WO1998032728A1 - Melanges d'esters a base de 1,3-diols, leur procede de preparation et leur utilisation - Google Patents

Melanges d'esters a base de 1,3-diols, leur procede de preparation et leur utilisation Download PDF

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Publication number
WO1998032728A1
WO1998032728A1 PCT/FI1998/000060 FI9800060W WO9832728A1 WO 1998032728 A1 WO1998032728 A1 WO 1998032728A1 FI 9800060 W FI9800060 W FI 9800060W WO 9832728 A1 WO9832728 A1 WO 9832728A1
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WO
WIPO (PCT)
Prior art keywords
propanediol
ester
dimethyl
diol
carboxylic acid
Prior art date
Application number
PCT/FI1998/000060
Other languages
English (en)
Finnish (fi)
Inventor
Kjell Ankner
Håkan RAHKOLA
Salme Koskimies
Maarit Salmi
Kari Rissanen
Original Assignee
Neste Oy
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 Neste Oy filed Critical Neste Oy
Priority to AU57668/98A priority Critical patent/AU5766898A/en
Publication of WO1998032728A1 publication Critical patent/WO1998032728A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/02—Emulsion paints including aerosols
    • C09D5/024—Emulsion paints including aerosols characterised by the additives
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/02—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen
    • C07C69/12—Acetic acid esters
    • C07C69/16—Acetic acid esters of dihydroxylic compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/02—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen
    • C07C69/22—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen having three or more carbon atoms in the acid moiety
    • C07C69/28—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen having three or more carbon atoms in the acid moiety esterified with dihydroxylic compounds

