MXPA00000952A - Aqueous sulfopolyurea colloidal dispersions - Google Patents

Abstract

The present invention relates to stable aqueous colloidal dispersions of sulfopolyureas and self-supporting films formed from the dispersions which display good mechanical properties from about room temperature to temperatures exceeding 150°C. The films of the invention, which are formed with no volatile organic compound (VOC) emissions and no post-coating chemical or ionic cross-linking, are not redispersible in water and may be used to form heat resistant abrasive articles.

Description

Aqueous colloidal dispersions of sulfopolyurea BACKGROUND The present invention relates to stable aqueous colloidal dispersions of sulfur-polyureas and support films by themselves that are formed from dispersions which exhibit good mechanical properties from near room temperature to temperatures in excess of 150 ° C. Films of the invention, which are formed with emissions of non-volatile organic compounds (C04) and non-post-coated chemicals or ionic cross-links, are not redispersible in water and can be used to form heat-resistant abrasive articles. Polyurethanes are a well-established class of high-performance polymers, which can be easily adapted to exhibit a unique combination of tensile strength, rigidity and flexibility. As a result of this versatility, polyurethanes have found utility in a variety of applications including binder resins, abrasion resistant coatings, protective coatings and membranes. The polyurethanes can be discharged to a substrate as a thermoplastic or thermosetting material by a REF. 32625 extrusion process, such as a wet cure or two parts of the curing system, usually of an organic solvent or as an aqueous dispersion of a colloidal polymer system. Two parts of polyurethanes are generally used in ligation or coating applications where they are released from mixtures of organic solvents, blocked finished isocyanate compounds and polyols, or mixtures of organic solvents, a finished diisocyanate compound and polyols. Aqueous polyurethane dispersions have been developed as a means to release polyurethane coatings to substrates such as fibers, textiles and paper. Such dispersions offer advantages over two-part polyurethane systems in which they have reduced emissions of volatile organic compounds (VOC), can eliminate exposure to toxic isocyanate or diamine compounds during coating, and provide a simplified overall process. Tests to improve the properties of thermal stability and flow resistance of aqueous polyurethane materials by the incorporation of crosslinked monomers which react with the fundamental polyurethane (eg, epoxy resins) have been only partially successful. Improved high temperature performance has typically been acquired at the expense of reduced stiffness and elongation, and the coefficient increased dramatically.

SUMMARY OF THE INVENTION The present invention relates to stable aqueous sulfopolyurea colloidal dispersions comprising a plurality of units (a) and (b) having the formula (b) interconnected by segments that have the formula wherein each Ri is independently a divalent aliphatic group having an average molecular weight of 200 to 600 comprising ether or ester functional groups preferably including -CH2-CH2- (OCH2-CH2-) n-, -C (CH3) H -CH2- (OC (CH3) H-CH2) n-, and groups -0- (CH2) m-C0-f-0- (CH2) m-C0-] n-; each R2 is independently a divalent straight or branched chain alkylene group or cycloaliphatic group having 2 to 15 carbon atoms or a divalent aliphatic group having a molecular weight of 200 to 2,000 comprising ether or ester functional groups including preferably - CH2-CH2- (0CH2-CH2-) n-, -C (CH3) H-CH2- (OC (CH3) H-CH2-) n-, -CH2-CH2-CH2-CH2- (0CH2CH2-CH-CH2 ) n-, and groups -O- (CH2) m-C0- [-0- (CH2) m-C0-] n-; each R3 group is a methylene-4, '-diphenyl group, a 1,4-phenyl group, a 4, 4'-biphenyl group, a 1,6-naphthyl group, a N, N-di ((p-methylphenyl) group ) phenyl) -carbodiimide or mixtures thereof; m is an integer from almost 2 to almost 5; n is an integer from almost 2 to almost 15; x equal to 1; and is an integer between 0 and 4; z is an integer between 0 and 6; and M is a cation of sodium, lithium or potassium. The sulfopolyurea compositions have an equivalent weight of sulfonate from almost 1, 000 to almost 8,500. The invention also relates to support films themselves as well as heat resistant abrasive articles which use the sulfopolyurea dispersions of the present invention. Such abrasive articles comprise an organic matrix with a novel, resistant, thermally stable, adherent elastomeric resin binder system comprising a sulfopolyurea. These abrasive articles can be urged against a high-pressure, high-speed workpiece by rubbing the small or non-undesirable surface or transferring it to the surface of the workpiece. In this application: "colloidal dispersion" means a discrete distribution of particles that have an average size of less than almost 1 miera, typically less than almost 500 nanometers in an aqueous medium (typically water); "crystalline melting point", Tm, is the temperature at which the last hint of crystallinity disappears under equilibrium conditions; "ester / urethane-containing" means divalent alkyl groups which contain ester or urethane carboxylic acid linkage groups; "hard segment" means the urethane-urea bond containing segments of the sulfopolyurea chain (more generally formed by the reaction of the isocyanate groups and functional groups derived from amine or alcohol) which are associated through the hydrogen bond; "separate phase" means the morphological phenomenon in a polyurea or film coating where discrete regions of hard and soft segments are formed by association of the hard segment interactions of the hydrogen bond; "Polyurea" means a polymer obtained by a polymerization reaction in which the mechanism of chain growth is entirely the formation of urea and biuret bonds by the reaction of isocyanate groups with amine or urea groups, with predominance of the Urea link formation; "soft segment" means that portion of the fundamental polyurea which is located between hard segments, typically comprising one or more polyols that are contained within the fundamental polymer; "stable aqueous colloidal dispersion" means a uniform dispersion of polymer particles having an average diameter from almost 10 nanometers to almost 1 miera in water which does not agglomerate in the absence of agitation (either continuous or intermittent); "sulfonate equivalent weight" means the sum of the atomic weights of all the atoms in the sulfopolyurea divided by the number of sulfonate groups that are contained in the polymer molecule; "Sulfopolyurea" means a high molecular weight of polyurea containing a plurality of sulfonate groups covalently attached to and slopes of the polymer chain; and "tension storage coefficient (E ')" is a measure of stiffness of a material at a given temperature, which is obtained by measuring the response of the material to a tension stress oscillatoryly imposed at the temperature of interest.

BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is an indication of the curves of the stress data for the sulfopolyurea films that were prepared as described in Examples 1-4. Figure 2 is an indication of the data of the Dynamic Mechanical Analysis (AMD), graphic representation of the Stress Storing Coefficient (E ') as a function of temperature, of the sulfopolyurea films prepared as described in Examples 1-4.

