KR20010077846A - Improved polymeric compositions - Google Patents

Abstract

PURPOSE: Provided is a new composition capable of maintaining its tackiness under a condition applied to a building and other constructions exposed to an extreme outside temperature. CONSTITUTION: The polymer composition contains mainly an aqueous emulsion polymer of an acrylic polymer, which has a glass transition temperature (Tg) of -90 to 20 deg.C, and is formed by performing a free radical polymerization of at least one ethylenically unsaturated nonionic acrylic monomer with 0.5-5 wt.% ethylene-based unsaturated carboxylic acid monomer based on the total weight of the above polymer until 90-99.7 wt.% above monomers are converted to the polymer based on the total weight of the above polymer, and then converting at least one half of residual monomer in the presence of 0.1-1.0 wt.% t-hydroperoxide. The obtained aqueous composition is suitable for the use in the case of drying condition as improved elastic coating, coking agent, sealant or pressure-sensitive adhesive.

Description

IMPROVED POLYMERIC COMPOSITIONS

The present invention provides an aqueous composition suitable for use in drying as an elastomeric coating, caulk, sealant or pressure sensitive adhesive, an improved elastomeric coating, coke, sealant or A method for preparing an aqueous emulsion polymer suitable for use as a pressure sensitive adhesive and a method for providing an improved elastomeric coating, coke or sealant, or a pressure sensitive adhesive. More specifically, 0.5-5% by weight of the ethylenically unsaturated carboxylic acid monomer based on the total weight of the polymer and at least one ethylenically unsaturated nonionic acrylic monomer is 90-99.7% by weight of the monomer based on the total weight of the polymer. Free radical polymerization which is converted to a polymer until; And a glass transition temperature formed by subsequent polymerization in which at least half of the weight of the residual monomers is polymerized in the presence of 0.1-1.0% by weight of t-amyl hydroperoxide based on the total weight of the polymer, An aqueous composition suitable for use in drying as an improved elastomeric coating, coke, sealant or pressure sensitive adhesive comprising a large amount of acrylic aqueous emulsion polymer.

The present invention provides an aqueous composition suitable for use in drying as an improved elastomeric coating, coke or sealant to maintain its original performance without cracking under pressure even at temperatures below 0 ° C. Elastomeric coatings, cokes and sealants are often applied to buildings and other structures used in outdoor temperature extremes and preferably maintain their original performance under such conditions. In addition, the present invention provides an aqueous composition suitable for use in drying as an improved pressure sensitive adhesive having an improved improved tact on its own, or alternatively, with a tensile or shear strength that retains a useful level of tack. The same provides a basis for the improvement of other adhesive properties.

U. S. Patent 5,540, 987 discloses emulsion polymers having low residual formaldehyde and providing saturated cellulosic webs with improved tensile strength. The polymer is formed by the use of hydrophobic hydroperoxide and ascorbic acid initiator over the course of the reaction.

The problem faced by the present inventors is to provide an aqueous composition suitable for use in drying as an improved elastomeric coating, coke, sealant or pressure sensitive adhesive. Surprisingly, the inventors have found that the use of t-amyl hydroperoxide in the final stage of polymerization is sufficient to provide an improved elastomeric coating, coke, sealant or pressure sensitive adhesive polymer.

In one aspect of the invention,

Free conversion of 0.5-5% by weight of ethylenically unsaturated carboxylic acid monomer to 90-99.7% by weight of monomer, based on the total weight of polymer, based on the total weight of at least one ethylenically unsaturated nonionic acrylic monomer and polymer Radical polymerization; And a glass transition temperature (T g) of the polymer formed by subsequent polymerization in which at least half of the residual monomers are polymerized into the polymer in the presence of 0.1-1.0 wt% of t-amyl hydroperoxide based on the total weight of the polymer. An aqueous composition suitable for use in drying is provided as an improved elastomeric coating, coke, sealant or pressure sensitive adhesive comprising a large amount of acrylic aqueous emulsion polymer, ˜20 ° C.

