CN1451028A - Thermoplastic superabsorbent polymer blend compositions and their preparation - Google Patents

Abstract

Disclosed are extrudable thermoplastic superabsorbent polymer blend compositions that are particularly suitable for preparing extruded or molded articles such as single-layer films, multilayer films, nonwoven webs, sheets, foams, profiles, multilayer laminates, fibers, tubing, rods, or tubes, which themselves are particularly suitable for preparing powders and communication cables or disposable absorbent articles such as diapers, sanitary napkins, hemostatic pads, incontinence products, hospital gowns, or mattresses.

Description

Thermoplastic superabsorbent polymer blend composition and its preparation

The present invention relates to thermoplastic polymer blend compositions comprising superabsorbent polymers and methods for their preparation.

Superabsorbent polymers are well known materials used in a variety of applications ranging from personal care articles such as diapers to water barrier applications in the construction industry to water blockers in communication cables to liquid absorbents in food packaging systems. These polymers are known to absorb several times their weight in, for example, moisture, water, saline solutions, urine, blood, and serous fluids.

One challenge of using superabsorbent polymer particles in absorbent devices is the capacity or fixation of the superabsorbent polymer particles. Depending on the particular absorbent article, different approaches have been taken for containing or immobilizing superabsorbent polymers. For example, disposable absorbent products such as diapers, sanitary napkins, tampons, and incontinence products typically include pads or batting surrounded by a liner, wherein the batting typically includes superabsorbent polymer in particulate form, see U.S. Patent No. 3,670,731. However, loss of particles and/or redistribution of particles within the device, sometimes referred to as shakeout, often occurs.

Attempts to reduce shakeout are taught in U.S. Patent No. 4,806,598 which discloses a nonwoven web made from a thermoplastic polymer composition comprising a polyoxyethylene superabsorbent and a thermoplastic polymer, the polyoxyethylene superabsorbent The agent includes a soft segment bonded to a hard segment by reaction with a third segment. However, there is minor interaction between polyoxyethylene superabsorbent and thermoplastic polymer and the blend is not stable with respect to phase separation. Furthermore, webs made from thermoplastic polymer compositions do not exhibit sufficient wet strength and attempts to improve web wet strength by substituting low density polyethylene for some thermoplastic polymer compositions have resulted in a substantial reduction in the water absorbency of the web.

In power and communication cable applications, different approaches have been tried to bond or immobilize superabsorbent polymers as water blocking agents. See, for example, U.S. Patent No. 4,966,809 which discloses a water blocking tape prepared by mixing a superabsorbent polymer and a polymeric binder and then spreading the mixture on a nonwoven fabric; see U.S. Patent No. 5,461,195, This document discloses a superabsorbent polymer mixed with a thixotropic agent to form a gel, which is used to fill the space between the wires of the cable; or see U.S. Patent No. 5,925,461 which discloses the use of a superabsorbent Hot melt adhesive coated or impregnated reinforcement elements or buffer tubes.

Blends of superabsorbent polymers and adhesives are characterized by a number of disadvantages and/or limitations, such as manufacturing and operating temperature limitations, lack of adhesion of the substrate to which the blend is applied, and when the article is pulled in the direction of stretching delamination, which causes wear when the article is manufactured. Furthermore, tapes add an additional component to the cable construction, causing a rather undesirable increase in their cost and diameter. Cables using filler gels are characterized by a number of disadvantages and/or limitations, such as manufacturing and operating temperature limitations, void formation leading to water migration pathways, and difficulty in meeting industry standards.

Other methods for bonding superabsorbent polymers are known. See, for example, U.S. Patent No. 5,516,585 which discloses a method of coating discontinuous fibers with a thermosetting binder material binding superabsorbent particles, wherein the discontinuous fibers are formed into a web. In the method described in U.S. Patent No. 4,392,908, superabsorbent polymer particles are coated with a thermoplastic resin and fixed to a water-absorbing substrate by applying heat to soften the thermoplastic coating of the particles and compressing the particles and substrate. material to cause the particles to adhere to the substrate. These methods are expensive, require special equipment and/or many steps and have limited commercial applicability.

Furthermore, films and laminates of superabsorbent polymers have been prepared from solutions of superabsorbent polymers, followed by heating and/or removal of the solvent. For examples of crosslinked superabsorbent polymer films and laminates, see U.S. Patent Nos. 3,926,891, 4,076,673 and 4,117,184. For examples of non-crosslinked superabsorbent polymer films, see U.S. Patent Nos. 3,935,099, 3,997,484, and 4,090,013. U.S. Patent No. 3.699.103 describes the preparation of thin foamed polyurethane thermoset sheets comprising superabsorbent polymer particles. Unfortunately, these methods of forming films, laminates and sheets are not suitable for large-scale commercial use.

There is a need for superabsorbent polymer compositions having improved containment of superabsorbent polymer particles for use in absorbent articles such as personal care articles and cable wrapping assemblies while maintaining good absorbent properties. Furthermore, there is a need for such superabsorbent polymer compositions to be easily and conveniently molded into various useful forms, especially on an industrial scale.

The present invention is such a composition. It is a thermoplastic superabsorbent polymer blend composition comprising: (a) superabsorbent polymer (b) thermoplastic resin and optionally (c) surfactant, wherein components (a) and ( b) Interact ionically or covalently with each other and eg the blend composition can be formed by extrusion into films, sheets, laminates, foams, profiles and injection molded articles.

In another aspect, the present invention is a method of making the extrudable thermoplastic superabsorbent polymer blend composition described above.

In another aspect, the present invention is directed to a method of extruding or molding the extrudable thermoplastic superabsorbent polymer blend composition described above.

In yet another aspect, the present invention is directed to extruded articles (eg, films, sheets, foams, and laminates) or molded articles of the extrudable thermoplastic superabsorbent polymer blend compositions described above.

In another aspect, the present invention is directed to an article comprising an extruded or molded article of the extrudable thermoplastic superabsorbent polymer blend composition described above.

The blend compositions and extruded or molded articles of the present invention are useful in a wide variety of applications known in the art, for example, cable wrapping assemblies and components and constructions of various disposable absorbent articles such as sanitary napkins, disposable Diapers, hospital gowns or mattresses.

The superabsorbent water-swellable or lightly cross-linked hydrophilic polymer suitable for use in the present invention can be any known hydrophilic polymer capable of absorbing large quantities of liquid. These polymers are well known in the art and are widely available commercially.

Examples of some suitable polymers and methods of making superabsorbent polymers, including gel polymerization methods, are disclosed in the following documents: U.S. Patent Nos. , 4,076,663, 4,190,562, 4,286,082, 4,857,610, 4,958,518 and 5,145,906. Also, see Buchholz, F.L. and Graham, A.T., "Modern Superabsorbent Polymer Technology", John Wiley & Sons (1998) and Lisa Brannon-Peppas and Roland S. Harland, "Absorbent Polymer Technology" Elsevier (1990).

Preferred superabsorbent polymers are prepared from water-soluble α,β-ethylenically unsaturated monomers such as monocarboxylic acids, vinyl polycarboxylic acids, acrylamides and their derivatives. More preferred superabsorbent polymers are cellulose or starch graft-copolymerized such as starch-g-poly(acrylonitrile) and starch-g-poly(acrylic acid), polyacrylamide, polyvinyl alcohol, poly(acrylic acid), High molecular weight polymers, preferably cross-linked polymers of ethylene oxide (EO) and propylene oxide (PO), monomers containing sulfonic acid groups, such as vinylsulfonic acid, sodium sulfoethyl methacrylate, 2- Copolymer of acrylamido-2-methylpropanesulfonic acid or sodium salt (AMPS).

Most preferred superabsorbent polymers are crosslinked, partially neutralized and/or surface treated. Preferably, the level of crosslinking is selected to obtain the desired swelling properties for a particular application. Generally, the degree of neutralization is 30-100%, more preferably 50-80%. Neutralization with an alkaline material comprising a Group I metal ion, such as sodium, is preferred. A preferred surface treatment consists of post-polymerization for effecting surface crosslinking of the superabsorbent polymer.

The amount of superabsorbent polymer included in the thermoplastic superabsorbent polymer blend compositions of the present invention depends on, for example, the type of superabsorbent polymer used, the type of thermoplastic resin used, the desired extrusion or molding The end use of the product, the extruded or molded product, the changes required in the end use to block, absorb or stop the migration of water and/or other fluids.

