WO2013075806A2

WO2013075806A2 - Epoxy compositions

Info

Publication number: WO2013075806A2
Application number: PCT/EP2012/004768
Authority: WO
Inventors: Denis Heymans; Christophe Steinbrecher; Cédric Le Fevere de Ten Hove
Original assignee: Momentive Specialty Chemicals Research Beigium Sa; Momentive Specialty Chemicals Inc.
Priority date: 2011-11-25
Filing date: 2012-11-15
Publication date: 2013-05-30
Also published as: WO2013075806A3; WO2013075806A8

Abstract

The invention relates to epoxy compositions comprising a mixture of α,α-branched alkane carboxylic glycidyl esters derived from butene oligomers characterized in that the sum of the concentration of the blocked and of the highly branched isomers is at least 50%, preferably above 60% and most preferably above 75% on total composition.

Description

EPOXY COMPOSITIONS

The invention relates to epoxy resin curable compositions more particularly to epoxy curable compositions, comprisi resins to be cured with curing agent in the presence of a reactive diluent, and which are intended for the

impregnation of fibers applicable to the manufacturing of composite structures, laminates, coatings, flooring and putties applications. The reactive diluent is comprising a mixture of , - branched alkane carboxylic glycidyl esters derived from butene oligomers , the presence of which can lead for example to improved hardness. More in particular the invention relates to epoxy resin curable compositions comprising aliphatic tertiary saturated carboxylic acids or α, -branched alkane carboxylic acids, which contain 9 or 13 carbon atoms and which provide glycidyl esters with a branching level of the alkyl groups depending on the olefin feedstock used and/or the oligomerisation process therof, and which is defined as below .

It is generally known from e.g. US 2,831,877, US 2,876,241, US 3,053,869, US 2,967,873 and US 3,061,621 that mixtures of α,α-branched alkane carboxylic acids can be produced, starting from mono-olefins , such as butenes and isomers such as isobutene, carbon monoxide and water, in the presence of a strong acid. The glycidyl esters can be obtained according PCT/EP2010/003334 or the US6433217.

We have discovered that well chosen blend of isomers of the glycidyl ester of, for example, neononanoic acids give different and unexpected performance in combination with some particular resins such as epoxy resins.

The isomers are described in Table 1 and illustrated in Scheme 1.

We have found that the performance of the glycidyl ester compositions derived from the branched acid is depending on the branching level of the alkyl groups R¹, R² and R³, for example the neononanoic acid has 3, 4 or 5 methyl groups.

Highly branched isomers are defined as isomers of neo-acids having at least 5 methyl groups.

Neo-acids, for example neononanoic acids (V9) with secondary or a tertiary carbon atoms in the β position defined as blocking isomers.

Mixture compositions of neononanoic acids glycidyl esters of the present invention providing for example a high hardness of the cured matrix, is a mixture where the sum of the concentration of the blocked and of the highly branched isomers is at least 50%, preferably above 60% and most preferably above 75% on total composition. The composition of the glycidyl ester mixture is comprising

2,2-dimethyl 3,3-dimethyl pentanoic acid glycidyl ester or 2-methyl 2-isopropyl 3-methyl butanoic acid glycidyl ester or 2-methyl 2-ethyl 3,3-dimethyl butanoic acid glycidyl ester . The composition of the glycidyl ester mixture is comprising 2,2-dimethyl 3-methyl 4-methyl pentanoic acid glycidyl ester and 2,2-dimethyl 4,4-dimethyl pentanoic acid glycidyl ester .

