CA2204274A1 - Stain resistant polyurethanes - Google Patents
Stain resistant polyurethanesInfo
- Publication number
- CA2204274A1 CA2204274A1 CA 2204274 CA2204274A CA2204274A1 CA 2204274 A1 CA2204274 A1 CA 2204274A1 CA 2204274 CA2204274 CA 2204274 CA 2204274 A CA2204274 A CA 2204274A CA 2204274 A1 CA2204274 A1 CA 2204274A1
- Authority
- CA
- Canada
- Prior art keywords
- stain resistant
- polyurethane
- resistant polyurethane
- mixtures
- group
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/69—Polymers of conjugated dienes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/36—Hydroxylated esters of higher fatty acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2101/00—Manufacture of cellular products
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
- Paints Or Removers (AREA)
Abstract
The present invention relates to polyurethanes and more particularly, stain resistant polyurethanes which are hydrophobic in nature which are useful for various commercial applications. An added feature of the present invention is that the stain resistant polyurethanes can be tailored to a desired hardness.
Description
- CA 02204274 1997-0~-01 STAIN RESISTANT POLYURETHANES
FIELD OF THE INVENTION
The ~,resen~ invention relates to stain ,~s;sla,ll polyu,ell,ai,es and more particularly to stain resisla"l polyu~tl~ane-based elaslomers foams and coatings.
BACKGROUND OF THE INVENTION
Polyurethanes have become increasinyly useful for a wide range of commercial 5 applications. Such "~alerials are generally cl,a~a~terized by outstanding mechanical properties and resis~a~Ice to dey,~Jalioll c~used by heat oxidation ozone attack or ultraviolet radiation. Polyurethanes are often less expensive to process than rubber and thermo~.laslics thus making them highly desirable for use in industry.
While many polyurelhane based compositions are known a perceived 10 drawback of the known ll,alerials lies in their susce~ libility to staining i.e. discoloration due to the absorption of water-soluble ",alerials. For exampl~ urethane-based elaslo,ners employed as protective and/or decorali~e edging for furniture and cou"lel lops tend to beco, l~e .'i~ red over time when fluids such as coffee and tea among others have been spilled lhereG". Thus there is a need for urethane-based 15 ela~lul "er~ and foams which have outstanding "~ecl ,a" c ~I properties are resi~lal ,ce to deyladalion and are stain ~esi~la"l.
CA 02204274 1997-0~-01 SUMMARY OF THE INVENTION
Accordir,y to a preferred embodiment, the present invention relates to stain resistant polyurall~a"es formed as the reaction product of a mixture, cor~ ,isi,lg:
a) an organic isocyanate;
b) a hydrophobic co,n~.ound selected from the group co"si~li"~ of hydrophobic compounds having at least two isocyanate reactive hydrogens, hy-llupllobic long chain hydrocarbons and mixtures thereof;
c) optionally, when b) includes less than sufficient isocyanate reactive hydrogens to form a polyurethane, at least one second compound which is sufficiently reactive with said organic isocyanate to form a polyurethane; and d) o~Jliol,ally, one or more components selected from the group consisting of blowing agents, cross-linkers, catalysts, anti-oxidanls, UV-stabilizers, flame retardants, water scavengers, ~.laslici~ers, fillers, coloring agents and mixtures thereof.
Under an alternative preferred embodiment, the invention relates to stain resistant polyurethane formed as the reaction product of a mixture comprising:
a) an oryanic isocyanate;
b) at least one hydrophobic compound capable of reacting with said or~anc isocyanate to form a polyurethane, said compound having at least two isocyanate reactive hydrogens; and CA 02204274 1997-0~-01 c) optionally, one or more components selected from the group consisli, ,9 of blowing agents, cross-linkers, catalysts, anti-oxidal,ls, UV-stabilizers, flame ~lar~la~,ls, water scavenyer~
~,laslici~ers, fillers, CO'Glilly agents and mixtures thereof.
The stain lesislai1l polyul~ll,a"es can be used for a number of different products including but not limited to furniture and countertop edging, appliance handles, shelving edges, and decorative moldings, for exa",,,le. In general, it is conlem~Jlaled that the poly~ hane compositions of the present invention can be employed under any a~ tion where stain res;sla"ce is a consiJeration.
In addition to stain res;sla"l u-e~l,ane com~.osilions, the present invention also relates to the formation of prepolymers which are storage stable and readily useful for the formation of various polyu.~lha"e products.
An unique aspect of the stain resisla"t ~ t,al,e compositions of the present invention is that they may be l"odlfieJ such that the resulting product has the desired hardness, e.g., ranging from Shore A to Shore D upon curing.
The present invention also relates to the method of prepa~ing both the stain resistant polyurethanes and prepolymers of the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
The stain I esi~lanl polyur~tl ,~"es of the pres6l ,l invention can be utilized to form a variety of products including but not limited to furniture and cou"~ello~ edging, appliance handles, shelving edges, and uleco,ali~e moldings, among others. In general, it is co"~em~ldled that the ~rere~l~d ~-~etl ,a"es of the present invention can CA 02204274 1997-0~-01 be employed in the production of various products where stain ~esisla,lce is a particular co"cer~ ,. As used herein, the phrase "stain resislalll polyurell ,anes" should be understood to include both filled and unfilled polyurethane based co~ osilions including, generally, ela:,lomers, foams and coatings.
Hydrophobic compounds having at least two isocyanate reactive hydrogens which are considered useful, without limitation, in accordance with the teachings of the present invention include polyols having a carbon chain length of at least about C10 or higher. rleter,ed examples of such polyols include castor oil, castor-oil based or derived compounds, polybutadiene and saturated hydrocarbon polyols. By saturatedhydrocarbon polyols, it is meant that the polyols have no double bonds in their molecular structure.
Of the aforementioned, castor oils are considered to be particularly preferred.
While numerous commercially available castor oil products are useful in accordance with the teachings of the present invention, one known as DB Oil which is available from CasChem, Inc., of Bayonne, NJ, has been found to be particularly useful. In this regard, it has been observed that castor oil not only appea!s to enhance the hydrophobicity of the polyurethane compositions, i.e. resisl~"ce to water soluble staining materials such as coffee and tea, for example, but also enhances the fire retardancy characteristics of the resulting product due to char ~o~ aliu~l caused by the relatively long hydrocarbon chain length.
Under certain applications, the hydrophobic compound employed optionally or alternatively will include or employ compounds which do not have at least two isocyanate-reactive hydrogens, such compounds being referred to herein as long chain hydrocarbons. Examples of such long chain hydrocarbons include, for example, CA 02204274 1997-0~-01 and without inle"di"g to be limiting ~a,affi"s olefins vegetable and animal oils and modifications of such Illalelials. Particularly useful of the so-called long chain hydrocarbons are hydloca,bo" oils and mono-flJ"ctiol,al long c,hain hydrocarbon compounds such as alcohols and/or fatty (long chain hy~ irLon) acids and fine 5 powders.
By long chain hydlocarL.o"s it Ts meant that the hydrocal~oI~s will have a carbon chain length of at least C,0 more ~,, e~e, ~bly of at least C,2 still more preferably at least C,~ and still more prererauly will have a carbon chain length of C,~ or y, ealer.
In general the longer the hydloca, bon chain length the more hydrophobic in nature 10 the hydrocarbon will be.
It should be noted that the amount of hyd,opl)obic compound employed will depend in large part on the clesired application for the end product. For example while high quantities of castor oil will generally give rise to products having the best stain r~sislal)l cllaréct~ris~ics the resulting polyurethane-based product may be too 15 soft for certain applicdliol ,s. By the same token dilution of the castor oil or other such hydrophobiccompoundwithlesshyd~ 1,ol cpolyols chainextenders cross-linkers and other additives will give rise to products which are typically less stain resislanl.
Thus the amount of hydrophobic co"1pound employed in the stain-l esislanl polyurethane con~.osition will be determinative upon a large number of factors 20 including the end use of the product. At a minimum the preferred stain res;slal, polyu, ell ,anes of the ~.rese, ll invention will generally include at least about 10.0 weight percent of a hydrophobic com,oound based on the total weight of composition prior to reaction with the orga,.i~ isocyanate.
CA 02204274 1997-0~-01 In addition to the hydrophobic compound, the polyurethane-based compositions of the p, esenl invention can oplio~ ,ally employ one or more conventional additive components at art-di-.,lQse-3 levels selected from the group ~;o"si~ ,y of chain extenders, cross-linkers, catalysts, anti-oxidants, UV-stabilizers, flame retardants, 5 water sca\~enyer~ fillers, coloring agents and mixtures thereof.
Suitable examples of chain e~lenders useful in the stain ,esi~tanl urethanes of the present invention include polyoxyalkylene polyether polyols which are the polymerization product of an alkylene oxide with a polyhydric alcohol. Suitable polyhydric alcohols include those di3~,10sed above for use in the pre,)alalion of the 10 hydroxy-ter")i"aled polyesters. Any suitable alkylene oxide and mixtures thereof may be used such as ethylene oxide, propylene oxide, butylene oxide, amylene oxide, and mixtures of these oxides, p,eterably propylene oxide. Polyoxypropylene polyether polyols are more hydrophobic than their ethylene oxide counterparts. The polyalkylene polyether polyols may be prepared from other starting materials such as 15 tetrahydrofuran and alkylene oxide-tetrahydrofuran mixtures; epihalohydrins such as epichlorohydrin; as well as aralkylene oxides such as styrene oxide. The polyalkylene polyether polyols may have either primary or secondary hydroxyl groups. Included among the polyether polyols are polyoxyethylene glycol, polyoxypropylene glycol, polyoxybutylene glycol, polytel~",ell~ylene glycol, block copolymers, for example, 20 combinations of polyoxypropylene and polyoxyethylene glycols, poly-1,2-oxybutylene and polyoxyethylene glycols, poly-1,4 tel, amell ,ylene and polyoxyethylene glycols, and copolymer glycols prepared from blends or addition of two or more alkylene oxides.