In the second aspect of the present invention,

Free conversion of 0.5-5% by weight of ethylenically unsaturated carboxylic acid monomer to 90-99.7% by weight of monomer, based on the total weight of polymer, based on the total weight of at least one ethylenically unsaturated nonionic acrylic monomer and polymer Forming a large amount of acrylic aqueous emulsion polymer having a glass transition temperature (Tg) of −90 to 20 ° C. by radical polymerization; And subsequently polymerizing such that at least half of the residual monomers polymerize into the polymer in the presence of 0.1-1.0% by weight of t-amyl hydroperoxide based on the total weight of the polymer; Provided are methods for preparing an aqueous emulsion polymer suitable for use as an improved elastomeric coating, coke, sealant or pressure sensitive adhesive.

In the third aspect of the present invention,

A method of coating a substrate with an aqueous composition for elastomeric coating on the substrate is provided.

In a fourth aspect of the invention, the invention provides a method of applying an aqueous coke or sealant composition to a substrate.

In a fifth aspect of the invention, the invention provides a method of providing a pressure sensitive adhesive on a substrate.

The present invention provides 0.5-5% by weight of ethylenically unsaturated carboxylic acid monomer based on the total weight of the polymer with at least one ethylenically unsaturated nonionic acrylic monomer and up to 90-99.7% by weight of the monomer based on the total weight of the polymer. The glass transition temperature, formed by the free radical polymerization to be converted and the subsequent polymerization in which at least half the weight of the residual monomer is polymerized into the polymer in the presence of 0.1-1.0% by weight of t-amyl hydroperoxide based on the total weight of the polymer ( An aqueous composition suitable for use in drying with an elastomeric coating having improved low temperature elongation comprising a large amount of acrylic aqueous emulsion polymer having a Tg) of -90 to 20 ° C.

The large amount of acrylic aqueous emulsion polymer comprises at least one copolymerized ethylenically unsaturated nonionic acrylic monomer. As used herein, "a large amount of acrylic" means that the polymer is derived from (meth) acrylic monomers such as, for example, (meth) acrylate esters, (meth) acrylamides, (meth) acrylonitrile, and (meth) acrylic acid. It means that the copolymerized unit contains at least 50% by weight. The term "(meth)" used before other terms such as acrylate or acrylamide throughout this specification means acrylate or acrylamide and both methacrylate and methacrylamide, respectively. As used herein, "nonionic monomer" means that the copolymerized monomer residue does not have an ionic charge between pH = 1-14.

Ethylenically unsaturated nonionic acrylic monomers include, for example, methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, decyl acrylate, lauryl acrylate, methyl methacrylate, butyl methacrylate, (Meth) acrylic ester monomers including isodecyl methacrylate, lauryl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate. Other ethylenically unsaturated nonionic monomers that may be incorporated into the polymer in such a condition that the polymer should be a large amount of acrylic in the composition include, for example, styrene and substituted styrenes; butadiene; Vinyl acetate, vinyl butyrate and other vinyl esters; And vinyl monomers such as vinyl chloride, vinylidene chloride. Preferred are all-acrylic, styrene / acrylic and vinyl acetate / acrylic polymers.

Emulsion polymers are based on total monomer weight, for example, with acrylic acid, methacrylic acid, crotonic acid, itaconic acid, fumaric acid, maleic acid, monomethyl itaconate, monomethyl fumarate, monobutyl fumarate and maleic anhydride. The same copolymerized monoethylenically-unsaturated carboxylic acid monomer 0.5 to 5% by weight.

The emulsion polymers used in the present invention are based on monomer weight, for example, allyl methacrylate, diallyl phthalate, 1,4-butylene glycol dimethacrylate, 1,2-ethylene glycol dimethacrylate, 1 0 to 1% by weight of copolymerized multi-ethylenically unsaturated monomers such as, 6-hexanediol diacrylate and divinyl benzene.

The glass transition temperature (“Tg”) of the emulsion polymer is -90 to 20 ° C. as measured by differential scanning calorimetry (DSC), which takes the mid-point of the heat flow versus temperature transition as the Tg value, to achieve the required polymer Tg range. The monomers and amount of monomers selected for are well known in the art. The preferred Tg of the emulsion polymer for the elastomeric wall coating is -40 to 20 ° C; Preferable Tg of coke and sealant is -60-20 degreeC; Preferable Tg of a pressure sensitive adhesive is -90-0 degreeC.

