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WO1994005623A1 - Esters - Google Patents

Esters Download PDF

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Publication number
WO1994005623A1
WO1994005623A1 PCT/EP1993/002396 EP9302396W WO9405623A1 WO 1994005623 A1 WO1994005623 A1 WO 1994005623A1 EP 9302396 W EP9302396 W EP 9302396W WO 9405623 A1 WO9405623 A1 WO 9405623A1
Authority
WO
WIPO (PCT)
Prior art keywords
alcohols
weight
composition
mixture
cyclic
Prior art date
Application number
PCT/EP1993/002396
Other languages
English (en)
Inventor
Allen David Godwin
Original Assignee
Exxon Chemical Patents Inc.
De Greef, Jan, Josef, Peeter
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Exxon Chemical Patents Inc., De Greef, Jan, Josef, Peeter filed Critical Exxon Chemical Patents Inc.
Priority to AU49576/93A priority Critical patent/AU4957693A/en
Publication of WO1994005623A1 publication Critical patent/WO1994005623A1/fr

Links

Classifications

    • 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
    • C08K5/10—Esters; Ether-esters
    • C08K5/12—Esters; Ether-esters of cyclic polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/76—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring
    • C07C69/80—Phthalic acid esters

Definitions

  • Esters This invention relates to esters, more especially to esters suitable for use as plasticizers, and to a process for their manufacture.
  • Esters of aliphatic or aromatic polycarboxylic acids and aliphatic alcohols are extensively used in industry as plasticizers for, inter alia, vinyl resins. They are manufactured in large quantities by reaction of the acids or their anhydrides with the alcohols.
  • plasticized polymers have various requirements of the plasticizer and the resulting plasticized resin both in the manufacturing process and in the end product. These requirements differ from manufacturer to manufacturer depending on the manufactur ⁇ ing process and the end use of the product; in many cases there is a conflict between a given manufacturer's processing requirement and end use requirement.
  • plasticizer to be "fast fluxing", i.e., the temperature at which a mixture of the resin and plasticizer fuses, as in plastisol transformation or conversion to form a film, should be as low as possible. This requirement may be
  • plasticizer esters include a low tendency to migrate in or out of the polymer, good colour stability, and compatibility with other components of the resin.
  • the present invention provides a mixed ester composition obtainable from a polybasic acid and a mixture of aliphatic and cyclo- aliphatic monohydroxy compounds, the mixture comprising at least 80% by weight of C 5 and C 6 alcohols, at least 50% by weight of the mixture being primary alcohols and cycloaliphatic alcohols having the hydroxy group on a ring carbon atom (hereinafter "cyclic alcohols”) .
  • cyclic alcohols cyclic alcohols
  • the mixed ester composition will contain the possible esters in proportions depending on the propor ⁇ tions of the alcohols present in the mixture and on their relative reactivities in the conditions of reaction. For example, if the mixture consisted of a single C 5 alcohol and a single C 6 alcohol, the ester composition would contain di-Cs ester, di-Cg ester and mixed CsCg ester.
  • C 5 and Cg alcohols advantageously constitute at least 90%, and preferably at least 93%, by weight of the mixture.
  • the mixture contains, by weight, at most 10% C alcohols, at least 15% C 6 alcohols, at least 45% primary alcohols and at least 15% and preferably from 15% to 18%, cyclic alcohols, and at most 40% secondary and tertiary alcohols.
  • the mixture consists essentially of C5 and Cg alcohols. Any remainder of the mixture preferably comprises also C and C 7 alcohols, and more preferably only C 4 and C 7 alcohols.
  • Cyclic and primary alcohols advantageously constitute at least 60%, preferably at least 70%, by weight of the alcohol mixture.
  • the weight ratio of primary to cyclic alcohol is advantageously within the range of 1:1 to 10:1, preferably in the range of from 1:1 to 5:1, and most preferably about 3:1.
  • Secondary and any possible tertiary alcohols should desirably be present in a proportion of at most 40%, and preferably at most 20%, by weight of the mixture.
  • the invention provides a composition comprising a mixed ester of a polybasic acid and aliphatic and cycloaliphatic alcohols, in which at least 80% by weight of the esterifying alcohols are C 5 and C 6 alcohols and at least 50% by weight of the esterifying alcohols are primary and cyclic alcohols.