The composition of the glycidyl ester mixture in which the sum of the following content of glycidyl ester mixture, comprising 2,2-dimethyl 3,3-dimethyl pentanoic acid glycidyl ester and 2-methyl 2-isopropyl 3-methyl butanoic acid glycidyl ester and 2-methyl 2-ethyl 3,3-dimethyl butanoic acid glycidyl ester, is above 10% weight, preferably above 15% weight and most preferably above 25% weight on total composition. The composition of the glycidyl ester mixture in which the sum of the following content of glycidyl ester mixture, comprising 2,2-dimethyl 3,3-dimethyl pentanoic acid glycidyl ester and 2— ethyl 2—isopropyl 3— ethyl butanoic acid glycidyl ester and 2-methyl 2-ethyl 3,3-dimethyl butanoic acid glycidyl ester and 2,2-dimethyl 3-methyl 4- methyl pentanoic acid glycidyl ester and 2,2-dimethyl 4,4- dimethyl pentanoic acid glycidyl ester, is above 40% weight, preferably above 50% weight and most preferably above 60% weight on total composition.

The composition of the glycidyl ester mixture in which the content of 2-methyl 2-ethyl hexanoic acid glycidyl ester is below 40% weight, preferably below 30% weight and most preferably below 20% weight on total composition.

The composition of the glycidyl ester mixture in which the glycidyl ester mixture is comprising 2,2-dimethyl 3,3- dimethyl pentanoic acid glycidyl ester in 1 to 99 weight% or 2-methyl 2-isopropyl 3-methyl butanoic acid glycidyl ester in 1 to 99 weight% or 2-methyl 2-ethyl 3,3-dimethyl butanoic acid glycidyl ester in 1 to 99 weight% on total composition .

A preferred composition of the glycidyl ester mixture in which the glycidyl ester mixture is comprising 2,2-dimethyl 3,3-dimethyl pentanoic acid glycidyl ester in 2 to 50 weight% or 2-methyl 2-isopropyl 3-methyl butanoic acid glycidyl ester in 5 to 50 weight% or 2-methyl 2-ethyl 3,3- dimethyl butanoic acid glycidyl ester in 3 to 60 weight% on total composition.

A further preferred composition of the glycidyl ester mixture in which the glycidyl ester mixture is comprising

2.2-dimethyl 3,3-dimethyl pentanoic acid glycidyl ester in 3 to 40 weight% or 2-methyl 2-isopropyl 3-methyl butanoic acid glycidyl ester in 10 to 35 weight% or 2-methyl 2-ethyl

3.3-dimethyl butanoic acid glycidyl ester in 5 to 40 weight% on total composition.

The composition of the glycidyl ester mixture in which the glycidyl ester mixture is comprising 2,2-dimethyl 3-methyl 4-methyl pentanoic acid glycidyl ester in 1 to 99 weight% or 2,2-dimethyl 4,4-dimethyl pentanoic acid glycidyl ester in 0.1 to 99 weight%.

A preferred composition of the glycidyl ester mixture in which the glycidyl ester mixture is comprising 2,2-dimethyl 3-methyl 4-methyl pentanoic acid glycidyl ester in 2 to 50 weight% or 2,2-dimethyl 4,4-dimethyl pentanoic acid glycidyl ester in 0.1 to 80 weight%.

A further preferred composition of the glycidyl ester mixture in which the glycidyl ester mixture is comprising 2,2-dimethyl 3-methyl 4-methyl pentanoic acid glycidyl ester in 4 to 25 weight% or 2 , 2-dimethyl 4 , 4-dimethyl pentanoic acid glycidyl ester in 0.2 to 45 weight% .

The above glycidyl esters compositions can be used for example, as reactive diluent in formulations comprising epoxy resins such as EPIKOTE 828. The curing agents can be amines, anhydrides or acids, like diethylenetriamine, nadic methyl anhydride or cyclohexanedicarboxylic acid, respectively .

The glycidyl esters compositions can be used as reactive diluent for epoxy based formulations such as examplified in the technical brochure of Momentive (Product Bulletin: Cardura E10P The Unique Reactive Diluent MSC-521) or in the Shell Chemical Bulletin (Bulletin / starting formulation (EPIKOTE epoxy resins) : EPIKOTE 816MV / EPI-CURE F205 based trowellable floor and patching compound; EK 5.2.1.6 Issued March 2001) .

