ES2364489T3 - USE OF POLYOXYPROPYLENE / POLYOXYETHYLENE COMPOUND COMPOUNDS FOR EMULSION POLYMERIZATION. - Google Patents

Abstract

Latex comprising at least one compound of Formula (I): ZY- [CH (R 3) -CH (R 4) -O] n- [CH2CH2-O] mR 5 in which Z represents a group having the following formula: where: r is 1 to 6; R 3 and R 4, which may be identical or different, represent hydrogen or a C1-C22 saturated or unsaturated, linear, branched or cyclic hydrocarbon group, provided that at least one of the R 3 or R 4 groups is not hydrogen; R 5 is hydrogen, -SO3M, -PO3 (M) 2, - (CH2) r-COOM or - (CH2) z-SO3M; Y represents -CH2-C (R 1) (R 2) -O- or -O-CH (R '1) -CH (R' 2) -O-, where R 1, R 2, R '1 and R '2, which may be identical or different, represent hydrogen or a C1-C22 hydrocarbon group, saturated or unsaturated, linear, branched or cyclic; z is 1 to 6; M represents hydrogen, an alkali metal or an N (R) 4 + ammonium function, where R, which may or may not be identical, represents hydrogen or a C1-C22 hydrocarbon group, saturated or unsaturated, linear, branched or cyclic, which may be hydroxylated; n is an integer or fractional number from 0 to 20, both inclusive; and m is an integer or fractional number from 2 to 80, inclusive.

Description

Field of the Invention

The present invention relates to emulsion polymerization using terpene-based surfactants as emulsifiers. Terpene-based surfactants comprise oxypropylene and oxyethylene units. The invention also relates to emulsion polymerization using sulfate and phosphate salts of terpene-based surfactants as emulsifiers. In addition, the present invention relates to methods for using said emulsions formed from terpene-based surfactants.

Background of the Invention

Polymers, both synthetic and natural, have been used in aqueous solutions as thickeners and flocculants. They have found their commercial use in many different final uses, such as wastewater treatment, water purification, papermaking, oil recovery, oil sludge drilling stabilizers and latex. Latex is a water-based polymer dispersion widely used in industrial applications.

Polymerization is a preferred technology used to make emulsion polymers and polymeric latexes. The use of latex, obtained by emulsion polymerization, in the production of paints or coatings for substrates is well known in the art. However, such paints or coatings are negatively affected by the presence of the necessary emulsifiers of the emulsion polymerization process. Often, emulsifiers cause foaming in the paint or coating. It would be convenient to obtain an emulsifier that had few foaming effects as well as improved stability properties.

In addition, in the polymerization of the latex, surfactants are needed to provide a stable monomer pre-emulsion, polymerization stability and overall stability to the final latex. However, traditional surfactants for the polymerization of latexes and emulsions have a tendency to foam when agitated and cause other difficulties during the polymerization process and in latex-containing final formulations. To overcome it, a defoamer is usually required. Unfortunately, the addition of a defoamer has multiple disadvantages, including the coating lagging as well as the increase in the cost of the raw material. It would be convenient to obtain a polymerization surfactant with few foaming effects and improved stability properties.

Summary of the Invention

The present invention provides processes for producing emulsion polymers of polyoxypropylene and polyoxyethylene terpene surfactants and the resulting emulsion polymer products. Surfactants based on polyoxypropylene and polyoxyethylene terpene produce emulsion polymers with greatly improved properties compared to emulsion polymers produced from conventional surfactants.

In particular, the invention relates to the use of polyoxypropylene and polyoxyethylene terpene based surfactants for latex synthesis. More particularly, the invention relates to the use of alkoxylate surfactants and their sulfate and phosphate salts useful in the emulsion and synthesis of latex. Even more particularly, the invention relates to the use of 6,6-dimethylbicyclo [3,1,1] hept-2-ene-2-ethanol alkoxylates and their sulfate and phosphate salts as emulsifiers useful in the emulsion and polymerization of the latex.

In addition, the polyoxypropylene and polyoxyethylene terpene based surfactants can be nonionic or anionic.

Detailed Description of the Invention and Preferred Embodiments

The present invention relates to the use, in emulsion polymerization, of a terpene-based surfactant. The terpene-based surfactant according to the invention comprises at least one compound having the following formula:

Z-Y- [CH (R3) -CH (R4) -O] n- [CH2CH2-O] m-R5

wherein Z represents a bicyclo [a, b, c] heptenyl or bicyclo [a, b, c] heptyl group, and a + b + c = 5 and a = 2, 3 or 4; b = 2 or 1; and c = 0 or 1. R3 and R4, identical or different, represent hydrogen or a C1-C22 saturated or unsaturated, linear, branched or cyclic hydrocarbon group, provided that at least one of the R3 or R4 groups is not hydrogen; and R5 represents hydrogen or a group selected from the following:

-SO3M -PO3 (M) 2

- (CH2) r-COOM

- (CH2) z-SO3M

in whose formula, M represents hydrogen, an alkali metal or an ammonium function N (R) 4+, where R, which may or may not be

5 identical, represents hydrogen or a C1-C22 hydrocarbon group, saturated or unsaturated, linear, branched or cyclic, which may be hydroxylated; r is in the range of 1 to 6; z is in the range of 1 to 6; n is an integer or a fractional number in the range of 0-20, both inclusive; m is an integer or a fractional number in the range of 2-80, inclusive.