Polymerization techniques used to prepare aqueous emulsion-polymers are well known in the art. Conventional surfactants in emulsion polymerization processes include, for example, ammonium salts of alkali metal alkyls, aryl or alkylaryl sulfates, sulfonates or phosphates; Alkyl sulfonic acid; Sulfosuccinate salts; fatty acid; Ethylenically unsaturated surfactant monomers; And anionic and / or nonionic emulsifiers such as ethoxylated alcohols or phenols. The amount of surfactant used is usually 0.1 to 6% by weight, based on the weight of the monomer. Thermal or redox initiation processes may be used. The reaction temperature is maintained at a temperature of less than 100 ° C. over the course of the reaction. Preferable reaction temperature is 30-95 degreeC, More preferably, it is 50-90 degreeC. The monomer mixture can be added as it is or as an emulsion in water. The monomer mixture can be added to one or more additives or added continuously, linearly or otherwise, or in a combination thereof over the reaction period.

Typical free radical initiators include, for example, hydrogen peroxide, sodium peroxide, potassium peroxide, t-butyl hydroperoxide, cumene hydroperoxide, ammonium and / or alkali metal persulfate, sodium perborate, perforate Sporic acid and salts thereof, potassium permanganate and alkali metal salts of ammonium or peroxydisulfonic acid can typically be used at levels of 0.01 to 3.0% by weight, based on the weight of the total monomers. For example sodium sulfoxylate formaldehyde, ascorbic acid, isoascorbic acid and for example sodium sulfite, bisulfite, thiosulfate, hydrosulfite, sulfides, hydrosulfides or dithionite, formadisulf Alkali metals and ammonium salts of sulfur-containing acids such as pinic acid, hydroxymethanesulfonic acid, acetone bisulfite, amines such as ethanolamine, glycolic acid, glyoxylic acid hydrates, lactic acid, glyceric acid, malic acid, tartaric acid and the aforementioned acids Redox systems using the same initiator that combines with a suitable reducing agent such as salts of may be used. Redox reactions that promote metal salts of iron, copper, manganese, silver, platinum, vanadium, nickel, chromium, palladium or cobalt can be used. However, after 90-99.7% by weight of monomer, preferably 95-99.7% by weight, based on the total weight of the polymer is converted to the polymer, at least half of the remaining monomers are 0.1% t-amyl hydroperoxide based on the total weight of the polymer. Conversion to polymer in the presence of -1.0% by weight. Some of these reactions can be carried out as soon as the conversion of monomers to polymers in the same reaction vessel or kettle is 90-99.7%, preferably 95-99.7%. This can be done in a reaction vessel or kettle different from the polymerization predecessor or after a certain time has elapsed. It is preferred that t-amyl hydroperoxide is present after only 90%, more preferably 95%, conversion of the monomers to the polymer is complete.

Halogen compounds such as, for example, tetrabromomethane; Allyl compounds; Or to lower the molecular weight of polymers in which chain transfer agents are formed, such as alkyl thioglycolate, alkyl mercaptoalkanoate and mercaptans such as C ₄ -C ₂₂ linear or branched alkyl mercaptans and / or alternatively any free-radical -May be used to provide other molecular weight distributions that can be obtained with the production initiator (s). Preference is given to linear or branched C ₄ -C ₂₂ alkyl mercaptans such as n-dodecyl mercaptan and t-dodecyl mercaptan. The chain transfer agent (s) are added linearly or otherwise, either continuously or continuously, to one or more additives over almost all or all reaction periods or during limited reaction periods such as, for example, kettle loading and reduction of residual monomers. Can be.

The average particle diameter of the emulsion-polymerized polymer particles is preferably 30 to 500 nm as measured by the BI-90 Particle Sizer.

