# Patent

## Title
Acrylic polyol resins compositions

## Abstract

The invention relates to compositions of hydroxyl functional acrylic resins (acrylic polyols) 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 maximum 55%, preferably below 40%, and most preferably below 30% weight on total composition.

## Background
RELATED APPLICATION DATA
This application claims the benefit of PCT Application PCT/EP2012/004318 with an International Filing Date of Oct. 16, 2012, published as WO 2013/056812 A1, which further claims priority to European Patent Application No. EP11075230.0 filed Oct. 19, 2011 and European Patent Application No. EP 12002494.8 filed Apr. 5, 2012; the entire contents of all are hereby incorporated by reference.
The present invention relates to a composition of acrylic polyol resins based on a composition of hydroxyl functional acrylic resins (acrylic polyols) 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 maximum 55%, preferably below 40%, and most preferably below 30% weight on total composition, which lead for example to improved leveling of the coatings derived thereof.
More in particular the invention relates to acrylic polyol resins compositions comprising aliphatic tertiary saturated carboxylic acids or α,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 oligomerization process thereof, and which is defined as below.
The glycidyl ester derived from olefins containing 5 to 10 carbon atoms in the alkyl chain are used by the industry to introduce modified resins by reaction such a glycidyl ester with acrylic resins, such as given in U.S. Pat. No. 6,136,991.
It is generally known from e.g. U.S. Pat. No. 2,831,877, U.S. Pat. No. 2,876,241, U.S. Pat. No. 3,053,869, U.S. Pat. No. 2,967,873 and U.S. Pat. No. 3,061,621 that mixtures of α,α-branched alkane carboxylic acids can be produced, starting from mono-olefins, carbon monoxide and water, in the presence of a strong acid.
One of the more recent methods has been disclosed in EP 1033360A1. The problem of providing better softening derivatives of α,α-branched acids, manufactured from alkenes, carbon monoxide and water and a nickel catalyst was solved therein by a process, which actually comprised:

    
    
        (a) oligomerization of butene;
        (b) separation of butene dimers and/or trimers from the oligomeriszate;
        (c) conversion of the butene dimers and/or trimers into carboxylic acids;
        (d) conversion of the carboxylic acids into the corresponding vinyl esters showing attractive softening properties when mixed into other polymers or if used as comonomers in coatings.
    
    


