GLYCIDYL ESTERS OF ALPHA, ALPHA BRANCHED ACIDS FROM RENEWABLE SOURCES AND FORMULATIONS THEREOF

Abstract

The invention relates to compositions of α,α-branched alkane carboxylic acids glycidyl esters which derived from rosin and or hydrogenated rosin reacted with an epihalohydrin. The above glycidyl esters compositions can be used for example, as monomer in binder compositions for paints or adhesives, as reactive diluent or as acid scavenger. This invention is also about the uses of rosin and or hydrogenated rosin glycidyl ester in combinations with polyester polyols, or acrylic polyols, or polyether polyols.

Claims

1. (canceled)

2. (canceled)

3. (canceled)

4. (canceled)

5. (canceled)

6. (canceled)

7. (canceled)

8. (canceled)

9. (canceled)

10. (canceled)

11. (canceled)

12. (canceled)

13. (canceled)

14. (canceled)

15. (canceled)

16. (canceled)

17. A binder composition comprising a resin formulation wherein the resin formulation comprises a glycidyl ester of rosin and/or hydrogenated rosin and a resin, wherein in the resin is selected from the group consisting of a polyester polyol resin, an acrylic polyol resin, a polyether polyol resin, a polyether-ester polyol resin, an epoxy resin and combinations thereof, for use in paints, adhesives, as reactive diluents and as acid scavengers.

18. The binder composition of claim 17 wherein the resin is a polyester polyol resin obtained by the reaction of a polycarboxylic acid compound and a mixture of rosin and/or hydrogenated rosin glycidyl esters, and wherein the polycarboxylic acid compound is obtained by the reaction of one or more multifunctional polyol with one or more anhydrides or acid anhydrides.

19. The binder composition of the claim 18 wherein the polyester polyol resin has an acid value lower than 20 mg KOH/g based on solids.

20. The binder composition of the claim 18 having a number average molecular weight (Mn) between 300 and 7000 Daltons, and a hydroxyl value between 40 and 320 mg KOH/g based on solids.

21. The binder composition of claim 17 wherein the resin is an acrylic polyol resin obtained by the incorporation of a mixture of rosin and/or hydrogenated rosin glycidyl esters into the acrylic polyol resins by the reaction of an epoxy group with a carboxylic acid group of an ethylene carboxylic acid compound 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.

22. The binder composition of the claim 21 having a calculated hydroxyl value between 50 and 180 mgKOH/g and a number average molecular weight (Mn) between 1500 and 50000 Dalton.

23. A clear coating composition comprising 10 to 40 weight % of an aliphatic isocyanate, 0-25 weight % of the polyester polyol of claim 18, and 40-70 weight % acrylic polyol of claim 21, with the weight % being based on solids after evaporation of the solvent.

24. A coating composition comprising the binder composition of claim 17.

Description

EXAMPLES OF SYNTHESIS OF THE GLYCIDYL ESTERS OF ROSIN AND HYDROGENATED ROSIN

Example 1

[0080] 750 grams hydrogenated Gum Rosin, 321 grams of toluene and 21.8 grams (0.04 mol/mol hydrogenated gum rosin) tetra methyl ammonium chloride (as 50% aqueous solution) were charged to the reactor and heated to 70° C.; epichlorohydrin was dosed to the reactor while cooling the reaction medium to about 70° C., the addition rate was kept low to allow for appropriate cooling; in total 253 grams epichlorohydrin were added over a period of about 90 minutes (1.1 mol/mol hydrogenated gum rosin). The addition time is hence a function of the cooling efficiency. The reaction was monitored and at the present conditions this took about 7 hours.

[0081] The ring closure reaction was performed in the presence of caustic at 70° C.; in total 246 g NaOH 50% (1.24 mol/mol hydrogenated gum rosin) was used. The NaOH was dosed, using a linear profile in 90 minutes. After 210 minutes of post reaction time the ring closure reaction was completed. Another 1375 grams of Toluene and 653 grams of water was added to wash out the salt. The brine phase has been removed after phase separation followed by a final water wash. The Toluene was removed from the product by stripping at reduced pressure.

[0082] The EGC of the product was analysed and found to be 2567 mmol/kg; the Colour Gardner (50% in Toluene) was 1.

