KR970000489B1 - Superabsorbent thermoplastic compositions and nonwoven webs prepared therefrom - Google Patents

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Description

Superabsorbent Thermoplastic Compositions and Nonwoven Webs Made from the Compositions

The present invention relates to superabsorbent thermoplastic compositions, superabsorbent thermoplastic polymer mixtures and meltblown or spunbond webs prepared therefrom.

Disposable absorbent products, such as diapers, sanitary napkins, tampons, incontinence products, etc., typically consist of a liner covered cotton or absorbent portion. The cotton typically consists mainly of cellulose fibers and the liner is typically a nonwoven web of polyolefins such as polyethylene or polypropylene.

Meltblowing techniques are known in the art to form nonwoven webs or nonwoven materials from fibers made of thermoplastic resins, relatively small in diameter, and disorderly deposited fibers. For example, the manufacture of fibers by meltblowing is known as van A. Van A. Wente's paper, "Superfine Thermoplastic Fibers," Industrial and Engineering Chemistry, Vol. 48, No. 8, pp. 1342-1346 (1956). This paper is Washington. It is based on a study conducted by Naval Research Laboratories of C. See Naval Research Laboratory Report 111437 (April 15, 1954). A more recent paper on general properties is Robert R .. Robert R. Butin and Wheat Tea. Dwight T. Lohkamp, “Melt Blowing-A One-Step Web Process for New Nonwoven Products” by Melt Blowing, Journal of the Technical Association of the Pulp and Paper Industry, Vol. 56, No. 4, pages 74-77 (1937).

In general, meltblowing techniques involve heating a thermoplastic fiber-forming resin in a molten state and then extruding the molten resin as threads from a die having a plurality of small-diameter capillary tubes arranged linearly. The molten thread or filament flows out of the die into a high velocity air stream of heating gas (usually air). The heating gas tapers or draws the threads of the molten resin to form fibers having a diameter smaller than the capillary diameter of the die. The fibers thus obtained are typically deposited in disordered form on a mobile porous collection device (eg, screen or wire) to form a nonwoven web. For illustrative purposes only, some specific examples of meltblowing techniques are described in US Pat. Nos. 3,016,599, 3,775,527, 3,704,198, 3,849,241, and 4,100,324.

In the past, considerable efforts have been made to find methods for making disposable absorbent products that are more effective or desirable to consumers. Most of these efforts have focused on increasing the absorbency of the product per unit mass and at the same time increasing the retention of body fluids absorbed by the product. The ability of products to remove and retain body fluids from the skin is recognized as a desirable attribute and is believed to play a part in reducing skin diseases such as rashes caused by diapers.

Such increased absorption and body fluid retention have typically been achieved by incorporating superabsorbent materials into the absorbent cotton.

The superabsorbent material is usually in particulate form. Unfortunately, particulate superabsorbents often exhibit gel-blocking phenomena that leach out of the absorbent product or fall off from the absorbent product and / or prevent body fluids from moving to the central portion of the superabsorbent particles. In addition, the use of particulate superabsorbents complicates the manufacturing process and the particulate nature of the superabsorbents limits the application of the superabsorbents.

The challenges arising from the use of particulate superabsorbents in disposable absorbent articles can all be minimized or even eliminated when the superabsorbent is in the form of a nonwoven web. However, superabsorbent nonwoven webs are unknown before the present invention, although there are many literatures on superabsorbents and products incorporating these superabsorbents.

Superabsorbent materials (also referred to as "hydrogels") are often based on polymers and copolymers of acrylates and methacrylates. Other hydrogels are based on starch or modified starch. Hydrogels made from hydrolyzed crosslinked polyacrylamides and crosslinked sulfonated polystyrenes or based on maleic anhydride (or similar compounds) are known. Finally, another hydrogel is based on polyoxyalkylene glycols, examples of which include polyurethane hydrogels.

Known polyoxyalkylene glycol based superabsorbents generally fall into one of the following classes, as long as they are reasonably related to the present invention.

(1) cross-linked poly (oxyalkylene) glycols, (2) cross-linked isocyanate sock-end poly (oxyalkylene) glycols, ie polyurethanes or polyureas, (3) polyfunctional prepolymers or resins and diisocyanates One polyurethane, (4) an isocyanate sock end polyester or a poly (oxyalkylene) glycol and a polyurethane made from a bifunctional weight agent, (5) a poly (oxyalkylene) glycol, an isocyanate sock end low molecular weight prepolymer and a multifunctional Polyurethane made from low molecular weight components.

First class-crosslinked poly (oxyalkylene) glycol

United States Patent No. 3,783,872 describes absorbent pads containing insoluble hydrogels. This hydrogel may be present in the form of a powder or a film in the pad. This hydrogel is made of crosslinked poly (alkylene oxide). Examples of suitable materials include poly (alkylene oxide) such as poly (ethylene oxide), poly (vinyl alcohol), poly (vinyl methyl ether), copolymers of maleic anhydride with ethylene, and maleic anhydride and vinyl methyl ether And copolymers thereof. The polymer is crosslinked with ionizing radiation.

Very preferred groups of polymers include poly (ethylene oxide), copolymers of ethylene oxide and propylene oxide, and alkyl substituted phenyl ethers of ethylene oxide polymers, wherein the alkyl group is an ethyl group and / or a butyl group.

In addition, the polymers that can be used are those which have a reduced viscosity relative to their molecular weight. Clearly, the polymers may have an average molecular weight of less than about 150,000 or up to about 10,000,000.

Second class-crosslinked isocyanate sock end poly (oxyalkylene) glycols, ie polyurethanes or polyureas

U.S. Patent No. 3.939,105 describes microporous polyurethane hydrogels. This hydrogel is the reaction product of a poly (oxyalkylene) polyol with an average molecular weight of approximately 25,000 and an organic diisocyanate slightly crosslinked with water or an organic amine. In practice, the polyol is reacted with diisocyanate to obtain a polyol whose end isocyanate group. Before crosslinking the isocyanate sock end polyol, a liquid nonsolvent is added thereto in an amount such that no precipitate is precipitated. By adding a nonsolvent, a microporous hydrogel is produced. The nonsolvent is typically an aliphatic hydrocarbon or dialkyl ether.

US Pat. No. 3,939,123 discloses similar content to that of the patent, except that no nonsolvent is used.

As a variation of the process described in the two preceding patents, US Pat. No. 3,940,542 discloses a solution of the isocyanate ended poly (oxyalkylene) polyols described in the two patents containing a coagulation bath containing water or an organic polyamine as a crosslinking agent or A method of extruding into a crosslinking bath to obtain a water swellable slightly crosslinked hydrogel polymer tape or fiber is described. U. S. Patent No. 4,209, 605 describes another modification method, in which predetermined raw materials containing poly (alkyleneoxy) polyols, diisocyanates and catalysts are charged into the reaction zone and the resulting high viscosity polymer Hydrogels are prepared by extrusion through and then crosslinking by exposure to atmospheric humidity.

U.S. Patent No. 4,182,827 discloses a method of increasing the wetting rate of the hydrogels described in these three patents. This wetting rate is increased by treating the surface of the solid hydrogel with a particular ketone, alcohol, organic amine, aromatic hydrocarbon, or aqueous alkali metal hydroxide solution.

Class 3-Polyfunctional Prepolymers or Polyurethanes Hydrophilic Polyurethanes Made of Resin and Diisocyanate

Polymers are described in US Pat. No. 3,822,238. This polymer is prepared by reacting diisocyanate with a polyfunctional prepolymer or resin. This prepolymer or resin is, among others, ethylene oxide, propylene oxide, ethylene imine, propylene amine, dioxolane or mixtures thereof and polyhydroxy compounds, hydroxy carboxylic acids, low molecular weight hydrolyzed poly (vinyl acetate) ), Polyacrylic acid, or polymethacrylic acid, or a mixture thereof. Examples of polyhydroxy compounds include ethylene glycol, propylene glycol, glycerol, trimethylolpropane, erythritol, pentaerythritol, anhydroene neheptitol, sorbitol, mannitol, sucrose and lactose (US Pat. No. 3,822,238) See US Pat. No. 3,975,350, which describes a carrier system using the hydrophilic polyurethane polymers of US Pat.

Class 4-Isocyanate Sodium End Polyesters or Poly (oxyalkylene) glycols and Polyurethanes Prepared with Bifunctional Weight Agents

Segmented urethane polymers are described in British Patent Application No. 2,154,886A. Briefly stated, a polyester or polyether glycol having a molecular weight of at least about 200 is reacted with excess organic diisocyanate to form an isocyanate terminated prepolymer. This prepolymer is then reacted with a bifunctional weight agent and optionally with a very small amount of monofunctional material acting as molecular weight regulator. Polyether glycols such as poly (tetramethyleneether) glycol having a molecular weight of at least about 600, for example from about 800 to about 5,000, are very suitable.

Diisocyanates are typically aromatic diisocyanates such as 4,4'-diphenylmethane diisocyanate and toluene diisocyanate. Excess diisocyanate is used, for example, in about 1.2 to about 1.9 moles of diisocyanate per mole of glycol.

Multifunctional weight agents have two groups that react with isocyanates. This weighting agent may be a diol, an amine having at least one amino hydrogen per amino group or water. Examples of suitable weighting agents include water, 1,4-butanediol, diethylene glycol, ethylene glycol, ethylene diamine, diphenylmethane diamine, 1,3-cyclohexylenediamine, 1,4-cyclohexylene diamine, and the like. Can be.

Similar polymers are described in US Pat. Nos. 2,929,800, 2,929,804, 3,428,711 and 3,557,044.

Polyurethane made from the fifth class-poly (oxyalkylene) glycol, isocyanate sonic end low molecular weight prepolymer and multifunctional low molecular weight components.

Polyurethanes similar to the polyurethane hydrogels are described in British Patent Application No. 2,157,703A. This material is not described at all in terms of absorbent properties but is described as useful for coating fabrics and fabrics.

According to this patent, polyurethane is a reaction mixture consisting of an isocyanate terminated prepolymer, a polyol component containing at least 25% by weight of polyoxyethylene units based on the total weight of the constituents, and a low molecular weight component having an active hydrogen functionality of at least 2 Is formed. If desired, the viscosity of the reaction mixture can be increased by the addition of one or more additional low molecular weight components having a functionality of at least 2, suitably at least 3, and it is preferred to use those additional components which function as crosslinking agents.

The prepolymer is formed from the reaction product of a polyisocyanate having at least two isocyanate groups per molecule with a low molecular weight component having at least two active hydrogen functionalities. Such components are diamines, dihydrazides, diamides, diols, dithiols, dicarboxylic acids, disulfonic acids or mixtures thereof. Among them, diols are suitable, and typical examples of the components include thiol glycol, ethylene glycol, diethylene glycol, and 1,4-butanediol. Trifunctional compounds such as trimethylolpropane, diethylenetriamine, and compounds having two or more different types of functional groups can be included. Low molecular weight components having a molecular weight of 200 or less are suitable.

The polyisocyanate used to prepare the prepolymer can be any of those known to be useful in the preparation of polyurethanes. Examples of this polyisocyanate include toluene-2,4-diisocyanate, toluene-2,6-diisocyanate, a mixture of these two compounds, 1,6-hexamethylene diisocyanate, 1,5-naphthalene diisocyanate, 4,4 ' -Diphenylmethane diisocyanate, 1,4-cyclohexanediisocyanate, 1,4-phenylene diisocyanate, m- and p-tetra methylxylyl diisocyanate and mixtures thereof, isophorone diisocyanate and 4,4'-dicy Chlorohexyl methane diisocyanate. Of these, the last two compounds are suitable.

The polyol component contains at least 25% polyoxyethylene units. Preferred polyoxyethylene containing compounds are polyethylene glycols having a molecular weight of about 400 to about 2000. Other preferred compounds include block copolymers of ethylene oxide and other 1,2-alkylene oxides (e.g., propylene oxide and butylene oxide), and copolymers formed by reaction of ethylene oxide with polyols, polyamines and polythiols. Can be.

The polyol component consists of a material, some of which do not contain pollingoxyethylene units (eg, polyester polyols and polyether polyols). Examples of polyester polyols include polycaprolactone diols, dicarboxylic acids (e.g., oxalic acid, maleic acid, succinic acid, adipic acid, suveric acid, sebacic acid, and isomeric phthalic acid) and polyols (e.g., ethylene glycol, diethylene glycol , 1,4-butanediol, 1,6-hexanediol, mixtures thereof, glycerol, trimethylolpropane, pentaerythritol, sorbitol and sucrose). Suitable as examples of polyester polyols are polytetramethylene glycols.

The low molecular weight component can generally be a compound of the same type as the low molecular weight component described above.

If necessary, crosslinking agents such as triisocyanate and melamine-formaldehyde resin can also be used.

The inventors are similar to those of the fourth class, but certain compositions based on bifunctional poly (oxyethylene) having a molecular weight of at least about 5.000 and mixtures with thermoplastic polymers with these particular compositions are particularly meltblown or spunbonded. It has been found that it can be formed into a nonwoven web or a nonwoven fabric, and that this composition (unlike the fourth class of compositions) has superabsorbency.

