WO2001070840A1

WO2001070840A1 - Dispersible polyurethanes

Info

Publication number: WO2001070840A1
Application number: PCT/US2001/004730
Authority: WO
Inventors: Wally Liyuan Chang
Original assignee: Crompton Corporation
Priority date: 2000-03-21
Filing date: 2001-02-14
Publication date: 2001-09-27

Abstract

A solid polyurethane elastomer comprising a solvent-free reaction product of a sulfonate-containing polyester polyol and a polyisocyanate, said sulfonate-containing polyester polyol containing greater than 40 meq of sulfonate groups per hundred grams of polyester is provided.

Description

DISPERSIBLE POLYURETHANES

Field of the Invention

The present invention relates to polyurethane elastomers and, in particular, to a solid polyurethane elastomer that disperses readily and freely in water. The present invention also relates to polyurethane dispersions made from the solid polyurethane elastomer of the present invention, wherein said dispersions have a zero volatile organic content (VOC) .

Background of the Invention

Polymers known as polyurethane include materials that incorporate the carbamate functional group into the polymer. Other functional groups such as esters, ethers, amides, and urea may also be present in polyurethane polymers. Polyurethane polymers are usually produced by the reaction of a polyfunctional isocyanate, most often with hydroxyl - containing reactants. Since the functionality of the hydroxyl -containing reactant can vary, a wide variety of branched or crosslinked polymers can be formed.

Moreover, the hydroxyl -containing reactants cover a wide range of molecular weights and types, including polyester and polyether polyols. The polyfunctional isocyanates can be aromatic, aliphatic, cycloaliphatic or polycyclic in structure and can be used directly as produced, or modified. This flexibility in reactants leads to a wide range of physical properties that allow polyurethanes to play an important role in producing products from synthetic polymers. Polyurethanes find use in many applications, including coatings, paints, adhesives, and the manufacture of fiber and solid articles. Polyurethanes are typically soluble in organic solvents, and exhibit little, if any, solubility in aqueous solvents or in systems in which water and a second water- soluble solvent are employed. Organic solvent -based resin solutions thus have been the vehicle of choice for use in forming coatings and other like polyurethane products. However, many organic solvents commonly used in conjunction with such resins have environmental concerns associated therewith. There has thus been a growing interest in the use of aqueous resin compositions as a means of eliminating toxicity problems associated with organic solvents.

Aqueous polyurethane dispersions are well known and are described, for example, in U.S. Patent No. 3,479,310; U.S. Patent No. 4,746,717; Angew. Chem. , 82, 53(1972); and Progress in Organic Coating, 9, 281(1981). In such literature, a polyurethane prepolymer is dispersed in water to form a fully chain extended NCO-free polyurethane dispersion having internal salt groups. The prior art polyurethane dispersions are typically prepared by: (1) making a water dispersible NCO- terminated prepolymer; (2) dispersing the prepolymer in water; and (3) chain-extending the dispersed prepolymer in water to make a fully reacted and NCO-free polyurethane in water; or, alternatively, by (1) making a NCO- terminated prepolymer; (2) chain-extending the prepolymer in a solvent, e.g., acetone, with a water soluble amine extender; and (3) dispersing (2) in water to make a fully reacted and NCO-free polyurethane in water.

Polyurethane dispersions (PUDs) formed in accordance with the foregoing prior art methods are then sold and shipped to customers for commercial application. Because the PUDs are largely water, much of the cost associated with shipping, handling and storage are attributable to the volume and weight of the water itself. Additionally, because the products are in the form a liquid dispersion, greater concerns exist relative to the type and construction of the containers as well as environmental risks and impact in the event of spills or accidents. Environmental concerns are increased with respect to the latter type of PUDs due to the presence of organic solvents. Finally, although the end-use performance of these PUDs may be adequate, they suffer from relatively poor stability resulting in separation upon long term storage. Consequently, these PUDs must be used within a relatively short period of time, e.g., about six months, from their date of manufacture.

Thus there is need to develop a solid polyurethane which can be dispersed easily and readily in water by the end-user at the site of use. It would also be desirable to produce PUDs from solid polyurethanes, not just polyurethane prepolymers, without the use of organic solvents. Polyurethanes capable of being easily and readily dispersed in water would markedly reduce costs associated with packaging, shipping, handling, storage and use, in the case of VOC containing PUDs. They would also allow for greater flexibility in that the end user could make the dispersion in just the amount needed, thus avoiding concerns with stability and storage. In general, it would allow for a much more cost effective and user friendly product.

Summary of the Invention

One aspect of the present invention relates to solid polyurethane elastomers which readily disperse in water, without the need for organic solvents, and that manifest equivalent, and most often higher loadings than attained heretofore. The polyurethanes of the invention are believed to be the first polyurethanes, as opposed to polyurethane prepolymers, which are soluble in water without the need for solvents. The polyurethanes of the invention are essentially 100% solids, which, for purposes of this application, means there is no or essentially no solvents in the solid polyurethane.

The solid polyurethane elastomer of the present invention comprises a reaction product of a sulfonate-containing polyester polyol and a polyisocyanate, said sulfonate- containing polyester polyol containing greater than 40 miliequivalents (meq) of sulfonate groups per hundred grams of polyester. Other optional components such as comonomers, chain extenders, and silane-containing crosslinking agents may also be present in the solid polyurethane elastomer of the present invention.

A further aspect of the present invention relates to a method of manufacturing the 100% solid polyurethane elastomer aforesaid. In accordance with this aspect of the invention, the solid polyurethane elastomer is produced by the steps of:

(a) providing a sulfonate -containing polyester polyol, said sulfonate- containing polyester polyol containing greater than 40 meq of sulfonate groups per hundred grams of polyester;

(b) mixing said sulfonate-containing polyester polyol with a polyisocyanate to provide a polyurethane reaction mixture, wherein said polyisocyanate is present in said reaction mixture in an amount such that the mole equivalent ratio of NCO to OH of the polyurethane forming reactants is from about 0.5:1 to about 1.5:1, preferably from about 0.8:1 to about 1.2:1 and, most preferably, about 1:1; and

(c) reacting said polyurethane reaction mixture formed in step (b) so as to form a solid polyurethane elastomer that is capable of being completely dispersed in water.