EXAMPLES OF BINDER PREPARATION AND FORMULATIONS

Example 1 Comparative

[0083] The following constituents were charged to a reaction vessel equipped with a stirrer, a condenser and a thermometer: 92.4 grams of Cardura™ E10P, 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 1h20 while keeping the temperature constant: 27.5 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.

Example 2a

[0084] The following constituents were charged to a reaction vessel equipped with a stirrer, a condenser and a thermometer: 92.4 grams of Rosin GE, 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 1h18 while keeping the temperature constant: 16.7 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.

Example 2b

[0085] The following constituents were charged to a reaction vessel equipped with a stirrer, a condenser and a thermometer: 92.4 grams of H-Rosin GE, 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 1h18 while keeping the temperature constant: 16.8 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.

Observations: Tg of acrylic polyols is impacted by the choice of glycidyl ester.

Example 3

[0086] The adducts of Rosin GE or H-Rosin GE (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-US-00001 TABLE 3 Compositions of the adducts intakes in parts by weight Rosin Rosin H-Rosin H-Rosin GE GE GE GE Acrylic Meth acrylic Acrylic Meth acrylic acid acid acid acid adduct adduct adduct adduct Initial reactor charge Rosin GE 250 250 H-Rosin GE 250 250 Acrylic acid 51.0 51.4 Methacrylic acid 62.5 63.0 Radical Inhibitor 4-Methoxy 0.463 0.463 0.463 0.463 phenol Catalyst DABCO T9 (0.07 0.175 0.175 0.175 0.175 wt % on Glycidyl ester) [0087] DABCO T9 and 4-Methoxy phenol (185 ppm calculated on glycidyl ester weight), are charged to the reactor. [0088] The reaction is performed under air flow (in order to recycle the radical inhibitor). [0089] 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. [0090] 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 4

Acrylic Resins

[0091] A glass reactor equipped with stirrer was flushed with nitrogen, and the initial reactor charge (see table 4) heated to 140° C. The monomer mixture including the initiator was then gradually added to the reactor via a pump over 5 hours at this temperature. Additional initiator was then fed into the reactor during another period of 1 hour at 140° C. Finally, the polymer is cooled down to 135° C. and diluted to a solids content of about 75% with butyl acetate.

TABLE-US-00002 TABLE 4 Acrylic resins recipe Example Ex. 4a Ex. 4b Ex. 4c Ex. 4d Initial Reactor Charge Weight % Weight % Weight % Weight % Cardura ™ E10P 25.0 0 20.0 25.0 Rosin GE 0 0 5.0 0 H-Rosin GE 0 25.0 0 0 Butyl Acetate 14.0 14.0 14.0 14.0 Di t-Amyl peroxide 0.5 0.5 0.5 0.5 Feeding materials Weight % Weight % Weight % Weight % Meth Acrylic acid 9.9 5.4 9.2 9.9 Hydroxy- 10.0 16.0 10.8 9.5 ethylmethacrylate Styrene 20.0 20.0 20.0 20.0 Methyl methacrylate 14.0 12.6 13.9 0 isoBornyl Methacrylate 0 0 0 30.6 Butyl Acrylate 21.1 20.0 21.1 5.0 Di t-Amyl peroxide 6.5 6.5 6.5 6.5 Post cooking Weight % Weight % Weight % Weight % Di t-Amyl peroxide 1.0 1.0 1.0 1.0 Solvent adding Weight % Weight % Weight % Weight % at 130° C. Butyl Acetate 18.0 18.0 18.0 18.0 Final solids content 75.2% 75.6% 75.0% 76.2% Hydroxyl content 3.1% 3.2% 3.0% 3.0% Color (Pt/Co) 15 42 238 64

[0092] A clearcoat was then formulated (table 5) with the following ingredients and applied by barcoat 80 μm wet:

TABLE-US-00003 TABLE 5 Clearcoat formulation Resin of BYK 10 wt % DBTDL 1 wt % example ex 4(a-d) Tolonate HDT in ButAc in ButAc Butyl Acetate 60.0 g 16.3 g 0.44 g 2.26 g Dilute until viscosity 40-55 mPa .Math. s

[0093] Comparative properties are shown in Table 6.

