CA1187107A

CA1187107A - Colorless hydroxyl-terminated poly (chloroalkylene ethers)

Info

Publication number: CA1187107A
Application number: CA000326143A
Authority: CA
Inventors: Loren L. Barber, Jr.; Chung I. Young
Original assignee: Minnesota Mining and Manufacturing Co
Current assignee: 3M Co
Priority date: 1978-05-17
Filing date: 1979-04-23
Publication date: 1985-05-14
Also published as: FR2426060B1; JPS54150497A; GB2021606A; IT1116819B; BR7903018A; AU4710079A; GB2104403B; DE2919834A1; FR2426060A1; AU534485B2; GB2104403A; JPS6332813B2; DE2919834C2; IT7949061A0; CH653693A5; GB2021606B

Abstract

ABSTRACT

This invention is directed to colorless hydroxyl-terminated poly(chloroalkylene ethers) and to the catalyst system employed in their manufacture.
The ethers 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 known which are colored, slow to react, unstable to heat and light;
crystalline or of low molecular weight. The foregoing dis-advantages of the prior art are overcome by the colorless ethers of the invention.
The ethers are especially useful where the color of the finished product is important. Such utilities in-clude urethane flooring systems, adhesives, and coatings.

Description

~ 7~ FN 914,787 COLORLESS HYDROXYL-TERMINATED
POLY(CHLOROALKYLENE ETHERS) This invention is directed to substantial'ly color-,less hydro~yl-terminated poly(,chloroalkylene ethers), processes for their preparation and novel catalyst systems useful in said processes.
Hydroxyl-terminated poly(chloroalkylene ethers) and processes for their preparation are known. Frequently the processes utilize cationic polymerization techniques wherein oxirane monomers, such as alkylene oxidesg alcohols and acid catalysts are employed to synthesize hydroxyl-functional prepolymers. Thus see United States Patents 3,850,856; 3,910,878; 3,910,879; and 3,980,579.
The products and processes described in these patents have not proven entirely satisfactory. For example, it has been found very dif~icult to control the temperature of the polymerization reaction. Additionally the products are dark in color; tend to be very slow to react with various materials such as isocyanates unless substantial quantities of catalysts are employed therewith; and have been found to be unstable upon exposure to sunlight and temperatures above 50C~ Thus such materials have also been found to become even darker in color and increase in acidity and water content when exposed to light and heat.
Still further the products described in United States ~a~ent 3~980,57g adversely affect the catalytic activity of amine catalysts utilized in the preparation of polyurethane foam.