Methods used

The isomer distribution of neo-acid can be determined using gas chromatography, using a flame ionization detector (FID). 0.5 ml sample is diluted in analytical grade dichloromethane and n-octanol may be used as internal standard. The conditions presented below result in the approximate retention times given in table 1. In that case n-octanol has a retention time of approximately 8.21 minute .

The GC method has the following settings:

Column: CP Wax 58 CB (FFAP) , 50 m x 0.25 mm, df = 0.2 m Oven program: 150°C (1.5 min) - 3.5°C/min - 250°C (5 min) - 35 min

Carrier gas : Helium Flow : 2.0 mL/min constant

Split flow : 150 mL/min

Split ratio: 1:75

Injector temp 250°C

Detector temp 325°C

Injection volume 1 L

CP Wax 58 CB is a Gas chromatography column available from Agilent Technologies.

The isomers of neononanoic acid as illustrative example have the structure (R¹ R² R³) -C-COOH where the three R groups are linear or branched alkyl groups having together a total of 7 carbon atoms .

The structures and the retention time, using the above method, of all theoretical possible neononanoic isomers are drawn in Scheme 1 and listed in Table 1.

The isomers content is calculated from the relative peak area of the chromatogram obtained assuming that the response factors of all isomers are the same.

Retention

Methyl time

Rl R2 R3 groups Blocking [Minutes]

V901 Methyl Methyl n-pentyl 3 No 8.90

V902 Methyl Methyl 2-pentyl 4 Yes 9.18

V903 Methyl Methyl 2-methyl butyl 4 No 8.6

V904 Methyl Methyl 3-methyl butyl 4 No 8.08

1 , 1-dimethyl

V905 Methyl Methyl propyl 5 Yes 10.21

1 , 2-dimethy

V906 Methyl Methyl propyl 5 Yes 9.57

2, 2-dimethyl

V907 Methyl Methyl propyl 5 No 8.26

V908 Methyl Methyl 3-pentyl 4 Yes 9.45

V909 Methyl Ethyl n-butyl 3 No 9.28

V910 Kl Methyl Ethyl s-butyl 4 Yes 9.74

V910 K2 Methyl Ethyl s-butyl 4 Yes 9.84

V911 Methyl Ethyl i-butyl 4 No 8.71

V912 Methyl Ethyl t-butyl 5 Yes 9.64

V913 Methyl n-propyl n-propyl 3 No 8.96

V914 Methyl n-propyl i-propyl 4 Yes 9.30

V915 Methyl i-propyl i-propyl 5 Yes 9.74

V916 Ethyl Ethyl n-propyl 3 No 9.44

V917 Ethyl Ethyl i-propyl 4 Yes 10.00

Table 1: Structure of all possible neononanoic isomers

The isomer distribution of glycidyl esters of neo-acid can be determined by gas chromatography, using a flame ionization detector (FID). 0.5 ml sample is diluted in analytical grade dichloromethane .

The GC method has the following settings:

Column: CP Wax 58 CB (FFAP), 50 m x 0.2 mm, df = 0.52 μπι

Oven : 175°C (5 min)- l°C/min - 190°C (0 min) - 10°C/min - 275°C (11.5 min)

Flow : 2.0 mL/min, constant flow

Carrier gas: Helium

Split ratio: 1:75

Injection volume:! L

S/SL injector: 250°C CP Wax 58 CB is a Gas chromatography column available from Agilent Technologies.

The isomers of glycidyl esters of neononanoic acid as

illustrative example have the structure (R¹ R² R³) -C-COO-CH₂- CH(0)CH2 where the three R groups are linear or branched alkyl groups having together a total of 7 carbon atoms.

GC-MS method can be used to identify the various isomers providing that the analysis is done by a skilled analytical expert .

Test methods

REACTIVITY OF THE FORMULATION Procedure for the determination of the gelation time of blends of epoxy resin and curing agent.

Gelation time: the time in minutes required for a mixture of resin and curing agent, maintained at a fixed temperature, to reach the stage in the process of hardening at which the resistance to the movement of a slowly reciprocating plunger immersed in the mixture reaches a specific value.