It is noted that step (b) above does not involve the formation of a prepolymer which is thereafter dispersed in water prior to formation of the final polyurethane product. Instead, step (b) forms a substantially uniform mixture of the various components that are used in forming the final polyurethane product which is a solid that can be sold directly to a customer requiring the need of the same. After purchasing the inventive solid polyurethane product, the customer may then disperse the same in water just prior to use.

A still further aspect of the present invention relates to a polyurethane dispersion which comprises the inventive solid polyurethane elastomer completely dispersed in water. Since the inventive polyurethane dispersion does not require any organic solvents to dissolve the same, it contains zero volatile organic content.

For the purpose of this application, the term "zero volatile organic content" means that the polyurethane is free of or essentially free of volatile organic components. Residual or trace levels of volatiles may be present due to incomplete polymerization of the reactants or, if solvents are used at any point of the process, due to incomplete stripping of the volatiles.

Detailed Description of the Invention d) φ co O Ti CO TJ A β O SH β 4-> rH Φ φ TJ φ o

(ti β n 0 -H 4 β β 4-1 4J TJ β β cti o Λ -H Φ φ -. o £ (ti β O o 0 •H CO β Φ β (ti tn Φ

4 N SH A Φ co 4 0 β I ⁾ o MH & Φ o SH Φ rH •

H to n 4 (ti ^■rl g . 0 (ti 4-> SH Φ -\ (ti g 4-> β SH co CO 0 β tn β (ti 44 β (ti Cti σ o . β 4J CO CO Φ > O ^■H (ti <-i (ti

H β Φ O (ti 4-⁾ Φ O SH O β a g g -l υ 4-1 a g tn M-l o CO rH (ti M (ti β tn g rH Φ Λ O β (ti 0 0 0 β 0 β Φ 1 o 4-1 α, o TS 4-> tn M u o o 4-) (ti Λ 0 SH 4-> co Cn SH -H o ,β r-l u β a ⁽ti β Φ 4-1 O u Ti o o CO (ti SH & co co β UH φ 4 4-> o Φ

0 0 β g 0 CO φ o rH in Φ g tT (ti •H -H Λ β 4-) a β 4-1

TJ H o ^■H O rH o 0 1 O 0 o rH τ3 β co Φ β β β

^•H 4-1 4-1 0 TJ a 4-1 r-\ M 4-1 Φ o φ ^•H ^■H σ β Φ ^■rl SH 0 rH 4J TJ co U rH >, β 4-⁾ β 0 MH 4-1 rH >1 (ti o O > Φ TJ υ

0 &> (ti Φ (ti β O rH β β SH O rH a o (ti Φ rH 4 ro

TJ a O & β Ti 4-1 Φ to ,-β Λ Λ o Φ Λ CO CO β U β ^■H β φ g Φ co Λ Φ

Λ 4-⁾ -H Φ O a Λ 4-⁾ (ti 44 -H O Φ (ti T3 0 rH 4 0 rH Φ •rl & o\° SH SH (ti SH (ti co O 4J 4H a ,β ⁽ti 0 & β u 4-1 rH SH 4-1

O -U β O Φ a SH Φ Φ g Φ β ^-i 4J φ g 0 β <-} υ

O cti O CO β Ti Φ a O O CO β 0 β σ Φ SH φ (ti Λ rH Φ ! o CO » rH φ (ti β β 4 4-1 rH SH g rH Λ CO Φ 4-> CO (ti o CO CO a Φ β CO TJ Λ O (ti co co 0 MH (ti Cti (ti g β T3 (ti 1 Φ TJ I

(ti Φ SH 4 ^•H Φ a tJ¹ a SH > UH β β tn 0 r- SH φ tn r-

> Φ φ Φ 4-> rH >1 β Φ 1 T 0 o rH (ti 0 \ 4-⁾ o a CO β β «. co Φ a Λ H o O r-l o g tn rH CO >1 O MH K a 0 Φ m

Φ to β (ti ! 0 SH β Λ o rH 4-1 rH o tn Φ A β φ in

TJ » £ φ rH a >1

^•H a t? o ^•H iti o ,β Λ β co rH β M rH SH ,β 4-> Λ ι en TJ o rH M 0 ^ β SH rH 4 (ti β -rt 4-⁾ Φ CO tn Φ 4-1 (ti _^

> Φ β 0 a tn Φ -H Φ rl 0 β 4-> g 4J 4-) 0 4-1 Φ in o to Φ a Φ β 4J i MH SH _^ Φ g rH (ti Φ φ D β ct β CO MH 4-1 β >

SH β H .β •H (ti φ 4 Φ Φ CO L (ti O 4-) ^-\ i ι o φ o 0 Cti TJ

Pi Q⁾ (ti H J 4-) Φ β β φ β SH a φ φ r-\ a 4J Λ Λ ! β Ό A β a ,β -H ^■H 4J -H O ^<: 0 a o φ rH β g cti rH SH & cti

,β CO. 4-> rH CO co (ti MH 4-1 o CO a Λ o CO O 4H X⁾ o Φ o Φ „_^ υ Φ O Φ Φ 4-1 rH Φ a 4J 4-) a φ u 0 Φ g a g β 4J Φ <£>

•H TJ _^ co co >1 β β Λ φ G¹ υ Φ SH β o O ! (ti g CM ! ^■m 4 ^-i o CO 4-1 Φ o (ti 1+4 SH 4-⁾ rl SH tn 4-1 β (ti t >

& 1 β Φ SH o υ (ti g SH SH O ^■H Φ Φ (ti φ g 4H β CO rH o CO

H H Φ , & a M-l >1 β Γ I a g 4-> A Λ SH ^■H (ti rH MH CO β -H o 4-⁾ 4-1 g Φ O r-l 0 o 4J CO 4-⁾ 4J g Φ i β <-\ Φ r-^ φ o- o TJ a β O tn 4-⁾ A MH in Φ Ό r-H (ti Φ β 4-1 4-1 ^■rl Φ £ β A KΩ

-H (ti o -. υ β (ti σ (ti rH 4-⁾ φ rH Λ 1 -. 3 β Φ Cti CO 4-1 _^

4 φ (ti u Φ -H β Φ SH β 4-1 (ti ^H ^■rl 4-⁾ r- 5 •Ό ^ 4 Φ Φ in β SH > β β o g Φ co β β SH 4J O O rH _^^ . β β A tn

0⁾ Φ o 0 0 •H -l MH O O Φ CO i a r- 0 W O _^ J o (ti (ti υ β .

