CA1184943A - Hydroxyl-terminated poly(haloalkylene ethers) - Google Patents
Hydroxyl-terminated poly(haloalkylene ethers)Info
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- CA1184943A CA1184943A CA000369016A CA369016A CA1184943A CA 1184943 A CA1184943 A CA 1184943A CA 000369016 A CA000369016 A CA 000369016A CA 369016 A CA369016 A CA 369016A CA 1184943 A CA1184943 A CA 1184943A
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Abstract
ABSTRACT
This invention is directed to hydroxyl-terminated poly(haloalkylene ethers) and to the catalyst system employed in their manufacture.
The ethers preferably have the formula wherein R1 and R2 = hydrogen or methyl;
R3 and R4 = hydrogen, lower alkyl containing 1 to 10 carbon atoms or lower chloroalkyl containing 1 to 2 carbon atoms provided that at least one of R3 or R4 is lower chloroalkyl;
R5 = residue of a hydroxyl material which originally contained 1 to 6 hydroxyls;
b = integer of 1 to 50;
d = integer of 1 to 6.
Poly(chloroalkylene ethers) are preferred and have a color magnitude of less than 10.
These ethers are especially useful where the color of the finished product is important. Such utilities include urethane flooring systems, adhesives, and coatings.
This invention is directed to hydroxyl-terminated poly(haloalkylene ethers) and to the catalyst system employed in their manufacture.
The ethers preferably have the formula wherein R1 and R2 = hydrogen or methyl;
R3 and R4 = hydrogen, lower alkyl containing 1 to 10 carbon atoms or lower chloroalkyl containing 1 to 2 carbon atoms provided that at least one of R3 or R4 is lower chloroalkyl;
R5 = residue of a hydroxyl material which originally contained 1 to 6 hydroxyls;
b = integer of 1 to 50;
d = integer of 1 to 6.
Poly(chloroalkylene ethers) are preferred and have a color magnitude of less than 10.
These ethers are especially useful where the color of the finished product is important. Such utilities include urethane flooring systems, adhesives, and coatings.
Description
76 ,557 CA~I/JVL
EIYDROXYL--TERI~I~IATF:D
POLY(HALOALKYLENE ETHERS) This invention is related to hydroxyl-terminated poly(haloalkylene ethers). More particularly it i5 related to hydroxyl-terminated poly(haloalkylene ethers) wherein the halogen atoms are pre~era~ly bromine c~r chlorine, to processes LOr the1r preparation, and to novel catalyst systems use-Eul in saic3 processes. In the case o hydroxyl terminated poly(chloroalkylerIe ethers) the products are substantially colorless.
For the purposes o~ convenience, the hy-3roxyl-terminated poly(haloalkylene ethers) are sometimes referred to hereinafter as polyols. For purposes of this disclosure, the term "polyols" includes materials which have at least one terminal hydroxyl group.
Hydroxyl-terminated poly(haloalkylene ethers) and processes for their prepartion are known. Frequently the processes utilize cationic polymeri~ation techniques wher~in oxirane monomers (e.g. 7 alkylene oxides, alcohols and acid catalysts are employed to synthesize hydroxyl-functional prepolymers. Thus, for example, see United States Patents 3,850j856; 3,910,878; 3,910,879, and 3,g80,57g.
The products described in these patents have not proven entirely satisfactory. For example, it has been found very difficult to control the temperature of the polymerization during their preparation. Additionally, the chloroalkylene products are dark in color and tend to be very slow to react with various materials (such as isocyanates~ unless substantial ~uantities oE catalysts are employed. Furthermore, these products have been found to be unstable when exposed to light (e.g., sunli~ht) and heat (e.g., temperatures above 50C). Thus, they become even darker in color and increase in acidity and water content when exposed to such conditions. Still further the hydroxyl-terminated materials described in United ~J~
States Patent 3,980,579 adversely afEect the catal~tic activity of amine catalysts utilized in ~he preparatiorl of polyurethane Eoam.
Other techniques for the preparation o hydroxyl-terminated poly(haloalkylene) ethers are also known, Thus, U.S. Patent 3,450,774 teache3 the preparation of hydroxyl~terminated polymers hy the cleavage of high molecular wei~ht, cryst.-lLIinQ
poly(epihalohydrin) in the pre~sence oE ce~tain ;I]kali compounds. The resulting polymers are cry3t~llLin~ and have low molecular weic3ht. Moreover, these polylne~; are only partially hydroxyl functional. trhus, t~ley ~ay have carbonyl and ethynyl end groups in place of the hydroxyl end groups~
Other poly(haloalkylene ethers) are clescribed in U.S. Patents 3,636,163 and 3,850,857. The former patent describes the reaction of epibromohydrin and a phosphorous compound in the presence of a Friedel-Crafts catalyst.
The latter paten~ describes the polymerization of epihalo-hydrin in ~he presence of a catalyst of a trialkyl onium salt or HMF6 wherein M is a Group V element.
The present invention provides novel hydroxyl~
terminated poly(haloalkylene ethers), processes for their preparation, and catalyst systems useful therein. The chloroalkylene ethers of the present invention represent a preferred class of mat~Qrials that is optically clear and colorless. Thus, the chloroalkylene ethers appear to have the same optical clarity as distilled water~ Moreover, they exhibit a color magnitude (described more fully hereinafter) of less than about 10. Additionally, they are stable to the effects of heat and light (i~e., they resist degradation due to such conditions) and they possess excellent chemical reactivity ~ith isocyante materials.
The poly(chloroalkylene ethers) are particularly useEul where the color o the 1Einished product is important (e.g., where the true color of the product is critical). Thus, for ex~mple, they are particularly useful in tne preparation of cast urethane syste~ns ~lhich can be used for such things as floor1n-J materials, coatings, and adhesives. ~oreover, the urethanes pro~3uced with the polyols of the invention have be~n found to exhibit improved properties over prior a~t urethanes.
Thus, or example, .such urethanes exhi~it excellent resistance to grease and oiL.
In accordance with the p~e/(-nt invent1O~I th~r(?
are provided amorphous, hydroxyl-terlnirlatecl poly(haloalkylene ethers) havin~J the ~ormula R5~o wherein Rl and R2 are each selected from hydrogen and methyl; R3 and R4 are selected from hydrogen, lower alkyl groups containing from 1 to 10 carbon atoms, and lower haloalkyl groups containing from 1 to 2 carbon atoms and ~rom 1 to 5 halogen atoms, provided that at least one of R3 and R4 is said lower haloalkyl group~ X5 is the residue of hydroxyl material which contained from 1 to 6 hydroxyl groups; b is an integer of from 1 to 50; and d is an integer oE from 1 to ~.
Preferably the polyols of the invention are poly(bromoalkylene ethers) or poly(chloroalkylene ethers).
The poly(chloroalkylene ethers) preferably contain from about 20g to 60% by weight chlorine.
The poly(haloalkylene ether) polyols of the present inven-tion are amorphous materials. Thus, they do not exhibit a melting point. Moreover, they may vary rom low molecular weight (i.e., about 250 MW) to high molecular weight (i.e., about 5000 MW) materials based upon the average hydroxyl functionality oE the polyols.
Also provided is a novel two cornponent catal~st systc~n use~ul in the preparation of the polyols. It comprises (i) HF; and (ii) a polyvalent tin compound havlny th~: Eonnu:La ~6 ~5 1 _~7 (1~, wherein g is 0 or 1; R and R are tlle catne or d.i.~ e~ent and a~f~ '`Je.leCted ErOIII
saturated and unsaturated aliphatic and aromatic hydrocclrbyL g~oups cOntaininCJ
from 1 to 10 carbon atoms; R is selected Erom the yroup COIlSiStiny of oxygen and saturated and unsaturated aliphatic and aroma tiC hydrocarbyl yroups contain-ing from 1 to 10 carbon atoms, provided that when R is oxygen then g is 0i and R is selected from the group consisting of fluorine, acyloxy groups containing less than 10 carbon atoms, and O - Sn - R
The molar ratio of the polyvalent tin compound to the HF is in the range of 1.13:1 to 3:1O Preferably -this ra-tio is in the range of 1.2:1 to 2:1.
Still further there is provided a method of makiny the polyols of the invention utilizing the novel catalyst system wherein a hydroxyl containing material having from 1 to 6 hydroxyl groups is combined with an alkylene oxide and polymerized in the presence of the above-described catalyst SyStenl.
The hydroxyl-terminated poly(haloalkylene ethers) of the invention are prepared by combining the hydroxyl-corltaining material, the alkylene oxide (at least about 50% by weight of which is haloalkylene oxide), and the catalyst system of -the inven-tion, and polymerizing the resultant mixture. Polymerization may be carried out at a -temperature in the range of about 0 C to 110 C. PreEer-9~3 ably polymerization is carried out at a temperature in the range of about 40 C
to ~0C.