TABLE-US-00004 TABLE 6 Properties of clearcoats Clearcoats of Example Ex. 4a Ex. 4b Ex. 4c Ex. 4d VOC (g/l) 418 448 404 441 Initial viscosity (mPa .Math. s) 53.1 54.9 51.3 43.6 Dust free time (min) 16.5 9.5 8.5 10.0 Koenig hardness 6 hrs (sec) 3 8 6 7

Acrylic Resins

[0094] A glass reactor equipped with stirrer was flushed with nitrogen, and the initial reactor charge (see table 7) heated to 150° C. The monomer mixture including the initiator was then gradually added to the reactor via a pump over 5 hours at this temperature. Additional initiator was then fed into the reactor during another period of 1 hour at 150° C. Finally, the polymer is cooled down to 135° C. and diluted to a solids content of about 70% with butyl acetate.

TABLE-US-00005 TABLE 7 Acrylic resins recipe Example Ex. 4f Ex. 4g Ex. 4h Ex. 4i Initial Reactor Charge W % W % W % W % Cardura ™ E10P 25.0 0 15.0 0 Cardura ™ 9 0 25.0 0 0 Rosin GE 0 0 10.0 0 H-Rosin GE 0 0 0 25.0 Butyl Acetate 5.0 5.0 5.0 5.0 Di t-Amyl peroxide 0.5 0.5 0.5 0.5 Feeding materials W % W % W % W % Meth Acrylic acid 9.8 10.3 8.4 6.3 Hydroxy ethyl methacrylate 16.4 16.4 19.3 22.5 Styrene 20.0 20.0 20.0 20.0 Methyl methacrylate 12.0 12.6 12.0 12.0 Butyl Acrylate 16.8 16.3 15.3 14.2 Di t-Amyl peroxide 5.0 5.0 5.0 5.0 Post cooking W % W % W % W % Di t-Amyl peroxide 0.5 0.5 0.5 0.5 Solvent add at 130° C. W % W % W % W % Butyl Acetate 35.0 35.0 35.0 35.0 Final solids content 70.8% 70.2% 72.1% 72.2% Hydroxyl content 3.9% 4.0% 4.0% 4.0%

[0095] A clearcoat was then formulated (table 8) with the following ingredients and applied by barcoat 80 μm wet:

TABLE-US-00006 TABLE 8 Clearcoat formulation Resin of BYK 10 wt % DBTDL 1 wt % example ex 4 Tolonate HDT in ButAc in ButAc Butyl Acetate 60.0 g 19.5 g 0.44 g 2.28 g Dilute until viscosity 40-55 mPa .Math. s

[0096] Comparative properties are shown in Table 9.

TABLE-US-00007 TABLE 9 Properties of clearcoats Clearcoats of Example Ex. 4f Ex. 4g Ex. 4h Ex. 4i VOC (g/l) 427 428 472 474 Initial viscosity (mPa .Math. s) 54.9 55.5 53.4 55.8 Dust free time (min) 14.0 13.0 9.0 7.5 Koenig hardness 6 hrs (sec) 7 8 12 12

Acrylic Resins

[0097] A glass reactor equipped with stirrer was flushed with nitrogen, and the initial reactor charge (see table 10) heated to 140° C. The monomer mixture including the initiator was then gradually added to the reactor via a pump over 5 hours at this temperature. Additional initiator was then fed into the reactor during another period of 1 hour at 140° C. Finally, the polymer is cooled down to 135° C. and diluted to a solids content of about 75% with butyl acetate.

TABLE-US-00008 TABLE 10 Acrylic resins recipe Example Ex. 4k Ex. 4l Ex. 4m Ex. 4n Initial Reactor Charge W % W % W % W % Cardura ™ E10P 25.0 25.0 15.0 0 Rosin GE 0 0 10.0 0 H-Rosin GE 0 0 0 25.0 Butyl Acetate 14.0 14.0 14.0 14.0 Di t-Amyl peroxide 0.5 0.5 0.5 0.5 Feeding materials W % W % W % W % Cardura ™ E10P 0 0 0 0 Meth Acrylic acid 9.9 9.9 8.4 6.3 Hydroxy ethyl methacrylate 17.1 17.1 19.3 22.5 Styrene 20.0 20.0 20.0 20.0 Methyl methacrylate 20.0 0 20.0 20.0 isoBornyl Methacrylate 0 28.0 0 0 Butyl Acrylate 8.0 0.0 7.3 6.2 Di t-Amyl peroxide 6.5 6.5 6.5 6.5 Post cooking W % W % W % W % Di t-Amyl peroxide 1.0 1.0 1.0 1.0 Solvent add at 130° C. W % W % W % W % Butyl Acetate 27.0 27.0 27.0 27.0 Final solids content 69.7% 70.2% 71.5% 71.7% Hydroxyl content 4.0% 4.0% 4.0% 4.0% Color (Pt/Co) 17 19 273 39