If the olefin feed is based on Raf. II or Raf III or any mixture rich in n-butene isomers on the total olefins, the subsequently mixture of neo-acid (C9 or C13 acids) derivatives will provide a mixture where the concentration of blocked and highly branched isomers is maximum 55%, preferably below 40%, and most preferably below 30%.
The glycidyl esters can be obtained according to PCT/EP2010/003334 or the U.S. Pat. No. 6,433,217.
We have discovered that well chosen blend of isomers of the glycidyl ester of mixture compositions of neo-acid (C9 or C13 acids) glycidyl ester, is providing for example a good leveling of a coating, is a mixture where the sum of the concentration of blocked and highly branched isomers is maximum 55%, preferably below 40%, and most preferably below 30% weight on total composition.
We have further 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 polymers such as acrylic polyols.
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 a secondary or a tertiary carbon atoms in the β position are defined as blocking isomers.
Mixture compositions of neononanoic (C9) acids glycidyl esters providing for example a good leveling of a coating, is a mixture where the sum of the concentration of the blocked and of the highly branched isomers derivatives is maximum 55%, preferably below 40%, and most preferably below 30% weight on total composition.
Furthermore the above compositions of neononanoic acids glycidyl esters mixture is comprising 2,2-dimethyl heptanoic acid glycidyl ester or 2-methyl 2-ethyl hexanoic acid glycidyl ester or 2-methyl 2-ethyl 3-methyl pentanoic acid glycidyl esters.
Furthermore the above compositions of neononanoic acids glycidyl esters mixture is comprising 2-methyl 2-ethyl 3-methyl pentanoic acid glycidyl esters (sum of stereoisomers) below 40%, preferably below 30% and most preferably below or equal 25% weight on total composition.
Furthermore the above compositions of neononanoic acids glycidyl esters mixture is comprising 2-methyl 2-ethyl hexanoic acid glycidyl ester above 10%, preferably above 30% and most preferably above 45% weight on total composition.
The above compositions of the glycidyl ester mixture is comprising 2,2-dimethyl heptanoic acid glycidyl ester and 2-methyl 2-ethyl hexanoic acid glycidyl ester and 2-methyl 2-ethyl 3-methyl pentanoic acid glycidyl esters (sum of stereoisomers) is above 40%, preferably 55% and most preferably 65% weight on total composition.
A preferred composition is comprising a mixture of 2,2-dimethyl heptanoic acid glycidyl ester in 1 to 15 weight % and 2-methyl 2-ethyl hexanoic acid glycidyl ester in 40 to 70 weight % and 2-methyl 2-ethyl 3-methyl pentanoic acid glycidyl esters (sum of stereoisomers) in 8 to 32 weight % on total composition.
A further preferred composition is comprising a mixture of 2,2-dimethyl heptanoic acid glycidyl ester in 2 to 10 weight % and 2-methyl 2-ethyl hexanoic acid glycidyl ester in 47 to 61 weight % and 2-methyl 2-ethyl 3-methyl pentanoic acid glycidyl esters (sum of stereoisomers) in 10 to 25 weight % on total composition.
The above glycidyl esters compositions can be used for example, as reactive diluent or as momomer in binder compositions for paints or adhesives.
The glycidyl esters compositions can be used as reactive diluent for epoxy based formulations such as exemplified in the technical brochure of Momentive (Product Bulletin: Cardura E10P The Unique Reactive Diluent MSC-521).
Other uses of the glycidyl ester are the combinations with polyester polyols, or acrylic polyols, or polyether polyols. The combination with acrylic polyols such as the one used in the car industry coating leads to coating system with attractive coating appearance.
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×0.25 mm, df=0.2 μm
    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 μL


CP Wax 58 CB is a Gas chromatography column available from Agilent Technologies.
The isomers of neononanoic acid as illustrative example have the structure (R1R2R3)—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.







TABLE 1







Structure of all possible neononanoic isomers

















Methyl

Retention time



R1
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


V905
Methyl
Methyl
1,1-dimethyl propyl
5
Yes
10.21


V906
Methyl
Methyl
1,2-dimethy propyl
5
Yes
9.57


V907
Methyl
Methyl
2,2-dimethyl propyl
5
No
8.26


V908
Methyl
Methyl
3-pentyl
4
Yes
9.45


V909
Methyl
Ethyl
n-butyl
3
No
9.28


V910 K1
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









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×0.2 mm, df=0.52 μm
    Oven: 175° C. (5 min)−1° 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: 1 μL
    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 (R1R2R3)—C—COO—CH2—CH(O)CH2 where the three R groups are linear or branched alkyl groups having together a total of 7 carbon atoms.
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.
GC-MS method can be used to identify the various isomers providing that the analysis is done by a skilled analytical expert.







Methods for the Characterization of the Resins

The molecular weights of the resins are measured with gel permeation chromatography (Perkin Elmer/Water) in THF solution using polystyrene standards. Viscosity of the resins are measured with Brookfield viscometer (LVDV-I) at indicated temperature. Solids content are calculated with a function (Ww−Wd)/Ww×100%. Here Ww is the weight of a wet sample, Wd is the weight of the sample after dried in an oven at a temperature 110° C. for 1 hour.
Tg (glass transition temperature) has been determined either with a DSC 7 from Perkin Elmer or with an apparatus from TA Instruments Thermal Analysis. Scan rates were respectively 20 and 10° C./min. Only data obtained in the same experimental conditions have been compared. If not, the temperature difference occurring from the different scanning rate has been proved not significant for the results compared.
Blocking Isomers
Whereas the carbon atom in alpha position of the carboxylic acid is always a tertiary carbon atom, the carbon atom(s) in β 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).