Solvents may be employed during polymeri7ation. They are especially useful when one or more of the ingredients of the mixture :is a isolid. Suitable solvents solvate (but are otherwise inert to) the materials in the ~ 5 -,i i i`
llh~3 mixture. Representative examples oE ~uitable solvents are benzene, toluene, methylene chloride, carbon tetra-chloride, and l,2-dichloroethane.
Although the polymerization proceeds smoothly to cornpletion, there may be some unpolymerized h~loalkylene oxide left. This material may be separated from the poly(haloalkylene ethers) of the invention by warming the polymerization mixture (e.g., to 80C) and subjectiny the heated mixture to reduced pressure ~e.g., 0.01 Torr) fo~ a short period of time (e.y., 1-2 hours).
A wide variety o~ hydroxy1-containing rnaterials are useful in ~he present invention. They include, eor example, water, and liquid an~ solid organic materials which have a hydroxyl functionality of at least one. The organic materials may be monomeric or polymeric and are preferably selected from mono- and polyhydric alkanols, haloalkanols, and polymeric polyols.
The hydroxyl groups of the organic materials may be terminal or pendant (i.eO, other than terminal) groups.
Hydroxyl-containing materials containing both terminal and pendant hydroxyl groups may also be used. The molecular weight of the organic hydroxyl-containing material may vary over a rather wide range. For example it may be in the range of from 10 to 2,500.
Pref~rably, the organic hydroxyl-containing material is an aliphatic material which contains at least one primary or secondary aliphatic hydroxyl group (i.e~, the hydroxyl group is bonded directly to a non-aromatic carbon atom). Most preferably said organic material is an alkane polyol.
Mono- and polyhydric alkanols useful in the present invention include methanol, ethanol, isopropanol~
EIYDROXYL--TERI~I~IATF:D
POLY(HALOALKYLENE ETHERS) This invention is related to hydroxyl-terminated poly(haloalkylene ethers). More particularly it i5 related to hydroxyl-terminated poly(haloalkylene ethers) wherein the halogen atoms are pre~era~ly bromine c~r chlorine, to processes LOr the1r preparation, and to novel catalyst systems use-Eul in saic3 processes. In the case o hydroxyl terminated poly(chloroalkylerIe ethers) the products are substantially colorless.
For the purposes o~ convenience, the hy-3roxyl-terminated poly(haloalkylene ethers) are sometimes referred to hereinafter as polyols. For purposes of this disclosure, the term "polyols" includes materials which have at least one terminal hydroxyl group.
Hydroxyl-terminated poly(haloalkylene ethers) and processes for their prepartion are known. Frequently the processes utilize cationic polymeri~ation techniques wher~in oxirane monomers (e.g. 7 alkylene oxides, alcohols and acid catalysts are employed to synthesize hydroxyl-functional prepolymers. Thus, for example, see United States Patents 3,850j856; 3,910,878; 3,910,879, and 3,g80,57g.
The products described in these patents have not proven entirely satisfactory. For example, it has been found very difficult to control the temperature of the polymerization during their preparation. Additionally, the chloroalkylene products are dark in color and tend to be very slow to react with various materials (such as isocyanates~ unless substantial ~uantities oE catalysts are employed. Furthermore, these products have been found to be unstable when exposed to light (e.g., sunli~ht) and heat (e.g., temperatures above 50C). Thus, they become even darker in color and increase in acidity and water content when exposed to such conditions. Still further the hydroxyl-terminated materials described in United ~J~
States Patent 3,980,579 adversely afEect the catal~tic activity of amine catalysts utilized in ~he preparatiorl of polyurethane Eoam.
Other techniques for the preparation o hydroxyl-terminated poly(haloalkylene) ethers are also known, Thus, U.S. Patent 3,450,774 teache3 the preparation of hydroxyl~terminated polymers hy the cleavage of high molecular wei~ht, cryst.-lLIinQ
poly(epihalohydrin) in the pre~sence oE ce~tain ;I]kali compounds. The resulting polymers are cry3t~llLin~ and have low molecular weic3ht. Moreover, these polylne~; are only partially hydroxyl functional. trhus, t~ley ~ay have carbonyl and ethynyl end groups in place of the hydroxyl end groups~
Other poly(haloalkylene ethers) are clescribed in U.S. Patents 3,636,163 and 3,850,857. The former patent describes the reaction of epibromohydrin and a phosphorous compound in the presence of a Friedel-Crafts catalyst.
The latter paten~ describes the polymerization of epihalo-hydrin in ~he presence of a catalyst of a trialkyl onium salt or HMF6 wherein M is a Group V element.
The present invention provides novel hydroxyl~
terminated poly(haloalkylene ethers), processes for their preparation, and catalyst systems useful therein. The chloroalkylene ethers of the present invention represent a preferred class of mat~Qrials that is optically clear and colorless. Thus, the chloroalkylene ethers appear to have the same optical clarity as distilled water~ Moreover, they exhibit a color magnitude (described more fully hereinafter) of less than about 10. Additionally, they are stable to the effects of heat and light (i~e., they resist degradation due to such conditions) and they possess excellent chemical reactivity ~ith isocyante materials.
The poly(chloroalkylene ethers) are particularly useEul where the color o the 1Einished product is important (e.g., where the true color of the product is critical). Thus, for ex~mple, they are particularly useful in tne preparation of cast urethane syste~ns ~lhich can be used for such things as floor1n-J materials, coatings, and adhesives. ~oreover, the urethanes pro~3uced with the polyols of the invention have be~n found to exhibit improved properties over prior a~t urethanes.
Thus, or example, .such urethanes exhi~it excellent resistance to grease and oiL.
In accordance with the p~e/(-nt invent1O~I th~r(?
are provided amorphous, hydroxyl-terlnirlatecl poly(haloalkylene ethers) havin~J the ~ormula R5~o wherein Rl and R2 are each selected from hydrogen and methyl; R3 and R4 are selected from hydrogen, lower alkyl groups containing from 1 to 10 carbon atoms, and lower haloalkyl groups containing from 1 to 2 carbon atoms and ~rom 1 to 5 halogen atoms, provided that at least one of R3 and R4 is said lower haloalkyl group~ X5 is the residue of hydroxyl material which contained from 1 to 6 hydroxyl groups; b is an integer of from 1 to 50; and d is an integer oE from 1 to ~.
Preferably the polyols of the invention are poly(bromoalkylene ethers) or poly(chloroalkylene ethers).
The poly(chloroalkylene ethers) preferably contain from about 20g to 60% by weight chlorine.
The poly(haloalkylene ether) polyols of the present inven-tion are amorphous materials. Thus, they do not exhibit a melting point. Moreover, they may vary rom low molecular weight (i.e., about 250 MW) to high molecular weight (i.e., about 5000 MW) materials based upon the average hydroxyl functionality oE the polyols.
Also provided is a novel two cornponent catal~st systc~n use~ul in the preparation of the polyols. It comprises (i) HF; and (ii) a polyvalent tin compound havlny th~: Eonnu:La ~6 ~5 1 _~7 (1~, wherein g is 0 or 1; R and R are tlle catne or d.i.~ e~ent and a~f~ '`Je.leCted ErOIII
saturated and unsaturated aliphatic and aromatic hydrocclrbyL g~oups cOntaininCJ
from 1 to 10 carbon atoms; R is selected Erom the yroup COIlSiStiny of oxygen and saturated and unsaturated aliphatic and aroma tiC hydrocarbyl yroups contain-ing from 1 to 10 carbon atoms, provided that when R is oxygen then g is 0i and R is selected from the group consisting of fluorine, acyloxy groups containing less than 10 carbon atoms, and O - Sn - R
The molar ratio of the polyvalent tin compound to the HF is in the range of 1.13:1 to 3:1O Preferably -this ra-tio is in the range of 1.2:1 to 2:1.
Still further there is provided a method of makiny the polyols of the invention utilizing the novel catalyst system wherein a hydroxyl containing material having from 1 to 6 hydroxyl groups is combined with an alkylene oxide and polymerized in the presence of the above-described catalyst SyStenl.
The hydroxyl-terminated poly(haloalkylene ethers) of the invention are prepared by combining the hydroxyl-corltaining material, the alkylene oxide (at least about 50% by weight of which is haloalkylene oxide), and the catalyst system of -the inven-tion, and polymerizing the resultant mixture. Polymerization may be carried out at a -temperature in the range of about 0 C to 110 C. PreEer-9~3 ably polymerization is carried out at a temperature in the range of about 40 C
to ~0C.