The superabsorbent polymer is present in an amount equal to or greater than about 1 part by weight, preferably equal to or greater than 5 parts by weight, more preferably equal to or greater than 10 parts by weight, based on the weight of the thermoplastic superabsorbent polymer blend composition, and even more It is preferably equal to or greater than 15 parts by weight and most preferably equal to or greater than 20 parts by weight. The superabsorbent polymer is present in an amount equal to or less than about 70 parts by weight, preferably equal to or less than 65 parts by weight, more preferably equal to or less than 60 parts by weight, and even more, based on the weight of the thermoplastic superabsorbent polymer blend composition. It is preferably equal to or less than 55 parts by weight and most preferably equal to or less than 50 parts by weight.

In addition to the superabsorbent polymer, the blend compositions of the present invention comprise at least one thermoplastic resin that interacts (ie, ionically, covalently) with the superabsorbent polymer. For example, in thermoplastic resins containing acyl groups, the acyl groups can undergo nucleophilic attack, resulting in a substitution reaction in which leaving groups, such as -OH, -Cl, -OOCR, _-NH2 or -OR, are replaced by those present in the superabsorbent polymer another basic group instead. Another example is a thermoplastic resin that contains a carbonyl group that can undergo nucleophilic attack to gain a proton and add another basic group present in superabsorbent polymers. Under these conditions, the reaction product of the thermoplastic resin and superabsorbent polymer can form a homogeneous and/or cocontinuous non-separated polymer blend.

Preferred thermoplastic resins contain functional groups such as acyl or carbonyl groups (e.g., α,β-unsaturated carbonyl compounds, hydroxy acids, dicarboxylic acids, keto acids, anhydrides, carboxylic acids, aldehydes, ketones, acid halides, esters, amides, etc.), Sulfonyl groups, sulfonyl halides, ethers, phenols, aryl halides, epoxides, carbohydrates, alcohols, azides, and amines.

Preferred thermoplastic resins are acrylic polymers, most preferably polyacrylic acid (PAA), ethylene and acrylic acid copolymer (EAA), ethylene, tert-butyl acrylate and acrylic acid terpolymer (EtBAAA), ethylene and methacrylic acid copolymer (EMAA), ionomers of copolymers of ethylene and methacrylic acid especially sodium and zinc ionomers, terpolymers of ethylene, vinyl acetate and carbon monoxide (EVACO), copolymers of ethylene and carbon monoxide ( ECO), terpolymer of ethylene, acrylic acid and carbon monoxide (EAACO), terpolymer of ethylene, t-butyl acrylate and carbon monoxide (EnBACO) or blends thereof.

The most preferred thermoplastic resin is 1) EAA copolymer, wherein the EAA copolymer can be a blend of two or more EAA copolymers, preferably composed of 10-20 wt% acrylic acid, based on the weight of the copolymer, and at 190°C and 2. Melt flow rate (MFR) of 100-200 grams per 10 minutes (g/10min.) at an applied load of 16 kg, 2) EMAA ionomer, preferably zinc ionomer, 3) EVACO , preferably having a carbon monoxide content of at least 9%, based on the weight of the terpolymer or 4) blends thereof.

The thermoplastic resin is present in an amount equal to or greater than about 30 parts by weight, preferably equal to or greater than 35 parts by weight, more preferably equal to or greater than 40 parts by weight, and even more preferably equal to or greater than the weight of the thermoplastic superabsorbent polymer blend composition. Greater than 45 parts by weight and most preferably equal to or greater than 50 parts by weight. The thermoplastic resin is present in an amount equal to or less than about 99 parts by weight, preferably equal to or less than 95 parts by weight, more preferably equal to or less than 90 parts by weight, and even more preferably equal to or less than 90 parts by weight based on the weight of the thermoplastic superabsorbent polymer blend composition. Less than 85 parts by weight and most preferably equal to or less than 80 parts by weight.

It should be apparent to those skilled in the art that the present invention contemplates blends comprising two or more superabsorbent polymers and/or blends of two or more thermoplastic resins (e.g., EAA/EVACO, EMAA/EAA , first EAA/second EAA).

Although the blend compositions of the present invention comprise at least one superabsorbent polymer, depending on the level and absorbency of the superabsorbent polymer in the blend composition and the availability of the superabsorbent polymer to the aqueous medium properties, such blend compositions may or may not be superabsorbent.

The blend composition of the present invention may further be blended with other thermoplastic resins as follows: preferably low density polyethylene (LDPE), linear low density polyethylene (LLDPE), very low density polyethylene (VLDPE), polypropylene (PP ), polystyrene (PS), ethylene and methyl acrylate copolymer (EMA), ethylene and ethyl acrylate copolymer (EEA), ethylene and n-butyl acrylate copolymer (EnBA), grafted with maleic anhydride Polyethylene (PE g-MAH), ethylene and vinyl acetate copolymer (EVA), ethylene and vinyl acetate copolymer grafted with maleic anhydride (EVA g-MAH), or combinations thereof.

The blend compositions of the present invention may further include additional additives commonly used in compositions of this type, such as lubricants, extenders, compatibilizers, plasticizers, low and high molecular weight waxes, surfactants, stabilizers, Pigments, carbon black, and fillers such as talc, titanium dioxide (TiO ₂ ), calcium carbonate (CaCO ₃ ), magnesium oxide (MgO), and mica.

The blend composition of the present invention may further be blended with a solvent to form a dispersion or paste. The type and amount of solvent can be readily selected by one skilled in the art according to the particular end use.

The phrase "extrudable thermoplastic superabsorbent polymer blend composition" as used herein means that (1) the blend composition can be melt processed in extrusion, injection molding and/or blow molding processes, (2) The extrudate is converted into pellets or directly extruded or molded by extrusion manufacturing techniques, (3) pellets have measurable melt flow rate, melt draw rate and sometimes called melt draw rate. Melt strength and (4) pellets can be re-extruded by extrusion manufacturing techniques. Preferably, the blend compositions of the present invention do not cause clogging, die face buildup, melt fracture, pinholes, tearing and/or poor extrudate properties (i.e., strand dripping, layered).

Melt indexers are used to measure melt flow rate (MFR), melt tension and draw down rate. MFR is measured by ASTM D1238, and operating conditions (ie, temperature and applied load) are dependent on the thermoplastic resin used. Melt tension is measured from a load cell attached at the bottom of the melt indexer, which requires the extrudate to be pulled from the melt indexer die at some given speed measured in feet per minute (fpm) to the load on the take-up shaft. Shrinkage (fpm) is determined by how quickly the extrudate coming out of the melt indexer can be pulled before it breaks. The thermoplastic superabsorbent polymer blend composition has a melt shrinkage of 5-100 fpm and a melt tension of 0.1-10 when the MFR conditions are selected to obtain an MFR of 0.1-300 g/10 min.

The components of the extruded blend composition can be co-continuous phases or separate phases (one phase is continuous and one or more phases are dispersed therein), so long as the phase separation is critical to the melt processability of the blend composition or There were no significant deleterious effects on performance.

Preferred extrusion fabrication includes making meltblown or cast films; extrusion coatings; (co)extruded nonwoven webs, including spunbond nonwoven webs, meltblown nonwoven webs, or composites, sheets including combinations thereof , foams, profiles, multilayer laminates, fibers including monofilament fibers and bicomponent monofilament fibers, pipes, rods or tubes; blow molded articles; injection molded articles (including solid, coextruded, structural foam and gas assist in injection molding). Preferred nonwoven webs include spunbond nonwoven webs comprising one or more bicomponent fibers, meltblown nonwoven webs comprising one or more bicomponent fibers, and at least one layer comprising one or more A composite structure of a spunbond nonwoven web and at least one layer of one or more meltblown nonwoven webs, wherein one or more layers of the composite include bicomponent fibers.

The thermoplastic superabsorbent polymer blend compositions of the present invention can be extruded using chemical or physical blowing agents. In addition, thermoplastic superabsorbent polymers can be blended with other miscible or compatible thermoplastic polymers such as LDPE, LLDPE, VLDPE, PP, PE, EEA, EMA, ENBA, PE g-MAH, EVA, or EVA g-MAH. One skilled in the art can select the type and amount of blowing agent and other polymers for blending with the thermoplastic superabsorbent polymer for a particular end use to modify the desired thermoplastic superabsorbent polymer foam properties. Pore size, structure, porosity, microporous nature and absorption properties.

