MXPA98002552A - Promoter of adhesion of poliolefina transported in - Google Patents

Abstract

This invention relates to a polyolefin composition carried in water which is useful as an adhesion promoter and is prepared by emulsifying crystalline, non-oxidized, non-maleated, non-chlorinated polyolefins and amorphous, maleated, non-chlorinated polyolefins in the presence of a surfactant, an amine and ag

Description

PROMOTER OF ADHESION OF POLYCLEPHINE TRANSPORTED IN WATER DESCRIPTION DB THE INVENTION This invention relates to a polyolefin composition transported in water which is useful as an adhesion promoter and is prepared by emulsifying polyolefin crystals, non-oxidized, non-mallowed (non-hydrophilic), non-chlorinated and non-chlorinated polyolefins, mallowed (slightly hydrophilic), amorphous in the presence of a surfactant, an amine and water. Polyolefins generally require organic solvents or chemical modification either by oxidation or by maleation (introduction of slight hydrophilicity) prior to elation. The use of organic solvents, however, causes environmental damage, and the chemical modification of polyolefins provides unwanted end-use properties to formulated products that incorporate polyolefins and add cost to the products. U.S. Patent No. 4,613,679 describes emulsifiable polyolefin waxes prepared by reacting low molecular weight homopolymers and copolymers containing at least one monomer of an alpha-olefin having at least three carbon atoms with maleic acid diesters in the presence from a source of free radicals. The grafting of maleic acid diesters onto poly-alpha-olefins is carried out in an inert atmosphere. The disadvantage of the process of U.S. Patent No. 4,613,679 is that it requires the polyolefin alloy which modifies the end-use properties of the products due to the change in molecular structure. U.S. Patent No. 3,644,259 discloses a method for preparing latex solid concentrates of olefin polymers which are prepared by: (1) heating a fluid, aqueous, low solids emulsion of the tertnoplastic organic addition polymer in its alkaline salt at a temperature between the softening point of the polymer and the point at which the polymer degrades while simultaneously decreasing the pH of the emulsion to a value between 6.0-8.3 and (2) concentrating the emulsion to fluid latex containing the polymer in the range of about 40-65% by weight. The process requires acrylic monomers to be copolymerized with unsaturated olefins in the presence of the free radical. U.S. Patent No. 3,919,176 discloses water dispersible polyolefin compositions which are useful as hot melt adhesives. such hot melt adhesives are prepared using an esterified carboxylated polyolefin. The disadvantage of the adhesive compositions described in U.S. Patent No. 3,919,176 is that the polyolefin undergoes chemical modification by a maleation process in the presence of free radicals and alkali neutralization to disperse in water. U.S. Patent No. 5,373,048 discloses an aqueous coating composition containing maleated polyolefins (slightly hydrophilic), a nonionic surfactant, an amine and water which are emulsified. The aqueous coating composition described in U.S. Patent No. 5,373,048 provides poor adhesion to certain polymer substrates such as polypropylene. There is a need for a non-halogenated adhesion promoter, transported in water to improve the adhesion of paints, dyes and coatings to polymer substrates such as propylene, thermoplastic olefins, and polyethylene. The present invention relates to a polyolefin composition carried in water to promote adhesion, especially on polymer substrates. The polyolefipa carried in water has a particle size of 0.02 to 150 microns and comprises: (A) 0.1 to 10 weight percent of at least one non-oxidized, non-mauled, non-chlorinated, crystalline polyolefin having an average weight of weight molecular from 2,000 to ,000 and a density of less than 1.0 g / cc. (B) 10 to 40 weight percent of at least one non-chlorinated, mallowed, amorphous polyolefin having an average molecular weight of at least 500 and an acid number of 15 to 95; (C) 0.1 to 10 weight percent of at least one surfactant having a hydrophobic-lipophilic balance of 6 to 18; (D) 0.1 to 5 weight percent of at least one amine compound having a molecular weight of at least 150; and (E) 50 to 95 percent by weight of water, percentages by weight are provided based on the total weight of the composition carried in water. The polyolefin composition transported in water is prepared by a process comprising the steps of: (I) mixing (A) 0.1 to 10 weight percent of at least one non-oxidized, non-mauled, non-chlorinated, crystalline polyolefin having a average molecular weight weight of 2,000 to 15,000 and a density of less than 1.0 g / cc. (B) 10 to 40 weight percent of at least one non-chlorinated, maleated, amorphous polyolefin having an average molecular weight of at least 500 and an acid number of 15 to 95; (C) 0.1 to 10 weight percent of at least one surfactant having a hydrophilic-lipophilic balance of 6 to 18; (D) 0.1 to 5 weight percent of at least one amine compound having a molecular weight of at least 150; and (E) 50 to 95 weight percent water; (II) heating the mixture of step (I) at a temperature of 120 ° C to 200 ° C and a pressure of 60 Pa to 1500 kPa to form a polyolefin emulsion transported in water; and (III) cooling the polyolefin emulsion transported in water formed in step (II) at a temperature of ° C to 70 ° C to form a polyolefin composition carried in water, it is provided that the percentages by weight are based on the total weight of the composition. The present invention relates to a water-borne polyolefin composition which is useful as an adhesion promoter and is prepared by emulsifying non-oxidized, un-maleated, non-chlorinated, crystalline and non-chlorinated polyolefins, maleated, amorphous polyolefins in the presence of a surfactant, an amine and water. The process involves three stages. In step (I), at least one non-oxidized, non-mallowed, non-chlorinated, crystalline polyolefin, component (A), at least one non-chlorinated, maleated, amorphous polyolefin, component (B), at least one surfactant, component ( C), at least one amine compound, component (D), and water, component (E), are mixed in a pressure vessel such as a Parr reactor equipped for agitation to form a mixture. Step (I) is carried out at a temperature of 80 ° C to 250 ° C, more preferably 120 ° C to 180 ° C, and a pressure of 68.95 kPa (10 Psi) to 1378.96 kPa (200 Psi), preferably 413.69 kPa (60 Psi) at 620.53 kPa. Preferably, the temperature and pressure are maintained for 10 to 150 minutes, more preferably, 30 to 45 minutes. The non-oxidized, non-halogenated, non-mallowed, crystalline polyolefins have an average molecular weight weight of 2000 to 15,000, preferably 3000 to 13,000. These polyolefins, component (A), are available as EPOLENE N-type polyolefins which are available in different grades from Eastman Chemical Company, Kingsport, TN. EPOLENE N polyolefin examples are listed in Table 1. TABLE 1 POLENB: VISCOSITY • RBSP, DENSITY WEIGHT 257 '»F (125 ° C), CP ßF (° C) Q / CC MOLECULAR (P") N-10 1500 232 (111) 0.95 10000 N-ll 350 226 (108) 0.921 6000 N-14 150 223 (106) 0.920 4000 N-34 450 217 (103) 0.910 6200 N-20 3275 * 246 (119) 0.930 15000 N-21 350 * 248 (120) 0.950 6500 N-15 600 * 325 (163) 0.900 12000 EPOLENE type N polyolefins are usually polyethylene or polypropylene. The viscosity of these EPOLENE N polyolefins are reported at 125 ° C, except EPOLENE N-20, EPOLENE N-21 and EPOLENE N-15. For EPOLENE N-15, the viscosity is reported at 190 ° C, while the viscosity for EPOLENE N-20 and EPOLENE N-21 is reported at 150 ° C as shown in Table 1. Amorphous amorphous polyolefins are not halogenated, component (B), are selected from the following: (1) amorphous, amorphous, non-chlorinated polypropylene having an acid number in the range of 15 to 95, preferably 30 to 50, and an average molecular weight of at least 500; (2) amorphous, unchlorinated propylene-ethylene copolymer having propylene units in the range of 60 to 98 mole percent, preferably 80 to 95 mole percent, ethylene units in the range of 40 to 2 percent in mole, preferably 20 to 5 percent in mole, an acid number in the range of 15 to 95, preferably 30 to 50 and an average molecular weight of at least 500; (3) amorphous, unchlorinated propylene-hexene copolymer having propylene units in the range of 30 to 98 mole percent, preferably 35 to 95 mole percent, hexene units in the range of 70 to 2 percent in mole, preferably 65 to 5 percent in mole, an acid number in the range of 20 to 65, preferable 25 to 65, and an average molecular weight of at least 500; (4) amorphous, nonchlorinated propylene butene butene copolymer having propylene units in the range of 40 to 98 mole percent, preferably 45 to 90 mole percent, butene units in the range of 60 to 2 percent in mol, preferable 55 to 10, and an acid number in the range of 15 to 50, preferable 25 to 45 and an average molecular weight of at least 500; (5) amorphous, nonchlorinated propylene-ethylene-butene terpolymer having propylene units in the range of 40 to 89 mole percent, preferably 50 to 80 mole percent, ethylene units in the range of 1 at 20 percent, preferably 15 to 49 percent mol, and an acid number in the range of 15 to 50, preferably 20 to 45 and an average molecular weight of at least 500; and (6) amorphous, nonchlorinated, propylene-ethylene-hexene terpolymer having units of propylene in the range of 40 to 80 mole percent, ethylene units in the range of 1 to 20 mole percent, units of hexene in the range of 20 to 60 percent mol, and an acid number in the range of 15 to 50 and an average molecular weight of at least 500. Amorphous, maleated, non-halogenated polyolefins (MAPOs), component (B), are derived from amorphous polyolefins (APO's) by a maleation process. The maleation introduces slight hydrophilicity to amorphous, non-halogenated amorphous polyolefins. Therefore, the amorphous, maleated, non-halogenated polyolefins can be emulsified to achieve the products transported in water. The amine compound, component (C), is a primary, secondary or tertiary amine having a molecular weight of less than 150, preferably less than 100, and a functionality of 1 to 3. The amine may be an aromatic or aliphatic amine. Aliphatic amines having amine functionality between 1 and 3 are preferred. Optionally, the amines may contain other oxygen-containing functional groups. The amine compound is present in the polyolefin compositions carried in water in an amount of 0.1 to 5. % by weight based on the total weight of the composition. The amine compound is present in an amount of 2 to 30 weight percent, preferably 5 to 15 weight percent, based on the weight of the polyolefins. Examples of amine compounds have the formula: I - «- i R.