[0098] A clearcoat was then formulated (table 11) with the following ingredients and applied by barcoat 80 μm wet:

TABLE-US-00009 TABLE 11 Clearcoat formulation Resin of BYK 10 wt % DBTDL 1 wt % example ex 4 Tolonate HDT in ButAc in ButAc Butyl Acetate 60.0 g 19.7 g 0.44 g 2.27 g Dilute until viscosity 40-55 mPa .Math. s

[0099] Comparative properties are shown in Table 12.

TABLE-US-00010 TABLE 12 Properties of clearcoats Clearcoats of Example Ex. 4k Ex. 4l Ex. 4m Ex. 4n VOC (g/l) 424 406 449 429 Initial viscosity (mPa .Math. s) 51.6 51.0 51.0 53.4 Dust free time (min) 12.5 9.5 9.0 7.0 Koenig hardness 6 hrs (sec) 7 13 14 14

Example 5

Clear Coats for Automotive Refinish

[0100] Solvents were blended to yield a thinner mixture of the following composition (table 13):

TABLE-US-00011 TABLE 13 Thinner composition Thinner Weight % in solvent blend, theory Toluene 30.1% ShellSol A 34.9% 2-ethoxyethyl acetate 10.0% n-Butyl acetate 25.0% Total  100%

[0101] A clearcoat was then formulated (table 14) with the following ingredients (parts by weight):

TABLE-US-00012 TABLE 14 Clearcoat formulation Resin of BYK 10 wt % in DBTDL 1 wt % in example ex 4 Desmodur N3390 ButAc ButAc Thinner 60.0 g 19.5 g 0.44 g 2.28 g Dilute until viscosity 40-55 mPa .Math. s

[0102] These clear-coats can be applied by spray.

Pigmented 2K Polyurethane

[0103] The same type of resin can be also be used in pigmented systems for industrial applications. An example of a white paint formulation is given below:

TABLE-US-00013 TABLE 15 Example of pigmented paint formulation Intakes Ingredients (part in grams) PART A Acrylic polymer from example 4 31.6 (70% solids) Dysperbyk 110 2.5 BYK 358N 2.3 BYK 077 2.3 Solthix 250 4.5 Ti-Pure TS-6200 143.3 Ethyl To achieve rolling dought-nut under Ethoxypropionate high speed agitation LETDOWN Acrylic polymer from example 4 151.3 (70% solids) Tinuvin 123 3.2 Tinuvin 1130 4.1 Ethyl Ethoxypropionate 35.3 Methyl amyl ketone 14.2 Dibutyl tin dilaurate 0.07 PART B N3300 (1.1:1 NCO:OH ratio) 76.7

Example 6

Rosin GE or H-Rosin GE Based Acrylic Polymers for Medium Solids First-Finish Clear Coats

[0104] A reactor for acrylic polyols is flushed with nitrogen and the initial reactor charge (see table 16) heated to 140° C. At this temperature the monomer mixture including the initiator is added over 5 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-US-00014 TABLE 16 Acrylic resins recipe Weight % Initial reactor charge Rosin GE or H-Rosin GE 25.0 Xylene 24.8 Monomer mixture Acrylic acid 6.4 Butyl methacrylate 12.9 Butyl acrylate 8.2 Hydroxy-ethyl methacrylate 10.6 Styrene 30.0 Methyl methacrylate 7.9 Initiator Di-tert.-amyl peroxide (DTAP) 1.5 Post addition Di-tert.-amyl peroxide 1.0 Solvent (to dilute to 60% solids) Butyl acetate 41.3

Clear Lacquer Formulation

[0105] Clear lacquers are formulated (see table 17) 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-US-00015 TABLE 17 Clear lacquer formulations Intakes Ingredients (part by weight) Acrylic polymer 60.0 Cymel 1158 8.8 Butyl acetate to application viscosity

Application and Cure

[0106] 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 7

[0107] A glass reactor equipped with stirrer was flushed with nitrogen, and the initial reactor charge (see table 18) heated to 140° C. The monomer mixture including the initiator was then gradually added to the reactor via a pump over 5 hours at this temperature. Additional initiator was then fed into the reactor during another period of 1 hour at 140° C. Finally, the polymer is cooled down to 135° C. and diluted to a solids content of about 75% with butyl acetate.