> ,β TJ -H A •H (ti rH o Φ Φ Λ m 4H Φ Φ CO o -H o φ υ A β ^■H O β o ^■H β (ti 4 4 β SH A (ti H φ «. 4J Φ Λ ^-~ o SH 4-) 4-1 CO M 0

^■H ^■H > (ti β β O PH 4J β SH & 0 A o\° , KΩ SH Φ Φ (ti (ti s rβ 0 tJi TS φ o β β CO a Φ β 4-) SH O ^- U Φ 4J SH - .. g 5 4-> £ M Φ > 0 Φ (ti «. (ti g 0 o >1 ^•H 4 4H (ti β 4-1 φ 4J

∞ β a O 4-1 β A Λ • >1 Λ m >1 CO β rH X Λ β Φ β >1 rH MH β

O Φ (ti ^•H φ 4-) 4 SH rH 4-) O H O ^■H SH 0 ^ o SH o r-i CO a O Φ

CO. Φ 0 Φ υ 4-) Φ Λ rH If) Φ (ti Λ a MH 0 TJ g 4J

Φ e 4-> r-\ ^■H 4-) (ti β H 4-1 cti SH σ (ti κ- 4J 4-) 4J Ό -. cti rH a β (ti co (ti

SH o •H H • β β Φ CO SH Φ Φ -rl H β CO Φ rH >1 β β TJ C a 4-) 4-1 -H β φ 0 Φ 4-1 Φ Φ 4-1 g υ 4-) Φ Φ Λ SH Λ o o r-{ CO TJ 0 φ o co Φ ⁽ti ⁽ti CO m (ti >1 MH (ti Φ β • CO 1 Φ 1 4J A ^■H Q< A •

Φ (ti 4-) H 4-1 Φ rH Φ Φ rH Φ Φ o a 0 V Φ rH 4-) 4J Φ ^-\ CP Φ r-H g SH 4J cn

Λ rH (ti O Φ CO β ,β M O SH SH o O Λ φ SH O O (ti Λ 0 o -H Λ O 0 0 Φ •

Φ £ > TJ < a CO tn a a t? φ (ti g a a β 5 EH a rH Λ EH CO υ fe g

•

SH

Φ g

Pi r-i

O a

Φ

A

4-1

The sulfonate-containing polyester polyol employed in the present invention typically has a Group IA cation, e.g., Na, K, Li, associated therewith. Moreover, the sulfonate- containing polyester polyol is preferably aliphatic substituted.

As used herein, the term "polyester polyol" is meant to include polyesters, polyamides, polyether esters, polyether amides, polyester amides and polyetherester amides terminated at one or both ends with a functional group selected from the group consisting of -NH₂, -OH and -COOH. The preferred polyester polyols useful in the practice of the present invention are generally represented by the formula:

H- [0-R-0]_a[NH-R' -NH]_b[ [X]_c[Y]_d] [C (0) R"C (0) 0- ] _e-H

wherein,

X is represented by the formula -C (0) -R" -C (0) -0-R-O- ;

Y is represented by the formula -C (0) -R" -C (0) -NH-R' -NH- ; each R and each R' , which may be the same or different in each instance, is selected from saturated or unsaturated, linear or branched, aliphatic hydrocarbons having from about 2 to about 12 carbon atoms and linear or branched polyethers of the formula - [ (R" ' -0) _X(R" ' ) ] - in which each R" ' is the same or a different linear or branched, aliphatic hydrocarbon of 2 to 6 carbon atoms and x = 1-100, preferably 10-30; each R" is the same or a different, saturated or unsaturated, linear or branched aliphatic hydrocarbon having from about 2 to about 12 carbon atoms; a = 0 or 1, b = 0 and a+b = 0 or 1; c = 0-70 , d = 0-70 and c+d = 1-70; and e = 0 or 1; provided that at least a portion of the R, R' and/or R" groups in a percentage of the total number of polyester polyol chains contain a sulfonate or sulfonate salt group such that the sulfonated polyester polyol has more than 40 meq. sulfonate per 100 grams of the total polyester polyol component.

In the above representation, is it understood that where mixtures of diols, mixtures of diacids and/or mixtures of diamines are used, the resultant copolymers may be block or random or partially both or the terminal monomer may be different from the equivalent monomer used in preparing the polymer chain. Furthermore, it is understood that the polyester polyol may include a blend of sulfonated polyester polyols and unsulfonated polyester polyols.

The polyester polyol can be prepared by reacting a diacid component with a diol component using conventional techniques, i.e., condensation polymerization, well known to those skilled in the art. The term "diacid" as used herein denotes dicarboxylic acids, anhydrides of dicarboxylic acids, or mixtures thereof .

The dicarboxylic acids that can be used in the present invention include, but are not limited to: aliphatic dicarboxylic acids, alicyclic dicarboxylic acids, aromatic dicarboxylic acids, ethylenically unsaturated alkenyl dicarboxylic acids, or mixtures of two or more of these acids. Examples of some useful dicarboxylic acids include: oxalic, malonic, dimethylmalonic, succinic, glutaric, adipic, trimethyladipic, pimelic, 2 , 2 -dimethylglutaric, azelaic, sebacic, suberic, 1, 3 -cyclopentanedicarboxylic acid, 1,2- cyclohexanedicarboxylic acid, 1, 3 -cyclohexanedicarboxylic acid, 1, 4 -cyclohexanedicarboxylic acid, phtlialic, terphthalic, isophthalic, tetrahydrophthalic, 2,5- norbornanedicarboxylic acid, 1, 4 -naphthalic, diphenic, 4,4'- oxydibenzoic, diglycolic, thiodipropionic, 4,4'- sulfonyldibenzoic and 2 , 5 -napthalene dicarboxylic acids. Anhydrides of any of the foregoing are also contemplated. Suitable diols that can be employed in the present invention include: diethylene glycol, ethylene glycol, 1, 3 -propylene glycol, 1, 2 -propylene glycol, 2 , 2 -diethyl - 1 , 3 -propanediol ,