The blend composition used to prepare the foam may further include additional additives commonly used in this type of composition, such as lubricants, extenders, nucleating agents, compatibilizers, plasticizers, low and high molecular weight waxes, surface Activators, stabilizers, pigments, carbon black, and fillers such as talc, titanium dioxide (TiO ₂ ), calcium carbonate (CaCO ₃ ), magnesium oxide (MgO), and mica.

Additionally, extruded pellets or sheets can be compression molded, calendered, vacuum formed or thermoformed. Preparation of the thermoplastic superabsorbent polymer blend compositions of the present invention can be accomplished by any suitable mixing means known in the art. The components and any additional additives are blended in powder, particulate and/or pellet form in a tumbler or shaker, typically with sufficient agitation to obtain their thorough distribution. The polymers can be mixed at a temperature sufficient to heat soften and melt, for example, in an extruder, with or without vacuum, or other mixing equipment (e.g., Banbury mixer, roller compactor, Henschel mixer, ribbon blending machine), the dry blended formulations were subjected to shear stress. Furthermore, additional powder, particulate and/or liquid additives may be added to the composition during the mixing process. Such melt blended materials can be extruded to make finished articles (ie films, sheets, foams, profiles) or recovered in the form of pellets, powder or flakes, preferably pellets. The extrudate can be converted into pellets by any conventional means such as strand choppers or underwater die face cutters.

The extrudate from melt mixing can be cooled by any method known in the art, such as air cooling, gas cooling, belt cooling, and liquid cooling by passing through a liquid bath. Preferably a stainless steel band cooler is used, such as a cooler made by Sandvik Process Systems, Sweden or a Compact Conti cooler made by BBA AG, Switzerland, or an aqueous liquid bath, preferably one in which the pH is less than 1.0 or the water hardness is greater than 25 Frech Degree A liquid bath, more preferably an aqueous liquid bath having a specific gravity greater than 1.05 as measured with a desitometer. The aqueous bath preferably contains a saturated salt solution containing Group I _metal ions, preferably sodium, such as sodium chloride (NaCl), sodium sulfate ( _Na2SO4 ), and sodium bicarbonate ( _NaHCO3 ).

Furthermore, to minimize the effect of water on the superabsorbent compound, it has been found that maintaining the temperature of the liquid bath at less than 23°C and preferably less than 20°C effectively cools the pellets without very activating the superabsorbent polymer in the blend composition .

It has further been found that when using an underwater pelletizer, optimizing the length of the transfer pipe from the underwater pelletizer to the separation dryer minimizes activation of the superabsorbent polymer in the blend composition.

Blowing cool air in the pellet collection vessel, such as using a fluid bed cooler, to drive off residual moisture on the pellets further improves the drying process.

It has been found that using a process involving an underwater die face cutter, depending on the superabsorbent polymer, the concentration of the superabsorbent polymer in the blend composition and the base thermoplastic resin, a saturated _NaHCO3 solution with a specific gravity greater than 1.05 and less than A temperature of 20°C and blowing of cooling air in the pellet collection container resulted in a free-flowing plastic pellet form with a moisture content of 0.2-4 wt%, where the moisture weight percent is based on the weight of the blend composition.

The melt blended material (powder, flake or pellet) can be reextruded or molded to make a finished article. Dry blends of the blend compositions can also be directly injection molded or dosed into another melt manufacturing process without pre-melt mixing.

The extrudable thermoplastic superabsorbent polymer blend composition of the present invention is used in pellet, flake or powder form for use in cat litter, solidified gas/liquid, gelled ice, soil conditioner, blooming Containment, agricultural delivery systems, gelled biohazards, spill control, for the manufacture of articles such as foams such as closed, semi-porous or microporous or open-celled, bi-component fibers and waterproof or water-blocking coating systems , Thick films or sheets for the following applications: disposable absorbent articles such as sanitary napkins, disposable diapers, hospital gowns, and mattresses, films for the following applications: moisture sensitive systems, absorbent structures, e.g. in packaging , transportation, and construction applications, diaper liners, meat trays, carpet liners or powder and communication cable water blocking tapes, films for laminated structures such as laminated foam structures, laminated nonwoven structures, Films of laminate material for cable shielding tapes in power cables or communication cables, such as fiber optic cables, copper pair cables, and coaxial cables, as disclosed in U.S. Patent Nos. 3,795,540, 4,449,014, 4,731,504 and 4,322,574.

It is further required that when the present invention is used in the construction of cables such as power cables and communication cables such as fiber optic cables, copper pair cables, and coaxial cables, the cables meet certain requirements for water penetration. More desirably, cable structures comprising extrudable thermoplastic superabsorbent polymer blend compositions prevent the penetration of water through the cable in the longitudinal direction, sometimes referred to as water blocking.

In order to illustrate the practice of the present invention, examples are described below.

Example Thermoplastic superabsorbent polymer zone blend composition

In Comparative Examples A-ZZ and Examples 1-13, different resins were melt blended in a Brabender Plasticoder with CABLOC ^™ 850-13, a sodium polyacrylate superabsorbent polymer that is a surface-crosslinked polymer. Associative, particle size distribution 1-300 micron, available from Stockhausen and powder supplied by Stewart Superabsorbents LLC. Unless otherwise stated, the ratio of superabsorbent polymer to thermoplastic resin was 40:60. Brabender Plasticoder conditions are: barrel temperature of 275-420°F depending on the resin used; mixing revolutions per minute (RPM) of 80; and mixing time of 1.5-2 minutes. Melt indexers are used to measure melt flow rate, melt tension and melt shrinkage of polymer blends.

Table 1 lists the compositions of Comparative Examples A-ZZ and Examples 1-13 and their properties. In Table 1, blend compositions that can be melt blended and extruded or molded into a sheet or article in some way, but do not meet the criteria described here as extrudable are termed non-extrudable.

Comparative Examples AB-AN and Examples 14-17 were compounded on a WP ZK30 twin-screw extruder. The SAP and polymer were fed separately into the feed section of the extruder, the extruder vent was open to the atmosphere and the extrudate was air cooled.

The compositions and extruder temperatures of Comparative Examples AB-AN and Examples 14-17 are shown in Table 2. The superabsorbent polymer is present in parts by weight, based on the weight of the thermoplastic superabsorbent polymer blend composition. In Table 2, compositions showing die face buildup and/or clogging are referred to as "not" extrudable.

Table 1 Example comparative example thermoplastic resin Thermoplastic superabsorbent polymer blend composition Grade supplier type MFR, condition MFR, g/10min Melt tension, unit Shrinkage rate fpm extrudable A ALATHON ^™ M6060 Equistar HDPE E. 5.20 no B LDPE 4005 Dow Chemical Co. LDPE E. 1.98 no C LDPE 4012 Dow Chemical Co. LDPE E. 4.5 0.8 <5 no D. LDPE 681 Dow Chemical Co. LDPE E. 0.72 no E. DOWLEX ^™ 2247A Dow Chemical Co. LLDPE E. 1.33 no f ASPUN ^™ 6821 Dow Chemical Co. LLDPE B 11.2 no G ATTANE ^™ 4201 Dow Chemical Co. VLDPE E. 0.417 no h ATTANE 4402 Dow Chemical Co. VLDPE E. 1.16 no I AFINITY ^™ 1880 Dow Chemical Co. INSrrE ^TM PE E. 0.594 no J ENGAGE ^™ 8200 DuPont Dow INSITE PE E. 3.26 no K PP 861 Montell PP L 7.6 no L PS 680 Dow Chemical Co. P.S. G 5.8 no m Chevron 2252-T Chevron EMA E. 0.42 no N Chevron 2255 Chevron EMA E. 1.30 no o Chevron 1802 Chevron EnBA E. 0.44 no P ENGAGE SM8400 Dow Chemical Co. PEg-MAH/high MAH E. 0.28 no Q FUSABOND ^™ 190D DuPont EVAg-MAH/High MAH E. 0.5 no R FUSABOND 197D DuPont EVAg-MAH/High MAH E. 0.1 no S FUSABOND 226D DuPont LLDPEg-MAH/High MAH E. 0.1 no T FUSABOND 274D DuPont EPDMg-MAH/medium MAH E. 0.1 no u FUSABOND 413D DuPont PEg-MAH MAH E. no V FUSABOND 423G DuPont EA terpolymer g-MAH/medium MAH E. 1.43 no W FUSABOND 353D DuPont PPg-MAH/very high MAH 160℃/0.353Kg 2.62 no x BYNEL ^™ E418 DuPont Maleic anhydride modified EVA E. 2.41 no