The polyalkylene polyether polyols may be prepared by any known process such as, for example, the process ~Jisclosed in the Encyclopedla of Chemical Technology, Vol.
CA 02204274 1997-0~-01 7, pp. 257-262, published by l"lt,r~cle.,ce Publishers, Inc. (1951) or in U.S. Pat. No.
1,922,459; all of which are ex~ressly inc~l,uor~led herein by reference. Extensive lists of suitable polyol may be found in columns 2 and 3 of U.S. Pat. No. 3,652,639;
columns 2-6 of U.S. Pat. No. 4,421,872; and columns ~6 of U.S. Pat. No. 4,310,632, these three pdlellls being hereby incor~ol~led by let~re,)ce. The polyether polyols employed will generally have prer~"acJ molecular wsi~llls from 500 to 10,000, more ~rereraLly from 750 to 8000, and still more ~,efelal,ly from 1000 to 6000.
While polyester polyols are generally less preter~ed than polyether polyols in that they tend to be less soluble than polyether polyols, polyester polyols may also be employed. Suitable hydroxy-terminated polyesters include those obtained, for exar"p'e, from polycarboxylic acids and polyhydric alcohols. A suitable polycarboxylic acid may be used such as oxalic acid",~alon ~ acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassylic acid, thapsic acid, maleic acid, fumaric acid, gl-,laco"ic acid, a-hydromuconic acid, B-hydromuconic acid, a-butyl-a-ethyl-glutaric acid, a,B-diethylsuccinic acid, isophtalic acid, therphthalic acid, phthalic acid, hemimellitic acid, and 1,4-cyclohexanedicarboxylic acid. Mixtures may also be employed. A suitable polyhydric alcohol may be used such as ethylene glycol, propylene glycol, l, i"lelhylene glycol, 1,2-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 2-methyl-1,3-prG~ a"ediol, hydroquinone, resorcinol glycerol, glycerine,1,1,1 -trimethylol-propa"e,1,1,1 -trimethylolethane,1,2,6-hexanetriol, a-methyl glucoside, sucrose, and sorbilol. Again, mixtures of such alcohols may be employed. Also included within the term "polyhydric alcohol" as used herein are compounds derived from phenol such as 2,2-bis(4-hydroxyphenyl)-~ro~ a"e, commonly known as Bisphenol A. The polyester polyols, if employed, will preferably - CA 02204274 1997-0~-01 have molecular wei~hls from 500 to 10,000, more preferably from 750 to 8000, and still more ~.rere,ably from 1000 to 6000.
r~erer,ed chain ex~er,-Je,~ will have molecular w~i,Jhl~ of from 50 to 400 generally and preferably from 60 to 300. In order to obtain the ~esi, ~ hardness of 5 the polyu~ell,a"es, the amount of hydrophobic component having at least two isocyanate reactive hydl ~gel Is to chain exler,~Jer~ can be varied within a relatively wide molecular ratio, the hardness typically ir,c~asi"g with i"creasin~~ cor,lent of chain extenders. For example, less rigid poly~"~ll ,a"es (having a Shore A hardness of less than 95, ,I.reteral~ly from 75 to 85 after curing), will generally have molar ratios of hydrophobic component to chain extenders of from 10:1 to 20:1, preferably from 8:1 to 15:1. For more rigid polyurethanes, ffor example, those having a Shore D hardness of more than 50, preferably 60 to 80 Shore D, after curing) the molar ratios of hydlo,ulloL~ic component to chain extenders are from 2:1 to 3:1, ~r~reral~ly 4:1 to 5:1.
Suitable examples of cross-linkers useful in accor~ance with the practice of the 15 present invention include, without lirllildlioll, the alkylene oxide additio" products of trimethylolpropane, glycerine, sucrose, sorbitol, propylene glycol, dipropylene glycol, pentaerythritol, and 2,2-bis (4-hydroxyphenyl)-propane and blends thereof having equivalent weights of from 31-340.
Catalysts may also be employed in accorda,lce with the teachings of the 20 ,uresenl invention. The catalyst generally accelerate the , eactio" of the active hydrogen containing compounds (if ~resenl) with the organic polyisocya"ales.
Examples of useful catalyst~ include organic mctal compounds"~re~eral~ly organic tin compounds such as tin (Il) salts of o,gan c car~oxylic acids, e.g., tin(ll) acelale, tin(ll) octoate, tin(ll) ethyll,exoale and tin(ll) laurate, as well as the dialkyline(lV) salts of CA 02204274 1997-0~-01 oryan s carboxylic acids, e.g., dibutyltin ~liacet~le, dibutyltin maleate and dioctylin diaceldle. Specific exar~ 'es of oryan.c tin co,l"~ounds which are useful include, without limitation, dibutyltin dilaureate, dibutyltin sulfide and tin me,rca~ta"s, among others. Other organic metal co")~,ounds which are c~"sidered useful include zinc5 co~"pounds such as zinc o-,toale with bismuth col"~,ounds. Organol"elallic com,uounds useful as catalysts are generally disclosed in U.S. Pat. No. 2,846,408, herein i,,cor,uoraled by le~rence. The organic metal compounds are used alone or~re~r~L~ly in combination with strong basic amines. Examples include an ,idines such as 2,3-dimelhyl-3,4,5,6-tetrahydropyrimidine, tertiary amines such as triethylamine, 10 tributylamine, dimethylbenzylamine, N-methylmorpholine, N-ethylmorpholine, N-cyclohexylmorpholine, N,N,N,',N'-tetramethylethylenediamine, N,N,N',N'-tetramethylbutanedia" ,i"e,pentamethyldiethylenl, ia" line,tel~ a" ~ell ~yldiaminoethylester bis(dimethylaminopropyl) urea, dimethylpiperazine, 1,2-dimethylimidazle, 1-~a-bicyclo[3.3.0]octane and ,ureferaL,ly 1,4-dia~abi~yclo[2.2.2]octane, 1,8 15 dia~aL ~clo 5,4,0 undecene 7 and alkanola",i"e compounds such as lliell ~anolamine, Il ;;SO~JI o~ a"olamine, N-methyl-and N-ethyldiuthariola" ~ine and dimethyletha"ola" ,ine.
Suitable catalysts also includetris(dialkylamino)-s-hexahyd, ol, i~i"es, es,uecially tris(N,N-di"1elhylaminopropyl)-s-hexahy.ll ol, ia~;"e, tetraalkyla" " ,)on I m hydroxides such as tel, a" ,ell ,yla~" "onium dydl o.~icle, alkali hy.ll oxi.les such as sodium hydroxide 20 and alkali alcoholates such as sodium methylate and ,uolassium isopropylate as well as alkali salts of long-chain fatty acids with 10 to 20 carbons and optionally OH side groups. An effective amount of catalyst to l,ro" ~ote the reaction of isocyanate groups with the polyol, or with other isocyanate groups in the case of isocyanurates, is employed. 0.001 to 5 wt ,~erce"l, catalyst or catalyst com~-. ,alio" based on the CA 02204274 1997-0~-01 weight of polyol composition is preferred. Mixtures of amine, tin, and bismuth catalysts may be used.
Anti-oxida, lls may also be employed if necessary to retard the oAidalio, I of the reacted urethane. Fl e(e, l e~ among the numerous commercially available anti-o,~i.la, lls 5 which are co"sitJered useful are: Irganox, available from Ciba-Geigy Corp., of Greensboro, N.C.; and Cyanox, available from Cytec, Industries Inc., of Havre De Grace, MD; both are particularly useful. Mixtures of anti-oxidants may also be employed.
UV stabilizers which can be employed include, without lirllilalioll, 10 benzophe~ lo"es, L.e, I~ull i~oles, substituted acrylonitriles, phenol-nickel complexes, and mixtures thereof. Exan".les of commercially available UV-stabilizers include Tinuvin, available from Ciba-Geigy Corp., of Greensboro; N.C., and Uvinul, available from BASF Cor,~or~liol1 of Mt. Olive, N.J.
It may be cJesi,aLI~ in certain applications to employ one or more flame-15 retardants. For example, certain flame retardants which are reactive with isocyanateswhich may be employed include phosphor-based products such as Fyrol 6 and Fyrol 51, available from Akzo Chemicals, Inc., of Chicago, IL; and Vircol 82 available from Mûbil Chemical Co., of Nûrwalk, CT. Additionally, certain halogen based flame relarcJai,ls, such as FR-522 and Saytex FR-1138 (which are dibrûmopentyl giycû
20 based products available from AmeriBrom, Inc., and Ethyl Corporation of Richmond, VA, respectively), may be employed. Still other flame retardants which are generally non-reactive to the isocya"ales may be employed. Plerer~ed are the reactive FR
series flame retardants since they are homogeneous in nature, i.e. they do not m iyl ale to the surface of the polyurethanes. Mixtures may also be employed.