Method summary: Heat the individual components to such a temperature that, after mixing, the final temperature of the mixture will be 0 to 2°C below the test temperature. A 150 g mixture is prepared in a tin. A lOOg of the mixture is poured into the aluminum container. The plunger of the gel timer is moved up and down in the resin system. The time elapsed between the end of the mixing step (after 2 min mixing, the time = 0) , and the switching off of the gel timer is recorded.

Apparatus: Gel timer, according to BS 2782: Part 8, Method 835C, with disposable glass disk plungers. (Tecam Gel Timer, model GT3) . Aluminum container: ID 40 to 47 mm, depth not less than 75 mm and wall thickness 0.35 to 0.51 mm.

VISCOSITY Dynamic Viscosity of the mixture (resin + curing agent) in mPa.s, is measured according to ASTM D 2393. The temperature is 25°C. The apparatus used is a Brookfield DVII, with a spindle LV II (for low viscosities) . FIBRE WETTING

Procedure for the determination of the fiber wetting behavior of blends of epoxy resin and curing agent.

Wetting time: the time in minutes, needed for 2 grams of the mixture to penetrate a glass fiber mat, until the surface goes from a glossy to a matt appearance (the mixture is absorbed by the glass mat) .

Spot size: diameter of the spot in mm, after curing at 25°C of the 2 grams of the mixture.

Glass mat: a chopped strand mat of size-coated chopped strands, with a thickness of 450 g/m².

CHEMICAL RESISTANCE

Procedure for the determination of chemical resistance of castings to different test media by immersion.

Preparation of the test pieces: Test specimens of the dimensions (80X10X4) mm were cut from the casting sheets by a diamond saw. Moulds used for the castings consisted of 2 steel plates with a 4 mm frame in between. The castings were cured in the mould.

Resistance test: The relative rate of absorption of the immersed test pieces was measured according to ASTM D570-98 Standard Test Method. The test media were demineralized water, toluene and aqueous HC1 10%. Blocking isomers

Whereas the carbon atom in alpha position of the carboxylic acid is always a tertiary carbon atom, the carbon atom(s) in position can either be primary, secondary or tertiary.

Neononanoic acids (V9) with a secondary or a tertiary carbon atoms in the β position are defined as blocking (blocked) isomers (Schemes 2 and 3) .

Scheme 2 Scheme 3

Scheme 2: Example of a Non-blocked V9 Structure

Scheme 3: Example of a Blocked V9 Structure The use of the glycidyl esters compositions, discussed here above, can be as reactive diluent for epoxy curable compositions .

The epoxy curable compositions of the invention are based on a composition comprising a mixture of α,α-branched alkane carboxylic glycidyl esters derived from butene oligomers characterized in that the sum of the concentration of the blocked and of the highly branched isomers is at least 50%, preferably above 60% and most preferably above 75% on total composition .

A prefer composition is that the glycidyl ester mixture is based on neononanoic (C9) acid mixture where the sum of the concentration of the blocked and of the highly branched isomers is at least 50%, preferably above 60% and most preferably above 75% on total composition.

Further the neononanoic (C9) glycidyl ester mixture is comprising 2,2-dimethyl 3,3-dimethyl pentanoic acid glycidyl ester or 2-methyl 2-isopropyl 3-methyl butanoic acid glycidyl ester or 2-methyl 2-ethyl 3,3-dimethyl butanoic acid glycidyl ester .

An other embodiment is that the composition of the glycidyl ester mixture is comprising 2,2-dimethyl 3-methyl 4-methyl pentanoic acid glycidyl ester or 2,2-dimethyl 4,4-dimethyl pentanoic acid glycidyl ester.

A further embodiment is that the composition of the glycidyl ester mixture is comprising the sum of the following content of glycidyl ester mixture, comprising 2,2-dimethyl 3,3-dimethyl pentanoic acid glycidyl ester and 2-methyl 2-isopropyl 3-methyl butanoic acid glycidyl ester and 2-methyl 2-ethyl 3,3-dimethyl butanoic acid glycidyl ester, is above 10% weight, preferably above 15% weight and most preferably above 25% weight on total composition .