Table 1 continued Example comparative example thermoplastic resin Thermoplastic superabsorbent polymer blend composition Grade supplier type MFR, condition MFR, g/10min Melt tension, unit Shrinkage rate fpm extrudable Y CXA 3101 DuPont Acid/Acrylic Modified EVA E. 1.71 no Z CXA 4105 DuPont Anhydride modified LLDPE E. 0.84 no AAA BYNEL 50E561 DuPont Anhydride modified PP E. 0.90 no BB BYNEL 2174 DuPont Anhydride modified EA E. 0.75 no CC PLEXAR ^™ 3 Equistar Anhydride modified EVA E. 1.24 no DD PLEXAR 206 Equistar Anhydride modified HDPE E. 2.77 no EE STEREON ^™ 841A Firestone SBS block copolymer G 5.42 no FF VECTOR ^™ 421 Dexco Polymers SIS block copolymer G 11.58 no GG VECTOR 4461 Dexco Polymers SBS block copolymer G 9.72 no HH KRATON ^™ G1657 Shell SEBS block copolymer G 3.82 no II KRATON FG1901X Shell SEBS block copolymer G 0.25 no JJ VECTOR 4411 Dexco Polymers SIS block copolymer G 18.2 no KK Phillips DK-11 Phillips SBS block copolymer G 3.62 no LL Phillips DK-10 Phillips SBS block copolymer G 4.6 no MM VECTOR 8508 Dexco Polymers SBS block copolymer G 3.1 no NN ESI DE200 Dow Chemical Co. Ethylene-styrene copolymer G 4.75 no OO ESI DS201 Dow Chemical Co. Ethylene-styrene copolymer G 5.6 no PP ELVAX ^™ 3180 DuPont EVA, 28% VA E. 13.68 no QQ ELVAX VOW DuPont EVA, 49% VA B 1.5 no RR GRIL TEX ^™ 9 EMS Am. Grilon, Inc. Copolyester Hot Melt Adhesives C 4.4 no SS GRIL TEXD 1519EGF EMS Am. Grilon, Inc. Copolyester Hot Melt Adhesives C 2.3 no TT MACROMELT ^™ 6238 Henkel polyamide resin C no UU MACROMELT 6206 Henkel polyamide resin C 24.52 no VV PHAE Dow Chemical Co. thermoplastic phenoxy resin E. 7.5 no WW LDPE 457 Dow Chemical Co. ECO, 1% CO E. 0.33 no 1 ELVALOY ^™ HP441 DuPont EnBACO E. 3.1 1.5 5 yes 2 ELVALOY EP4924 DuPont EVACO E. 7.28 0.5 20 yes

Table 1 continued Example comparative example thermoplastic resin Thermoplastic superabsorbent polymer blend composition Grade supplier type MFR, condition MFR, g/10min Melt tension, unit Shrinkage rate fpm extrudable 3 A702 Chevron EEA E. 2.8 1.0 5 yes XX PRIMACOR ^™ 3330 Dow Chemical Co. EAA, 6.5%AA E. 2.2 no 4 PRIMACOR 1410 Dow Chemical Co. EAA, 9.7%AA E. 0.72 yes 5 PRIMACOR 1430 Dow Chemical Co. EAA,; 9.7% AA E. 2.43 1.0 5 yes 6 PRIMACOR 3460 Dow Chemical Co. EAA, 9.7%AA E. 8.98 0.6 20 yes 7 XUS70751.17 Dow Chemical Co. EAA, 20.5%AA B 0.84 1.5 10 yes YY PRIMACOR 5980 Dow Chemical Co. EAA, 20.5%AA B 0.3 no 8 PRIMACOR blend (a) Dow Chemlcal Co. EAA, 15.1%AA B 1.16 1.4 10 yes 9 ESCOR ^™ ATX 325 Exxon EMAAA E. 8.72 0.2 5 yes 10 NUCREL ^™ 699 DuPont EMAA B 4.6 0.5 5 yes 11 SURLYN ^™ 8660 DuPont Na-EMAA ionomer 125℃/5.0Kg 1.46 2.0 5 yes 12 SURLYN 1702 DuPont Zn-EMAA ionomer E. 6.0 0.9 45 yes 13 SURLYN 1702(b) DuPont Zn-EMAA ionomer E. 4.13 0.5 20 yes ZZ SURLYN 1702(c) DuPont Zn-EMM ionomer E. 2.58 no (a) 50/50 blend of PRIMACOR3460 and PRIMACOR5980 (b) 50/50 blend of SURLYN1702 and CABLOC 850-13 (c) 40/60 blend of SURLYN1702 and CABLOC 850-13 Ethylene LLDPE = Linear Low Density Polyethylene VLDPE = Very Low Density Polyethylene PP = Polypropylene PS = Polystyrene EMA = Copolymer of Ethylene and Methyl Acrylate EnBA = Copolymer of Ethylene and n-Butyl Acrylate PE = Polyethylene g-MAH = EVA grafted with maleic anhydride = Ethylene and vinyl acetate copolymer EPDM = Ethylene propylene diene monomer EA = Ethylene and acrylate copolymer SBS = Styrene, butadiene and styrene block copolymer SIS = Styrene, Isoprene and Styrene Block Copolymer SEBS = Styrene, Ethylene, Butylene and Styrene Block Terpolymer ESI = Ethylene and Styrene Interpolymer Block Copolymer ECO = Ethylene and Carbon Monoxide Copolymer EnBACO = terpolymer of ethylene, n-butyl acrylate and carbon monoxide EVACO = terpolymer of ethylene, vinyl acetate and carbon monoxide EEA = copolymer of ethylene and ethyl acrylate EAA = copolymer of ethylene and acrylic acid AA = acrylic acid EMAA = ethylene and methacrylic acid copolymer EMAAA = ethylene and methyl acrylate and acrylic acid copolymer Na = sodium Zn = zinc Condition B = 125°C/2.16kg Condition C = 150°C/2.16kg Condition E = 190°C/2.16kg Condition G = 200℃/5.0kg condition L＝230℃/2.16kg

Table 2 Example comparative example thermoplastic resin superabsorbent polymer Blend Composition, Parts extruder temperature extrudable Grade supplier type resin SAP °F AB LDPE 681 Dow Chemical Co. LDPE SAP-1 80 20 310-330 no AC LDPE 681 Dow Chemical Co. LDPE SAP-1 75 25 310-330 no AD LDPE 681 Dow Chemical Co. LDPE SAP-1 65 35 310-330 no AE LDPE 681 Dow Chemical Co. LDPE SAP-1 60 40 310-330 no AF ATTANE 4201 Dow Chemical Co. VLDPE SAP-2 80 20 335-370 no AG ATTANE 4203 Dow Chemical Co. VLDPE SAP-1 73 27 321-350 no AH ALATHON 6030 HPPE Equistar HDPE SAP-2 80 20 335-370 no AI DOWLEX 2045 Dow Chemical Co. LLDPE SAP-2 75 25 400-420 no AJ ELVAX 3180 DuPont EVA, 28%VA SAP-1 60 40 250-260 no AK Aqua Calk(a) Sumitomo Seika Chemlcal Co., Ltd. Polyethylene Oxide(a) SAP-1 60 40 250-260 no AL PRIMACOR 3530 Dow Chemical Co. EAA, 6.5% AA SAP-1 60 40 310-330 no 14 PRIMACOR 3460 Dow Chemical Co. EAA, 9.7% AA SAP-1 60 40 250-260 yes AM PRIMACOR 5980 Dow Chemical Co. EAA, 20.5% AA SAP-1 60 40 250-260 no 15 PRIMACOR blend (b) Dow Chemical Co. EAA, 15% AA SAP-2 60 40 250-260 yes AN PRIMACOR blend (b) Dow Chemical Co. EAA, 15% AA SAP-2 50 50 250-260 no 16 PRIMACOR 3460 Dow Chemical Co. EAA, 6.5% AA SAP-3 60 40 250-260 yes 17 ELVALOY EP4924 DuPont EVACO SAP-4 60 40 250-260 yes

(a) Aqua Calk is a thermoplastic, non-ionic, water-absorbing polymer manufactured by cross-linking polyethylene oxide

(b) 50/50 blend of PRIMACOR3460 and PRIMACOR5980

SAP = Super Absorbent Polymer

SAP-1 is a polyacrylic acid-based superabsorbent polymer commercially available from Stockhausen as CABLOC 1181, with a particle size distribution of about 1 to about 50 microns

SAP-2 is a polyacrylic acid based superabsorbent polymer commercially available from Stockhausen as CABLOC 80HS with a particle size distribution of about 1 to about 100 microns