Other techniqwes for the preparation of hydroxyl-terminated poly(chloroalkylene) ethers are also knownO Thus U.S Patent 3,450,774 teaches the preparation of polymers having hydroxyl end groups by the cleavage of high molecular weight crystalline poly(epihalohydrin) in the presence of certain alkali compounds. The resulting polymers are crystalline and have low molecular weight. Additionally they are only partially hydroxyl functional. Thus they may have carbonyl and ethynyl end groups in place of the hydroxyl end groups.
The present invention, however, provides hydroxyl-ter~inated poly(chloroalkylene ethers) which are optically clear and colorless, that is, they appear to have the same optical clarity as distilled water. Thus they exhibit a color magnitude ~described hereinafter) of less than about 10. Moreover, they are stable to the affects of heat and light, That is, they resist degradation due to such con-ditions. Moreover9 they possess excellent chemical reactivity towards isocyanate materials.
The colorless materials of the present invention are particularly useful where the color of the finished product is important (e.g., where the true color of the product is critical). Thus, for example, they are useful in the preparation of cast urethane systems which can be used as flooring materials, coatings and adhesives. More-over the urethanes produced with the materials of the invention have been found to Qxhibit improved properties over prior art urethanes. Thus9 for example, such urethanes exhibit excellent resistance to grease and oil.
For the purposes of convenience, the hydroxyl-terminated poly(chloroalkylene ethers) o-F the present invention are sometimes referred to hereinafter as polyols.
For purposes of this disclosure, the term "polyols" in-cludes materials which have at least one terminal hydroxylgroup.
In accordance with the present invention there are provided novel amorphous hydroxyl-terminated poly(chloro-alkylene ethers) having a color magnitude of less than about 10 and having the formula R5~ 1 3 ¦ ~ Jb ~ d Wherein Rl and R2 are each selected from hydrogen 15 and methyl; R3 and R4 are each selected from hydrogen, lower alkyl groups containing from 1 to 10 carbon atoms, and lower chloroalkyl groups containing from 1 to 2 carbon atoms and 1 to 5 chlorine atoms9 provided that at least one of R3 and R4 is a lower chloroalkyl group; R5 is the residue of an 20 organic hydroxyl material which originally contained from 1 to 6 hydroxyl groups; b is an integer o-f from 1 to 50;
and d is an integer of from 1 ~o 6. Preferably the polyols of the invention contain from 20% to 60% by weight chlorine.
In addition to being substantially colorlessg the poly(chloroalkylene) ether polyols of the present invention are amorphous materials. Consequently, they do not exhibit a melting point. Moreover they may be low - ~ -molecular weight materials (250 MW) or high molecular weight materials (5000 MW) based upon the average hydroxyl functionality of the polyols.
There are also provided herein novel catalyst systems. These catalyst systems are useful in the prep-aration of the novel polyols and comprise (i) a fluorinated acid selected from bis (fluorinated aliphatic sulfonyl) al-kanes and acids of the formula HmXFn~m wherein X is selected from boron, phosphorous, arsenic and antimony, m is 0 or 1 and n is 3 when X is boron and n is 5 when X is phosphorous, arsenic and antimony~
and (ii) a polyvalent tin compound having the formula R6 1! 1 7 R~-Sn-R' (R )g wherein 9 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 oxygen and saturated and unsaturated aliphatic and aromatic hydrocarbyl groups containing from 1 to 10 carbon atoms~ provid~d that ~ ~7~7 when R7 is oxygen then 9 is 0; and R8 is selected from fluorine, acyloxy groups containing less than lO carbon atoms, saturated aliphatic hydrocarbyl groups con-taining from 1 to 10 carbon atoms and o - ~n - R6 , provided that when R5, R6 and R7 are 1 n each saturated aliphatic hydrocarbyl groups then R8 is selected from fluorine, acyloxy groups containing less than 10 carbon atoms and - 0 - Sn - R6 The molar ratio of the polyvalent tin compound to the fluorinated acid in the catalyst system is dependent upon the particular acid utilized. Thus, for example, the ratio of the tin compound to the bis(fluorinated aliphatic sulfonyl) alkane is in the range of 0.2:1 to 2:1. Prefer-ably the ratio is in the range of 0.4:1 to 1,5:1.
The ratio of the tin compound to the fluor;nated acids of the formula HmXFn+m is in the range of 1.13:1 to 3:1. Preferably this ratio is in the range of 1.2:1 to 2:1.

Still further there is provided a method of making the polyols of the invention utilizin~ the novel cat-alyst 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 system.
The polyols of the invention are prepared by combining a hydroxyl-containing material, an alkylene oxide (at least about 50~ by weight of which is a chloroalkylene oxide) and the catalyst system of the invention and poly-merizing the resultant mixture. Polymerization may be car-ried out at a temperature in the range of 0C to 110C.
Preferably polymerization is carried out at a temperature in the range of ~0C to 80C.
Solvents may be employed in the polymerization mixture. They are especially useful when one or more of the ingredients of the mixture is a solid. Suitable sol-vents solvate (hut are otherwise inert to) the materials in the mixture and include benzene, toluene, methylene chloride, carbon tetrachloride and 1,2-dichloroethane.
Although the polymerization proceeds smoothly to completion, there may be solne unpolymerized chloroalkylene oxide left. This material may be sèpara~ed from the poly (chloroalkylene ethers) of the invention by warming the polymerization mixture to ~0C and subjecting the heated mixture to reduced pressure (0.01 Torr) for a short period of time (1-2 hours).