The Z group is optionally substituted with at least one (C1-C6) alkyl group and may comprise a skeleton selected from those indicated below or the corresponding skeletons minus the double bond:

image 1

image2

5

10

fifteen

twenty

25

30

35

40

Y represents -CH2-C (R1) (R2) -O- or -O-CH (R’1) -CH (R’2) -O-, where

R1, R2, R’1 and R’2, which may be identical or different, represent hydrogen or a saturated C1-C22 hydrocarbon group

or unsaturated, linear, branched or cyclic, preferably C1-C6.

In a preferred embodiment of the invention, a suitable terpene-based surfactant comprises the use of Nopol-derived surfactants. Accordingly, the invention further provides for the new use of Nopol-derived surfactants to make emulsion polymers or polymeric latexes. In one aspect, the present invention relates to a method for making Nopol alkoxylate surfactants of 6,6-dimethylbicyclo [3,1,1] hept-2-ene-2-ethanol. The alkoxylate surfactants can be nonionic or anionic. The anionic alkoxylate surfactants are preferably 6,6-dimethylbicyclo alkoxylate sulfates or phosphates [3,1,1] hept-2-ene-2-ethanol. Suitable alkoxylate compounds are described in US Patent Application No. 10 / 820,929.

Preferred alkoxylated surfactants have the general formula:

image2

where R is hydrogen, CH3, or C2H5; n is from 0 to 20, both inclusive; m is from 2 to 80, both inclusive; and X represents a hydrogen atom, a phosphate, sulfate, sulphonate or carboxylate group. The part qualified by the integer "n" corresponds to oxypropylene units. Oxypropylene can also be substituted by oxybutylene or similar alkoxylates. The part qualified by the integer "m" corresponds to oxyethylene units. The oxypropylene and oxyethylene units may be block distribution or intermingled randomly or gradually decrease distribution along the chain ("tapered"). The compounds of the formula can also be described as 6,6-dimethylbicyclo alkoxylates [3,1,1] hept-2-ene-2-ethanol.

Preferred anionic alkoxylated surfactants have the general formula mentioned above where X represents a sulfate or phosphate group, and preferred non-ionic alkoxylated surfactants have the general formula mentioned above representing X a hydrogen group.

The terpene-based surfactants described above are used in latex emulsion polymers or as emulsifiers / surfactants in emulsion polymerization. Latex, the aqueous dispersions of polymers obtained by emulsion polymerization, are widely used in various applications, such as paints, adhesives, paper coatings, carpet backing and rheology modifiers (HASE).

As discussed above, the surfactants used to stabilize the latex can increase foaming during latex manufacturing and in the final application, and require the addition of a defoamer, which can lead to other drawbacks, for example the delayed of the coating that causes the formation of "fish eyes" in the paint film. The phenomenon of foaming is also harmful to the quality of the paint and should be avoided. The terpene-based surfactant of the present invention can be used in substitution of the traditional foaming emulsifiers employed in emulsion polymerization and eliminate or avoid the problem or inconvenience in the resulting latex and its final applications such as paints, coatings, adhesives or rheology modifiers.

In another aspect, the present invention relates to a method for making an emulsion polymer by emulsion polymerization in the presence of a terpene-based surfactant. For example, an emulsion polymer is produced by emulsion polymerization, in the presence of a Nopol surfactant of the formula:

image2

where R is hydrogen, CH3 or C2H5.

Nopol surfactant can be made in different ways. For example, a preferred surfactant where X is a sulfate group, for example -OSO3H2, can be obtained by sulphating the esterification product of a 6,6-dimethylbicyclo alkoxylate [3,1,1] hept-2-ene- 2-ethanol A Nopol surfactant can be obtained where X is a sulfate group, -OSO3H2, or a sulphonate group, -SO3H, by sulfating one of the alkoxylate hydroxyl groups or replacing the hydroxyl group with a sulphonate group, and then esterifying the remaining hydroxyl group of the alkoxylate with a functional vinyl carboxylic acid, or with an anhydride or an acid halide thereof.

Emulsion polymerization is described in G. Pohlein, "Emulsion Polymerization," Encyclopedia of Polymer Science and Engineering, vol. 6, pp. 1-51 (John Wiley & Sons, Inc., N.Y., N.Y., 1986). Emulsion polymerization is a heterogeneous reaction process in which unsaturated monomers or monomer solutions are dispersed in a continuous phase with the assistance of an emulsifying system and polymerized with free radical or redox initiators. The product, a colloidal dispersion of the polymer or polymer solution, is called latex.

Comonomers that are typically employed include monomers such as methyl acrylate, ethyl acrylate, methyl methacrylate, butyl acrylate, 2-ethylhexyl acrylate, other acrylates, methacrylates and combinations thereof, acrylic acid, methacrylic acid, styrene, vinyltoluene, vinyl acetate, vinyl esters of carboxylic acids superior to acetic acid, for example vinyl versatate, acrylonitrile, acrylamide, butadiene, ethylene, vinyl chloride and mixtures thereof.

In the above process, suitable initiators, reducing agents, catalysts and surfactants are well known in the art of emulsion polymerization. Typical initiators include ammonium persulfate (APS), hydrogen peroxide, sodium peroxydisulfate, potassium or ammonium, dibenzoyl peroxide, lauryl peroxide, ditert-butyl peroxide, 2,2'-azobisisobutyronitrile, t-butyl hydroperoxide and benzoyl peroxide.

Suitable reducing agents are those that increase the rate of polymerization and include, for example, sodium bisulfite, sodium hydrosulfite, sodium formaldehyde sulfoxylate, ascorbic acid, isoascorbic acid and mixtures thereof.