Figure 3 is an indication of the stress data curves for films prepared from five commercially available floating polyurethanes (Comparative Examples C1-C5). Figure 4 is an indication of the data (AMD), graphic representation of E 'as a function of temperature, of films prepared from two commercially available floating polyurethanes (Comparative Examples Cl &C2). Figure 5 is an indication of the AMD data, graphical representation of E 'as a temperature function of the films prepared from two commercially available floating polyurethanes (Comparative Examples C3 &C4). Figure 6 is an indication of the AMD data, graphic representation of E 'as a temperature function of a film prepared from commercially available floating polyurethanes (Comparative Example C5). Figure 7 is an indication of a portion of the Differential Thermal Analysis (DTA) curve of the sulfopolyurea film of Example 9 which shows the Tm of the polymer.

Figure 8 is an indication of a portion of the wide-angle X-ray scattering spectrum (DXAA) of the I sulfopolyurea film of Example 9.

Detailed Description of the Invention The present invention provides stable aqueous sulfopolyurea colloidal compositions comprising one or more soft hydrophilic segments comprising a centrally disposed triaryl group comprising a sulfonic acid salt and two carboxylic acid ester groups, the ester groups which they further comprise divalent alkyl radicals containing ether or ester functionalities, and optional modifying groups comprising a divalent branched or straight chain alkylene group or cycloaliphatic group, the soft hydrophilic segments and optional modifying segments preferably being interconnected by hard segments which comprise less a bivalent radical of diphenylmethane groups, 1,4-phenyl groups, 4,4'-biphenyl groups, 1,6-naphthyl groups, N, N-di ((p-methylphenyl) phenyl) -carbodiimide groups, or mixtures of them interconnected by the urea groups.

The sulfopolyurea compositions of the present invention have a significantly higher hard segment content than conventional polyurea compositions which are soluble solvent compositions or wet cures as the extended chain of the crystallizable hard segment is formed during the polymerization step. dispersion. The conventional aqueous dispersible polyurea or polyurethane / urea compositions are limited to hard segments which do not crystallize or which are present in low concentrations to allow the prepolymer process. As a result of the high content of the hard segment, the films based on the sulfopolyurea compositions of the present invention are substantially insensitive to water and are not redispersible in water without the post-formation of the crosslink film. Additionally, films that are based on the sulfopolyurea compositions of the present invention unexpectedly exhibit significantly better high temperature properties than conventional polyurethane / urea compositions. For example, films that are based on the sulfopolyurea compositions of the present invention are thermally stable and show small or no flow at temperatures in excess of 150 ° C, preferably showing small or no flow at temperatures in excess of 200 ° C. , and more preferably showing small or no flow at temperatures in excess of 250 ° C. In addition, films based on the sulfopolyurea compositions of the present invention have comparatively low loss in storage coefficient at temperatures in excess of 100 ° C. The sulfopolyurea compositions of the present invention comprise polymers having a plurality of segments (a) and (b) having the formula (b) interconnected by segments that have the formula where; each Ri is independently a divalent aliphatic group having an average molecular weight of 200 to 600 comprising ether or ester functional groups, each R2 is independently a divalent straight or branched chain alkylene group or cycloaliphatic group having an average of 2 to 15 carbon atoms or a divalent aliphatic group having an average molecular weight of 200 to 2,000 comprising ether or ester functional groups. R3 is a methylene-4,4'-diphenyl group, a 1,4-phenyl group, a 4,4'-biphenyl group, a 1,6-naphthyl group, a N, N-di ((p-methylphenyl) group ) phenyl) -carbodiimide or mixtures thereof; m is an integer from almost 2 to almost 5; n is an integer from almost 2 to almost 15; x is equal to 1; and is an integer between 0 and 4; z is an integer between 0 and 6; and M is a cation of sodium, lithium or potassium. Preferred sulfopolyurea compositions of the invention include those compositions wherein Ri comprises an equimolar mixture of average molecular weight of about 400 divalent aliphatic polyoxyethylene groups and about 425 average molecular weight of divalent aliphatic polyoxypropylene groups; R2 comprises an equimolar mixture of about 400 average molecular weight of divalent aliphatic polyoxyethylene groups and about 425 average molecular weight of divalent aliphatic polyoxypropylene groups, and a divalent aliphatic polyoxypropylene group of about 1000 average molecular weight; R3 comprises the methylene-4, '-diphenyl group; x is l, y is 0 to l.5 and z is 0 to 5. More preferably, y is 1 and z is 0 to 3. Other preferred sulfopolyurea compositions of the invention include those where W? it comprises almost 600 average molecular weight of the divalent aliphatic polyoxyethylene group; R2 comprises a mixture of two equivalents in nearly 600 average molecular weight of the divalent aliphatic polyoxyethylene group and one equivalent of a divalent aliphatic polyoxypropylene group of nearly 1000 average molecular weight; R3 comprises methylene-4,4'-diphenyl groups; x is 1, and is 1, z is 0 to 5. More preferably, z is 0 to 3. The sulfopolyurea compositions of the invention preferably have an equivalent sulfonate weight from about 1,000 to almost 8,500, more preferably from about 2,500 to almost 7,000 and a hard segment content from almost 20% by weight to almost 60% by weight, preferably from almost 30% by weight to almost 50% by weight. The preparation of the sulfopolyureas of the invention is schematically described in the reaction sequence shown below. In this reaction sequence, the sulfopolyol (III) is prepared by transesterification reaction of dimethyl-5-sodiosulfoisophthalate (I) with a polyol (II) in Step 1. A prepolymer is subsequently prepared from the sulfopolyol in Step 2 where the Sulfopolyol (III) is converted to a terminated isocyanate sulfoprepolymer (V) by reaction with a polyisocyanate (IV). When an excess of polyol (II) is used in Step 1, the reaction