SAP-3 is a polyacrylic acid-based superabsorbent polymer available from Dow Chemical Company as DRYTECH 2035, with a particle size distribution of about 1 to about 500 microns

SAP-4 is a polyacrylic acid based superabsorbent polymer commercially available from Stockhausen as CABLOC 80HS with a particle size distribution of about 1 to about 150

Comparative Examples AO-AW are different neat thermoplastic resins, Comparative Example AU is neat superabsorbent polymer CABLOC 850-13, AV is neat superabsorbent polymer CABLOC 80HS, AW is neat superabsorbent polymer CABLOC 88HS and implements Examples 18-30 are different thermoplastic resins compounded with superabsorbent polymers. A ZSK 58 micron (mm) co-rotating twin-cam twin-screw extruder with low shear mixing screws and 10 temperature zones was used. The superabsorbent polymer was added using a side port powder screw feeder between zones 4 and 5. Mixing takes place in zone 6. The transition point between zones 8 and 9 is the vent. There is a kneading and mixing section before the discharge port. The temperature range for the first 3 zones is 65-120°F, for zones 4 and 5 it is 240-255°F, for zones 6-8 it is 320-335°F and for zones 9 and 10 it is 270- 330°F. The melt temperature was maintained at 310°F.

The blend _composition was extruded through a 24-hole underwater die with a hole diameter of 0.110 inches into a liquid bath containing _a NaHCO solution having a specific gravity greater than 1.05 as measured by a desitometer and maintained at a temperature below 20°C. A Gala underwater pelletizer with 3 cutting blades was used to pelletize the extrudate. Optimize the distance from the underwater granulator to the separation dryer to minimize water absorption. Additionally, cool air was blown over the pellets in the pellet collection container to drive off any remaining moisture on the pellets.

The absorbent capacity (WAC ): For thermoplastic superabsorbent polymer blend compositions, a sample weighing W measured as containing ₁ gram of superabsorbent polymer (based on the percent superabsorbent polymer in the blend composition) was placed in 1.5 liters of distilled water and shaking on a shaker for 2 hours. Filter water from swollen particles through a 75 micron mesh. The weight (W ₂ ) of the swollen particles was then measured. The amount W _a of absorbed water is W ₂ −W ₁ . For neat resin and neat superabsorbent polymer, samples weighing 1 gram were subjected to the same procedure as described herein above.

The compositions and absorbed water of Comparative Examples AO-AW and Examples 18-30 are shown in Table 3, and the superabsorbent polymer is expressed in parts by weight, based on the weight of the thermoplastic superabsorbent polymer blend composition and water absorption reported is the grams of distilled water absorbed per gram of superabsorbent polymer.

table 3 Example comparative example thermoplastic resin CABLOC850-13, parts CABLOC80HS, parts CABLOC80HS, parts Water absorption, g AO SURLYN 1702 0 18 SURLYN 1702 35 3 19 SURLYN 1702 45 212 20 PRIMACOR blend (a) 40 214 twenty one ELVALOY EP4924 40 231 twenty two PRIMACOR 3460 40 239 twenty three SURLYN 1702 20 2 twenty four PRIMACOR blend (a) 20 1 25 PRIMACOR blend (a) 30 2 AP PRIMACOR blend (a) 0 26 PRIMACOR blend (b) 40 126 AQ ELVALOY EP4924 0 27 ELVALOY EP4924 20 2 28 PRIMACOR 3460 40 118 AR XUS60751.17 0 29 SURLYN 1702 35 1 AS PRIMACOR 1430 0 30 SURLYN 1702 45 96 AT PRIMACOR 5980 0 AU 100 172 AV 100 198 AW 100 153 (a) 50:50 blend of PRIMACOR 3460/PRIMACOR 5980 (b) 50:50 blend of PRIMACOR 1430 and XUS 60751.17 (EAA with 20.5% PAA) thermoplastic superabsorbent polymer blended with polyethylene

In Examples 31-38, the thermoplastic superabsorbent polymer was blended in a Brabender Plasticoder with a 70:30 LLDPE:LDPE polymer blend. The thermoplastic superabsorbent polymer includes 40wt% CABLOC T5066-F and 60wt% 50:50 PRIMACOR5980: PRIMACOR 3460 polymer blend, CABLOC T5066-F is a sodium polyacrylate superabsorbent polymer, the polymer is surface crosslinked , with a particle size distribution of about 1 to about 60 microns, available from Stochkausen and powders supplied by Stewart Superabsorbents LLC. The Brabender Plasticoder conditions were: the resin barrel temperature was set at 275°F; the mix RPM was 80; and the mix time was 1.5-2 minutes. Melt indexers are used to measure melt flow rate, melt tension and melt shrinkage of polymer blends. The blend composition is considered extrudable. See Table 4 for the compositions of Examples 31-38 and their MFR, melt tension and shrinkage.

Table 4 Example Thermoplastic resin: superabsorbent polymer "A" LLDPE:LDPE polymer blend "B" Blend ratio A:B MFR, condition MFR, g/10min Melt tension, unit Shrinkage, fpm extrudable 31 60:40 PRIMACOR blend: CABLOC T5066F 70:30LLDPE:LDPE 90:10 C 3.51 0.7 50 yes 32 60:40 PRIMACOR blend: CABLOC T5066F 70:30LLDPE:LDPE 80:20 C 4.43 0.8 48 yes 33 60:40 PRIMACOR blend: CABLOC T5066F 70:30LLDPE:LDPE 60:40 C 6.01 0.9 48 yes 34 60:40 PRIMACOR blend: CABLOC T5066F 70:30LLDPE:LDPE 20:80 C 6.17 1.0 34 yes 35 60:40 PRIMACOR blend: CABLOC T5066F 70:30LLDPE:LDPE 90:10 E. 24.7 0.5 100 yes 36 60:40 PRIMACOR blend: CABLOC T5066F 70:30LLDPE:LDPE 80:20 E. 25.7 0.6 100 yes 37 60:40 PRIMACOR blend: CABLOC T5066F 70:30LLDPE:LDPE 60:40 E. 28.1 0.7 100 yes 38 60:40 PRIMACOR blend: CABLOC T5066F 70:30LLDPE:LDPE 20:80 E. 21.9 0.8 100 yes PRIMACOR blend: 50:50 blend of PRIMACOR 3460/PRIMACOR 5980 LLDPE = linear low density polyethylene LDPE = low density polyethylene Condition C = 150°C/2.16kg Condition E = 190°C/2.16kg monolayer film

Examples 39-42 are monolayer films of thermoplastic superabsorbent polymer blend compositions produced using a cast line process. A thermoplastic superabsorbent polymer blend composition includes a thermoplastic resin and CABLOC 850-13. The temperature zone for the cast film process is 250°F-320°F. Feedblock and die temperatures were 270°F-320°F. Uniform films greater than 6.0 mil smooth pattern or webs less than 6.0 mil thick can be produced depending on take-up speed.

The compositions and properties of Monolayer Film Examples 39-42 are shown in Table 5, with superabsorbent polymer expressed in parts by weight, based on the weight of the thermoplastic superabsorbent polymer blend composition. Absorbency in pure water was measured as described above.

table 5 Example thermoplastic resin CABLOC 850-13, parts Water absorption, g 39 SURLYN 1702 35 25 40 SURLYN 1702 45 226 41 PRIMACOR blend (a) 40 219 42 ELVALOY EP4924 40 238

(a) Monolayer film of 50:50 blend of PRIMACOR 3460/PRIMACOR 5980 containing surfactant

Examples 43-46 are monolayer films containing surfactant. Thermoplastic superabsorbent polymers were melt blended in a Brabender Plasticoder with commercially available polyethylene containing surfactant compounds. Surfactant-containing polyethylene was purchased from AMPACET as ANTIFOG PE MB and contained 10 wt% active surfactant, mono- and diglycidyl esters, in the LLDPE/LDPE base polymer. Thermoplastic superabsorbent polymers include 40 wt% CABLOC T5066-F and 60 wt% 50:50 PRIMACOR 5980:PRIMACOR 3460 polymer blend, CABLOC T5066-F is a sodium polyacrylate superabsorbent polymer, the polymer is a surface crosslinked Combined, particle size distribution of about 1 to about 60 microns, available from Stochkausen and powders supplied by Stewart Superabsorbents LLC. The Brabender Plasticoder conditions were: the resin barrel temperature was set at 275°F; the mix RPM was 80; and the mix time was 1.5-2 minutes. Water absorption and absorption rate were measured by placing 2 inch disc samples of 5-7 mil compression molded film in a 2 inch diameter cylinder. At the bottom of the cylinder is a fine mesh screen of 75 microns or less. A Teflon disk was placed on top of the film sample to hold it in place during testing. Place the cylinder containing the sample on top of the 4 inch glass column with the membrane sample and screen facing the glass column. A filter paper is placed between the cylinder and the glass column. Place the glass column, filter and cylinder in a container containing water so that the water reaches the height of the glass column. Water is continuously removed and replenished. The entire setup is on a Mettler PG3001-S balance. Once the cylinder containing the sample was placed on the balance, the balance was tared and the water uptake and water uptake rate were generated using the Mettler BalanceLink data acquisition software package. Table 6 lists the compositions of Examples 43-46 and their water absorption amounts and rates.