Suitable catalysts are those compounds that increase the polymerization rate and which, in combination with the reducing agents described above, favor the decomposition of the polymerization initiator under the reaction conditions. Suitable catalysts include transition metal compounds such as, for example, ferrous sulfate heptahydrate, ferrous chloride, cupric sulfate, cupric chloride, cobalt acetate, cobalt sulfate and mixtures thereof.

Surfactants that can be used in conjunction with the Nopol surfactant include ionic and non-ionic surfactants such as alkyl polyglycol ethers, for example the ethoxylation products of lauryl, tridecyl, oleyl and stearyl alcohol; alkylphenol polyglycol ethers such as the ethoxylation products of octyl- or nonyl-phenol, diisopropylphenol, triisopropylphenol; ammonium or alkali metal salts of sulphonates, sulfates, alkyl, aryl or alkylaryl phosphates, including sodium lauryl sulfate, octylphenol glycol ether ether sulfate, sodium dodecylbenzene sulfonate, sodium lauryl diglycol sulfate and ammonium tri-tert-butylphenol , as well as penta- and octaglycol sulphonates, sulphosuccinate salts such as ethoxylated nonylphenol half ester of sulfosuccinic acid, disodium noctildecyl sulfosuccinate, dioctyl sodium sulfosuccinate.

A typical preferred emulsion polymerization process involves the loading of water into a reactor and the feeding by separate streams of a pre-emulsion of the monomer and a solution of the initiator. A small amount of the pre-emulsion and a part of the initiator can be initially charged to the reaction temperature to produce a "seeding" latex. The "seeding" latex procedure results in better reproducibility of the particle size. Under "normal" initiation conditions, ie initiation conditions in which the initiator is heat activated, polymerization is usually carried out at 60-90 ° C. A typical "normal" initiator process, for example, could employ ammonium persulfate as the initiator at a reaction temperature of 80 ± 2 ° C. Under "redox" initiation conditions, ie initiation conditions in which the initiator is activated by a reducing agent, polymerization is usually carried out at 60-70 ° C. Normally, the reducing agent is added as a solution separately. A typical "redox" initiated process, for example, could employ potassium persulfate as initiator and sodium metabisulfite as a reducing agent at a reaction temperature of 65 ± 2 ° C.

In the above emulsions, the polymer is preferably present in the form of generally spherical particles, dispersed in water, with a diameter of 50 nanometers to 500 nanometers.

In particular, the terpene-based surfactants of the present invention can be incorporated in effective amounts in aqueous polymeric systems to enhance the stability of polymer emulsions. The monomers commonly used in the manufacture of acrylic paints are butyl acrylate, methyl methacrylate and ethyl acrylate. In acrylic paint compositions, the polymer is composed of one or more esters of acrylic or methacrylic acid, typically a mixture, for example at 50/50 by weight, of a high Tg monomer (by

10 example, methyl methacrylate) and a low Tg monomer (for example butyl acrylate), with small proportions, for example 0.5% to 2% by weight, of acrylic or methacrylic acid. Vinyl acrylic paints normally include vinyl acetate and butyl acrylate and / or 2-ethylhexyl acrylate and / or vinyl versatate. In the compositions of vinyl-acrylic paints, at least 50% of the polymer formed is composed of vinyl acetate, the rest being selected from esters of acrylic or methacrylic acids. Styrene-acrylic polymers are typically similar to polymers

Acrylics, where all or part of the methacrylate monomer thereof is replaced by styrene.

In order to further illustrate the invention and the advantages thereof, the following non-limiting examples are presented.

Examples

Example 1

20 Tests 1 to 13 for latex were prepared by the following formulation:

Description: Pressure Sensitive Adhesive Acrylic Latex

Total solids (by formula):

55%

Boiler load

Formula by weight (g) Active in weight (g) % BOTM1

Deionized water

191.50 0.00 0.00%

Sodium bicarbonate

0.55 0.55 0.10%

192.05 0.55

Monomer Emulsion

Deionized water

154.1 0.00 0.00%

Surfactant

5.50 3.19 0.58%

Butyl Acrylate

533.5 533.50 97.00%

Hydroxyethyl acrylate

11.0 11.00 2.00%

Acrylic acid

5.5 5.50 1.00%

709.6 553.19 550.0 = total grams of monomer

Initiating Solution

Deionized water

107.0 0.00 0.00%

Ammonium persulfate

2.2 2.20 0.40%

109.2 2.20

Total 1,010.8 555.94 Installation of the reactor: Glass boiler reactor 2 pieces of 1,200 ml. Initiator solution Rod stirrer with glass shaft / Teflon paddle wheel.

PROCEDURE 1. Heat the boiler load to 80 ° C while purging with nitrogen. Maintain the purge with nitrogen throughout the process. Adjust the stirring for a homogeneous mixture throughout the process. 2. Add 5% monomer emulsion (35.5 g). Wait 5 minutes until the temperature decreases. 3. Add 25% (27.3 g) of initiator solution and keep at 80 ° C for 15 minutes. 4. Feed the rest of the monomer emulsion and the initiator solution for a period of 2.5-3 hours. 5. Maintain the reaction temperature at 80 ° C in all feeds. 6. After the addition, heat to 85 ° C and hold for 30 minutes. 7. Cool below 30 ° C. Adjust the pH to 8 ± 0.2 with NH4OH and filter through a 100 mesh mesh. 1% based on total monomer concentration.

Surfactant substitutions and changes in the percentage concentrations of surfactant were as indicated in the following tests.