product of Step 2 comprises a mixture of terminated isocyanate sulfoprepolymer (V) and terminated isocyanate polyol (VI). It was understood that the term polyol excess includes excess of the polyol used in the initial transesterification reaction or that more of the same polyol or a different polyol is added to the reaction product of the transesterification reaction, where the different polyol includes lower molecular weight of polyols having molecular weights in the range from almost 62 to almost 200. The reaction product of Step 2 may also contain unreacted polyisocyanate / excess (VI). The terminated isocyanate sulfoprepolymers produced by the process described above are described in U.S. Pat. Nos. 4,558,149, 4,746,717 and 4,855,384. Alternatively, the sulfopolyol (III) can be reacted with a lactone to form a lactonized sulfo-organodiol which is subsequently reacted with a polyisocyanate to form a terminated isocyanate sulfoprepolymer. A colloidal dispersion of a sulfopolyurea (VII) can be prepared from the finished isocyanate sulfoprepolymer (V) [or prepolymer mixture (V, VI and II)] in Stage 3 by injecting the finished isocyanate sulfoprepolymer-prepolymer (V) [or prepolymer mixture (V, VI and II)] into a microfluidizer and maintaining high mixing agitation of the mixture of reaction at about 70 ° C under an N 2 atmosphere for a period from about 5 to about 60 minutes. Other mixing methods can be employed which provide adequate levels of cutting or stirring in order to avoid formation of macroscopic gel particles. The free fixed films were prepared from the colloidal dispersions of the sulfopolyurea (VII) by rotary casting or other standard film forming techniques. The polyols (II) suitable for use in the preparation of the sulfopoliols (III) are typically lower molecular weight diols, including, but not limited to, 400 average molecular weight polyethylene glycol (available from DuPont Chemicals, Wilmington, DE), 600 average molecular weight polyethylene glycol (available from Union Carbide Chemical and Plastics Co., Inc., Danbury, CT), 425 average molecular weight polypropylene glycol (available from Arco Chemical, Newton Square, PA), and polycaprolactonediol (PCP-200, available from Union Carbide Corp.). The sulfopoliols (III) are prepared under typical transesterification reaction conditions, using one or more of the indicated polyols (II), dimethyl-5-sodiosulfoisophthalate (I) and a catalytic transesterification reaction. The methanol is distilled from the reaction mixture to bring the reaction to term. The sulfopolyol (III) can be prepared by the use of a single polyol or a mixture of two or more polyols. Typically an excess of polyol (II) (above more than 4: 1 molar of excess polyol relative to dimethyl-5-sodiosulfoisophthalate) is used in the formation of sulfopolyol (III), which produces a mixture of sulfopolyol (III) and polyol (II) which is transferred to the isocyanate-terminated sulfoprepolymer in the Stage 2 . SEQUENCE OF THE REACTION STAGE 1 STAGE 2 Sulfur-terminated isocyanate polymer V excess polyisocyanate thermolin: polyisocyanate VI water absorption step 3 The polyisocyanates (IV) which are used in the preparation of the terminated isocyanate sulfoprepolymer (V) have a high aromatic content to promote hard segment formation and the subsequent separation phase in the final sulfopolyurea (VII). Suitable polyisocyanates include, but are not limited to, 4,4'-diisocyanatodiphenylmethane (available from Aldrich Chemical Co., Milwaulkee, WI), 1,4-diisocyanatobenzene, 4,4'-diisocyanatobiphenyl, 1,6-diisocyanatophthalene and Isonate 2143L (available from Dow Chemical Corp., Midland, MI) or mixtures of two or more of the same. The terminated isocyanate sulfoprepolymer (V) can be prepared by the use of a simple sulfopolyol or a mixture of a sulfopolyol (III) and one or more polyols (II). The formation reaction of the prepolymer (V) typically utilizes excess polyisocyanate (III) (about 1 to 50 mol% of excess isocyanate groups relative to the hydroxyl end groups), which produces a mixture of the finished isocyanate sulfoprepolymer (V), terminated isocyanate polyol (VI) and unreacted polyisocyanate (IV). The amounts of the sulfopolyl and polyisocyanate reactants are adjusted to produce sulfopolyurea compositions ranging from almost 20% by weight to almost 60% by weight, preferably from almost 30% by weight to almost 50% by weight of hard segment content. Injection of the terminated isocyanate sulfoprepolymer (V) [or the mixture of (V), (VI) and (II)] in water with sufficient agitation to avoid macroscopic gel formulation, such as those produced using an icrofluidizer, produces a colloidal dispersion of precursors that ultimately produce the sulfopolycerases (VII) of the present invention. Subsequent to being introduced into the aqueous environment, a portion of the isocyanate groups are hydrolyzed to amino groups which, in turn, react with non-hydrolyzed isocyanate groups to form the urea bonds of the sulfopolyurea (VII). This process produces a discrete distribution or dispersion of sulfopolyurea particles (VII) of less than one diameter, typically in a range from about 10 nanometers to almost 500 nanometers in diameter, in water. The dispersions have a translucent, bluish appearance characteristic of a colloidal dispersion. The particles have sufficient hydrophilicity imparted to them by the pending sulfonate groups since the dispersion exhibits good stability, showing substantially no agglomeration in the absence of cutting or stirring under extended storage at ambient conditions without the supplemental surfactants. Supplementary surfactants can be added to the dispersions, for example, to facilitate soaking of various substrates, without adversely affecting the stability of the dispersion. Dispersions can be applied to a variety of substrates, including but not limited to metals, plastics, wood, etc. to form protective coatings. The dispersions can also be applied to fibrous substrates to provide a polyurea binder to the substrate. Fixed free films or support films by themselves are easily prepared from colloidal dispersions by removal of water from the composition and allow the particles to coalesce. Conventional spinning or film coating techniques can be used to form these films. Aqueous dispersions can be added to the aqueous dispersions to facilitate the formation of the film and / or the wetting of substrates without adversely affecting the stability of the colloidal dispersions of the invention.