Thus, the invention relates to (a) 86 to about 98 weight percent of a poly (oxyethylene) soft segment dir 86 to about 98 weight percent, based on the total weight of the composition, and a weight average molecular weight of about 5,000 to about 50,000, and (b) Based on the total weight, the melting point is higher than the ambient temperature and lower than the temperature at which decomposition of the composition or the soft segment occurs, is necessarily insoluble in water, and is separated from the shaft segment, and is a polyurethane, polyamide, polyester, poly About 2 to about 14 weight percent of a hard segment selected from the group consisting of urea and mixtures thereof, wherein the soft and hard segments are separated by urethane, amide, ester, or secondary urea bonds or mixtures thereof. Provided is a superabsorbent thermoplastic polymer composition that is covalently bonded together.

The present invention also provides a nonwoven web of fibers made of the superabsorbent thermoplastic polymer composition.

The present invention also provides a nonwoven web consisting of a plurality of discontinuously, substantially disorderly, monofilaments made substantially identically from the superabsorbent thermoplastic polymer composition.

The present invention also provides a nonwoven web consisting of a plurality of monofilaments that are continuously and substantially indiscriminately deposited from the superabsorbent thermoplastic polymer composition.

The invention also consists of a matrix of meltblown thermoplastic polymer fibers and a plurality of individualizing fibers disposed throughout the matrix, at least a portion of the matrix fibers being bound so that the matrix fibers are spaced apart from each other at regular intervals, The individualized fibers are mechanically entangled with each other such that the individualized fibers are interconnected and fixed in the matrix, and are formed into a cohesive integral fiber structure by mechanical entanglement and interconnection of the matrix fibers and individualized fibers, wherein the matrix fibers or It provides a nonwoven web in which the individualized fibers consist of the superabsorbent thermoplastic polymer composition described above.

The present invention also provides a superabsorbent thermoplastic polymer composition having the following general formula.

In the formula, S represents Z ₁ -X _1- (Y ₁ -P ₁ -Y ₂ -X ₂ ) _P -Z ₂ , and H represents Z ₃ -X _3- (Y ₃ -X ₅ -Y ₄ -X ₄ ) _m- Z ₄ , wherein P is a poly (oxyethylene) component having a weight average molecular weight of about 5,000 to about 50,000, and Y ₁ , Y ₂ , Y ₃ and Y ₄ are each independently urethane, amide, ester or Represents a secondary urea chain, X ₁ , X ₂ , X ₃ , X ₄ and X ₅ each independently represent a divalent aliphatic, alicyclic, aromatic or heterocyclic group, and Z ₁ , Z ₂ , Z ₃ , and Z ₄ each independently represents a monovalent functional group that reacts with another functional group to form a urethane, amide, ester or secondary urea chain, m is an integer from 0 to about 50, n is an integer from about 1 to about 20, p Is an integer from about 1 to 10, S is a soft segment from about 86% to about 98% by weight of the total composition, H is a hard segment from about 2% to about 14% by weight of the total composition, Selected from the group consisting of polyurethanes, polyamides, polyesters, polyureas, and mixtures thereof, which are higher than the ambient temperature and lower than the temperature at which decomposition of the composition or soft segment occurs, which are necessarily insoluble in water, and which the phases are separated from the soft segments. do.

In a suitable embodiment, the hard segment is polyurethane. In another suitable embodiment, the hard segment is a 1,4-butanediol based polyurethane.

The present invention also relates to (A) reacting a first compound with a second compound for a time sufficient to effect essentially complete reaction at about 50 ° to about 200 ° C., and (B) subjecting the product obtained in step (A) to a third Provided is a process for preparing a superabsorbent thermoplastic polymer composition comprising reacting a compound at about 80 ° to about 200 ° C. for a time sufficient to achieve a melt flow rate of less than about 1,000 g per 10 minutes under the test conditions described below.

Here, the first compound is a bifunctional poly (oxyethylene) having a weight average molecular weight of about 5,000 to about 50,000, and the second compound is an aliphatic, alicyclic, aromatic, or two having a functional group that reacts with the functional group of the second compound. Heterocyclic compound, the molar ratio of the second compound to the first compound is about 2 to about 100, the third compound is an aliphatic, alicyclic, aromatic, heterocy having two functional groups reacting with the functional group of the second compound Click or polymerizable compound, the reaction product of the first compound and the second compound (excluding the excess second compound) is about 86 to about 98% by weight of the final composition, the third compound and the excess of the second compound The total amount is about 2 to about 14 weight percent of the final composition.

In a suitable embodiment, the second compound is aliphatic or aromatic diisocyanate. In another suitable embodiment, the third compound is an aliphatic or aromatic diol of 2 to about 24 carbon atoms.

The present invention also provides a superabsorbent nonwoven web composed of fibers comprised of a superabsorbent thermoplastic polymer composition.

The present invention also provides a superabsorbent nonwoven web consisting of a plurality of monofilaments that are discontinuously and substantially disorderly deposited substantially identically from superabsorbent thermoplastic polymer compositions.

The invention also comprises a matrix of meltblown thermoplastic polymer fibers and a plurality of individualized fibers disposed throughout the matrix, wherein at least a portion of the matrix fibers are joined so that the matrix fibers are spaced from each other at regular intervals, and The individualized fibers are mechanically entangled with each other to provide a nonwoven web consisting of the individualized fibers being co-connected and secured in the matrix, wherein only the mechanical entanglement and interconnection of the matrix fibers and the individualized fibers form a cohesive integral fiber structure. The mattress fibers or individualized fibers are composed of the superabsorbent thermoplastic polymer composition described above.

In addition, the present invention is directed to heating a superabsorbent thermoplastic polymer composition at a temperature range in which the melt flow rate of the composition is at least about 20 g per 10 minutes under a test condition described below to a temperature range in which significant degradation of the composition begins to occur and forming the heated composition. It relates to a method for producing a super absorbent product consisting of steps.

The superabsorbent thermoplastic polymer composition of the present invention is also heated at a temperature in which the melt flow rate of the composition is at least about 20 g per 10 minutes to a temperature range in which significant degradation of the composition begins to occur, and the heated composition is gas streamed through a plurality of extrusion orifices. Extruded to form a gas stream carrying a plurality of monofilaments made substantially identically tapered by the gas stream, and depositing the stream of monofilaments substantially disorderly onto a multi-poly collection screen and It is to provide a method for producing a superabsorbent nonwoven web comprising the step of forming a.

In a suitable embodiment, the superabsorbent thermoplastic polymer composition is polyurethane.

The present invention also provides a stable, non-reactive, thermoplastic polymer mixture consisting of about 10 to about 95 weight percent of superabsorbent thermoplastic polymer composition and about 90 to about 5 weight percent of one or more thermoplastic polymers.

The invention also relates to a nonwoven web comprising fibers composed of a stable, non-reactive, thermoplastic polymer mixture consisting of about 10 to about 95 weight percent of superabsorbent thermoplastic polymer composition and about 90 to about 5 weight percent of one or more thermoplastic polymers. To provide.

The present invention is also prepared substantially identically from a steady, non-reactive, thermoplastic polymer mixture consisting of about 10 to about 95 weight percent of superabsorbent thermoplastic polymer composition and about 90 to about 5 weight percent of one or more thermoplastic polymers. It is to provide a nonwoven web consisting of a plurality of monofilaments that are discontinuous and substantially disordered.

The present invention is additionally substantially identical from a superabsorbent thermoplastic polymer composition and a stable, non-reactive, thermoplastic polymer mixture consisting of about 10 to about 95 weight percent and about 90 to about 5 weight percent of one or more thermoplastic polymers. It is to provide a nonwoven web consisting of a plurality of monofilaments that are successively and substantially disorderly deposited.

The invention also consists of a matrix of meltblown thermoplastic polymer fibers and a plurality of individualizing fibers disposed throughout the matrix, at least a portion of the matrix fibers being bound such that the matrix fibers are spaced apart from each other at regular intervals, and the matrix fibers And the individualized fibers are mechanically entangled with each other such that the individualized fibers are interconnected and fixed within the matrix, wherein the matrix fibers and the individualized fibers are formed into a cohesive integral fiber structure by mechanical entanglement and interconnection, the matrix fibers Or a nonwoven web composed of a stable, non-reactive, thermoplastic polymer mixture wherein the individualized fibers are comprised of about 10 to about 95 weight percent of the superabsorbent thermoplastic polymer composition and about 90 to about 5 weight percent of the at least one thermoplastic polymer. .

In a suitable embodiment, the polymerizable composition component of the polymer mixture is a superabsorbent thermoplastic polymer composition of the present invention as already described above.

In another suitable embodiment, the polymer composition comprises about 30-90% by weight of the polymer mixture. In another suitable embodiment, the polymer composition comprises about 40 to about 75 weight percent of the polymer mixture.

Although the term "superabsorbent" has been used strictly in the prior art, the term "superabsorbent" described herein means that the composition absorbs at least about 10 g (10 g / g) of water per gram of the composition.

The superabsorbent articles of the present invention have wide range applications in the manufacture of disposable absorbent articles. The method of the present invention has application of light level in the second of the superabsorbent article by a suitable method. Examples of suitable methods include molding methods such as injection molding and extrusion methods such as continuous melt extrusion for forming films or fibers. In particular, a useful method is to melt blow the thermoplastic superabsorbent to provide a superabsorbent nonwoven web.

It is generally known that the properties of superabsorbent thermoplastic polymer compositions are not critically important, but in the present invention the properties must meet the criteria described herein. Particularly suitable compositions are those of the present invention described below. Particularly suitable are the superabsorbent thermoplastic polyurethanes described herein.

Such particularly suitable polyurethanes have been used in the examples of the present invention.

The superabsorbent thermoplastic polymer composition of the present invention consists of soft and hard segments, each segment described herein in terms of the segment component or composition and in the general formula.

Soft segments typically comprise about 86 to about 98 weight percent of the total composition. Preferably, the soft segment comprises from about 90% to about 97%, most preferably from about 95% to about 97% by weight of the total composition.

Generally, the soft segments are based on the first compound having a weight average molecular weight of about 5,000 to about 50,000.

Preferably, the molecular weight of the first compound is in the range of about 8,000 to about 50,000, more preferably about 8,000 to about 30,000, most preferably about 8,000 to 16,000.

More specifically, the first compound is a bifunctional poly (oxyethylene). These functional groups react with the second compound to form a urethane, amide, ester or secondary urea chain, and more preferably a functional group that forms a urethane chain. Examples of suitable functional groups may be hydroxy, carboxy, amino, epoxy, imino, isocyanate and the like. Preferably, the groups are all the same, and most preferably the groups are all hydroxy groups.

When the functional groups of the first compound are all hydroxy groups, the first compound becomes the most preferred poly (oxyethylene) diol. However, other functional groups may be present either by direct synthesis or by reacting the poly (oxyethylene) diol with the denaturant (preferably the latter method). However, the denaturing agent should not introduce any functional groups other than hydroxy groups. For purposes of explanation, diols are obtained upon reaction of poly (oxyethylene) diol with propylene oxide or hydroxy substituted carboxylic acids.

The use of denaturing agents involves processes known to those of ordinary skill in the art. In further detail, poly (oxyethylene) diamine is obtained by reacting poly (oxyethylene) diol with ethyleneamine. This diamine is also obtained when the diol is reacted with an amino substituted carboxylic acid. For convenience, the first compound obtained using the denaturant will be referred to herein as modified poly (oxyethylene) diol, although the functional groups present are hydroxy groups. This term also means including poly (oxyethylene) having two functional groups other than hydroxy groups prepared by other methods, rather than prepared by the use of a modifier. Likewise, the term “poly (oxyethylene) diol” is not limited to diols, which are polycondensation products of ethylene oxide, rather the term is used to refer to two or more poly (oxyethylene) diols by coupling agents (eg diisocyanates). Diols comprising substantially a plurality of oxyethylene units, including diols prepared by covalently coupling molecules together.

The soft segment is a reaction product of the first compound and the second compound, but the excess second compound that may be present is not part of the soft segment. Thus, the soft segment is the second compound terminal poly (oxyethylene). The chain in which the first compound is covalently bonded to the second compound is independently selected from the group consisting of urethane, amide, ester and secondary urea chains. Such a chain is preferably worked, the most preferred is a urethane chain.

The second compound is a compound having two functional groups which react with the functional group of the first compound to form a urethane, amide, ester and secondary urea chain, provided that the properties of the resulting soft segment are significantly counterproductive by the choice of the second compound. Should not be received. Thus, the second compound can be an aliphatic, cycloaliphatic, aromatic or heterocyclic compound. Also, for a functional group of a given first compound, one of ordinary skill in the art will be able to select a suitable functional group for the second compound.

As mentioned above, the reaction between the first compound and the second compound preferably forms a urethane chain. Since the preferred functional group of the first compound is hydroxy, a suitable functional group of the second compound is an isocyanate group. Thus, the most suitable second compound is diisocyanate.