Solvents may be employed during polymeri7ation. They are especially useful when one or more of the ingredients of the mixture :is a isolid. Suitable solvents solvate (but are otherwise inert to) the materials in the ~ 5 -,i i i`
llh~3 mixture. Representative examples oE ~uitable solvents are benzene, toluene, methylene chloride, carbon tetra-chloride, and l,2-dichloroethane.
Although the polymerization proceeds smoothly to cornpletion, there may be some unpolymerized h~loalkylene oxide left. This material may be separated from the poly(haloalkylene ethers) of the invention by warming the polymerization mixture (e.g., to 80C) and subjectiny the heated mixture to reduced pressure ~e.g., 0.01 Torr) fo~ a short period of time (e.y., 1-2 hours).
A wide variety o~ hydroxy1-containing rnaterials are useful in ~he present invention. They include, eor example, water, and liquid an~ solid organic materials which have a hydroxyl functionality of at least one. The organic materials may be monomeric or polymeric and are preferably selected from mono- and polyhydric alkanols, haloalkanols, and polymeric polyols.
The hydroxyl groups of the organic materials may be terminal or pendant (i.eO, other than terminal) groups.
Hydroxyl-containing materials containing both terminal and pendant hydroxyl groups may also be used. The molecular weight of the organic hydroxyl-containing material may vary over a rather wide range. For example it may be in the range of from 10 to 2,500.
Pref~rably, the organic hydroxyl-containing material is an aliphatic material which contains at least one primary or secondary aliphatic hydroxyl group (i.e~, the hydroxyl group is bonded directly to a non-aromatic carbon atom). Most preferably said organic material is an alkane polyol.
Mono- and polyhydric alkanols useful in the present invention include methanol, ethanol, isopropanol~
2-butanol, l-octanol~ oc~adecanol, 3~methyl-2-butanol, 5-propyl-3-hexanol, cyclohexanol, ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6 hexanediol, 1,4-cyclohexanedimethanol, glycerol, and sorbitol.
Mono- and polyhydric haloalkanols use~ul in the present inventon include 2-chloroethanol,
Mono- and polyhydric haloalkanols use~ul in the present inventon include 2-chloroethanol,
3-chloropropanol, 2,3-dichloropropanol, 3,4 dihromo-1,2-butanediol, 2,3-dibromo-1,4-butanediol, and 1,2,5,6-tetrabromohexane-3,4-diol.
Polymeric hydroxyl-containiny materials useful in the present invention lnclude polyoxyethylene and polyoxypropylene glycols and triols o~ molecul~r weights from 200 to 2000 ~correspondin~ to hy~roxyl e~uivalerlt weights of 100 to 1000 for ~he cliols and 70 ~o 630 Eor triols); hydroxy-terminated polyalkadienes; and polyte-tramethylene glycols o varying molecular weight, such as the Polymeg~ series of glycols available from Quaker Oats Company as Polymeg~ 650, 100~, and 2000.
The foregoing list oE useEul hydroxyl-containing materials is intended to be illustrative only. Still other hydroxyl containing materials are also useful as will be clear as a result of this disclosure.
The exact hydroxyl-containing material selected for use in the presen~ invention is dependent upon the terminal hydroxyl functionality desired in the poly~chloroalkylene ether) polyol. It has been found that the polyols of the invention have the same hydroxyl functionality as that of said hydroxyl-containing starting material and that the hydroxyl-functionality is present as a terminal hydroxyl group. Thus, for example, when a monofunctional hydroxyl-containing material is used~ a monohydric polyether is obtained; when a difunctional hydroxyl-containing material is used, a dihydric polyether ~olyol is obtained; etc~
Mixtures of hydroxyl~containing compounds may be used if desired. For example, one may use mixture of two or more poly-functional hydroxyl compounds, one or more mono-functional hydroxyl compounds with one or more polyfunctional hydroxyl compounds, etc.
A wide variety of haloalkylene oxides are useful in the present invention. They include, for example, epichlorohydrin, epiromohydrin, l-chloro-2-methyl-2,3-epoxypropane, 1,4-dibromo-2,3-epoxybutane, 1,4-dichloro-2,3-epoxybutane, l-bromo-2-methyl-2,3-epoxybutane, and 1-chloro-2,3-dimethyl-2,3-epoxy-butane. More highly halogenated monoalkylene oxides are also useful in the present invention. Representative examples of these materials include l,l-dichloro-2,3-epoxypropane, 1,1,1-trichloro-2,3-epoxypropane, 1-bromo-1,1-dichloro-2,3-epoxypropane, 1,1-dichloro-1-fluoro-2,3-epoxypropane, 1,1-difluoro-1-c~lloro-2,3-epoxypropane, etc. Stil:L other useful haloalkylene oxides include 1,1 dichloro-2-methyl-2,3-epoxypropane, 1,1,1-trichloro-3,4-epoxybutane, 1,l~dichloro-3,4-epoxybutane, 1,1,1,2,2-pentachloro-3,4-epoxybutane, 1,1,1,4,4-pentachloro-2,3-epoxybutane, 1,1,1,2,2-mixed pentahalo-3,4 epoxybutane and 1,1,1,2,2-pentachloro-2-methyl-2,3-epoxybutane.
Tetrachloroepoxybutanes such as 1,1,4,4-tetrachloro-2,3-epoxybutane, 1,1,2/2 tetrachloro-3,4-epoxybutane and 1,1,1,2-tetrachloro-3,4-epoxybutane may also be sued.
Mixtures of any of the foregoing haloalkylene oxides can be used as well as mixtures of at least one haloalkylene oxide with up to 50% by weight of one or more non-halogenated alkylene oxides. Exemplary of useful non-halogenated alkylene oxides are propylene oxide, l~hexylene oxide, cyclohexane oxide, styrene oxide, methyl glycidyl ether and phenyl glycidyl ether.
By controlling the proportions of alkylene oxide to hydroxyl-containing material, it is possible to limit the degree of addition and, consequently, the molecular weight of the polyols of the invention. Thus, the molar ratio of alkylene oxide material to hydroxyl group in said hydroxyl-containing material may he in the ran~e of 1:1 to _9_ S0:1 preferably the molar ratio i5 in the range o~ 1:1 to 20-1.
Catalyst systems useful in the present invention comprise (i) a fluorinated ~cid selected from the group described above and (ii) a polyvalent tin compound as is described above. As little as 0.05~ by weic3ht o~ the catalyst system based on the combined weight o~ the hydroxyl-containing material and allc~lene oxi-1e is effective in providin~ the polyols o~ the invention~
As discussed above, the molar ratlo of the polyvalent tin compound to the fluorlnated acid is dependent upon which fluorinated acid is em~)loyed in the catalyst system. However, whatever the exact ratio used is, the catalyst system may be easily prepared by simply adding each of the ingredients to the polymerization mixture.
As has been previously s~ated, the fluorinated acid useful in the catalyst system is selected Erom the group consisting of bis(fluorinated aliphatic sulfonyl) alkanes, HF, and acids of the formula HmXFn~m. The bis(fluorinated aliphatic sulfonyl) alkanes are preterably highly fluorinated alkanes containing from 1 to 15 carbon atoms~ Additionally, they include compounds which liberate such alkanes in the presence of heat or moisture.
For example, bisthighly fluorinated alkylsulfonyl)alkenes, upon hydrolysis~ will yield bis(highly fluorinated alkylsulfonyl~alkanes.
As it is used herein, the term highly fluorinated aliphatic radical encompasses Eluorinated, saturated, ~onovalent, aliphatic radicals having 1 to 10 carbon atoms~ The skeletal chain o the radical may be straight, branched or, if sufficiently large (e.~.~ at l~ast 3 or 4 atoms), cycloaliphatic. Moreover~ the skeletal chain may be interrupted by divalent oxygen atoms or trivalent nitrogen atoms bonded only to carbon atoms.
Rre~erably, the chain of the fluorinated aliphatic radical does not contain more than one hetero atom (i.e., nitrogen , or oxygen) for every two carbon atoms in the skeletal chain. A fully ~luorlnated yroup is pre~erred, but hydrogen or chlorine atoms may be present as .sut3stituents in the fluorinated aliphatic radical provided th~t not 5 more than one atom of either is present in the radical for each carbon atom. Preferably, the fluoroaliphatic radical is a saturated perfluoroalkyl ra~ical h~viny a skeletal chain -that is straiyht or branchec~ and has the formula C~F2X+l- wherein x has a value oE erc~ln I to l8.
The preferred bis~luorinclt~d aLi~hatic sulfonyl) alkanes are those co~npound3 hclving ~he ~ormul.