The use of the glycidyl esters compositions, discussed here above, can be as monomer in binder compositions for paints and adhesives. These binders can be based on an acrylic polyol resin comprising the above composition glycidyl.
The acrylic polyol resins of the invention are based on a composition of hydroxyl functional acrylic resins (acrylic polyols) 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 maximum 55%, preferably below 40%, and most preferably below 30% weight on total composition.
A preferred 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 maximum 55%, preferably below 40%, and most preferably below 30% weight on total composition.
Further the neononanoic (C9) glycidyl ester mixture is comprising 2,2-dimethyl heptanoic acid glycidyl ester or 2-methyl 2-ethyl hexanoic acid glycidyl ester or 2-methyl 2-ethyl 3-methyl pentanoic acid glycidyl ester.
Another embodiment is that the composition of the glycidyl ester mixture is comprising 2-methyl 2-ethyl 3-methyl pentanoic acid glycidyl esters (sum of stereoisomers) below 40%, preferably below 30% and most preferably below or equal 25% 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 above 10%, preferably above 30% and most preferably above 45% weight on total composition.
A further embodiment is that the composition of the glycidyl ester mixture is comprising 2,2-dimethyl heptanoic acid glycidyl ester and 2-methyl 2-ethyl hexanoic acid glycidyl ester and 2-methyl 2-ethyl 3-methyl pentanoic acid glycidyl esters (sum of stereoisomers) is above 40%, preferably 55% and most preferably 65% weight on total composition.
A further embodiment is that the composition of the glycidyl ester mixture is comprising 2,2-dimethyl heptanoic acid glycidyl ester in 1 to 15 weight % and 2-methyl 2-ethyl hexanoic acid glycidyl ester in 40 to 70 weight % and 2-methyl 2-ethyl 3-methyl pentanoic acid glycidyl esters (sum of stereoisomers) in 8 to 32 weight % on total composition.
A further embodiment is that the composition of the glycidyl ester mixture is comprising 2,2-dimethyl heptanoic acid glycidyl ester in 2 to 10 weight % and 2-methyl 2-ethyl hexanoic acid glycidyl ester in 47 to 61 weight % and 2-methyl 2-ethyl 3-methyl pentanoic acid glycidyl esters (sum of stereoisomers) in 10 to 25 weight % on total composition.
The invention is also about the process to prepare the acrylic polyol resins compositions, which are obtained by the incorporation of the mixture of α,α-branched alkane carboxylic glycidyl esters, as characterized above, into a hydroxyl functional acrylic resins by the reaction of the epoxy group with the carboxylic acid group of ethylene carboxylic acid compounds from hydroxyl ethylene carboxylate ester monomers which are then reacted with one or more unsaturated monomers via a radical polymerization reaction, in one step or more.
The ethylene carboxylic acid compounds are for example acrylic acid, methacrylic acid, and the like.
The other unsaturated monomers are selected from the group consisting of octyl acrylate, octyl methacrylate, nonyl acrylate, nonyl methacrylate, decyl acrylate, decyl methacrylate, undecyl acrylate, undecyl methacrylate, dodecyl acrylate, dodecyl methacrylate, isodecyl acrylate, isodecyl methacrylate, isotridecyl acrylate, isotridecyl methacrylate, tridecyl acrylate, tridecyl methacrylate, tridecyl acrylate, tridecyl methacrylate, stearyl acrylate, and stearyl methacrylate, lauryl acrylate, lauryl methacrylate, styrene, alpha-methyl styrene, C1 to C10 (cyclo)alkyl acrylate, acrylic acid, methacrylic acid, maleic acid, fumaric acid or a combination thereof.
A further process to prepare the acrylic polyol resins of the invention are cooked it while having a polyester polyol or a polyether polyol or a mixture thereof as initial reactor charge.
The acrylic polyol resins of the invention prepared according to the above processes will have a calculated hydroxyl value between 50 and 180 mgKOH/g on solid and or the number average molecular weight (Mn) is between 2500 and 50000 Dalton according polystyrene standard.
The invention is also related to a binder composition useful for coating composition comprising at least any hydroxyl functional acrylic resins as prepared above.
The said binder compositions are suitable for coating metal or plastic substrates.