The polyurea films sulfoprepolymer thus produced pass through the separation phase in the removal of water, which separates into substantially amorphous, soft segments comprising sulfopolyurea segments which contain a centrally arranged triaryl group comprising a sulfonic acid salt and two carboxylic acid ester groups, the ester groups further comprise divalent alkyl radicals containing ether functionalities or ester and hard semicrystalline segments comprising segments comprising the urethane and urea linkage containing segments of the sulfopolyurea chain. While this separation phase occurs at ambient temperatures, it can be accelerated by annealing the films at elevated temperatures. The typical range of annealing temperatures is from 40-70 ° C. By careful selection of the annealing conditions (i.e., time and temperature), it is possible to promote crystallization in the hard segment of the sulfopolyureas of the present invention to achieve Tm 's in excess of 300 ° C for those segments. The unexpected high temperature performance properties of the films prepared from the sulfopolyurea compositions of the present invention are apparent from an examination of the analysis data.

Thermal Gravimetric (AGT) and Dynamic Mechanical Analysis (AMD) of films prepared from sulfopolyurea compositions of the present invention compared to similar data for films made from commercially available floating polyurethane / urea compositions.

The thermal stability of the sulfur-polyureas relative to the comparative polyurethane / ureas is demonstrated dramatically in the AGT analysis of the sulfur-polyureas and comparative polyurethane / ureas where the film samples were fastened at 550 ° C under an N2 atmosphere. In all cases, the sulfopolyurea compositions of the present invention had residues after exposure to 550 ° C of at least 12% as high as 27% relative to the weight of the original unheated sample while the comparative polyurethane / ureas had residues less than almost 3%. AMD also demonstrates the unexpected high temperature performance properties of the sulfopolyurea compositions of the present invention. In Figure 1, the AMD curves for the stress storage coefficient (E ') of the film as a function of temperature are plotted for films of the sulfopolyureas of the present invention. The AD curves, which correspond to the compositions of Examples 1-4 respectively, all show initial values of E 'which are part of the plateau of the curve (plateau) at almost 0-50 ° C, followed by a fall while that the temperature of the film reaches approximately 40-75 ° C, to the point where the E 'substantially plateau at temperatures in excess of about 150 ° C. Data for the corresponding AMD films based on the commercially available comparative polyurethane / ureas are presented in Figures 4-6. In all cases the E 'value for these films shows a stable decline with the increase in film temperature. The analysis of these data provides a measure of the storage coefficient retention and stiffness as a function of the temperature increase. More specifically, the E 'losses from almost 13% to 77% were observed in the temperature range of 100-135 ° C and the E' losses from almost 9% to 133% in the 100-200 temperature range ° C were observed for the sulfopolyurea compositions of Examples 1-4. This resists in contrast to the E 'losses from almost 126% to almost 902% in the temperature range of 100-135 ° C for Comparative Examples C1-C4. Changes of E 'in the temperature range of 100-200 ° C could not be determined by the Comparative samples as long as they become very soft and the coefficient of the smoothed samples was below the detection limits of the analytical instrumentation. Adjutor, which includes but not limited to antistatic materials, biocides, funnels, grinding aid, lubricants, pigments and rheological additives may be incorporated into the compositions of the present invention without adversely impacting the thermal properties of the compositions. The abrasive products of the present invention can take any of a variety of conventional forms such as sheets, blocks, strips, belts, brushes, rotating covers, discs or solid or cellular wheels. Especially useful forms are wheels in the form of a disk or right circular cylinder having dimensions which can be very small, for example, a very small cylinder of the class of a few millimeters, or very long, for example, two meters or more, and a diameter that can be very small, for example, of the class of a few centimeters, or very long, for example, one meter or more. The wheels typically have a central opening for supporting by an appropriate shaft or other mechanical membership which means allowing the wheel to rotate in use. The dimensions of the wheel, configurations, support means and rotation means are well known in the art. The matrix can be either a solid or cellular organic polymer or a nonwoven fibrous tissue. Such matrices are also well known in the prior art. An example of an eminent matrix, non-woven fibrous formed from curled raw material fibers adhered to contact points with the binder which contains abrasive particles which is taught in U.S. Pat. No. 2,958,593 (Hoover et al.). The U.S. Patent No. 4,227,350 (Fitzer) publishes a matrix that is formed of three-dimensionally continuous wavy inter-meshed continuous filaments joined together. The abrasive products of the present invention can be prepared by appropriate techniques which are also well known in the art. For example, a wheel shape can be punched from a slab of the abrasive material. Additionally, bands, strips or elongated segments of the abrasive material can be wound spirally into a wheel shape while the binder system is uncured or partially cured and then cured to produce a wheel. In addition, the uncured or partially cured webs can be cut into sheets or discs, which are stacked in yet another and then compressed and cured under compression to make a higher density abrasive product. Such training techniques are well known to those skilled in the art. The abrasive articles of this invention are favorable for use in a wide variety of applications. They can be adapted for use in any work piece composition that includes metal, wood, plastics, composites, glass, ceramics, concrete and others. They can be designed for the aggressive removal of material from a workpiece, cleaning a workpiece in preparation for painting, metal coating, etc., to polish a surface to a glossy finish or to delicately rub a surface free of liquids, etc. . Preferred abrasive articles according to the present invention can include a plurality of coatings, although only a single coat is essential to realize their benefits. For example, nonwoven web may be lightly coated with a hard thermoset binder or a hard, elastomeric binder to create a substrate for subsequent coatings. This initial coating is known as a "pre-bond". A second or "made" coating can then be applied for more reinforcement, more hardness, more strength and / or provide more abrasive particles to the composite. A third or "size" coating can also be applied to apply applied abrasive particles and / or for further strengthening of the abrasive composition. The sulfopolyurea binder system of this invention can be used in any or all of the coatings and as evidenced in this presentation, it is capable of withstanding all the qualities necessary to produce such an abrasive composition. Optionally, for a particular abrasive article, all coatings applied thereto can consist essentially of the binder system of the present invention.

Procedures AGT (Thermal Gravimetric Analysis) Thermal gravimetric analyzes were run on an AGT TA Instrument (available from TA Instruments, Amherst, MA). The temperature was skipped from 200 ° C to 550 ° C at 10 ° C / minute under nitrogen. The percentage of residue was measured after constant weight loss at 550 ° C.

AMD (Dynamic Mechanical Analysis) The AMD spectrum was generated in an instrument Rheometrics RSA II dynamic mechanical analysis (available from Rheometrics Scientific, Piscatawny, NJ).

Samples with a typical dimension of 20-25 mm in length, 7 mm in width and 0.2-0.7 mm in thickness were mounted on an object embedded in the fiber / film site and a static tension force applied to prevent buckling of the sample . An oscillating force was applied to the sample at lOrad / sec and the resulting sinusoidal voltage was measured as a function of temperature. An extension of the typical temperature profile was from -50 to 250 ° C at 5 ° C / min. The correlation of the resulting sinusoidal voltage with the imposed force allows the calculation of the voltage storage coefficient (E '), the voltage loss coefficient (E' ') and tan d. The transition temperatures of the glass were determined by the temperature corresponding to the first maximum in tan d. The points were generated for each material which measure storage coefficients as a function of temperature in order to measure flow resistance as a function of temperature.

Voltage Analysis Voltage measurements were performed on a Sintech machine (available from Sintech, Inc., Research Triangle Park, NC) at a speed of 12.54 cm / min. The samples were punched in the shape of dog bones, 2.54 cm long and 0.47 cm wide. Three replicawere taken for each sample.

Determination of Particle Size Particle size was determined by the use of standard dynamic light scattering methods using a Malvern PCS 4700 instrument (available from Malvern Instruments LTD., MALVERN Worcs UK, Malvern Instruments Ltd., Spring Lane South MALVERN Worcs WR14 1XZ, UK) equipped with a 75 mW Argon laser. The concentrated dispersions were prefiltered through a 5μm nylon filter and then diluted to 0.001% by weight with the use of filtered DI water (0.45μm) and analyzed. The five measurements were measured and the values were averaged. The yield provides average diameter and polydispersity results as determined by Cumulents analyzes.

Differential Scanning Calorimeter (CED) Typically, approximately 10 mg of sample of the material of interest is placed in a sample cylinder and placed in the sample head of a CED instrument (TA Instruments, New castle, Delaware). The temperature of the sample chamber is raised in a controlled mode and the energy is supplied in a variant sequence to the sample to store a constant temperature relative to an empty reference cylinder in the reference head. The energy supplied to the sample relative to the reference is represented as a function of temperature. Typically, the clue is presented by indication of endothermic transitions, such as melting points, in downward direction.