Table 1: Latex assays comparing Nopol propoxy (PO) / ethoxy (EO) sulfate control surfactant as indicated

Test #

one 2 3 4 5

Surfactant Substitution

Rhodapex CO-436 control Nopol 3PO / 2.5EO Sulfate NH4 + Nopol 5PO / 3EO Sulfate NH4 + Nopol 5PO / 5EO Sulfate NH4 + Nopol 5PO / 7EO Sulfate NH4 +

% Tens. total BOTM

0.58 0.58  0.58 0.58 0.58

% Tens. BOTM in the boiler load

0.0  0.0 0.0 0.0 0.0

% Wet Clot (BOTL)

0.05  0.01 0.03 0.05 0.14

% Wet granule (100 mesh BOTL)

trace trace 0.01 0.01 0.04

% Total solids

54.39 54.2 54.3 54.2 54.3

% Conversion

98.9 98.5  98.8 98.5 98.7

Average particle diameter / Dev. Ltd. (nm)

292.1 / 40  406.7 / 35.1 364.7 / 34.7  361.1 / 49.7 400.8 / 60.3

pH

 2.0 2.3 2.6 2.4 2.5

Viscosity (cP) at T Environment

140  67.5 85 70 85

Freeze / thaw cycles. #

0 0 0 0 0

Stability in oven at 60ºC

30 days pass 30 days pass 30 days pass 30 days pass 30 days pass

BOTM = Based on the total monomer BOTL = Based on the total liquid nm = Nanometer cP = Units in centipoise Rhodapex CO-436® (commercially available from Rhodia Inc.) is a sulfated alkyl phenol ethoxylate surfactant

The results in Table 1 showed that similar properties of the latex with Nopol PO / EO sulfates of various ranges of different molecular weights can be obtained.

Table 2: Latex tests comparing Nopol propoxy (PO) / ethoxy (EO) sulfate control surfactant as indicated

Test #

6 7 8 9

Substitute surfactant

Rhodapex CO436 control Nopol 3PO / 2.5EO Sulfate NH4 + Nopol 5PO / 3EO Sulfate NH4 + Nopol 5PO / 5EO Sulfate NH4 +

% Tens. total BOTM

0.58 0.58 0.58 0.58

% Tens. BOTM load in boiler

0 0.025 0.03 0.03

% of wet clot (BOTL)

0.05  0.05 0.08 0.06

% Wet granule (100 mesh BOTL)

trace trace 0.01 0.11

% Total solids

54.4 54.2 54.2 53.7

% Conversion

98.9 98.6 98.6 97.7

Medium diameter part./Desv.Std. (nm)

292/40  260/32 257/23 288/19

pH

 2.0 2.4 2.4 2.7

Viscosity (cP) at T Environment

78 88 80 85

BOTM = Based on the total monomer BOTL = Based on the total liquid nm = Nanometer cP = Units in centipoise Rhodapex CO-436® is a commercially available alkyl phenol ethoxylate sulfated surfactant from Rhodia.

The results shown in Table 2 indicate that similar properties of the latex with Nopol PO / EO sulfates of various ranges of different molecular weights can be obtained. Table 2 further illustrates the effect of the addition of Nopol PO / EO sulfate to the boiler load and the ability to vary the particle size in the latex.

10 final (compare with Table 1).

Tests 7-9 were performed to "adjust" the particle size of Nopol PO / EO sulfate so that it was in the range of 250-300 nm. The Rhodapex CO-436 (6 # test) was also in the 250-300 nm range. The particle size was controlled so as not to cause interference or variations in the tests that could be affected by the variation of the particle size, such as freezing / thawing, foaming, Ca ++ and mechanical stability.

Table 3: Latex assays comparing Nopol propoxy (PO) / ethoxy (EO) sulfate control surfactant as indicated

Test #

6 7 8 9

Substitute surfactant

Rhodapex CO436 control Nopol 3PO / 2.5EO Sulfate NH4 + Nopol 5PO / 3EO Sulfate NH4 + Nopol 5PO / 5EO Sulfate NH4 +

Stability test with Ca ++ (highest highest conc.)

Past (0.01 M) Past (0.01 M) Past (0.01 M) Past (0.01 M)

Foam test - Initial height (ml)

42  28 28 30

Foam test - Height in 5 min. (ml)

40  26 25 24

Foam test - Height in 15 min. (ml)

40  2. 3 twenty-one 22

Mechanical stability (Waring mixer at 20,000 rpm for 5 minutes)

Pass Pass Pass Pass

Surface tension (dynes / cm)

39.01  43.05 42.05 41.19

Movie Appearance

Good transparent film Good transparent film Good transparent film Good transparent film

Freezing / defrosting (stability according to # cycles)

(0) (0) (0) (0)

Stability in oven at 60ºC

30 days pass 30 days pass 30 days pass 30 days pass

M = molar

The results in Table 3 continue to show that Nopol PO / EO sulfates of several different molecular weights produce similar latex properties such as mechanical, chemical and thermal stability, film quality and surface tension compared to the control surfactant. The appearance of the movie was

10 excellent for all the latexes tested in Table 3, producing drops that were transparent and free of defects. No appreciable difference was observed between the control latex and sulfate Nopol PO / EO films. The results in Table 3 also illustrate that Nopol PO / EO sulfates of several different molecular weights can be used to produce latexes with lower foaming properties, as seen in the lower initial foam height as well as foam height lower over time.

15 Table 4: Adherence Results Adhesion Tests without Additional Pressure and Peeling

Test #

Description Adhesion without additional pressure (Max Load - N) Chipped at 180º (N / cm)

6

Control latex manufactured with Rhodapex CO-436 9.80  2.19

7

Latex made with Nopol 5PO / 3EO sulfate 11.06  2.41

8

Latex made with Nopol 5PO / 5EO sulfate 13.34  2.81

9

Latex made with Nopol 5PO / 7EO sulfate 13.18  2.66

The adhesion and chipping properties of four PSA latexes were tested. The tested latex tests are described in Table 2.

