
Francisco Javier RIVERA GÁLVEZ
Luis Javier GONZÁLEZ ORTIZ
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Universidad De Guadalajara
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Publication of WO2018167699A1 publication Critical patent/WO2018167699A1/fr

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    • 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
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
    • 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
    • C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F12/02—Monomers containing only one unsaturated aliphatic radical
    • C08F12/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F12/06—Hydrocarbons
    • C08F12/08—Styrene
    • 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
    • C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F12/02—Monomers containing only one unsaturated aliphatic radical
    • C08F12/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F12/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by hetero atoms or groups containing heteroatoms
    • C08F12/16—Halogens
    • C08F12/18—Chlorine
    • 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
    • C08F14/00—Homopolymers and 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 a halogen
    • C08F14/02—Monomers containing chlorine
    • C08F14/04—Monomers containing two carbon atoms
    • 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
    • C08F18/00—Homopolymers and 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
    • C08F18/02—Esters of monocarboxylic acids
    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/22—Emulsion polymerisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/08—Styrene
    • 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
    • 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
    • C08F222/00—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 a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/04—Anhydrides, e.g. cyclic anhydrides
    • C08F222/06—Maleic anhydride
    • C08F222/08—Maleic anhydride with vinyl aromatic monomers

Definitions

  • the object of the invention consists in a process that allows obtaining three-component polymeric materials with variable oriented composition, by means of sequential emulsion copolymerizations in semicontinuous reactors with feed gradient.
  • the advantage of this synthesis process is that being scalable at the industrial level, it allows to obtain three-component polymer systems with considerable average molecular weights (eg> 10 5 g / mol), where evolution, through the modification of the feeding profile, is promoted desired in the compositions of the chains that are formed throughout the reaction, with the intention of achieving a distribution of compositions that enhances the contribution of each component in the polymeric material (that is, trying to combine the properties that each component would present as homopolymer).
  • polymers are required to be partially compatible, which greatly reduces the chances of forming useful mixtures via simple mixing. This has led to the use of coupling agents to generate attractive forces (secondary bonds) between the structures of both polymeric materials, which has allowed the expansion of the mix formation range and its applications.
  • Another way that has been used in the mixtures is to prepare, first, one of the polymers (polymer A) that functions as a matrix, to later diffuse in it, for a certain time, a monomer B, and finally polymerize "in situ "that monomer to generate a polymer B.
  • a material thus obtained is known as a chemical mixture, with which mixing at a microscopic level is achieved, the phase separation of the polymers is reduced and, thus, better properties than with physical mixtures (1). If it is also achieved that in a mixture If there is a chemical variation in the composition at the spatial level (gradual change or gradient of composition at the volumetric level), materials can be achieved that combine the optimal contribution of each component to mechanical properties (2), or that a property is optimized in the surface (3).
  • copolymers there is the particularity that the interaction between the components is the best possible, because the bonds are present at the primary level (eg covalent bonds).
  • bonds are present at the primary level (eg covalent bonds).
  • random copolymers have been reported (where two monomers are "loaded” or placed in a vessel, or reactor, and allowed to react), alternating, block, or graft, which have been applied in various fields.
  • polymerization reactions have been used via free radicals, by ionic route and, more recently, by radical route, controlled with various types of catalysts. This last route allows to control the monomer that is added until reaching a certain size (4), with which, seeking to combine properties, the synthesis or formation of copolymers with composition gradient has been reported at the laboratory level.
  • copolymers can be synthesized to the desired molecular size (medium, high or very high, eg 100 to 10,000 link chains) with great ease, adjusting the amount of initiator for the reaction, and that the reaction can be done in industrial scale reactors, varying the feeding of the comonomers in a semi-continuous scheme (6,7).
  • the composition of the chains to be formed at a given moment of the reaction depends on the affinity or ability of the monomers to react with themselves, or with the other monomer, when wanting to form a copolymer. Such capacity is completely related to the chemical structure of both components.