DXAA Spectrum Procedure The film samples were examined by wide-angle X-ray scattering techniques employing a Philips vertical diffractometer (reflection geometry, available from the Philips Electronic Instruments Company, Mahwah, NJ), Ka copper radiation and recording Proportional detector of scattered radiation. The diffractometer is equipped with variable input slots, fixed output slots and graphite diffracted emission monochromator. The scanning stages were conducted within the range of dispersion angle of 5 to 55 degrees (2?) Using a stage size of 0.04 degrees and 4 seconds of residence time. The generator positions were 40kV and 35mA. The analysis of the resulting data was developed with the use of the Philips PC-APD software. High temperature scans were conducted by the use of a similar diffractometer adapted with a platinum strip oven and Paar HTK controller.

Rub test The method for testing the tendency of an abrasive wheel to transfer parts of itself to a workpiece or smear is as follows. The 75 mm diameter wheels with a hole in the center of 9.5 mm and 6 mm thick were mounted on the shaft of an air force tool which was rotated at a non-resistance speed of 14,000 to 18,000 revolutions per minute . The tool was stationary and loaded to force the wheel against the test work piece. The rotating wheel was forced to 35.6 N (or sufficient force to cause smears in a control sample) against a titanium metal plate of 60 mm by 300 mm, which was mounted on a transverse table that moved, causing the Wheel make a path of length of 200 mm on the metal plate at the speed of 25 mm per second. For comparative purposes, the tendency of an abrasive article to transfer material to smears subjectively is classified by the following scheme: EXAMPLES PREPARATION OF POLYOL Preparation of Sulfopoliol A A reactor equipped with a mechanical stirrer, purge nitrogen and distillation apparatus was charged with dimethyl-5-sodiosulfoisophthalate (42.6 g, 0.144 mol, available from Du Pont Chemicals) 400 molecular weight polyethylene glycol ( 115.1 g, 0.288 mol, available from Union Carbide Chemical and Plastics Co., Inc.) and 425 molecular weight polypropylene glycol (122.3 g, 0.288 mol, available from Arco Chemical Co.) and xylene (75 g). The reactor was slowly heated to 220 ° C above a period of 1 hour to remove the xylene. The zinc acetate (0.2 g) was then added to the contents of the flask and the temperature of the reaction mixture was maintained at 220 ° C for 4 hours with concomitant distillation of methanol from the reaction. The temperature was then reduced to 160 ° C and 0.2 torr of vacuum applied to the reaction mixture for 30 minutes. The contents of the flask were subsequently cooled to 120 ° C under nitrogen and drained to produce a clear, colorless, liquid polyol. The equivalent weight of the OH of this polyol was found to be 310 g / mol of OH (theoretical OH of 320). The equivalent weight of the theoretical sulfonate of the polyol mixture is 1882 g of polymer / mol of sulfonate.

Preparation of Sulfopolol B Sulfopolol B was substantially prepared according to the procedure described for the preparation of the Sulfopoliol A except that the loading of the reactant was dimethyl-5-sodiosulfoisophthalate (27.5 g, 0.09 mole), 600 mole-weight polyethylene glycol (222.6 g, 0.37 mole, available from Union Carbide Chemical and Plastics Co., Inc.) and xylene (75 gr). The OH equivalent weight of this polyol was 425 g / mol of OH (theoretical OH of 439) and the theoretical equivalent weight of the sulfonate was 2632 g of polymer / mol of sulfonate.

Preparation of Sulfopoliol C A sulfopolyester polyol was generally prepared by following the procedure in Example 1 of U.S. Pat. No. 4,746,717. The reactor was equipped with a mechanical stirrer, a nitrogen purge system, distillation head and receiving flask, and instrument with its vacuum distillation accessories and the receiving flask was cooled by the use of a dry ice / acetone bath . The reactor was charged with dimethyl-5-sodiosulfoisophthalate (296 g, 1 mol) and polycaprolactonediol (1060 g, 2 mol), PCP-0200 available from Union Carbide Chemical and Plastics Co., Inc.). The contents of the flask were heated to 230 ° C under stirring and nitrogen purge and tetraisopropyl titanate (0.13 g) added as an esterification catalyst. The reaction mixture was maintained at 230 ° C for a period of 4 hours, during which 50 to 75 percent of the condensed methanol was removed. The pressure in the reactor was reduced to 20 torr and maintained for 15 minutes followed by the filling of the system with nitrogen. A low viscosity product was removed from the bottle while it was heated. This polyol had a hydroxyl equivalent weight of 840 mol of OH per gram of polymer and a theoretical equivalent weight of the sulfonate of 1292 g of polymer / mol of sulfonate.

Example 1 Synthesis of the terminated isocyanate prepolymer sulfo A reactor equipped with a mechanical stirrer and nitrogen purge was charged with 4,4'-diisocyanatodiphenylmethane (183.9 g, 0.736 moles, available from Bayer Corp., Pittsburgh, PA) and sulfonic acid ethane (0.25 g, available from Aldrich Chemical Company; Milwaukee, Wl) and the mixture heated to 70 ° C. The polyol A (216.1 g) was slowly added to the reaction mixture over a period of 30 minutes with stirring (NCO: OH final remaining deformation charge ratio of 2.1: 1). The mixture was heated for an additional 5 hours and drained under nitrogen purge to produce a clear, viscous liquid.

Synthesis of Sulfopoliurea Dispersion Deionized water (1000 gr) was charged to a HC-8000 Microfluidizer (Microfluidics, Inc., Newton, MA) equipped to recirculate through a heat exchanger at a temperature of 68 ° C. The finished isocyanate prepolymer (175 g) described above was preheated to 85 ° C and then injected into a microfluidizer operating at a pressure of 50 MPa for a period of 20 minutes producing a stable, bluish translucent dispersion with 18% solids and pH 7. The average particle size was found to be approximately 40 nm by light laser scanning as described above. The theoretical equivalent weight of the dispersed polymer sulfonate was 3387 g of polymer / mol of sulfonate and the hard segment content was 45%. Approximately 50 g of the dispersion prepared in this way was injected into a rapidly rotating Teflon drum maintained at 55 ° C for 12 hours to produce a clear 19-mil thick sulfopolyurea film which had a Tg of 65.1 ° C by AMD. The film was not dispersible in boiling water, had a permanent deformation stress of 49.4 MPa at a force of 0.05, a breaking stress of 35.7 MPa, rupture elongation of 93% and a Young's coefficient of 1.486 MPa (Figure 1, Curve A) determined by tests according to the procedure for the stress analysis described above. The AGT analysis as described above indicated 20.0% residue after heating the film at 550 ° C under nitrogen. The AMD data for E 'as a function of film temperature is shown in Figure 2, Curve A.