R1, - fl fl - - RR, - N fl- - R wherein Rx to R7 are independently selected from hydrogen or straight or branched chain alkyl, hydroxyalkyl, or alkoxylalkyl groups having 1 to 20 carbon atoms; R1-R7 may additionally include a substituted alkyl group, ie, where one or more of the carbons in the radical is replaced with or has substituted therein another functional group, for example, an amine, ether, hydroxy or mercapto moiety; for example, tris- (3-aminopropyl) amine. Another group of amine compounds are those primary, secondary or tertiary amines of the above formula in which R? -R7 is especially substituted with or contains one or more of hydroxyl functionalities (-OH). Examples of amine compounds have the formula: R2- (NH2) n wherein n is 1 or 2 and Rt, R9, R_0 and Ru are independently selected from straight or branched chain alkyl, hydroxyalkyl or alkoxyalkyl groups having from 1 to 20 carbon atoms. These chains can also be substituted with another functional group as described above. The amine compounds may also contain one or more ether or alkoxy linkages. Such materials are sometimes referred to as poly (oxyalkylene) diamines. Ethoxylated or propoxylated materials are particularly preferred. Amine compounds suitable for use in the waterborne polyolefin compositions of the present invention include: 2-amino-1-butanol, 4-amino-1-butanol, 2-aminoethanethiol, 2-aminoheptane. 2-amino-1-hexanol, 6-amino-1-hexanol, allylamine, 2-amino-3-methyl-1-butanol, 2-amino-2-methyl-1,3-propanediol, 2-amino-2- methyl-1-propanol, 2-amino-1-pentanol, 5-amino-1-pentanol, 3-amino-1-propanol, ammonium hydroxide, amylamine, butylamine, N, N'-bis (2-aminoethyl) - 1,3-propanediamine, N, N'-bis (3-aminopropyl) -1,3-propanediamine, 1,3-bis (3-aminopropyl) -2-propanol, 1 - [N, N-bis (2- hydroxyethyl) amino] -2-propanol, N, N'-bis (2-hydroxyethyl) ethylenediamine, decylamine, 1,4-diaminobutane, 1,10-diaminodecane, 1, 12-diaminododecane, 1,7-diaminoheptane, 1, 3-diamino-2-hydroxypropane, 3, 3-diamino-N-methyldipropylamine; 1, 2-diamino-2-methylpropane, 1,9-diaminononane, 1,8-diaminooctane, 1,5-diaminopentane, 1,2-diaminopropane, 1,3-diaminopropane, dibutylamine, 3- (dibutylamino) propylamine, diethanolamine , diethylamine, 5-diethylamino-2-pentanol, 3- (diethylamino) -1, 2 -propanol, l-diethylamino-2-propanol, 3-diethylamino-1-propanol, 3-diethylaminopropylamine, diethylenetriamine, N, N-diethylethanolamine , N, N-diethylethylenediamine, N, N-diethylmethylamine, N, N'-diethyl-1,3-propanediamine, diisobutylamine, diisopropanolamine, diisopropylamine, 2- (diisopropylamino) ethanol, 3-diisopropylamino-1,2-propanediol, NN -diisopropylethylamine, 1-dimethylamino-2-propanol, 2-dimethylaminoethanol, 3-dimethylamino-1-propanol, 3-dimethylaminopropylamine, 1, 3-dimethylbutylamine, 3, 3, -dimetilbutilamina, N-dimethylethanolamine, 3,3-dimethylbutylamine, N, N-dimethylethanolamine, N, N-dimethylethylamine, N, N-dimethylethylenediamine, N, N dimethyl-N'-ethylethylenediamine, N, N '-dimethyl-1, 6-hexanediamine, 2,5-dimethyl-2, 5-hexanediamine, 1, 5-dimethylhexylamine, 2, 2-dimethyl-1, 3 -propandiamina 1, 2-dimethylpropylamine, diproprilamina, dodecylamine, ethanolamine, 3 -etoxipropilamina, ethylamine, 2- (ethylamino) ethanol, N-eitlbutilamina, 2-ethylbutylamine, N-ethyldiethanolamine, ethylenediamine, hexamethylenediamine, 1,6-hexanediamine, hexylamine, isoamylamine, isopropylamine, N-isopropiletilendiamina, N'-isopropyl- 2-methyl-l, 2 -propandiamina, N, N, N ', N'-tetramethyl-l, 4-butanediamine, N, N, N' -tetrametildiaminometano, N, N, N'N'-tetramethylethylenediamine, N, N, N N'- tetramethyl-1,3-propanediamine, N, N, 2,2-tetramethyl-1,3-propanediamine, tributylamine, tridecylamine, triethanolamine , triethylamine, triisooctylamine, triisopropylamine, tr imetilamina, methylamine, 2 - (meth ylamino) ethanol, N-methylbutylamine, 1 -metilbutilamina, 2 -met iLA ylbut ina, N- ethyldiethanolamine, N-methylethylenediamine, N-methyl-1,3-propanediamine, morpholine, nonylamine, octylamine , tert-octylamine, propylamine, 2- (propylamino) ethanol, 1-tetradecyl ina, and tri (3-aminopropyl) amine. Mixtures of amines can also be used. Preferred amine compounds are morpholine, 2-amino-2-methyl-1-propanol, 2-dimethylaminoethanol and ammonium hydroxide. The surfactant, component (D), is a nonionic, anionic, cationic or amphoteric surfactant. The choice of surfactant depends on the end-use application of the polyolefin composition carried in water. The hydrophilic-lipophilic balance (HLB) of the surfactant is an expression of the equilibrium of the size and strength of the hydrophilic (polar) and lipophilic (non-polar) groups of the surfactant. The surfactant has an average HLB of 6 to 8. The hydrophilic-lipophilic HLB values can be determined in a variety of ways. For example, numbers of hydrophilic-lipophilic balance for certain types of nonionic surfactants such as polyoxyethylene derivatives of fatty alcohols and fatty acid esters polyhydric alcohols surfactants, including those of polyglycols, can be calculated with the help of the following equation: HLB = 20 (1-S / A) For other surfactants such as coarse oil esters and rosin, beeswax, lanolin, and the like, the hydrophilic-lipophilic equilibrium values can be calculated from the equation: HLB = (E + P) / S Where E is the weight percent oxyethylene and P is the weight percent of the polyhydric alcohol. While the above formulas are satisfactory for many surfactants, the hydrophilic-lipophilic equilibrium values for many surfactants must be estimated by experimental methods. The experimental method of determining the hydrophilic-lipophilic equilibrium value involves mixing the unknown surfactant in various proportions with a surfactant having a known hydrophilic-lipophilic equilibrium value, then using the mixture to emulsify an oil for which the hydrophilic equilibrium The lipophilicity required to emulsify the oil is known. The mixture which works best is considered to have a hydrophilic-lipophilic equilibrium value approximately equal to the required HLB of the oil, such that the hydrophilic-lipophilic equilibrium value for the unknown material can be calculated.