RfSO~- f ~SO2Rf ~1 wherein each Rf group is the same or difEerent and is a fluorinated (preferably a highly fluorinated or perfluorinated) alkyl group containing from 1 to 10 carbon atoms and R9 is selected from hydrogen, halogen alkyl groups having from 1 ~o 10 (preferably 1 to 4) carbon atoms, alkenyl groups containing from 1 to 3 carbon atoms, aryl groups (e.g., phenyl, naphthyl), and alkaryl groups of up to 10 carbon atoms. The alkyl, aryl and alkaryl may be substituted by one or more constituents selected from halogen, highly fluorinated alkyl sulfonyl groups, carbonyl groups, alkoxycarbonyl groups, nitro groups, alkoxy groups, and acetoxy groups.
Fully fluorinated groups are preferred, but hydrogen or chlorine atoms may be present as substituents in the group provided that not more than one atom of either is present in the radical for every two carbon atoms. The alkyl groups generally contain not more than 10 carbon atoms and preferably they contain less than 8 carbon atoms. Most preferahly they contain up to 4 carbon atoms.
Representative examples o~ uselul bis(perfluoroalkylsulfonyl) alkanes are:
bis(trirluoromethylsulfonyl) methane, bis(difluorochloromethylsulfonyl) methane, tri(trifluoromethylsulfonyl)tnethane, bis(trifluoromethylsul fonyl)-4-t)romophenylme~hane, bis(trifluoromethylsul follyl)-2-thienylmeth~me, bis(trifluoromethylsulfonyl) chloromctll.me, bis(trifluoromethylsulfollyl)l)enzyllllcthallc, bis(trifluoromethylsulfonyl)phenylmethane, bis(trifluoromethylsulfonyl)-l-naphthylmethane bis(perfluorobutylsulfonyl)methane, bis(2,2,3,3,4,4,4-heptafluorobutylsulfonyl)methane, perfluorobutylsulfonyltrifluoromethylsulfonylmethane, 1,2,2,3,3,4,4,4-heptafluorobutyltrifluoromethylsulfonylmethane, ethyl-6,6-bis-(perfluoromethylsulfonyl)-4-bromohexanoate, methyl-4,4-bis(perflucromethyl-sulfonyl)-2-carbomethoxy-2-bromobutanoate, ethyl-4,4-bis(perfluoromethyl-sulfonyl)-2-carboethoxy-2-nitrobutanoate, 1,1,3,3-tetra(trifluoromethylsulfonyl)-propane, and l,l-bis(trifluoromethylsulfonyl)octadecane.
Representative examples of useful bis(fluorinated aliphatic sulfonyl)-alkanes are also described in U.S. Patents 3,632,843 3,704,311; 3,701,40~;
3,776,960 and 3,794,687.
Another class of fluorinated acids useful in the present invetltion are substantially fully fluorinated and have the formula }InXFm+n wherein X, m and n are as described above. Specific examples of useful fluorinated acids of this 3 4 5~ 6~ Fs~ ~IPF6, AsF5 and HAsF6.
The polyvalent tin compounds useful in the catalyst system of tlle pre-sent invention have the formula ,~
l l h f~ 3 R5-Sn-R7 (~)g whereln R5, R6, R7, R8 and 9 are each as described above.
Specific examples of polyvalent tin compound~s of this type include diphenyl dibutyl tin, divinyl dibutyl tin, diallyl dibutyl tin, tributyl tin ~luoride, ~riphenyl tin acetate, dibutyl tin oxide, and bis(tributyl tin oxide)~
As has been stated, the chloroaLkylene ether polyols of the present invention are optically clear and substantially colorless, as i'3 demon~trated by their color magnitude (i.e., they have a color magnitude o~ less than 10). Color magnitude represents the deviation of the color of a given material from the color oE distilled water when both colors are measured at about 25C. The color of the water and of the samples is measured by a Hunterlab Model D25-4 Color Difference ~eter available from ~lunder-Associates Laboratory, 9529 Lee IIighway~
Fairfax, Virginia. The meter measures three parameters which characterize the color of a sample. These para-meters are (i) the gray component "L" of the sample;
(îi) the red~greed compnent l'a" of the sample (a plus value indicating redness and a minus value indicating greenness~; and (iii) the yellow-blue compnent "b" of the sample (a plus value indicating yellowness and a minus value indicating blueness). The color magnitude ~ E) is calculated from the formula E = ~ ) + (~a) + (~b) wherein ~L, ~a and ~b respectively represent the difference between the L~ a and b values of distille~
water and the sample being tested. Distilled water has a color magnitude of 0 at 25Ct Color magnitude values of less than 10 represent optically clear and substantially colorless materials~
The color of a material having a color magnitude o~ 10 is very light yellow and a thln film of such a material remains optically clear. As the color magnitude increa~es (i.e., as E increases) the color and the optical clarity of the sample decreases. Thus, at a color maynitude oE 20 the material has light brown color and a thin film thereo~
has a hazy optical clarity. At a color magnitude o~ 50 the material has a very dark brown color and a thin Eilm thereof is difficult to see through~
The invention is further illustra~ed by means of ~he following examples wherein the term "part~" refers ~o parts by weight unless otherwise indicated. In the examples the poly(alkylene ether) polyols were prepared according to the following general procedure.
The polyethers were prepared in a glass reaction flask which was equipped with a stirrer, thermometer, and a dropping funnel. A dry atmosphere was maintained in the flask during the reaction.
In each preparation the hydroxyl-containing material (ethylene glycol, 6~.0 g, l mole) and the catalyst system were charged to the flask and stirred and heated to about 40~ - ~0C. The composition and quantity of the catalyst system was varied in each reaction. The haloalkylene oxide (epichlorohydrin or epibromohydrin) was then slowly charged to the stirred mixture over a period of about 3 hours. The reaction was allowed to proceed until it was substantially complete. The temperature of the reaction mixture was maintained between about 40 and 85C. The amount of haloalkylene oxide employed was varied so as to control the hydroxyl-equivalent weight o the product. Thus, for example, 938 g (lOol moles) of epichlorohydrin were employed in order to provide a product having a theoretical hydroxyl equivalent weight of about 500. On the other hand 1938 g (21 moles) of epichlo-rohydrin were employed in order to provide a product having a theoretical hydroxyl equivalent weight of about 1000.
.
~XAMPL.ES 1-25 Examples 1-25 represent a numL~er o~ polylchloro-alkylene ether) polyols prepared accordiny to the above described general procedure utilizing both prior art catalyst systems and catalyst sys~ems o~ the invention.
The exac~ nature of the catalyst system utilized and the results obtained are given in Table 1 The catalyst system utilized in rl~xan~le3 1-3 was BF3; that in Example 4 was ~lSbF6~El2O; khat in ~xalnE~Ie 5 was (C~Hs)3O+p~l6- and that in Example 6 was ';bF~ can be seen the poly(chloroalkylene ether) polyols pre~ar~!d ~rom these catalyst systems were darkly colored as is demonstrated by their high E values (i.e., between 30 and 523~
Examples 7-9 demonstrate the effect of the individual components of the catalyst system oE the present invention upon the poly(chloroalkylene ether) polyols produced~ Thus, in Example 7 the catalyst system was a polyvalent tin compound of the formula R5-Sr,_R7 (~8)~
(i-e-~ (C6H5)2Sn(C4H9)2)- As can be seen from Example 7 there was no reaction even after 5 hours of mixing when the diphenyl dibutyl tin compound was used as the catalyst system. When the catalyst system was the sulfonyl alkane compound (Examples 8 and 9) darker products than those of the invention were obtained as is shown by their color magnitude.
Examples 10-12 demonstarate the criticality of the molar ratio of the HmXFm_n fluorinated acid to the tin compound in the catalyst composition of the invention.
Thus in Examples 10 and 11 the ratio was 1:1 and 1.1:1.
In each case the resulting product had a very daL^k brown ~hL~ 3 (i.e., ~E of 53.1 and 52.9 respectively). However, in Example 12 the molar ratio was 1.13:1 and the resulting product was optically clear and substantially colorles~
(i.e., a color magnitude of 2.1).
Examples 12-24 demonstrate the present invention. In each o~ these examples an optically clear and substantially colorless poly(chloroalkylene ~ther) polyol was obtained, This is demonstrated by the lo~l~E
values obtained (i.e., QE less than about 5). ~xamples 12-16 show the effect oE varying the molar ratio o the ~mXFm+n fluorinated acid to the polyvalent tin compound.