Table 6 Example Thermoplastic superabsorbent polymers, parts AMPACET polymer, part Water absorption, g Time to reach 50% absorption value, sec The time to reach the maximum absorption value, sec 43 100 0 1 55 225 44 90 10 2.2 40 80 45 80 20 2.6 60 120 46 20 80 1.4 45 80

Thermoplastic superabsorbent polymer = 60 wt% 50:50 PRIMACOR 5980: PRIMACOR 3460 polymer blend + 40 wt% CABLOC T5066-F. multilayer film

Comparative Examples AX-AZ and Examples 47-49 are multilayer films of thermoplastic superabsorbent polymer blend compositions produced using a blown film process. The extruder temperature zone for the thermoplastic superabsorbent polymer blend composition (Layer 1) was 250°F to 300°F. Depending on the polymer used, the extruder temperature zone for layers 2 and 3 was 250°F-400°F and the die temperature was 250°F-400°F. See Table 7 for compositions and descriptions of Multilayer Blown Film Comparative Examples AX-AZ and Examples 47-49.

Examples 50-53 are blown films prepared as described herein, wherein the level of CABLOC 850-13 was varied in the PRIMACOR blend resin while the composition and ratio of layers 2 and 3 were kept constant. The absorbency described above and the time to reach a gel block in pure water were measured. The time for the superabsorbent polymer to gel in the pure water used for the superabsorbent film, called gel block, under its absorbency, was measured according to the following procedure. A sample of thermoplastic superabsorbent film composition comprising 0.15 grams of superabsorbent polymer was in a vial containing 25.6 grams of distilled water. The mixture is shaken by hand until it forms a gel-like mass. Swell onset time is the time from when water is added to the superabsorbent polymer to the first observable swelling.

Table 8 lists the compositions and film ratings for Multilayer Film Comparative Example AAA and Examples 50-53. Table 9 lists the water uptake, swelling onset time and gel block properties of the multilayer films Comparative Example AAA and Examples 50-53 and neat CABLOC 850-13 (Comparative Example AAB).

Table 7 Example comparative example Layer 1 Composition Layer 2 Composition Layer 3 Composition layer ratio graduation product description 1 2 3 mil AX 20 parts CABLOC 118180 parts LDPE 681 100% ATTANE 4201 100%PRIMACOR3330 20 60 20 4.0 Frequent pinholes in the film, die face buildup AY 30 parts of CABLOC 118170 parts of ELVAX 3180 20% ATTANE 420180% LDPE 681 100%PRIMACOR3330 20 60 20 2.0 Frequent pinholes in the film, die face buildup AZ 30 parts of CABLOC 80HS70 parts of PRIMACOR 3330 100% ATTANE 4201 100%PRIMACOR3330 20 60 20 4.5 Some pinholes in the film, die face build up 47 40 parts of CABLOC 80HS60 parts of PRIMACOR 3460 30%ATTANE 420170%LDPE 681 100%PRIMACOR3330 30 50 20 1.0-2.3 Works well, no pinholes, no die face buildup 48 40 parts of CABLOC 88HS 60 parts of ELVALOY 4924 50% ENGAGE 810050% LDPE 681 100%PRIMACOR3330 30 50 20 2.3 Works well, no pinholes, no die face buildup 49 40 parts CABLOC 850-1360 parts PRIMACOR blend (a) 80%ATTANE 440220%LDPE 681 100%PRIMACOR3330 30 50 20 2.3 Works well, no pinholes, no die face buildup

(a) 50:50 blend of PRIMACOR 3460/PRIMACOR 5980

Table 8 Example comparative example Layer 1 Composition Layer 2 Composition Layer 3 Composition layer ratio graduation 1 2 3 mil AAA 100% PRIMACOR blend (a) 80% ATTANE 420120% LDPE 681 100%PRIMACOR3330 30 50 20 4.0 50 10 parts CABLOC850-1390 parts PRIMACOR blend (a) 80% ATTANE 420120% LDPE 681 100%PRIMACOR3330 30 50 20 2.0 51 20 parts CABLOC850-1380 parts PRIMACOR blend (a) 80% ATTANE 420120% LDPE 681 100%PRIMACOR3330 30 50 20 4.5 52 30 parts CABLOC850-1370 parts PRIMACOR blend (a) 80% ATTANE 420120% LDPE 681 100%PRIMACOR3330 30 50 20 1.0-2.3 53 40 parts CABLOC850-1360 parts PRIMACOR blend (a) 80% ATTANE 420120% LDPE 681 100%PRIMACOR3330 30 50 20 2.3

(a) 50:50 blend of PRIMACOR3460/PRIMACOR5980

Table 9 Example comparative example Water absorption, g Swelling start time, sec Time to reach the gel block, sec AAA 0 50 127.25 <15 no gel clumping 51 203.3 <15 840-900 52 225.9 <10 360-420 53 257.65 <5 90-200 AAB 180.0 <5 60-90 Multilayer films coated with surfactant solutions

Examples 54-57 used a 2.0 mil multilayer blown film. The multilayer film comprises as layer 1 a thermoplastic superabsorbent polymer blend comprising a 50:50 blend of 60 wt% PRIMACOR 3460/PRIMACOR 5980 and 40 wt% CABLOC T5066F, as layer 2 LDPE4005 and as layer PLEXAR 107 for 3, EVAg-MAH from Equistar. The extruder temperature zone for the thermoplastic superabsorbent polymer blend composition (layer 1) was 250°F to 300°F, the zone temperature for layer 2 was 305°F to 310°F and the zone temperature for layer 3 was 350°F-370°F. The thickness ratio of the layers 1:2:3 is 30:50:20. Layer 1 of the multilayer film, the thermoplastic superabsorbent layer, was sprayed with a surfactant solution of 0-8% surfactant. The surfactant used in the study was alcohol ether sulfate. After spraying the film, it was dried in an air circulating oven at 50°C for 1-2 minutes. Water uptake and absorption rate were measured according to the procedure in the above section. Table 10 summarizes the amounts and rates of water uptake for Examples 54-57.

Table 10 Example comparative example Water absorption, g Time to reach initial absorption, sec Time to reach 50% absorption value, sec The time to reach the maximum absorption value, sec 54 0 1.7 15 60 170 55 2 2.0 0 31 112 56 5 1.9 0 29 160 57 8 1.8 0 27 135 Super Absorbent Films and Metal Laminates

Example 58 was a thermal lamination process in which the multilayer film described in Example 53 was laminated to 6.0 mil electrochrome plated steel (ECCS). The adhesive layer of the film (layer 3) was used to bond the film to the steel surface. High absorbency film/metal laminates can find use in power and communication cable construction. The metal substrate can provide shielding and the thermoplastic superabsorbent polymer layer can be used to bond to itself or another substrate and can be used to stop, block and absorb water in the cable. Table 11 shows the adhesion properties of the superabsorbent film of Example 57 to the metal laminate.

Table 11 Example membrane metal type Peel strength (a), (lb/in) Heat Seal (a) Strength, (lb/in) Sheath(b) Bond Strength, (lb/in) 58 Example 53 ECCS 5.0 13.1 31.8 (a) Peel strength and heat seal strength are measured according to ASTM B736 and the heat seal strength is the adhesive strength of the thermoplastic superabsorbent polymer to itself.

(b) Jacket material is DFDD 6069 BK 9865 modified LLDPE which is a standard wire and cable jacketing resin manufactured by Union Carbide. Sheath Bond (Composite of Sheath Material and Laminate Made in a Press) Strength Measures the force to separate the sheath from the laminate, measured according to ASTM D4365-86 modified to hold the sample at 180°C.