Example 2 Synthesis of Finished Isocyanate Sulfoprepolymer A reactor equipped with a mechanical stirrer and nitrogen purge was charged with 4,4'-diisocyanatodiphenylmethane (126.6 g, 0.506 mol) and ethane sulphonic acid (0.13 g) and heated to 70 ° C. C. Polyol A (113.2 g) and 1000 molecular weight polypropylene glycol (60.3 g, 0.06 mol, Arco Chemical Co.) were premixed and then slowly added to the reaction mixture for a period of 30 minutes with stirring (NCO: OH Final residual deformation load ratio of 2.1: 1). The mixture was heated for an additional 5 hours at 70 ° C and drained under a nitrogen purge, producing a clear, viscous liquid.

Sulfopolyurea Dispersion Synthesis The finished isocyanate sulfoprepolymer was preheated to 85 ° C and dispersed in deionized water (lOOOgr) according to the procedure described in Example 1 to produce a stable, bluish-white dispersion containing 17% solids, which had a theoretical equivalent weight of sulfonate of 4864 g of polymer / mol of sulfonate, a hard segment content of 41% and an average particle size of 106 nm with a Polydispersity index of 0.17. A fixed film free of sulfopolyurea had a Tg of 37.8 ° C per AMD, was not dispersible in boiling water, had a breaking stress of .48.6. MPa, elongation at break of 263%, no effort of permanent deformation and Young's coefficient of 476 MPa (Figure 1, Curve B). The TFA analysis as described above indicated 12.1% residue after heating the film at 550 ° C under nitrogen. The AMD data for E 'as a function of film temperature is shown in Figure 2, Curve B.

EXAMPLE 3 Synthesis of Terminated Isocyanate Sulfoprepolymer The procedure of Example 3 was repeated by the use of a polyol B (205.1 g), molecular weight of 1000 polypropylene glycol (79.5 g, 0.08 mol), Isonate 2143L (196.4 gr) and ethane sulphonic acid (0.1 gr) (NCO: OH final remaining deformation load ratio of 2.1: 1).

Synthesis of the Sulfopolyurea Dispersion The finished isocyanate sulfoprepolymer (175 g) was dispersed in deionized water (800 g) according to the procedure of Example 1 to produce a stable white dispersion which contained 18% solids, had a theoretical equivalent weight of sulfonate of 5850 gr of polymer / mol of sulfonate, a hard segment content of 40% and an average particle size of 91 nm with a Polydispersity index of 0.14. A fixed film free of this sulfopolyurea produced as described above had a Tg of 18.9 ° C because AMD was not dispersible in boiling water, had a breaking stress of 29.8 MPa, elongation at break of 412%, no stress strain and Young's coefficient of 13.0 MPa (Figure 1, Curve C). The TFA analysis as described above indicated 27.1% residue after heating the film at 550 ° C under nitrogen. The AMD data for E 'as a function of film temperature are shown in Figure 2, Curve C.

Example 4 The dispersions of Example 2 and Example 3 were mixed together by stirring to produce a stable dispersion comprising 50% by weight of each polymer. A fixed film free of this sulfopolyurea mixture produced as described above had a Tg of 29.0 ° C per AMD, was not dispersible in boiling water, had a breaking stress of 33.9 MPa, elongation of break of 363%, no effort of permanent deformation and Young's coefficient of 152 MPa (Figure 1, Curve D). The AGT analysis described above indicated 16.1% residue after heating the film at 550 ° C under nitrogen. The AMD data for E 'as a function of film temperature are shown in Figure 2, Curve D.

Comparative Examples: Comparative analyzes (stress analysis, AMD and AGT) were conducted by the use of commercially available floating polyurethanes listed below as Comparative Examples Cl through C5. The films of the samples were prepared as described above by Examples 1-4.

Stress Analysis The stress analysis data for Comparative Examples C1-C5 is presented in Figure 3. The strain strain, force and breaking force exhibited by the materials of Comparative Examples C1-C5 are very similar to those exhibited by the films of the present invention as described in Examples 1-4.

AMD Analysis Dynamic mechanical analyzes were conducted in comparative examples C1-C5 using the procedures described above by examples 1-4 (see Figures 4, 5 and 6).

AMD curve data for examples 1-4 and C1-C5 (Figures 2, 4, 5 and 6) were analyzed to provide a measure of the retention of the storage coefficient as a function of the temperature increase. The percentage change in E 'in the temperature range from 100 ° C to 135 ° C and percentage change in E' in the temperature range from 100 ° C to 200 ° C is shown below for all samples.

Table 1? E 'as a High Temperature Function (a) Not measurable due to the soft and concomitant drop in coefficients below the detection limits of the instrument AGT Analysis The thermal gravimetric analyzes were conducted on film samples as described above (see Table 1). After a prolonged heating to 550 ° C of Examples 1-4, prepared according to the teachings of the present invention, produced hard, breakable residues with final weights in excess of 12% by weight and in some cases in excess of 25% by weight. % by weight relative to the original sample not heated. Comparative examples C1-C5 all showed residual levels below 3% by weight.

Table 2 Residual Weights of the AGT Experiment Example 5 A reactor equipped with nitrogen purge, mechanical stirrer and distillation apparatus was charged with Sulfopolyol C (91.2 g) and methyl ethyl ketone (MEK, 300 g). The contents of the reactor were dried by heating the reactor to 120 ° C and distilling approximately 50 g of MEK, the mixture subsequently cooled to 70 ° C and ethane sulfonic acid (0.1 g) was added to the reactor followed by Isonate 2143L (34.9 gr, 0.24 moles of NCO, NCO: OH of 2.25: 1). The reaction mixture was then stirred under dry nitrogen at 70 ° C for 6 hours. A reactor equipped with an additional tube that equalizes the pressure and nitrogen purge, mechanical stirrer and distillation apparatus was charged with deionized water (700 g) and the water was heated to boiling. The finished isocyanate prepolymer described above was added to the water for a period of 1 hour under a heavy purge nitrogen and high stirring speed while MEK was continuously removed. The pressure in the bottle was then gradually reduced under suction pressure to remove the residual MEK and a portion of water (approximately 225 g). The resulting dispersion (21% solids) was golden and transparent in appearance. A fixed 19 mil thick film of this sulfopolyurea produced as described in Example 1 had a Tg of 10.4 ° C, was not dispersible in the boiling water, had a tensile force of 53.5 MPa, elongation at break of 407 %, a coefficient at 100% elongation of 15.0 MPa.

Example 6 A terminated isocyanate prepolymer was prepared according to the procedure of Example 5 by the use of a filler of sulfopolyol C (159.0 g, 0.19 mol OH), neopentyl glycol (9.84 g, 0.19 mol OH, available from Aldrich Chemical Co.) and Isonate 2143L (108.27 gr, 0.76 moles of NCO, NCO: OH of 2: 1); the sulfopolyol and neopentyl glycol reached the azeotrope in dry form as a mixture. The prepolymer was heated to 70 ° C and dispersed in distilled water (700 g) according to the procedure of Example 6. The resulting dispersion was obtained in 27% solids in water and was white and translucent in appearance. A film of this polymer prepared as described in Example 1 was resistant and transparent, and was insoluble in boiling water. The polymer had a Tg (by DSC) of 46.7 ° C, a theoretical equivalent of sulfonate of 2928 g of polymer per mol of sulfonate, a tensile force of 57.5 MPa, elongation at break of 253% and coefficient at 100% elongation of 39.0 MPa.