EXAMPLES
Chemicals Used


    CarduraTM E10: available from Momentive Specialty Chemicals
    Neononanoic glycidyl ester from Momentive Specialty Chemicals
    GE9S: neononanoic glycidyl ester of composition A (see Table 2 below)
    GE9H: neononanoic glycidyl ester of composition B (see Table 2 below)
    Neononanoic glycidyl ester of composition C (see Table 2 below)
    Neononanoic glycidyl ester of composition D (see Table 2 below)
    Neononanoic glycidyl ester of composition E (see Table 2 below)









TABLE 2







Composition of the neononanoic glycidyl ester (according


to the described gas chromatography method for glycidyl


esters of neo-acid)












Glycidyl ester of







acid V9XX


(described in


Table 1)
A (%)
B (%)
C (%)
D (%)
E (%)















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 K1
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









    GES: 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 50 wt %, Toluene 30 wt %, ShellsolA 10 wt %, 2-Ethoxyethylacetate 10 wt %. 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: ‘DBTDL 1 wt %’ which is Dibutyl Tin Dilaurate diluted at 1 wt % in butyl acetate
    Catalyst: ‘DBTDL 10 wt %’ which is Dibutyl Tin Dilaurate diluted at 10 wt % in butyl acetate


Example 01
The following constituents were charged to a reaction vessel equipped with a stirrer, a condenser and a thermometer: 92.4 grams of GE9S, 24.0 grams of Butyl Acetate. That initial reactor charge has been heated up to 135° C. Then, the following mixture was added over a period of 1 h 20 while keeping the temperature constant: 30.7 grams of acrylic acid, 1.2 grams of Di-t-Amyl Peroxide, 12.0 grams of n-Butyl Acetate. After further adding 1.2 grams of Di-t-Amyl Peroxide and 20.4 grams of n-Butyl Acetate, a post-cooking was pursued at 135° C. for 1 h. The acrylic polyol had a molecular weight (Mw) of 11400 Daltons and a Tg of about −10° C.
Example 02 Comparative
The following constituents were charged to a reaction vessel equipped with a stirrer, a condenser and a thermometer: 92.4 grams of GE9H, 24.0 grams of Butyl Acetate. That initial reactor charge has been heated up to 135° C. Then, the following mixture was added over a period of 1 h 18 while keeping the temperature constant: 30.2 grams of acrylic acid, 1.2 grams of Di-t-Amyl Peroxide, 12.0 grams of n-Butyl Acetate. After further adding 1.2 grams of Di-t-Amyl Peroxide and 20.4 grams of n-Butyl Acetate, a post-cooking was pursued at 135° C. for 1 h. The acrylic polyol had a molecular weight (Mw) of 8600 Daltons and a Tg of about +26° C.
Observations:
Tg of acrylic polyols is impacted by the composition of the neononanoic glycidyl ester (see examples 01, 02).
Example 03
The adducts of Glycidyl neononanoate, GE9S and acrylic acid or methacrylic acid.
The adducts of Glycidyl neononanoate GE9S (see Table 3) with acrylic acid (ACE-adduct) and with methacrylic acid (MACE-adduct) are acrylic monomers that can be used to formulate hydroxyl functional (meth)acrylic polymers.







