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WO1997002230A1 - Diluants reactifs - Google Patents

Diluants reactifs Download PDF

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Publication number
WO1997002230A1
WO1997002230A1 PCT/GB1996/001570 GB9601570W WO9702230A1 WO 1997002230 A1 WO1997002230 A1 WO 1997002230A1 GB 9601570 W GB9601570 W GB 9601570W WO 9702230 A1 WO9702230 A1 WO 9702230A1
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WO
WIPO (PCT)
Prior art keywords
ofthe
octadienyl
ester
formulation
succinate
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/GB1996/001570
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English (en)
Inventor
Henry Deans
Benjamin Patrick Gracey
Christopher Hallett
Philip Kenneth Gordon Hodgson
Robert Paul Klaasen
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BP Chemicals Ltd
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BP Chemicals Ltd
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 BP Chemicals Ltd filed Critical BP Chemicals Ltd
Priority to AU63110/96A priority Critical patent/AU6311096A/en
Publication of WO1997002230A1 publication Critical patent/WO1997002230A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D167/08—Polyesters modified with higher fatty oils or their acids, or with natural resins or resin acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/007—Esters of unsaturated alcohols having the esterified hydroxy group bound to an acyclic carbon atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
    • C07C69/67—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of saturated acids
    • C07C69/708—Ethers
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/20—Diluents or solvents