An approximation of the hydrophilic-lipophilic equilibrium value for a range of surfactants can be obtained by evaluating the water solubility of the particular surfactant as summarized in the following table. Behavior when water is added Range HLB Non-dispersibility in water 1-4 Poor dispersion 3-6 Light dispersion after 6-8 vigorous agitation Light stable dispersion 8-10 (upper end almost translucent) Translucent dispersion at 10-13 clear Clear solution 13+ Surfactants suitable for use in polyolefin compositions transported in water include: mono and diglycerides, sorbitan fatty acid esters, polyoxyethylene sorbitol esters, polyoxyethylene alcohols, ethoxylated alkylphenols, ethoxylated alcohols, polyalkylene glycol ethers, mono and diglycerides phosphate citric acid esters of monoglycerides, diacetylated tartaric acid esters of monoglycerides, glycerol monooleate, sodium stearoyl lactylates, calcium stearoyl lactylates, phospholipids, phosphatidylethanolamine, glycerol monostearate, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitol esters, polyoxyethylene acids, polyoxyethylene alcohols, polyoxyethylene alkylamines, alkylaryl sulfonates, and ethoxylated alkylphenols. A combination of surfactants may also be used. The amount of water, component (E), can vary widely depending on numerous factors, such as the manufacturer's need, transportation efficiencies and particular application needs. Water is preferably present in the polyolefin composition carried in water in an amount of 50 to 95% by weight, preferably 55 to 90% by weight, based on the total weight of the composition. Water-borne polyolefin compositions can be prepared using less water than would typically be required to apply the compositions as a coating since the water can be subsequently added later to prepare the diluted composition. In this way the manufacturer can prepare a "concentrated" product which has a low water content and is less expensive to transport. A "concentrated" product is also often desired if the composition of the adhesion promoter is to be used as an additive to the paint in order to avoid excessive dilution of the paint.