ECCS = Electrochrome Plated Steel Armored Cable

The superabsorbent film was laminated to the ECCS and slit into 2.25 inch wide steel strips. Tapes were used to prepare Armored Cable Examples 59-62. The strip is corrugated to 32 corrugations per inch (corrugations can be achieved with or without oil). The corrugated strip is formed longitudinally by a series of forming dies. A PVC sheath insulated copper twin cable core with an outside diameter of 0.60 inches was placed into the formed armor tape. Jacket resin was then extruded onto the formed armor tape to produce a final cable with a final outer diameter of 0.742 inches. The final gap between the inner sheath and the armor tape is about 0.015 inches (0.381 mm).

The properties of cables comprising thermoplastic superabsorbent polymer laminates (Examples 59-62, Table 12) were compared to those comprising ZETABON CJBS262 armor tape available from Dow Chemical Company (Comparative Example AAC) and additionally comprising . Comparison of cables produced with nonwoven superabsorbent tape 3E252 (comparative example AAD). Nonwoven superabsorbent tape is the wire and cable industry standard for dry cable designs. Nonwoven superabsorbent tapes include superabsorbent particles sandwiched between two nonwoven materials. For this evaluation, a nonwoven high-absorbency tape was helically wrapped around the copper twin-ply cable core before the cable core was placed into the formed armor tape. In the wire and cable industry, nonwoven superabsorbent tapes are typically formed longitudinally along the cable core.

The water barrier properties of the cables are measured by EIA/TIA-455-82A ("L-Test"). Tape or seal the ends of the cable core so that water cannot migrate through the wires of the cable core. The cable length is 1 meter, the test duration is 24 hours, the water column is 1 meter and the time to penetration is measured.

Table 12 Example comparative example Laminate Composition non-woven tape time to penetration AAC Layer 1 metal core Layer 2 AAD EAA film 6 mil ECCS EAA film no within 1 minute 59 EAA film 6 mil ECCS EAA film yes (a) 60 EAA film 6 mil ECCS film 1 no no penetration 61 EAA film 6 mil ECCS film 2 no no penetration 62 EAA film 6 mil ECCS film 3 no no penetration EAA film 6 mil ECCS film 4 no no penetration

(a) Test results change from no penetration to penetration within 15-24 hours

EAA film = 90% PRIMACOR 3330/10% LDPE 681

Film 1 composition: Layer 1: 30%-40 parts CABLOC 850-13/60 parts (50/50PRIMACOR 3460/PRIMACOR5980)

Layer 2: 50%-80% ATTANE 4201/20% LDPE 681

Layer 3: 20% - PRIMACOR 3330

Film 2 composition: Layer 1: 30%-40 parts CABLOC 80HS/60 parts (50/50 PRIMACOR 3460/PRIMACOR 5980)

Layer 2: 50%-80% ATTANE 4201/20% LDPE 681

Layer 3: 20% - PRIMACOR 3330

Film 3 composition: Layer 1: 30%-40 parts CABLOC 1181/60 parts (50/50 PRIMACOR3460/PRIMACOR5980)

Layer 2: 50%-80% ATTANE 4201/20% LDPE 681

Layer 3: 20% - PRIMACOR 3330

Film 4 composition: Layer 1: 30%-40 parts CABLOC 80HSB/60 parts (50/50 PRIMACOR3460/PRIMACOR 5980)

Layer 2: 50%-80% ATTANE 4201/20% LDPE 681

Layer 3: 20% - PRIMACOR 3330

CABLOC 80HSB has a particle size distribution of about 1 to about 20 microns

Film layer 1 is the laminate side for bonding the jacket resin

Membrane 2 is an armored cable with a thermoplastic superabsorbent polymer coated with a surfactant on the laminate side facing the core

A superabsorbent film is laminated to the ECCS. The superabsorbent layer of the film is pre-coated or post-coated with a glycol ether sulfate surfactant solution. The concentration of the surfactant solution is 2wt%-8wt%. Also use a defoamer, Dow Coming Anti Foam 1520-US. The amount of defoamer used was 2500 ppm. The coated laminate was slit into 1.375 inch wide steel strips. Tapes were used to prepare Armored Cable Examples 63-68 (Table 13). The strip is corrugated to 32 corrugations per inch (corrugations can be achieved with or without oil). The corrugated strip is formed longitudinally by a series of forming dies. A 0.375 inch outside diameter HDPE core tube, available from United States Plastic Corporation, was placed into the formed armor tape. The sheathing resin is then extruded onto the formed armor tape to make the final cable. The final gap between the inner sheath and the armor tape is calculated to be about 0.020 inches (0.508 mm).

The performance of cables comprising thermoplastic superabsorbent polymer laminates (Examples 63-68) was compared to cables comprising ZETABON CJBS262 armor tape available from The Dow Chemical Company (Comparative Example AAC).

The water barrier properties of the cables were measured by EIA/TIA-455-82A ("L-Test"). Tape or seal the ends of the cable core so that water cannot migrate through the wires of the cable core. The cable length is 1 meter, the test duration is 24 hours, the water column is 1 meter and the time to penetration is measured.

Table 13 Example comparative example Laminate Composition surface treatment time to penetration Layer 1 metal core Layer 2 AAC EAA film 6 mil ECCS EAA film within 1 minute 63 EAA film 6 mil ECCS film 1 in advance pass 64 EAA film 6 mil ECCS film 2 in advance pass 65 EAA film 6 mil ECCS film 2 back pass 66 EAA film 6 mil ECCS film 2 back pass 67 EAA film 6 mil ECCS film 3 back pass 68 EAA film 6 mil ECCS film 3 back pass

EAA film = 90% PRIMACOR 3330/10% PE

Film 1 composition: Layer 1: 30%-40 parts CABLOC 850-13/60 parts (50/50 PRIMACOR3460/PRIMACOR 5980)

Layer 2: 50% - LDPE 4005

Layer 3: 20% - PIEXAR 107

Film 2 composition: Layer 1: 30%-40 parts CABLOC T5066F/60 parts (50/50 PRIMACOR3460/PRIMACOR 5980)

Layer 2: 50% - LDPE 4005

Layer 3: 20% - PIEXAR 107

Film 3 composition: Layer 1: 30%-40 parts Norsocryl XFS/60 parts (50/50 PRIMACOR 3460/PRIMACOR5980)

Layer 2: 50% - LDPE 4005

Layer 3: 20% - PIEXAR 107

Norsocryl is a cross-linked copolymer of acrylic acid and sodium acrylate supplied by elf atochem ATO

PLEXAR 107 is a grafted maleic anhydride EVA copolymer supplied by Equistar

Film layer 1 is the laminate side for bonding the jacket resin

Membrane Layer 2 is core facing laminate side foamed thermoplastic superabsorbent polymer

Examples 69-77 are extruded foams of thermoplastic superabsorbent polymer blend compositions. About 12 parts per hundred (pph) HCFC142B physical blowing agent was used. The extruder temperature zone was 110°C-150°C and the die temperature was 85°C-90°C. See Table 14 for the composition and description of the foam. The obtained foam is soft, flexible and not brittle. Superabsorbent particles are evenly distributed on the skin and through the foam's cell structure.

Table 14 Example Thermoplastic superabsorbent polymer type foam type 69 1 semi-porous to closed-cell foam 70 2 semi-porous to closed-cell foam 71 3 semi-porous to closed-cell foam 72 4 semi-porous to closed-cell foam 73 5 semi-porous to closed-cell foam 74 6 semi-porous to closed-cell foam 75 7 semi-porous to closed-cell foam 76 8 semi-porous to closed-cell foam 77 9 semi-porous to closed-cell foam 1 Composition: 10 parts of CABLOC T5066F/60 parts (50/50 PRIMACOR 3460/PRIMACOR 5980) 2 Composition: 20 parts of CABLOC T5066F/60 parts (50/50 PRIMACOR 3460/PRIMACOR 5980) 3 Composition: 30 parts of CABLOC T5066F /60 parts (50/50 PRIMACOR 3460/PRIMACOR 5980) 4 Composition: 30 parts CABLOC 80HS/60 parts (50/50 PRIMACOR 3460/PRIMACOR 5980) 5 Composition: 20 parts CABLOC HCF/60 parts (50/50 PRIMACOR 3460/PRIMACOR 5980) 6 Composition: 20 parts Norsocryl XFS/60 parts (50/50 PRIMACOR 3460/PRIMACOR 5980) 7 Composition: 20 parts Norsocryl S35/60 parts (50/50 PRIMACOR 3460/PRIMACOR 5980) 8 Composition : 30 parts Norsocryl S35/60 parts (50/50 PRIMACOR 3460/PRIMACOR 5980) 9 Composition: 35 parts Norsocryl S35/60 parts (50/50 PRIMACOR 3460/PRIMACOR 5980) Norsocryl is acrylic acid and sodium acrylate supplied by elfatochem ATO Crosslinked Copolymer Norsocryl XFS Particle Size Distribution 1-67 Microns Norsocryl S25 Particle Size Distribution 1-225 Microns