  • Preferred embodiments are as described for the first embodiment except that the preferred primary:cyclic ratio is from 5:1 to 10:1.
  • the primary alcohols may be linear or branched.
  • the alcohols are advantageously saturated.
  • the alcohols may contain substituents or functional groups that do not interfere with manufacture of esters or their plasticizer function but are preferably unsubstituted.
  • the mixture comprises al anols and cyclo- alkanols.
  • Suitable alcohol mixtures are, by weight,
  • the alcohol mixture is conveniently one obtained by the Fischer-Tropsch process, by passing steam over hot coal or peat, passing the resulting carbon monoxide and hydrogen over a metallic catalyst, advantageously iron- based, at high temperature and pressure, and recovering the low molecular weight alcohols (which are inter alia C to C 7 ) produced.
  • the product may be hydrofinished if desired or required to remove aldehyde or olefin impurities.
  • the invention also provides the use of an alcohol mixture, obtained by the Fischer-Tropsch process from coal or peat and separation from the products of a fraction comprising at least 80% by weight of C 5 and Cg alcohols in which fraction primary alcohols and cyclic alcohols constitute at least 70% by weight, in the manufacture of a plasticizer ester composition.
  • the invention further provides a process for the manufacture of an ester of a polybasic acid and a mixture of alcohols, which comprises subjecting coal or peat to the Fischer-Tropsch process, separating from the products a fraction comprising at least 80% by weight of C 5 to Cg alcohols in which fraction primary alcohols and cyclic alcohols constitute at least 50% by weight, and esterify ⁇ ing the alcohol-containing fraction with a polybasic acid or acidic derivative thereof.
  • the invention still further provides a process for the manufacture of a plasticized polymer which comprises carrying out the above-specified ester-manufacturing process and incorporating the ester in a polymer.
  • the polybasic acid is advantageously tribasic or, preferably, dibasic.
  • the acid may be inorganic or organic; if the latter, carboxylic acids are preferred. Among organic acids, aromatic acids are preferred.
  • acids suitable for making fast fluxing esters with the alcohol mixture there may be mentioned phthalic, isophthalic, terephthalic, adipic, fumaric, azeleic, sebacic, trimellitic, pyromellitic, and phosphoric acids.
  • the esters may be produced by methods known per se or described in the literature from the alcohols and the relevant acid or, preferably, where appropriate, the anhydride, optionally in the presence of a solvent. Elevated, temperatures are employed to drive the reaction toward completion by removal of the water produced. Catalysts may be employed. Suitable catalysts include, for example, a titanium catalyst e.g. a tetraalkyl titanate, especially tetra-propyl ortho titanate, or a sulphonic acid, e.g., p-toluene sulphonic acid. Any catalyst present in the reaction product may be removed by alkali treatment and water washing.
  • the alcohol is used in slight molar excess relative to- the number of acid groups in the acid.
  • the ester composition of the invention advantageously has a viscosity of at most 50 mPas, and preferably between 35 and 45 mPas, at 20°C.
  • the ester composition of the invention may be used as a plasticizer for numerous polymers, for example, cellulose acetate; homo- and copolymers of aromatic vinyl compounds e.g. styrene or of vinyl esters with carboxylic acids e.g., ethylene/vinyl acetate copolymers; halogen-containing polymers, especially vinyl chloride homo- and copolymers, more especially those copolymers with vinyl esters of carboxylic acid, esters of unsaturated carboxylic acids and/or olefins; nitrile rubbers; and post-chlorinated vinyl chloride polymers.
  • Poly(vinyl chloride) is of especial interest.
  • the proportion of plasticizer may vary within wide limits, but is generally 10 to 200 parts by weight per 100 parts of polymer, more especially 20 to 60 parts per 100.
  • the ester composition of the invention may be used alone as plasticizer, or in admixture with other plas ⁇ ticizers, for example, dibutyl, dipentyl, dihexyl, diheptyl, dioctyl, dinonyl or didecyl (iso- or n- in each case) phthalates or adipates, or butyl benzyl phthalate. If used in admixture, it is the total proportion of plasticizer that is advantageously within the ranges given above.