Definitions

  • This invention relates to novel esters of 2,7-octadienol and the use thereof as reactive diluents in paint and polymer formulations.
  • esters of unsaturated alcohols are well known.
  • One such method is the direct telomerisation of butadiene with a carboxylic acid in the presence of a homogeneous catalyst comprising a noble metal compound such as eg palladium acetyacetonate and a phosphine.
  • a homogeneous catalyst comprising a noble metal compound such as eg palladium acetyacetonate and a phosphine.
  • a noble metal compound such as eg palladium acetyacetonate
  • phosphine phosphine
  • octadienol is reacted with a carboxylic acid or anhydride in the presence of other catalysts (see JP- A-47046568 (Mitsubishi) which describes the use of a zinc acetate catalyst and JP-A- 04049266 (Kuraray) which describes the use of a KCN transesterification catalyst).
  • esters of octadienol, especially the maleates and fumarates are well known and methods of their preparation are described in JP-A-47-46568 (Mitsubishi).
  • the use of these esters as (a) comonomers during polymerization of other monomers to form thermosetting resins, (b) plasticizers, (c) lubricating oils and (d) textile treatment agents are disclosed in this reference.
  • JP-A-49-28175 (Mitsubishi) describes the use of some ofthese synthetic esters as drying oils.
  • US-A-4378251 (Eastman Kodak) describes the use of some ofthese esters to form polymers with a viscosity of > 200 cP, preferably from 700-900 cP in coating compositions which contain in addition an organic salt of cobalt or manganese.
  • US-A- 4408029 (Eastman Kodak) claims a low molecular weight polymer derived from octadienyl maleate or fumarate and having a fluid viscosity of at least 200 cP.
  • Reactive diluents are usually compounds or mixtures of compounds of relatively low viscosity, a relatively high boiling point (i.e. low saturated vapour pressure) which act as solvents during the formulation and processing ofthe coating.
  • a feature of reactive diluents is that such diluents can copolymerise with a resin, e.g. an alkyd. Hence reactive diluents may be used to replace part or all ofthe traditional solvents normally used in such formulations thereby reducing losses ofthe solvent to atmosphere on drying ofthe coating.
  • Use of esters of di- and polyhydric alcohols which have been partially etherified with allyl alcohol as reactive diluents is described for example in EP-A-0 263 474.
  • Alkyd resins are well known components of decorative paints (see, for example, "The Technology of Paints, Varnishes and Lacquers” by Martens, C R, Ed., published by Robert Krieger Publishing (1974)) and can be prepared from polybasic acids or anhydrides, polyhydric alcohols and fatty acids or oils. US-A-3 819 720 describes methods of preparing such alkyd formulations. Alkyd resins are available commercially and are used in coating compositions which usually contain large amounts of solvents (eg white spirits, aromatic hydrocarbons).
  • esters of octadienyl alcohols which can be produced in commercially viable yields and purity have relatively low viscosity and therefore can be used as reactive diluents in a wide variety of polymer formulations.
  • the present invention is 2-(2,7-octadienoxy) di-(2,7-octadienyl) succinate, a novel compound.
  • the 2-(2,7-octadienoxy) di-(2,7-octadienyl) succinate ester can be derived by reacting in the presence of a catalyst a compound ofthe formula:
  • R' and R" may be OH or the same or different C1-C10 alkenoxy group, or, may be such that the two taken in combination represent an -O- function thereby making (II) an acid anhydride.
  • (I) may be 2,7-octadienol or an ester thereof.
  • (II) may be maleic anhydride, maleic acid, fumaric acid or a dialkyl ester of maleic or fumaric acid, especially the dimethyl esters.
  • 2,7- octadienol is normally produced by telomerisation and such a process yields a mixture of isomeric octadienols ie l,7-octadien-3-ol and 2,7-octadienol. This mixture can be used to prepare the esters.
  • the reaction between (I) and (II) is suitably carried out in the liquid phase and in the presence of a catalyst which does not cause undue polymerisation or rearrangement ofthe allylic groups the molecule of (I) thereby giving rise to hydrocarbyl fragments capable of forming coloured products.
  • a suitable catalysts include acidic or amphoteric catalysts, and may be homogeneous or heterogeneous. Specific examples of such catalysts include inter alia dibutyl tin oxide, stannous oxalate, zinc acetate, magnesium acetate, para-toluene sulphonic acid, methane sulphonic acid and phosphoric acid.
  • the esterification reaction is suitably carried out at a temperature from 80-200°C, preferably from 100- 160°C. Within these temperature ranges, the density ofthe ester formed tends to increase at the higher temperatures due to resinification of the carboxylate reactant or ester product.
  • the esterification ofthe octadienyl compound (I) with the dicarboxylic compounds (II) to form the desired succinate ester either by direct- or trans-esterification may lead to a mixture of esters under some reaction conditions. Such a mixture of esters can be due to incomplete transesterification. This will be especially true where less than one molar equivalent of octadienyl compound (I) is used per mole ofthe dicarboxylic compound (II) in the reaction.
  • the reaction is suitably carried out using a molar ratio of (I) : (II) in the range of 2 : 1 to 10 : 1, preferably from 2.5 : 1 to 5 : 1.
  • the preparative conditions employed will have a strong influence on the type of material obtained from the esterification (or transesterification) reaction, including those used for producing the esters of octadienol (I).