For the purpose of explanation, suitable diisocyanates that can be used as suitable second compounds include the following compounds. Namely, toluene-2,4-diisocyanate, toluene-2,6-diisocyanate, ethylidene diisocyanate, propylene-1,2-diisocyanate, cyclohexylene-1,2-diisocyanate, cyclohexylene-1 , 4-diisocyanate, m-phenylene diisocyanate, 4,4'-biphenylene diisocyanate, 3,3'-dichloro-4,4'-biphenylene diisocyanate, 1,4-tetramethylene diisocyanate, 1 , 6-hexamethylene diisocyanate, 1,10-decamethylene diisocyanate, xylene diisocyanate, chlorophenylene diisocyanate, diphenylmethane-4,4'-diisocyanate, naphthalene-1,5-diisocyanate, cumene- 2,4-diisocyanate, 4-methoxy-1,3-phenylenediisocyanade, 4-chloro-1,3-phenylene diisocyanate, 4-bromo-1,3-phenylene diisocyanate, 4 -Ethoxy-1,3-phenylene diisocyanate, 2,4-diisocyanatodiphenyl Ter, 5,6-dimethyl-1,3-phenylene diisocyanate, 2,4-dimethyl-1,3-phenylene diisocyanate, 4,4'-diisocyanatodiphenyl ether, benzidine diisocyanate, xylene- Alpha-alpha'-diisothiocyanate, 3.3'-dimethyl-4,4'-biphenylene diisocyanate, 2.2 ', 5,5'-tetramethyl-4,4'-biphenylene diisocyanate, 4, 4'-methylenebis (phenylisocyanate). 4,4'-sulfonylbis (phenylisocyanate), 4,4'-methylene di-o-tolyl isocyanate, 1,4-bis (2-isosia neatoisopropyl) benzene, ethylene diisocyanate, trimethylene di Isocyanates, mixtures thereof and the like.

Most suitable second compounds are toluene-2,4-diisocyanate, toluene-2,6-diisocyanate, mixtures of toluene-2,4- and toluene-2,6-diisocyanate, 4,4-methylenebis (phenyl Isocyanate) and 1,6-hexamethylene diisocyanate.

Hard segments generally comprise about 2 to about 14 weight percent of the total composition. Suitably, the hard segment is about 3 to about 10 weight percent of the total composition, most suitably about 3 to about 5 weight percent.

Hard segments must have a melting point higher than the ambient temperature and lower than the temperature at which decomposition of the composition or soft segment occurs. In addition, the hard segment must be essentially insoluble in water and the phase must be separated from the soft segment.

The hard segment is selected from the group consisting of polyurethanes, polyamides, polyyl esters, polyureas, and mixtures thereof. This hard segment may be a polymer from scratch or may be produced in situ by reaction between a second compound and a third compound. Regardless of how hard segments are made, polyurethanes are suitable. Most suitably, it is a hard segment obtained by reacting a second compound with a third compound.

In other words, the third compound may be a polymer or a monomer. In either case, the reaction between the functional group of the third compound and the functional group of the second compound results in a covalent linking bond between the hard segment and the soft segment.

If the third compound is a monomer, the excess second compound must be present to cause a polycondensation reaction between the third compound and the excess second compound, such a polycondensation reaction often obtaining the proper properties of the hard segment. Is requested.

As described above, the monomeric third compound is preferable. If necessary, a mixture of two or more third compounds can be used. In addition, mixtures of at least one monomeric tertiary compound and at least one polymerizable tertiary compound can also be considered, and the mixture is within the scope of the present invention. Generally, the third compound is a compound having two functional groups which react with the second compound to form a urethane, amide, ester or secondary urea chain. Thus, the third compound is aliphatic, aromatic or heterocyclic.

The functional group of the third compound is any of those listed for the first compound. Suitably, the functional group of the third compound is the same as the functional group of the first compound. Therefore, the preferred functional group of the third compound is Higi group.

Most preferred third compounds are aliphatic and aromatic diols having 2 to about 24 carbon atoms. Suitable examples of the most preferred third compounds include, among others, ethylene glycol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,3-pentanediol, 1, 5-pentanediol, 1,6-hexanediol, 1,6-heptanediol, 1,4-dodecanediol, 1,16-hexadecanediol, resorcinol, 4-hydroxymethylphenol, 1,4- Bis (2-hydroxyethylene) benzene, 1,3-bis (2-hydroxyethyl) benzene, bis (2-hydroxyethyl) terephthalate and the like.

The superabsorbent thermoplastic polymer composition of the present invention can be represented by the following general formula.

Where S is

Where H is

Wherein P is a poly (oxyethylene) moiety, and Y ₁ , Y ₂ , Y ₃ and Y ₄ each independently represent a urethane, amide, ester or secondary urea chain, and X ₁ , X ₂ , X ₃ , X ₄ and X ₅ each independently represent a divalent aliphatic, cycloaliphatic, aromatic or heterocyclic group, and Z ₁ , Z ₂ , Z ₃ and Z ₄ each independently react with other functional groups to form urethane, amide, Represents a monovalent functional group forming an ester or secondary urea chain, m is an integer from 0 to about 50, n is an integer from about 1 to about 20, p is an integer from about 1 to about 10, and S is the entire composition Is about 86 to about 98% by weight of the soft segment, has a weight average molecular weight of about 5,000 to about 50,000, H is a hard segment of about 2 to about 14% by weight of the total composition, the melting point is higher than the ambient temperature and or Explode the soft segment Is lower than the temperature at which it occurs, is necessarily insoluble in water, and the phase is separated from the soft segment and is selected from the group consisting of polyurethanes, polyamides, polyesters, polyureas and mixtures thereof.

The general formulas (1) to (3) above represent essentially ideal ones. For example, formula (1) does not include terminal moieties. In addition, since the polymer molecules do not all have the same length (or molecular weight), the values of m, n and p are seldom integers, and these values are expressed as decimals which formally average. As a result, the term "integer" as used herein means to include both integers and decimals.

By the general formulas (2) and (3), the first, second and third compounds may each have two different functional groups. However, as a practical matter, this is rarely the case. As a result, typically X ₁ = X ₂ , Y ₁ = Y ₂ , Z ₁ = Z ₂ , X ₃ = X ₄ , Y ₃ = Y ₄ , and Z ₃ = Z ₄ . Also, typically, X ₅ = X ₁ and Y ₃ = Y ₁ . Under such a situation, general formulas (2) and (3) can be represented as the following general formulas (4) and (5) respectively.

One of ordinary skill in the art will recognize that the terminal moiety of the polymer composition may be soft segment or hard segment. When the terminal moiety is a soft segment, formulas (4) and (5) combine to form formula (6).

Similarly, general formula (7) is produced when the terminal moiety is a hard segment.

There is always a relationship between the molecular weight of the soft segment (or the first compound) and the hard segment (or amount) present in the composition, that is, the amount of hard segment is partially dependent on the value of m, the number of repeat units in the hard segment. The amount of hard segment present in the composition also has a functional relationship with the molar ratio of soft segments to hard segments, so that the molar ratio of soft segments to hard segments can vary between 2 and 0.5. Has a composition represented by general formulas (6) and (7), respectively, and the molar ratio of 2 or more or less than 0.5 causes the composition to contain unreacted soft segments or unreacted hard segments, respectively.

The above relationship to compositions based on poly (oxyethylene) diox, 4,4'-methylenebis (phenylisocyanate) and 1,4-butanediol, i.e., representative compositions made in the examples, is described next. This relationship is summarized in Tables 1-6 below, wherein the percentages of abundance of hard segments in the composition relative to the soft segments of the molecular weights given in this table, and the molar ratios of different m-values to hard segments (S: H) in each of the three soft segments Indicated. The molecular weight of the soft segment and the hard segment was calculated from the general formulas (2) and (3), respectively.

As desired, similar calculations may be made to the molar ratios of the soft segments or any mixtures of the first compound, the second and third compounds, the m-values, the soft segments for the hard segments, thus providing common knowledge in the art. A person having an easy determination of the molar ratio of the first, second, and third compounds can easily determine the amount of material needed to prepare a composition within the scope of the present invention.

For the purpose of explanation, when choosing m to be 3, one mole of hard segment must contain three moles of the second compound and four moles of the third compound. In addition, it may be assumed that the molar ratio of soft segments to hard segments is selected to be 1.5: 1. Since each mole of the soft segment must contain 2 moles of the second compound and 1 mole of the first compound, the molar ratio of S: H 1.5: 1 requires 3 moles of the second compound and 1.5 moles of the first compound per mole of the hard segment compound. . As a result, this reaction requires 1.5 mol of the first compound, 6 mol of the second compound and 4 mol of the third compound. Based on the desired scale and the molecular weight of the compound to be used, it is simple to calculate the amount of each compound required. In this respect, it can be seen that the preferred molar ratio of the soft segment to the hard segment is about 1. Thus, the preferred range of m is 0 to about 24.

From the foregoing description, it has been clarified that the molar ratio of soft segments to hard segments in the polymer composition cannot be more than 2 or less than 0.5. If the reaction mixture S: H molar ratio is outside this range, there will always be unreacted soft segments or unreacted hard segments in the final reaction mixture. While these results fall within the scope of the present invention, the unreacted segments generally increase the water solubility of the unreacted final reaction product, typically to remove unreacted material and / or unnecessary by-products of the reaction, and increase the absorbency. As a result of the reduction, such results are not suitable.

As a practical matter, the acceptable molecular weight range of the first compound and the soft segment should be essentially the same, because the molecular weight of the second compound is relatively small when compared to the molecular weight of the first compound. Thus, for convenience, the molecular weight of the first compound and the soft segment are all used in the same range in the present invention, (1) this range is only approximate, and (2) in practice, the molecular weight range of the soft segment is equal to the first compound. Slightly larger than the molecular weight range of the first compound as a result of the reaction between the second compound.

From the above description, it is evident that X ₁ , X ₂ and X ₅ represent non-functional moieties of the second compound, and these non-functional moieties are identical to each other since only one second compound is usually used. Similarly, X ₃ and X ₄ represent the non-functional site of the third compound, and X ₂ and X ₄ are typically identical to each other since only one third compound is commonly used. In addition, Z ₁ and Z ₂ and Z ₃ and Z ₄ represent functional group moieties of the second compound and the third compound, respectively.

In addition, Y <_1> and Y <_2> and Y <_3> and Y <_4> represent the chain which arises from reaction of the functional group of a 2nd compound, and the functional groups of a 1st and 3rd compound, respectively. Typically, such chains will all be identical.

As described above, the superabsorbent thermoplastic polymer composition of the present invention can be prepared by the following method.

(A) reacting the first compound with the second compound for about 50 ° to about 200 ° C. for a time sufficient to fully react, and (B) the product obtained in step (A) with the third compound from about 80 ° to about 200 The reaction is carried out at 캜 for a time sufficient to obtain a melt index of less than about 1,000 g per 10 minutes under the test conditions described below.

Here, the first compound is a bifunctional poly (oxyethylene) having a weight average molecular weight of about 5,000 to about 50,000, and the second compound is an aliphatic, alicyclic, having two functional groups reacting with the functional groups of the first compound. An aromatic or heterocyclic compound, the molar ratio of the second compound to the first compound is about 2 to about 100, and the third compound is an aliphatic, alicyclic having two functional groups that react with the functional groups of the second compound Group, aromatic, heterocyclic or polymerizable compound, the reaction product of the first compound with the second compound (except for the excess of the second compound) is about 86 to about 98% by weight of the final composition, The total amount of second compound is about 2-14 weight percent of the final composition.

In the first step of the method, the first compound is reacted with the second compound at about 50 ° to about 200 ° C. for a time sufficient to achieve a complete reaction. The reaction temperature is preferably about 80 ° to about 150 ° C, most preferably about 95 ° to about 120 ° C. The reaction time is not critical, but the reaction time is typically about 20 minutes to about 3 hours when the reaction is carried out within the most preferred temperature range.

The molar ratio of the second compound to the first compound should range from about 2 to about 100. Since the hard segment must be a polymer, when the third compound is a monomer, more excess second compound is required for the first compound, in which case the polymer hard segment is formed in situ. However, if desired, the third compound may be a polymer. What is required in this case is to provide the composition of the present invention by using the second compound in an amount sufficient to covalently bond the first compound with the third compound. Thus, when the third compound is a monomer, the preferred molar ratio of the second compound to the first compound is about 2.5 to 50, and the most preferred molar ratio is about 2.5 to about 26.

When the third compound is a polymer, the preferred molar ratio of the second compound to the first compound is about 2 to about 5.

Suitably, the first compound has a weight average molecular weight of about 8,000 to about 50,000, more suitably about 8,000 to about 30,000, and most suitably about 8,000 to about 16,000.

As mentioned above, the most suitable compound as the first compound is poly (oxyethylene) diol. In the case of using such a compound, most suitable as the second compound is diisocyanate, and most suitable as the third compound is diol. In a suitable embodiment, the first compound is a poly (oxyethylene) diol having a weight average molecular weight of about 8,000 to 16,000, the second compound is 4,4'-methylenebis (phenyl isocyanate), and the third compound is 1,4 Butanediol, the percentage of hard segments in the composition is about 3 to 5 weight percent of the total composition.

The second step of the process of the present invention is to react the product obtained in the first step with the third compound at about 80 ° to 200 ° C. for a sufficient time to obtain a melt flow rate of less than about 1,000 g per 10 minutes. The reaction temperature is suitably from about 90 ° to about 150 ° C, most suitably from about 110 ° to about 130 ° C.

The use of a solvent is not usually necessary, but one or more solvents may be used in either or both of the above steps as necessary. For example, the use of a solvent can be convenient when the viscosity of the reaction mixture in the first step is too high to make the mixture sufficiently difficult to perform. Generally any solvent may be used as long as it does not react with any of the constituents of the reaction mixture, wherein the reactants must be sufficiently soluble.