Adhesion Test without Additional Pressure

5 Samples were prepared by stretching the neutralized latex on a PET film with a 3 thousand 3 ”(7.6 cm) stretch bar. The drops were allowed to air dry and hardened in an oven at 105 ° C for 5 minutes before covering the film with removable paper. A 1 ”(2.54 cm) wide strip of the PET / adhesive / removable paper interleaving was cut and cut to a length of 7” (18 cm) with the adhesive in the middle for adhesion test without additional pressure The ends were lined with tape for fasteners and tests were performed

10 reducing the adhesive coated PET film strip to 1 ”(2.54 cm) from the SS test surface. Setting at 1 ”(2.54 cm) ensures that each sample is forced against the surface of SS with the same pressure. An Instron Tensiometer® tensiometer was used to lift the mesh at 12 ”/ minute (30.5 cm / minute) and the maximum force required to remove the mesh was recorded.

180º Chipping Test

15 The sample preparation was somewhat different for the chipping test in which the fall was made at the lower end of the PET film, compared to the medium. It was done so that there was a long "tail" of PET for the upper hold in order to grab the chipping test. Standard SS substrates were used and the pressure applied to the adhesive coated PET film was kept uniform by a standard roller for the same number of passes at approximately the same speed.

20 Generally, good strength and strong adhesion to flaking in pressure sensitive adhesive latexes are desirable and both properties can have a potential impact depending on the surfactant used to make the latex.

The data in Table 4 summarize the results of adhesion tests without additional pressure and chipping at 180º. Multiple replications were performed for each sample. The Nopol sulfate latex showed an equivalent or better yield with respect to the control.

Table 5: Propoxy (PO) / ethoxy (EO) Nopol sulfate latex assays as indicated

Test #

10 eleven 12 13

Substitute surfactant

Nopol 5PO / 19EO Sulfate NH4 Nopol 5PO / 19EO Sulfate NH4 + Nopol 5PO / 25EO Sulfate NH4 + Nopol 5PO / 25EO Sulfate NH4 +

% Tens. Total BOTM

0.58 0.58 0.58 0.58

% Tens. loaded in boiler BOTM

0 0.06 0 0.06

% Wet Clot (BOTL)

0.11 0.09 0.06 0.10

% Wet granule (100 mesh BOTL)

0.03  0.10 0.04 1.27

% Total solids

54.4 54.2 54.4 53.6

% Conversion

98.9 98.6 98.9 97.4

Average particle diameter / Dev. Ltd. (nm)

449/43  256/28 457/71 408/76

pH

 2.6 2.9 2.5 2.7

Viscosity (cP) at T Environment

73  78 65 70

BOTM = Based on total monomer BOTL = Based on total liquid nm = Nanometer cP = Units in centipoise SS = Stainless steel PET = Polyethylene terephthalate

The results shown in Table 5 show that similar properties of the latex with Nopol PO / EO sulfates of various ranges of different molecular weights can be obtained compared to the control surfactant. Table 5 illustrates the effect of the addition of Nopol PO / EO sulfate to the boiler load and the ability to vary the particle size in the final latex.

Example 2

Tests 14 to 27 of latex were prepared by means of the following formula: PROCEDURE

Description: Acrylic Latex for Total Solid Paints (by formula): 51%

Boiler load

Forum weight (g) Active weight (g) % BOTM1

Deionized water

191.22 0.00 0.00%

Surfactant

 1.74 0.02 0.20%

192.96 1.02

Monomer Emulsion

Deionized water

191.67 0.00 0.00%

Surfactant

 15.37 9.02 1.80%

Methyl methacrylate

260.00 260.00 52.00%

Butyl Acrylate

235.00 235.00 47.00%

Methacrylic acid

5.00 5.00 1.00%

707.04 509.02 500.00 = total grams of monomer

Initiating Solution

Deionized water

98.00 0.00 0.00%

Ammonium persulfate

2.00 2.00 0.40%

100.00 2.00

Total 1,000.00 512.04 Reactor installation: Glass boiler reactor in 2 pieces of 1,200 ml. Rod shaker with glass shaft / Teflon paddle wheel.

one.

 Heat the kettle load to 82 ° C while purging with nitrogen. Maintain the purge with nitrogen throughout the process. Adjust the stirring for a homogeneous mixture throughout the process.

2.

 Add 2% monomer emulsion (14.14 g). Wait 5 minutes for the temperature to decrease.

3.

 Add 25% (25.0 g) of initiator solution and keep at 80 ° C for 15 minutes.

Four.

Feed the rest of the monomer emulsion and the initiator solution for a period of 2.5-3 hours.

5.

 Maintain the reaction temperature at 80 ° C in all feeds.

6.

 After the addition, heat to 85 ° C and hold for 30 minutes.

7.

 Cool below 30 ° C. Adjust the pH to 9 with NH4OH and filter through a 100 mesh mesh. 1% based on total monomer concentration.

Surfactant substitutions and changes in the percentage concentrations of surfactant were as indicated in the following tests.