Aqueous compositions are prepared by techniques well known in the coating art. Initially, at least one pigment is COWLES if the elastomeric coating, coke, sealant or pressure sensitive adhesive composition is colored. It is well dispersed in aqueous medium under high shear as provided by a mixer or in a more viscous composition such as coke and sealant, as an aqueous medium in a high strength mixer or mill. A waterborne polymer is then added under low shear agitation along with other elastomeric coatings, cokes, sealants or pressure sensitive adhesion aids if desired. Alternatively, an aqueous emulsion polymer can be included in the pigment dispersion step. Aqueous compositions include, for example, conventional adhesives such as tackfiers, pigments, emulsifiers, binders, buffers, neutralizers, thickeners or rheology modifiers, humectants, wetting agents, fungicides, plasticizers, antifoams, colorants, waxes and antioxidants. Elastomeric coatings, cokes, sealants or pressure sensitive adhesion aids.

Solids content of the aqueous coating composition may be about 10 to 85% by volume. The viscosity of the aqueous composition is 0.05-2000 Pa.s (50-2,000,000 cps) as measured by a Brookfield viscometer; Appropriate viscosities are used for other end uses and various application methods may be contemplated.

Aqueous compositions are, for example, roll coating, doctor-blade applications, printing methods, air-atomic sprays, air-assisted sprays, airless sprays, solid low pressure sprays, air-assisted airless sprays, It can be applied by conventional application methods such as brushing and spraying methods such as caulk guns and trowels.

Aqueous compositions may or may not be subjected to substrate pretreatment such as acid etch or corona discharge or primers, for example, sheets and films, wood, metals, prepainted surfaces, cementitious substrates, asphalt substrates. It can be applied to a substrate such as.

The aqueous composition coated on the substrate is typically dried or allowed to dry at a temperature of 20-95 ° C.

Hereinafter, the present invention will be described with reference to examples, and the results obtained by the test method are shown.

Abbreviation

AA = acrylic acid

BA = butyl acrylate

MMA = methyl methacrylate

AN = acrylonitrile

EHA = 2-ethylhexyl acrylate

DI water = deionized water

Example 1 and Comparative Example A. Preparation of Large Amount of Acrylic Emulsion Polymer

Polymerization was carried out in a 3-liter, four-caliber, round bottom glass flask in a nitrogen atmosphere equipped with a mechanical blade stirrer, thermocouple for temperature monitor, reflux condenser, and means for heating and cooling. 400 g DI water was charged to the flask and heated to 83 ° C. The monomer pre-emulsion was prepared with 280 g DI water, 11 g sodium dodecylbenzene sulfonate (23% aqueous solution), BA 885 g, 100 g MMA and 15 g AA. 16 g (based on solids) of 100 nm seed latex containing 4 g of ammonium persulfate dissolved in 20 g of DI water and a total of 29 g of DI water were charged to the reaction flask. 1.5 g of ammonium persulfate dissolved in 45 g of residual pre-emulsion and DI water were added over 3 hours. The heating and cooling necessary to maintain the reaction temperature at 83 ° C. were applied. After the addition was complete, the pre-emulsion vessel was rinsed into the flask with 30 g of DI water. After 30 minutes, the flask was cooled to 60 ° C. A sample was taken and analyzed by gas chromatography to find that the monomer conversion to polymer was 99.62% by weight. The contents of the reaction flask were equally divided into two 3-liter glass flasks mounted as described above. Both flasks were kept at 55 ° C.

In Example 1, 0.008 g of FeSO ₄ 7H ₂ O dissolved in 5 g of DI water was added, followed by 3.0 g of 85% aqueous tert -amyl hydroperoxide dissolved in 45 g of DI water and sodium form dissolved in 45 g of DI water. 2.3 g of aldehyde sulfoxylate were added dropwise over 1 hour. The reaction mixture was cooled to 45 ° C. and pH adjusted with 14 g 14% aqueous ammonia. After cooling to room temperature, the emulsion polymer was filtered off. The emulsion polymer of Example 1 was 49.3 wt% solids content, 360 nm particle size and pH 8.1. Monomer conversion to polymer was analyzed by gas chromatography and found to be greater than 99.99% by weight.