Examples of suitable solvents include aliphatic ketones (e.g. acetone, methyl ethyl ketone, methyl propyl ketone, etc.), aliphatic esters of lower aliphatic carboxylic acids (e.g., acyl acetate, methyl propionate, butyl acetate, etc.), aliphatic ethers (e.g., Diethyl ether, methyl propyl ether, etc.), aromatic hydrocarbons (e.g. benzene, toluene, xylene, etc.), halogenated aliphatic hydrocarbons (e.g. methylene chloride, etc.), dioxane, tetrahydrofuran, dimethyl formamide, N-methylpyrroli You can list money. It is not known that the amount of solvent used is important. However, it is not suitable that a significant amount of solvent is present in the reaction mixture at the end of the second stage.

As noted above, the melt flow rate of the reaction mixture at the end of the second stage should be less than about 1,000 g per 10 minutes. The melt flow rate value is for the reaction mixture without solvent. The target value of the melt flow rate depends largely on the intended use of the resulting composition. For example, when converting the composition to a nonwoven web or nonwoven, the melt flow rate is about 20 to about 500 g per 10 minutes, suitably about 50 to about 500 g per 10 minutes, most suitably about 80 to about 10 minutes 30 g. On the other hand, when the composition is extruded into a film, the melt flow rate of the final reaction mixture should probably be about 10 to about 30 g per 10 minutes.

Melt flow rate is determined using ASTM Test Method D 1238-82, a model VE 4-78 extruded plastometer (manufactured by Tinius Olsen Testing Machine Co., Willow Grove, Pennsylvania). “Standard Test Method for Flow Rates of Thermoplastics by Extrusion Plastometer” was measured by a slightly modified method. The modification method is as follows.

(1) Before loading a sample, it is made to dry in advance at reduced temperature around pressure. (2) Do not preheat the piston. (3) The sample is charged within 2 to 3 minutes. (4) Preload the loaded sample for 5 minutes. In all cases, the charge was 2.16 kg and the orifice diameter was 2.0955 ± 0.0051 mm. As noted above, the stable, non-reactive, thermoplastic polymer mixture consists of about 10 to 95 weight percent of the superabsorbent thermoplastic polymer composition and about 90 to about 5 weight percent of one or more thermoplastic polymers. The concentration of the polymer composition present in this mixture is suitably about 30 to about 90 weight percent, most suitably about 40 to about 75 weight percent.

The term “stable, unreactive, thermoplastic polymer mixture” described herein refers to (1) the mixture is stable at temperatures between ambient temperature and the maximum temperature at which the mixture is melt treated, and (2) the composition of the mixture. It means that the components do not react to each other to a great extent and (3) this mixture can be melt processed without causing significant degradation or other harmful effects. The term “stability” relates primarily to chemical stability, which excludes such phase separations as long as possible phase separations do not have a significant detrimental effect on the melt processability of the mixture.

In other words, phase separation is acceptable when it does not have a significant detrimental effect on the melt processability of the mixture.

Phase separation may occur at or below the melt processing temperature. In fact, the components of the mixture do not need to form a homogeneous mixture at any stage of the melt processing.

In addition to the superabsorbent thermoplastic polymer composition, the mixture will also contain one or more thermoplastic polymers. The thermoplastic polymer may be any thermoplastic polymer that produces a stable, non-reactive, thermoplastic polymer mixture.

Examples of thermoplastic polymers may be exemplified as follows:

Socks end protection polyacetals (e.g., poly (oxymethylene) or polyformaldehyde, poly (trichloroacetaldehyde), poly (n-valericaldehyde), poly (acetaldehyde), poly (propionaldehyde), etc.), acrylic polymers [Eg, polyacrylamide, poly (acrylic acid), poly (methacrylic acid), poly (ethyl acrylate), poly (methyl methacrylate), etc.], fluorocarbon polymers [eg, poly (tetrafluoroethylene) , Perfluorinated ethylene-propylene copolymer, ethylene-tetrafluoroethylene copolymer, poly (chlorotrifluoroethylene), ethylene-chlorotrifluoroethylene copolymer, poly (vinylidene fluoride), poly (vinylfluoro Ride), etc.], polyamide (e.g., poly (6-aminocaprinic acid) or poly (-caprolactam), poly (hexamethyleneadipamide), poly (hexamethylene sebaamide), poly (11-amino Unde Acid), etc.], polyamide (eg, poly (amino-1,3-phenyleneiminoisophthaloyl) or poly (m-phenyleneisophthalamide), etc.), parylene [eg, poly-p- Xylene, poly (chloro-p-xylene), etc.], polyaryl ethers [eg, poly (oxy-2,6-dimethyl-1,4-phenylene) or poly (p-phenylene oxide)]], polyaryl Sulfones [eg, poly (oxy-1,4-phenylenesulfonyl-1,4-phenylenesulfonyl-1,4-phenylene oxy-1.4-phenylene-isopropylidene-1,4-phenylene), poly (Sulfonyl-1,4-phenylenesulfonyl-4,4'-biphenylene) and the like, polycarbonates (eg, poly (bisphenol A) or poly (carbonyldioxy-1,4-phenyleneisopropyl) Polyester, eg poly (ethylene terephthalate), poly (tetramethylene terephthalate), poly (cyclohexylene-1,4-dimethylene terephthalate) or poly (oxy) Methylene-1,4-cyclohexylene methyleneoxyterephthaloyl), etc.], polyaryl Feeds (eg, poly (p-phenylene sulfide) or poly (thio-1,4-phenylene), etc.), polyamides (eg, poly (pyromellitimido-1,4-phenylene), etc.] , Polyolephine [eg, polyethylene, polypropylene, poly (1-butene), poly (2-butene), poly (1-pentene), poly (2-pentene), poly (3-methyl-1-pentene) , Poly (4-methyl-1-pentene), 1,2-poly-1,3-butadiene, 1,4-poly-1,3butadiene, polyisoprene, polychloroprene, polyacrylonitrile, poly (vinylacetate ), Poly (vinylidene chloride), polystyrene and the like], copolymers of the above compounds (eg acrylonitrile-butadiene-styrene (ABS) copolymers and the like).

Suitable thermoplastic polymers are polyolefins, of which polyethylene and polypropylene are most suitable.

It will be apparent to those skilled in the art that the present invention relates to two or more superabsorbent thermoplastic polymer compositions and / or mixtures containing two or more thermoplastic polymers. In addition, the mixture of the present invention is easily obtained by a known method.

The mixture contains one or more superabsorbent thermoplastic polymer compositions, but the mixture may or may not be superabsorbent depending on the level and absorbency of the superabsorbent thermoplastic polymer composition and the effectiveness of the polymer composition on the aqueous medium in the mixture. have.

Since the compositions and mixtures of the present invention are thermoplastic, these can be melted to obtain films, petroleum, nonwoven webs, molded articles, powders, granules, rods, tubs and the like. Such compositions are particularly useful for the production of nonwoven webs by meltblowing and spunbonding [US Pat. Nos. 3,016,599, 3,755,527, 3,704,198, 3,849,241, 3,341,394, 3,692,681. And 4,349,563. Such compositions can also be used in variations thereof. For example, this composition can be used to make suitable nonwoven materials as generally described in US Pat. No. 4,100,324. The patents are described herein by reference.

Therefore, forming fibers in the compositions of the present invention by melt spinning techniques is the most important field.

However, as used herein, the term “fiber” includes not only the fibers of the composition of the invention alone, but also multicomponent fibers, wherein at least one component of the multicomponent is a composition of the invention.

Multicomponent fibers are well known in the art, of which two of the most common are sheath-core fibers and parallel bicomponent fibers. The seed core fiber may have a polypropylene core and a seed of the composition of the present invention. Alternatively, the side and core polymers can be two different compositions of the present invention.

In the case of this other method, the core may be a higher molecular weight polymer having an absorbance lower than that of the seed composition. Similar polymer selections are also possible with parallel bicomponent fibers.

Ternary minutes and more multicomponent fibers are known. In this case, one or more of these components may be a composition of the present invention.

Although the compositions of the present invention are particularly suitable for the formation of nonwoven webs by meltblowing and coforming, the production of nonwovens by other methods is contemplated, which is also within the scope of the present invention.

For example, continuous filaments can be produced by melt spinning techniques, collected as tow, and converted into staple fibers. The nonwoven can then be produced by carding, air forming, or the like. In the production of staple fibers, for example, deformation such as flammable treatment, crimping, and the like can be carried out as necessary.

The invention is further illustrated by the following examples which illustrate specific embodiments. This embodiment should not be construed as limiting the principle or scope of the invention in any way. In the examples, all temperatures are in parts by weight, unless otherwise noted. In all cases, the poly (oxyethylene) diol was dried overnight at 95 ° C. under reduced pressure to reduce the water content to 0.01% by weight or less, and the assembled resin kettle, on the one hand, was cleaned with nitrogen gas. The outer surface of the cattle was heat dried using a portable butane burner flame.

A. Preparation of Thermoplastic Superabsorbents

Example 1

PEG-8,000, 웨스트 버지니아주, 사우드 찰스톤에 소재하는 유니온 카바이드 코포레이션(Union Carbide Corporation)사 제품)203g(0.025몰)과 4,4'-메틸렌비스(페닐이소시아네이트)(뉴욕주 로체스터에 소재하는 이스트만 코닥 코. (Eastman Kodak Co.)제품) 19.5g (0.078몰)을 넣었다. 덮개를 부착하고, 질소 유입구, 온도계, 콘덴서 및 강력한 토크(torque)기계교반기(카나다 온타리오에 소재하는 위아톤(Wiarton)사 제품, Caframa, 유형 RZR 50, CSA

; 미합중국 펜실베니아주 피츠버그에 소재하는 피셔 사이언티픽(Fisher Scientific)사의 Fisher Catalog 14-500)를 설치했다. 이 케틀을 질소로 세정하고, 질소 분위기 하에서 유지했다. 반응 혼합물을 1시간 동안 100℃로 가열시키고, 이 온도에서 교반하면서 1시간 동안 유지했다. 이어서, 이 케틀에 1,4-부탄디올(미합중국 뉴저지주 필립스버그에 소재하는 제이. 티. 베이커 케미칼 코.(J.T. Baker Chemical Co.)제품)4.8g(0.053몰)을 넣었다. 100℃에서 교반과 가열을 약 15분 동안 계속하고, 이 기간 중 반응 혼합물의 점도는 혼합물이 교반기의 샤프트(shaft)에 기어오를 정도로 증가했다. 반응 혼합물을 냉각시키고, 케틀에서 분리해서, 저장했다.Round glass flange with four-necked carver, 500 ml, wide inlet, two-piece resin kettle with molecular weight of 8,000 poly (oxyethylene) diol (CARBOWAX

203 g (0.025 mol) of PEG-8,000, Union Carbide Corporation, Saud Charleston, West Virginia, and 4,4'-methylenebis (phenylisocyanate) (Eastman, Rochester, NY) 19.5 g (0.078 moles) of Kodak Co. was added. Covered, nitrogen inlet, thermometer, condenser and powerful torque mechanical stirrer (Wiarton, Ontario, Canada, Caframa, type RZR 50, CSA

; Fisher Scientific 14-500 of Pittsburgh, Pennsylvania, USA, has been installed. The kettle was washed with nitrogen and kept under nitrogen atmosphere. The reaction mixture was heated to 100 ° C. for 1 hour and maintained at this temperature for 1 hour with stirring. This kettle was then charged with 4.8 g (0.053 mol) of 1,4-butanediol (JT Baker Chemical Co., Phillipsburg, NJ). Stirring and heating were continued at 100 ° C. for about 15 minutes, during which time the viscosity of the reaction mixture increased to such that the mixture climbed onto the shaft of the stirrer. The reaction mixture was cooled down, separated from the kettle and stored.

The resulting composition was composed of 94.8% by weight of the soft segment and 5.2% by weight of the hard segment, calculated as follows. In formula (2), the weight of the soft segment is approximately equal to the amount of the second compound or diisocyanate that is twice the amount of the first compound or poly (oxyethylene) diol and the amount of the first compound. The remaining amount of layer of the second compound and the third compound or 1,4-butadiol constitutes the weight of the hard segment. Since 0.025 mole of the first compound was used, the amount of the second compound to be added to the weight of the first compound is 0.05 mole x 250 g / mole or 12.5 g. Thus, the weight of the soft segment is 203g plus 12.5g or 215.5g, while the weight of the composition must equal the sum of the weights of the components or 227.3g. As a result, the percentage of soft segments present in the composition is equal to (215.5 × 100) /227.3 or 94.8%. Of course, the rest is hard segments.

Example 2

The procedure of Example 1 was repeated, with the exception that the second or B stage reaction time was 240 minutes. The viscosity of the final reaction mixture was comparable to that of Example 1. As in Example 1, the composition consisted of 94.8% by weight soft segment and 5.2% by weight hard segment.

