WO2012174620A1 - Composition de plastifiants primaires exempte de phtalates, procédé d'obtention et ses utilisations - Google Patents

Composition de plastifiants primaires exempte de phtalates, procédé d'obtention et ses utilisations Download PDF

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Publication number
WO2012174620A1
WO2012174620A1 PCT/BR2012/000176 BR2012000176W WO2012174620A1 WO 2012174620 A1 WO2012174620 A1 WO 2012174620A1 BR 2012000176 W BR2012000176 W BR 2012000176W WO 2012174620 A1 WO2012174620 A1 WO 2012174620A1
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WIPO (PCT)
Prior art keywords
oil
epoxide
plasticizer
range
epoxidized vegetable
Prior art date
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PCT/BR2012/000176
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English (en)
Portuguese (pt)
Inventor
Massayochi Mário HOCIKO
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Kekapar Administração E Participações S/A.
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Application filed by Kekapar Administração E Participações S/A. filed Critical Kekapar Administração E Participações S/A.
Publication of WO2012174620A1 publication Critical patent/WO2012174620A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/15—Heterocyclic compounds having oxygen in the ring
    • C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
    • C08K5/1515—Three-membered rings

Definitions

  • the present invention relates to phthalate-free primary (or main) plasticizers. More particularly, the plasticizers of the invention are plasticizing compositions of epoxidized vegetable oil monoacetates and / or diacetates used in vinyl chloride (PVC) polymers to reduce their high stiffness.
  • PVC vinyl chloride
  • plasticizers are an example of additives incorporated into thermoplastic polymers. Plasticizers are substances that improve the processability of finished products, reducing system viscosity and increasing the mobility of macromolecules. In physicochemical terms, plasticizers cause Tg to shift to lower temperatures. The polymer that accepts the highest concentration of plasticizer is PVC.
  • plasticizer Basically, the action of plasticizer is to decrease the binding intensity between the polymer molecules. These Bonds (known as Van der Walls forces) can give the polymer, for example, PVC, an extremely high stiffness. The plasticizer decreases these forces, reducing intermolecular attraction and thereby increasing the flexibility of the polymer chain and causing interference with processing conditions and end product properties such as hardness, Vicat softening temperature, flexibility, etc.
  • the main characteristics of a suitable plasticizer are: purity; compatibility in the processing of thermoplastic mass; high permanence index, ie low migration; low toxicity, improvement of properties conferred to the polymer as a function of its content in the mixture; no color, ie no change in polymer color; heat and light stability; resistance to leaching (water extraction) and to be tasteless and odorless.
  • Plasticizers are widely used in improving the processability of thermoplastic polymers.
  • the types of plasticizers commonly used are: phthalic acid esters (phthalates), trimethylates, epoxy and polymeric (linear thermoplastic polyesters).
  • Phthalates for example dioctyl phthalate (DOP), diisononyl phthalate (DINP), diisobutyl phthalate (DIBP), diisodecyl phthalate (DIDP) are the cheapest and therefore the most widely used.
  • BRPI0705276 describes compounds of ethyl and / or isoamyl esters of fatty acids from vegetable oils as primary PVC plasticizers. These compounds are obtained from the transesterification reaction of at least one type of vegetable oil with ethanol or isoamyl alcohol and subsequent epoxidation. The resulting plasticizers have an oxiranic index of 8 or less.
  • Document BRPI0705621 discloses epoxidized bioesters obtained by partial transesterification of vegetable oils with ethyl alcohol or glycerin, followed by acetylation and epoxidation, resulting in primary plasticizers for PVC with oxiranic index equal to or less than 8.