2 , 2 -dimethyl -1,3 -propanediol , 2 - ethyl - 2 -butyl -1,3 -propanediol , 2-ethyl-2-isobutyl-l, 3 -propanediol , 1, 3 -propanediol, 1,3- butanediol, 1, 4 -butanediol , 1, 5-pentanediol , 1, 6 -hexanediol, 2,2,4- trimethyl -1,6 -hexanediol , 2,4- imethyl -2 -ethylhexane - 1,3 -diol, 1, 2 -cyclohexanediol, 1 , 3 -cyclohexanedimethanol , 1,4- cyclohexanedimethanol , p-xylenediol, and 2 , 2 , 4 , 4 - tetramethyl - 1 , 3 -cyclobutanediol . Polyethylene glycol, polypropylene glycol, copoly (ethylene/propylene) glycol and polybutylene glycol as well as corresponding poly (alkylene ether) glycols such as polyethylene ether) glycol, poly (propylene ether) glycol, copoly (ethylene ether/propylene ether) glycol and poly (butylene ether) glycol may also be employed herein.

A preferred sulfonate -containing polyester polyol that may be used in the present invention is sodium sulfonate-containing poly (butylene adipate) glycol. Illustrative examples of other sulfonate-containing polyester polyols include, but are not limited to: sodium sulfonate -containing poly (ethylene adipate) glycol, sodium sulfonate-containing poly (hexamethylene adipate) glycol, or mixed glycols such as sodium sulfonate - containing poly (hexamethylene/neopentyl adipate) glycol and sodium sulfonate -containing poly (butylene/hexamethylene adipate) glycol. The above mentioned sulfonate- containing polyester polyols are supplied by itco Corporation. In the above mentioned polyester polyols, sodium may be replaced with another Group IA cation.

After formation of the polyester polyol, it is optionally subjected to dehydration under conditions sufficient to

m O m O m o

CN m

diisocyanato-dicyclohexyl -propane- (2,2) ; 1, 4 -diisocyanato- benzene, toluene diisocyanates such as 2 , 4 -diisocyanatotoluene and 2, 6 -diisocyanatotoluene; 4 , 4 ' -diphenylmethane diisocyanate, 4 , 4 ' -diisocyanatodiphenyl -propane- (2 , 2) , p- xylene-diisocyanate, a, a, a ' , a' - tetramethyl-m or p-xylene- diisocyanate. Mixtures of any of the foregoing can also be used.

The mole equivalent ratio of NCO to OH of the polyurethane forming reactants, including the chain extenders, is from about 0.5:1 to about 1.5:1, with about 0.8:1 to about 1.2:1 being more preferred. The most preferred mole equivalent ratio of NCO to OH is about 1:1. It should be understood that the mole or molar equivalent OH is intended to include the mole equivalent of NH functionality should diamines be used in the preparation of the polyester polyol or as a chain extender for the polyurethane.

As stated above, the mixing of the polyester polyol component with the polyisocyanate can optionally be carried out in the presence of a comonomer such as a lower diol containing 2 to 12 carbon atoms, e.g., 1, 4 -butanediol . Typical amounts of such a comonomer are up to 20 wt.% of the total amount of all reactants present in the reaction mixture.

Additionally, chain extenders may be used in the present invention. Satisfactory chain extenders include: diamines such as hydrazine, and alkyl and aromatic polyols, and water especially diols, and alkyl and aromatic diamines and triamines, wherein the alkyl moiety contains a total of 2 to 12 carbon atoms or the aromatic moiety contains 6 to 10 carbon atoms. Other examples of chain extenders include: ethylene diamine, diethylene triamine, 1, 2 -diaminopropane, 1,3- diaminopropane, 1, 4 -diaminobutane, and 3 , 3 , 5 - trimethyl - 5 - aminomethyl cyclohexylamine; and ethylene glycol, 1,2- dihydroxypropane and 1 , 6 -dihydroxyhexane . The chain extenders are typically used in amounts up to about 20 weight % based on the total amount of all reactants present in the reaction mixture.

Another optional component of the present invention is a silane-containing crosslinking agent. Exemplary silane- containing crosslinking agents that may be employed in the present invention include, but are not limited to: N-beta- (aminoethyl) -gamma -aminopropyltrimethoxysilane. Other conventional silane-containing crosslinking agents that are well known to those skilled in the art can also be employed in the present application. The silane-containing crosslinking agents, which can be used in the presence or absence of comonomers and/or chain extenders, are typically used in amounts up to about 20 weight % based on the total weight of all reactants present in the reaction mixture.

The sulfonate-containing polyester polyol or substantially dehydrated polyester polyol is typically added to a conventional reaction vessel containing a stirring means at a temperature of from about 20° to about 90°C. The other components are typically added at room temperature; although they may also be added at an elevated temperature. In the practice of the invention, the mixing step is carried out without a solvent. That is, the solid polyurethane elastomer of the present invention is an solvent-free reaction product of at least a sulfate -containing polyester polyol as hereinbefore described with a polyisocyanate.

The added components are then stirred at room temperature for a time period of about 1 minute or greater. This ensures Φ o Φ tn o

> g ,β (ti O 0

(ti φ S O o O • Λ X

A Φ μ m (ti O Φ (ti g Φ Φ TJ o tn • β ^•H Φ •H (ti Φ A O M K P β (ti cti g 0 SH 0 A •H Φ X O Φ D

5 β φ Φ p SH • o A Φ cti β A Φ • • 0 CM

TJ -H A 0 o o Φ A Φ £ TJ o cti SH TJ TJ Φ (ti O A (ti 0 Φ β o 0 Φ

&, > A Φ cti φ 0 SH g Φ σ Εr< g > Φ H a CJ A o β Φ 0 SH SH Φ φ β β O

SH φ ,β Φ β g X (ti a ! TJ SH g ^-» g -H (ti Φ TS a β 0 o •H ^•H Φ β 0 • SH O O A 0 -H