A further embodiment is that the composition of the glycidyl ester mixture is comprising the sum of the following content of glycidyl ester mixture, comprising 2,2-dimethyl 3,3-dimethyl pentanoic acid glycidyl ester and 2-methyl 2-isopropyl 3-methyl butanoic acid glycidyl ester and 2-methyl 2-ethyl 3,3-dimethyl butanoic acid glycidyl ester and 2,2-dimethyl 3-methyl 4-methyl pentanoic acid glycidyl ester and 2,2-dimethyl 4,4-dimethyl pentanoic acid glycidyl ester, is above 40% weight, preferably above 50% weight and most preferably above 60% weight on total composition .

A further embodiment is that the composition of the glycidyl ester mixture is comprising 2-methyl 2-ethyl hexanoic acid glycidyl ester is below 40% weight, preferably below 30% weight and most preferably below 20% weight on total composition. A further embodiment is that the composition of the glycidyl ester mixture is comprising 2,2-dimethyl 3, 3-dimethyl pentanoic acid glycidyl ester in 1 to 99 weight% or 2-methyl 2-isopropyl 3-methyl butanoic acid glycidyl ester in 1 to 99 weight% or 2- methyl 2-ethyl 3, 3-dimethyl butanoic acid glycidyl ester in 1 to 99 weight% on total composition and a prefer is in that the glycidyl ester mixture is comprising 2,2-dimethyl 3, 3-dimethyl pentanoic acid glycidyl ester in 2 to 50 weight% or 2-methyl 2-isopropyl 3-methyl butanoic acid glycidyl ester in 5 to 50 weight% or 2-methyl 2-ethyl 3, 3-dimethyl butanoic acid glycidyl ester in 3 to 60 weight% on total composition, and a most prefer composition is that the glycidyl ester mixture is comprising 2,2-dimethyl 3, 3-dimethyl pentanoic acid glycidyl ester in 3 to 40 weight% or 2-methyl 2-isopropyl 3-methyl butanoic acid glycidyl ester in 10 to 35 weight% or 2-methyl 2- ethyl 3, 3-dimethyl butanoic acid glycidyl ester in 5 to 40 weight% on total composition.

A further embodiment is that the composition of the glycidyl ester mixture is comprising 2,2-dimethyl 3-methyl 4-methyl pentanoic acid glycidyl ester in 1 to 99 weight% or 2,2- dimethyl 4,4-dimethyl pentanoic acid glycidyl ester in 0.1 to 99 weight%, a prefer composition is that the glycidyl ester mixture is comprising 2,2-dimethyl 3-methyl 4-methyl pentanoic acid glycidyl ester in 2 to 50 weight% or 2,2-dimethyl 4,4- dimethyl pentanoic acid glycidyl ester in 0.1 to 80 weight%, and a most prefer composition is that the glycidyl ester mixture is comprising 2,2-dimethyl 3-methyl 4-methyl pentanoic acid glycidyl ester in 4 to 25 weight% or 2,2-dimethyl 4,4- dimethyl pentanoic acid glycidyl ester in 0.2 to 45 weight%. The invention is also about the process to prepare the epoxy resin curable compositions, which are obtained by the incorporation of the mixture of α,α-branched alkane carboxylic glycidyl esters, as characterized above, into a mixture comprising epoxy resins and curing agents. Above mentioned resins can be for instance aromatic or aliphatic halogenated or not halogenated glycidyl ether resins. Commercially available halogenated resins are for example EPON 1163, EPIKOTE 5123, EPIKOTE 5119 and EPIKOTE 5112 (EPON/EPIKOTE are Resolution Performance Products Trademarks) or any other glycidyl ether of tetra-bromo-Bis-Phenol derivatives which contains more than 10 weight% of brome on resinous material. Examples of non halogenated epoxy resins are the diglycidyl ether of Bisphenol A, and/or Bisphenol F and/or polyglycidyl ethers of phenol/cresol-formaldehyde novolacs, and the like. Commercial examples of such resins are: EPIKOTE 828, EPIKOTE 834, EPIKOTE 1001, EPIKOTE 1002, EPIKOTE 154, EPIKOTE 164.