Table 16 shows the absorbent capacity (WAC) in pure water of thermoplastic superabsorbent foam Examples 78-80 (Table 15) extruded by the extrusion foam process described above. WAC was measured according to the following procedure: The foam was cut into 0.125 inches by 0.625 inches by 0.125-0.25 inches and weighed W1 was measured as a sample containing 0.1 grams of superabsorbent polymer (based on the percent superabsorbent polymer in the foam composition ) into 0.150 liters of distilled water and shake on a shaker for 2 hours. Filter water from swollen particles through a 75 micron mesh. The weight of the swollen foam (W2) is then measured. The amount of water absorbed (W _a ) was calculated by the following formula,

W _a =(W2-W1)*10

Table 15 Example Thermoplastic superabsorbent polymer type Foam Water absorption, g 78 2 yes 87 79 3 yes 67 80 3 yes 43

2 Composition: 20 parts of CABLOC T5066 F/60 parts (50/50 PRIMACOR 3460/PRIMACOR 5980)

3 Composition: 30 parts of CABLOC T5066F/60 parts (50/50 PRIMACOR 3460/PRIMACOR 5980)

9 Composition: 35 parts of Norsocryl S35/60 parts (50/50 PRIMACOR 3460/PRIMACOR 5980)

From these data it can be seen that the extrudable thermoplastic superabsorbent polymer blend compositions of the present invention comprise one or more superabsorbent polymers and one or more thermoplastic resins, wherein the thermoplastic resin comprises The functional groups of the absorbent polymer interact to obtain the best balance of superabsorbent polymer containment, processability, formability and absorbency.

The present invention has been found to provide improved thermoplastic superabsorbent polymer blend compositions and methods of making, furthermore, monolayer films, multilayer films, nonwoven webs, sheets, foams, profiles, multilayer laminates, fibers , pipe, rod, and tube. It can be seen that by using the described extrudable thermoplastic superabsorbent polymer blend composition, surprisingly improved parts or structures obtained according to the present invention, and extruded, shaped or otherwise manufactured articles will be easy to manufacture, improved performance and reduce the cost of absorbent articles made therefrom.

Claims (31)

1. but an extruded thermoplastic superabsorbent polymer blend compositions comprises

(a) one or more superabsorbent polymers and

(b) one or more comprise the thermoplastic resin with the functional group of (a) ion or covalent interaction.

2. but the extruded thermoplastic superabsorbent polymer blend compositions of claim 1, under temperature that obtains the about 300g/10min melt flow rate (MFR) of about 0.1-and applying load condition, melt pulling-down rate is that about 100 feet per minutes of about 5-and melt tension are about 0.1-about 10.

3. but the extruded thermoplastic superabsorbent polymer blend compositions of claim 1, wherein from water-soluble α, β-ethylenically unsaturated monomer prepares superabsorbent polymer.

4. but the extruded thermoplastic superabsorbent polymer blend compositions of claim 3, wherein said α, β-ethylenically unsaturated monomer are monocarboxylic acid, vinyl poly carboxylic acid, acrylamide or its mixture.

5. but the extruded thermoplastic superabsorbent polymer blend compositions of claim 1, wherein said superabsorbent polymer be cellulose graft copolymer, starch graft copolymer, starch-g-poly-(vinylformic acid), polyacrylamide, polyvinyl alcohol, poly-(vinylformic acid), contain the monomeric multipolymer of sulfonic acid group or its mixture.

6. the superabsorbent polymer of claim 5 is crosslinked, part neutral, surface-treated or its combination.

7. but the extruded thermoplastic superabsorbent polymer blend compositions of claim 1, wherein said thermoplastic resin is polyacrylic acid, ethylene and acrylic acid copolymer, ethene, the ionomer of tert-butyl acrylate and acrylic terpolymer, copolymer from ethylene and methacrylic acid, copolymer from ethylene and methacrylic acid, ethene, vinyl acetate and carbon monoxide terpolymer, ethene and carbon monoxide multipolymer, ethene, vinylformic acid and carbon monoxide terpolymer, ethene, n-butyl acrylate and carbon monoxide terpolymer or its blend.

8. but the extruded thermoplastic superabsorbent polymer blend compositions of claim 1 further comprises tensio-active agent.

9. but the extruded thermoplastic superabsorbent polymer blend compositions of claim 1,3 or 8 further comprises polyethylene, poly multipolymer, polypropylene, polyacrylic multipolymer or polystyrene.

10. but the preparation method of an extruded thermoplastic superabsorbent polymer blend compositions comprises the step in conjunction with following material:

(a) one or more superabsorbent polymers and

(b) one or more comprise the thermoplastic resin with the functional group of (a) ion or covalent interaction.

11. the method for claim 10 further comprises the step in conjunction with (c) tensio-active agent.

But 12. one kind prepare extruding or the method for moulded parts of extruded thermoplastic superabsorbent polymer blend compositions, comprise the steps:

1) but preparation comprises the extruded thermoplastic superabsorbent polymer compositions of following material

(a) one or more superabsorbent polymers and

(b) one or more comprise with the thermoplastic resin of the functional group of (a) ion or covalent interaction and

2) this thermoplastic superabsorbent polymer composition is extruded or is molded as extrude or moulded parts.

13. the method for claim 12, wherein said superabsorbent polymer compositions further comprise (c) tensio-active agent.

14. the method for claim 12 or 13, wherein said extruded product are unitary film, multilayer film, nonwoven web, sheet material, foam, section bar, layer laminates, fiber, tubing, bar or pipe.

15. the method for claim 12 or 13, wherein said extruded product are monfil, bicomponent monofilament fiber, spunbond nonwoven web-webs, melt-blown non-woven net or the matrix material that comprises its binding substances.

16. the method for claim 12 or 13, wherein said extruded product is the nonwoven web that comprises spunbond nonwoven web-webs, this spunbond nonwoven web-webs comprises one or more conjugate fibers, comprises the melt-blown non-woven net of one or more conjugate fibers or comprises one or more spunbond nonwoven web-webs of one deck and the composite structure of one or more melt-blown non-woven nets of one deck at least at least that one or more layers of wherein said matrix material comprises conjugate fiber.

17. the composition of claim 1 or 8, form is for extruding or moulded parts.

18. extruding or moulded parts of claim 17 is unitary film, multilayer film, nonwoven web, sheet material, foam, section bar, layer laminates, fiber, tubing, bar or pipe.

19. extruding or moulded parts of claim 17 is monfil, bicomponent monofilament fiber, spunbond nonwoven web-webs, melt-blown non-woven net or the matrix material that comprises its binding substances.

20. extruding or moulded parts of claim 17, it is the nonwoven web that comprises spunbond nonwoven web-webs, this spunbond nonwoven web-webs comprises one or more conjugate fibers, comprises the melt-blown non-woven net of one or more conjugate fibers or comprises one or more spunbond nonwoven web-webs of one deck and the composite structure of one or more melt-blown non-woven nets of one deck at least at least that one or more layers of wherein said matrix material comprises conjugate fiber.

21. the unitary film of claim 18 or multilayer film are laminated on the metal.

22. a power cable comprises the metal laminates of claim 21.

23. a communication cable comprises the metal laminates of claim 21.

24. a power cable comprises the unitary film or the multilayer film of claim 18.

25. a communication cable comprises the unitary film or the multilayer film of claim 18.

26. a disposable absorbent article comprises extruding or moulded parts of claim 18.

27. the disposable absorbent article of claim 26 is diaper, sanitary towel, tampon, incontinence product, hospital's coat or mattress.

28. a disposable absorbent article comprises extruding or moulded parts of claim 19.

29. the disposable absorbent article of claim 28 is diaper, sanitary towel, tampon, incontinence product, hospital's coat or mattress.

30. a disposable absorbent article comprises extruding or moulded parts of claim 20.

31. the disposable absorbent article of claim 30 is diaper, sanitary towel, tampon, incontinence product, hospital's coat or mattress.