Example 3

PEG-14,000)214g(0.015몰)과디이소시아네이트 10.5g(0.042몰)로 이루어졌으며, 1,4-부타디올의 양은 2.43g(0.027몰)이 었고, 제2단계 또는 B 단계 반응시간은 83분이었다. 얻어진 조성물은 소프트 세그멘트 97.3중량%와 하드 세그멘트 2.7중량%로 이루어졌다.The procedure of Example 1 was repeated, but the initial charge in the kettle was a poly (oxyethylene) diol having a molecular weight of 14,000 (Union Carbide Corporation, Saud Charleston, West Virginia, USA), CARBOWAX

PEG-14,000) consisted of 214 g (0.015 mole) and 10.5 g (0.042 mole) diisocyanate, the amount of 1,4-butadiol was 2.43 g (0.027 mole), and the reaction time of the second or B step was 83 minutes. . The resulting composition consisted of 97.3% by weight soft segment and 2.7% by weight hard segment.

Example 4

The process of Example 3 was repeated, but the amount of poly (oxyethylene) diol was slightly reduced to 196 g (0.014 mol), the amount of diisocyanate was 14.5 g (0.058 mol), and the amount of 1,4-butanediol was 4.21 g (0.044 mole) and the second or B reaction time was 96 minutes. The composition thus obtained consisted of 94.7% by weight soft segment and 5.3% by weight hard segment.

Example 5

The procedure of Example 3 was repeated 11 times, with the exception that a 2 L kettle was used, with 857 g (0.061 mol), 42 g (0.168 mol) of poly (oxyethylene) diol, diisocyanate, and 1,4-butanediol ) And 9.6 g (0.107 mol) each weighted four times. In addition, the second or B stage reaction was continued until the torque of the stirrer reached about 3686 gcm (about 3.2 lbin), at which time 10.5 g (0.14 mol) of n-butanol was added as the molecular weight limiting agent. . Eleven batches were labeled 5A-5K each.

As in Example 3, the composition consisted of 97.3% by weight soft segment and 2.7% by weight hard segment.

Since high molecular weight poly (oxyethylene) diol was not available in sufficiently pure form, low molecular weight poly (oxyethylene) diol was coupled by urethane chains and the degree of coupling was controlled by the ratio of diol and diisocyanate. . Indeed, the coupling reaction produced soft segments. As a result, the preparation of the final superabsorbent thermoplastic composition requires the addition of both the second and third compounds for the second or B stage reaction. This coupling reaction and subsequent formation of the final composition is illustrated by Examples 6-9 below.

Example 6

211 g (0.0264 mol) of poly (oxyethylene) diol used in Example 1 and 4,4 'in a two-piece resin kettle with a round glass flange and a four-hole cover, with a capacity of 500 ml, a wide mouth. 9.9 g (0.0396 mol) of methylenebis (phenylisocyanate) (molar ratio of diisocyanate to PEG 3: 2) was added. The cover was attached and the ones described in Example 1 were installed. The kettle was washed with nitrogen and kept under nitrogen atmosphere. The reaction mixture was heated to 100 ° C. for 1 hour and stirred for 1 hour while maintaining this temperature. Subsequently, 3.3 g (0.0132 mol) of diisocyanate additions and 2.4 g (0.0266 mol) of 1.4-butanediol were put into this kettle. Stirring and heating at 100 ° C. were continued for about 134 minutes, during which time the viscosity of the reaction mixture increased to such an extent that the mixture climbed on the shaft of the stirrer. The reaction mixture was cooled down, spattered out of the kettle and stored. The resulting composition consisted of 97.5% by weight soft segment and 2.5% by weight hard segment.

Before carrying out the next step, the modified poly (oxyethylene) diol obtained in the first step and the step A reaction is two molecules of poly (oxyethylene) diol bonded to each other by diisocyanate. Poly (oxyethylene) diol. This modified poly (oxyethylene) diol can be schematically represented as follows. That is, MDI-PEG-M-PEG-MDI, where MDI represents diisocyanate and PEG represents poly (oxyethylene) diol, such modified poly (oxyethylene) diol or soft segment of about 16,750 Had a molecular weight.

Example 7

Repeat the procedure of Example 6 twice, with the exception of 2 liter resin kettles in each case, initially containing 845 g (0.106 mole) of poly (oxyethylene) diol and diisocyanate (mole ratio of diisocyanate to PEG) 39.6 g (0.158 mol) was added to the kettle, followed by 13.2 g (0.053 mol) of diisocyanate and 9.6 g (0.107 mol) of 1,4-butanediol.

The reaction time of the second stage or the stage B for the two processes was 113 minutes and 159 minutes, respectively.

Two polymer batches were labeled 7A and 7B each. As in Example 6, the composition consisted of 97.5% by weight soft segment and 2.5% by weight hard segment.

Example 8

Repeat the procedure of Example 6, with the exception of 240 g (0.017 mol) of poly (oxyethylene) diol initially used in Example 6 in the kettle and 6.4 g of diisocyanate (molar ratio of diisocyanate to PEG is 3: 2). (0.026 mol) was added, followed by 3.5 g (0.021 mol) of diisocyanate and 2.7 g (0.030 mol) of 1,4-butanediol. The second or B stage reaction time was 124 minutes. The resulting composition consisted of 96.8% by weight soft segment and 3.2% by weight hard segment.

The modified poly (oxyethylene) diol obtained in the first stage or the A stage reaction consisted of two molecules of poly (oxyethylene) diol bonded to each other by diisocyanate. This modified poly (oxyethylene) diol can be schematically represented as follows.

That is, MDI-PEG-M-PEG-MDI. This modified poly (oxyethylene) diol or soft segment had a molecular weight of about 28,750.

Example 9

Repeat the procedure of Example 6 with the exception of 211 g (0.026 mole) of poly (oxyethylene) diol initially used in Example 3 in the kettle and 8.3 g of diisocyanate (molar ratio of diisocyanate to PEG is 5: 4) (0.033 mol) was added, followed by 5.0 g (0.020 mol) of diisocyanate and 1.4 g (0.027 mol) of 1,4-butanediol. The second or stage B reaction time was 200 minutes. The resulting composition consisted of 96.8% by weight soft segment and 3.2% by weight hard segment.

The modified poly (oxyethylene) diol obtained in the first stage or the A stage reaction consisted of four molecules of poly (oxyethylene) diol bonded to each other by diisocyanate. This modified poly (oxyethylene) diol can be schematically represented as follows. That is, MDI-PEG-MDI-PEG-MDI-PEG-MDI-PEG-MDI. The modified poly (oxyethylene) diol or soft segment had a molecular weight of about 33,250.

As mentioned above, Examples 6-9 illustrate the simultaneous manufacture of the hard composition and the on-site manufacture of a hard segment and the target composition following manufacture of a soft segment. Of course, after both the soft and hard segments are prepared separately, these can be mixed to obtain a superabsorbent thermoplastic composition. This procedure is described in Example 10 below.

Example 10

Manufacture of hard segments

1,4-butanediol (J. T. Baker, Phillipsburg, NJ) with a round glass flange and three-necked carver, 500 ml capacity, wide mouth, two-piece resin kettle 9.96g (0.01107 mol) and 4,4'-methylenebis (phenylisocyanate) (Isitman Kodak Corporation, Rochester, NY) '' manufactured by JT Barker Chemical Co. 3.83 g (0.0553 mol) was added. A cover was attached and a nitrogen inlet, condenser and mechanical stirrer (Taboys Engineering Corp., Emerson, NJ, laboratory T-stirrer, Motel No. 134-2) were installed. This kettle was washed with nitrogen and kept under nitrogen atmosphere. After heating the reaction mixture in a 72 ° C. oil bath for 10 minutes, a solid material formed. The resulting hard segment was melted at 175 ° -185 ° C.

This hard segment evaluated the molecular weight of the hard segment or the degree of coupling of the diol to the diisocyanate based on its hydroxyl group. The hydroxyl group defined by the number of mg of potassium hydroxide corresponding to the hydroxyl content in 1 g of the sample was measured as follows. About 1.5 g of a pair of samples were placed in a fresh single-neck round bottom flask and weighed. In each flask, exactly 25 ml of the phthalating agent which becomes 42.0 g of phthalic anhydride in 300 ml of freshly distilled pyridine was participated. A condenser was attached to each flask and it wash | cleaned gradually with nitrogen gas. The flask was placed in an oil bath at 115 ° C. for 1 hour. Using 5 drops of phenolphthalein solution as an indicator, the reaction solution of each flask was titrated and, on the other hand, warmed by addition of 0.5N aqueous sodium hydroxide solution so that the faint pink endpoints lasted for 15 total. Blank samples were tested with phthalating agents only. Subsequently, the hydroxyl group was calculated by dividing the required milli equivalents of potassium hydroxide (corrected for the blank value) by the weight of the sample. The bacterial hydroxyl group obtained in two identical tests was 270. The hydroxyl group had a apparent molecular weight of 416. The theoretical molecular weight of the hard segment is 430, indicating that there is a slight excess of 1,4-butanediol in the reaction mixture of the hard segment.

Fabrication of Soft Segments

Round glass flange with four-necked carver, 500 ml, wide inlet, two-piece resin kettle 391.5 g (0.028 mol) poly (oxyethylene) diol and diisocyanate used in Example 3 13.9 g (0.056 mol) was added.

; 미합중국 펜실베니아주 피츠버그 소재, 피셔 사이언티픽(Fisher Scientific)의 Fisher Catalog No. 14∼500 참조)를 설치했다. 이 케틀을 질소로 세정하고, 질소 분위기 하에서 유지했다. 반은 혼합물을 100℃까지 1시간 동안 가열시키고, 이 온도를 유지시키면서 231분 동안 교반했다.Nitrogen inlet, thermometer, condenser and powerful torque machine agitator (Wiarton, Ontario, Canada, Catrama, type RZR50, CSA)

; Fisher Scientific No. of Fisher Scientific, Pittsburgh, Pennsylvania, United States. 14 to 500). The kettle was washed with nitrogen and kept under nitrogen atmosphere. Half the mixture was heated to 100 ° C. for 1 hour and stirred for 231 minutes while maintaining this temperature.

Preparation of Super Absorbent Thermoplastic Compositions

To the resulting soft segment was added 11.63 g (0.027 mol) of hard segment dissolved in about 40 mL of dry N-methyl-2-pyrrolidone. The resulting mixture was heated at 72 ° -82 ° C. for 158 minutes to afford the desired composition, and the solvent was removed under reduced pressure for the last 15 minutes. The resulting composition consisted of 97.2% by weight soft segment and 2.8% by weight hard segment.

The compositions prepared in all of the above examples are polyether urethanes based on poly (oxyethylene) diol and aliphatic tertiary compounds, 1,4-butanediol. In addition, in the case of coupling a poly (oxyethylene) diol to obtain a modified poly (oxyethylene) diol derived from a molecular weight soft segment, the coupling used diisocyanate to form a urethane bond. As a result, all such compositions contained only ether and urethane chains. However, as described above, the compositions of the present invention are not limited to aliphatic tertiary compounds or ether and urethane chains, as demonstrated by the following five examples.

Example 11

Preparation of Polyether Urethane Ester

According to the method of Example 1, 212.8 g (0.0266 mol) of poly (oxyethylene) diol used in Example 1 was put into the resin kettle. When diol was heated to 95 degreeC, 2.70 g (0.133 mol) of terephthaloyl chloride (recrystallized from hexane) was added to this resin kettle. Unlike the use of diisocyanates as coupling agents, the use of terephthaloyl chloride prevents the formation of soft segments. The resulting reaction mixture was heated at 95 ° C. for about 1.5 hours with stirring under a nitrogen atmosphere. Subsequently, 10.0 g (0.040 mol) of the diisocyanate used in Example 1 was added to this kettle, and the temperature of the reaction mixture was 104 degreeC. After further elapsed, 2.40 g (0,0267 mol) of 1,4-butanediol was added to this mixture. The reaction mixture was heated for at least 1 hour, at which time 2.0 g (0.027 mol) of n-butanol was added as described in Example 5. The resulting composition contained 97.5% by weight soft segment and 2.5% by weight hard segment.

Example 12

Preparation of Third Compound Containing Aromatic Group

Repeat the process of Example 1, except that initially 305.6 g (0.0382 mol) of poly (oxyethylene) diol and 19.1 g (0.0764 mol) of diisocyanate were added to the kettle, and in the second step reaction, 1,4- Butanediol was replaced with 7.56 g (0.038 mol) of hydroquinone bis (2-hydroxyethyl) ether (Eastman Kodak, Kingsport, Tenn.) And the second or B reaction time was 47 minutes. The molar ratio of 1st compound: 2nd compound: 3rd compound was 1: 2: 1. The resulting composition contained 97.7% by weight soft segment and 2.3% by weight hard segment.

Example 13

In order to evaluate the effect of replacing the third compound used in Example 12 with the aliphatic diol in Examples 1 to 10, the procedure of Example 12 was repeated, and the first compound; Second compound; The molar ratio of the third compound was set to 1: 2: 1 as in Example 12.

Thus, the kettle initially contained 208 g (0.026 mole) of poly (oxyethylene) diol and 13.25 g (0.053 mole) of diisocyanate, and the amount of 1,4-butanediol was 2.34 g (0.026 mole), and the second step or B The step reaction time was 280 minutes. The resulting composition consisted of 98.8% by weight soft segment and 1.2% by weight hard segment. The decrease in the percentage of hard segments for the composition of Example 12 is due to the low molecular weight of 1,4-butanediol.