Amines, anhydrides and acids can be used as curing agent (hardener) .

Above mentioned amines can be for instance an an aliphatic amine such as diethylenetriamine (DETA) , triethylenetetramine (TETA) , teraethylenepentamine (TEPA) , isophorone diamine (IPD), para-aminocyclohexane methylene (PACM), diamino cyclohexane (DCH) , meta-Xylene diamine (mXDA) , , 4¹ -Diamino 3 , 3¹ -dimethyl diCyclohexyl methane (DDCM) and adducts of aliphatic amines such as based on DETA, TETA, TEPA, IPD, PACM, DCH, mXDA, DDCM and the like; or aromatic amine such as MDA.

Above mentioned anhydrides that could be used as hardener can be for instance cycloaliphatic anhydride. Curable compositions disclosed herein may include one or more cycloaliphatic anhydride hardeners. Cycloaliphatic anhydride hardeners may include, for example, nadic methyl anhydride, hexahydrophthalic anhydride, trimellitic anhydride, dodecenyl succinic anhydride, phthalic anhydride, methyl hexahydrophthalic anhydride, tetrahydrophthalic anhydride, and methyl tetrahydrophthalic anhydride, among others. Anhydride curing agents may also include copolymers of styrene and maleic acid anhydrides and other anhydrides as described in US 6,613,839. Hardener that can be used for curable compositions disclosed herein also include acids for instance derived from any above mentioned anhydride .

The invention is also related to a epoxy resin curable compositions useful for the impregnation of fibers applicable to the manufacturing of composite structures, laminates, coatings, flooring and putties applications comprising at least a mixture of α,α-branched alkane carboxylic glycidyl esters described above.

According to another embodiment of the present invention, therein before specified composition can be used in flooring applications where high chemical resistance is required.

According to still another aspect of the present invention, said above composition is that it could be used in making composite material with glass, carbon or natural fiber by the technology known in the art.

Examples

Chemicals used

Cardura™ E10: available from Momentive Specialty Chemicals Neononanoic glycidyl ester from Momentive Specialty

Chemicals

GE9S: neononanoic glycidyl ester of composition A (see Table 2)

GE9H: neononanoic glycidyl ester of composition B (see Table 2)

- Neononanoic glycidyl ester of composition C (see Table 2) Neononanoic glycidyl ester of composition D (see Table 2) Neononanoic glycidyl ester of composition E (see Table 2) Glycidyl

ester of

acid V9XX A (%) B (%) c ( % ) D (%) E (%) (described

in Table 1)

V901 6.5 0.1 3.7 0.1 0.1

V902 0.6 2.55 0.6 2.4 2.65

V903 1.1 0.7 0.3 1.0 0.4

V904 0.8 1 0.1 2.2 0.4

V905 0.2 13.1 0.5 4.1 14.5

V906 0.4 11.6 0.4 9.6 12.6

V907 0.2 15.4 0.1 36.4 5.6

V908 0.1 0 0.1 0.0 0.0

V909 54.8 2.55 52.8 2.4 2.65

V910 Kl 7.8 0 10.0 0.0 0.0

V910 K2 7.7 0.6 12.8 0.4 0.7

V911 2.4 1.2 0.7 2.0 0.8

V912 0.0 28.3 0.0 22.4 33.5

V913 6.8 0.1 6.4 0.1 0.1

V914 4.5 0 3.8 0.0 0.0

V915 0.6 22.3 0.6 16.8 25.3

V916 4.4 0.1 5.2 0.1 0.1

V917 1.1 0.4 2.1 0.1 0.4

Table 2: Composition of the neononanoic glycidyl ester (according to the described gas chromatography method for glycidyl esters of neo-acid) GE5: glycidyl ester of pivalic acid obtained by reaction of the acid with epichlorhydrin .