Example 7 Synthesis of Terminated Isocyanate Sulfoprepolymer The procedure of Example 2 was repeated using a charge of Sulfopolyol B (62.2 g), Isonate 2143L (62.8 g) and ethane sulphonic acid (0.1 g), to produce a viscous liquid prepolymer with an NCO: OH final charge ratio of final remaining strain of 3: 1.

Synthesis of the Sulfopolyurea Dispersion The isocyanate sulfoprepolymer thus prepared (125 g) was dispersed in water (700 g) according to the procedure of Example 2 to produce a stable appearance, whitish-blue, 18% dispersion solids . The described emptying procedures were used to prepare a fixed film free of this dispersion. The film had a Tg of 31.2 ° C by the CED, was not dispersible in boiling water, had a breaking stress of 49.1 MPa, elongation at break of 201%, stress of permanent deformation of 26.7 MPa and Young's coefficient of 713 MPa .

Example 8 A finished isocyanate prepolymer was prepared according to the procedure of Example 6 using a charge of polyol C (200.0 g, 0.24 mol of OH) and Isonate 2143L (68.0 g, 0.48 mol of NCO; NCO: OH of 2: 1). The prepolymer in methyl ethyl ketone in dry form reached its azeotrope, heated to 70 ° C and dispersed in distilled water (2500 g) according to the procedure of Example 5. The resulting dispersion was obtained in 10% solids in water and was transparent and golden color in appearance. A film of this polymer prepared as described in Example 1 was resistant and transparent, and was insoluble in boiling water. The polymer had a Tg (by the CED) of 1.8 ° C, a theoretical equivalent weight of the sulfonate of 2200 g of polymer per mole of sulfonate, a tensile strength of 43.8 MPa and elongation at break of 462%.

Example 9 A terminated isocyanate prepolymer was prepared according to the procedure of Example 5, which uses a charge of methyl ethyl ketone (800 g), 4,4'-diisocyanatodiphenylmethane (423.1 g, 1.69 mol) and polyol A (467.9 gr, 1.54 mol of OH, NCO: OH of residual final deformation load ratio of 2.2: 1). The prepolymer in methyl ethyl ketone was then heated to 70 ° C and dispersed in distilled water (2500 g) according to the procedure of Example 5. The resulting stable dispersion was obtained at 28% solids in water and was translucent bluish in water. appearance and pH. A film of this polymer prepared as described in Example 1 was resistant and transparent and was insoluble in boiling water. The polymer had a theoretical equivalent sulfonate weight of 3416 g of polymer per mole of sulfonate, a permanent strain stress of 57.9 MPa at 0.053 force, a breaking stress of 47.3 MPa, Young's coefficient of 1679 MPa and elongation of rupture of 162%. A sample of this film was annealed under nitrogen for 10 hours at 110 ° C. Samples of the original and tempered films were evaluated by a wide-angle X-ray disperser which showed an increase in order to prefer annealing (Figure 7). The Differential Scanning Calorimeter of the annealed sample showed a Tm of 342 ° C. The increase in annealing preference is evident from the appearance of the discrete dispersion intensity in the DXAA spectrum of the annealed film. This increase is perhaps associated with the formation of the crystalline domains, an increase in the size of the existing crystalline domains or order of increase in the existing crystalline domains.

Example 10 A thickness of 15 mm thickness of low density non-woven fabric weighing 80 gr / m2 was formed from 13 denier of nylon-6,6 fibers in a weaving machine available under the trade designation "Rando Webber "by Rando Machine Corporation, Macedon, NY The resulting low density fabric was wound coated with a pre-bond resin to provide an aggregate dry weight of 45 g / m2 using a coating solution consisting of 39.3% xylol, 16.1% solution of 35 parts of methylene dianiline (MDA) and 65 parts of 2-ethoxyethanol acetate, 44.6% of blocked ketoxime poly-1,4-butylene glycol diisocyanate having a molecular weight of almost 1500 (sold under the trade designation "Adiprene BL-16" by Uniroyal Chemicals Division of Compton &Knowles Corporation) and a hint of a silicone defoamer ("Q2", available from Dow Corning Corporation, Midland, MI). The pre-bond resin was vulcanized to a non-stick condition by the passage of the coated fabric through a convection oven maintained at 150 ° C for a residence time of almost 7 minutes. The resulting prewoven nonwoven fabric was about 10 mm thick and weighed about 126 g / m2. An adhesive binder consisting of 39.8% of diethylene glycol monoethyl ether, 59% of a catalyzed phenol-formaldehyde base resin having 70% non-volatiles, 1.2% of an aqueous sodium hydroxide solution (1: lNaOH: water) and 0.06% of a fluorochemical surfactant (available from the Minnesota Mining and Manufacturing Company, St. Paul, MN under the trade designation "FC 170") was rolled coated at the rate of 54 g / m2 dry in the pre-linked fabric described above. The wet adhesive coated fabric was uniformly coated throughout with 100 sands (average particle size of 140 microns) of aluminum oxide abrasive granules at the rate of 950 g / m2 by the dispersion of the abrasive granules in an air stream. which simultaneously went on the larger surfaces of the fabric. The segments of the abrasive coated fabric were then rolled up coated with the size binder resin using size resins identified as "A" or "B" to produce adhesive fabrics arranged according to size such that the dry additive of the size adhesive is 205 grams / m2 in the case of resin "A" and 100 g / m2 in the case of resin "B". Each fabric arranged according to size was passed through a convection oven maintained at 70 ° C for a residence time of 2 to 4 minutes to partially dry and remove all but 20% of the volatiles.

Resin of Size "A" Resin of size "A" consisted of 10.52 Ib of the composition of Example 8 prepared at 30% solids in water that was modified by the addition of 0.3 Ib of zinc stearate emulsion lubricant "AQUAZINC (Witco Corporation, Organics Division, New York, NY), 0.3 Ib thick powder "LAPONITE XLG" (Southern Clay Products Inc., TX).

Resin of Size "B" The resin of size "B" consisted of resin of size "A", adjusted to 25% solids, by the addition of 3% of aqueous gel "METHOCEL F4M" (960 grams, 3% solids, available from Dow Chemical Company, Midland, MI).