TABLE-US-00016 TABLE 18 Acrylic resins recipe Example Ex. 7a Ex. 7b Ex. 7c Initial Reactor Charge W % W % W % Cardura ™ E10P 15.0 0 0 Rosin GE 0 15.0 0 H-Rosin GE 0 0 15.0 Butyl Acetate 14.0 14.0 14.0 Di t-Amyl peroxide 0.5 0.5 0.5 Feeding materials W % W % W % Cardura ™ E10P 10.0 0 0 Rosin GE 0 10.0 0 H-Rosin GE 0 0 10.0 Meth Acrylic acid 9.9 5.4 5.4 Hydroxy ethyl methacrylate 10.0 16.0 16.0 Styrene 20.0 20.0 20.0 Methyl methacrylate 14.0 12.6 12.6 Butyl Acrylate 21.1 20.0 20.0 Di t-Amyl peroxide 6.5 6.5 6.5 Post cooking W % W % W % Di t-Amyl peroxide 1.0 1.0 1.0 Solvent adding at 130° C. W % W % W % Butyl Acetate 18.0 18.0 18.0 Final solids content 75.0% 75.0% 75.0% Hydroxyl content 3.1% 3.1% 3.2%

Example 8

Polyester by Polyaddition

[0108] Trimethylol propane, methylhexahydrophthalic anhydride or succinic anhydride and n-Butyl Acetate were charged to a reaction vessel and heated at boiling of butyl acetate until complete conversion. Cardura E10P or Rosin GE or H-Rosin GE is then dropwise added, and the reaction pursued at 150° C. until acceptable acid value is reached. The polyesters have a solid content of about 80.0 wt %. Recipes and properties are defined in Table 19.

TABLE-US-00017 TABLE 19 Recipes of polyester polyols Example Ex. 8a Ex. 8b Ex. 8c Ex. 8d Ex. 8e Initial Reactor Charge Weight % Weight % Weight % Weight % Weight % Trimethylol propane 14.2 10.8 10.8 13.5 11.7 Methylhexahydrophthalic anydride 36.0 27.4 27.2 34.1 0 Succinic anhydride 0 0 0 0 26.2 Butyl Acetate 25.0 25.0 25.0 25.0 25.0 Feeding materials Weight % Weight % Weight % Weight % Weight % Cardura ™ E10P 49.8 0 0 39.2 62.1 Rosin GE 0 0 62.0 13.2 0 H-Rosin GE 0 61.8 0 0 0 Final solids content 81.3% 79.7% 80.3% 83.3% 81.3% Hydroxyl content 5.3% 4.0% 4.0% 5.1% 4.4% Acid value (mgKOH/g) 7.0 5.6 6.4 7.1 4.7

[0109] The resins of the example 8 can be formulated in coating compositions such as 2K (polyurethane) with a low VOC (volatile organic compound) level and providing excellent appearance combined with high drying speed.

Polyester by Polycondensation

[0110] The same type of polyesters described in Table 20 can also be prepared by using multi-functional acids instead of anhydrides. The reaction of the acidic functions with hydroxyls is performed at temperature around 200-240° C. until adequate conversion in presence of an azeotropic solvent like xylene to remove the water generated during the process.

Example 9

[0111] The resins of the example 8 can be blended with acrylic polyols in order to obtain suitable resins for e.g. automotive coatings. An example of acrylic resin is given in Table 19.

[0112] A glass reactor equipped with stirrer was flushed with nitrogen, and the initial reactor charge (see table 20) heated to 140° C. The monomer mixture including the initiator was then gradually added to the reactor via a pump over 5 hours at this temperature. Additional initiator was then fed into the reactor during another period of 1 hour at 140° C. Finally the polymer is cooled down to 135° C. and diluted to a solids content of about 75% with butyl acetate.