Ethylene glycol from Aldrich

- Monopentaerythritol : available from Sigma - Aldrich

3,3,5 Trimethyl cyclohexanol : available from Sigma Aldrich

Maleic anhydride : available from Sigma - Aldrich

- Methylhexahydrophtalic anhydride: available from Sigma Aldrich

Hexahydrophtalic anhydride: available from Sigma - Aldrich

- Boron trifluoride diethyl etherate (BF3-OEt2) from Aldrich

- Acrylic acid : available from Sigma - Aldrich

- Methacrylic acid : available from Sigma - Aldrich

- Hydroxyethyl methacrylate : available from Sigma - Aldrich

Styrene : available from Sigma - Aldrich

2-Ethylhexyl acrylate : available from Sigma - Aldrich

- Methyl methacrylate : available from Sigma - Aldrich

Butyl acrylate : available from Sigma - Aldrich

- Di-t-Amyl Peroxide is Luperox DTA from Arkema

tert-Butyl peroxy-3 , 5 , 5-trimethylhexanoate : available from Akzo Nobel

Xylene

n-Butyl Acetate from Aldrich - Dichloromethane from Biosolve

- Thinner: A: is a mixture of Xylene 50wt%, Toluene 30wt%, ShellsolA 10wt%, 2-Ethoxyethylacetate 10wt%. Thinner B: is butyl acetate

Curing agents, HDI : 1 , 6-hexamethylene diisocyanate trimer, Desmodur N3390 BA from Bayer Material Science or Tolonate

HDT LV2 from Perstorp - Leveling agent: "BYK 10 wt%' which is BYK-331 diluted at 10% in butyl acetate

- Catalyst: ^λ DBTDL 1 wt%' which is Dibutyl Tin Dilaurate diluted at lwt% in butyl acetate

- Catalyst: 'DBTDL 10 wt%' which is Dibutyl Tin Dilaurate diluted at 10wt% in butyl acetate.

Example 01

Preparation for Vacuum infusion of composite structures A resin for vacuum infusion of large structures such as yacht and wind turbines was prepared by mixing 27.7 part by weight of curing agent blend and 100 part of epoxy resins blend described here :

Epoxy resins blend: 850 part by weight Epikote 828 and 150 part of glycidyl neononanoate , GE9H.

Curing Agent blend: 650 part by weight of Jeffamine D230 and Jeffamine D230 is a polyoxyalkyleneamines available from Huntsman Corporation. Epikote 828 is an epoxy resin available from Momentive Specialty Chemicals

Example 02

Example of trowellable floor and patching compound

The ingredients presented in the table 3 below were mixed for the preparation of a trowellable flooring compound

BASE COMPONENT Weight Volume Supplier

(parts) (parts)

EPIKOTE 828LVEL 63.2 126.3 Momentive GE9H 11.1 22.3

Byk A530 4.8 13.4 Byk Chemie

Mix the additives into the EPIKOTE resin before filler addition

Total 79.1 162.0

FILLERS Weight Volume Supplier

(parts) (parts)

Sand 1-2 mm 582.3 496.4 SCR Sibelco Sand 0.2-0.6 298.4 254.4 SCR Sibelco Total 880.7 750.8

Disperse into the base component using a concrete mixer

CURING AGENT Weight Volume Supplier

COMPONENT (parts) (parts)

EPIKURE F205 40.2 87.2 Momentive

Total 40.2 87.2

Mix the curing agent well with the EPIKOTE resin base and Fillers before application

Total formulation 1000.0 1000.0

Table 3: Preparation of a trowellable flooring comp Example 03

Formulation for a water based self-leveling flooring

The ingredients presented in the Table 4 below were mixed for the preparation of a waterbased self leveling flooring system. CURING AGENT Weight Supplier

COMPONENT (A) (parts ) Comment

EPIKURE 8545-W-52 164.00 Momentive

(HEW = 320 g/eq)

EPIKURE 3253 4.00 Momentive Accelerator

BYK 045 5.00 BYK CHEMIE defoamer

Antiterra 250 4.00 BYK CHEMIE Dispersing

Byketol WS 5.00 BYK CHEMIE Wetting agent

Bentone EW (3% in 20.00 Elementis

water) Anti-settling

Mix the additive into the EPIKURE curing agents before filler addition

Titanium dioxide 2056 50.00 KronosTitan

Disperse the pigment for 10 minutes at 2000 rpm.