0 cti μ g a TJ 0 Φ β o ,β 0

Φ a co TJ SH g a O (ti o O Φ o o tn

SH g Φ Φ Φ Φ £ a υ -H Φ Φ Φ SH (ti -H o o o a o O Φ • Φ A υ Φ a SH g o υ A o\° TJ Φ SH 0 Φ υ (ti Φ ^<: tn

Φ SH SH φ o g Φ SH 0 SH A -H

SH -β β TJ (ti S u 0 cti β ti a (ti a O Φ φ

Φ υ υ o (ti •« TJ 0 co SH a co a Λ 3:

, ti X (ti -H β Φ o Φ Φ Φ β

Φ -H O co SH co SH co ti ti Φ TJ a A co • - Φ -. g co Φ φ SH φ A g TS £ ⁽0

(ti a Φ Φ (ti g e Φ A O Φ Φ O -H o (ti o

0 ti SH A o a ,β Φ > β o o o φ cti Φ o tn Φ φ 0 φ Φ

Φ g £ SH co tn g SH -H SH A \

0 SH g (ti cti O TJ O Q> o β Φ t Φ Q o υ O o o -H g o a Φ TJ SH D

Q< (ti (ti SH O SH o Φ Φ . S SH o SH (ti Φ TS Φ a CM g Φ φ (ti (ti -H Φ A Φ TJ Φ u > φ D Φ Φ o A SH O SH a g φ Φ Φ β (ti Φ a φ -H CM TJ Λ (ti SH Φ υ •H a SH SH > >! (ti > cti (ti a tn = υ A

SH co (ti 0 TJ Φ A (ti Λ . g ti φ

TS Φ -H g (ti Φ A Ti Φ TJ Φ Φ φ tn TJ 0

Φ (ti > A tn 0 0 T a Φ Φ TJ Φ A β β β

TJ -H β o u res Φ SH TJ β ~-' cti o φ ti

TS TJ (ti J β β φ β O > A SH cti β O >. φ cti β Φ g Φ o (ti tn φ a Φ TJ g Φ (ti co Φ co TJ SH φ Φ A g Φ a a φ

Φ SH φ φ Φ φ Φ SH φ β o O φ a Λ cti SH Φ

A o SH Λ ,β SH o SH (ti a SH A O a X SH

• φ (ti EH φ β a a a (ti o (ti g cti Φ β TJ Φ

Φ Φ o φ β β Φ a Φ φ O β a β SH A -H H 0 (ti β Φ H Φ ΠJ A A X tn o g φ o β β β a A -Q • A SH 0 SH A -H Λ A υ TJ φ β a .. β

O (ti (ti Φ -H (ti TJ β Φ β Φ ^•H (ti TJ t_n X ^•H ^ SH Φ i o SH (ti g tn A 5 φ A β ^•H rj 4-> & (t

0 β SH g SH MH φ SH υ O 0 TJ Λ > φ

-H H e β β 0 β Φ T) 0 0 SH Φ 0 co o Φ

X (ti TJ . co A β a SH σ 15 φ TJ φ SH cti

00 © -H -H X β O SH co Φ SH (ti Φ O ^ 0 Φ o φ SH β A t; g β •H O Φ 0 U a φ (ti a Φ A SH TJ H tn O

^- β (ti g u g φ CN a o g υ TJ g φ (ti (ti S H φ

SH (ti o Λ Φ Φ O 0 φ SH SH o Φ O SH o Φ SH SH T) A , SH TJ A Φ β Λ = a a Φ Φ co o β o co υ Φ to Φ a β T (ϋ P O . o A J ti 0 0 (ti cti ^•H φ cti σ Φ Φ > D o Φ

SH β Φ β H Λ Λ 0 φ A cti A (ti (ti φ CO A TJ β CM (ti o A o a CO SH β φ 0 (ti (ti SH D Φ S S EH Φ :s g TS SH β EH (ti H υ a

m o O >n o CN CN m

100 as measured by a Labwave 9000 device obtained from CEM Company. The mean particle size of the dispersed solid polyurethane was determined by a particle size analyzer. The cast films were prepared by drawing the polyurethane dispersion on a glass surface, drying the drawn polyurethane dispersion overnight at room temperature, further heating at 120°C for 15 minutes, cooling and then peeling the dried PU films from the glass surface.

Example 1

Preparation of 100% solid polyurethane elastomer

¹denotes a sodium sulfonate -containing poly (butylene adipate) glycol, OH^#104, containing pendant sodium sulfonate group concentration of 100 meq per hundred grams of polyester, supplied by Witco Corporation.

²denotes isophorone diisocyanate.

The polyester polyol was vacuum-dehydrated to a moisture content of less than 0.03% prior to elastomer preparation. The polyol at 80°C, IPDI at 25°C and 1 , 4 -butanediol at 25°C were added into a pint can. The mixture, after one minute of stirring, was poured into a Telfon-coated pan, followed by heating at 100°C for 24 hours in an oven. The solid polyurethane (PU) elastomer was removed from the oven and cut into small pieces.

Preparation of dispersible polyurethane (DPU)

270.0 grams of PU pieces were added to 1530.0 grams of water with a moderate speed agitation at room temperature. After about one hour of mixing, a finely divided and transparent dispersion having a solid content of 14.5% by weight and a mean particle size of 35 nm was obtained. The dispersion was very stable under heat ageing at 52 °C for one month. The physical properties of the film casted from the dispersion showed a tensile strength (as measured by ASTM D412) of 4262 psi, a modulus 100% (as measured by ASTM D412) of 1368 psi, a modulus 200% (as measured by ASTM D412) of 2772 psi, and an elongation (as measured by ASTM D412) of 275%. The adhesion (as measured by ASTM D1876) to poly (vinyl) chloride (PVC) after one day showed a very good peeling strength of 4.8 Kg/cm.

Example 2

Preparation of inventive 100% solid polyurethane elastomer

The polyol was vacuum-dehydrated to a moisture content of less than 0.03% prior to elastomer preparation. The polyol at 80 °C and IPDI at 25 °C were added into a pint can. The mixture, after one minute of stirring, was poured into a Telfon-coated pan, followed by heating at 100 °C for 24 hours in an oven. The solid polyurethane (PU) elastomer was removed from the oven and cut into small pieces.