Definitions

  • the present invention relates to ester compositions according to the preambles of claims 1 and 3, containing esters formed by 2-alkyl- or 2,2-dialkyl-l,3-diols and aliphatic carboxylic acids.
  • the invention also concerns a process according to the preamble of claim 6 for preparing carboxylic acid esters of 1,3 -diols and the use according to claim 16.
  • the invention further relates to an aqueous paint composition according to the preamble of claim 19, which contains a binder and additives and admixtures known per se.
  • Good film fo ⁇ ning chemicals are, e.g., phenyl ethers of ethylene glycol, 2,2,4- trimethyl-l,3-pentanediol monoisobutyrate (TEXANOL) and the n-butylether acetate of diethyleneglycol.
  • TEXANOL 2,2,4- trimethyl-l,3-pentanediol monoisobutyrate
  • the problem of these known compounds is their low volatility and/or low stability against hydrolysis.
  • the present invention is based on selective esterification of 1,3-diols with - C g -carboxylic acids so as to obtain a product having good film forming properties.
  • the present invention makes it possible to produce mono- and diesters or mixtures of mono/diesters of 2- or 2,2-alkyl substituted diols having good hydrolytic stability due to their structure. Less than half of such mixtures is generally formed by the diester and more than half of the mixture is made up by the monoester.
  • Suitable carboxylic acids are, as far as the invention is concerned, branched or linear aliphatic acids containing 1 to 8 carbon atoms.
  • Esterification can be carried out by an acid-catalysed reaction between the 1,3-diol and the carboxylic acid, or preferably by transesterification of the acid with a methyl or ethyl ester, an ion exchanger being used as a catalyst. In both cases, the reaction comprises a selective esterification process.
  • ester composition according to the present invention is mainly characterized by what is stated in the characterizing parts of claims 1 and 3.
  • the invention also provides a new extraction-based process for separating water-soluble diols from the reaction mixture.
  • the invention can be used particularly when the separation of diols and monoesters by, e.g. distillation, is difficult.
  • Figures 1 and 2 show the film forming temperatures of dispersions containing various solvents versus solvent concentration.
  • the base dispersion used comprises a styrene-acrylate-dispersion which is commercially available under the product name Finndisp A 10, whereas an anionic acrylate-dispersion sold under the name of Finndisp
  • Figure 3 depicts the influence of various solvents on the hardness of the film versus time.
  • the present invention comprises esterification of 2-, and 2,2-dialkylated 1,3- propanediols for producing solvents which can be used as film forming agents.
  • the alkyl groups of in position 2 of the 1,3-diols can be the same or different and they generally represent substituted or unsubstituted alkyl or cycloalkyl groups.
  • the alkyl groups are selected from linear or branched alkyl groups containing 1 to 6 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert.-butyl, amyl, isoamyl or hexyl groups.
  • 2,2-dimethyl-l,3-propanediol neopentylglycol, NPG
  • 2-butyl-2-ethyl- 1,3-propanediol BEPD
  • 2,2-diethyl-l,3-propanediol are examples of preferred 1,3- diols.
  • the hydroxyl group(s) of the 1,3-diol is (are) esterified with an aliphatic carboxylic acid residue containing 1 to 8 carbon atoms.
  • the carboxylic acid residue can be linear or branched and it can be derived from, e.g., formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, pentanoic acid or hexanoic acid.
  • the esterification can be carried out as an esterification reaction between the acid and the diol or as transesterification.
  • acids corresponding to the carboxylic acid residues can be used (i.e.
  • esterification agent used comprises alkyl esters, methyl and ethyl formate, acetate, propionate and n- or i- butylate being preferred examples.
  • an ester composition which comprises an ester formed by 2,2-dimethyl-l,3-propandiol and an aliphatic carboxylic acid and containing 0.1 - 40 wt-% of a diester of 2,2-dimethyl-l,3- propandiol and 60 - 99.9 wt-% of a monoester of 2,2-dimethyl-l,3-propanediol.
  • it contains 1 - 30 wt-% (or 2 - 30 wt-%) diester and 70 - 99 wt-% (70 - 98 wt-%) monoester.
  • An ester composition according to another preferred embodiment of the invention comprises an ester formed by 2-butyl-2-ethyl-l,3-propandiol and an aliphatic carboxylic acid, containing 0.1 - 40 wt-% of a diester of 2-butyl-2-ethyl-l,3-propanediol and 60 - 99.9 wt-% of a monoester of 2-butyl-2-ethy 1-1,3 -propanediol. In particular it contains 1 - 30 wt-% (or 2 - 30 wt-%) diester and 70 - 99 wt-% (70 - 98 wt-%) monoester.
  • the monoester portion of the film forming agent mixture improves solubility in water which positively influences the final properties of the paint surface.
  • An optimal result is obtained not only with pure monoesters but also with mixtures of mono- and diesters.
  • the esterification catalysed with an ion exchanger directly gives a suitable mixture of mono- and diesters.
  • the reaction of an organic acid or acid anhydride or ester (transesterification) with a monoalcohol by using an acid ion exchanger resin is known from EP Patent Application No. 0 552 541.
  • Said publication does not, however, disclose the characteristic feature of the present invention, according to which the end product can be steered towards the mono-ester (producing e.g. a suitable mixture or more monoester than normally) when a diol is esterified using an ion exchanger catalyst. This facilitates the separation of the end product and makes it economically interesting. Recirculation of by-products is minimized.