TABLE-US-00018 TABLE 20 Example of acrylic polyol for blending Example Ex. 9 Initial Reactor Charge Weight % Cardura ™ E10P 25.0 Butyl Acetate 14.0 Di t-Amyl peroxide 0.5 Feeding materials Weight % Meth Acrylic acid 9.9 Hydroxy ethyl methacrylate 10.0 Styrene 20.0 Methyl methacrylate 14.0 isoBornyl Methacrylate 0 Butyl Acrylate 21.1 Di t-Amyl peroxide 6.5 Post cooking Weight % Di t-Amyl peroxide 1.0 Solvent adding at 130° C. Weight % Butyl Acetate 18.0 Final solids content 75.2% Hydroxyl content 3.1%

[0113] The acrylic polyol is then blended with the polyester polyols from the example 8 at a level of 25 wt % polyester polyols for 75 wt % of acrylic polyol. The blend is used to formulated a clearcoat (Table 21) and applied by barcoat 80 μm wet:

TABLE-US-00019 TABLE 21 Blending of acrylic polyol with polyester polyols BYK 10 wt % in DBTDL 1 wt % in Blend 75/25 Tolonate HDT ButAc ButAc Butyl Acetate 60.0 g 17.9-19.9 g 0.45 g 2.3 g Dilute until adapted to OH % viscosity 40-55 mPa .Math. s

[0114] Comparative properties are shown in Table 22.

TABLE-US-00020 TABLE 22 Properties of clearcoats Clearcoats of Example Ex. 9a Ex. 9b Ex. 9c Ex. 9d Ex. 9e VOC (g/l) 384 383 392 386 381 Initial viscosity 53.7 54.3 52.8 54.6 52.8 (mPa .Math. s) Dust free time 44.0 17.5 15.0 26.0 46.5 (min) Koenig 1 7 7 3 3 hardness 6 hrs (sec)

Example 10

[0115] The acrylic and polyester polyols from the example 8 and the example 9 can be prepared in the same reactor in a hybrid process. The polyester polyol is first synthesized and used as initial reactor charge to prepare the acrylic polyol on the go during the same reaction. An example of such process is described in Table 23 with Cardura E10P used in polyester polyols, but Rosin GE or 11-Rosin GE can also be used in the preparation.

[0116] Trimethylol propane, methylhexahydrophthalic anhydride and n-Butyl Acetate were charged to a reaction vessel and heated at boiling of butyl acetate until complete conversion. Cardura E10P or Rosin GE or f-Rosin GE is then dropwise added and the reaction pursued at 150° C. for another hour to complete the acid conversion. The temperature inside the reactor is then dropped to 140° C. and the monomer mixture including the initiator was then gradually added to the reactor via a pump over 5 hours at this temperature. Additional initiator was then fed into the reactor during another period of 1 hour at 140° C. Finally the polymer is cooled down to 135° C. and diluted to a solids content of about 75% with butyl acetate.

TABLE-US-00021 TABLE 23 Polyester based acrylic polyol cooking (hybrid process) Ex.10a Ex.10b Ex.10c 1°/Polyester cooking, constituent in weight % Trimethylol propane 3.5 2.7 2.7 Methylhexahydrophthalic anhydride 9.0 6.8 6.8 n-Butyl acetate 5.0 5.0 5.0 Cardura E10P 12.5 15.5 15.5 2°/Acrylic polyol cooking, initial reactor charge in weight % Cardura E10P 18.8 0 0 Rosin GE 0 0 18.8 H-Rosin GE 0 18.8 0 Butyl acetate 10.0 10.0 10.0 3°/Acrylic polyol cooking, feeding material in weight % Methacrylic Acid 7.0 4.8 4.8 Hydroxyethyl methacrylate 9.8 12.0 12.0 Styrene 15.0 15.0 15.0 Butyl Acrylate 15.0 15.0 15.0 Methyl methacrylate 9.4 9.4 9.4 Di-t-Amyl Peroxide 5.3 5.3 5.3 4°/Acrylic polyol post cooking, feeding material in weight % Di-t-Amyl Peroxide 0.75 0.75 0.75 5°/Acrylic polyol solid content adjustment, solvent adding in weight % n-Butyl acetate 17.0 17.0 17.0

[0117] When applied in coatings, it has been observed that combining Rosin GE or H-Rosin GE with such hybrid process improves significantly both VOC (volatile organic compound) and early drying development.