Preparation of dispersible polyurethane (DPU)

375.0 grams of PU pieces were added to 1125.0 grams of water with a moderate speed agitation at room temperature. After about one hour of mixing, a finely divided and transparent dispersion having a solid content of 24.2% and a mean particle size of 21 nm was obtained. The dispersion was very stable under heat ageing at 52 °C for one month. The physical properties of the casted film showed a tensile strength of 464 psi, a modulus 100% of 341 psi, a modulus 200% of 353 psi, a modulus at 300% (as measured by ASTM D412) of 364 psi, a modulus at 700% (as measured by ASTM D412) of 427 psi, and an elongation of 716%. The adhesion to poly (vinyl) chloride (PVC) after one day showed a very good peeling strength. Example 3

Preparation of 100% solid polyurethane elastomer

³denotes 4 , 4 ' -diphenylmethane diisocyanate

The polyol was vacuum-dehydrated to a moisture content of less than 0.03% prior to elastomer preparation. The polyol at 80 °C and MDI at 25 °C were added into a pint can. The mixture, after one minute of stirring, was poured into a Telfon-coated pan, followed by heating at 100 °C for 24 hours in an oven. The solid polyurethane (PU) elastomer was removed from the oven and cut into small pieces.

Preparation of dispersible polyurethane (DPU)

375.0 grams of PU pieces were added to 1125.0 grams of water with a moderate speed agitation at room temperature. After about one hour of mixing, a finely divided and transparent dispersion having a solid content of 24.9% and a mean particle size of 21 nm was obtained. The dispersion was very stable under heat ageing at 52 °C for one month. The physical properties of the casted film showed a tensile strength of 384 psi, a modulus 100% of 197 psi, a modulus 200% of 222 psi, a modulus at 300% of 229 psi, a modulus at 800% (as measured by _ASTM D412) of 282 psi, and an elongation of 800%. The adhesion to poly (vinyl) chloride (PVC) after one day showed a very good peeling strength of 8.0 Kg/cm. Example 4

Preparation of 100% solid polyurethane elastomer

⁴denotes a sodium sulfonate-containing poly (butylene adipate) glycol, OH^#84, containing pendant sodium sulfonate group concentration of 60 meq per hundred grams of polyester, supplied by Witco.

The polyol was vacuum- dehydrated to a moisture content of less than 0.03% prior to elastomer preparation. The polyol at 80 °C and IPDI at 25 °C were added into a pint can. The mixture, after one minute of stirring, was poured into a Telfon-coated pan, followed by heating at 100 °C for 24 hours in an oven. The solid polyurethane (PU) elastomer was removed from the oven and cut into small pieces.

Preparation of dispersible polyurethane (DPU)

270.0 grams of PU pieces were added to 1530.0 grams of water with a moderate speed agitation at room temperature. After about one hour of mixing, a finely divided and translucent dispersion having a solid content of 14.6% and a mean particle size of 78 nm was obtained. The dispersion was very stable under heat ageing at 52 °C for one month. The adhesion to poly (vinyl) chloride (PVC) after one day showed a very good peeling strength of 3.8 Kg/cm. Example 5

Preparation of 100% solid polyurethane elastomer

⁵denotes dicylcohexylmethane diisocyanate.

The polyol was vacuum- dehydrated to a moisture content of less than 0.03% prior to elastomer preparation. The polyol at 80 °C and H₁₂MDI at 25°C were added into a pint can. The mixture, after one minute of stirring, was poured into a Telfon-coated pan, followed by heating at 100 °C for 24 hours in an oven. The solid polyurethane (PU) elastomer was removed from the oven and cut into small pieces.

Preparation of dispersible polyurethane (DPU)

270.0 grams of PU pieces were added to 1530.0 grams of water with a moderate speed agitation at room temperature. After about one hour of mixing, a finely divided and translucent dispersion having a solid content of 14.5% and a mean particle size of 13 nm was obtained. The dispersion was very stable under heat ageing at 52 °C for one month. The adhesion to poly (vinyl) chloride (PVC) after one day showed a very good peeling strength of 3.8 Kg/cm. Example 6 Preparation of 100% solid polyurethane elastomer

⁶denotes a sodium sulfonate-containing poly (butylene adipate) glycol, 0H^#115 containing pendant sodium sulfonate group concentration of 80 meq per hundred grams of polyester, supplied by Witco.

⁷denotes N-beta- (aminoethyl) - gamma - aminopropyltrimethoxysilane.

The polyol was vacuum- dehydrated to a moisture content of less than 0.03% prior to elastomer preparation. The polyol at

80°C, IPDI at 25°C, 1 , 4 -butanediol and Silquest A-1120 at 25 °C were added into a pint can. The mixture, after one minute of stirring, was poured into a Telfon-coated pan, followed by heating at 100 °C for 24 hours in an oven. The solid polyurethane (PU) elastomer was removed from the oven and cut into small pieces.

Preparation of dispersible polyurethane (DPU)

10.10 grams of PU pieces were added to 40.0 grams of water with a moderate speed agitation at room temperature. After about one hour of mixing, a finely divided and transparent dispersion having a solid content of 20.0% was obtained. The dispersion was very stable under heat ageing at 52 °C for one month.

Example 7

Preparation of 100% solid polyurethane elastomer

denotes a sodium sulfonate-containing poly (hexamethylene adipate) glycol, OH^#112, containing pendant sodium sulfonate group concentration of 80 meq per hundred grams of polyester, supplied by Witco Corporation.

The polyester polyol was vacuum-dehydrated to a moisture content of less than 0.03% prior to elastomer preparation. The polyol at 80 °C, IPDI at 25 °C and 1, 4 -butanediol at 25 °C were added into a pint can. The mixture, after one minute of stirring, was poured into a Telfon-coated pan, followed by heating at 100 °C for 24 hours in an oven. The solid polyurethane (PU) elastomer was removed from the oven and cut into small pieces.

Preparation of dispersible polyurethane (DPU)

10.0 grams of PU pieces were added to 56.7 grams of water with a moderate speed agitation at room temperature. After about one hour of mixing, a finely divided and translucent dispersion having a solid content of 15.0% was obtained. The dispersion was very stable under heat ageing at 52 °C for one month. Example 8

Preparation of 100% solid polyurethane elastomer

⁹ denotes a sodium sulfonate-containing poly (hexamethylene adipate) glycol, OH*112, containing pendant sodium sulfonate group concentration of 60 meq per hundred grams of polyester, supplied by Witco Corporation.