In Comparative Example A, 0.008 g of FeSO ₄ 7H ₂ O dissolved in 5 g of DI water was added, followed by 3.0 g of 70% aqueous tert -butyl hydroperoxide dissolved in 45 g of DI water and sodium form dissolved in 45 g of DI water. 2.3 g of aldehyde sulfoxylate were added dropwise over 1 hour. The reaction mixture was cooled to 45 ° C. and pH adjusted with 14 g 14% aqueous ammonia. After cooling to room temperature, the emulsion polymer was filtered off. The comparative example had a solids content of 49.5% by weight, a particle size of 360 nm and a pH of 8.2. Monomer conversion to polymer was analyzed by gas chromatography and found to be greater than 99.99% by weight.

Example 2 and Comparative Example B. Preparation of Large Amounts of Acrylic Emulsion Polymers

Example 2 and Comparative Example B were prepared in the same manner as in Example 1 and Comparative Example A, except that the polymer composition was 91.5 BA / 7 AN / 1.5 AA wt%. At the end of the first (typical) phase of the reaction, a sample was taken and analyzed by gas chromatography and the monomer conversion to polymer was 98.02 wt.

In Example 2, 0.008 g of FeSO ₄ 7H ₂ O dissolved in 5 g of DI water was added, followed by 3.0 g of 85% aqueous tert -amyl hydroperoxide dissolved in 45 g of DI water and sodium form dissolved in 45 g of DI water. 2.3 g of aldehyde sulfoxylate was added dropwise over 1 hour. The reaction mixture was cooled to 45 ° C. and pH adjusted with 14 g 14% aqueous ammonia. After cooling to room temperature, the emulsion polymer was filtered off. The emulsion polymer of Example 2 had a solids content of 49.6 wt%, a particle size of 370 nm and a pH of 8.6. Monomer conversion to polymer was analyzed by gas chromatography and found to be greater than 99.99% by weight.

In Comparative Example B, 0.008 g of FeSO ₄ 7H ₂ O dissolved in 5 g of DI water was added, followed by 3.0 g of 70% aqueous tert -butyl hydroperoxide dissolved in 45 g of DI water and sodium form dissolved in 45 g of DI water. 2.3 g of aldehyde sulfoxylate were added dropwise over 1 hour. The reaction mixture was cooled to 45 ° C. and pH adjusted with 14 g 14% aqueous ammonia. After cooling to room temperature, the emulsion polymer was filtered off. The comparative example was 49.8 weight% of solids content, particle size 370 nm, and pH 8.1. Monomer conversion to polymer was analyzed by gas chromatography and found to be greater than 99.99% by weight.

Example 3 and Comparative Example C. Preparation of Large Amounts of Acrylic Emulsion Polymers

Comparative Example C was synthesized by the following method: 389.75 g DI water, 8.30 g polymerized seed and 4.00 g ferrous sulfate (0.15% aqueous) and tert -butyl hydroperoxide (70% aqueous) dissolved in 52.00 DI water in an empty reactor. 3.71 g was added. A monomer emulsion was formed containing 120.00 g DI water, 36.90 g sodium dodecylbenzenesulfonate surfactant, 552.00 g BA, 187.50 g EHA, and 10.50 g AA. The reactor contents were heated to 65 ° C. before adding the oxidizing solution. The monomer emulsion was fed to the vessel simultaneously with a separate reducing solution consisting of 2.22 g of sodium sulfoxylate formaldehyde dissolved in 52.00 g of DI water to maintain a temperature of 65 ° C. by polymerization and external heat. The monomer conversion to polymer at the completion of the monomer emulsion and initiator feed was 95.5% by weight. A redox tracking system was then prepared containing 3.71 g tert -butyl hydroperoxide (70% aqueous) dissolved in 52.00 DI water and 2.22 g sodium sulfoxylate formaldehyde dissolved in 52.00 DI water. The oxidizing solution was all added immediately and a reducing agent was fed to the reactor. After the addition of the reducing agent, the reactor temperature was lowered below 45 ° C. The final polymer contained 69 ppm of residual monomer. Ammonium hydroxide (28% aqueous) was used to increase the pH of the batch to 7.5 and the sample was then filtered through a 100 mesh screen.