CA 02204274 1997-0~-01 For non-foaming applicdlio"s, water scave"yers~ otherwise r~rerra~l to herein as water absorbing agents, may be employed so that any water co"lai"ed in the composition is prevented from reacting with the isocyanales which in,turn prevents the ror",alioi) of CO2 and this limits or preclu~les foaming. Molecular sieves which are 5 generally silica based have proven useful in this regard. Ad~ ally, Zolidine, which is a liquid oY~olidine available from Angus Cl,err,ic~'s, Inc. of Buffalo Grove, IL, is co,1lei))plaled as being useful.
For d~ ~!,s~tions wherein the stain r~sisla,n polyurethanes of the present invention are foams, blowing agents are typically required. Suitable blowing agents 10 are those of the reactive type such as water, formic acid or tertiary alcohols; physically active blowing agents having a boiling point below 28 degrees C. and which vaporize at or below the len,,ueral-lre of the foaming mass comprising chlorofluorocarbons having at least one hydrogen (soft CFC's) and volatile hydrocarbons, or mixtures thereof. Soft CFC's useful herein are those having an ozone ~le,~lE~ion potential of less than 0.2 including 1,1,1 trichlJroelha"e, 1,1,1 ,2-tel, dtlouoroetl ,a"e, HCFC-1 41b, HCFC-22, HCFC-123, and HCFC-142b. Volatile hyd~ocdrbol)s include butane, pentane, hexane, heptane, cyclopentane, cyclohexane, pentene, and heptene.
A surface-active subsla,)ce is generally necessa,y for production of high grade polyurethane foam according to the presenl invention, since in the absence of same, 20 the foams may collapse. Examples of surface active suL,slal ,ces include compounds that support the homoye"i~dlion of the slailil,y materials and are o~liol1ally also suitable for regulating the cell structure. An e~lensive list of surface-active subslal ,ces useful in accolda,1ce with the teachings of the present invention are disclosed in U.S.
CA 02204274 1997-0~-01 Patent No. 5,045,885 to Sampara et al., which is hereby expressly incorporated by reference.
Other conve"liol1al additives including, but not limited to"~)laslici~ers, reactive and non-reactive silicone oils, fillers and coloring agents including dyes and pi~me, lls 5 may also be employed, at conventional or art-disclosed levels. Included in the class of additive ",alerials generally referred to herein as fillers are fibrous and particulate materials, non-polar polymeric "l~ler;als and inorganic anti-block agents. Eka",ples of such l)~ale,ials include glass and carbon fibers, silicas, calcium carbonate, clay, mica, talc, carbon black, particulate graphite and metallic flakes, among others.
10To gain a further understanding of the various optional components which can be employed, reference can be made to various technical publ ~alions including, for example, the article by J.H. Saunders and K.C. Frisch, High Polymers, Volume XVI, Polyurethane, Parts 1 and 2 (I"ler~ ce Publishers 1962 and 1964), Ku"stoslor~-Handbuch, Volume 7, Polyu,ell,a,)e 1st and 2nd Editions (Carl Hanser Verlag, 1966 15and 1994) or DE-A 29 01 774, which are hereby expressly incorporated by reference.
As alluded to previously, the hydrophobic components of the present invention are particularly useful when blended with certain isocyanate compounds. Among the numerous isocyal ~ales, otherwise refer, ed to herein as organic isocyaoales, which are considered useful are those including a, o" ,alic, aliphatic, and cycloaliphatic 20 polyisocya, lales and combinations thereof. Examples of such isocyanates may found at columns 8 and 9 of U.S. Pat. No. 4,690,956, herein incorporated by reference.
Represe"k,li,/e polyisocy~nates are the diisocyanates such as m-phenylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, mixtures of 2,4- and 2,6-toluene diisocyanate, he,car,)ell)ylene diisocyanate, tel,~"~lhylene diisocyanate, CA 02204274 1997-0~-01 cyclohexane-1,4 diisocyanate, hexahydrotoluene diisocyanate (and isomers), r ,a~ hlhalene-1 ,~diisocyanate, 1 -l l ,ell ,oxyphenyl-2,Wiisocyanate, 4,4'-diphenyl~, letl ,al ,e diisocyanate, 4,4'-biphenylenediisocyanate, 3,3'-dimethoxy-4,4'-biphenyldiisocyanate, 3,3'-diimethyl-4,4'-biphenyl diisocyanate and 3,3'-5 dimethyldiphenylmethane-4,4'-diisocyanate; the triisocyanates such as 4,4',4"-t, i~l ,enyll nelhal ,e triisocyanate, and toluene 2,4,6-triisocyanate; and the tel,ahocyai)ales such as 4,4'-dimethyldiphenylmelharle-2,2'-5,5'-lelraisocyanate and polymeric polyisocyanates such as polymethylene polyphenylene polyisocyanate, and mixtures thereof.
For preparation of the stain les;sla, ll polyurethanes of the present invention, the ratio of the equivalent weight number of NCO groups of the isocyanate (a) to the sum of hydroxyl groups of con,,~.o"ent (b) is from 300:100 to 95:100, preferably 105:100 to 100:100. By equivalent weight number, it is meant the weight of an element that comL)i"es chemically with 8 grams of oxygen or its equivalent. For example, since 8 15 grams of oxygen combines with 1.008 grams of hydrogen, the latter is considered equivalent to 8 grams of oxygen.
Suitable methods of preparing the stain lesisla~,l polyurethanes of the present invention include adding the hydrophobic compound to a vessel and heating to appro,(imalely 140-F. Therearler, each of the other compol)ents including one or 20 more compounds selected from the group co"sisling of chain e~le"de,s, cross-linkers, catalysts, anti-oxida"ls, UV-sldL.ili~ers, flame lelarda,lts, ~laslici~er~, fillers, coloring agents and mixtures thereof, exce~.li"y any water scavengers are charged to the mixing vessel and blended with the hydrophobic compound. Upon blending, the water level of the composition is typically measured to determine whether the water ~ CA 02204274 1997-0~-01 level is below a,u~roximalely 0.03 wt.% based on the total weight of the colll~osiliGI).
If the water is above that level, the composition is heated further under vacuum to drive off water; however, H the water level is at or below this level, a water scavenger is added to the mixture with blending. Upon thoroughly l,le"di. ,g the components, a 5 resinous material results. Tl ,eredrler, the resin is blended with the oryal, c isocyanate to form the stain les;sla"t polyurethane of the prese,lt invention as set forth by way of non-limiting examples below.
Other conver,lional or art-disclosed methods may also be employed to prepare the resins and prepolymers of the ~resenl invention.
A stain resisl~"l polyurethane in accorda, Ice with the teachings of the present invention was prepared by first charging 85.7 wt.% of DB oil to a clean, dry blend tank equipped with a dry air or nitrogen purge. The DB oil was heated to 140-F and thereafter 10.0 wt.% FR-522, 0.5 wt.% Tinuvin 328, 0.5 wt.% Tinuvin T765, 0.5 wt. %
Irganox 245, and 0.3 wt.% Fomrez UL 28 were slowly added with mixing to the DB oil and the composition was mixed for one hour. The composition was continuously mixed until the water level was below about 0.03 wt.% at which time 2.5 wt.% of an A-3 molecular sieve was added and the composition was mixed for a~ ~roxi" ,ately one half hour to form the desired resin, which was liquid and had a viscosily of a~.~Jro,~imately 700 cps and a density of 1.0 g/cc or 8.2 Ibs/gal. at 77-F.
One hundred parts by weight of the resin were blended with 45 parts by weight of dicyclohexylmethane diisocyanate having a viscosity of approximately 30 cps and a density of 1.07 g/cc or 8.9 Ibs./gal at 77-FF and molded. The mold was ~"ai~ ,la;, ~ed CA 02204274 1997-0~-01 at a le""~erature of between about 130-150-F. As a result of blending the resin and isocyanate loyell~er and molding the same an urell,a"e based elaslo~oer product which is aliphatic light stable and sufficiently flame retardant at a thickness of 0.5 inch to attain a UL94VO rating was obtained. The resulting polyuIell)a"e product had a I,ard"ess as measured by ASTM D2240 of 75 tensile sl,e"ylh of 1300 PSI accordingto ASTM D412 elo"y~lio" at break of 200 and Graves Tear accordi. ,9 to ASTM D1004 of 90 Ibs/in.
A second stain tesisla"~ polyu,~ll,a,)e was prepared by charyi,,y 39.15 wt.%
DB Oil to a similar blend tank and adding 17.5 wt.% dipropylene glycol with mixing.
The mixture was heated to 140-F and ll,ere~rler 0.2 wt.% Fomrez UL 28 0.5 wt.%
Tinuvin 328 0.5 wt.% Tinuvin T765 0.5 wt. % Irganox 245 and 39.15 wt.% Pluracol 726 were added and the composition mixed until the water level was below about 0.03 wt.% at which time 2.5 wt.% of an A-3 molecular sieve were added. The resulting composition was mixed for appro~i,nalely one half hour with the resulting liquid resin having with 2.5 wt.% A-3 molecular sieve being added after the water level was below a viscosity of approximately 700 cps and a density of 0.99 g/cc or 8.2 Ibs/gal. at 77-F.