In Step (II), the mixture formed in Step (I) is heated to a temperature of 120 ° C to 200 ° C and a pressure of 60 kPa to 1500 kPa to form a polyolefin emulsion carried in water. Preferably the mixture is heated to a temperature of 120 ° C to 170 ° C, more preferably 150 ° C to 165 ° C while continuously stirring to form a polyolefin emulsion carried in water. Step (II) is preferably performed at a pressure of 200 kPa at 1000 kPa, more preferably 400 kPa at 700 kPa. The water, component (E), can optionally be injected at high pressure into the mixture in Step (II) to form the polyolefin emulsion transported in water instead of adding the water to Step (I) or in addition to the added water in Stage (I). In Step (III), the polyolefin emulsion transported in water formed in Step (II) is cooled, by methods known in the art at a temperature of 20 ° C to 70 ° C to form a polyolefin composition carried in water. . Preferably, the polyolefin emulsion transported in water is cooled to a temperature of 25 ° C to 40 ° C. It is important to note that a polyolefin emulsion transported in water that incorporates the components (A) to (E) can be prepared by a process which involves combining the components (A) and (B) at a temperature of 80 ° C to 250 ° C. ° C to form a mixture, cool the mixture and add the components (C), (D) and (E). The resulting mixture is heated to a temperature of 120 ° C to 200 ° C to form a polyolefin composition carried in water. In the present it has been determined, however, that a polyolefin composition transported in water prepared by this method does not work as well as an adhesion promoter. In contrast, the waterborne polyolefin compositions prepared by the process of the present invention function as excellent adhesion promoters to improve the adhesion of paints to polymer substrates. The polyolefin compositions transported in water may contain an additive. Suitable additives include, for example, thickeners, wetting agents, flow aids, pigments, resins, fillers, stabilizers, antioxidants, buffers, colorants, dyes, and organic solvents. Such additives, their amounts, and their use are well known in the art. The polyolefin compositions transported in water have a suitably small particle size to make the compositions useful in coating applications. The polyolefins transported in water have a particle size of 0.02 to 150 microns, preferably 0.1 to 50 microns. In this way, the compositions of this invention include not only "emulsions" and "dispersions" but also mixtures. For example, mixtures containing water in which the particle size is in the range of 1.0 to 10"4 mm (0.1 μ) to 1.0 x 10" 2 mm (10 μ) have been characterized as "emulsions". Mixtures containing water in which the particle size is greater than 1.0 x 10.2 mm (10 microns) have been characterized as a "dispersion". While both types of mixtures are within the scope of this invention, the invention is not limited to these or any other particular type of mixture and includes all possible types of blends regardless of their physical form as long as the particle size is small enough for the mixtures have utility in coatings applications. While the compositions of this invention are particularly useful as adhesion promoters for improving the adhesion of paints to polymer substrates, the compositions are to be used by themselves as paints to form a final protective coating which is not within the scope of the invention. It only protects the substrate but it is also decorative as a result of the addition of pigments. The test materials and procedures used for the results shown herein are as follows: The acid numbers of polyolefins are determined by ASTM D1386.