  • the plasticized polymeric compositions of the invention may be made up in numerous forms and have various end-uses. For example, they may be in the form of a dryblend, a paste, or a plastisol, depending on the grade of the resin employed. They may be used, for example, as coatings, in dipping, spraying, rotational moulding, or self-supporting films and sheets, and may readily be foamed. End uses include flooring materials, wall coverings, moulded products, upholstery materials, leather substitutes, and coated fabrics.
  • Sample A which contained as its major components, by gas chromatographic analysis, 1-pentanol 35.4%, 2-hexanol 12.7%, cyclo- pentanol 12.0%, l-hexanol 8.0%, methyl-cyclopentanol 5.0%, 3-methyl-l-butanol 4.8%, 2-methyl-l-butanol 4.0%, 2-heptanol 2.7% and 2-methyl-2-pentanol 1.2%, was used in this preparation.
  • the product had a residual alcohol content less than 0.1%, a water content less than 0.1%, an acidity less than 0.1 mg KOH/g and, at 20°C, a density of 1.03 ⁇ 0.005 and a viscosity of 42 ⁇ 2mPas.
  • the resulting ester was saponified to determine the proportion of the major components. These were found to be 1-pentanol 28.6%, 2-hexanol 15.6%, l-hexanol 12.8%, 2-heptanol 5.6%, cyclopentanol 3.9%, methyl-cyclopentanol 3.9%, 3-methyl-l-butanol 3.7%, 2-methyl-l-butanol 3.7%, 2-methyl-2-pentanol 1.4%, and cyclohexanol 1.1%, giving a proportion of primary and cyclic alcohol-derived groups in the mixed ester of at least 57.7%.
  • Example 3 Tests on plasticized resins
  • the mixed ester prepared in Example 1 was used as a plasticizer for poly(vinyl chloride) and the properties of the plasticized resin in plastisol and finished forms compared with those of the same resin plasticized with commercially available plasticizer esters.
  • the resin was Solvic (trade mark) 367 NC, an emulsion polymer.
  • stabilizer 0.5 part dibutyl tin mercaptide was used per 100 parts of resin.
  • the esters used were as follows:
  • each plasticizer identified in Table 1 above 50 parts were blended with 100 parts of poly(vinyl chloride) and 0.5 part stabilizer to form a plastisol.
  • the Haake viscosity of the plastisols ranged between 12 Pas for the plastisol containing ester A, E, or H to 26 Pas for C and D, at low shear rates (about 10 sec -1 ) , falling to values within the range of 7.0 to 11 Pas at higher shear rates (200 to 450 sec -1 ) with the exception, at the higher shear rates, of the mixture J which actually increased its viscosity to 18 Pas as shear rate was increased to between 100 and 200 sec -1 .
  • the material plasticized by the ester of the invention had a viscosity of about 24 Pas at low shear rate falling to 8 Pas at 300 sec -1 .
  • the gelation temperature of each formulation was determined using a Geigy temperature gradient gelation block. Plastisols generally show a transition from the liquid to the solid phase extending over a distinct temperature range, the lower end being the gelation temperature, (G in Table 2 below) and the higher the tack-free temperature (TF in Table 2 below) , the range for a given resin varying with the plasticizer. The results for the plasticizer esters tested are shown in Table 2 below.
  • the gelation and tack free temperatures are about 10°C below those noted for the formulation using G, di-2- ethylhexyl phthalate, the most commonly used commercial plasticizer, and compare favourably with those obtained using F, butyl benzyl phthalate, commonly used when a fast fluxing plastisol is required, and very favourably with those using J, the mixture of di-2-ethylhexyl and butyl benzyl phthalates.
  • the ester mixture according to the invention accordingly meets the requirements for a fast fluxing plasticizer.
  • Table 3 illustrates the volatility of the plasticizers, measured by heating the plastisols for 5 minutes at 160°C and 180°C.
  • the table gives the percentage weight loss in each case, and a relative weight loss, using the di-2-ethylhexyl phthalate- plastisol material G as standard.
  • Formulations containing the various plasticizers were made into films , and subjected to staining with yellow dye, black marker, blue ball point pen ink, ketchup , mustard, and shoe polish.
  • Formulations E and G was equalled or surpassed by Formulation 1. None of the films showed any sign of plasticizer incompatibility and no differences were observed in the transparencies or greying effect between the formulations E, F, G and 1.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Esters plastifiants obtenus à partir d'un mélange d'alcools comprenant des alcools cycliques et aliphatiques C5 et C6 primaires.
PCT/EP1993/002396 1992-09-04 1993-09-03 Esters WO1994005623A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU49576/93A AU4957693A (en) 1992-09-04 1993-09-03 Esters