Example 14

Preparation of Holy Ether Urethane Amide

According to the method of Example 11, 63.81 g (0.00798 mol) of poly (oxyethylene) diol used in Example 1 and 250 ml of dry N-methyl-2-pyrrolidinone were put into the resin kettle. After the reaction mixture was heated and the diol was dissolved, 3.99 g (0.0159 mol) of the diisocyanate used in Example 1 was added to this kettle. The reaction solution was heated at 65 ° C. for 1 hour. Subsequently, 1.17 g (0.00798 mol) of adipic acid, 100 mL of N-methyl-2-pyrrolidinone, and a catalytic amount of sodium hydride were added to the resin kettle. The resulting solution was heated at 120 ° C. for 1 hour. The film was cast from the reaction solution, dried with air and then dried at 80 ° C. under reduced pressure. The composition consisted of 98.3% by weight soft segment and 1.7% by weight hard segment.

Example 15

Preparation of Polyether Urethane Amides

According to the method of Example 14, 45.02 g (0.0032 mol) of poly (oxyethylene) diol of Example 3, 4.89 g (0.0196 mol) of diisocyanate and 300 ml of dry N-methyl-2-pyrrolidinone were added to a resin kettle. Put in. Half the mixture was heated to 100 ° C. for at least 1.5 hours and held at this temperature for 1.5 hours. Next, 2.40 g (0.016 mol) of adipic acid and a catalytic amount of sodium hydride were added to this kettle. Continued heating further. The composition consisted of 89.1% by weight soft segment and 10.9% by weight hard segment.

The following examples briefly summarize the activity that increases with proportion to the specific composition prepared in the above examples.

Example 16

The procedure of Example 6 was repeated several times in batches of about 22.7 kg (501b) and about 90.7 kg (2001b) using an appropriate multiple of reactants. The second stage reaction was carried out at 130 ° ± 30 ° C. for 4 hours. In each case, 1,4-butanediol was added to zinc octoate at a concentration of 8 g of zinc octoate per 453.6 kg (1,0001b) of polymer. Of course, each composition consisted of 97.5% by weight soft segment and 2.5% by weight hard segment.

The compositions obtained in the above examples were characterized by a number of methods as follows.

1. Infrared Analysis (IR)

Samples of the composition were ground in Newsol. Perkin-Elme as an Instrument

r) A Model 710B spectrophotometer (Perkin-Elmer Corp., Norwall, Conn., US) was used.

2. Quantum Nuclear Magnetic Resonance Analysis (NMR)

Samples were dissolved in chloroform at a concentration of 10% by weight. The instrument was an IBM Instruments Model NR / 250AF 250 MHz spectrophotometer (IBM Corp., Armonk, NY).

3. Elemental Molecules (EA)

Fortune analysis was performed at Atlantic Microlabs, Atlanta, Georgia, USA.

4. Intrinsic Viscosity (Ⅳ)

우베로데 점도계(Ubbelohde Viscometer)(독일연방공화국 마인즈 소재, 제나에르 글라쓰베르크 초트 앤드 겐.(Jenaer Glasswerk Schott Gen.)사 제품)을 사용했다. 시료를 용적당 0.5중량%농도로 m-클레졸에 용해시켰다. 이 용액을 중간 프리트 소결시킨 유리 깔데기를 통해서 여과시키고, 유속을 측정하기 전에 항온조(미합중국 펜실베니아주 보울스버그 소재, 캐너 인스트루 먼트 캄파니(Canner Instrument Company)제품) 중에서 30℃에서 30분 동안 평형시켰다.Schotte Gerate KPG with Level Bulb Suspended as Device

Ubbelohde Viscometer (manufactured by Jenaer Glasswerk Schott Gen., Maines, Germany) was used. Samples were dissolved in m-clesol at a concentration of 0.5% by weight. The solution was filtered through a medium frit sintered glass funnel and equilibrated for 30 minutes at 30 ° C. in a thermostat (Canner Instrument Company, Bowlsburg, Pa.) Prior to measuring the flow rate. I was.

5. Melting point (MP)

The melting point range of the samples was measured by hotbench (C. Reichert Ag., Vienna, Austria).

6. Melt Flow Rate (MFR)

The melt flow rate measured the method described earlier in this specification.

7. Tensile Strength (TS) (final modulus)

Tensile strength was measured on a film sample using an Instron Model 1122 (Instron Corp., Canton, Mass., USA). The film was fabricated by Carver Laboratory Press Model 2518 (Fred S. Carver, Inc., Menomi Falls, Wisconsin, U.S.A.) at pressures of less than 100 pounds and 175 ° C. Were made, and the minimum gauge pressure was read. In each case, about 5 g of polymer was used, and the film thickness varied from 0.25 to 0.79 mm (0.010 inches to 0.031 inches), so the estimated pressure range was about 0.136 to about 0.608 atm (about 2 to about 10 psi). . The film was balanced for at least 1 day at ambient temperature and humidity. A rectangular film sample measured at 12.7 x 38.1 mm (0.5 x 1.5 inches) was cut from the film. The ends of the samples were wrapped with masking tape. Instron grips were 25.4 × 38.1 mm (1 × 1.5 inches) in size and had a smooth rubber surface. The gauge length was 25.4 mm (1 inch) and the crosshead speed was 50.8 mm (2 inches) per minute.

8. Thermogravimetric Analysis (TGA)

Thermogravimetric analysis was performed using a DuPont Model 1090 Thermal Analyzer (DuPont Instruments, Wilmington, Delaware, USA) with a DuPont Model 1091 Disk Memory and a Model 950 Thermogravimetric Analyzer. Each polymer sample (8-10 mg) ) Was weighed in a weighed platinum sample plate and heated to 550 ° C. at a rate of 10 ° C./min.

9. Differential Scanning Calorimeter (DSC)

Each polymer was analyzed with a differential scanning calorimeter using a DuPont Model 1090 thermal analyzer (Dufeng Instruments, Walmington, Delaware, USA) with a DuPont Model 1091 disk memory and a Model 910 differential scanning calorimeter. The polymer (about 4 g) was weighed in a weighed aluminum pan that was not weld sealed and the sample cell was cooled to -80 ° C using a liquid nitrogen jacket. The sample was then heated to 550 ° C. at a rate of 10 ° C./min.

10. Centrifugal Absorption (A) and Solubility (S)

피복 포일을 사용해서 0.28mm(0.0109인치)의 필름 두께를 성취했다. 필름을 1평방 센티미터로 절단 해서 칭량했다. 각개의 장방형 필름을 주위 온도에서 물또는 합성 뇨 중에 놓고, 4시간 동안 적셨다. 적신 시료를 원심분리 튜우브 어댑터에 넣었다. 이 어댑터(adapter)는 그 저부에 샘플에 대한 배리어를 가지며, 이 샘플은 원심분리 조건하에서 시험액체에 침투될 수 있다. 이어서, 시료를 1,000rpm(196×G)로 30분 동안 원심분리했다. 가능한 정도로, 시료를 원심분리 튜우브 어댑터에서 분리해서 칭량된 알루미늄 칭량 접시에 놓았다. 이 시료의 중량을 칭량하고, 90℃에서 3시간 동안 건조시킨 후, 다시 칭량했다. 이어서, 흡수도를 다음과 같은 식으로 계산했다.Absorbance was measured using water (WA) or synthetic urine (SUA). Briefly, the polymer sample was melt-pressed and formed into a film as described in Method 7 (tensile strength). TEFLON with flat metal spacer strip

The coating foil was used to achieve a film thickness of 0.28 mm (0.0109 inches). The film was cut to 1 square centimeter and weighed. Each rectangular film was placed in water or synthetic urine at ambient temperature and soaked for 4 hours. The wet sample was placed in a centrifuge tube adapter. The adapter has a barrier to the sample at its bottom, which can penetrate the test liquid under centrifugation conditions. The sample was then centrifuged at 1,000 rpm (196 x G) for 30 minutes. To the extent possible, samples were separated from centrifugal tubing adapters and placed in weighed aluminum weighing dishes. The weight of this sample was weighed, dried at 90 ° C. for 3 hours, and then weighed again. Subsequently, the absorbance was calculated by the following equation.

A = (wet weight-final dry weight) / final dry weight

Thus, the absorbance was the number of g of the test liquid absorbed per gram of sample, and the soluble sample was calibrated. When synthetic urine was used, the final dry weight was also corrected for the solids present in the absorbed liquid.

The solubility of the test sample was expressed as a percentage and calculated from the water absorption data as follows.

S = 100 × (initial dry weight-final dry weight) / initial dry weight

The synthetic urine test liquid contained the following components in the following amounts per liter of liquid.

The compounds were added to 900 ml of distilled water in a 1000 ml volumetric flask, rinsed well and washed with chromic acid, in the order described, and each compound was dissolved completely before adding the next. Distilled water was then added to the mark. The total solids content in the synthetic urine was 20.606 g / l, which was about the same as 2.01 wt%.

IR and NMR analysis supported the structures described herein for the compositions of the present invention, as in the case of EA. Melting point measurements had a wide range, indicating a wide molecular weight distribution. The thermogram obtained by DSC showed endotherms at about 50 ° to 60 ° C. and 410 ° to 430 ° C., indicating the presence of block copolymers. Finally, TGA demonstrated that the compositions were stable up to about 260 ° C. at least in a nitrogen atmosphere, and these compositions degraded by less than 1% by weight. Some of the other characteristic results are summarized in Table 7 below, and it should be noted that the temperature suitable for the measurement of the melt flow rate is 195 ° C.

A) Percentage of solubilization in water at ambient temperature, b: measured with polymer chips less than 0.5 cm moistened for approximately 24 hours, c: range of values obtained from multiple batches.

Finally, the intrinsic viscosity and final modulus were measured for each of the polymers of Examples 3 and 4. The values obtained are shown in Table 8 below.

Several compositions prepared in Examples 1 to 16 were measured for molecular weight by gel permeation chromatography. The device is a Beppa Model 112 solvent delivery system (Beckman Instruments, Inc., Fullerton, Calif.), Chloroform, HPLC-grade (Equip. Waters 500, 103 and 104 in Burdick and Jackson Laboratories, Inc., a subsidiary of American Hospital Supply Corporation, McGow, Illinois, USA Angstrom Styragel columns (Waters Chromatography Division, Millipore Corporation, Milford, Mass.).

Sample injection was 0.5% by weight 50 per volume of polymer solution in HPlC-grade chloroform. The flow rate of the eluent (chloroform) was maintained at 1 ml per minute. Sample peaks were measured by changes in refractive index using a Waters model 410 differential refractometer. The calibration curve was made using standard water in the molecular weight range of about 600 to 600,000, and below about 18,000 the standard was made from polyethylene glycol (American Polymer Standards Corp., Mentor, Ohio, USA). Product), and at about 18,000 or more this standard was a poly (ethylene oxide) standard (Stow, Ohio, Polymer Laboratories Inc., USA).

Data was obtained with the Nelson Analysis Model 760 interface and IBM Personal Computer AT (from IBM Corp., New York, USA) for Nelson Analysis GPC Software, Version 3.6 (Nelson Analytical, Cupertino, CA).

In general, the manufacturer's instructions are as follows: However, the most appropriate data acquisition parameters are as follows.

Min Peak Width 15.00 sec

1.50 seconds for one sample

Real time float full scale 500 millivolts for CH.O.

1 volt full scale range of A. D. C.

The results of the areare reject 1000.00 molecular weight measurements of the reference peaks are summarized in Table 9 below.

Note) a: In each case, a main peak having a shoulder was obtained. b: weight average molecular weight, c: number average molecular weight, d: main peak, e: shoulder, f: approximate.

The standard used to create the calibration curve may not be the most appropriate standard for the type of study polymer, so the shoulder can only refer to a relatively low molecular weight oligomer with narrow polydispersity. The shoulders can represent soft or hard segments that are not incorporated into the polymer. On the other hand, the main peak clearly shows a relatively high molecular weight polymer suitable for light source polydispersity. Due to the limitation of the data, the correlation between the molecular properties and / or polydispersity with the polymer properties such as solubility in water, water absorption is unknown.

B. Fabrication of Meltblown Nonwoven Webs

[Examples 17 to 22]

In order to measure the stability of the composition of the nonwoven web formation of the present invention, several compositions obtained in the above examples were extruded by a vent-scale device having a single orifice at the die tip. The device became a cylindrical steel reservoir with a capacity of about 15 g. The reservoir was surrounded by an electrically heated steel jacket. The temperature of the reservoir was controlled by a thermostat with a feedback thermocouple mounted to the body of the reservoir. The extrusion orifice had a diameter of 0.41 mm (0.016 inches) and a length of 1.51 mm (0.060 inches). The second thermocouple was settled near the die tip. The outer surface of the die tip was flushed into the reservoir body. Polymer extrusion was done with a compressed air piston in a reservoir. The extruded filaments were tapered by being surrounded by a cylindrical air stream exiting the circular 1.9 mm (0.075 inch) cap. The formation distance was 20-51 cm (8-20 inches). Tapered extruded filaments were collected on a clean plastic film of a 0.5 x 11 inch loose leaf protector with a black phase insert.

In Examples 17 to 22, six separate melt blowing experiments were performed using the above-described Bench scale apparatus. Meltblowing conditions are shown in Table 10 below. The temperature (° C.), air pressure (unit: atm (psig)), and formation distance (unit: cm (in)) of the polymer (see previous example), reservoir, die tip and air stream used in this table are shown. .