  • the catalyst is used in an amount of 1 to 40 % of the esterification agent during esterification.
  • Suitable esterification catalysts are represented by p-toluenesulphonic acid, benzenesulphonic acid, sulphuric acid, tin and zinc salts and oxides and titanates.
  • Suitable transesterification catalyst are alkali metal alkoxides, such as potassium or sodium alkoxides, sulphuric acid, hydrochloric acid and acid ion exchanger resins.
  • diesterification catalysts are, according to the present invention, p- toluenesulphonic acid, methanesulphonic catalyst and tin oxides.
  • particularly preferred catalysts comprise acid ion exchanger resins.
  • an ion exchanger resin preferably an acid ion exchanger and in particular a strongly acid ion exchanger, are used for preparing carboxylic acid esters of 1,3 -diols.
  • ion exchange resins can be divided into cation exchanger resins, anionic exchanger resins and amphotheric ion exchanger resins. Depending on the acidity or alkalinity of the ionogenic group, the resins are characterized as strongly or weakly acid cation exchanger resins.
  • the activity and selectivity of supported catalytic groups is strongly influenced by so called "polymeric effects". The interaction between the polymeric matrix and the environment influences the properties of the resin and the reasons underlying this phenomenon can be both physical and chemical.
  • the resin matrices are either of gel type or macroporous.
  • the matrix of a gel-type resin is obtained as a gel from polymerization.
  • gel denotes a macroscopically homogeneous polymer of an elastic character and containing solvent from the production process.
  • Gel-type resins are not permanently porous; instead they exhibit variable swelling in polar solvents which opens up their structure.
  • the spaces between crosslinks filled with a swelling solvent can be considered a kind of micropores. These spaces contain solvent, but also partially dissolved polymer segments. Migration within the micropores is restricted by the high viscosity of the solutions.
  • Macroporous resins are obtained when a solvent is used during polymerization.
  • the macroporous resins have a great internal porosity and prevention of a breaking down of the structure requires the use of a large amount of crosslinking agent.
  • the macroporosity of the resin also increases its surface which gives rise to improved contact between the reactants and it also often increases reaction rate.
  • both gel-type and macroporous strong cation exchanger resins can preferably be used as catalysts of the esterification reaction.
  • the diol and the esterification agent are contacted with a cation exchanger resin at a molar ratio of 10: 1 - 1:10, preferably 5:1 - 1:5.
  • the reaction can be carried out at a temperature of 15 - 120 °C, preferably 20 - 100 °C.
  • the upper limit is formed by the heat resistance of the cation exchanger resin used.
  • the amount of the catalyst is about 1 - 40 weigth-%, as previously mentioned.
  • the esterification reaction can be carried out batch-wise or semibatch-wise or as a continuous reaction. Continuous processes are preferably carried out in a fixed bed reactors using an ion exchanger resin of column quality. In the batch and semibatch processes the resin is separated from the reaction medium by filtering after the reaction and regenerated by means known per se.
  • the catalyst comprises a strongly acid cation exchanger resins having a functional group selected from, e.g., sulphonic acid and fluorosulphonic group.
  • Hammet's acid function (Ho) for an ion exchanger resin is typically - 1...- 15.
  • the resin matrix used can comprise comonomers made from vinylmonomers or traditional condensation polymers.
  • Particularly preferred ion exchanger resins are represented by mixed polymers made from styrene and polyvinylbenzene and perfluorosulphonic acid polymers (a copolymer of tetrafluoroetene and perfluoro[2-(fluorosulphonylethoxy)]poly(vinyl ether).
  • mixed polymers made from styrene and polyvinylbenzene and perfluorosulphonic acid polymers (a copolymer of tetrafluoroetene and perfluoro[2-(fluorosulphonylethoxy)]poly(vinyl ether).
  • the products marketed under the product names of AMBERLITE, DOWEX, FINEX and NAFION can be mentioned, e.g.
  • the esterification method according to the invention can be used for preparing alkyl esters at least from 2,2-dimethyl-l,3-propanediol or 2-butyl-2-ethyl-l,3-propanediol. It is preferred to use the ion exchanger for manufacturing ester compositions in which the monoesters form the majority of the esters.
  • the monoesters of 1,3-diols are then preferably being prepared by using an excess of diol in respect to the esterification agent.
  • the monoester has been found to advantageous. Preferably it is greater than 3, in particular about 4 to 6. Since an excess of diol is fed into the reaction, the monoester has to be separated from the unreacted diol after the reaction. If the boiling points of the monoester and the diol are sufficiently far apart, the separation of the products and the reactant can be carried out by, e.g., distillation. In some cases, the boiling points of the monoester and the diol are, however, so close to each other that it is preferred to remove the unreacted diol from the reaction mixture by extraction. Thus, for neopentylglycol water has been found to be a very good and useful extraction solvent.
  • Esterification is carried out in a non-polar hydrocarbon, such as toluene, xylene or chlorinated hydrocarbons. If the diol is a liquid at the esterification temperature, the reaction can also be carried out without a separate medium. This case is exemplified by esterification of BEDP. It is also possible to operate in a melt formed by the reactants.