TABLE 3







Compositions of the adducts intakes in parts by weight










Acrylic acid
Meth acrylic acid



adduct
adduct













Initial reactor charge




GE9S
250
250


Acrylic acid
80


Methacrylic acid

96.5


Radical Inhibitor


4-Methoxy phenol
0.463
0.463


Catalyst


DABCO T9 (0.07 wt % on Glycidyl
0.175
0.175


ester)









    DABCO T9 and 4-Methoxy phenol (185 ppm calculated on glycidyl ester weight), are charged to the reactor.
    The reaction is performed under air flow (in order to recycle the radical inhibitor).
    The reactor charge is heated slowly under constant stirring to about 80° C., where an exothermic reaction starts, increasing the temperature to about 100° C.
    The temperature of 100° C. is maintained, until an Epoxy Group Content below 30 meq/kg is reached. The reaction mixture is cooled to room temperature.


Example 04
Acrylic Resins for High Solids Automotive Refinish Clearcoats
A glass reactor equipped with stirrer was flushed with nitrogen, and the initial reactor charge (see table 4) heated to 160° C. The monomer mixture including the initiator was then gradually added to the reactor via a pump over 4 hours at this temperature. Additional initiator was then fed into the reactor during another period of 1 hour at 160° C. Finally the polymer is cooled down to 135° C. and diluted to a solids content of about 68% with xylene.







TABLE 4







Acrylic resins recipe










Weight %
in Reactor 1 L (g)















Initial Reactor Charge





GE9S or GE9H (Comparative)
28.2
169.1



Xylene
2.7
16.2



Feeding materials



Acrylic acid
10
59.8



Hydroxy ethyl methacrylate
16.0
96.0



Styrene
30.0
180.0



Methyl methacrylate
15.8
95.0



Di t-Amyl peroxide
4.0
24.0



Xylene
8.3
49.8



Post cooking



Di t-Amyl peroxide
1.0
6.0



Xylene
3.0
18.0



Solvent adding at 130° C.



Xylene
50.8
305.0



Final solids content
61.8%



Hydroxyl content
4.12%










Example 05
Clear Coats for Automotive Refinish
Solvents were blended to yield a thinner mixture of the following composition (table 5):







TABLE 5







Thinner composition










Thinner
Weight % in solvent blend, theory







Toluene
30.1%



ShellSolA
34.9%



2-ethoxyethyl acetate
10.0%



n-Butyl acetate
25.0%



Total
 100%










A clearcoat was then formulated (table 6) with the following ingredients (parts by weight):







TABLE 6







Clearcoat formulation











Resin of
Desmodur
BYK 10 wt % 
DBTDL 1 wt % 



example ex 04
N3390
in ButAc
in ButAc
Thinner





80.1
27.01
0.53
1.17
40.45





















Clearcoat properties
GE9H (Comparative)
GE9S







Volatile organic content
480 g/l
481 g/l


Initial viscosity
54 cP
54 cP


Dust free time
12 minutes
14.5 minutes


Koenig Hardness after 6 hours
8.3 s
7.1 s









Example 06
Acrylic Resins for First Finish Automotive Topcoats
GE9S based (28%) acrylic polymers for medium solids first-finish clear coats.
A reactor for acrylic polyols is flushed with nitrogen and the initial reactor charge (see Table 7) heated to 140° C. At this temperature the monomer mixture including the initiator is added over 4 hours to the reactor via a pump. Additional initiator is fed into the reactor during one hour, and then the mixture is kept at 140° C. to complete the conversion in a post reaction. Finally the polymer is cooled down and diluted with butyl acetate to a solids content of about 60%.







TABLE 7







Acrylic resins recipe









Intakes (parts by weight)














Initial reactor charge




GE9S
164.40



Xylene
147.84



Monomer mixture



Acrylic acid
53.11



Butyl methacrylate
76.88



Butyl acrylate
48.82



Hydroxy-ethyl methacrylate
27.20



Styrene
177.41



Methyl methacrylate
47.31



Initiator



Di-tert.-amyl peroxide (DTAP)
8.87



Post addition



Di-tert.-amyl peroxide
5.91



Solvent (to dilute to 60% solids)



Butyl acetate
246.00



Total
1000.0










Clear Lacquer Formulation

Clear lacquers are formulated (see table 8) from the acrylic polymers by addition of Cymel 1158 (curing agent from CYTEC), and solvent to dilute to spray viscosity. The acidity of the polymer is sufficient to catalyze the curing process, therefore no additional acid catalyst is added. The lacquer is stirred well to obtain a homogeneous composition.