  • the degree of esterification (or transesterification) achieved there is the possibility that samples prepared at relatively higher temperatures could isomerise to the fumarate and may have relatively higher densities due to some resinification.
  • One ofthe esters in the ester product formed contains an additional alkyleneoxy function in its structure arising from the Michael addition ofthe alcohol reactant across the unsaturated linkage ofthe unsaturated acid or anhydride or ester.
  • the product when octadienol is reacted with dimethyl maleate, the product contains 2-(2,7-octadienoxy) di-(2,7-octadienyl) succinate.
  • reaction mixture may comprise primarily 2-(2,7-octadienoxy) di-(2,7- octadienyl) succinate, di-(2,7-octadienyl) fumarate and di-(2,7-octadienyl) maleate.
  • esters A mixture comprising these esters will hereafter be termed the "ester product".
  • the present invention is a formulation comprising a paint or a polymer and an ester product comprising 2-(2,7-octadienoxy) di-2,7-octadienyl succinate and at least one other ester selected from di-(2,7-octadienyl) fumarate and di-(2,7-octadienyl) maleate, said ester product having a viscosity of less than 200 mPa s (cP).
  • the succinate ester ofthe present invention can function essentially as reactive dilutents when used in paint and polymer formulations. In this context it is not necessary to isolate the individual esters in the mixed ester product formed during the production ofthe succinate ester.
  • the mixed ester product may be used as such, if necessary after separation ofthe catalyst, colour forming impurities, acid and excess alcohol reactant, for use as reactive diluents. Thus, curing ofthe reactive diluent after applying the formulation on a substrate surface is likely to result in the formation of a coating of hardened material.
  • Ester products having low volatility and low viscosity ie less than 200 mPa s (cP), and usually ofthe order of eg 10-80 mPa s (cP), can be produced by the process ofthe present invention.
  • Such properties enable them to be used as reactive diluents for cured paint and polymer formulations, especially for formulations comprising alkyd resins.
  • the low viscosity esters of octadienol are of relatively low colour.
  • films formed from paint formulations containing the low viscosity esters of octadienol as reactive diluents show relatively little yellowing with passage of time.
  • the relative ratios ofthe low viscosity esters used as reactive diluents to the alkyd resin in a formulation can be derived from the ranges quoted in published EP-A-0 305 006.
  • the ratio of reactive diluent to alkyd resin is suitably in the range from 1-50 : 99-50 parts by weight, eg 5-50 : 95-50 parts by weight, preferably from 5-25 : 95-75 and more preferably from 5-15 : 95-85 parts by weight.
  • such a diluent can replace all or part of a traditional solvent such as white spirit.
  • the formulations may contain further components such as catalyst, drier, antiskinning agent, pigments, pigment stabilisers, rheology controllers (e.g. for sag control), UV and oxidation stabilisers, flow additives, microgels (e.g. to enhance hardness) and other additives.
  • the formulations may also need to include water scavengers such as trialkyl orthoformates, molecular sieves or zeolites where the reactive diluent used is susceptible to hydrolysis such as eg some ofthe ester derivatives.
  • water scavengers such as trialkyl orthoformates, molecular sieves or zeolites where the reactive diluent used is susceptible to hydrolysis such as eg some ofthe ester derivatives.
  • impurities which can have a co-ordination affinity for the siccative drier can affect adversely the drying speed and stability ofthe paint.
  • impurities include maleic acid and triethyl amine.
  • a further aspect ofthe present invention is that such esters when used in a relatively pure state do not cause any haze in the formulation.
  • impurities such as eg resins or polymers formed during the synthesis ofthe esters used or during storage of such formulations
  • inhibitors such as eg butylated hydroxy-toluene (2,6-butoxy-4-methyl phenol) and 2,4,6-tert-butyl phenol.
  • Such inhibitors not only have the advantage of preventing haze formation but also render the formulations safer to handle by inhibition of other unwanted reactions in the formulation such as eg peroxidation.
  • Example S 1 Examples of the preparation of the reactive diluents Example S 1 : The following apparatus was assembled: A five-litre flanged flask with an insert pipe for a nitrogen sparge, a thermowell for thermocouple, and a Dean and Stark apparatus with double-walled condenser. The flask was heated with an electric heating mantle which was controlled with a eurotherm controller connected to the thermocouple. The nitrogen sparge pipe was inserted so that the nitrogen flow agitated the flask contents and provided mixing during the course of the reaction. The nitrogen flow also served to entrain out the liberated methanol and force the reaction to completion.
  • the reaction was adjudged complete when the level ofthe "half ester" (methyl octadienyl maleate/fumarate) fell to below 0.3% w/w, this took approximately 8 hours. At this point the heating was switched off and the reaction mixture allowed to cool to room temperature. The product from the reaction was then decanted from any solids in the reaction flask. This product was then charged to a heated decanter (40°C) with an equal volume of 5% w/w aqueous sodium hydroxide solution. The mixture was stirred for 20 minutes and then allowed to separate and the lower aqueous phase decanted. The base wash was then repeated and the remaining organic phase was washed with saturated brine until the aqueous phase reached a steady pH.