  • a non-polar hydrocarbon such as toluene, xylene or chlorinated hydrocarbons.
  • the monoesters, diesters or mono/diesters of 2-alkyl- and 2,2-dialkyl-l,3-diols according to the present invention are useful as film-forming agents in aqueous paint compositions.
  • Esters of 2,2-dimethyl-l,3-propanediol or 2-butyl-2-ethyl-l,3-propanediol containing 1 to 8 carbon atoms in their ester group are, in particular, used in such paint compositions. It has been found that the mono- and diisobutyrates of 2,2-dimethyl- 1,3- propandiol (neopentylglycol) are particularly advantageous.
  • the ester according to the invention can be formulated into a water and/or solvent based dispersion, which contains the binder together with adjuvants and additives. It is particularly preferred to prepare aqueous dispersions.
  • the binders or vehicles can be selected from, e.g., binder or latex pains, such as poly (vinyl acetate)s and polyacrylates, and alkydes.
  • the last-mentioned substances generally contain a condensate product formed from a bivalent polyol and a fatty acid or a natural oil.
  • the amount of the binder is 40 - 80 wt-% of the dispersion.
  • the dispersion additives and adjuvents are exemplified by surface active substances, dispergants, thickening agents, conversion agents/fungicides, anti-foaming agents and fillers and pigments, such as calcium carbonate and titanium dioxide and pH regulating agents, such as ammonia.
  • the dispersions according to the present invention contain 0.01 to 5 wt-% of a film fo ⁇ ning agent comprising a monoester, diester or a mixture of mono- and diesters of 2- or 2,2-dialkyl-substituted diols.
  • they contain 0.1 - 1 wt-% of esters of 2,2-dimethyl-l,3-propanediol or 2- butyl-2-ethyl-l ,3-propanediol ester.
  • Figures 1 to 3 depict the influence of NPG-monoisobutyrate and NPG-diisobutyrate on the film forming temperature of two different dispersion and the influence of said ester on the hardness of the film.
  • the figures also contain the results obtained in corresponding test with 12 known film fo ⁇ ning agents.
  • the film forming agents have been added to dispersions which are commercially available under the product names FINNDISP A 10 and FINNDISP 4300, respectively, and which comprise unplasticized, solvent-free dispersions, the first mentioned of which contain a styrene acrylate -based binder and the second an anionic acrylate binder.
  • the mono- and diisobutyrate esters of NPG provide film formation already at modestly low temperature increases. In this respect, they are as good or better than the commonly used Texanol and significantly better than some ethers.
  • Figure 3 depicts the influence of the NPG mono- and diisobutyrates on the hardness of the coating as a function of time, which indicates that these products give a good degree of hardness and a relatively fast drying.
  • Diesterification was carried out by weighing all reactants, the diol, NPG (neopentyl glycol) or BEPD (2-butyl-2-ethyl-l,3-propanediol), the acid and the catalyst into a reaction flask.
  • NPG neopentyl glycol
  • BEPD 2, butyl-2-ethyl-l,3-propanediol
  • the acid and the catalyst into a reaction flask.
  • the water separation tube was also filled with that solvent.
  • a slow nitrogen flow was fed below the surface of the reaction mixture.
  • the mixture was refluxed for 2 to 12 h, depending on the reaction rate, at a temperature of 100 140 °C.
  • the progress of the esterification was monitored using gas chromatography with 1 hour intervals.
  • the amount of sample subjected to analysis by gas chromatography was about 0.1 ml, the aliquots being dissolved in 1.0 ml of methanol. After refluxing the reaction mixture was allowed to cool and then it was washed three times with 30 ml of a 10 % Na 2 CO 3 solution and three times with 30 ml of water while being agitated with a magnet agitator. Finally, the product was dried overnight on Na 2 SO 4 , it was weighed and a gas chromatogramme was run on a gas chromatograph and the yield calculated for the diester.
  • the transesterification was carried out by weighing all reactants, the diol, the ester and the catalyst into a reaction flask.
  • the catalyst used for transesterification comprised a strongly acidic cation exchanger (Dowex 50W x 2). In two tests, toluene was used as a solvent. The mixtures were refluxed for 1.5 to 5 hours.
  • Example 14 a distillator was connected to reaction vessel for distillation of the ethanol formed during transesterification. After the refluxing, the monoester concentration was, based on gas chromatography, only 30 to 50 % and the concentration of the reactant (NPG) was 35 to 40 %.
  • Monoesters were prepared by using an excess of diol.
  • the catalyst used in the reaction comprised a strongly acidic cation exchanger resin, which was added in an amount of 1.0 g acid for each 0.10 - 0.20 g.
  • the catalyst, the cation exchanger resin, used for the monoesterifications was five times regenerated.
  • the solvent comprised toluene which was used in excess.
  • the reaction mixture was reluxed for 3 to 7 hours depending on the reaction rate at a temperature of 100 to 150 °C. After the refluxing the catalyst was filtered off from the reaction mixture and regenerated for reuse. Excess amounts of diol were removed from the product by extracting the mixture three times with water, and then the product was dried over night on Na 2 SO 4 . Finally, the solvent was removed by evaporating on a rotary evaporator, the product was weighed and it was subjected to gas chromatography in order to obtain the yield for the monoester.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