Examples 17-20 show the use of the bis(fluorinated aliphatic sulfonyl)alkanes and the use of varying ratios of this acid to the tin compound in the catalyst system~
Examples 21-24 show the use of differing tin compounds in the catalyst system. Example 25 shows that highly halogenated alkylene oxides (e.g., l,l,l-trichlorobutylene oxide) can also be used in the present invention~
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_ _ EXA~PLES 26-27 A series of hydroxyl-terminated poly(halo-alkylene ethers) were prepared as described in the general procedure. The resultant polyethers were tested for initial color magnitude then subjected to heat (80C~ for 14 hours after which time the polyethers were tested Eor final color magnitude. Example 26 was per-formed usiny a sample from the polyol prepared in Example 13 oE Table 1.
Example 27 was per~ormed using a ~90 hydroxyl equivalent ]0 weight polyether prepared according to the general procedure but employing (C2H5)3O~PF6~ ~0.~% by weight o~
the combîned weight of the ethylene glycol and the epichlorohydrin) as the catalyst system.
Example EI ~EF
2~ 1.51 1.56 27 18.55 30.41 ~EI is the initial color of the polyol in the test. AEF
is the color of the polyol after heat aging at 80C for a 14 hour period9 The behavior of Example 26 is characteristic of all the polyols of the invention. As can be seen, poly(chloroalkylene ether)polyols of the invention exhibit essentially no change in color magnitude while prior art poly(chloroalkylene ether)polyols darken drama~ically in color.
EXAMPLES_28-34 A series of polyurethanes were made using various poly(chloroalkylene ether)polyols, and a poly-functional polyisocyanate. The polyols were prepared as described in the general procedure. The polyfunctional isocyanate was "Mondur MRS'~(a polymethylene polyphenyl isocyanate having an average oE about 2.6 isocyanate groups per ~olecule and being available Erom Mobay Company)~
r The polyurethanes were prepared by combining the ingredients in a suitable reaction vessel and stir~ing them for 1-2 minutes at a temperature of about 25C~ A
moisture free atmosphere was maintained in the reaction vessel. These was no catalyst added to promote the reaction.
Examples 28 and 29 utilized poly(chloroalkylene ether)polyols accordiny to the invention, These polyol3 were prepared using the same cataly~t sy3tem ancJ amount~
thereof as are set forth in Example 15. The polyol employed in Example 28 had a theoretical hydroxyl~
equivalent weight of 325 while the polyether employed in Example 29 had a theoretical hydroxyl equivalent weight of 500.
Examples 30-34 utilized poly(chloroalkylene ether)polyols prepared from prior art catalyst systems.
The polyol employed in Example 30 had a theoretical hydroxyl equivalent weight of 1000 and was prepared utilizing BF3 (0.3~ by weight of the combined weight of the epichlorohydrin and the ethylene glycol~ as the catalyst system. ThP polyols employed in Examples 31 and 32 had theoretical hydroxyl equivalent weights of 500 and 325 respectively and were prepared utilizing ~C2Hs)3O+PF6-(0.2% by weight of the epichlorohydrin and the ethylene glycol) as the catalyst system. The polyGls employed in Examples 33 and 34 had theoretical hydroxyl equivalent weights of 500 and 325 respectively and were prepared with HSbF6-6H2O (0.1% by weight of the combined weight of the epichlorohydrin and the ethylene glycol) as the catalyst system.
The results of the preparations are given in Table 3. As can be seen the polyurethanes of Examples ~8 and 29 ~prepared according to the invention) gelled quickly while the polyurethanes of Examples 30-34 ~prepared according to the prior art) did not gell even after ~4 hours. Moreoever, the polyurethanes of Examples 28-29 cured within 24 hours while those of Examples 30-34
Polymeric hydroxyl-containiny materials useful in the present invention lnclude polyoxyethylene and polyoxypropylene glycols and triols o~ molecul~r weights from 200 to 2000 ~correspondin~ to hy~roxyl e~uivalerlt weights of 100 to 1000 for ~he cliols and 70 ~o 630 Eor triols); hydroxy-terminated polyalkadienes; and polyte-tramethylene glycols o varying molecular weight, such as the Polymeg~ series of glycols available from Quaker Oats Company as Polymeg~ 650, 100~, and 2000.
The foregoing list oE useEul hydroxyl-containing materials is intended to be illustrative only. Still other hydroxyl containing materials are also useful as will be clear as a result of this disclosure.
The exact hydroxyl-containing material selected for use in the presen~ invention is dependent upon the terminal hydroxyl functionality desired in the poly~chloroalkylene ether) polyol. It has been found that the polyols of the invention have the same hydroxyl functionality as that of said hydroxyl-containing starting material and that the hydroxyl-functionality is present as a terminal hydroxyl group. Thus, for example, when a monofunctional hydroxyl-containing material is used~ a monohydric polyether is obtained; when a difunctional hydroxyl-containing material is used, a dihydric polyether ~olyol is obtained; etc~
Mixtures of hydroxyl~containing compounds may be used if desired. For example, one may use mixture of two or more poly-functional hydroxyl compounds, one or more mono-functional hydroxyl compounds with one or more polyfunctional hydroxyl compounds, etc.
A wide variety of haloalkylene oxides are useful in the present invention. They include, for example, epichlorohydrin, epiromohydrin, l-chloro-2-methyl-2,3-epoxypropane, 1,4-dibromo-2,3-epoxybutane, 1,4-dichloro-2,3-epoxybutane, l-bromo-2-methyl-2,3-epoxybutane, and 1-chloro-2,3-dimethyl-2,3-epoxy-butane. More highly halogenated monoalkylene oxides are also useful in the present invention. Representative examples of these materials include l,l-dichloro-2,3-epoxypropane, 1,1,1-trichloro-2,3-epoxypropane, 1-bromo-1,1-dichloro-2,3-epoxypropane, 1,1-dichloro-1-fluoro-2,3-epoxypropane, 1,1-difluoro-1-c~lloro-2,3-epoxypropane, etc. Stil:L other useful haloalkylene oxides include 1,1 dichloro-2-methyl-2,3-epoxypropane, 1,1,1-trichloro-3,4-epoxybutane, 1,l~dichloro-3,4-epoxybutane, 1,1,1,2,2-pentachloro-3,4-epoxybutane, 1,1,1,4,4-pentachloro-2,3-epoxybutane, 1,1,1,2,2-mixed pentahalo-3,4 epoxybutane and 1,1,1,2,2-pentachloro-2-methyl-2,3-epoxybutane.
Tetrachloroepoxybutanes such as 1,1,4,4-tetrachloro-2,3-epoxybutane, 1,1,2/2 tetrachloro-3,4-epoxybutane and 1,1,1,2-tetrachloro-3,4-epoxybutane may also be sued.
Mixtures of any of the foregoing haloalkylene oxides can be used as well as mixtures of at least one haloalkylene oxide with up to 50% by weight of one or more non-halogenated alkylene oxides. Exemplary of useful non-halogenated alkylene oxides are propylene oxide, l~hexylene oxide, cyclohexane oxide, styrene oxide, methyl glycidyl ether and phenyl glycidyl ether.
By controlling the proportions of alkylene oxide to hydroxyl-containing material, it is possible to limit the degree of addition and, consequently, the molecular weight of the polyols of the invention. Thus, the molar ratio of alkylene oxide material to hydroxyl group in said hydroxyl-containing material may he in the ran~e of 1:1 to _9_ S0:1 preferably the molar ratio i5 in the range o~ 1:1 to 20-1.
Catalyst systems useful in the present invention comprise (i) a fluorinated ~cid selected from the group described above and (ii) a polyvalent tin compound as is described above. As little as 0.05~ by weic3ht o~ the catalyst system based on the combined weight o~ the hydroxyl-containing material and allc~lene oxi-1e is effective in providin~ the polyols o~ the invention~
As discussed above, the molar ratlo of the polyvalent tin compound to the fluorlnated acid is dependent upon which fluorinated acid is em~)loyed in the catalyst system. However, whatever the exact ratio used is, the catalyst system may be easily prepared by simply adding each of the ingredients to the polymerization mixture.
As has been previously s~ated, the fluorinated acid useful in the catalyst system is selected Erom the group consisting of bis(fluorinated aliphatic sulfonyl) alkanes, HF, and acids of the formula HmXFn~m. The bis(fluorinated aliphatic sulfonyl) alkanes are preterably highly fluorinated alkanes containing from 1 to 15 carbon atoms~ Additionally, they include compounds which liberate such alkanes in the presence of heat or moisture.
For example, bisthighly fluorinated alkylsulfonyl)alkenes, upon hydrolysis~ will yield bis(highly fluorinated alkylsulfonyl~alkanes.
As it is used herein, the term highly fluorinated aliphatic radical encompasses Eluorinated, saturated, ~onovalent, aliphatic radicals having 1 to 10 carbon atoms~ The skeletal chain o the radical may be straight, branched or, if sufficiently large (e.~.~ at l~ast 3 or 4 atoms), cycloaliphatic. Moreover~ the skeletal chain may be interrupted by divalent oxygen atoms or trivalent nitrogen atoms bonded only to carbon atoms.