Table 6: Latex tests comparing NPO propoxy (PO) / ethoxy (EO) sulfate control surfactants as indicated

Test #

14 fifteen 16 17

Surfactant Substitution

Rhodapex CO436 control Rhodapex AB20 control Rhodapex LA40 / S control Nopol sulfate 5PO / 7EO

% BOTM Total Surfactant

2.00  2.00  2.00  2.00

% BOTM boiler surfactant

0.20  0.20  0.20  0.20

Cog. wet,% BOTL

0.01 0.03 0.48 0.06

Wet granule,% BOTL

0.04  null  1.08 0.01

pH

9.1 9 9 9

% Solids

49.91  49.93  49.68  49.98

% Conversion

97.48 97.71 97.2 97.77

Particle size

Mean diameter, nm

114.6  123.6  121.1  137.2

Standard Deviation, nm

20.2 18 8.8 21.3

Standard deviation, %

17.6 14.5 7.3 15.5

Viscosity, 25 ° C, cP.

457.9  565.9  535.9  300.9

BOTM = Based on total monomer

BOTL = Based on total liquid nm = Nanometer cP = Units in centipoise Rhodapex CO-436 is a commercially available alkyl phenol ethoxylate sulfated surfactant

of Rhodia. Rhodapex AB-20 is a sulfated ethoxylate alcohol commercially available from Rhodia. Rhodapex LA-40 / S is a sulfated ethoxylate alcohol commercially available from Rhodia.

Table 6 shows the latex properties of the Nopol PO / EO sulfate formulation of Example 2 compared to three commercially available surfactants. Table 6 illustrates that similar properties of latex with Nopol PO / EO sulfate were obtained compared to commercial control surfactants.

Table 7: Latex tests comparing propoxy (PO) / ethoxy (EO) 5 Nopol sulfate as indicated

Test #

18 19 twenty twenty-one 22

Surfactant Substitution

5PO / 5EO Nopol Sulfate 5PO / 7EO Nopol Sulfate 5PO / 19EO Nopol Sulfate 5PO / 25EO Nopol Sulfate 5PO / 30EO Nopol Sulfate

% BOTM Total Surfactant

2.00  2.00 2.00 2.40 2.40

% Tens. loaded in boiler BOTM

0.20  0.20 0.20 0.20 0.20

% BOTL wet clot

0.04  0.09 0.04 0.02 0.04

% BOTL wet granule

0.16  0.01 0.01 null 0.02

pH

 9 9 9 9 9

% Solids

fifty 49.94 50.09 49.78 50.62

% Conversion

97.8 97.72  97.83 97.01 98.47

Particle size

Mean diameter, nm

149.5  147.7 162.5 191 176.2

Dev. estd., nm

31.1 10.9 16.1 24.9 10

Def. est.,%

20.8 7.4 9.9 13.0 5.6

Viscosity, 25ºC, cP

107 269 252 94 274.5

BOTM = Based on total monomer BOTL = Based on total liquid nm = Nanometer cP = Units in centipoise

The results in Table 7 show that similar latex properties can be obtained with Nopol EP / EO sulfates of various ranges of different molecular weights, as compared to the control surfactants (Table 6).

Table 8: Latex tests comparing control surfactants with propoxy (PO) / ethoxy (EO) Nopol sulfate as indicated

Test #

2. 3 24 25 26 27

Surfactant Substitution

Rhodapex CO-436 control Rhodapex AB-20 control Rhodapex LA-40 / S control 5PO / 5EO Nopol Sulfate 5PO / 7EO Nopol Sulfate

% BOTM Total Surfactant

2.00  2.00 2.00 2.00 2.00

% Tens. loaded in boiler BOTM

0.05  0.15 0.10 0.20 0.20

% BOTL wet clot

0.05  0.04 0.01 0.06 0.02

% BOTL wet granule

0.06  0.08 0.02 0.01 0.01

pH

 9 9 9 9 9

% Solids

49.83 50.03  50.11 49.98 50.3

% Conversion

97.32 97.71  97.72 97.77 98.4

Particle size

Mean diameter, nm

140.6  153.1 143.2 137.2 145.6

Standard deviation, nm

17 20.4 20.2 21.3 16.4

Standard deviation,%

12.1 13.3 14.1 15.5 12.6

Viscosity, 25 ° C, cP.

180.0  239.4 247.9 300.9 227.0

Foam Test

Initial volume of liquid, ml

200 200 200 200 200

Initial Foam Height, ml

425 420 410 355 372.5

Height at 5 minutes, ml

425 415 400 350 370

Height at 15 minutes, ml

415 410 390 3. 4. 5 365

Initial increase in volume,%

113  110 105 78 86

BOTM = Based on the total monomer BOTL = Based on the total liquid nm = Nanometer cP = Units in centipoise Rhodapex CO-436 is a commercially available alkyl phenol ethoxylate sulfated surfactant from Rhodia. Rhodapex AB-20 is a sulfated ethoxylate alcohol commercially available from Rhodia. Rhodapex LA-40 / S is a sulfated ethoxylate alcohol commercially available from Rhodia.

The results in Table 8 show that the size of latex particles can be adjusted ("tuned") by changing the amount of surfactant added directly to the boiler load while maintaining the same total amount of surfactant used in the polymerization . (See, for comparison, the control surfactant assays in Table 6). When the control surfactants and Nopol PO / EO sulfate were adjusted to the same particle size range, as in Table 8, formation results were obtained

of lower foam with Nopol PO / EO sulfate compared to commercially available surfactants. Example 3 Tests 28 to 32 of latex were prepared by the following formula:

Description: Vinyl-Acrylic Latex for Total Solid Paints (by formula): 51.7%

Boiler load

Formula weight (g) Active weight (g) % BOTM1

Deionized water

199.50 0.00 0.00%

Sodium bicarbonate

 0.50 0.50 0.10%

200.00 0.50

Monomer Emulsion

Deionized water

154.26 0.00 0.00%

Surfactant A

25.85 7.50 1.50%

B surfactant

7.69 5.00 1.00%

Sodium bicarbonate

1.50 1.50 0.30%

Vinyl acetate

400.00 400.00 80.00%

Butyl Acrylate

92.50 92.50 18.50%

Methacrylic acid

7.50 7.50 1.50%

689.30 514.00 500.00 = total grams of monomer

Initiating Solution

Water

 98.00 0.00 0.00%

Deioniz sodium persulfate.