  • the improvement in properties or performance that has been obtained with a composition gradient can be used for the preparation of three component polymers.
  • the implicit difficulty in using the method of obtaining a terpolymer is that the number of possible growth reactions with three components (if the three monomers are placed in a load reactor) is nine (while in a copolymer there are only four ); In such a synthesis, the achievement of the desirable ratio between the 3 monomers in the chains being formed is greatly complicated, preventing the achievement of their contribution or fundamental characteristic as a polymer for each component. For this reason, a "terpolymer" of industrial importance such as poly (acrylonitrile-butadiene-styrene, (ABS)) has traditionally been made in two stages by charges, polymerizing separately one of the monomers and the other two by copolymerization ( 12).
  • ABS acrylonitrile-butadiene-styrene
  • this process begins with the preparation of a seeding of the homopolymer of one of the comonomers (first stage), which is described in the following paragraph.
  • Table 1 shows the quantities used of the different components required for the synthesis of the seeds and the reference “terpolymer” (synthesized in two stages).
  • the procedure for obtaining the polymeric materials of three monomers proposed herein, in which a semi-continuous process with feed gradient is used, is detailed in the following paragraphs.
  • the process of the invention begins in a stirred reactor at constant reaction temperature and pressure, which may contain a previously prepared sowing latex and, if required, adjusted in concentration, so that the total amount of solids in the reactor is less than or equal to 10% of the total mass to be polymerized;
  • the procedure for obtaining a sowing latex is in the public domain, was briefly described in the background and is not part of the claims.
  • a certain amount of a surfactant is added to said reactor, maintaining stirring and bubbling nitrogen gas to try to have an aqueous system saturated with nitrogen and free of oxygen (which inhibits the reaction), before adding the comonomers.
  • two monomers are fed simultaneously to the reactor, following a semi-continuous scheme with a feed gradient, defining a certain number of stages (for example: between 5 and 40) and modifying in each of them the amounts of the comonomers, which are semi-continuous added.
  • the pre-established amounts of initiator allowing free radicals to be generated by heating
  • surfactant and pH buffer are added in a single charge.
  • Table 2 shows the feed flows of an example (applicable to vinyl monomers) or, the fed doughs (applicable to the other ingredients) at each stage of the various components, used in the synthesis of a type 1 material ( G1).
  • Table 3 shows, as an example, the equivalent information for a type 2 material (G2). In both tables the gradient feed sequence of the A / B and, B / C comonomers is evidenced.
  • Figure 1 It shows the distribution of the comonomer units in the gradient copolymer chains formed through the reaction time, for: (a) controlled root copolymerization and (b) free radical copolymerization.
  • Figure 2. It shows the stress-strain behavior of the "terpolymer” obtained with forced feed gradient type 1 (- -) and, the one obtained by the reference method (-). Test temperature: 40 ° C; crosshead speed for deformation: 5 mm / min.
  • Figure 3. It shows the stress-strain behavior of the "terpolymer” obtained with forced feed gradient type 2 (- -) and, the one obtained by the reference method (-). Test temperature: 25 ° C; crosshead speed for deformation: 5 mm / min.
  • Figure 4.- Shows the loss module as a function of the temperature for the "terpolymers" G1 (- -), G2 ( ⁇ ) and, of reference (-); frequency: 1 Hz.
  • Material G1 prepared with styrene (S), butyl acrylate (BA), and 4-vinylbenzyl chloride (CIVB), of overall composition S / BA / CIVB 25/60/15% by weight was obtained by emulsion polymerization semi-continuous following the generic steps described below: 1) adding latex seeds to the reactor (250 g of 20% latex in solids, equivalent to 50 g of PS; 10% of the total amount of G1 material to be obtained), 2) adding water to complete a total of 1400 g of water, 3) start stirring at 400 rpm with bubbling nitrogen gas for at least 1 hour, 3) adding the amount set out in Table 2 for the first loading of ingredients additional (sodium dodecyl sulfate, DSS, potassium persulfate, PSK; sodium bicarbonate, BS; 2% each with respect to the amount of monomer to be added at the stage in question, which are fed into a global solution containing 30 g of water), 4) start feeding the first pair comonom
  • Table 2 shows the feed flows or, the masses fed at each stage, corresponding to the various components used in the synthesis of type 1 material (G1).
  • the G2 material was synthesized in a totally equivalent way to that used in the synthesis of the G1 material, with the only variation of feeding the first and second comonomic pair following the flows indicated in Table 3, instead of those indicated in Table 2.
  • the G1 and G2 systems, as well as the two-stage reference system (2-E) were prepared with the same chemical system and with the same overall proportions of the monomers; that is, 25% by weight of butyl acrylate, 60% by weight of styrene and 15% by weight of 4-vinylbenzyl chloride.
  • the same equipment and the same general reaction conditions were used, ie temperature (70 ° C) and reactor agitation speed (400 rpm).
  • Table 3 shows the feed flows or, the masses fed at each stage, corresponding to the various components used in the synthesis of type 2 material (G2).