The inherent viscosity (I.V.) is measured at 23 ° C. Using 0.50 g of polymer per 100 ml of a solvent consisting of 60% by weight of phenol and 40% by weight of tetrachloroethane. The following examples are proposed to illustrate, but not limit, the scope of this invention. All parts and percentages in the examples are based on weight unless otherwise stated. EXAMPLE 1 This example illustrates the emulsification of crystalline polyolefin, non-oxidized, non-halogenated, unmanned, almost chemically inert (EPOLENE N-15) using non-halogenated amorphous polyolefins (MAPO), a non-ionic surfactant, amine and water. The ingredients and their amount are used as follows: Ingredients Canti »rtfld (g) (% by weight) EPOLENE • N-15 6.0 3.71 (POLYPROPYLENE) MAPO (copolymer of 34.0 21.01 propylene-hexene) No. Acidity = 50 GENAPOL UD050 12.0 7.42 (non-ionic surfactant) 2-amino-2-methyl-l- 5.8 3.58 propanol Water 104.0 64.28 The emulsion is prepared as follows: (1) EPOLENE N-15, amorphous, non-halogenated, mallowed polyolefins (MAPO), surfactant, amine and water are added to a Parr depression reactor. (2) Seal the reactor and heat to 338 ° F (170 ° C), while stirring the ingredients continuously. The reactor pressure is approximately 620.53 kPa (90 psi) - 689.48 kPa (100 psi). (3) The reactor temperature is maintained at 338 ° F (170 ° C) for approximately 30-45 minutes, while stirring the mixture continuously. (4) The reactor is allowed to cool to approximately 86 ° F (30 ° C), while stirring continuously with the agitator. (5) The emulsion is removed from the reaction chamber, and stored in a suitable container. The emulsion is milky in color with a particle size of less than 0.09 mm (90 microns). The pH of the polyolefin transported in water is 10.15. A stable dispersion is obtained. EXAMPLE 2 Example 1 is repeated except that the amount of EPOLENE N-15 is 3.0 grams instead of 6.0 grams. The ingredients used to prepare the polyolefins transported in water are as follows.

Ingredients Quantity: (g) (% by weight) EPOLENE • N-15 3.0 1.88 (POLYPROPYLENE) MAPO (copolymer of 37.0 23.14 propylene-hexene) No. Acidity = 50 GENAPOL UD050 10.5 6.56 (non-ionic surfactant) 2-amino-2-methyl-l-5.4 3.38 propanol Water 104.0 65.04 The pH of the emulsion is 10.24 with particle size in the range of 0.02 mm (20.0 μ) -0.09 mm (90.0 μ). The polyolefins transported in water are milky in color. EXAMPLE 3 Example 1 is repeated except that a non-halogenated, amorphous, amorphous polyolefin (MAPO) is used instead of adding EPOLENE N-15 and amorphous, maleated, non-halogenated polyolefin separately to the reactor. The homogenous mixture of EPOLENE N-15 and amorphous, malleated, non-halogenated polyolefins is prepared by heating amorphous, maleated, non-halogenated polyolefin at 356 ° F (180 ° C) -365 ° F (185 ° C) in order to dissolve EPOLENE N-15 in amorphous polyolefins, malleable, non-halogenated, melted. The material after which the mixing is finished is cooled to room temperature. This mixture is used to prepare an emulsion in a pressure Parr reactor. The composition is as follows: Inscription Canti ad (g) (% by weight EPOLENE ® N-15 6.0 3.71 (POLYPROPYLENE) MAPO (copolymer of 34.0 21.01 propylene-hexene) No. Acidity = 50 GENAPOL UD050 12.0 7.42 (nonionic surfactant) 2 -amino- 2 -methyl -1- 5.8 3.58 propanol Water 104.0 64.28 The process described in Example 1 is used to prepare an emulsion. The emulsion is translucent (almost clear), and the particle size is in the range between 2.0 x 10.5 mm (0.02 μ) -2.0x 10 ~ 2 mm (20.0 μ). The uniform blend of EPOLENE N-15 in amorphous, maleated, non-halogenated, molten polyolefins provides a nearly clear small size emulsion compared to adding EPOLENE N-15 and amorphous, maleated, non-halogenated polyolefins to the pressure reactor. The pH of the emulsion is approximately 10.12. EXAMPLE 4 Example 3 is repeated except that a homogeneous mixture of EPOLENE N-15 and amorphous, maleated, non-halogenated polyolefins (MAPO) is prepared using a 30/70 ratio (EPOLENE N-15 / amorphous polyolefins, malenate, not halogenated) instead of 15/85). The ingredients are as below: Ingredients Quantity (g) (% by weight) EPOLENE »N-15 12.0 7.41 (POLYPROPYLENE) MAPO (copolymer of 28.0 17.31 propylene-hexene) No. Acidity = 50 GENAPOL UD050 12.0 7.42 (non-ionic surfactant) 2-amino-2-methyl-l- 5.8 3.58 propanol Water 104.0 64.28 The process described in Example 1 is used to prepare an emulsion. The emulsion is milky in color. The particle size is 2.0 x 10"5 mm (0.02 μ) -5.0x 10" 2 mm (50.0 μ). The pH of polyolefins transported in water is 10.21. EXAMPLE 5 Example 1 is repeated except that amorphous, maleated, non-halogenated polyolefins (MAPO) (propylene homopolymer) are used in place of amorphous, maleated, non-halogenated polyolefins based on the propylene-hexene copolymer. The ingredients used to emulsify EPOLENE N-15 are as follows: Ingredients Quantity (g) (% by weight) EPOLENE • N-15 6.0 3.70 (POLYPROPYLENE) MAPO (copolymer of 34.0 20.96 propylene-hexene) No. Acidity = 50 GENAPOL UD050 12.0 7.40 (non-ionic surfactant) 2-amino-2-methyl-l- 6.2 3.82 propanol Water 104.0 64.12 The ingredients are heated for two hours at 320 ° F (160 ° c9 in an air-tight pressure reactor.) The milky emulsion is filtered before being used.The pH of the emulsion is . 19. The particle size is in the range 2.0 x 10"5 m (0.02 μ) -2.0x 10" 1 mm (100.0 μ). EXAMPLE 6 Example 2 is repeated except that EPOLENE N-34 is used in place of EPOLENE N-15 to prepare polyolefin mixtures at a temperature of 180 ° C to 185 ° C. This mixture is used to emulsify EPOLENE N-34 according to the process described in example 1. The ingredients used to emulsify EPOLENE N-34 are as follows: Ingredients (g) (% by weight) EPOLENE • N-34 13.36 8.30 (POLYPROPYLENE) MAPO (copolymer of 26.64 16.57 propylene-hexene) No. Acidity = 50 GENAPOL UD050 12.0 7.46 (non-ionic surfactant) 2-dimethylaminoethanol 4.8 2.98 Water 104.0 64.69 The particle size is less than 0.03 mm (30 μm). The emulsion is milky in color.