2.00 2.00 0.40%

100.00 2.00

Chaser Solutions

Deionized water

5.0 0.00 0.00%

T-BHP (70%) 2

 0.40 0.28 0.06%

0.00

 0.00%

Deionized water

5.00 0.00 0.00%

Isoascorbic acid

0.30 0.30 0.06%

0.00

 0.00%

 10.70

0.58

Total 1,000.00 517.08 Installation of the reactor: Boiler reactor in 2 pieces of 1,200 ml. Rod shaker with glass shaft / Teflon paddle wheel.

PROCESS

one.

 Heat the boiler load to 80 ° C while purging with nitrogen. Maintain the purge with nitrogen throughout the process. Adjust the stirring for a homogeneous mixture throughout the process.

2.

 Add 3% monomer emulsion (20.68 g). Wait 5 minutes for the temperature to recede.

3.

 Add 25% (25.0 g) of initiator solution and keep at 80 ° C for 15 minutes.

Four.

 Feed the rest of the monomer emulsion for 3.75 hours and the initiator solution for 4.25 hours.

5.

 Maintain the reaction temperature at 80 ° C in all feeds.

6.

 After the addition, keep at 80 ° C for 15 minutes.

7.

 Cool the reactor to 65 ° C. Add the chaser solutions. Maintain the temperature at 63 ± 2 ° C for 20 minutes.

8.

 Cool below 30 ° C, adjust the pH to 7.0-7.5 with NH4OH and filter through a 100 mesh mesh.

one

   % based on total monomer concentration.

2

   tert-butyl hydroperoxide, 70%

Surfactant substitutions and changes in the percentage concentrations of surfactant were as indicated in the following tests.

Table 9: Latex tests comparing NPO propoxy (PO) / ethoxy (EO) sulfate control surfactants as indicated

Test #

28 29 30 31 32

Description

Tensioac replacement. A,% BOTM Total Surfactant

Rhodapex LA-40 / S control, 1.5% Rhodapex LA40 / S 1.5% control 5PO / 7EO Nopol sulfate, 1.5% Rhodapex LA40 / S control, 1.5% 5PO / 7EO Nopol sulfate, 1.5%

Tensioact substitution. B,% BOTM Total Surfactant

Rhodasurf 3065 control, 1% Rhodasurf 3065 control, 1% Rhodasurf 3065 control, 1% NPO 5PO / 30EO, 1%, NPO 5PO / 30EO, 1%

BOTL Wet Co%

0 0 0 0 0

% BOTL wet granule

0.09  0.07 0.26 0.38 0.28

pH

 7.4 7.3 7.15 7.45 7.35

% Solids

49.53 49.71  49.28 50.15 49.77

% Conversion

95.91 96.29  93.02 96.6 96.33

Particle size

Mean diameter, nm

149.8  159.63 184.6 148.17 186.06

Deviation std., Nm

17.9  12.6 25.5 23.2 30.27

Deviation std.,%

13.13 7.97  13.83 12.33 16.33

Viscosity, 25 ° C, cP.

280 285 230 275.0 220

Foam Test

Initial volume of liquid, ml

200  200 200 200 200

Initial Foam Height, ml

415  415 385 435 405

Height at 5 minutes, ml

415  415 385 435 405

Height at 15 minutes, ml

415  415 385 435 405

Initial increase in volume,%

108  108 93 118 103

BOTM = Based on the total monomer BOTL = Based on the total liquid nm = Nanometer cP = Units in centipoise Rhodasurf 3065 is an ethoxylate (non-ionic) alcohol commercially available from Rhodia.

Rhodapex LA-40 / S is a sulfated (anionic) ethoxylate alcohol commercially available from Rhodia.

Table 9 shows the latex properties of the formulations of Example 3, which uses both an anionic surfactant (Surfactant A) and a nonionic surfactant (Surfactant B). Anionic surfactants, such as sulfated alcohol ethoxylates, carry a negative charge. The agents

5 nonionic surfactants, such as alcohol ethoxylates, have a neutral charge. Some latex formulations use both types of surfactants to optimize certain properties, such as stability and salt resistance.

The results in Table 9 compare two commercially available standard surfactants with a Nopol PO / EO sulfate (anionic) and also a Nopol PO / EO (nonionic). In Test # 30, the PO / EO sulfate from

10 Nopol is replaced by the anionic surfactant control agent. In Test # 31, the Nopol PO / EO is replaced by the non-ionic control surfactant. In Test # 32, both Nopol surfactants were replaced by control surfactants.

As illustrated in Table 9, similar latex properties were obtained with Nopol-based surfactants. Table 9 further illustrates that lower foaming properties were obtained by replacing the anionic control surfactant with Nopol PO / EO sulfate.