Rre~erably, the chain of the fluorinated aliphatic radical does not contain more than one hetero atom (i.e., nitrogen , or oxygen) for every two carbon atoms in the skeletal chain. A fully ~luorlnated yroup is pre~erred, but hydrogen or chlorine atoms may be present as .sut3stituents in the fluorinated aliphatic radical provided th~t not 5 more than one atom of either is present in the radical for each carbon atom. Preferably, the fluoroaliphatic radical is a saturated perfluoroalkyl ra~ical h~viny a skeletal chain -that is straiyht or branchec~ and has the formula C~F2X+l- wherein x has a value oE erc~ln I to l8.
The preferred bis~luorinclt~d aLi~hatic sulfonyl) alkanes are those co~npound3 hclving ~he ~ormul.
RfSO~- f ~SO2Rf ~1 wherein each Rf group is the same or difEerent and is a fluorinated (preferably a highly fluorinated or perfluorinated) alkyl group containing from 1 to 10 carbon atoms and R9 is selected from hydrogen, halogen alkyl groups having from 1 ~o 10 (preferably 1 to 4) carbon atoms, alkenyl groups containing from 1 to 3 carbon atoms, aryl groups (e.g., phenyl, naphthyl), and alkaryl groups of up to 10 carbon atoms. The alkyl, aryl and alkaryl may be substituted by one or more constituents selected from halogen, highly fluorinated alkyl sulfonyl groups, carbonyl groups, alkoxycarbonyl groups, nitro groups, alkoxy groups, and acetoxy groups.
Fully fluorinated groups are preferred, but hydrogen or chlorine atoms may be present as substituents in the group provided that not more than one atom of either is present in the radical for every two carbon atoms. The alkyl groups generally contain not more than 10 carbon atoms and preferably they contain less than 8 carbon atoms. Most preferahly they contain up to 4 carbon atoms.
Representative examples o~ uselul bis(perfluoroalkylsulfonyl) alkanes are:
bis(trirluoromethylsulfonyl) methane, bis(difluorochloromethylsulfonyl) methane, tri(trifluoromethylsulfonyl)tnethane, bis(trifluoromethylsul fonyl)-4-t)romophenylme~hane, bis(trifluoromethylsul follyl)-2-thienylmeth~me, bis(trifluoromethylsulfonyl) chloromctll.me, bis(trifluoromethylsulfollyl)l)enzyllllcthallc, bis(trifluoromethylsulfonyl)phenylmethane, bis(trifluoromethylsulfonyl)-l-naphthylmethane bis(perfluorobutylsulfonyl)methane, bis(2,2,3,3,4,4,4-heptafluorobutylsulfonyl)methane, perfluorobutylsulfonyltrifluoromethylsulfonylmethane, 1,2,2,3,3,4,4,4-heptafluorobutyltrifluoromethylsulfonylmethane, ethyl-6,6-bis-(perfluoromethylsulfonyl)-4-bromohexanoate, methyl-4,4-bis(perflucromethyl-sulfonyl)-2-carbomethoxy-2-bromobutanoate, ethyl-4,4-bis(perfluoromethyl-sulfonyl)-2-carboethoxy-2-nitrobutanoate, 1,1,3,3-tetra(trifluoromethylsulfonyl)-propane, and l,l-bis(trifluoromethylsulfonyl)octadecane.
Representative examples of useful bis(fluorinated aliphatic sulfonyl)-alkanes are also described in U.S. Patents 3,632,843 3,704,311; 3,701,40~;
3,776,960 and 3,794,687.
Another class of fluorinated acids useful in the present invetltion are substantially fully fluorinated and have the formula }InXFm+n wherein X, m and n are as described above. Specific examples of useful fluorinated acids of this 3 4 5~ 6~ Fs~ ~IPF6, AsF5 and HAsF6.
The polyvalent tin compounds useful in the catalyst system of tlle pre-sent invention have the formula ,~
l l h f~ 3 R5-Sn-R7 (~)g whereln R5, R6, R7, R8 and 9 are each as described above.
Specific examples of polyvalent tin compound~s of this type include diphenyl dibutyl tin, divinyl dibutyl tin, diallyl dibutyl tin, tributyl tin ~luoride, ~riphenyl tin acetate, dibutyl tin oxide, and bis(tributyl tin oxide)~
As has been stated, the chloroaLkylene ether polyols of the present invention are optically clear and substantially colorless, as i'3 demon~trated by their color magnitude (i.e., they have a color magnitude o~ less than 10). Color magnitude represents the deviation of the color of a given material from the color oE distilled water when both colors are measured at about 25C. The color of the water and of the samples is measured by a Hunterlab Model D25-4 Color Difference ~eter available from ~lunder-Associates Laboratory, 9529 Lee IIighway~
Fairfax, Virginia. The meter measures three parameters which characterize the color of a sample. These para-meters are (i) the gray component "L" of the sample;
(îi) the red~greed compnent l'a" of the sample (a plus value indicating redness and a minus value indicating greenness~; and (iii) the yellow-blue compnent "b" of the sample (a plus value indicating yellowness and a minus value indicating blueness). The color magnitude ~ E) is calculated from the formula E = ~ ) + (~a) + (~b) wherein ~L, ~a and ~b respectively represent the difference between the L~ a and b values of distille~
water and the sample being tested. Distilled water has a color magnitude of 0 at 25Ct Color magnitude values of less than 10 represent optically clear and substantially colorless materials~
The color of a material having a color magnitude o~ 10 is very light yellow and a thln film of such a material remains optically clear. As the color magnitude increa~es (i.e., as E increases) the color and the optical clarity of the sample decreases. Thus, at a color maynitude oE 20 the material has light brown color and a thin film thereo~
has a hazy optical clarity. At a color magnitude o~ 50 the material has a very dark brown color and a thin Eilm thereof is difficult to see through~
The invention is further illustra~ed by means of ~he following examples wherein the term "part~" refers ~o parts by weight unless otherwise indicated. In the examples the poly(alkylene ether) polyols were prepared according to the following general procedure.
The polyethers were prepared in a glass reaction flask which was equipped with a stirrer, thermometer, and a dropping funnel. A dry atmosphere was maintained in the flask during the reaction.
In each preparation the hydroxyl-containing material (ethylene glycol, 6~.0 g, l mole) and the catalyst system were charged to the flask and stirred and heated to about 40~ - ~0C. The composition and quantity of the catalyst system was varied in each reaction. The haloalkylene oxide (epichlorohydrin or epibromohydrin) was then slowly charged to the stirred mixture over a period of about 3 hours. The reaction was allowed to proceed until it was substantially complete. The temperature of the reaction mixture was maintained between about 40 and 85C. The amount of haloalkylene oxide employed was varied so as to control the hydroxyl-equivalent weight o the product. Thus, for example, 938 g (lOol moles) of epichlorohydrin were employed in order to provide a product having a theoretical hydroxyl equivalent weight of about 500. On the other hand 1938 g (21 moles) of epichlo-rohydrin were employed in order to provide a product having a theoretical hydroxyl equivalent weight of about 1000.
.
~XAMPL.ES 1-25 Examples 1-25 represent a numL~er o~ polylchloro-alkylene ether) polyols prepared accordiny to the above described general procedure utilizing both prior art catalyst systems and catalyst sys~ems o~ the invention.
The exac~ nature of the catalyst system utilized and the results obtained are given in Table 1 The catalyst system utilized in rl~xan~le3 1-3 was BF3; that in Example 4 was ~lSbF6~El2O; khat in ~xalnE~Ie 5 was (C~Hs)3O+p~l6- and that in Example 6 was ';bF~ can be seen the poly(chloroalkylene ether) polyols pre~ar~!d ~rom these catalyst systems were darkly colored as is demonstrated by their high E values (i.e., between 30 and 523~
Examples 7-9 demonstrate the effect of the individual components of the catalyst system oE the present invention upon the poly(chloroalkylene ether) polyols produced~ Thus, in Example 7 the catalyst system was a polyvalent tin compound of the formula R5-Sr,_R7 (~8)~
(i-e-~ (C6H5)2Sn(C4H9)2)- As can be seen from Example 7 there was no reaction even after 5 hours of mixing when the diphenyl dibutyl tin compound was used as the catalyst system. When the catalyst system was the sulfonyl alkane compound (Examples 8 and 9) darker products than those of the invention were obtained as is shown by their color magnitude.
Examples 10-12 demonstarate the criticality of the molar ratio of the HmXFm_n fluorinated acid to the tin compound in the catalyst composition of the invention.