COMPARATIVE EXAMPLE 7 Example 1 is repeated except that amorphous, maleic, non-halogenated polyolefins (MAPO) polyolefin (propylene-hexene copolymer) of the formulation are removed. The process is the same as described in Example 1. The composition is as follows: Ingredients Quantity (g)% by weight) EPOLENE ® N-15 40.0 24.72 (POLYPROPYLENE) GENAPOL UD050 12.0 7.42 (non-ionic surfactant) 2 -amino-2-methi1 - 1 - 5.8 3.58 propanol Water 104.0 64.28 EPOLENE N-15 is in solid form and does not emulsify. Two different phases are observed after the process.

Example 1 is repeated except that TRITON N-surfactant is used in place of the Genapol UD050 surfactant to prepare the water-borne polyolefin (EPOLENE N-15). The ingredients used are as follows: Ingredients Amount (g) (% by weight) EPOLENE ß N-15 6.0 3.77 (POLYPROPYLENE) MAPO (copolymer of 34.0 21.38 propylene-hexene) No. Acidity = 50 Surfactant TRITON 9.2 5.79 N-101 2-amino-2-methyl-l- 5.8 3.65 propanol Water 104.0 65.41 The emulsion it appears milky in color, the particle size of the emulsion is less than 0.1 mm (100 microns). The pH of the emulsion is approximately 10.19. The results in Examples 1-6 and 8 clearly show that it is essential to mix EPOLENE N-15 with amorphous, maleated, non-halogenated polyolefins (MAPO) in order to emulsify EPOLENE N-15. In Comparative Example 7 the amorphous, maleated, non-halogenated polyolefin is not present as a result EPOLENE N-15 does not emulsify.

TABLE II DESIGNATION AND COMPOSITION OF FINE POLLEN OIL TRANSPORTED IN WATER QUANTITY (% WEIGHT) INGREDIENTS ABC (*) DEF POLYOLEPHINS OF SERTE EPOI-ENE N EPOLENE N-15 EPOLENE N-34 3.71 1.88 3.71 3.70 - 3.77 8.30 MOLDED POI.TOLEFTK-AS (MAPQ1 COPOLYMER PROPYLENE-HEXENUM 21.01 23.14 21.01 - 16.57 21.38 HOMOPOLIMERO PROPYLENE - - - 20.96 oo SURFACTANT GENAPOL UD050 7.42 6.5 7.42 7.40 7.46 TRITON N-101 -. - - -. 5.79 2 - . 2 -AMINO-2 -METIL- 1- PROPANOL 3.58 3.38 3.58 3.82 - 3.65 2-DIMETHYLAMINOBTANOL - - - - 2.98 WATER 64.3 65.0 64.3 64.1 64.7 65.4 (*) A HOMOGENEOUS MIXTURE OF EPOLENE N-15 AND MAPO IS PREPARED BEFORE THE PROCESS 5 EMULSIFICATION EXAMPLE 9 The polyolefin transported in water (a) is prepared according to the procedure indicated in Example 1 and tested for adhesion on a thermoplastic polyolefin substrate (TPO, Himont 3131). The polyolefin carried in water (a) is further diluted with water to approximately 10.0% by weight of solid content. The diluted polyolefin (a) is applied by spraying it on TPO substrate panels. The sprayed material is dried at 170.6 ° F (77 ° C) for 10 minutes. Adhesion panels are examined according to the ASTM procedure D3359M. The coated panels are also visually examined for the degree of blistering according to the ASTM D714-87 procedure. The integrity of the coated film is evaluated. The degree of blistering is classified as follows: CLASSIFICATION FOR FORMATION OF AMPOLLAS 10 »excellent: no blistering 8 = formation of small blisters observed with the naked eye D» dense MD = dense medium F = little The results are as continued TIME (DAYS)% ADHESION RATIO PROPORTION AMPOLE FORMATION 0 100 10 6 100 10 12 100 10 24 100 10 The results in Example 9 demonstrate that the waterborne polyolefins of this invention have excellent adhesion without blistering on a approximately 24 hours. Similar results are obtained using polyolefins transported in water b, c, d, e, and f of Table II. EXAMPLE 1Q Example 9 is repeated except that the coated panels are placed at 0 ° F (-17.78 ° C) instead of room temperature to examine adhesion and blistering. The results indicate that adhesion is retained 100% without blistering during the test period. Similar results are obtained for polyolefins transported in water b, c, d, e, and f of Table II. EXAMPLE 11 Example 9 is repeated except that the coated panels are placed at 250 ° F (121.11 ° C) instead of room temperature to examine adhesion and blistering. The results indicate that adhesion is retained 100% without blistering during the test period of approximately 24 hours. Similar results are obtained for polyolefins transported in water b, c, d, e, and f of Table II. EXAMPLE 12 This example illustrates the adhesion of automotive OEM paint PPG BC / CC on TPO in the presence of waterborne polyolefins of this invention used as a promoter. The TPO panels are coated as described in Example 9. After drying the panels promoted at 170.6 ° F (77 ° C) for 10 minutes, the panels are coated with automotive OEM PPG BC / CC paint. The coated panels are examined for paint adhesion as described in Example 9. The results for paint adhesion and blistering are as follows: TIME (DAYS)% ADHESION RATIO PROPORTION AMPOLE FORMATION 0 100 10 1 100 10 2 100 10 3 100 10 The results demonstrate that the waterborne polyolefins of this invention exhibit excellent adhesion properties without blistering over a period of at least three months.