TABLE 8







Clear lacquer formulations and properties of the polymers









Intakes



(part by weight)














Ingredients




Acrylic polymer
60.0



Cymel 1158
8.8



Butyl acetate (to application viscosity)
24.1



Properties



Solids content [% m/m]
45.3



Density [g/ml]
0.97



VOC [g/l]
531










Application and Cure

The coatings are applied with a barcoater on Q-panels to achieve a dry film thickness of about 40 μm. The systems are flashed-off at room temperature for 15 minutes, then baked at 140° C. for 30 minutes. Tests on the cured systems are carried out after 1 day at 23° C.
Example 07
In a reactor equipped with an anchor stirrer, a thermometer, condenser and monomer/initiator feeding system, 188.6 g of GE9S and 90 g of ethoxypropanol (EPR) were loaded and heated to about 150° C. (see Table 9). A mixture of 52 g of hydroxyethylmethacrylate (HEMA), 160 g of styrene, 68 g of acrylic acid (AA), 10 g of dicumylperoxide (DCP), 37.7 g of GE9S and 40 g of ethoxypropanol (EPR) were added over 2 hours 30 minutes to the reactor while keeping its content at 150° C. After the feed, the reactor content was held for 30 minutes at this temperature. After the 30 minutes hold period, 108 g of HEMA, 30 g of AA, 142 g of isobutyl methacrylate (IBMA), 5 g of DCP and 45 grams of EPR were added over 2 hours and 30 minutes at about 150° C. followed by a rinsing step for the feed system with 5 g of EPR. After the rinsing step, the content of the reactor was held for 2 hours at 150° C. The reactor content was cooled down to 100° C. and 100 parts of EPR were distilled off at atmospheric pressure.
The polyacrylate polyol has a solids content of the solution of 90% by weight.







TABLE 9







Composition of polyol










Materials
Intake (g)















Initial charge
EPR
90




GE9S
188.6



Monomer Addition 1
AA
68




Styrene
160




GE9S
37.7




HEMA
52




EPR
40




DCP
10



Monomer Addition 2
AA
30




IBMA
142




HEMA
108




DCP
5




EPR
45



TOTAL

976.3










Example 08
Maleate Diester Based Resin Prepared According to the Teaching of WO2005040241
Equipment: Glass reactor equipped with an anchor stirrer, reflux condenser and nitrogen flush.
Manufacturing Procedure of the Maleate Diester:
Maleic anhydride was reacted with the selected alcohol (3,3,5 trimethyl cyclohexanol) in an equimolar ratio at 110° C. to form a maleate monoester in presence of around 5 wt % butyl acetate. The reaction was continued until conversion of the anhydride had reached at least 90% (Conversion of the anhydride is monitored by acid-base titration.). Methanol was added to open the remaining anhydride in a 1.2/1 molar ratio of methanol/anhydride and the reaction was continued for 30 minutes.
GE9S was fed to the reactor in 30 minutes in an equimolar ratio to the remaining acid in the system whilst keeping the temperature at 110° C. The system was then allowed to react further for 1 hour at 110° C.
Manufacturing Procedure of the Maleate-Acrylic Resin (See Table 10):
The reactor was flushed with nitrogen and the initial reactor charge was heated to the polymerization temperature of 150° C. The first charge of Di ter-amylperoxide was then added in one shot. Immediately after this addition, the monomer-initiator mixture was dosed continuously to the reactor in 330 minutes at the same temperature. The monomer addition feed rate was halved during the last hour of monomer addition. After completion of the monomer addition, the third charge of Di ter-amylperoxide was then fed together with a small amount of the butyl acetate to the reactor in 15 minutes. The reactor was kept at this temperature for 60 more minutes. Finally, the polymer was cooled down.