In each case, a cohesive superabsorbent nonwoven web was obtained.

[Examples 23 and 24]

In a variation of the method described in Examples 17-22 above, two batch scale devices were provided at 90 ° to each other. One device was placed vertically at the die tip downward and the other device was placed horizontally at the die tip facing the vertically placed device. The straight line distance between the two die tips was 14.5 cm (5.75 inches). Thus, the extruded filaments met at 10.2 cm (4 inches) at each die tip. The joining filament stream is 45 ° in the vertical direction. Formation distance was 10.2 or 30.5 cm (4 or 12 inches) as measured at the confluence of the collection device. The collection device is a 400-opening / 6.45 cm (1 in 2) screen attached to a vacuum hose.

Polypropylene (Himont U.S.A. Inc., Wilmington, Delaware, USA) was placed in the vertical unit. The composition of Example 5 (specifically a mixture of 5D and 5F) was placed in a horizontal apparatus.

The experiment was performed twice. In Example 23, the formation distance was 10.2 cm (4 inches) and the weight ratio of polypropylene to superabsorbent composition was about 60:40. For Example 24, the formation distance was 30.5 cm (12 inches) and the weight ratio of polypropylene to superabsorbent composition was about 70:30. Meltblowing conditions of these two examples are summarized in Tables 11 and 12, respectively.

A) The diameter of the extrusion orifice was 0.25 mm (0.010 inch), b: the temperature of the air was initially 157 ° C, but changed to 223 ° C near the middle of the experiment, c: the air pressure was initially 0.272 atm (4 psig). ), But changed to 0.816 atm (21 psig) at about 1 / 5th of the experiment time.

A) The extrusion orifice diameter was 0.25 cm (0.010 inch).

In each case, a cohesive superabsorbent nonwoven web was obtained.

[Examples 25 to 41]

Since the Benz scale meltblowing test was successful, the compositions obtained in the examples were mostly meltblown in a pilot scale apparatus (see US Pat. No. 4,663,220). Meltblowing of the various thermoplastic superabsorbent polymers of Examples 1-16 comprises a Brabender extruder with a diameter of 19 mm (0.75 inches) and nine extruded capillaries per inch of the die tip (about 3.5 per linear cm). The polymer was extruded through a melt blowing die having a capillary tube). Each capillary tube had a diameter of about 0.37 mm (about 0.0145 inch) and a length of about 2.9 mm (about 0.113 inch).

The variables of the process were generally as follows. Die tips calculated in capillary polymer viscosity (poise), polymer extrusion rate (g / capillary / minute) and extrusion temperature (° C), extrusion pressure (atm (psig)), negative (concave) or positive (block) Name, resin die tip distance, air flow width, damped air temperature (° C.) and pressure (atm (psing)) and formation distance, these cement blowing process parameters are summarized for Examples 25-41 in Tables 13-15 below. .

Note: a: A mixture of viscosity (poise) at extrusion temperature, b: 25% by weight of polymer (5H) and 75% by weight of polymer (11B).

A) Vertical distance or vertical die tip distance in mm from the plane of the air plate lip.

b: or 0.110 in, c: or 0.010 in.

A) Air passage width (mm), b: cm, c: or 0.090 in, d: or 38 in, e: or 25 in, f: or 0.060 in.

The collection device consists of a rotating drum 6 inches wide by 76.2 cm (30 inches). The surface of the drum is a screen coated with spunbonded polypropylene to prevent the meltblown web from sticking to the screen. The nonwoven web was allowed to stay on the forming screen for at least 10 seconds to ensure sufficient web strength for removal and ripening. A nonwoven web that was molded well and had cohesiveness and superabsorbency was obtained.

Synthetic urine absorption of the meltblown webs obtained in Examples 28-39 and Example 4 was measured by a saturation dose test. The device consisted of a stainless steel vacuum tank 28 cm high, 60 cm long and 35 cm wide. The government of the tank is a detachable stainless steel grid. This grid was about 59.5 × 34 cm and had holes of about 844 mm in diameter per 100 cm 2. Latex rubber dams are attached to one government edge on the larger side of the tank, which is sized to easily cover the grid without stretching. Emissions from the tank were achieved by a combination pressure / vacuum combination pump (Gast Manufacturing, Fisher Scientific No. 01-094, Fisher Scientific, Pittsburgh, Pa.). The pump was measured to read the achieved pressure drop in centimeters of water converted to atmospheric pressure.

To perform the test, at least three 7.6 cm (3 inch) square samples were cut out of each meltblown web and the spunbonded carrier was separated from each sample. Each sample was then dried for at least 1 hour at ambient temperature under reduced pressure. For each specimen, two 10.2 cm (4 inch) squares were cut from a polypropylene meltblown web having a normal basis weight of 25 to 34 g / m 2. Two accompanying polypropylene melt blown square webs of each sample were separated and weighed.

The sample was placed on one square polypropylene web and the sample at the bottom of the web of square polypropylene was immersed in a synthetic urine bath at 37 ° C. (98.6 ° F). The sample was carefully separated into the bath and placed in a second polypropylene square placed on a vacuum tank grid, and the sample was sandwiched between two polypropylene squares. After draining for 1 minute, the sample sandwich was weighed.

This sample sandwich was placed on the grid. The grid was completely covered with a rubber dam and the pressure in the tank was reduced to 0.034 atm (0.5 psi) below atmospheric pressure. That is, the pressure difference from one side of the sample sandwich to the other side was 0.034 atm (0.5 psi). This pressure difference was maintained for 5 minutes, after which the sample sandwich was weighed. This method was repeated three more times at pressure differences of 0.068 atm (1.0 psi), 0.136 atm (0.2 psi) and 0.204 atm (3.0 psi). After the sample sandwich was weighed at a pressure difference of 0.204 atm (3.0 psi), the samples were removed from the sandwich and separated from each other.

In order to calculate the absorbance at each pressure difference, it was necessary to correct the weight of each sandwich with respect to the weight of the wet polypropylene square body (WPPS). This was corrected by subtracting the sample weight from the sandwich weight at the same pressure difference with a pressure difference of 0.204 atm (3.0 psi). Next, the absorbency A of each sample was calculated as follows at each pressure difference.

A = (sandwich weight-WPPS weight-dry sample weight) / dry sample weight

Thus, the absorbance value at each pressure difference is the number of g of synthetic urine absorbed per gram of sample.

The results of the saturation capacity test are shown in Table 16 below. Absorbances described are averages for at least three samples.

It should be noted that the data in Tables 7 and 16 above were obtained by two different test methods, respectively. In addition, the data in Table 7 were obtained for the polymer film, while the data in Table 16 was obtained for the meltblown web.

A large scale meltblowing test was conducted to produce preformed webs as described in US Pat. No. 4,663,220. These large scale tests are described in Examples 42 to 66 below. In each case, the thing of Example 16 was used for the superabsorbent thermoplastic composition used.

Example 42

A fibrous, co-formed nonwoven web was formed by meltblowing the superabsorbent thermoplastic composition of the present invention and shaking polyester staple fibers.

Meltblowing of the superabsorbent thermoplastic composition was carried out in a 3.75 cm (1.5 inch) Johnson extruder through an meltblowing die having about 5.9 extruded capillaries (15 extruded capillaries per linear inch) per straight line of the die tip. Each capillary tube had a diameter of about 0.46 mm (0.018 inches) and a length of about 3.6 mm (about 0.14 inches). The composition was extruded through about 0.5 g of pumice capillary per capillary per minute at a temperature of about 184 ° C. The extrusion pressure shown in the composition in the die tip ranges from about 12.25 to 13.60 atm (about 180 to 200 psig). The composition viscosity in the die tip under these conditions is about 500 poise.

The die tip placement was adjusted to have a positive vertical die tip distance of about 0.25 mm (about 0.010 inch). The air gap of the two damped air passages was adjusted to be about 0.15 mm (about 0.060 inch). Molding air to melt blown the composition was fed to the air passages at about 209 ° C. and a pressure of about 0.136 atm (dir 2 psig). The thus shaped fibers were deposited on a forming screen drum about 46 cm (about 18 inches) below the die tip and 51 cm (20 inches) behind the die tip.

It is shown in FIG. 5 of US Pat. No. 4,663,220 and, according to the method described, is 3.765 cm (1.5 inches) in length and 15 denier per filament polyester staple is shaken into a stream of meltblown fibers prior to deposition on a forming drum. . Polyester fibers were first molded into mats having a basis weight of about 100 g / m 2 by a Rando Webber mat forming apparatus. The mat was transferred to the picker roll by a feeding roll placed about 018 mm (about 0.007 inches) away from the picker roll surface. The picker rolls were rotated at about 3,000 revolutions per minute and the fiber transport air was fed to the picker rolls at a pressure of about 0.204 atm (dir 3 psig). Although no actual measurement of the nozzle position of the eutectic apparatus with respect to the strip of meltblown fibers was made, about 5.1 cm (about 2 inches) below the die tip of the meltblowing die and about 5.1 cm (about 2 inches) at the die tip Was evaluated).

A molded nonwoven web having a width (lateral machine direction) of about 51 cm (about 20 inches) and composed of about 25% by weight meltblown fibers and about 75% by weight of polyester fibers was molded.

The basis weight of this web was about 200 g / m 2.

Example 43

The procedure of Example 42 was repeated with the exception of the co-molded web consisting of about 50 wt% meltblown fibers and about 50 wt% polyester fibers.

Example 44

The procedure of Example 43 was repeated with the exception that the basis weight of the formed web was about 400 g / m 2.

Example 45

The procedure of Example 42 was repeated with the exception that the coformed web consisted of about 75 wt% meltblown fibers and about 25 wt% polyester fibers.

Example 46

The procedure of Example 45 was repeated except the staples were 5.1 cm (2 inches) long, 5.5 denier per filament polyester staple.

Example 47

The procedure of Example 46 was repeated with the exception that the coformed web consisted of about 50 wt% meltblown fibers and about 50 wt% polyester fibers.

Example 48

The procedure of Example 46 was repeated with the exception that the coformed web consisted of about 25 wt% meltblown fibers and about 75 wt% polyester fibers.

Example 49

The procedure of Example 42 was repeated with the exception that polyester fibers were replaced with International Paper Super Soft pulp fibers. The pulp mat had a basis weight of about 200 g / m 2 and the mat feeding roll was about 0.76 mm (about 0.030 inch) at the picker roll surface.

It had a width (cross machine direction) of about 51 cm (about 20 inches) and formed a spun-shaped nonwoven web consisting of about 50% by weight meltblown fibers and about 50% by weight pulp fibers. The basis weight of this web was about 200 g / m 2.

Example 50

The procedure of Example 49 was repeated with the exception that the coformed web consisted of about 25% by weight meltblown fibers and about 75% by weight of pump fibers, with a basis weight of about 400 g / m 2.

Example 51

The procedure of Example 50 was repeated with the exception that the coformed web consisted of about 50% by weight meltblown fibers and about 50% by weight pulp fibers.

Example 52

The procedure of Example 51 was repeated with the exception that the basis weight of the formed web was about 200 g / m 2.

Example 53

The procedure of Example 42 was repeated with the exception that the meltblowing throughput was about 0.25 g per capillary per hour at about 181 ° C., the extrusion pressure at the die tip was about 19.189 atm (282 psig) and the viscosity of the composition Was about 1500 poises, the forming air temperature was about 197 ° C., the forming pressure was about 0.204 atm (about 3 psig), the forming screen drum was about 19 cm (about 7.5 inches) away from the die tip, No addition to the meltblown stream.

A nonwoven web was formed having a width (lateral machine direction) of about 51 cm (about 20 inches) and a basis weight of about 60 g / m 2.

Example 54

The procedure of Example 53 was repeated with the exception that the molding air of the meltblowing was supplied at a pressure of about 0.408 atm (about 6 psig) and the forming screen drum was about 43.2 cm (about 17 inches) from the die tip.

Example 55

The procedure of Example 42 was repeated with the exception of the meltblowing conditions of Example 53, with the mat feeding rolls being about 0.13 mm (about 0.005 inches) from the picker roll surface.

It had a width (cross machine direction) of about 51 cm (about 20 inches) and formed a spun-shaped nonwoven web composed of about 30% by weight meltblown fibers and about 70% by weight of polyester fibers. The basis weight of this web was about 200 g / m 2.

Example 56

Repeat the process of Example 55 with the exception that the blowing air of the meltblowing is about 0.408a

Feed was at a pressure of tm (dir 6 psig) and the forming screen drum was about 43.2 cm (about 17 inches) at the die tip and fiber transport air was fed to the picker roll at a pressure of about 0.136 atm (about 2 psig).

Example 57

The procedure of Example 56 was repeated except that the coformed web consisted of about 60% by weight meltblown fibers and about 40% by weight of polyester fibers, with a basis weight of about 160 g / m 2.

Example 58

The procedure of Example 42 was repeated with the exception that the meltblowing drootput rate was about 0.40 g per capillary per minute at about 204 ° C., the extrusion pressure at the die tip was about 19.597 atm (about 288 psig) and the viscosity of the composition was about 950 poise, the temperature of the forming air was 231 ° C., the pressure was about 0.204 atm (about 3 psig), the forming screen drum was about 43.2 cm (about 17 inches) from the die tip, and the secondary fiber process parameters were Example 55 Same as those, except the forming air pressure was about 0.136 atm (2 psig).