EXAMPLE 13 Example 12 is repeated except adhesion and blistering are studied in a humid environment (eg, Cleveland humidity cabinet at 49 ° C or 120 ° F) instead of room temperature. The results are reported in an average value of three readings. Adhesion of paint PPG BC / CC: After 24 hours - 100%; no blister formation After 72 hours = 100%; no blister formation EXAMPLE 14 Example 12 is repeated except that an automotive OEM paint is used, two-part polyurethane elastomeric enamel pigmented with Red Spot (white) instead of PPG BC / CC paint to coat the TPO panels. The initial adhesion of paint on TPO is excellent and blistering is observed at room temperature for a period of at least three months. EXAMPLE 15 Example 14 is repeated except adhesion and blistering are studied in a humid environment (e.g., Cleveland humidity cabinet at 49 ° C or 120 ° F) instead of room temperature. The results are reported in an average value of three readings.

Adhesion of two-part polyurethane paint pigmented with Red Spot (white): After 24 hours = 100%; no blister formation After 72 hours = 100%; no blister formation After 336 hours = »100%; no blister formation EXAMPLE 16 Example 15 is repeated to compare adhesion on TPO automotive parts using EPOLENE N-15 / MAPO of the present invention and MAPO emulsion prepared according to the process described in U.S. Pat. 5,373,048. The degree of blister formation is determined according to the method indicated in Example 9. The results obtained are recorded as an average of three readings as follows: ACCESS DATA PRESENT INVENTION PATENT OF THE STATES UNITED NO. 5,373,048 % OF ADHESION ETENIDO Initial adhesion 100 100 Resistance to humidity 24 hours 100 70 96 hours 100 0 432 hours 100 0 576 hours 94 0 FORMATION OF AMPOLE. { *) Initial 10 10 Resistance to humidity 24 hours 10 10 96 hours 10 10 432 hours 10 576 hours 10 The data presented in the above table clearly indicate that EPOLENE N-15 containing water-borne polyolefins of the present invention exhibit superior adhesion compared to the product prepared according to the process described in U.S. Patent No. 5,373,048.

Claims (25)