  • the "half ester" methyl octadienyl maleate/fumarate
  • the organic phase was then heated (100°C) under reduced pressure ( ⁇ 500 Pa ( ⁇ 5 mBar)) on a rotatory evaporator to remove residual water and the majority ofthe excess octadienol.
  • the product was filtered and transferred to a 5-litre three necked round bottomed quickfit flask .
  • This flask was equipped with a still head condenser and receiver flask (Perkin triangle), a thermocouple, a steam inlet pipe, and a eurotherm controlled heating mantle.
  • the apparatus was evacuated to 4000 Pa (40 mBar) and the product heated to 120°C. The supply of steam was then connected and the residual traces of octadienol were removed.
  • the GC/MS used a VG Trio- 1000, operated according to the manufacturers instructions under the following conditions: - GC column 25mx0.32mm DB5 (0.25 micron film) temperature programme 40°C (3 mins) @ 10°C/min to 320°C(10mins) injection 1 microlitre (1% solution in acetone) on column 40°C ammonia chemical ionisation (CI) - scan range 50-800 scan rate 1/s It was found that the deduction of molecular weights from the CI spectra is rather less straightforward than is usual on account of (a) extensive rearrangements of
  • a five-litre flanged flask with an insert pipe for a nitrogen sparge, a thermowell for thermocouple, and a Dean and Stark apparatus with double-walled condenser was heated with an electric heating mantle which was controlled with a eurotherm controller connected to the thermocouple.
  • the nitrogen sparge pipe was inserted so that the nitrogen flow agitated the flask contents and provided mixing during the course ofthe reaction. The nitrogen flow also served to entrain out the liberated methanol and force the reaction to completion.
  • the reaction was adjudged complete, when the level ofthe "half ester" (methyl octadienyl maleate/fumarate) fell to below 0.3% w/w and this took approximately 72 hours. At this point the heating was switched off and the reaction mixture allowed to cool to room temperature. The product from the reaction was then decanted from any solids in the reaction flask. This product was then charged to a heated decanter (40°C) with an equal volume of 5% w/w aqueous sodium hydroxide solution. The mixture was stirred for 20 minutes and then allowed to separate and the lower aqueous phase decanted. This base wash was then repeated and the remaining organic phase was washed with saturated brine until the aqueous phase reached a steady pH.
  • a heated decanter 40°C
  • the organic phase was then heated (100°C) under reduced pressure ( ⁇ 500 Pa ( ⁇ 5 mBar)) on a rotatory evaporator to remove residual water and the majority ofthe excess octadienol.
  • the product was filtered and transferred to a 5 -litre three-necked round-bottomed quickfit flask .
  • This flask was equipped with a still head condenser and receiver flask (Perkin triangle), a thermocouple, a steam inlet pipe, and a eurotherm controlled heating mantle.
  • the apparatus was evacuated to 4000 Pa (40 mBar) and the product heated to 120°C. The supply of steam was then connected and the residual traces of octadienol were removed.
  • the GC assignment was supported by GC/MS and a H nmr and C nmr studies.
  • the GC/MS used a VG Trio- 1000, operated according to the manufacturers instructions under the following conditions:
  • the following apparatus was assembled: A five-litre flanged flask with an insert pipe for a nitrogen sparge, a thermowell for thermocouple, and a Dean and Stark apparatus with double-walled condenser.
  • the flask was heated with an electric heating mantle which was controlled with a eurotherm controller connected to the thermocouple.
  • the nitrogen sparge pipe was inserted so that the nitrogen flow agitated the flask contents and provided mixing during the course of the reaction. The nitrogen flow also served to entrain out the liberated methanol and force the reaction to completion.
  • the reaction was adjudged complete when the level ofthe "half ester" (methyl octadienyl maleate/fumarate) fell to below 0.3% w/w and this took approximately 31 hours. At this point the heating was switched off and the reaction mixture allowed to cool to room temperature. The product from the reaction was then decanted from any solids in the reaction flask. This product was then charged to a heated decanter (40°C) with an equal volume of 5% w/w aqueous sodium hydroxide solution. The mixture was stirred for 20 minutes and then allowed to separate and the lower aqueous phase decanted. This base wash was repeated and the remaining organic phase was washed with saturated brine until the aqueous phase reached a steady pH.
  • the "half ester" methyl octadienyl maleate/fumarate
  • the organic phase was then heated (100°C) under reduced pressure ( ⁇ 500 Pa ( ⁇ 5 mBar)) on a rotatory evaporator to remove residual water and the majority ofthe excess octadienol.
  • the product was filtered and transferred to a 5-litre three-necked round-bottomed quickfit flask .
  • This flask was equipped with a still-head condenser and reciever flask (Perkin triangle), a thermocouple, a steam inlet pipe, and a eurotherm controlled heating mantle.
  • the apparatus was evacuated to 4000 Pa (40 mBar) and the product heated to 120°C. The supply of steam was then connected and the residual traces of octadienol were removed.