Thus in Examples 10 and 11 the ratio was 1:1 and 1.1:1.
In each case the resulting product had a very daL^k brown ~hL~ 3 (i.e., ~E of 53.1 and 52.9 respectively). However, in Example 12 the molar ratio was 1.13:1 and the resulting product was optically clear and substantially colorles~
(i.e., a color magnitude of 2.1).
Examples 12-24 demonstrate the present invention. In each o~ these examples an optically clear and substantially colorless poly(chloroalkylene ~ther) polyol was obtained, This is demonstrated by the lo~l~E
values obtained (i.e., QE less than about 5). ~xamples 12-16 show the effect oE varying the molar ratio o the ~mXFm+n fluorinated acid to the polyvalent tin compound.
Examples 17-20 show the use of the bis(fluorinated aliphatic sulfonyl)alkanes and the use of varying ratios of this acid to the tin compound in the catalyst system~
Examples 21-24 show the use of differing tin compounds in the catalyst system. Example 25 shows that highly halogenated alkylene oxides (e.g., l,l,l-trichlorobutylene oxide) can also be used in the present invention~
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_ _ EXA~PLES 26-27 A series of hydroxyl-terminated poly(halo-alkylene ethers) were prepared as described in the general procedure. The resultant polyethers were tested for initial color magnitude then subjected to heat (80C~ for 14 hours after which time the polyethers were tested Eor final color magnitude. Example 26 was per-formed usiny a sample from the polyol prepared in Example 13 oE Table 1.
Example 27 was per~ormed using a ~90 hydroxyl equivalent ]0 weight polyether prepared according to the general procedure but employing (C2H5)3O~PF6~ ~0.~% by weight o~
the combîned weight of the ethylene glycol and the epichlorohydrin) as the catalyst system.
Example EI ~EF
2~ 1.51 1.56 27 18.55 30.41 ~EI is the initial color of the polyol in the test. AEF
is the color of the polyol after heat aging at 80C for a 14 hour period9 The behavior of Example 26 is characteristic of all the polyols of the invention. As can be seen, poly(chloroalkylene ether)polyols of the invention exhibit essentially no change in color magnitude while prior art poly(chloroalkylene ether)polyols darken drama~ically in color.
EXAMPLES_28-34 A series of polyurethanes were made using various poly(chloroalkylene ether)polyols, and a poly-functional polyisocyanate. The polyols were prepared as described in the general procedure. The polyfunctional isocyanate was "Mondur MRS'~(a polymethylene polyphenyl isocyanate having an average oE about 2.6 isocyanate groups per ~olecule and being available Erom Mobay Company)~
r The polyurethanes were prepared by combining the ingredients in a suitable reaction vessel and stir~ing them for 1-2 minutes at a temperature of about 25C~ A
moisture free atmosphere was maintained in the reaction vessel. These was no catalyst added to promote the reaction.
Examples 28 and 29 utilized poly(chloroalkylene ether)polyols accordiny to the invention, These polyol3 were prepared using the same cataly~t sy3tem ancJ amount~
thereof as are set forth in Example 15. The polyol employed in Example 28 had a theoretical hydroxyl~
equivalent weight of 325 while the polyether employed in Example 29 had a theoretical hydroxyl equivalent weight of 500.
Examples 30-34 utilized poly(chloroalkylene ether)polyols prepared from prior art catalyst systems.
The polyol employed in Example 30 had a theoretical hydroxyl equivalent weight of 1000 and was prepared utilizing BF3 (0.3~ by weight of the combined weight of the epichlorohydrin and the ethylene glycol~ as the catalyst system. ThP polyols employed in Examples 31 and 32 had theoretical hydroxyl equivalent weights of 500 and 325 respectively and were prepared utilizing ~C2Hs)3O+PF6-(0.2% by weight of the epichlorohydrin and the ethylene glycol) as the catalyst system. The polyGls employed in Examples 33 and 34 had theoretical hydroxyl equivalent weights of 500 and 325 respectively and were prepared with HSbF6-6H2O (0.1% by weight of the combined weight of the epichlorohydrin and the ethylene glycol) as the catalyst system.
The results of the preparations are given in Table 3. As can be seen the polyurethanes of Examples ~8 and 29 ~prepared according to the invention) gelled quickly while the polyurethanes of Examples 30-34 ~prepared according to the prior art) did not gell even after ~4 hours. Moreoever, the polyurethanes of Examples 28-29 cured within 24 hours while those of Examples 30-34
4~
d.id not cure even after 3 days.
Polyurethane Viscosity (cp~) Initial Final Example NCO/OH (Time=0 hours) (Time=24 hour~) 28 1.2:1 4800 Gelled wlthin 15*
minute~
29 1.2:1 220U Gel.led within 15*
minutes 1.2:1 5900 24000 31 1.2:1 5~00 16000 32 1.2:1 2300 5400 33 1.2:1 4~00 15000 34 1~2:1 2200 27000 *Gellation occurs when the viscosity >1,000,000 cps.
A series of hydroxyl-terminated poly(chloro-alkylene ethers) according to the invention were prepar~d according to the general procedure except that various hydroxyl containing materials were substituted for ethylene glycole In each of these examples the catalyst system comprised 0.1% HSbF6-6H20 and 0.224~ diphenyl dibutyl tin (both percentages being percentage~s by weight of the combined weight of the hydroxyl material and the epichlorohydrin~. The resulting polyols were then tested for percent conversion, hydroxyl equivalent weight and color magnitude. Th exact ingredients used to prepare the polyols, the amounts of each and the results obtained are reported in Table 4.
a~
O ~ o o o o o g u~ r Lf) I` L~) er O
4 co a~
cP ~ ~ a~
~ ~n .~ 1~ a~ co oo ~ co r~
~ ¢
\U ~
o A hydroxyl-terminated po1y(bromoalkylene ether) according to the invention was prepared. A mixture of cyclohexanedimethanol (72 g, MW 144, 0.5 mol~s) and methylene chloride (500 ml) was heated to ~0C and the catalyst system (48% aqueous fluoboric acid arld 1.8 g of diphenyl dibutyl tine) 3.~ g was added. Epibromohydrin (purified by distillation, 52% g) was then added slow1y over a period of one hour into the mixture ~nd the reaction temperature was maintained at ~0-45C. The mixture was allowed to stir at ~0C for 16 hour~ after which 58% ammonium hydroxide was added and stirred until the mixture reached a pE~=7. Anhydrous magnesium sulfate and Celite~ were added slowly, stirred and filtered. The solvent and residual epibromohydrin were removed under vacuum~ A 96% yield of a yellowish polyepibromohydrin was obtained. It had a hydroxyl equivalent weight of 358, a weight average molecular weight of 1023, a number average molecular weight of 817 ! and a bromine content of 46~7%.
A hydroxyl terminated poly(chloroalkylene ether) according to the invention was prepared. A mixture of cyclohexane dimethanol (36 g, MW 144, 0.25 moles) and the catalyst system (0.31 g of 48% aqueous hydrofluoric acid and 0.17 g of diphenyl dibutyl tin) was heated to 60-65C.
Epichlorohydrin (214 g, 2.31 moles) was added slowly to the mixture while maintaining the same temperature. The reaction mixture was allowed to stir for an additional 16 hours. Vacuum distillation provided a yield of 72~ of colorless and slightly cloudy poly~chloroalkylene ether) according to the invention, The product had a hydroxyl equivalent weight of 332~ a weight average molecular weight of 838, and a color magnitude of 1.69.
The yield of the chloroalkylene ether may be improved to 97.3~ by utilizing a catalyst system of 0.75 g of 48% aqueous hydrofluoric acid and 0.5 g of diphenyl dibutyl tin. The product obtained from this reaction has a hydroxyl equivalent weight of ~07.
d.id not cure even after 3 days.
Polyurethane Viscosity (cp~) Initial Final Example NCO/OH (Time=0 hours) (Time=24 hour~) 28 1.2:1 4800 Gelled wlthin 15*
minute~
29 1.2:1 220U Gel.led within 15*
minutes 1.2:1 5900 24000 31 1.2:1 5~00 16000 32 1.2:1 2300 5400 33 1.2:1 4~00 15000 34 1~2:1 2200 27000 *Gellation occurs when the viscosity >1,000,000 cps.