TABLE 10







Composition of TMCH maleate based resin









Parts by



weight















Initial Reactor
BuAc
8



Charge [g]
Maleate diester
40.7



Initiator start [g]
Di tert amyl peroxide
0.4



Monomer feed [g]
BuAc
3




Hydroxyethyl methacrylate
21.5




Styrene
20




Methyl methacrylate
17.8




Methacrylic Acid
2.2




Di tert amyl peroxide
3.6



Post cooking [g]
DTAP (with 10 g BuAc)
1



Total intake [g]

118.2










Example 09
Polyester-Ether Resin
The following constituents were charged to a reaction vessel equipped with a stirrer, a thermometer and a condenser: 456 g of GE9S, 134 g of dimethylolpropionic acid and 0.35 g of stannous octoate.
The mixture was heated to a temperature of about 110° C. for about 1 hour and then steadily increased to 150° C. in 3 hours and then cooled down.
This polyester-ether was then formulated in high solids and very high solids 2K polyurethane topcoats either as sole binder or as reactive diluent for an acrylic polyol.

## Claims

1. An hydroxyl functional acrylic resin composition comprising a mixture of α,α-branched alkane carboxylic glycidyl esters wherein a sum of a concentration of blocked isomers and of highly branched isomers is a maximum amount of 55 wt % based on a total weight of the mixture.

2. The composition of claim 1 wherein the mixture of α,α-branched alkane carboxylic glycidyl esters is based on a neononanoic (C9) acid mixture wherein the sum of the concentration of the blocked isomers and of the highly branched isomers is a maximum amount of 55 wt % based on the total weight of the mixture.

3. The composition of claim 2 wherein the mixture of α,α-branched alkane carboxylic glycidyl esters comprises 2,2-dimethyl heptanoic acid glycidyl ester, 2-methyl 2-ethyl hexanoic acid glycidyl ester or 2-methyl 2-ethyl 3-methyl pentanoic acid glycidyl esters.

4. The composition of claim 2 wherein the mixture of α,α-branched alkane carboxylic glycidyl esters comprises 2-methyl 2-ethyl 3-methyl pentanoic acid glycidyl ester stereoisomers in an amount below 40 wt % based on the total weight of the mixture.

5. The composition of claim 2 wherein the mixture of α,α-branched alkane carboxylic glycidyl esters comprises 2-methyl 2-ethyl hexanoic acid glycidyl ester in an amount above 10 wt % based on the total weight of the mixture.

6. The composition of claim 2 wherein the mixture of α,α-branched alkane carboxylic glycidyl esters comprises 2,2-dimethyl heptanoic acid glycidyl ester, 2-methyl 2-ethyl hexanoic acid glycidyl ester and 2-methyl 2-ethyl 3-methyl pentanoic acid glycidyl ester stereoisomers in an amount above 40 wt % based on the total weight of the mixture.

7. The composition of claim 2 wherein the mixture of α,α-branched alkane carboxylic glycidyl esters comprises 2,2-dimethyl heptanoic acid glycidyl ester in an amount of 1 to 15 wt %, 2-methyl 2-ethyl hexanoic acid glycidyl ester in an amount of 40 to 70 wt % and 2-methyl 2-ethyl 3-methyl pentanoic acid glycidyl ester stereoisomers in an amount of 8 to 32 wt % based on the total weight of the mixture.

8. The composition of claim 2 wherein the mixture of α,α-branched alkane carboxylic glycidyl esters comprises 2,2-dimethyl heptanoic acid glycidyl ester in an amount of 2 to 10 wt %, 2-methyl 2-ethyl hexanoic acid glycidyl ester in an amount of 47 to 61 wt % and 2-methyl 2-ethyl 3-methyl pentanoic acid glycidyl ester stereoisomers in an amount of 10 to 25 wt % based on the total weight of the mixture.