L'invention concerne une composition d'esters qui comprend un ester formé par le 2,2-diméthyl-propanediol ou le 2-butyl-2-éthyl-1,3-propanediol, et un acide carboxylique aliphatique. Selon l'invention, la composition contient 0,1 à 40 % en poids d'un diester de 1,3-propanediol et 60 à 99,9 % en poids d'un monoester de 2,2-diméthyl-1,3-propanediol. L'invention concerne également un procédé permettant de préparer des esters d'acide carboxylique de 1,3-diols. Selon le procédé, on met à réagir un 1,3-diol avec un agent d'estérification en présence d'un catalyseur constitué d'une résine échangeuse d'ions acides. Ces compositions d'esters, ainsi que les monoesters, les diesters et les mélanges de monoesters/diesters de 1,3-diols préparés selon l'invention, peuvent être utilisés notamment comme agents filmogènes dans des compositions de peintures solubles dans l'eau.
PCT/FI1998/000060 1997-01-22 1998-01-22 Melanges d'esters a base de 1,3-diols, leur procede de preparation et leur utilisation WO1998032728A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU57668/98A AU5766898A (en) 1997-01-22 1998-01-22 Mixtures of 1,3-diol-based esters, process for the preparation of 1,3-diol-basedesters and the use thereof

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FI970269 1997-01-22
FI970269A FI970269A (fi) 1997-01-22 1997-01-22 1,3-diolipohjaisten esterien seokset, menetelmä 1,3-diolipohjaisten esterien valmistamiseksi sekä esterien käyttö

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WO1998032728A1 true WO1998032728A1 (fr) 1998-07-30

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016118882A1 (fr) 2015-01-23 2016-07-28 cP2 SCIENCE, INC. Compositions d'arôme et de fragrance comprenant du diacétate de néopentylglycol
WO2020173726A1 (fr) 2019-02-25 2020-09-03 Basf Se Utilisation du (3-acétoxy-2,2-diméthyl-propyl) acétate en combinaison avec du (3-hydroxy-2,2-diméthyl-propyl) acétate en tant que produit chimique aromatique

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0066935A1 (fr) * 1981-06-09 1982-12-15 Unilever N.V. Esters lubrifiants
EP0518567A1 (fr) * 1991-06-07 1992-12-16 Hatco Corporation Base lubrifiante synthétique formée à partir de mélanges d'acides dont une grande partie à chaînes ramifiées
WO1996028525A1 (fr) * 1995-03-14 1996-09-19 Exxon Chemical Patents Inc. Compositions d'ester de polyol contenant des groupes hydroxyle non convertis
WO1997049786A1 (fr) * 1996-06-24 1997-12-31 Perstorp Ab Ester lubrifiant

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0066935A1 (fr) * 1981-06-09 1982-12-15 Unilever N.V. Esters lubrifiants
EP0518567A1 (fr) * 1991-06-07 1992-12-16 Hatco Corporation Base lubrifiante synthétique formée à partir de mélanges d'acides dont une grande partie à chaînes ramifiées
WO1996028525A1 (fr) * 1995-03-14 1996-09-19 Exxon Chemical Patents Inc. Compositions d'ester de polyol contenant des groupes hydroxyle non convertis
WO1997049786A1 (fr) * 1996-06-24 1997-12-31 Perstorp Ab Ester lubrifiant

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
STN INTERNATIONAL, File CAPLUS, CAPLUS Accession No. 1985:129120, DAIHACHI CHEMICAL INDUSTRY CO., LTD., "Binders for Cellulose Acetate Fibers"; & JP,A,59 174 670 (03-10-84) SHOWA. *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016118882A1 (fr) 2015-01-23 2016-07-28 cP2 SCIENCE, INC. Compositions d'arôme et de fragrance comprenant du diacétate de néopentylglycol
US10072233B2 (en) 2015-01-23 2018-09-11 P2 Science, Inc. Fragrance and flavor compositions comprising neopentyl glycol diacetate
WO2020173726A1 (fr) 2019-02-25 2020-09-03 Basf Se Utilisation du (3-acétoxy-2,2-diméthyl-propyl) acétate en combinaison avec du (3-hydroxy-2,2-diméthyl-propyl) acétate en tant que produit chimique aromatique

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Publication number Publication date
FI970269A0 (fi) 1997-01-22
AU5766898A (en) 1998-08-18
FI970269A (fi) 1998-07-23

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