1. RglVINDICACTONUfl 1. a polyolefin composition transported in water to promote adhesion, the polyolefin transported in water having a particle size of 0.02 to 150 microns characterized in that it comprises: (A) 0.1 to 10 weight percent of at least one polyolefin not oxidized, unmanned, non-chlorinated, crystalline having an average molecular weight weight of 2,000 to 15,000 and a density of less than 1.0 g / cc. (B) 10 to 40 weight percent of at least one non-chlorinated, maleated, amorphous polyolefin having an average molecular weight of at least 500 and an acid number of 15 to 95; (C) 0.1 to 10 weight percent of at least one surfactant having a hydrophilic-lipophilic balance of 6 to 18; (D) 0.1 to 5 weight percent of at least one amine compound having a molecular weight of at least 150; and (E) 50 to 95 percent by weight of water, percentages by weight are provided based on the total weight of the composition carried in water.
2. 2. A polyolefin composition transported in water to promote adhesion, the polyolefin transported in water having a particle size of 0.02 to 150 microns characterized in that it comprises: (A) 0.5 to 5 weight percent of at least one non-oxidized polyolefin , non-mauled, non-chlorinated, crystalline that has an average molecular weight of 5,000 to 12,000 and a density of less than 1.0 g / cc. (B) 15 to 35 weight percent of at least one non-chlorinated, maleated, amorphous polyolefin having an average molecular weight of at least 500 and an acid number of 15 to 95; (C) 1 to 5 weight percent of at least one surfactant having a hydrophilic-lipophilic balance of 8 to 14; (D) 0.1 to 5 weight percent of at least one amine compound having a molecular weight of at least 100; and (E) 55 to 90 weight percent water, the percentages by weight are provided based on the total weight of the composition carried in water
3. 3. A process for preparing a polyolefin composition carried in water useful as an adhesion promoter wherein the polyolefin transported in water has a particle size of 0.02 to 150 microns, the process characterized in that it comprises the steps of: (I) mixing (A) 0.1 to 10 weight percent of at least one non-oxidized polyolefin, malenate, non-chlorinated, crystalline having an average molecular weight weight of 2,000 to 15,000 and a density of less than 1.0 g / cc. (B) 10 to 40 weight percent of at least one non-chlorinated, maleated, amorphous polyolefin having an average molecular weight of at least 500 and an acid number of 15 to 95; (C) 0.1 to 10 weight percent of at least one surfactant having a hydrophilic-lipophilic balance of 6 to 18; (D) 0.1 to 5 weight percent of at least one amine compound having a molecular weight of at least 150; and (E) 50 to 95 weight percent water; (II) heating the mixture of Step (I) at a temperature of 120 ° C to 200 ° C and a pressure of 60 kPa to 1500 kPa to form a polyolefin emulsion carried in water; and (III) cooling the polyolefin emulsion transported in water formed in step (II) at a temperature of 20 ° C to 70 ° C to form a polyolefin composition carried in water, it is provided that the percentages by weight are based on total weight of the composition.
4. 4. A process for preparing a polyolefin composition transported in water useful as an adhesion promoter wherein the polyolefin transported in water has a particle size of 0.02 to 150 microns, the process characterized in that it comprises the steps of: (I) mixing (A) 0.1 to 10 weight percent of at least one non-oxidized, non-maimed, non-chlorinated, crystalline polyolefin having an average molecular weight weight of 2,000 to 15,000 and a density of less than 1.0 g / cc. (B) 10 to 40 weight percent of at least one non-chlorinated, mallowed, amorphous polyolefin having an average molecular weight of at least 500 and an acid number of 15 to 95; (C) 0.1 to 10 weight percent of at least one surfactant having a hydrophilic-lipophilic balance of 6 to 18; (D) 0.1 to 5 weight percent of at least one amine compound having a molecular weight of at least 150; and (E) 50 to 95 weight percent water; (II) heating the mixture of Step (I) to a temperature of 120 ° C to 200 ° C and a pressure of 60kPa to 1500 kPa by injecting 50 to 95 weight percent of water into the mixture of Step (II) to form a polyolefin emulsion transported in water; and (III) cooling the polyolefin emulsion transported in water formed in step (II) at a temperature of 20 ° C to 70 ° C to form a polyolefin composition carried in water, it is provided that the percentages by weight are based on total weight of the composition.
5. 5. The polyolefin composition carried in water according to claim 1, characterized in that the amorphous, maleated polyolefin, component (B), has an acid number in the range of 30 to 50.
6. 6. The process according to the claim 3 characterized in that the amorphous, maleated polyolefin, component (B), has an acid number in the range of 30 to 50.
7. 7. The polyolefin composition carried in water according to claim 1, characterized in that the amorphous polyolefin is selected from the group consisting of malleoned polypropylene, malleable propylene-ethylene, malleoned propylene-hexene, malleable propylene-butene, malleable propylene-ethylene-butene, and malleable propylene-ethylene-hexene.
8. 8. The process according to claim 3, characterized in that the amorphous polyolefin is selected from the group consisting of malleated polypropylene, malleated propylene-ethylene, mallowed propylene-hexene, maleic propylene-butene, malleable propylene-ethylene-butene, and propylene- ethylene-hexene.
9. 9. The polyolefin composition carried in water according to claim 1 characterized in that the amorphous polyolefin has a repeating unit selected from the group consisting of ethylene, propylene, butene, hexene, and combinations thereof. The process according to claim 3 characterized in that the amorphous polyolefin has a repeating unit selected from the group consisting of ethylene, propylene, butene, hexene, and combinations thereof. 11. The polyolefin composition transported in water according to claim 9, characterized in that the amorphous polyolefin is a homopolymer having propylene units in the range of 15 to 95 mol percent. 12. The process in accordance with the claim 10 characterized in that the amorphous polyolefin is a homopolymer having propylene units in the range of 15 to 95 mole percent. 13. The polyolefin composition carried in water according to claim 9, characterized in that the amorphous polyolefin is a copolymer having propylene units in the range of 30 to 98 mole percent. 14. The process according to claim 10 characterized in that the amorphous polyolefin is a copolymer having propylene units in the range of 30 to 98 mole percent. 15. The polyolefin composition carried in water according to claim 9, characterized in that the amorphous polyolefin is a terpolymer having propylene units in the range of 40 to 80 mole percent. 16. The process according to claim 10 characterized in that the amorphous polyolefin is a terpolymer having propylene units in the range of 40 to 80 mole percent. 17. The polyolefin composition carried in water according to claim 9, characterized in that the amorphous polyolefin is a terpolymer having ethylene units in the range of 1 to 20 mol percent. 18. The process in accordance with the claim 10 characterized in that the amorphous polyolefin is a terpolymer having ethylene units in the range of 1 to 20 mol percent 19. The process according to claim 3 characterized in that Stage (II) is carried out at a temperature of 140 °. C at 180 ° C. 20. The polyolefin composition carried in water according to claim 1 characterized in that the amine, component D, is selected from the group consisting of morpholine, 2-amino-2-methyl-1-propanol, 2-dimethylaminoethanol, hydroxide ammonium, and combinations thereof. 21. The process according to claim 3 characterized in that the amine, component D, is selected from the group consisting of morpholine, 2-amino-2-methyl-1-propanol, 2-dimethylaminoethanol, ammonium hydroxide, and combinations of the same. 22. The polyolefin composition carried in water according to claim 1, characterized in that the polyolefin carried in water has a particle size of 5 to 100 microns. 23. The process according to claim 3, characterized in that the polyolefin carried in water has a particle size of 5 to 100 microns. 24. The process in accordance with the claim 3 characterized in that Stage (II) is carried out at a pressure of 200 kPa to 1000 kPa. 25. The polyolefin composition carried in water according to claim 1, characterized in that it is applied to a substrate selected from the group consisting of polymer, wood, concrete, and glass.