  • the GC/MS used a VG Trio- 1000, operated according to the manufacturers instructions under the following conditions: - GC column 25mx0.32mm DB5 (0.25 micron film) temperature programme 40°C (3 mins) @ lOC/min to 320°C(10mins) injection 1 microlitre (1% solution in acetone) on column 40°C - ammonia chemical ionisation (CI) scan range 50-800 scan rate 1/s It was found that the deduction of molecular weights from the CI spectra is rather less straightforward than is usual on account of (a) extensive rearrangements of fumarates
  • Example S4 The process of Example S l was repeated to give a product with the following analysis: OH number - ⁇ 1 mg KOH/g (titration) total acid - 91 ppm KOH/g (titration) maleic acid / anhydride - ⁇ lOppm (HPLC)
  • Zinc - ⁇ 5ppm (atomic abso ⁇ tion, detection limit) sodium - ⁇ 20ppm ( atomic abso ⁇ tion) chlorine - ⁇ 1 Oppm (atomic abso ⁇ tion detection limit)
  • Lactones Species believed to be lactones have been identified in the octadienyl ester samples. Whilst there appear to be two possible ⁇ isomers of this lactone, the C NMR data fits the following structure:
  • the viscosity of each diluent was measured at 25°C using a suspended level viscometer. Densities ofthe diluents were taken as an average of three readings made at 25°C using density bottles with a nominal 10 cm- capacity, calibrated with water.
  • Table 2 demonstrates that the esters / reactive diluents of this invention have relatively low viscosity ( ⁇ 200 mPa.s) and are suitable for use as reactive diluents.
  • Reactive diluents such as those ofthe present invention, must meet a range of criteria including low odour and low toxicity, low viscosity and the ability to "cut" the viscosity ofthe paint to facilitate application on the surface to be coated therewith. Furthermore, the diluent should not have a markedly adverse effect on the properties ofthe paint film such as drying speed, hardness and degree of wrinkling.
  • the reactive diluents described above have therefore been tested in paint applications using both clear and pigmented paints. The diluents have been compared with paints formulated using white spirit, a conventional thinner. The results demonstrate the excellent performance ofthe diluents of this invention.
  • % reactive diluent refers to the ratio of reactive diluent to alkyd (e.g. 30% reactive diluent implies 30g diluent to every 70g alkyd).
  • ⁇ ) Pigmented paint formulations based on a high solids alkyd resin High solids alkyd reference with white spirit diluent In a mini motor mill 534 grams of a high solids alkyd (Setal® 293, ex. Akzo Nobel Resins) and 423 grams of titanium dioxide (Kronos® 2310, ex. Kronos) were milled. Thereafter 40 grams of a combi siccative (Nuodex Combi® APB, ex.
  • K ⁇ nie hardness (ISO 1522) was measured at 23°C, 50% RH (s) of a coating film applied with a 100 ⁇ m applicator on a glass substrate.
  • the Fischer spherical indention test is based on ISO6441 (um) and was performed on a coating film applied with a 100 ⁇ m applicator on a glass substrate.
  • Paints containing 30% reactive diluent were prepared from the diluents AK1, AK2, AK2R.
  • Tables 8 and 9 summarise the drying and hardness test data from the pigmented paint formulations based on conventional alkyd resins.
  • the drying data in Table 8 show that the paints based on the reactive diluents of this invention dry in a period acceptable to the industry, even after storage at 35°C for two weeks. Furthermore, the hardness ofthe paint films is excellent.
  • Unpigmented (“clearcoat”) paint formulations were prepared using the high solids alkyd resin SETAL® 293 described above in Section 3. l(a)(i). In addition to the diluent, Siccatol® 938 drier (ex AKZO NOBEL) and methyl ethyl ketone-oxime (hereafter "MEK-oxime”) anti-skinning agent were used. Where used, the white spirit was Exxon type 100. The nominal proportions of the above materials in the paint formulations were:
  • Viscositv The viscosity of each formulation was measured according to BS 3900 Part A7 with an ICI cone and plate viscometer (supplied by Research Equipment (London) Limited) at 23°C and at a shear rate of 10,000 reciprocal seconds.
  • Drying performance was measured using films applied to 30 cm x 2.5 cm glass strips and BK drying recorders.
  • the BK recorders were enclosed in a Fisons controlled temperature and humidity cabinet so that the drying experiment could be performed at 10°C and at 70% relative humidity.
  • Sample performance was assessed on the basis ofthe dust drying time, T2.
  • Incorportion of the diluent into the paint film An indication that the reactive diluent is incorporated into the paint film during the "cure", rather than undergoing evaporation, was obtained by monitoring the weight ofthe paint film following application. Weight measurements were done on a coating film applied with a 150 ⁇ m applicator on a glass substrate at
  • Weight measurements of two coated films are summarised in Table 13, and show that the diluent remains in the paint film, rather than evaporating.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Cette invention concerne un 2-(2,7-octadiénoxy) di(2,7-octadiényle) succinate, ainsi qu'un procédé de préparation de l'ester de succinate, lequel consiste à faire réagir, en présence d'un catalyseur, un composé de la formule (I) CH2=CH.CH2.CH2.CH2.CH=CH.CH2.OR avec un composé dicarboxylique de la formule (II) R'.C(O).CH=CH.C(O).R', où R représente H ou un groupe acyle possédant 1 à 6 atomes de carbone, R' et R' peuvent représenter OH ou le même groupe alcoxyle C1-C10 ou un groupe différent, ou bien, R' et R' peuvent être tels que la combinaison des deux représente une fonction -O-, produisant ainsi (II) un anhydride d'acide. L'invention concerne l'utilisation de tels esters en tant que diluants réactifs dans des formulations de polymères ou de peintures.
PCT/GB1996/001570 1995-06-30 1996-06-28 Diluants reactifs Ceased WO1997002230A1 (fr)