It had a width (cross machine direction) of about 51 cm (about 20 inches) and formed a co-molded nonwoven web composed of about 60 wt% of meltblown fibers and about 40 wt% of polyester fibers. The basis weight of the web was about 200 g / m 2.

Example 59

The procedure of Example 49 was repeated with the exception that the meltblowing drootput rate was about 0.35 g per capillary per minute at about 194 ° C., the extrusion pressure at the die tip was about 18.576 atm (dir 273 psig), and the viscosity of the composition was about 1030 poise, and the temperature of the forming air was about 206 ° C.

It had a width (cross machine direction) of about 51 cm (about 20 inches) and formed a spun-shaped nonwoven web consisting of about 30% by weight meltblown fibers and about 70% by weight pulp fibers. The basis weight of this web was about 200 g / m 2.

Example 60

The procedure of Example 59 was repeated with the exception of forming blown air of meltblowing at a pressure of about 0.408 atm (dir 6 psig) and the forming screen drum was about 43.2 cm (about 17 inches) from the die tip.

Example 61

The procedure of Example 59 was repeated except the melting temperature was 196 ° C., the extrusion pressure of the die tip was about 17.216 atm (about 253 psig), the viscosity of the composition was about 960 poise, and the molding air pressure was about 0.408 atm ( 6 psig).

It had a width (lateral machine direction) of about 51 cm (about 20 inches) and formed a spun-formed nonwoven web consisting of about 30% by weight meltblown fibers and about 70% by weight pulp fibers. The basis weight of this web was about 200 g / m 2.

Example 62

The procedure of Example 61 was repeated with the exception of forming air pressure of about 0.24 atm (about 3 psig).

It had a width (cross machine direction) of about 51 cm (about 20 inches) and formed a spun-shaped nonwoven web consisting of about 30% by weight meltblown fibers and about 70% by weight of pump fibers. The basis weight of this web was about 250 g / m 2.

Example 63

The procedure of Example 62 was repeated with the exception that fiber transport air was supplied to the picker roll at a pressure of about 0.136 atm (about 2 psig), with the web being about 40% by weight meltblown fiber and about 60% by weight pulp fiber The basis weight of the web was about 216 g / m 2.

Example 64

The procedure of Example 62 was repeated with the exception that the pulp fibers were Weyerhauser XB-309 pulp fibers and the fiber transport air pressure was about 0.136 atm (about 2 psig).

It had a width (cross machine direction) of about 51 cm (about 20 inches) and formed a spun-formed nonwoven web consisting of about 44 weight percent meltblown fibers and about 56 weight percent pump fibers. The basis weight of the web was about 250 g / m 2.

Example 65

The procedure of Example 64 was repeated with the exception of forming air pressure of about 0.408 atm (about 6 psig).

It had a width (cross machine direction) of about 51 cm (about 20 inches) and formed a spun-formed nonwoven web consisting of about 44 weight percent meltblown fibers and about 56 weight percent pump fibers. The basis weight of this web was about 250 g / m 2.

Example 66

The procedure of Example 65 was repeated. A co-molded nonwoven web having a width (lateral machine direction) of about 51 cm (about 20 inches) and consisting of about 30% by weight meltblown fiber and about 70% by weight pulp fiber was formed. The basis weight of this web was about 200 g / m 2.

The nonwoven webs obtained in Examples 43-50 and Examples 53-66 were subjected to a saturation dose test to measure synthetic urine absorbency. The results are summarized in Table 17 and the absorbance values described are the average of at least three samples. Note that the test procedure does not require the removal of the spunbond carrier because no spunbond carrier is used.

Example 67

Repeating the procedure of Example 31, with the exception of the polymer composition of Example 5J, 67% by weight of the polymer composition of Example 5J and low density polyethylene (US S. Chemicals, New York City, NY, USA) It was replaced with a mixture consisting of 33% by weight of &lt; RTI ID = 0.0 &gt; And Chemicals &lt; / RTI &gt;

According to the manufacturer, the polyethylene had a density of 0.903 g / cc, Brookfield viscosity (190 ° C.) 3300 centipoise (ASTM D 3236) and an equivalent melt index of 2000 g / 10 min (ASTM D 1238).

The extrusion drootput rate was estimated to be about 0.47 g / capillary / min at about 188 ° C. The extrusion input at the die tip was about 14.970 atm (220 psig). The viscosity of the mixture in the capillary was calculated to be 340 poise.

As before, well formed, cohesive nonwoven webs were formed. At this time, the web exhibited significant wet strength in terms of excess water present. The web had a water absorption of 16.2 g (average of two samples) per gram of web, corresponding to 24.3 grams per gram of superabsorbent thermoplastic polymer composition in the mixture by centrifugation. Two additional samples showed an average value of 24 g per g of web, corresponding to 37 g per g of polymer composition. The average absorbance of these two samples was 52% by weight by centrifugation.

Claims (49)

(A) about 86 to 98 weight percent of a poly (oxyethylene) soft segment having a weight average molecular weight of about 5,000 to 50,000, and (B) a melting point higher than the ambient temperature based on the total weight of the composition, Harder than the temperature at which decomposition of the composition or the soft segment occurs, which is necessarily insoluble in water, separated from the soft segment and selected from the group consisting of polyurepan, polyamide, polyester, polyurea and mixtures thereof About 2 to 14 weight percent of the segment, wherein the soft segment and the hard segment are covalently bonded to each other by urethane, amide, ester or secondary urea chain or a combination thereof, and the soft segment has a water content of 0.01% by weight or less. A superabsorbent thermoplastic polymer composition, characterized in that. The polymer composition of claim 1, wherein the weight average molecular weight of the soft segment is about 8,000 to 50,000. The polymer composition of claim 2, wherein the soft segment has a weight average molecular weight of about 8,000 to 30,000. 4. The polymer composition of claim 3, wherein the weight average molecular weight of the soft segment is about 8,000 to 16,000. The polymer composition of claim 1, wherein the soft segment is present at about 90-97 weight percent. The polymer composition of claim 5, wherein said soft segment is present at about 95-97 weight percent. The polymer composition of claim 1, wherein the soft segment is present in about 3 to 10 weight percent. 8. The polymer composition of claim 7, wherein said hard segment is present in about 3 to 5 weight percent. The polymer composition of claim 1, wherein the soft segment is derived from poly (oxyethylene) diol. 10. The polymer composition of claim 9, wherein said hard segment is polyurethane. The polymer composition of claim 10, wherein the polyurethane is derived from 1,4-butanediol. Superabsorbent thermoplastic polymer composition of the general formula: -(SH) n; In the above formula, S is Z ₁ -X _1- (Y ₁ -PY ₂ -X ₂ ) pZ ₂ , H is Z ₃ -X ₃ (Y ₃ -X ₅ -Y ₄ -X ₄ ) mZ ₄ , Wherein P represents a poly (oxyethylene) component having a weight average molecular weight of about 5,000 to 50,000, Y ₁ , Y ₂ , Y ₃ and Y ₄ each independently represent a urethane, amide, ester or secondary urea chain, and X ₁ , X ₂ , X ₃ , X ₄ and X ₅ each independently represent a divalent aliphatic, cycloaliphatic, aromatic or heterocyclic group, and Z ₁ , Z ₂ , Z ₃ and Z ₄ each independently represent another functional group. A monovalent functional group that reacts to form a urethane, amide, ester or secondary urea chain, m is an integer from about 0 to 50, n is an integer from about 1 to 20, p is an integer from about 1 to 10, Soft segment S represents about 86 to 98% by weight of the total composition, hard segment H is about 2 to 14% by weight of the total composition, and this hard segment H has a melting point higher than the ambient temperature and lower than the temperature at which decomposition of the composition or the soft segment occurs, is insoluble in water in water, and is separated from the soft segment, polyurepan, polyamide, polyester, polyurea and It is selected from the group which consists of these mixtures. The polymeric composition of claim 12, wherein m is an integer from about 0 to 24. 13. The polymer composition of claim 12, wherein the poly (oxyethylene) component has a weight average molecular weight of about 8,000 to 50,000. 15. The polymer composition of claim 14, wherein the poly (oxyethylene) component has a weight average molecular weight of about 8,000 to 30,000. The polymer composition of claim 15 wherein the weight average molecular weight of the poly (oxyethylene) component is between about 8,000 and 16,000. The composition of claim 12, wherein the soft segment S is about 90-97 weight percent of the total composition. 18. The composition of claim 17, wherein said soft segment S is about 95 to 97 weight percent of the total composition. The composition of claim 12, wherein the hard segment H is about 3-10% by weight of the total composition. 20. The composition of claim 19, wherein said hard segment H is 3-6 weight percent of the total composition. 13. The polymer composition of claim 12, wherein the soft segment S is derived from poly (oxyethylene) diol. The polymer composition of claim 21 wherein the hard segment H is polyurethane. The polymer composition of claim 22 wherein said polyurethane is derived from 1,4-butanediol. The stable, non-reactive candle according to claim 1, further comprising about 90 to 5% by weight of at least one thermoplastic polymer other than about 10 to 95% by weight of the superabsorbent thermoplastic polymer composition of claim 1. Absorbent thermoplastic polymer composition. The polymer composition of claim 24 wherein the total composition of the polymer composition of claim 1 is from about 30 to 90 weight percent. The polymer composition of claim 25, wherein the total composition of the polymer composition of claim 1 is about 40-75 weight percent. 27. The polymer composition of claim 26, wherein said at least one thermoplastic polymer is a polyolefin. The polymer composition of claim 27 wherein said polyolefin is polypropylene or polyethylene. The polymer composition of claim 24 or 27, wherein the polymer composition of claim 1 comprises about 86 to 98% by weight of a poly (oxyethylene) soft segment having a weight average molecular weight of about 5,000 to 50,000, based on the total weight of the composition (A), (B) based on the total weight of the composition, the melting point is higher than the ambient temperature and lower than the temperature at which decomposition of the composition or the soft segment occurs, is insoluble in water, separated from the soft segment, polyurethane, polyamide, Consisting of about 2 to 14 weight percent hard segments selected from the group consisting of polyesters, polyureas, and mixtures thereof, wherein the soft and hard segments are shared with each other by urethane, amide, ester or secondary urea chains or combinations thereof A polymer composition bonded, wherein the soft segment has a water content of 0.01% by weight or less. The polymer composition of claim 29 wherein the weight average molecular weight of the soft segment is between about 8,000 and 50,000. 30. The polymer composition of claim 29, wherein said hard segment is present in about 3 to 10 weight percent. 30. The polymer composition of claim 29 wherein the soft segment is derived from poly (oxyethylene) diol. 33. The polymer composition of claim 32, wherein said hard segment is polyurethane. The polymer composition of claim 33, wherein the polyurethane is derived from 1,4-butanediol. (A) reacting the first compound and the second compound at a temperature of about 50 to 200 ° C. for a time sufficient to sufficiently complete the reaction, and (B) the product obtained in step (A) is about 80 Reacting for a time sufficient to obtain a melt flow rate less than about 1,000 g per 10 minutes at a temperature of from 200 ° C., wherein the first compound is a bifunctional poly (oxyethylene) having a weight average molecular weight of about 5,000 to 50,000. Wherein the second compound is an aliphatic, cycloaliphatic, aromatic, or heterocyclic compound having two functional groups reactive with the functional group of the first compound, wherein the molar ratio of the second compound to the first compound is about 2 to 100, wherein the third compound is an aliphatic, cycloaliphatic, aromatic, heterocyclic, or polymer compound having two functional groups reacting with the functional group of the second compound, wherein the first compound and the second The reaction product of the mixture (excluding the excess second compound) is about 86-98% by weight of the final composition, the total amount of the third compound and the excess of the second compound is about 2-14% by weight of the final composition, A process for producing the superabsorbent thermoplastic polymer composition of claim 1, wherein the melt flow rate is measured at an orifice diameter of 2.0955 ± 0.0051 mm under a load of 2.16 kg at a temperature of 195 ° C. 36. The method of claim 35, wherein said first compound has a weight average molecular weight of about 8,000 to 30,000. 36. The method of claim 35, wherein the total amount of the third compound and excess second compound is about 3 to 10 weight percent. 36. The method of claim 35, wherein said first compound is poly (oxyethylene) diol. The method of claim 38, wherein said second compound is a diisocyanate. 36. The method of claim 35, wherein said third compound is a monomer. 41. The method of claim 40, wherein the molar ratio of said second compound to said first compound is about 2.5 to 50. 42. The method of claim 41 wherein the molar ratio of the second compound to the first compound is about 2.5 to 26. 41. The method of claim 40, wherein said third compound is a diol. 36. The method of claim 35, wherein said third compound is a polymer. 45. The method of claim 44, wherein the molar ratio of the second compound to the first compound is about 2-5. 36. The method of claim 35, wherein step (A) is performed at about 80 to 150 ° C. 36. The method of claim 35, wherein step (B) is performed at about 90 to 150 ° C. 36. The method of claim 35, wherein step (B) is performed at a melt flow rate of about 30 to 500 g per 10 minutes. 36. The method of claim 35, wherein step (B) is performed at a melt flow rate of about 10 to 30 g per 10 minutes.