  • BRPI0802148 describes a plasticizer composition obtained from vegetable oils comprising a compound of formula R1-0-R2 obtained by a process consisting of the steps of: (1) methanol and / or ethanol interesterification of mono-, di- and triglycerides present in vegetable oils with an iodine index greater than 100; (2) interesterification of the ethyl and / or methyl esters thus obtained with cyclohexanol and (3) epoxidation of the cyclohexyl esters thus obtained, where RI corresponds to the acyl portion of the mono-, di- and triglycerides of the vegetable oils with index of iodine greater than 100, epoxidized in its unsaturation and R2 corresponds to the cyclohexyl radical.
  • oleic, linoleic, palmitic acids to monoalcohols or polyalcohols by direct esterification and (2) epoxidation of such esterified products (containing saturated or unsaturated fatty acids) to increase the polarity and compatibility of these PVC resin reaction products .
  • the present invention discloses a plasticizer composition containing as a major component phthalate-free vegetable oil monoacetate.
  • the present invention aims to provide plasticizing compositions containing as a major component phthalate-free vegetable oil monoacetate for use in processing halogen-containing polymers, preferably polyvinyl chloride, to improve their processability.
  • a first embodiment of the invention relates to a plasticizer composition
  • a plasticizer composition comprising vegetable oil derivatives, said derivatives being esterified products of epoxidized vegetable oils, mostly epoxidized vegetable oil monoacetates.
  • the compositions of the invention have an oxiranic index in the range of 5.0 to 5.8%, and an acidity index in the range of 0.3 to 0.6 mg / g of sample.
  • a second embodiment of the invention relates to a process for obtaining a plasticizer containing as a major component epoxidized vegetable oil monoacetate, said process comprising reacting epoxidized vegetable oil, or mixing epoxidized vegetable oils with glycerine triacetate present in reaction mass in a molar ratio in the range from about 2: 1 to 4: 1.
  • the resulting product need not necessarily be homogeneous in the sense of a single molecular structure. Indeed, said product is preferably a more or less complex mixture of different epoxidized vegetable oil esters, preferably having the epoxidized vegetable oil monoacetate as the major component.
  • the invention relates to the use of the phthalate-free plasticizer composition for the preparation of yarns, cables or shoes.
  • Figure 1 presents a graph showing the specific rupture strain (%) of PVC compositions containing 100 PCR (Parts per Hundred Resin), 80 PCR, 60 PCR and 40 PCR of the plasticizer of the XYK invention.
  • Figure 2 presents a graph showing the maximum voltage
  • the process according to the invention is a transesterification reaction of glycerine triacetate epoxidized vegetable oil esters, preferably in the presence of an appropriate catalyst, and in the transesterification reaction the oxirane rings (epoxide groups) of the vegetable oil esters epoxidized remain intact.
  • Transesterification is carried out at a temperature in the range of 50 to 180 ° C, preferably in the range of 60 to 150 ° C, and more preferably in the range of 75 to 130 ° C, and for a period of time ranging from 1 hour to 5 ° C. hours, more preferably ranging from 1.5 hours to 3 hours, further stirring the reaction mass at a speed in the range of 80 to 250 rpm, more preferably in the range of 100 to 200 rpm.
  • the transesterification catalysts used in the present invention are known from the prior art and may be selected from the group consisting of basic compounds such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium methoxide, sodium ethylate; or tin (IV) compounds such as dibutyl tin butyrate.
  • Preferred catalysts of the process of the invention are sodium methoxide and sodium hydroxide.