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB929218762A GB9218762D0 (en) 1992-09-04 1992-09-04 Esters
GB9218762.4 1992-09-04

Publications (1)

Publication Number Publication Date
WO1994005623A1 true WO1994005623A1 (fr) 1994-03-17

Family

ID=10721408

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1993/002396 WO1994005623A1 (fr) 1992-09-04 1993-09-03 Esters

Country Status (5)

Country Link
CN (1) CN1083828A (fr)
AU (1) AU4957693A (fr)
GB (1) GB9218762D0 (fr)
WO (1) WO1994005623A1 (fr)
ZA (1) ZA936367B (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6281371B1 (en) 1997-08-13 2001-08-28 Biontex Laboratories Gmbh Lipopolyamines, and the preparation and use thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1520527A (fr) * 1967-02-10 1968-04-12 Melle Usines Sa Compositions plastifiées à base de résine vinylique et leur préparation
JPS5273954A (en) * 1975-12-18 1977-06-21 Nissan Chem Ind Ltd Alcohol compositions for use in plasticizers
FR2477535A1 (fr) * 1980-03-10 1981-09-11 Hercofina Procede de preparation d'esters du type des plastifiants a partir du residu de la fabrication du terephtalate de dimethyle, produits obtenus et utilisation de ces produits comme plastifiants pour des resines vinyliques et apparentees
EP0432124A2 (fr) * 1989-12-08 1991-06-12 Monsanto Company Composition de plastifiant, polyvinylbutyral plastifié et couches intermédiaires à base de ce polyvinylbutyral

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1520527A (fr) * 1967-02-10 1968-04-12 Melle Usines Sa Compositions plastifiées à base de résine vinylique et leur préparation
JPS5273954A (en) * 1975-12-18 1977-06-21 Nissan Chem Ind Ltd Alcohol compositions for use in plasticizers
FR2477535A1 (fr) * 1980-03-10 1981-09-11 Hercofina Procede de preparation d'esters du type des plastifiants a partir du residu de la fabrication du terephtalate de dimethyle, produits obtenus et utilisation de ces produits comme plastifiants pour des resines vinyliques et apparentees
EP0432124A2 (fr) * 1989-12-08 1991-06-12 Monsanto Company Composition de plastifiant, polyvinylbutyral plastifié et couches intermédiaires à base de ce polyvinylbutyral

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Week 7731, Derwent World Patents Index; AN 77-54879Y *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6281371B1 (en) 1997-08-13 2001-08-28 Biontex Laboratories Gmbh Lipopolyamines, and the preparation and use thereof

Also Published As

Publication number Publication date
CN1083828A (zh) 1994-03-16
GB9218762D0 (en) 1992-10-21
ZA936367B (en) 1994-03-25
AU4957693A (en) 1994-03-29

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