Claims (17)

1. Latex comprising at least one compound of Formula (I): Z-Y- [CH (R3) -CH (R4) -O] n- [CH2CH2-O] m-R5 (I) in which Z represents a group that has the following formula: image 1 image 1

 where:

5

R3 and R4, which may be identical or different, represent hydrogen or a C1-C22 saturated or unsaturated, linear, branched or cyclic hydrocarbon group, provided that at least one of the R3 or R4 groups is not hydrogen;

R5 is hydrogen, -SO3M, -PO3 (M) 2, - (CH2) r-COOM or - (CH2) z-SO3M;

Y represents -CH2-C (R1) (R2) -O- or -O-CH (R’1) -CH (R’2) -O-,

where R1, R2, R’1 and R’2, which may be identical or different, represent hydrogen or a hydrocarbon group

C1-C22, saturated or unsaturated, linear, branched or cyclic;

10

r is 1 to 6;

z is 1 to 6;

M represents hydrogen, an alkali metal or an ammonium function N (R) 4 +, where R, which may or may not be

identical, represents hydrogen or a C1-C22 hydrocarbon group, saturated or unsaturated, linear, branched or

cyclic, which may be hydroxylated;

fifteen

n is an integer or fractional number from 0 to 20, both inclusive; Y

m is an integer or fractional number from 2 to 80, both inclusive.

2.

Latex according to claim 1, characterized in that said compound has the formula:

image 1 where X represents a hydrogen, phosphate, sulfate, carboxylate or sulphonate group and R is hydrogen, CH3 or C2H5. 3. Latex according to claim 2, characterized in that said component has the formula: image 1

Four.

Latex according to claim 1, characterized in that said compound is non-ionic.

5.

Latex according to claim 1, characterized in that said compound is anionic.

6.

Latex according to claim 1 further comprising surfactants selected from the group consisting of ionic surfactants, non-ionic surfactants or combinations thereof.

7.

Latex according to claim 1, characterized in that at least one of R1, R2, R’1 or R’2 represents a saturated or unsaturated C1-C6 hydrocarbon group.

8.

Paint comprising the latex according to claim 1.

9.

Process for preparing latex comprising the stage of:

emulsion polymerization of a reaction mixture, said reaction mixture comprising at least one compound of formula (I): Z-Y- [CH (R3) -CH (R4) -O] n- [CH2CH2-O] m-R5 (I) in which Z represents a group that has the following formula: image2 image 1  where: R3 and R4, which may be identical or different, represent hydrogen or a C1-C22 hydrocarbon group, saturated or unsaturated, linear, branched or cyclic, provided that at least one of the R3 or R4 groups is not hydrogen; R5 is hydrogen, -SO3M, -PO3 (M) 2, - (CH2) r-COOM, or - (CH2) z-SO3M; Y represents -CH2-C (R1) (R2) -O- or -O-CH (R’1) -CH (R’2) -O-, where R1, R2, R’1 and R’2, which may be identical or different, represent hydrogen or a C1-C22 hydrocarbon group, saturated or unsaturated, linear, branched or cyclic; r is 1 to 6; z is 1 to 6; M represents hydrogen, an alkali metal or an ammonium function N (R) 4+, where R, which may or may not be identical, represents hydrogen or a C1-C22 hydrocarbon group, saturated or unsaturated, linear, branched or cyclic, which may be hydroxylated; n is an integer or fractional number from 0 to 20, both inclusive; Y m is an integer or fractional number from 2 to 80, both inclusive.

10.

Process according to claim 9 comprising the following steps: a) formation of a stable aqueous pre-emulsion from a monomer and the compound of formula (I), b) formation of said reaction mixture comprising the pre-emulsion, an initiator and water, c) introduction of the reaction mixture into a reactor and addition of 1 to 10% by weight of said pre

emulsion in said reaction mixture, and d) heating said reaction mixture obtained at the end of step c) at a temperature between 40 ° C and 90 ° C to generate a sowing formed of latex particles dispersed in water.

eleven.

Process according to claim 10 further comprising:

e) the reaction of sowing formed of latex particles in water dispersion obtained in step d) with an additional amount of initiator to produce latex, and f) optionally, the heating of the latex obtained in step e) at a temperature between 40 ° C and 90 ° C.

12.

Process according to claim 10, characterized in that said monomer is selected from the group consisting of methyl acrylate, ethyl acrylate, methyl methacrylate, butyl acrylate, 2-ethylhexyl acrylate, acrylates, methacrylates, acrylic acid, methacrylic acid, styrene, Vinyl toluene, vinyl acetate, vinyl esters of carboxylic acids superior to acetic acid, vinyl versatate, acrylonitrile, acrylamide, butadiene, ethylene, vinyl chloride and mixtures thereof.

13.

Process according to claim 10, characterized in that said initiator is selected from the group consisting of ammonium persulfate, hydrogen peroxide, sodium peroxydisulfate, potassium, ammonium, dibenzoyl peroxide, lauryl peroxide, di-tert-butyl peroxide, 2,2'-azobisisobutyronitrile, t-butyl hydroperoxide, benzoyl peroxide and mixtures thereof.

14.

Process according to claim 10, characterized in that 0.2% to 5% by weight of the compound of formula (I) is used with respect to the total weight of the water used during the polymerization.

fifteen.

Process according to claim 14, characterized in that from 1% to 4% by weight of the compound of formula (I) is used with respect to the total weight of the water used during the polymerization.

16.

Process according to claim 10, characterized in that from 1% to 8% by weight of the compound of formula (I) is used with respect to the total weight of the monomers used during the polymerization.

17.

Process according to claim 16, characterized in that from 2% to 5% by weight of the compound of formula (I) is used with respect to the total weight of the monomers used during the polymerization.

18.

Building materials, paper, paints, adhesives or rheology modifiers including the latex prepared according to the process according to claim 11.