Example 3 was synthesized as in Comparative Example C except that the monomer to polymer conversion after the monomer emulsion and initiator feed was complete was 96.3 wt%. The tracer oxidant used was 3.53 g of t-amylhydroperoxide (85% in t-amyl alcohol) added immediately with 52.00 DI water. The final polymer contained 155 ppm of residual monomer.

Example 4 Preparation of Aqueous Compositions and Evaluation of Elastomeric Coatings

Aqueous compositions were prepared by addition in the given order using the following ingredients.

ingredient Volume (g)

Water 106.77

Tamol 731 ¹ 12.28

Potassium Tripolyphosphate 3.1

Nopco NXZ ² 7.2

Acrysol RM 8W ¹ 17.7

Propylene Glycol 20.0

Tioxide TR-92 ³ 100.0

Durcal 5 ⁴ 447.3

Butyl Carbitol ⁵ 13.6

The components were mixed using a high shear Cowles mixer and the next amount of emulsion polymer was added with stirring.

Emulsion polymer Weight (g)

Example 1 502.5

Comparative Example A 500.9

Example 2 497.4

Comparative Example B 495.5

¹ Trademark of Rohm and Haas Company

² Trademark of Diamond Shamrock Chemical Company

³ Trademarks of Tioxide Europe Ltd.

⁴ Trademarks of OMYA, Inc.

⁵ Trademark of Union Carbide Chemical Co.

The aqueous composition was coated on a release paper (realease paper) with an equivalent volume of 1 mm wet thickness and dried for 23 days (at 25 ° C. and 50% relative humidity). A dumbbell-shaped test piece having a neck width of 10 mm and a neck length of 30 mm was cut out. The thickness of each sample was measured at the neck with a micrometer. Elongation was measured using Tinius Olsen UTM (Model No. H1OK-S, Tinius Olsen Testing Machine Co., Inc., Willow Grove, PA). The temperature chamber to be adjusted was set to -10 ° C. The separation rate was set at 5.08 cm / min (2 inches / min).

Containing emulsion polymer At rupture

Elastomeric Coating Cold elongation

Example 1 569

Comparative Example A 416

Example 2 249

Comparative Example B 235

Elastomeric coatings comprising the emulsion polymer Examples 1 and 2 of the present invention exhibited higher low temperature elongation at rupture compared to the corresponding comparative examples.

Example 5. Evaluation of Aqueous Composition as Pressure Sensitive Adhesive

The dried films of the emulsion polymers of Example 3 and Comparative Example C were tested according to the following method.

Peel: PSTC-1 Peel Adhesion of Single Coated Pressure Sensitive Tapes (PSTC = Pressure Sensitive Tape Council, 401 N. Michigan Avenue, # 00, Chicago, IL 60611) at 180 ° angle was applied to stainless steel.

Loop Tack: ASTM D6195 standard measurement for Loop Tack.

Shear: ASTM D6463 standard measurement (of time for failure of a reduced pressure article under sustained shear loads).

Evaluation of Pressure Sensitive Adhesive Properties Emulsion Polymers of Examples Redox / Tracking 180 Phil Shear, minute shear Loop adhesive oz / in 1 "x1", 1kg Failure mode oz Comparative Example C tBHP / tBHP 27.350C / 50A 51 C 30.5A 3 tBHP / tAHP 34.0C 3 C 56.5A

The dried emulsion polymer, pressure sensitive adhesive, of Example 3 of the present invention showed relatively improved tack compared to Comparative Example C.

The use of t-amyl hydroperoxide in the final stage of the polymerization thus provides an aqueous composition suitable for use in drying as an improved elastomeric coating, coke, sealant or pressure sensitive adhesive.