A series of hydroxyl-terminated poly(chloro-alkylene ethers) according to the invention were prepar~d according to the general procedure except that various hydroxyl containing materials were substituted for ethylene glycole In each of these examples the catalyst system comprised 0.1% HSbF6-6H20 and 0.224~ diphenyl dibutyl tin (both percentages being percentage~s by weight of the combined weight of the hydroxyl material and the epichlorohydrin~. The resulting polyols were then tested for percent conversion, hydroxyl equivalent weight and color magnitude. Th exact ingredients used to prepare the polyols, the amounts of each and the results obtained are reported in Table 4.
a~
O ~ o o o o o g u~ r Lf) I` L~) er O
4 co a~
cP ~ ~ a~
~ ~n .~ 1~ a~ co oo ~ co r~
~ ¢
\U ~
o A hydroxyl-terminated po1y(bromoalkylene ether) according to the invention was prepared. A mixture of cyclohexanedimethanol (72 g, MW 144, 0.5 mol~s) and methylene chloride (500 ml) was heated to ~0C and the catalyst system (48% aqueous fluoboric acid arld 1.8 g of diphenyl dibutyl tine) 3.~ g was added. Epibromohydrin (purified by distillation, 52% g) was then added slow1y over a period of one hour into the mixture ~nd the reaction temperature was maintained at ~0-45C. The mixture was allowed to stir at ~0C for 16 hour~ after which 58% ammonium hydroxide was added and stirred until the mixture reached a pE~=7. Anhydrous magnesium sulfate and Celite~ were added slowly, stirred and filtered. The solvent and residual epibromohydrin were removed under vacuum~ A 96% yield of a yellowish polyepibromohydrin was obtained. It had a hydroxyl equivalent weight of 358, a weight average molecular weight of 1023, a number average molecular weight of 817 ! and a bromine content of 46~7%.
A hydroxyl terminated poly(chloroalkylene ether) according to the invention was prepared. A mixture of cyclohexane dimethanol (36 g, MW 144, 0.25 moles) and the catalyst system (0.31 g of 48% aqueous hydrofluoric acid and 0.17 g of diphenyl dibutyl tin) was heated to 60-65C.
Epichlorohydrin (214 g, 2.31 moles) was added slowly to the mixture while maintaining the same temperature. The reaction mixture was allowed to stir for an additional 16 hours. Vacuum distillation provided a yield of 72~ of colorless and slightly cloudy poly~chloroalkylene ether) according to the invention, The product had a hydroxyl equivalent weight of 332~ a weight average molecular weight of 838, and a color magnitude of 1.69.
The yield of the chloroalkylene ether may be improved to 97.3~ by utilizing a catalyst system of 0.75 g of 48% aqueous hydrofluoric acid and 0.5 g of diphenyl dibutyl tin. The product obtained from this reaction has a hydroxyl equivalent weight of ~07.
Claims (4)
1. An amorphous, hydroxyl-terminated poly(halo-alkylene ether) having the formula wherein R1 and R2 are each selected from hydro-gen and methyl; R3 and R4 are each selected from hydrogen, lower alkyl groups containing from 1 to 10 carbon atoms, and lower haloalkyl groups containing from 1 to 2 carbon atoms and from 1 to 5 halogen atoms, provided at least one of R3 and R4 is said lower haloalkyl groups; R5 is the residue of a hydroxyl material which hydroxyl material contained from 1 to 6 hydroxyl groups, said hydroxyl material groups being selected from the group consisting of water, mono and polyhydric alkanols, haloalkanols, polyoxyethylene glycols and triols, poly-propylene glycols and triols, hydroxy-terminated poly-alkadienes, and polytetramethylene glycols; b is an integer of from 1 to 50; and d is an integer of from 1 to 6; said poly(haloalkylene ether) being prepared by the reaction of a hydroxyl material containing from 1 to 6 hydroxyl groups and a chloroalkylene oxide, said reaction being carried out in the presence of a two component catalyst system comprising (i) HF; and (ii) a polyvalent tin compound having the formula wherein g is 0 or 1;
R5 and R6 are the same or different and are selected from saturated and unsaturated aliphatic and aromatic hydrocarbyl groups containing from 1 to 10 carbon atoms;
R7 is selected from the group consist-ing of oxygen and saturated and unsaturated aliphatic and aromatic hydrocarbyl groups containing from 1 to 10 carbon atoms, provided that when R is oxygen then g is 0; and R8 is selected from the group consist-ing of fluorine, acyloxy groups containing less than 10 carbon atoms and
R5 and R6 are the same or different and are selected from saturated and unsaturated aliphatic and aromatic hydrocarbyl groups containing from 1 to 10 carbon atoms;
R7 is selected from the group consist-ing of oxygen and saturated and unsaturated aliphatic and aromatic hydrocarbyl groups containing from 1 to 10 carbon atoms, provided that when R is oxygen then g is 0; and R8 is selected from the group consist-ing of fluorine, acyloxy groups containing less than 10 carbon atoms and
2. An amorphous, hydroxyl-terminated poly(haloalkylene ether) according to claim 1 wherein said polyvalent tin compound is selected from the group consisting of diphenyl dibutyl tin, divinyl dibutyl tin, diallyl dibutyl tin, tributyl tin fluoride, triphenyl tin acetate, dibutyl tin oxide, and bis(tributyl tin oxide).
3. An amorphous, hydroxyl-terminated poly(chloroalkylene ether) according to claim 1 having a color magnitude of less than about 10.
4. A method for the preparation of amorphous hydroxyl-terminated poly(haloalkylene ethers) according to claim 1 which comprises reacting a hydroxyl material containing from 1 to 6 hydroxyl groups and a haloalkylene oxide in the presence of a catalytic amount of a two component catalyst system comprising (i) HF; and (ii) a polyvalent tin compound having the formula wherein g is 0 or 1;
R5 and R6 are the same or different and are selected from saturated and unsaturated aliphatic and aromatic hydrocarbyl groups containing from 1 to 10 carbon atoms;
R7 is selected from the group consisting of oxygen and saturated and unsaturated aliphatic and aromatic hydrocarbyl groups containing from 1 to 10 carbon atoms, provided that when R7 is oxygen then g is 0; and R8 is selected from the group consist-ing of fluorine, acyloxy groups containing less than 10 carbon atoms, saturated aliphatic hydrocarbyl groups containing from 1 to 10 carbon atoms and provided that when R5, R6 and R7 are each saturated aliphatic hydrocarbyl groups then R8 is selected from the group consisting of fluorine, acyloxy groups containing less than 10 carbon atoms and
R5 and R6 are the same or different and are selected from saturated and unsaturated aliphatic and aromatic hydrocarbyl groups containing from 1 to 10 carbon atoms;
R7 is selected from the group consisting of oxygen and saturated and unsaturated aliphatic and aromatic hydrocarbyl groups containing from 1 to 10 carbon atoms, provided that when R7 is oxygen then g is 0; and R8 is selected from the group consist-ing of fluorine, acyloxy groups containing less than 10 carbon atoms, saturated aliphatic hydrocarbyl groups containing from 1 to 10 carbon atoms and provided that when R5, R6 and R7 are each saturated aliphatic hydrocarbyl groups then R8 is selected from the group consisting of fluorine, acyloxy groups containing less than 10 carbon atoms and
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000369016A CA1184943A (en) | 1981-01-21 | 1981-01-21 | Hydroxyl-terminated poly(haloalkylene ethers) |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000369016A CA1184943A (en) | 1981-01-21 | 1981-01-21 | Hydroxyl-terminated poly(haloalkylene ethers) |
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| Publication Number | Publication Date |
|---|---|
| CA1184943A true CA1184943A (en) | 1985-04-02 |
Family
ID=4118978
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000369016A Expired CA1184943A (en) | 1981-01-21 | 1981-01-21 | Hydroxyl-terminated poly(haloalkylene ethers) |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103497322A (en) * | 2013-09-09 | 2014-01-08 | 江苏雅克科技股份有限公司 | Preparation method and application for reaction-type halogen-containing flame-retardant polyether polyol |
| CN104892451A (en) * | 2015-06-23 | 2015-09-09 | 西安近代化学研究所 | End ester base end ethyoxyl GAP(glycidyl azide polymer) oligomer and preparation method thereof |
| FR3087441A1 (en) * | 2018-10-23 | 2020-04-24 | Arianegroup Sas | Polyhydroxytelechelic derivatives of epichlorohydrin and their preparation |
-
1981
- 1981-01-21 CA CA000369016A patent/CA1184943A/en not_active Expired
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103497322A (en) * | 2013-09-09 | 2014-01-08 | 江苏雅克科技股份有限公司 | Preparation method and application for reaction-type halogen-containing flame-retardant polyether polyol |
| CN104892451A (en) * | 2015-06-23 | 2015-09-09 | 西安近代化学研究所 | End ester base end ethyoxyl GAP(glycidyl azide polymer) oligomer and preparation method thereof |
| FR3087441A1 (en) * | 2018-10-23 | 2020-04-24 | Arianegroup Sas | Polyhydroxytelechelic derivatives of epichlorohydrin and their preparation |
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