Example 11

[0118] A polyether was obtained by charging the following constituents to a reaction vessel: 2.5500 grams of a Rosin GE, 1.1571 grams of dichloromethane, 0.0137 grams of boron trifluoride diethyl etherate. The reaction took place for 3 days at room temperature and the solvent was then thoroughly removed by evaporation.

Example 12

[0119] A polyether was obtained by charging the following constituents to a reaction vessel: 2.5500 grams of H-Rosin GE, 1.1571 grams of dichloromethane, 0.0137 grams of boron trifluoride diethyl etherate. The reaction took place for 3 days at room temperature and the solvent was then thoroughly removed by evaporation.

Example 13 Comparative

[0120] A polyether was obtained by charging the following constituents to a reaction vessel: 2.5500 grams of Cardura E10P, 1.1571 grams of dichloromethane, 0.0137 grams of boron trifluoride diethyl etherate. The reaction took place for 3 days at room temperature and the solvent was then thoroughly removed by evaporation.

[0121] Observations: Tg of the modified polyether resin is impacted by the composition of the type of glycidyl ester, rosin-based glycidyl ester giving a higher Tg.

Example 14

Polyether Resin

[0122] The following constituents were charged to a reaction vessel equipped with a stirrer, a thermometer and a condenser: 138 grams of di-Trimethylol propane (DTMP), 862 grams of Rosin GE, 135.5 grams of n-butylacetate (BAC) and 2.5 grams of Tin 2 Octoate. The mixture was heated to its reflux temperature of about 180° C. for about 4 hours till the Rosin GE was converted to an epoxy group content of less than 0.12 mg/g. After cooling down the polyether had a solids content of about 88%.

Example 15

Polyether Resin

[0123] The following constituents were charged to a reaction vessel equipped with a stirrer, a thermometer and a condenser: 139 grams of di-Trimethylol propane (DTMP), 861 grams of H-Rosin GE, 135.5 grams of n-butylacetate (BAC) and 2.5 grams of Tin 2 Octoate. The mixture was heated to its reflux temperature of about 180° C. for about 4 hours till the H-Rosin GE was converted to an epoxy group content of less than 0.12 mg/g. After cooling down the polyether had a solids content of about 88%.

Example 16 Comparative

Polyether Resin

[0124] The following constituents were charged to a reaction vessel equipped with a stirrer, a thermometer and a condenser: 123 grams of monopentaerythritol, 877 grams of Cardura E10P, 194 grams of n-butylacetate and 3.552 grams of Tin (II) 2-ethylhexanoate. The mixture was heated to a temperature of about 180° C. for about 6 hours till the Cardura E10P was converted to an epoxy group content of about 25 mmol/kg. After cooling down the polyether had a solids content of about 95%.

Example 17

Polyether Resin

[0125] The following constituents were charged to a reaction vessel equipped with a stirrer, a thermometer and a condenser: 79 grams of monopentaerythritol, 921 grams of Rosin GE, 183 grams of n-butylacetate and 0.3550 grams of Tin (II) 2-ethylhexanoate. The mixture was heated to a temperature of about 180° C. for about 6 hours till the Rosin GE was converted to an epoxy group content of about 25 mmol/kg. After cooling down the polyether had a solids content of about 95%.

Example 18

Polyether Resin

[0126] The following constituents were charged to a reaction vessel equipped with a stirrer, a thermometer and a condenser: 79 grams of monopentaerythritol, 921 grams of H-Rosin GE, 185 grams of n-butylacetate and 3.572 grams of Tin (II) 2-ethylhexanoate. The mixture was heated to a temperature of about 180° C. for about 6 hours till the H-Rosin GE was converted to an epoxy group content of about 25 mmol/kg. After cooling down the polyether had a solids content of about 95%.

[0127] Observation: significant improvement (quicker hardness development) is observed when replacing Cardura E10P by Rosin Ge or H-Rosin GE for the polyether cooking.