  • the amounts of catalyst used in the process of the invention are preferably in the range 0.05 to 1.0% (w / w), more preferably in the range 0.1 to 0.5% based on the total amount of epoxidized vegetable oil esters and glycerine triacetate used.
  • the epoxidized vegetable oil esters preferably used in the process of the present invention are epoxidized esters. fatty acids and monohydroxyl alcohols, and in said epoxidized vegetable oil esters, the epoxidized fatty acid moiety is selected from the group consisting of soybean oil epoxide, flaxseed oil epoxide, sunflower oil epoxide, epoxide rapeseed oil, castor oil epoxide, canola oil epoxide, palm oil epoxide, peanut oil epoxide and other appropriate vegetable oil epoxides. Those skilled in the art know the meaning of the term "monohydroxyl alcohols" as used herein and no further definition is required. In a preferred embodiment of the invention a mixture of epoxidized vegetable oils may be used for transesterification with glycerine triacetate.
  • the molar ratio between the epoxidized vegetable oil ester glycerine triacetate reagents according to the invention is preferably adjusted to values in the range of 2: 1 to 4: 1.
  • the ratio of epoxidized vegetable oil esters to glycerine triacetate is in the range of 4: 1 to 2: 1, the predominant species will be epoxidized vegetable oil monoacetate, the preferred embodiment of the present invention.
  • the phthalate-free plasticizer compositions of the present invention are applied to thermoplastic polymer formulations, preferably PVC. Additionally, the formulations may contain additives commonly used in the preparation of plasticized polymers, such as stabilizers, antistatic agents, flame retardants, pigments and dyes, impact modifiers, reinforcing agents, among others.
  • the plasticizing compositions of the invention are characterized in that they are phthalate free and comprise a mixture of epoxidized vegetable oil esters, the major component of which is the epoxidized vegetable oil monoacetate.
  • Figures 1 and 2 the substantial improvement of the PVC properties containing the plasticizer composition of the present invention is demonstrated, specifically the specific deformation at break (%) and the maximum stress supported by the plasticized PVC measured in Kgf / mm 2 .
  • Tables 1 and 2 below show the comparison of these properties in PVC compositions containing the inventive plasticizers (XYK) and the usual state of the art plasticizers DOP (dioctyl phthalate), DINP (diisononyl phthalate).
  • the improvement in specific rupture strain (%) and maximum stress (kgf / mm 2 ) of the PVC composition with the plasticizer of the present invention is significantly greater than that of the prior art PVC compositions with plasticizers.
  • glycerine triacetate 54.5 g was transesterified with 472 g of epoxidized soybean oil in the presence of 2.1 g of sodium methoxide, the mixture being heated to 80 ° C. The mixture was allowed to react for 2 hours.
  • the epoxidized vegetable oil monoacetate obtained has the following characteristics:
  • Formulations FOR1-FOR5 comprise, as a primary plasticizer, the plasticizing compositions of the present invention; FOR6-FOR10 formulations comprise, as a primary plasticizer, dioctyl phthalate (DOP); and FOR11-FOR15 formulations comprise, as a primary plasticizer, diisononyl phthalate.
  • the amounts of the ingredients in Table 1 are in PCR (PIECES PER 100 PVC RESIN).
  • the Shore A hardness test was performed as known to those skilled in the art: in a becker, the materials that make up the formula were weighed and mixed.
  • the performance of the phthalate-free plasticizer compositions of the invention was equivalent, and even (in most tests) superior to that of the primary plasticizers.
  • the breaking load and elongation which showed higher values.
  • the breaking load was 11.56% higher and the elongation was 7.1% higher on a 65 SHORE A hardness crystal when compared to PVC containing state plasticizers. of technique;
  • the performance of PVC with the plasticizer of the invention had a 2.5% higher breaking load and a 1.85% greater elongation when compared to PVC containing prior art plasticizers.