One hundred parts by weight of the resin were then blended with 58 parts by weight of dicyclohexyll l lell Idl ,e diisocyanate having a v;scu~ity of a~,~., u~i" Idlely 30 cps and a density of 1.07 g/cc or 8.9 Ibs./gal at 77-F and molded. The mold was maintained at a temperalure of 6~l~ccn about 130-150-F. The resulting polyurethane product had a hardness as measured by ASTM D2240 of apt., oxi" ,a~ely 80-85 tensile CA 02204274 1997-0~-01 strength of 2100 PSI according to ASTM D412, elongation at break of 230 and Graves Tear according to ASTM D1004 of 90 Ibs/in.
A third polyurethane composition was prepared for purposes of con1pa, i~ lg the 5 stain lesi~la"l cl,alaote,i~lics of a currently employed commercial product versus those provided in accordance with the leachi,~gs of the present invention. This third example was pre~,ared by charging 89.5 parts by weight Pluracol 538 polyol commercially available from BASF Corporation to a blending tank at 140-F along with 9.0 wt.% diethylene glycol. The mixture was blended under vacuum and nitrogen purging at a temperalure of between 180 to 212-F until the water level was below 0.05%. Thereafter, the temperature was adjusted to between 120 to 140-F and 0.5 wt.% of Tinuvin 328 was added with the mixing. The mixture was blended for approximately 25 minutes and cooled to between 70 to 100-F at which time 0.5 wt.%
Tinuvin 765 and 0.5 wt.% Fomrez UL~32 catalyst were added and mixed for one half hour. The resulting resin which was liquid had a viscosily of 775 cps and a density of 1.03 g/cc or 8.6 Ibs/gal at 77~F.
One hundred parts by weight of the resin were mixed with 43.5 parts by weight of polymethylene polyphenylene diisocyanate, a MDI-prepolymer, having an NCO %
of 23, a viscosity of a~"~, oxi" ,ately 700 cps and a density of 1.2 g/cc or 10 Ibs/gal at 77~F. The mold was maintained at a temperature of about 130~F. The resulting polyurethane product had a hardness as measured by ASTM D2240 of approximately Shore 65 A, tensile sllellylll of 630 PSI according to ASTM D412, elongation at break of 190 and Graves Tear according to ASTM D1004 of 30 Ibs/in.
- CA 02204274 1997-0~-01 To analyze for stain resisla"ce, one saio~JlE of each of the Exam,u'Es 1, ll and lll was immersed in the same coffee solution and allowed to remain for a period of twenty four hours. Theredrler, each sample was removed and wiped lightly with a clean moist towel. Upon ViGW;n9 the sam~,!es, the sa",~les for~,1e.1 according to 5 Examples I and ll showed virtually no signs of staining; in co"l,asl, the sample of Example lll was clearly discolored.
As alluded to earlier, in addition to their use for prepa,i"y stain resi jldn polyurethanes, the hyd,o,~l,obic col"pound of the ~resent invention can also be employed in prepolymers. In this regard, the hycl~opl,obic resins, such as those 10 described in Exalllpl~s I and/or ll above, are blended with the isocyal)ates and heated at the desired temperature while mixing. The NCO CGnlenl of the blend is monitored during the reaction until the target % of NCO is oblai. ,ed at which time the coI"~osilion is cooled to alllb'e.1l, i.e. room temperature. The prepolymers formed in accordance with the teachings of the ,vreseill invention will generally have between approximately 1.0 to 32.0 % NCO.
While it will be apparent that the preferred embodiments of the invention disclosed are well calculated to fulfill the objects stated, it will be appreciated that the invention is susceptible to modification, variation and change without departing from the spirit ll,e,eor.
FIELD OF THE INVENTION
The ~,resen~ invention relates to stain ,~s;sla,ll polyu,ell,ai,es and more particularly to stain resisla"l polyu~tl~ane-based elaslomers foams and coatings.
BACKGROUND OF THE INVENTION
Polyurethanes have become increasinyly useful for a wide range of commercial 5 applications. Such "~alerials are generally cl,a~a~terized by outstanding mechanical properties and resis~a~Ice to dey,~Jalioll c~used by heat oxidation ozone attack or ultraviolet radiation. Polyurethanes are often less expensive to process than rubber and thermo~.laslics thus making them highly desirable for use in industry.
While many polyurelhane based compositions are known a perceived 10 drawback of the known ll,alerials lies in their susce~ libility to staining i.e. discoloration due to the absorption of water-soluble ",alerials. For exampl~ urethane-based elaslo,ners employed as protective and/or decorali~e edging for furniture and cou"lel lops tend to beco, l~e .'i~ red over time when fluids such as coffee and tea among others have been spilled lhereG". Thus there is a need for urethane-based 15 ela~lul "er~ and foams which have outstanding "~ecl ,a" c ~I properties are resi~lal ,ce to deyladalion and are stain ~esi~la"l.
CA 02204274 1997-0~-01 SUMMARY OF THE INVENTION
Accordir,y to a preferred embodiment, the present invention relates to stain resistant polyurall~a"es formed as the reaction product of a mixture, cor~ ,isi,lg:
a) an organic isocyanate;
b) a hydrophobic co,n~.ound selected from the group co"si~li"~ of hydrophobic compounds having at least two isocyanate reactive hydrogens, hy-llupllobic long chain hydrocarbons and mixtures thereof;
c) optionally, when b) includes less than sufficient isocyanate reactive hydrogens to form a polyurethane, at least one second compound which is sufficiently reactive with said organic isocyanate to form a polyurethane; and d) o~Jliol,ally, one or more components selected from the group consisting of blowing agents, cross-linkers, catalysts, anti-oxidanls, UV-stabilizers, flame retardants, water scavengers, ~.laslici~ers, fillers, coloring agents and mixtures thereof.
Under an alternative preferred embodiment, the invention relates to stain resistant polyurethane formed as the reaction product of a mixture comprising:
a) an oryanic isocyanate;
b) at least one hydrophobic compound capable of reacting with said or~anc isocyanate to form a polyurethane, said compound having at least two isocyanate reactive hydrogens; and CA 02204274 1997-0~-01 c) optionally, one or more components selected from the group consisli, ,9 of blowing agents, cross-linkers, catalysts, anti-oxidal,ls, UV-stabilizers, flame ~lar~la~,ls, water scavenyer~
~,laslici~ers, fillers, CO'Glilly agents and mixtures thereof.
The stain lesislai1l polyul~ll,a"es can be used for a number of different products including but not limited to furniture and countertop edging, appliance handles, shelving edges, and decorative moldings, for exa",,,le. In general, it is conlem~Jlaled that the poly~ hane compositions of the present invention can be employed under any a~ tion where stain res;sla"ce is a consiJeration.
In addition to stain res;sla"l u-e~l,ane com~.osilions, the present invention also relates to the formation of prepolymers which are storage stable and readily useful for the formation of various polyu.~lha"e products.
An unique aspect of the stain resisla"t ~ t,al,e compositions of the present invention is that they may be l"odlfieJ such that the resulting product has the desired hardness, e.g., ranging from Shore A to Shore D upon curing.
The present invention also relates to the method of prepa~ing both the stain resistant polyurethanes and prepolymers of the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
The stain I esi~lanl polyur~tl ,~"es of the pres6l ,l invention can be utilized to form a variety of products including but not limited to furniture and cou"~ello~ edging, appliance handles, shelving edges, and uleco,ali~e moldings, among others. In general, it is co"~em~ldled that the ~rere~l~d ~-~etl ,a"es of the present invention can CA 02204274 1997-0~-01 be employed in the production of various products where stain ~esisla,lce is a particular co"cer~ ,. As used herein, the phrase "stain resislalll polyurell ,anes" should be understood to include both filled and unfilled polyurethane based co~ osilions including, generally, ela:,lomers, foams and coatings.
Hydrophobic compounds having at least two isocyanate reactive hydrogens which are considered useful, without limitation, in accordance with the teachings of the present invention include polyols having a carbon chain length of at least about C10 or higher. rleter,ed examples of such polyols include castor oil, castor-oil based or derived compounds, polybutadiene and saturated hydrocarbon polyols. By saturatedhydrocarbon polyols, it is meant that the polyols have no double bonds in their molecular structure.
Of the aforementioned, castor oils are considered to be particularly preferred.
While numerous commercially available castor oil products are useful in accordance with the teachings of the present invention, one known as DB Oil which is available from CasChem, Inc., of Bayonne, NJ, has been found to be particularly useful. In this regard, it has been observed that castor oil not only appea!s to enhance the hydrophobicity of the polyurethane compositions, i.e. resisl~"ce to water soluble staining materials such as coffee and tea, for example, but also enhances the fire retardancy characteristics of the resulting product due to char ~o~ aliu~l caused by the relatively long hydrocarbon chain length.
Under certain applications, the hydrophobic compound employed optionally or alternatively will include or employ compounds which do not have at least two isocyanate-reactive hydrogens, such compounds being referred to herein as long chain hydrocarbons. Examples of such long chain hydrocarbons include, for example, CA 02204274 1997-0~-01 and without inle"di"g to be limiting ~a,affi"s olefins vegetable and animal oils and modifications of such Illalelials. Particularly useful of the so-called long chain hydrocarbons are hydloca,bo" oils and mono-flJ"ctiol,al long c,hain hydrocarbon compounds such as alcohols and/or fatty (long chain hy~ irLon) acids and fine 5 powders.