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AU63110/96A AU6311096A (en) 1995-06-30 1996-06-28 Reactive diluents

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GBGB9513317.9A GB9513317D0 (en) 1995-06-30 1995-06-30 Reactive diluents
GB9513317.9 1995-06-30

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998000387A1 (fr) * 1996-06-28 1998-01-08 Bp Chemicals Limited Melanges d'esters et leur utilisation
WO1998000388A1 (fr) * 1996-06-28 1998-01-08 Bp Chemicals Limited Esters de succinate 2-substitues
WO1999010336A1 (fr) * 1997-08-22 1999-03-04 Bayer Aktiengesellschaft 2-(1,4-dioxanne-2-one-3-yle)-ester d'acide acetique
WO2004099329A1 (fr) * 2003-05-08 2004-11-18 The University Of Southern Mississippi Research Foundation Diluants reactifs en formulation d'enrobage
US8124688B2 (en) 2006-03-30 2012-02-28 Akzo Novel Coatings International B.V. Coating composition comprising a reactive diluent of malonate
US8829151B2 (en) 2006-03-30 2014-09-09 Akzo Nobel Coatings International B.V. Coating composition comprising a reactive diluent of polyunsaturated alcohol ester
US12054630B2 (en) 2019-02-14 2024-08-06 The University Of Akron Modified cardanol as the reactive diluents for alkyd coating

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JPH0746568A (ja) * 1993-07-29 1995-02-14 Canon Inc 情報処理装置

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JPH0746568A (ja) * 1993-07-29 1995-02-14 Canon Inc 情報処理装置

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DATABASE WPI Week 7305, Derwent World Patents Index; AN 73-06275u, XP002012596, "octadienyl esters prodn-giving thermoplastic,transparent,heat and chemicals-resistant polymsn products" *

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998000387A1 (fr) * 1996-06-28 1998-01-08 Bp Chemicals Limited Melanges d'esters et leur utilisation
WO1998000388A1 (fr) * 1996-06-28 1998-01-08 Bp Chemicals Limited Esters de succinate 2-substitues
US6103801A (en) * 1996-06-28 2000-08-15 Bp Chemicals Limited 2-substituted succinate esters
US6130275A (en) * 1996-06-28 2000-10-10 Bp Chemicals Limited Mixture of esters and use thereof
WO1999010336A1 (fr) * 1997-08-22 1999-03-04 Bayer Aktiengesellschaft 2-(1,4-dioxanne-2-one-3-yle)-ester d'acide acetique
WO2004099329A1 (fr) * 2003-05-08 2004-11-18 The University Of Southern Mississippi Research Foundation Diluants reactifs en formulation d'enrobage
JP2006525402A (ja) * 2003-05-08 2006-11-09 ザ ユニバーシティ オブ サザン ミシシッピ リサーチ ファンデーション 塗料配合物中の反応性希釈剤
US8124688B2 (en) 2006-03-30 2012-02-28 Akzo Novel Coatings International B.V. Coating composition comprising a reactive diluent of malonate
US8829151B2 (en) 2006-03-30 2014-09-09 Akzo Nobel Coatings International B.V. Coating composition comprising a reactive diluent of polyunsaturated alcohol ester
US12054630B2 (en) 2019-02-14 2024-08-06 The University Of Akron Modified cardanol as the reactive diluents for alkyd coating

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GB9513317D0 (en) 1995-09-06
AU6310996A (en) 1997-02-05
WO1997002326A1 (fr) 1997-01-23
AU6311096A (en) 1997-02-05

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