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Polymerisation Methods In General (AREA)

Abstract

Différentes processus ont été utilisés pour optimiser la contribution de chaque composant dans des systèmes de deux monomères pour former des copolymères, étant donné que les structures de ceux-ci influencent fortement la composition des chaînes de type A-B susceptibles de se former lors de la réaction. Pour trois composants, la situation de se complique encore si l'on veut obtenir des séquences spécifiques, parce que le nombre possible de réactions de croissance augmente (9 pour les terpolymères au lieu de 4 pour le copolymères). Une manière de réguler la proportion relative des composants dans les chaînes de poids moléculaire élevé formées par des réactions classiques radicalaires, consiste à utiliser un procédé semi-continu avec un gradient d'alimentation, dans lequel les comonomères vinyliques sont alimentés séquentiellement par paires (A-B et B-C), de sorte à favoriser la formation de chaînes riches en A, de chaînes riches en B et de chaînes riches en C, en plus d'une certaine quantité de chaînes de copolymères A-B et B-C, couvrant le spectre de compositions intermédiaires, et qui agissent comme agents de compatibilité. Cette approche permet d'obtenir une conjonction synergique de propriétés dans le matériau final.
PCT/IB2018/051722 2017-03-16 2018-03-14 Procédé d'obtention de matériaux polymères à trois composants présentant une composition variable orientée, synthétisés par des copolymérisation séquentielle dans un réacteur semi-continu avec un gradient d'alimentation WO2018167699A1 (fr)

Applications Claiming Priority (2)

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MXMX/A/2017/003497 2017-03-16
MX2017003497A MX2017003497A (es) 2017-03-16 2017-03-16 Proceso para la obtencion de materiales poliméricos de tres componentes con composición variable orientada, sintetizados mediante copolimerizaciones secuenciales en reactor semicontinuo con gradiente de alimentación.

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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110301298A1 (en) * 2006-05-25 2011-12-08 Arkema Inc. Acid functionalized gradient block copolymers

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110301298A1 (en) * 2006-05-25 2011-12-08 Arkema Inc. Acid functionalized gradient block copolymers

Non-Patent Citations (7)

* Cited by examiner, † Cited by third party
Title
BERGMAN, J. ET AL.: "Role of the segment distribution in the microphase separation of acrylic diblock and triblock terpolymers", POLYMER, vol. 55, no. 16, 5 August 2014 (2014-08-05), pages 4206 - 4215, XP029013812, Retrieved from the Internet <URL:https://doi.org/10.1016/j.potymer.2014.O5.049> *
GUO, Y. ET AL.: "Mechanical Properties of Gradient Copolymers of Styrene and n-Butyl Acrylate", JOURNAL OF POLYMER SCIENCE , PART B: POLYMER PHYSICS, vol. 53, no. 12, 2015, pages 860 - 868, XP055539686, Retrieved from the Internet <URL:https://doi.org/10.1002/polb.23709> *
JASSO-GASTINEL C. ET AL.: "Synthesis and Characterization of Anionic Exchange Resins with a Gradient in Polymer Composition for the PS-co-DVB/PDEAMA-co-DVB System", POLYMER BULLETIN, vol. 59, no. 6, 2008, pages 777 - 785, XP055539689 *
JASSO-GASTINEL, C. ET AL.: "Gradients in Homopolymers, Blends, and Copolymers", MODIFICATION OF POLYMER PROPERTIES, 2017, pages 185 - 210, Retrieved from the Internet <URL:https://doi.org/10.1016/B978-0-323-44353-1.00008-7> *
JASSO-GASTINEL, C. ET AL.: "Synthesis and Characterization of Styrene-Butyl Acrylate Polymers, Varying Feed Composition in a Semicontinuous Emulsion Process", JOURNAL OF APPLIED POLYMER SCIENCE, vol. 103, no. 6, 2007, pages 3964 - 3971, XP055539668, Retrieved from the Internet <URL:https://doi.org/10.1002/app.25265> *
JASSO-GASTINEL, C. ET AL.: "Tailoring Copolymer Properties by Gradual Changes in the Distribution of the Chains Composition Using Semicontinuous Emulsion Polymerization", POLYMERS, vol. 72, no. 9, 2017, XP055539674, Retrieved from the Internet <URL:hffps://doi.org/10.3390/polym9020072> *
YUAN, X. ET AL.: "Effect of annealing on the phase structure and the properties of the film formed from P(St-co-BA)/P(MMA-co-BA) composite latex", JOURNAL OF COLLOID AND INTERFACE SCIENCE, vol. 346, no. 1, June 2010 (2010-06-01), pages 72 - 78, XP055539698 *

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