By long chain hydlocarL.o"s it Ts meant that the hydrocal~oI~s will have a carbon chain length of at least C,0 more ~,, e~e, ~bly of at least C,2 still more preferably at least C,~ and still more prererauly will have a carbon chain length of C,~ or y, ealer.
In general the longer the hydloca, bon chain length the more hydrophobic in nature 10 the hydrocarbon will be.
It should be noted that the amount of hyd,opl)obic compound employed will depend in large part on the clesired application for the end product. For example while high quantities of castor oil will generally give rise to products having the best stain r~sislal)l cllaréct~ris~ics the resulting polyurethane-based product may be too 15 soft for certain applicdliol ,s. By the same token dilution of the castor oil or other such hydrophobiccompoundwithlesshyd~ 1,ol cpolyols chainextenders cross-linkers and other additives will give rise to products which are typically less stain resislanl.
Thus the amount of hydrophobic co"1pound employed in the stain-l esislanl polyurethane con~.osition will be determinative upon a large number of factors 20 including the end use of the product. At a minimum the preferred stain res;slal, polyu, ell ,anes of the ~.rese, ll invention will generally include at least about 10.0 weight percent of a hydrophobic com,oound based on the total weight of composition prior to reaction with the orga,.i~ isocyanate.
CA 02204274 1997-0~-01 In addition to the hydrophobic compound, the polyurethane-based compositions of the p, esenl invention can oplio~ ,ally employ one or more conventional additive components at art-di-.,lQse-3 levels selected from the group ~;o"si~ ,y of chain extenders, cross-linkers, catalysts, anti-oxidants, UV-stabilizers, flame retardants, 5 water sca\~enyer~ fillers, coloring agents and mixtures thereof.
Suitable examples of chain e~lenders useful in the stain ,esi~tanl urethanes of the present invention include polyoxyalkylene polyether polyols which are the polymerization product of an alkylene oxide with a polyhydric alcohol. Suitable polyhydric alcohols include those di3~,10sed above for use in the pre,)alalion of the 10 hydroxy-ter")i"aled polyesters. Any suitable alkylene oxide and mixtures thereof may be used such as ethylene oxide, propylene oxide, butylene oxide, amylene oxide, and mixtures of these oxides, p,eterably propylene oxide. Polyoxypropylene polyether polyols are more hydrophobic than their ethylene oxide counterparts. The polyalkylene polyether polyols may be prepared from other starting materials such as 15 tetrahydrofuran and alkylene oxide-tetrahydrofuran mixtures; epihalohydrins such as epichlorohydrin; as well as aralkylene oxides such as styrene oxide. The polyalkylene polyether polyols may have either primary or secondary hydroxyl groups. Included among the polyether polyols are polyoxyethylene glycol, polyoxypropylene glycol, polyoxybutylene glycol, polytel~",ell~ylene glycol, block copolymers, for example, 20 combinations of polyoxypropylene and polyoxyethylene glycols, poly-1,2-oxybutylene and polyoxyethylene glycols, poly-1,4 tel, amell ,ylene and polyoxyethylene glycols, and copolymer glycols prepared from blends or addition of two or more alkylene oxides.
The polyalkylene polyether polyols may be prepared by any known process such as, for example, the process ~Jisclosed in the Encyclopedla of Chemical Technology, Vol.
CA 02204274 1997-0~-01 7, pp. 257-262, published by l"lt,r~cle.,ce Publishers, Inc. (1951) or in U.S. Pat. No.
1,922,459; all of which are ex~ressly inc~l,uor~led herein by reference. Extensive lists of suitable polyol may be found in columns 2 and 3 of U.S. Pat. No. 3,652,639;
columns 2-6 of U.S. Pat. No. 4,421,872; and columns ~6 of U.S. Pat. No. 4,310,632, these three pdlellls being hereby incor~ol~led by let~re,)ce. The polyether polyols employed will generally have prer~"acJ molecular wsi~llls from 500 to 10,000, more ~rereraLly from 750 to 8000, and still more ~,efelal,ly from 1000 to 6000.
While polyester polyols are generally less preter~ed than polyether polyols in that they tend to be less soluble than polyether polyols, polyester polyols may also be employed. Suitable hydroxy-terminated polyesters include those obtained, for exar"p'e, from polycarboxylic acids and polyhydric alcohols. A suitable polycarboxylic acid may be used such as oxalic acid",~alon ~ acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassylic acid, thapsic acid, maleic acid, fumaric acid, gl-,laco"ic acid, a-hydromuconic acid, B-hydromuconic acid, a-butyl-a-ethyl-glutaric acid, a,B-diethylsuccinic acid, isophtalic acid, therphthalic acid, phthalic acid, hemimellitic acid, and 1,4-cyclohexanedicarboxylic acid. Mixtures may also be employed. A suitable polyhydric alcohol may be used such as ethylene glycol, propylene glycol, l, i"lelhylene glycol, 1,2-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 2-methyl-1,3-prG~ a"ediol, hydroquinone, resorcinol glycerol, glycerine,1,1,1 -trimethylol-propa"e,1,1,1 -trimethylolethane,1,2,6-hexanetriol, a-methyl glucoside, sucrose, and sorbilol. Again, mixtures of such alcohols may be employed. Also included within the term "polyhydric alcohol" as used herein are compounds derived from phenol such as 2,2-bis(4-hydroxyphenyl)-~ro~ a"e, commonly known as Bisphenol A. The polyester polyols, if employed, will preferably - CA 02204274 1997-0~-01 have molecular wei~hls from 500 to 10,000, more preferably from 750 to 8000, and still more ~.rere,ably from 1000 to 6000.
r~erer,ed chain ex~er,-Je,~ will have molecular w~i,Jhl~ of from 50 to 400 generally and preferably from 60 to 300. In order to obtain the ~esi, ~ hardness of 5 the polyu~ell,a"es, the amount of hydrophobic component having at least two isocyanate reactive hydl ~gel Is to chain exler,~Jer~ can be varied within a relatively wide molecular ratio, the hardness typically ir,c~asi"g with i"creasin~~ cor,lent of chain extenders. For example, less rigid poly~"~ll ,a"es (having a Shore A hardness of less than 95, ,I.reteral~ly from 75 to 85 after curing), will generally have molar ratios of hydrophobic component to chain extenders of from 10:1 to 20:1, preferably from 8:1 to 15:1. For more rigid polyurethanes, ffor example, those having a Shore D hardness of more than 50, preferably 60 to 80 Shore D, after curing) the molar ratios of hydlo,ulloL~ic component to chain extenders are from 2:1 to 3:1, ~r~reral~ly 4:1 to 5:1.
Suitable examples of cross-linkers useful in accor~ance with the practice of the 15 present invention include, without lirllildlioll, the alkylene oxide additio" products of trimethylolpropane, glycerine, sucrose, sorbitol, propylene glycol, dipropylene glycol, pentaerythritol, and 2,2-bis (4-hydroxyphenyl)-propane and blends thereof having equivalent weights of from 31-340.
Catalysts may also be employed in accorda,lce with the teachings of the 20 ,uresenl invention. The catalyst generally accelerate the , eactio" of the active hydrogen containing compounds (if ~resenl) with the organic polyisocya"ales.
Examples of useful catalyst~ include organic mctal compounds"~re~eral~ly organic tin compounds such as tin (Il) salts of o,gan c car~oxylic acids, e.g., tin(ll) acelale, tin(ll) octoate, tin(ll) ethyll,exoale and tin(ll) laurate, as well as the dialkyline(lV) salts of CA 02204274 1997-0~-01 oryan s carboxylic acids, e.g., dibutyltin ~liacet~le, dibutyltin maleate and dioctylin diaceldle. Specific exar~ 'es of oryan.c tin co,l"~ounds which are useful include, without limitation, dibutyltin dilaureate, dibutyltin sulfide and tin me,rca~ta"s, among others. Other organic metal co")~,ounds which are c~"sidered useful include zinc5 co~"pounds such as zinc o-,toale with bismuth col"~,ounds. Organol"elallic com,uounds useful as catalysts are generally disclosed in U.S. Pat. No. 2,846,408, herein i,,cor,uoraled by le~rence. The organic metal compounds are used alone or~re~r~L~ly in combination with strong basic amines. Examples include an ,idines such as 2,3-dimelhyl-3,4,5,6-tetrahydropyrimidine, tertiary amines such as triethylamine, 10 tributylamine, dimethylbenzylamine, N-methylmorpholine, N-ethylmorpholine, N-cyclohexylmorpholine, N,N,N,',N'-tetramethylethylenediamine, N,N,N',N'-tetramethylbutanedia" ,i"e,pentamethyldiethylenl, ia" line,tel~ a" ~ell ~yldiaminoethylester bis(dimethylaminopropyl) urea, dimethylpiperazine, 1,2-dimethylimidazle, 1-~a-bicyclo[3.3.0]octane and ,ureferaL,ly 1,4-dia~abi~yclo[2.2.2]octane, 1,8 15 dia~aL ~clo 5,4,0 undecene 7 and alkanola",i"e compounds such as lliell ~anolamine, Il ;;SO~JI o~ a"olamine, N-methyl-and N-ethyldiuthariola" ~ine and dimethyletha"ola" ,ine.