The polyester polyol was vacuum-dehydrated to a moisture content of less than 0.03% prior to elastomer preparation. The polyol at 80 °C and IPDI at 25 °C were added into a pint can. The mixture, after one minute of stirring, was poured into a Telfon-coated pan, followed by heating at 100 °C for 24 hours in an oven. The solid polyurethane (PU) elastomer was removed from the oven and cut into small pieces.

Preparation of dispersible polyurethane (DPU)

10.32 grams of PU pieces were added to 50.0 grams of water with a moderate speed agitation at room temperature. After about one hour of mixing, a finely divided and translucent dispersion having a solid content of 17.0% was obtained. The dispersion was very stable under heat ageing at 52 °C for one month. Example 9

Preparation of 100% solid polyurethane elastomer

10d.enotes a sodium sulfonate-containing poly (hexamethylene adipate) glycol, OH*112, containing pendant sodium sulfonate group concentration of 50 meq per hundred grams of polyester, supplied by Witco Corporation.

Preparation of dispersible polyurethane (DPU)

2.0 grams of PU pieces were added to 50.0 grams of water with a moderate speed agitation at room temperature. After about one hour of mixing, a finely divided and translucent dispersion having a solid content of 3.8% was obtained. The dispersion was very stable under heat ageing at 52 °C for one month. Comparative Example

Preparation of comparative polyurethane elastomer

"denotes a sodium sulfonate-containing poly (hexamethylene adipate) glycol, OH^#112, containing pendant sodium sulfonate group concentration of 40 meq per hundred grams of polyester, supplied by Witco Corporation.

The polyester polyol which is outside the scope of the present invention was vacuum- dehydrated to a moisture content of less than 0.03% prior to elastomer preparation. The polyol at 80 °C and IPDI at 25 °C were added into a pint can. The mixture, after one minute of stirring, was poured into a Telfon-coated pan, followed by heating at 100 °C for 24 hours in an oven. The solid polyurethane (PU) elastomer was removed from the oven and cut into small pieces.

Preparation of comparative dispersible polyurethane (DPU)

11.09 grams of PU pieces were added to 50.0 grams of water with a moderate speed agitation at room temperature. After about eight hours of mixing, the PU pieces were not completely dissolved in water.

While this invention has been particularly shown and described with respect to preferred embodiments thereof, it will be understood by those skilled in the art that the foregoing and other changes in form and detail may be made without departing from the spirit and scope of the present invention. It is therefore intended that the present invention not be limited to the exact forms described and illustrated, but fall within the scope of the appended claims.

Claims

CLAIMSWhat is claimed is:

1. A solid polyurethane elastomer comprising a solvent -free reaction product of a sulfonate-containing polyester polyol and a polyisocyanate, said sulfonate-containing polyester poloyol containing greater than 40 meq of sulfonate groups per hundred grams of polyester.

2. The solid polyurethane elastomer of Claim 1 wherein said sulfonate-containing polyester polyol contains greater than about 50 meq of sulfonate groups per hundred grams of polyester.

3. The solid polyurethane elastomer of Claim 2 wherein said sulfonate-containing polyesters polyol contains from about 50 meq to about 200 meq of sulfonate groups per hundred grams of polyester.

4. The solid polyurethane elastomer of Claim 3 wherein said sulfonate-containing polyester polyol contains from about 60 meq to about 150 meq of sulfonate groups per hundred grams of polyester.

5. The solid polyurethane elastomer of Claim 4 wherein said sulfonate-containing polyester polyol contains from about 80 meq to about 100 meq per hundred grams of polyester.

6. The solid polyurethane elastomer of Claim 1 wherein said sulfonate-containing polyester polyol has a hydroxyl number of from about 10 to about 600.

7. The solid polyurethane elastomer of Claim 1 wherein said sulfonate-containing polyol and said polyisocyanate forming said reaction product have a mole equivalent ratio of NCO: OH of from about 0.5:1 to about 1.5:1.

8. The said polyurethane elastomer Claim 7 wherein said mole equivalent ratio of NCO: OH is from about 0.8:1 to about 1.2:1.

9. The said polyurethane elastomer of Claim 8 wherein said mole equivalent ratio of NCO: OH is about 1:1.

10. The solid polyurethane elastomer of Claim 1 wherein said sulfonate-containing polyester polyol is sodium sulfonate-containing poly (butylene adipate) glycol, sodium sulfonate-containing poly (ethylene adipate) glycol, sodium sulfonate-containing poly (hexamethylene adipate) glycol, sodium sulfonate-containing poly (hexamethylene/neopentyl adipate) glycol or sodium sulfonate-containing poly (butylene/hexamethylene adipate) glycol .

11. The solid polyurethane elastomer of Claim 10 wherein sodium is replaced with another Group IA cation.

12. The solid polyurethane elastomer of Claim 1 wherein the polyisocyanate has the formula Q (NCO) ₂ wherein Q is an aliphatic hydrocarbon group containing from 4 to 12 carbon atoms, a cycloaliphatic hydrocarbon group containing from 6 to 15 carbon atoms or an araliphatic hydrocarbon group containing 7 to 15 carbon atoms.

13. The solid polyurethane elastomer of Claim 12 wherein said polyisocyanate is isophorone diisocyanate. tetramethylene-diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, dodecamethylene- diisocyanate, 1, 4 -diisocyanato-cyclohexane, 1-isocyanato- 3, 3, 5- trimethyl-5-isocyanatomethyl cyclohexane, 4,4'- diisocyanatodicyclohexylmethane, 4 , 4 ' -diisocyanato- dicyclohexyl -propane- (2,2) ; 1, 4 -diisocyanato-benzene, toluene diisocyanates such as 2 , 4 -diisocyanatotoluene and 2, 6 -diisocyanatotoluene; 4,4' -diphenylmethane diisocyanate, 4 , 4 ' -diisocyanatodiphenyl -propane- (2 , 2) , p- xylene-diisocyanate, a, a, a ' , a' - tetramethyl -m or p-xylene- diisocyanate or mixtures of these compounds.