EWO-Heavy Spar 195.00 Sachtleben

Chemie Barium sulpha^'

Quartz powder W8 98.00 Westdeutsche

Quarzwerke

Disperse fillers at 2000 rpm for 10 minutes

Water 55.00

Sand 0.1-0.4 mm 400.00 Euroquarz

Total component A 1000.00

RESIN COMPONENT (B)

EPIKOTE 828LVEL 81.00 Momentive

GE9H 19.00

(B) into (A)

Total formulation 1081.00

A + B

Table 4: Preparation of a waterbased self leveling flooring system Formulation characteristics

Fillers+Pigment /

Binder ratio 3.9 by weight

PVC 37.7 % v/v

Density 1.9 g/ml Water content 12.5 % m/m

Claims

EPOXY COMPOSITIONS C L A I M S

1. An epoxy composition comprising a mixture of α, α-branched alkane carboxylic glycidyl esters derived from butene oligomers characterized in that the sum of the concentration of the blocked and of the highly branched isomers is at least 50%, preferably above 60% and most preferably above 75% on total composition .

2. The composition of claim 1 characterized in that the glycidyl ester mixture is based on neononanoic (C9) acid mixture where the sum of the concentration of the blocked and of the highly branched isomers is at least 50%, preferably above 60% and most preferably above 75% on total composition.

3. The composition of claim 2 characterized in that the glycidyl ester mixture is comprising 2,2-dimethyl 3,3-dimethyl pentanoic acid glycidyl ester or 2-methyl 2-isopropyl 3-methyl butanoic acid glycidyl ester or 2-methyl 2-ethyl 3,3-dimethyl butanoic acid glycidyl ester.

4. The composition of claim 3 characterized in that the glycidyl ester mixture is comprising 2,2-dimethyl 3-methyl 4- methyl pentanoic acid glycidyl ester or 2,2-dimethyl 4,4- dimethyl pentanoic acid glycidyl ester.

5. The composition of claim 3 characterized in that the sum of the following content of glycidyl ester mixture, comprising 2,2-dimethyl 3,3-dimethyl pentanoic acid glycidyl ester and 2- methyl 2-isopropyl 3-methyl butanoic acid glycidyl ester and 2- methyl 2-ethyl 3,3-dimethyl butanoic acid glycidyl ester, is above 10% weight, preferably above 15% weight and most preferably above 25% weight on total composition.

6. The composition of claim 4 characterized in that the sum of the following content of glycidyl ester mixture, comprising 2, 2-dimethyl 3,3-dimethyl pentanoic acid glycidyl ester and 2- methyl 2-isopropyl 3-methyl butanoic acid glycidyl ester and 2- methyl 2-ethyl 3,3-dimethyl butanoic acid glycidyl ester and 2, 2-dimethyl 3-methyl 4-methyl pentanoic acid glycidyl ester and 2, 2-dimethyl 4,4-dimethyl pentanoic acid glycidyl ester, is above 40% weight, preferably above 50% weight and most preferably above 60% weight on total composition.

7. The composition of claims 3 or 4 characterized in that the content of 2-methyl 2-ethyl hexanoic acid glycidyl ester is below 40% weight, preferably below 30% weight and most preferably below 20% weight on total composition.

8. The process to prepare the compositions of any claims 1 to 7 characterized in that the mixture of α,α-branched alkane carboxylic glycidyl esters is used as reactive diluent.