Eight 305 mm square segments of pieces of resin-coated fabric of a partially dry "A" size were assembled and the assembly took place in a pressure table heated to 135 ° C, compressed to 25.4 mm and then maintained for 40 minutes to produce an abrasive slab Each slab was removed from the press and further cured in an air convection oven for 120 minutes at 135 ° C. After allowing the cured slabs to cool to room temperature, the wheels having a diameter of 254 mm and a hole in the center of 3.18 mm were punched out of the thickness of the slab of 25.4 mm. The density of the wheels was 8.5 grams per cubic inch. The wheel was evaluated for its abrasive performance by rotation at a surface velocity of 5650 feet per minute while driving a stainless steel coupon punched against it such that there was a pressure of 10 psi across the contact separation surface. The test was interrupted every 2 minutes to weigh the test coupon and the wheel. The stainless steel coupon was observed to lose 4.7 grams per 2 minutes while the wheel lost 14.2 grams for the same period.

Thirteen 229 mm x 279 mm rectangular segments of pieces of partially dried "B" size resin-coated fabric were assembled and the assembly took place in a pressure table heated to 135 ° C, compressed to 25.4 mm and then maintained at 40 ° C. minutes to produce an abrasive slab. The slab was removed from the press and further cured in an air convection oven for 120 minutes at 135 ° C. After allowing the cured slab to cool to room temperature, a wheel having a diameter of 203 mm and 51 mm the center hole was punched out of the slab thickness of 25.4 mm. The density of the wheel was 12.19 grams per cubic inch. The wheel was evaluated for its abrasive performance by rotation at 2000 rpm while pushing a perforated stainless steel coupon against it such that there was a pressure of 7 psi across the contact separation surface. The test was interrupted every minute to weigh the test coupon and the wheel. The stainless steel coupon was observed to lose 0.8 to 1 gram per minute while the wheel lost 0.6 to 2 grams for the same period.

It is noted that in relation to this date, the best method known to the applicant to carry out the aforementioned invention, is the conventional one for the manufacture of the objects or products to which it refers.

Claims (1)

1. CLAIMS Having described the invention as above, the content of the following claims is claimed as property: A stable aqueous colloidal dispersion of a sulfopolyurea composition characterized in that it comprises a plurality of units (a) and (b) having the formula: (b) interconnected by units (c) that have the formula (c) where; each Ri is independently a divalent aliphatic group having an average molecular weight of 200 to 600 comprising ether or ester functional groups selected from the group consisting of -CH2-CH2- (OCH2-CH2-) n-, -C (CH3 ) H-CH2- (OC (CH3) H-CH2) n-, and groups -O- (CH2) m-C0- [-0- (CH2) m-C0-] n-; each R2 is independently a divalent straight or branched chain alkylene group or cycloaliphatic group having an average of 2 to 15 carbon atoms or a divalent aliphatic group having an average molecular weight of 200 to 600 comprising ether or ester functional groups selected from the group consisting of -CH2-CH2- (OCH2-CH2-) n-, -C (CH3) H-CH2- (OC (CH3) H-CH2-) n-, -CH2-CH2-CH2-CH2 - (OCH2CH2-CH2-CH2) n- / and groups -O- (CH2) m -CO- [-0- (CH2) m -CO-] n-; R3 is selected from the group consisting of a methylene-4, '-diphenyl group, a 1,4-phenyl group, a group 4,4'-biphenyl, a 1,6-naphthyl group, a N, N-di ((p-methylphenyl) phenyl) -carbodiimide group and mixtures thereof; m is an integer from almost 2-5; n is an integer from almost 2-15; x is 1; and is an integer from 0-4; z is an integer from 0-6; and M is a cation of sodium, lithium or potassium. wherein said sulfopolyurea has an equivalent sulfonate weight from almost 1,000 to almost 8,500. The aqueous colloidal dispersion of claim 1 characterized in that the sulfopolyurea composition has an equivalent sulfonate weight from about 2,500 to almost 7,000. The aqueous colloidal dispersion of claim 1 characterized in that it comprises colloidal particles having an average particle size of less than about 1 miera. The colloidal dispersion of claim 1 characterized in that the sulfopolyurea composition comprises hard domains and soft domains and where said hard domains are associated through the hydrogen bond. A thermally formed stable sulfopolyurea film of the colloidal dispersion of claim 1 characterized in that the film is separate phase into hard and soft domains and is not redispersible in water. The sulfopolyurea film of claim 5 characterized in that the film is thermally stable at a temperature of at least 200 ° C. The sulfopolyurea film of claim 5 characterized in that the film exhibits a resistance to flow at a temperature of at least 200 ° C. The sulfopolyurea film of claim 5 characterized in that the AMD analysis of the film according to Test Method A shows less than almost 100% loss in the storage coefficient between 100-135 ° C relative to the storage coefficient of the film at: 100 ° C. A stable aqueous colloidal dispersion characterized in that it is the reaction product of: (a) a finished isocyanate sulfopolyurethane having the formula (b) a finished isocyanate polyurethane having the formula (c) a polyisocyanate having the formula OCN-R3 + NCO wherein each Ri is independently a divalent aliphatic group having an average molecular weight of 200 to 600 comprising ether or ester functional groups selected from the group consisting of -CH2-CH2- (OCH2-CH2-) n-, -C ( CH3) H-CH2- (OC (CH3) H-CH2) n-, and groups -O- (CH2) m -CO- [-0- (CH2) m -CO-] n ~; each R2 is independently a divalent straight or branched chain alkylene group or cycloaliphatic group having an average of 2 to 15 carbon atoms or a divalent interconnected by units (c) having the formula where; each Ri is independently a divalent aliphatic group having an average molecular weight of 200 to 600 comprising ether or ester functional groups selected from the group consisting of -CH2-CH2- (OCH2-CH2-) n-, -C (CH3 ) H-CH2- (OC (CH3) H-CH2) n-, and groups -O- (CH2) m-C0- [-0- (CH2) m-CO-] n-; each R2 is independently a divalent straight or branched chain alkylene group or cycloaliphatic group having an average of 2 to 15 carbon atoms or a divalent aliphatic group having an average molecular weight of 200 to 600 comprising ether or ester functional groups selected from the group consisting of -CH2-CH2- (OCH2-CH2-) n-, -C (CH3) H-CH2- (OC (CH3) H-CH2-) n-, -CH2-CH2-CH2-CH2 - (OCH2CH2-CH2-CH2) n-, and groups -O- (CH2) m -CO- [-0- (CH2) m -CO-] n -i R2 is selected from the group consisting of a methylene group -4,4'-diphenyl, a 1,4-phenyl group, a 4,4'-biphenyl group, a 1,6-naphthyl group, a N, N-di ((p-methylphenyl) phenyl) -carbodiimide group and mixtures thereof; m is an integer from almost 2-5; n is an integer from almost 2-15; x is 1; and is an integer from 0-4; z is an integer from 0-6; and M is a cation of sodium, lithium or potassium; where sulfopolyurea has an equivalent weight of sulfonate from almost 1,000 to almost 8,500.