Suitable catalysts also includetris(dialkylamino)-s-hexahyd, ol, i~i"es, es,uecially tris(N,N-di"1elhylaminopropyl)-s-hexahy.ll ol, ia~;"e, tetraalkyla" " ,)on I m hydroxides such as tel, a" ,ell ,yla~" "onium dydl o.~icle, alkali hy.ll oxi.les such as sodium hydroxide 20 and alkali alcoholates such as sodium methylate and ,uolassium isopropylate as well as alkali salts of long-chain fatty acids with 10 to 20 carbons and optionally OH side groups. An effective amount of catalyst to l,ro" ~ote the reaction of isocyanate groups with the polyol, or with other isocyanate groups in the case of isocyanurates, is employed. 0.001 to 5 wt ,~erce"l, catalyst or catalyst com~-. ,alio" based on the CA 02204274 1997-0~-01 weight of polyol composition is preferred. Mixtures of amine, tin, and bismuth catalysts may be used.
Anti-oxida, lls may also be employed if necessary to retard the oAidalio, I of the reacted urethane. Fl e(e, l e~ among the numerous commercially available anti-o,~i.la, lls 5 which are co"sitJered useful are: Irganox, available from Ciba-Geigy Corp., of Greensboro, N.C.; and Cyanox, available from Cytec, Industries Inc., of Havre De Grace, MD; both are particularly useful. Mixtures of anti-oxidants may also be employed.
UV stabilizers which can be employed include, without lirllilalioll, 10 benzophe~ lo"es, L.e, I~ull i~oles, substituted acrylonitriles, phenol-nickel complexes, and mixtures thereof. Exan".les of commercially available UV-stabilizers include Tinuvin, available from Ciba-Geigy Corp., of Greensboro; N.C., and Uvinul, available from BASF Cor,~or~liol1 of Mt. Olive, N.J.
It may be cJesi,aLI~ in certain applications to employ one or more flame-15 retardants. For example, certain flame retardants which are reactive with isocyanateswhich may be employed include phosphor-based products such as Fyrol 6 and Fyrol 51, available from Akzo Chemicals, Inc., of Chicago, IL; and Vircol 82 available from Mûbil Chemical Co., of Nûrwalk, CT. Additionally, certain halogen based flame relarcJai,ls, such as FR-522 and Saytex FR-1138 (which are dibrûmopentyl giycû
20 based products available from AmeriBrom, Inc., and Ethyl Corporation of Richmond, VA, respectively), may be employed. Still other flame retardants which are generally non-reactive to the isocya"ales may be employed. Plerer~ed are the reactive FR
series flame retardants since they are homogeneous in nature, i.e. they do not m iyl ale to the surface of the polyurethanes. Mixtures may also be employed.
CA 02204274 1997-0~-01 For non-foaming applicdlio"s, water scave"yers~ otherwise r~rerra~l to herein as water absorbing agents, may be employed so that any water co"lai"ed in the composition is prevented from reacting with the isocyanales which in,turn prevents the ror",alioi) of CO2 and this limits or preclu~les foaming. Molecular sieves which are 5 generally silica based have proven useful in this regard. Ad~ ally, Zolidine, which is a liquid oY~olidine available from Angus Cl,err,ic~'s, Inc. of Buffalo Grove, IL, is co,1lei))plaled as being useful.
For d~ ~!,s~tions wherein the stain r~sisla,n polyurethanes of the present invention are foams, blowing agents are typically required. Suitable blowing agents 10 are those of the reactive type such as water, formic acid or tertiary alcohols; physically active blowing agents having a boiling point below 28 degrees C. and which vaporize at or below the len,,ueral-lre of the foaming mass comprising chlorofluorocarbons having at least one hydrogen (soft CFC's) and volatile hydrocarbons, or mixtures thereof. Soft CFC's useful herein are those having an ozone ~le,~lE~ion potential of less than 0.2 including 1,1,1 trichlJroelha"e, 1,1,1 ,2-tel, dtlouoroetl ,a"e, HCFC-1 41b, HCFC-22, HCFC-123, and HCFC-142b. Volatile hyd~ocdrbol)s include butane, pentane, hexane, heptane, cyclopentane, cyclohexane, pentene, and heptene.
A surface-active subsla,)ce is generally necessa,y for production of high grade polyurethane foam according to the presenl invention, since in the absence of same, 20 the foams may collapse. Examples of surface active suL,slal ,ces include compounds that support the homoye"i~dlion of the slailil,y materials and are o~liol1ally also suitable for regulating the cell structure. An e~lensive list of surface-active subslal ,ces useful in accolda,1ce with the teachings of the present invention are disclosed in U.S.
CA 02204274 1997-0~-01 Patent No. 5,045,885 to Sampara et al., which is hereby expressly incorporated by reference.
Other conve"liol1al additives including, but not limited to"~)laslici~ers, reactive and non-reactive silicone oils, fillers and coloring agents including dyes and pi~me, lls 5 may also be employed, at conventional or art-disclosed levels. Included in the class of additive ",alerials generally referred to herein as fillers are fibrous and particulate materials, non-polar polymeric "l~ler;als and inorganic anti-block agents. Eka",ples of such l)~ale,ials include glass and carbon fibers, silicas, calcium carbonate, clay, mica, talc, carbon black, particulate graphite and metallic flakes, among others.
10To gain a further understanding of the various optional components which can be employed, reference can be made to various technical publ ~alions including, for example, the article by J.H. Saunders and K.C. Frisch, High Polymers, Volume XVI, Polyurethane, Parts 1 and 2 (I"ler~ ce Publishers 1962 and 1964), Ku"stoslor~-Handbuch, Volume 7, Polyu,ell,a,)e 1st and 2nd Editions (Carl Hanser Verlag, 1966 15and 1994) or DE-A 29 01 774, which are hereby expressly incorporated by reference.
As alluded to previously, the hydrophobic components of the present invention are particularly useful when blended with certain isocyanate compounds. Among the numerous isocyal ~ales, otherwise refer, ed to herein as organic isocyaoales, which are considered useful are those including a, o" ,alic, aliphatic, and cycloaliphatic 20 polyisocya, lales and combinations thereof. Examples of such isocyanates may found at columns 8 and 9 of U.S. Pat. No. 4,690,956, herein incorporated by reference.
Represe"k,li,/e polyisocy~nates are the diisocyanates such as m-phenylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, mixtures of 2,4- and 2,6-toluene diisocyanate, he,car,)ell)ylene diisocyanate, tel,~"~lhylene diisocyanate, CA 02204274 1997-0~-01 cyclohexane-1,4 diisocyanate, hexahydrotoluene diisocyanate (and isomers), r ,a~ hlhalene-1 ,~diisocyanate, 1 -l l ,ell ,oxyphenyl-2,Wiisocyanate, 4,4'-diphenyl~, letl ,al ,e diisocyanate, 4,4'-biphenylenediisocyanate, 3,3'-dimethoxy-4,4'-biphenyldiisocyanate, 3,3'-diimethyl-4,4'-biphenyl diisocyanate and 3,3'-5 dimethyldiphenylmethane-4,4'-diisocyanate; the triisocyanates such as 4,4',4"-t, i~l ,enyll nelhal ,e triisocyanate, and toluene 2,4,6-triisocyanate; and the tel,ahocyai)ales such as 4,4'-dimethyldiphenylmelharle-2,2'-5,5'-lelraisocyanate and polymeric polyisocyanates such as polymethylene polyphenylene polyisocyanate, and mixtures thereof.
For preparation of the stain les;sla, ll polyurethanes of the present invention, the ratio of the equivalent weight number of NCO groups of the isocyanate (a) to the sum of hydroxyl groups of con,,~.o"ent (b) is from 300:100 to 95:100, preferably 105:100 to 100:100. By equivalent weight number, it is meant the weight of an element that comL)i"es chemically with 8 grams of oxygen or its equivalent. For example, since 8 15 grams of oxygen combines with 1.008 grams of hydrogen, the latter is considered equivalent to 8 grams of oxygen.
Suitable methods of preparing the stain lesisla~,l polyurethanes of the present invention include adding the hydrophobic compound to a vessel and heating to appro,(imalely 140-F. Therearler, each of the other compol)ents including one or 20 more compounds selected from the group co"sisling of chain e~le"de,s, cross-linkers, catalysts, anti-oxida"ls, UV-sldL.ili~ers, flame lelarda,lts, ~laslici~er~, fillers, coloring agents and mixtures thereof, exce~.li"y any water scavengers are charged to the mixing vessel and blended with the hydrophobic compound. Upon blending, the water level of the composition is typically measured to determine whether the water ~ CA 02204274 1997-0~-01 level is below a,u~roximalely 0.03 wt.% based on the total weight of the colll~osiliGI).
If the water is above that level, the composition is heated further under vacuum to drive off water; however, H the water level is at or below this level, a water scavenger is added to the mixture with blending. Upon thoroughly l,le"di. ,g the components, a 5 resinous material results. Tl ,eredrler, the resin is blended with the oryal, c isocyanate to form the stain les;sla"t polyurethane of the prese,lt invention as set forth by way of non-limiting examples below.
Other conver,lional or art-disclosed methods may also be employed to prepare the resins and prepolymers of the ~resenl invention.