14. The solid polyurethane elastomer of Claim 1 wherein the reaction product further includes at least one additional component, said at least one additional component being selected from the group consisting of comonomers, chain extenders, silane-containing crosslinking agents and mixtures thereof .

15. The solid polyurethane elastomer of Claim 14 wherein said comonomer can be present in amount of up to about 20 weight %.

16. The solid polyurethane elastomer of Claim 15 wherein said comonomer is a diol containing from 2 to 12 carbon atoms.

17. The solid polyurethane elastomer of Claim 14 wherein said chain extender can be present in an amount up to about 20 weight %.

18. The solid polyurethane elastomer of Claim 17 wherein said chain extender includes diamines, alkyl and aromatic polyols or water.

19. The solid polyurethane elastomer of Claim 18 wherein said chain extender is a diamine or a triamine.

20. The solid polyurethane elastomer of Claim 14 wherein said silane-containing crosslinking agent is present in an amount up to about 20 weight %.

21. The solid polyurethane elastomer of Claim 20 wherein said silane-containing crosslinking agent is N-beta- (aminoethyl) - gamma -aminopropyltrimethoxysilane.

22. A method of manufacturing a 100% solid polyurethane elastomer which comprises contacting a sulfonate- containing polyester polyol containing greater than 40 meq of sulfonate groups per hundred grams of polyester with a polyisocyanate under solvent -free conditions effective to form a solid polyurethane elastomer that is capable of being essentially completely dispersed in water, wherein said polyisocyanate in said reaction mixture is present in an amount such the mole equivalent ratio of NCO: OH of the polyurethane forming reactants is from about 0.5:1 to about 1.5:1.

23. The method of Claim 22 wherein said sulfonate-containing polyester polyol contains greater about 50 meq of sulfonate groups per hundred grams of polyester.

24. The method of Claim 23 wherein said sulfonate-containing polyester polyol contains from about 50 meq to about 200 meq of sulfonate groups per hundred grams of polyester.

25. The method of Claim 24 wherein said sulfonate-containing polyester polyol contains from about 60 meq to about 150 meq of sulfonate groups per hundred grams of polyester.

26. The method of Claim 25 wherein said sulfonate-containing polyester polyol contains from about 80 meq to about 100 meq per hundred grams of polyester.

27. The method of Claim 22 wherein said sulfonate-containing polyester polyol has a hydroxyl number of from about 10 to about 600.

28. The method of Claim 22 wherein said sulfonate-containing polyester polyol is sodium sulfonate-containing poly (butylene adipate) glycol, sodium sulfonate- containing poly (ethylene adipate) glycol, sodium sulfonate-containing poly (hexamethylene adipate) glycol, sodium sulfonate-containing poly (hexamethylene/neopentyl adipate) glycol or sodium sulfonate-containing poly (butylene/hexamethylene adipate) glycol.

29. The method of Claim 28 wherein sodium is replaced with another Group IA cation.

30. The method of Claim 22 wherein the polyisocyanate has the formula Q (NCO) ₂ wherein Q is an aliphatic hydrocarbon group containing from 4 to 12 carbon atoms, a cycloaliphatic hydrocarbon group containing from 6 to 15 carbon atoms or an araliphatic hydrocarbon group containing 7 to 15 carbon atoms.

31. The method of Claim 30 wherein said polyisocyanate is isophorone diisocyanate, tetramethylene-diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, dodecamethylene-diisocyanate, 1,4- diisocyanato-cyclohexane, l-isocyanato-3 , 3, 5-trimethyl- 5-isocyanatomethyl cyclohexane, 4,4'- diisocyanatodicyclohexylmethane, 4,4' -diisocyanato- dicyclohexyl -propane- (2,2) ; 1, 4 -diisocyanato-benzene, toluene diisocyanates such as 2 , 4 -diisocyanatotoluene and 2, 6 -diisocyanatotoluene; 4, 4 ' -diphenylmethane diisocyanate, 4 , 4 ' -diisocyanatodiphenyl -propane- (2 , 2) , p- xylene-diisocyanate, a, a, a ' , a' - tetramethyl -m or p-xylene- diisocyanate or mixtures of these compounds.

32. The method of Claim 22 wherein said sulfonate-containing polyester polymer is substantially dehydrated.

33. The method of Claim 32 wherein said substantially dehydrated sulfonate-containing polyester polyol has a moisture content of 0.05 weight % or below.

34. The method of Claim 22 further comprising mixing at least one other component with said sulfonate-containing polyester polyol and said polyisocyanate, said at least one other component being selected from the group consisting of comonomers, chain extenders, silane- containing crosslinking agents and mixtures thereof.

35. The method of Claim 34 wherein said comonomer can be present in amount of up to about 20 weight %.

36. The method of Claim 35 wherein said comonomer is a diol containing from 2 to 12 carbon atoms.

37. The method of Claim 34 wherein said chain extender can be present in an amount up to about 20 weight %.

38. The method of Claim 37 wherein said chain extender includes diamines, alkyl and aromatic polyols or water.

39. The method of Claim 38 wherein said chain extender is a diamine or a triamine.

40. The method of Claim 22 wherein said silane-containing crosslinking agent is present in an amount up to about 20 weight %.

41. The method of Claim 40 wherein said silane-containing crosslinking agent is N-beta- (aminoethyl) -gamma- aminopropyltrimethoxysilane.

42. The method of Claim 22 wherein said reacting step is carried out at a temperature of from about 60 ° to about 130°C for a time period of from about 5 to about 24 hours.

43. The method of Claim 22 wherein the mole equivalent ratio of NCO:OH is from about 0.8:1 to about 1.2:1.

44. The method of Claim 43 wherein the mole equivalent ratio of NCO:OH is about 1:1.

45. A polyurethane dispersion that contains zero volatile organic contents comprising the solid polyurethane elastomer of Claim 1 dispersed in water.

46. The polyurethane dispersion of Claim 45 further comprising at least one additional component, said at least one additional component being selected from the group consisting of comonomers, chain extenders, silane- containing crosslinking agent and mixtures thereof.