9. A process to prepare the composition of claim 1 comprising incorporating the mixture of α,α-branched alkane carboxylic glycidyl esters having epoxy groups into the hydroxyl functional acrylic resins by the reaction of the epoxy group with a carboxylic acid group of an ethylene carboxylic acid compounds from hydroxyl ethylene carboxylate ester monomers which are reacted with one or more unsaturated monomers via a radical polymerization reaction, in one step or more.

10. The composition of claim 1 wherein the hydroxyl functional acrylic resin composition has a calculated hydroxyl value between 50 and 180 mgKOH/g on solids or a number average molecular weight (Mn) between 2500 and 50000 Dalton according to a polystyrene standard.

11. A binder composition useful for a coating composition comprising the hydroxyl functional acrylic resin composition of claim 1.

12. A metal or plastic substrate coated with a coating composition comprising the binder composition of the claim 11.

13. The binder composition of claim 11 wherein the coating composition comprises 10 to 40 weight % of aliphatic isocyanate, 0-25 weight % of polyester polyol, and 40-70 weight % of the hydroxyl functional acrylic resin composition of claim 1, all weight % based on solid material after evaporation of the solvents.

14. The composition of claim 8 prepared in presence of polyester polyol.

15. An acrylic polyol copolymer resin comprising 5 to 70 weight percent of the reaction product of a secondary alcohol and maleic anhydride which has been subsequently reacted with the composition of claim 1.

16. A coating composition comprising a polyester-ether resin which is the reaction product of the composition of claim 1 and dimethylol propionic acid.

17. The composition of claim 1 wherein the sum of the concentration of the blocked isomers and of the highly branched isomers is below 40 wt % based on the total weight of the mixture.

18. The composition of claim 1 wherein the sum of the concentration of the blocked isomers and of the highly branched isomers is below 30 wt % based on the weight of the mixture.

19. The composition of claim 2 wherein the sum of the concentration of the blocked isomers and of the highly branched isomers is below 40 wt % based on the total weight of the mixture.

20. The composition of claim 2 wherein the sum of the concentration of the blocked isomers and of the highly branched isomers is below 30 wt % based on the total weight of the mixture.

21. The composition of claim 4 wherein the mixture of α,α-branched alkane carboxylic glycidyl esters comprises 2-methyl 2-ethyl 3-methyl pentanoic acid glycidyl ester stereoisomers in an amount below 30 wt % based on the total weight of the mixture.

22. The composition of claim 4 wherein the mixture of α,α-branched alkane carboxylic glycidyl esters comprises 2-methyl 2-ethyl 3-methyl pentanoic acid glycidyl ester stereoisomers in an amount below or equal to 25 wt % based on the total weight of the mixture.

23. The composition of claim 5 wherein the mixture of α,α-branched alkane carboxylic glycidyl esters comprises 2-methyl 2-ethyl hexanoic acid glycidyl ester in an amount above 30 wt % based on the total weight of the mixture.

24. The composition of claim 5 wherein the mixture of α,α-branched alkane carboxylic glycidyl esters comprises 2-methyl 2-ethyl hexanoic acid glycidyl ester in an amount above 45 wt % based on the total weight of the mixture.

25. The composition of claim 6 wherein the mixture of α,α-branched alkane carboxylic glycidyl esters comprises 2,2-dimethyl heptanoic acid glycidyl ester, 2-methyl 2-ethyl hexanoic acid glycidyl ester and 2-methyl 2-ethyl 3-methyl pentanoic acid glycidyl ester stereoisomers in an amount above 55 wt % based on the total weight of the mixture.

26. The composition of claim 6 wherein the mixture of α,α-branched alkane carboxylic glycidyl esters comprises 2,2-dimethyl heptanoic acid glycidyl ester, 2-methyl 2-ethyl hexanoic acid glycidyl ester and 2-methyl 2-ethyl 3-methyl pentanoic acid glycidyl ester stereoisomers in an amount above 65 wt % based on the total weight of the mixture.

27. The composition of claim 1 wherein the mixture of α,α-branched alkane carboxylic glycidyl esters is derived from butene oligomers.