A stain resisl~"l polyurethane in accorda, Ice with the teachings of the present invention was prepared by first charging 85.7 wt.% of DB oil to a clean, dry blend tank equipped with a dry air or nitrogen purge. The DB oil was heated to 140-F and thereafter 10.0 wt.% FR-522, 0.5 wt.% Tinuvin 328, 0.5 wt.% Tinuvin T765, 0.5 wt. %
Irganox 245, and 0.3 wt.% Fomrez UL 28 were slowly added with mixing to the DB oil and the composition was mixed for one hour. The composition was continuously mixed until the water level was below about 0.03 wt.% at which time 2.5 wt.% of an A-3 molecular sieve was added and the composition was mixed for a~ ~roxi" ,ately one half hour to form the desired resin, which was liquid and had a viscosily of a~.~Jro,~imately 700 cps and a density of 1.0 g/cc or 8.2 Ibs/gal. at 77-F.
One hundred parts by weight of the resin were blended with 45 parts by weight of dicyclohexylmethane diisocyanate having a viscosity of approximately 30 cps and a density of 1.07 g/cc or 8.9 Ibs./gal at 77-FF and molded. The mold was ~"ai~ ,la;, ~ed CA 02204274 1997-0~-01 at a le""~erature of between about 130-150-F. As a result of blending the resin and isocyanate loyell~er and molding the same an urell,a"e based elaslo~oer product which is aliphatic light stable and sufficiently flame retardant at a thickness of 0.5 inch to attain a UL94VO rating was obtained. The resulting polyuIell)a"e product had a I,ard"ess as measured by ASTM D2240 of 75 tensile sl,e"ylh of 1300 PSI accordingto ASTM D412 elo"y~lio" at break of 200 and Graves Tear accordi. ,9 to ASTM D1004 of 90 Ibs/in.
A second stain tesisla"~ polyu,~ll,a,)e was prepared by charyi,,y 39.15 wt.%
DB Oil to a similar blend tank and adding 17.5 wt.% dipropylene glycol with mixing.
The mixture was heated to 140-F and ll,ere~rler 0.2 wt.% Fomrez UL 28 0.5 wt.%
Tinuvin 328 0.5 wt.% Tinuvin T765 0.5 wt. % Irganox 245 and 39.15 wt.% Pluracol 726 were added and the composition mixed until the water level was below about 0.03 wt.% at which time 2.5 wt.% of an A-3 molecular sieve were added. The resulting composition was mixed for appro~i,nalely one half hour with the resulting liquid resin having with 2.5 wt.% A-3 molecular sieve being added after the water level was below a viscosity of approximately 700 cps and a density of 0.99 g/cc or 8.2 Ibs/gal. at 77-F.
One hundred parts by weight of the resin were then blended with 58 parts by weight of dicyclohexyll l lell Idl ,e diisocyanate having a v;scu~ity of a~,~., u~i" Idlely 30 cps and a density of 1.07 g/cc or 8.9 Ibs./gal at 77-F and molded. The mold was maintained at a temperalure of 6~l~ccn about 130-150-F. The resulting polyurethane product had a hardness as measured by ASTM D2240 of apt., oxi" ,a~ely 80-85 tensile CA 02204274 1997-0~-01 strength of 2100 PSI according to ASTM D412, elongation at break of 230 and Graves Tear according to ASTM D1004 of 90 Ibs/in.
A third polyurethane composition was prepared for purposes of con1pa, i~ lg the 5 stain lesi~la"l cl,alaote,i~lics of a currently employed commercial product versus those provided in accordance with the leachi,~gs of the present invention. This third example was pre~,ared by charging 89.5 parts by weight Pluracol 538 polyol commercially available from BASF Corporation to a blending tank at 140-F along with 9.0 wt.% diethylene glycol. The mixture was blended under vacuum and nitrogen purging at a temperalure of between 180 to 212-F until the water level was below 0.05%. Thereafter, the temperature was adjusted to between 120 to 140-F and 0.5 wt.% of Tinuvin 328 was added with the mixing. The mixture was blended for approximately 25 minutes and cooled to between 70 to 100-F at which time 0.5 wt.%
Tinuvin 765 and 0.5 wt.% Fomrez UL~32 catalyst were added and mixed for one half hour. The resulting resin which was liquid had a viscosily of 775 cps and a density of 1.03 g/cc or 8.6 Ibs/gal at 77~F.
One hundred parts by weight of the resin were mixed with 43.5 parts by weight of polymethylene polyphenylene diisocyanate, a MDI-prepolymer, having an NCO %
of 23, a viscosity of a~"~, oxi" ,ately 700 cps and a density of 1.2 g/cc or 10 Ibs/gal at 77~F. The mold was maintained at a temperature of about 130~F. The resulting polyurethane product had a hardness as measured by ASTM D2240 of approximately Shore 65 A, tensile sllellylll of 630 PSI according to ASTM D412, elongation at break of 190 and Graves Tear according to ASTM D1004 of 30 Ibs/in.
- CA 02204274 1997-0~-01 To analyze for stain resisla"ce, one saio~JlE of each of the Exam,u'Es 1, ll and lll was immersed in the same coffee solution and allowed to remain for a period of twenty four hours. Theredrler, each sample was removed and wiped lightly with a clean moist towel. Upon ViGW;n9 the sam~,!es, the sa",~les for~,1e.1 according to 5 Examples I and ll showed virtually no signs of staining; in co"l,asl, the sample of Example lll was clearly discolored.
As alluded to earlier, in addition to their use for prepa,i"y stain resi jldn polyurethanes, the hyd,o,~l,obic col"pound of the ~resent invention can also be employed in prepolymers. In this regard, the hycl~opl,obic resins, such as those 10 described in Exalllpl~s I and/or ll above, are blended with the isocyal)ates and heated at the desired temperature while mixing. The NCO CGnlenl of the blend is monitored during the reaction until the target % of NCO is oblai. ,ed at which time the coI"~osilion is cooled to alllb'e.1l, i.e. room temperature. The prepolymers formed in accordance with the teachings of the ,vreseill invention will generally have between approximately 1.0 to 32.0 % NCO.
While it will be apparent that the preferred embodiments of the invention disclosed are well calculated to fulfill the objects stated, it will be appreciated that the invention is susceptible to modification, variation and change without departing from the spirit ll,e,eor.
Claims (33)
1. A stain resistant polyurethane which is the reaction product of a mixture, comprising:
a) an organic isocyanate;
b) a hydrophobic compound selected from the group consisting of hydrophobic compounds having at least two isocyanate reactive hydrogens, hydrophobic long chain hydrocarbons and mixtures thereof;
c) optionally when b) includes less than sufficient isocyanate reactive hydrogens to form a polyurethane at least one second compound which is sufficiently reactive with said organic isocyanate to form a polyurethane; and d) optionally one or more components selected from the group consisting of blowing agents cross-linkers catalysts anti-oxidants, UV-stabilizers flame retardants, water scavengers, plasticizers, fillers, coloring agents and mixtures thereof.
a) an organic isocyanate;
b) a hydrophobic compound selected from the group consisting of hydrophobic compounds having at least two isocyanate reactive hydrogens, hydrophobic long chain hydrocarbons and mixtures thereof;
c) optionally when b) includes less than sufficient isocyanate reactive hydrogens to form a polyurethane at least one second compound which is sufficiently reactive with said organic isocyanate to form a polyurethane; and d) optionally one or more components selected from the group consisting of blowing agents cross-linkers catalysts anti-oxidants, UV-stabilizers flame retardants, water scavengers, plasticizers, fillers, coloring agents and mixtures thereof.
2. The stain resistant polyurethane of claim 1, wherein said hydrophobic compound has a carbon chain length of C10 or longer.
3. The stain resistant polyurethane of claim 1 wherein said compound having at least two isocyanate reactive hydrogens is a polyol.
4. The stain resistant polyurethane of claim 3, wherein said polyol is a castor oil.
5. The stain resistant polyurethane of claim 1, wherein component b) is present in an amount of at least 10.0% by weight based on the total weight of the composition.
6. The stain resistant polyurethane of claim 1 wherein the ratio of equivalent weight number of NCO groups of component a) to the sum of hydroxyl groups of component b) is from 300:100 to 95:100.
7. The stain resistant polyurethane of claim 1 wherein said long chain hydrocarbon is selected from the group consisting of paraffins, olefins, animal oils, vegetable oils and mixtures thereof.
8. The stain resistant polyurethane of claim 1, wherein said polyurethane is elastomeric.
9. The stain resistant polyurethane of claim 1, wherein said polyurethane is a foam.
10. The stain resistant polyurethane of claim 1, wherein component c) is a chain extender.
11. A stain resistant polyurethane which is the reaction product of a mixture, comprising:
a) an organic isocyanate;
b) at least one hydrophobic compound capable of reacting with said organic isocyanate to form a polyurethane, said compound having at least two isocyanate reactive hydrogens; and c) optionally, one or more components selected from the group consisting of blowing agents, cross-linkers, catalysts, anti-oxidants, UV-stabilizers, flame retardants, water scavengers, plasticizers, fillers, coloring agents and mixtures thereof.
a) an organic isocyanate;
b) at least one hydrophobic compound capable of reacting with said organic isocyanate to form a polyurethane, said compound having at least two isocyanate reactive hydrogens; and c) optionally, one or more components selected from the group consisting of blowing agents, cross-linkers, catalysts, anti-oxidants, UV-stabilizers, flame retardants, water scavengers, plasticizers, fillers, coloring agents and mixtures thereof.