Example 19

Preparation for Vacuum Infusion of Composite Structures

[0128] 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: [0129] Epoxy resins blend: 850 part by weight Epikote 828 and 150 part of Rosin GE or H-Rosin GE. [0130] Curing Agent blend: 650 part by weight of Jeffamine D230 and 350 part by weight of Isophorone diamine (IPDA). [0131] Jeffamine D230 is a polyoxyalkyleneamines available from Huntsman Corporation. [0132] Epikote 828 is an epoxy resin available from Hexion Chemicals

Example 20

Example of Trowelable Floor and Patching Compound

[0133] The ingredients presented in the table 24 below were mixed for the preparation of a trowelable flooring compound:

TABLE-US-00022 TABLE 24 Preparation of a trowelable flooring compound Weight Volume BASE COMPONENT (parts) (parts) Supplier EPIKOTE 828LVEL 63.2 126.3 Hexion Rosin GE or H-Rosin GE 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 Sand 1-2 mm 582.3 496.4 SCR Sibelco Sand 0.2-0.6 mm 298.4 254.4 SCR Sibelco Total 880.7 750.8 Disperse into the base component using a concrete mixer CURING AGENT COMPONENT EPIKURE F205 40.2 87.2 Hexion 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

Example 21

Formulation for a Water Based Self-Leveling Flooring

[0134] The ingredients presented in the table 25 below were mixed for the preparation of a waterbased self-leveling flooring system.

TABLE-US-00023 TABLE 25 Preparation of a waterbased self-leveling flooring system CURING AGENT Weight COMPONENT (A) (parts) Supplier Comment EPIKURE 8545-W-52 164.00 Hexion (HEW = 320 g/eq) EPIKURE 3253 4.00 Hexion 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 water) 20.00 Elementis 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 sulphate 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) EPIROTE 828LVEL 81.00 Hexion GE9H 19.00 Mix (B) into (A) Total formulation A + B 1081.00 Formulation characteristics Fillers + Pigment/Binder 3.9 by weight ratio PVC 37.7 % v/v Density 1.9 g/ml Water content 12.5 % m/m

Example 22

Preparation of a Water-Based Acrylic Polyol Obtained Via Secondary Dispersion.

[0135] A glass reactor equipped with stirrer was flushed with nitrogen, and the initial reactor charge (see table 26) heated to 140° C. The monomer mixture including the initiator was then gradually added to the reactor via a pump over 5 hours at this temperature. Additional initiator was then fed into the reactor during another period of 1 hour at 140° C. The polymer is then cooled down to 80° C. and n,n-dimethyl ethanolamine is added and allow to react for 15 minutes under vigorous stirring. Pre-heated water at 80° C. is gradually added for 2 hrs in the reactor with a temperature maintained at 80° C. The waterborne resin is then cooled down at room temperature and discharge.

TABLE-US-00024 TABLE 26 Waterborne acrylic polyol recipes Example Ex. 22a Ex. 22b Ex. 22c Initial Reactor Charge W % W % W % Cardura ™ E10P 30.0 0  0  Rosin GE 0  30.0 0  H-Rosin GE 0  0  30.0 Butyl Glycol 10.0 10.0 10.0 Feeding materials W % W % W % Acrylic acid 12.9  9.4  9.4 Hydroxy ethyl methacrylate 14.0 17.5 17.5 Styrene 20.0 20.0 20.0 Methyl methacrylate 14.1 14.1 14.1 Butyl Acrylate  9.0  9.0  9.0 Di t-Amyl peroxide  2.5  2.5  2.5 Post cooking W % W % W % Di t-Amyl peroxide  0.5  0.5  0.5 Final solids content 91% 91% 91% Hydroxyl content 4.0%  3.6%  3.6%  Acid Value (mgKOH/g) ±30   ±30   ±30   Neutralization for 100 g W g W g W g N,N-dimethyl ethanolamine  3.2  3.2  3.2 Dispersion for 100 g W g W g W g Water at 80° C. 128   128   128   Solids content of dispersion ±40%  ±40% ±40%

[0136] The resins of the example 22 can be formulated in coating compositions such as 2K waterborne (polyurethane) with a near zero VOC (volatile organic compound) level and providing excellent appearance while maintaining high drying speed. It has been observed that acrylic polyols containing Rosin GE or H-Rosin GE induce faster dust free time early hardness development.