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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)
  • Compositions Of Macromolecular Compounds (AREA)
  • Biological Depolymerization Polymers (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Organic Insulating Materials (AREA)
  • Insulated Conductors (AREA)

Abstract

La présente invention vise à obtenir des compositions plastifiantes contenant, comme constituant principal, le monoacétate d'huiles végétales exemptes de phtalate, en vue d'une utilisation dans le traitement de polymères contenant un halogène, de préférence du poly(chlorure de vinyle), pour en améliorer l'aptitude au traitement. Un premier mode de réalisation de l'invention se rapporte à une composition plastifiante comprenant des dérivés d'huiles végétales, lesdits dérivés étant des produits de l'estérification d'huiles végétales époxydées, majoritairement des monoacétates d'huiles végétales époxydées. Un deuxième mode de réalisation de l'invention concerne un procédé d'obtention d'un plastifiant contenant, comme constituant principal, le monoacétate d'une huile végétale époxydée, ledit procédé comprenant la réaction d'une huile végétale époxydée, ou d'un mélange d'huiles végétales époxydées, avec du triacétate de glycérine, ces éléments étant présents dans la masse réactionnelle selon un rapport molaire compris entre environ 2:1 et 4:1. Dans un troisième mode de réalisation, l'invention concerne l'utilisation de la composition plastifiante exempte de phtalate pour la préparation de fils, de câbles ou de chaussures.
PCT/BR2012/000176 2011-06-22 2012-06-11 Composition de plastifiants primaires exempte de phtalates, procédé d'obtention et ses utilisations WO2012174620A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
BRPI1102794 BRPI1102794A2 (pt) 2011-06-22 2011-06-22 composiÇço de plastificantes primÁrios isenta de ftalatos, processo de obtenÇço e seus usos
BRPI1102794-0 2011-06-22

Publications (1)

Publication Number Publication Date
WO2012174620A1 true WO2012174620A1 (fr) 2012-12-27

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AR (1) AR086706A1 (fr)
BR (1) BRPI1102794A2 (fr)
UY (1) UY34151A (fr)
WO (1) WO2012174620A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021154925A1 (fr) 2020-01-30 2021-08-05 Cargill, Incorporated Composition de plastifiant et procédé pour produire une composition de plastifiant

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB775326A (en) * 1954-04-12 1957-05-22 Waldo Clifford Ault Epoxidized fatty acid diacetoglycerides
EP1728818A1 (fr) * 2005-06-02 2006-12-06 Kao Corporation Plastifiant pour résine biodégradable
BRPI0602925A (pt) * 2006-06-28 2008-02-12 Teresa Cristina Da Ca Carvalho processo para preparação de ésteres de ácidos graxos vegetais e sua posterior epoxidação para a produção de plastificantes e produto resultante

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB775326A (en) * 1954-04-12 1957-05-22 Waldo Clifford Ault Epoxidized fatty acid diacetoglycerides
EP1728818A1 (fr) * 2005-06-02 2006-12-06 Kao Corporation Plastifiant pour résine biodégradable
BRPI0602925A (pt) * 2006-06-28 2008-02-12 Teresa Cristina Da Ca Carvalho processo para preparação de ésteres de ácidos graxos vegetais e sua posterior epoxidação para a produção de plastificantes e produto resultante

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
GAN, L. H. ET AL.: "Epoxidized Esters of Palm Olein as Plastifizers for Poly(Vinyl Chloride)", EUR. POLYM. J., vol. 31, no. 8, 1995, pages 719 - 724 *
HEVELINE DAL MAGRO FOLLMANN, UTILIZAÇÃO DE DERIVADOS DA GLICERINA NA PRODUÇÃO DE PLASTIFICANTES - TESE MESTRADO UNIVERSIDADE FEDERAL DO PARANÁ, 2009, pages 17 - 42 E 89-115 *
MADALENO, E. ET AL., ESTUDO DO USO DE PLASTIFICANTES DE FONTES RENOVÁVEL EM COMPOSIÇÕES DE PVC - POLIMEROS: CIÊNCIA E TECNOLOGIA, vol. 19, no. 4, 2009, pages 263 - 270 *
TIAGO HOMMERDING PEDROZO, ESTERES ETÍLICOS EPOXIDADOS DO OLEO DE MILHO COMO PLASTIFICANTE ALTERNATIVO PARA O PVC:- TESE DE MESTRADO - UNIVERSIDADE FEDERAL DO PARANÁ, 2009, pages 18 - 92 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021154925A1 (fr) 2020-01-30 2021-08-05 Cargill, Incorporated Composition de plastifiant et procédé pour produire une composition de plastifiant

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UY34151A (es) 2013-01-03
AR086706A1 (es) 2014-01-15
BRPI1102794A2 (pt) 2013-07-16

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