12. The stain resistant polyurethane of claim 11, wherein said hydrophobic compound has a carbon chain length of C10 or longer.
13. The stain resistant polyurethane of claim 11, wherein said hydrophobic compound is a polyol.
14. The stain resistant polyurethane of claim 13, wherein said polyol is a castor oil.
15. The stain resistant polyurethane of claim 11, wherein component b) is present in an amount of at least 10.0% by weight based on the total weight of the composition.
16. The stain resistant polyurethane of claim 11 wherein the ratio of equivalent weight number of NCO groups of component a) to the sum of hydroxyl groups of component b) is from 300:100 to 95:100.
17. The stain resistant polyurethane of claim 11 wherein compound b) further comprises a long chain hydrocarbon.
18. The stain resistant polyurethane of claim 17 wherein said long chain hydrocarbon is selected from the group consisting of paraffins, olefins animal oils vegetable oils and mixtures thereof.
19. The stain resistant polyurethane of claim 11 wherein said polyurethane is elastomeric.
20. The stain resistant polyurethane of claim 11 wherein said polyurethane is a foam.
21 21. A stain resistant polyurethane which is the reaction product of a mixture comprising:
a) an organic isocyanate; and b) a resinous material comprising at least one hydrophobic compound selected from the group consisting of compounds having at least two isocyanate reactive hydrogens, long chain hydrocarbons and mixtures thereof and optionally, one or more compounds selected from the group consisting of blowing agents cross-linkers, catalysts anti-oxidants, UV-stabilizers flame retardants, water scavengers, plasticizers, fillers, coloring agents and mixtures thereof.
a) an organic isocyanate; and b) a resinous material comprising at least one hydrophobic compound selected from the group consisting of compounds having at least two isocyanate reactive hydrogens, long chain hydrocarbons and mixtures thereof and optionally, one or more compounds selected from the group consisting of blowing agents cross-linkers, catalysts anti-oxidants, UV-stabilizers flame retardants, water scavengers, plasticizers, fillers, coloring agents and mixtures thereof.
22. The stain resistant polyurethane of claim 21, wherein said hydrophobic compound has a carbon chain length of C10 or longer.
23. The stain resistant polyurethane of claim 21, wherein said hydrophobic compound is a polyol.
24. The stain resistant polyurethane of claim 23, wherein said polyol is a castor oil.
25. The stain resistant polyurethane of claim 21 wherein component b) is present in an amount of at least 10.0% by weight based on the total weight of the composition.
26. The stain resistant polyurethane of claim 21 wherein the ratio of equivalent weight number of NCO groups of component a) to the sum of hydroxyl groups of component b) is from 300:100 to 95:100.
27. The stain resistant polyurethane of claim 21 wherein said long chain hydrocarbon is selected from the group consisting of paraffins, olefins, animal oils, vegetable oils and mixtures thereof.
28. The stain resistant polyurethane of claim 21, wherein the polyurethane is elastomeric.
29. The stain resistant polyurethane of claim 21 wherein said polyurethane is a foam.
30. A prepolymer useful for the production of stain resistant polyurethanes, comprising:
a) a resin comprising a hydrophobic compound selected from the group consisting of compounds having at least two isocyanate reactive hydrogens, long chain hydrocarbons and mixtures thereof, and optionally, one or more compounds selected from the group consisting of blowing agents, cross-linkers, catalysts, anti-oxidants, UV-stabilizers, flame retardants, water scavengers, plasticizers, fillers, coloring agents and mixtures thereof; and b) an isocyanate blended with said resin while heating, wherein the resulting composition has the desired % NCO.
a) a resin comprising a hydrophobic compound selected from the group consisting of compounds having at least two isocyanate reactive hydrogens, long chain hydrocarbons and mixtures thereof, and optionally, one or more compounds selected from the group consisting of blowing agents, cross-linkers, catalysts, anti-oxidants, UV-stabilizers, flame retardants, water scavengers, plasticizers, fillers, coloring agents and mixtures thereof; and b) an isocyanate blended with said resin while heating, wherein the resulting composition has the desired % NCO.
31. The prepolymer of claim 30, wherein the prepolymer has an NCO content of between approximately 1.0 to 32.0% NCO.
32. A process of making stain resistant polyurethanes comprising the steps of:
a) providing a hydrophobic compound selected from the group consisting of compounds having at least two isocyanate reactive hydrogens, long chain hydrocarbons and mixtures thereof to a reaction vessel and heating;
b) optionally blending in admission with component a) one or more compounds selected from the group consisting of blowing agents cross-linkers catalysts anti-oxidants UV-stabilizers flame retardants, plasticizers, fillers coloring agents and mixtures thereof and heating the resulting blend to drive off excess water, if any;
c) optionally adding a water scavenger to the blend or admixture of a) and b) once the detected water level is below about 0.05 wt.%;
and d) reacting the above admixture or blend with an organic isocyanate to form a stain resistant polyurethane.
a) providing a hydrophobic compound selected from the group consisting of compounds having at least two isocyanate reactive hydrogens, long chain hydrocarbons and mixtures thereof to a reaction vessel and heating;
b) optionally blending in admission with component a) one or more compounds selected from the group consisting of blowing agents cross-linkers catalysts anti-oxidants UV-stabilizers flame retardants, plasticizers, fillers coloring agents and mixtures thereof and heating the resulting blend to drive off excess water, if any;
c) optionally adding a water scavenger to the blend or admixture of a) and b) once the detected water level is below about 0.05 wt.%;
and d) reacting the above admixture or blend with an organic isocyanate to form a stain resistant polyurethane.
33. A process of making a prepolymer useful for the production of stain resistant polyurethanes comprising the steps of:
a) forming a resin consisting a hydrophobic compound selected from the group consisting of compounds having at least two isocyanate reactive hydrogens, long chain hydrocarbons and mixtures thereof, and optionally, one or more compounds selected from the group consisting of blowing agents, cross-linkers, catalysts, anti-oxidants, UV-stabilizers, flame retardants, water scavengers, plasticizers, fillers, coloring agents and mixtures thereof; and b) blending an organic isocyanate with said resin to form a prepolymer.
a) forming a resin consisting a hydrophobic compound selected from the group consisting of compounds having at least two isocyanate reactive hydrogens, long chain hydrocarbons and mixtures thereof, and optionally, one or more compounds selected from the group consisting of blowing agents, cross-linkers, catalysts, anti-oxidants, UV-stabilizers, flame retardants, water scavengers, plasticizers, fillers, coloring agents and mixtures thereof; and b) blending an organic isocyanate with said resin to form a prepolymer.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US65001196A | 1996-05-17 | 1996-05-17 | |
| US08/650,011 | 1996-05-17 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2204274A1 true CA2204274A1 (en) | 1997-11-17 |
Family
ID=24607115
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2204274 Abandoned CA2204274A1 (en) | 1996-05-17 | 1997-05-01 | Stain resistant polyurethanes |
Country Status (2)
| Country | Link |
|---|---|
| CA (1) | CA2204274A1 (en) |
| GB (1) | GB2313128A (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19928676A1 (en) | 1999-06-23 | 2000-12-28 | Basf Ag | Polyisocyanate poly-addition product, e.g. flexible polyurethane foam for cushions and padding, contains hydrophobic compounds and other special modifiers, e.g. metal salt, anhydride, sulfone or unsaturated acid |
| EP3080182B1 (en) * | 2013-12-10 | 2020-01-08 | Lubrizol Advanced Materials, Inc. | Highly resilient thermoplastic polyurethanes |
| GB201322936D0 (en) * | 2013-12-23 | 2014-02-12 | Croda Int Plc | Polyurethane |
| EP3219847B1 (en) * | 2016-03-18 | 2018-09-05 | Advanced Polymer Technology Corp. | Using a polyol mixture comprising pbd for creating a pu-based artificial turf |
| WO2017158183A1 (en) * | 2016-03-18 | 2017-09-21 | Advanced Polymer Technology Corp. | Using a polyol mixture comprising pbd for creating a pu-based artificial turf |
| US10870952B2 (en) | 2016-03-18 | 2020-12-22 | Advanced Polymer Technologies Corp. | Using a polyol mixture comprising PBD for creating a PU-based artificial turf |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE754325A (en) * | 1966-10-17 | 1971-02-03 | Minnesota Mining & Mfg | COMPOSITION OF POLYURETHANE AND ITS APPLICATION IN SURFACING OPERATIONS |
| GB2106526B (en) * | 1981-09-10 | 1985-03-27 | Deborah Coatings | Coating composition |
| US4742112A (en) * | 1987-01-23 | 1988-05-03 | Caschem, Inc. | Ricinoleate modified hydrocarbon polyols |
| US5106675A (en) * | 1989-12-29 | 1992-04-21 | Nihon Parkerizing Co., Ltd. | Nonaqueous coating composition and coated metal |
| US5569696A (en) * | 1995-07-13 | 1996-10-29 | The W. W. Henry Company | Stain resistant grout |
-
1997
- 1997-05-01 CA CA 2204274 patent/CA2204274A1/en not_active Abandoned
- 1997-05-15 GB GB9709914A patent/GB2313128A/en not_active Withdrawn
Also Published As
| Publication number | Publication date |
|---|---|
| MX9703469A (en) | 1997-11-29 |
| GB9709914D0 (en) | 1997-07-09 |
| GB2313128A (en) | 1997-11-19 |
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