Claims (10)

Free conversion of 0.5-5% by weight of ethylenically unsaturated carboxylic acid monomer to 90-99.7% by weight of monomer, based on the total weight of polymer, based on the total weight of at least one ethylenically unsaturated nonionic acrylic monomer and polymer Radical polymerization; And a glass transition temperature (Tg) formed by subsequent polymerization in which at least half of the residual monomer weight is polymerized into the polymer in the presence of 0.1-1.0% by weight of t-amyl hydroperoxide based on the total weight of the polymer. An aqueous composition suitable for use in drying as an improved elastomeric coating, coke, sealant or pressure sensitive adhesive comprising a large amount of acrylic aqueous emulsion polymer at 20 ° C. The aqueous composition of claim 1 wherein the t-amyl hydroperoxide is present after 90% of the monomers are converted to the polymer based on the total weight of the polymer. Free conversion of 0.5-5% by weight of ethylenically unsaturated carboxylic acid monomer to 90-99.7% by weight of monomer, based on the total weight of polymer, based on the total weight of at least one ethylenically unsaturated nonionic acrylic monomer and polymer Forming a large amount of acrylic aqueous emulsion polymer having a glass transition temperature (Tg) of −90 to 20 ° C. by radical polymerization; And subsequently polymerizing at least half of the residual monomers into the polymer in the presence of 0.1-1.0% by weight of t-amyl hydroperoxide based on the total weight of the polymer. Or a process for producing an aqueous emulsion polymer suitable for use as a pressure sensitive adhesive. 4. The method of claim 3 wherein the t-amyl hydroperoxide is present after 90% of the monomers are converted to the polymer based on the total weight of the polymer. Free conversion of 0.5-5% by weight of ethylenically unsaturated carboxylic acid monomer to 90-99.7% by weight of monomer, based on the total weight of polymer, based on the total weight of at least one ethylenically unsaturated nonionic acrylic monomer and polymer The glass transition temperature (Tg) of the polymer formed by radical polymerization and subsequent polymerization in which at least half of the residual monomers polymerize into the polymer in the presence of 0.1-1.0% by weight of t-amyl hydroperoxide, based on the total weight of the polymer, Forming an aqueous composition comprising a large amount of acrylic aqueous emulsion polymer, 40-20 ° C .; Applying the aqueous composition to a substrate; And Allowing the aqueous composition to dry or to dry; A method of coating a substrate with an aqueous composition providing an elastomeric coating on the substrate comprising a. 6. The method of claim 5 wherein the t-amyl hydroperoxide is present after 90% of the monomers are converted to the polymer, based on the total weight of the polymer. Free conversion of 0.5-5% by weight of ethylenically unsaturated carboxylic acid monomer to 90-99.7% by weight of monomer, based on the total weight of polymer, based on the total weight of at least one ethylenically unsaturated nonionic acrylic monomer and polymer The glass transition temperature (T g), formed by radical polymerization and subsequent polymerization in which at least half of the residual monomers are polymerized into the polymer in the presence of 0.1-1.0% by weight of t-amyl hydroperoxide based on the total weight of the polymer, is -60 Forming an aqueous composition comprising a large amount of acrylic aqueous emulsion polymer, ˜20 ° C .; Applying the aqueous composition to a substrate; And Allowing the aqueous composition to dry or to dry; A method of applying an aqueous coke or sealant composition comprising a substrate. 8. The method of claim 7, wherein the t-amyl hydroperoxide is present after 90% of the monomers are converted to the polymer based on the total weight of the polymer. Free conversion of 0.5-5% by weight of ethylenically unsaturated carboxylic acid monomers to 90-99.7% by weight of monomers, based on the total weight of the polymer, based on the total weight of at least one ethylenically unsaturated nonionic acrylic monomer and polymer. A glass transition temperature (Tg) of -90, formed by radical polymerization and subsequent polymerization in which at least half of the residual monomers are polymerized into the polymer in the presence of 0.1-1.0% by weight of t-amyl hydroperoxide based on the total weight of the polymer Forming an aqueous composition comprising a large amount of acrylic aqueous emulsion polymer, ˜0 ° C .; Applying the aqueous composition to a substrate; And Allowing the aqueous composition to dry or to dry; A method of providing a pressure sensitive adhesive comprising a pressure sensitive adhesive on a substrate. 10. The method of claim 9, wherein the t-amyl hydroperoxide is present after 90% of the monomers are converted to the polymer based on the total weight of the polymer.