A wide variety of hydroxyl-containing materials are useful in the present invention. They inc'lude ? for example 7 water and liquid and 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.e., other than terminal) groups.
Hydroxyl-containing materials containing both terminal and pendant hydroxyl groups may also be used. The molecular weight of the organic hydrox~yl-containing material may vary over a rather wide range. For example it may be in the range of from about 10 to about 2,500.
Preferably, 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 methano'l, ethanol, isopropanol,

2-butanol, l-octanol, octadecanol, 3-methyl-2 butanolg 5-propyl-3-hexanol, cyclohexanol, ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, 1,4-cyclohexanedimetnahol, g'lycerol and sorbitol.

~37~

Mono- and polyhydric haloalkanols useful in the present invention include 2-chloroethanol, 3-chloropropanol, 2,3-dichloropropanol, 3,4-dibromo-1,2-butanediol, 2,3-di-bromo-1,4-butanediol, l,2,576-tetrabromohexane-3,4 diol.
Polymeric hydroxyl-containing materials useful in the present invention include polyoxyethylene and polyoxy-~ropylene ylycols and triols of molecular weights from about 200 to about 2000 (corresponding to hydroxyl equiva-lent weights of 100 to 1000 for the diols and 70 to 630 for triols); hydroxy-terminated polyalkadienesi and poly-tetramethylene glycols of varying molecular weight such as the Polymeg~ series of glycols available from Quaker Oats Company as Polyme ~ 650, 1000 and 2000.
The foregoing list of useful 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 present invention is dependent upon the terminal hydroxyl-functionality desired in the poly(chloro-alkylene ether) polyol. It has been found that the polyols of the invention have the same hydroxyl functionality as that of the hydroxyl-containing star~ing material and that the hydroxyl-functionality is present as a terminal hydroxyl group. Thus, for example, when a monofunctional hydroxyl-containing ma~erial is used, a monohydric polyether is obtained; when difunctional hydroxyl-containing materials are used a dihydric polyether poly is obtained; and so forth.

7~L~7 g A wide variety of chloroalkylene oxides are useful in the present invention, They include, for example, epichlorohydrin, l-chloro-2-methyl-2,3-epoxypropane, 1,4-dichloro-2,3-epoxybutane, and 1-chloro-2,3-dimethyl-2,3-epoxy-butane ~ore highly chlorinated monoalkylene oxides are also useful in the present invention. Represen-tative examples of these materials include l,l-dichloro-2,

3-epoxypropane, 1,l,l~trichloro-2,3-epoxypropane, l-bromo-l,l-dichloro-2,3-epoxy-propane, l,l-dichloro-l-fluoro-2,3-epoxypropane, 1,1-difluoro-1-chloro-2,3-epoxy-propane, etc. Still other useful chloroalkylene oxides in-clude l,l-dichloro-2-methyl-2,3-epoxypropane, 1,1,1-~richloro-3,4-epoxybutane, 1,1-dichloro-3,4-epoxy-butane, 1,1,1,2,2-pentachloro-3,4-epoxybutane, 1,1,1,414-penta-chloro-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,~-epoxybutane and 1,1,1,2-tetrachloro-3,4-epoxybutane may also be used.
Mixtures of any of ~he foregoing chloroalkylene oxides can be used as well as mixtures of at least one haloalkylene oxide with up to about 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.

~137~
-1 o-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 be in the range oF l:l to 1:50, pre-Ferably the molar ratio is in the range of l:l to 1:20.
Catalyst systems useful in the present invention comprise (i) a fluorinated acid as is described above and (ii) a polyvalent tin compound as is described above. As little as about 0.05% by weight oF the catalyst system based on the combined we;ght of the hydroxyl-containing material and alkylene oxide is effective in providing the optically clear and substantially colorless polyols of the invention.
As discussed above the molar ratio of the poly-valent tin compound to the fluorinated acid is dependent upon which fluorinated acid is employed in the catalyst system. However, whatever the exact ratio used is, the catalyst system may be easily prepared by simply adding each of the in~redients to the polymerization mixture.
As has been previously stated, the fluorinated acid use~ul in the catalyst system is selected from the group consisting of bis~luorinated aliphatic sulfonyl) alkanes and acids of the formula HmXFn~m. The bis(fluor-inated aliphatic sul~onyl) alkanes are preferably highly fluorina~ed alkanes containing from 1 to about 15 carbon atoms. Additionally they include compounds which ,, ~

~7~7 1 , liberate such alkanes in the presence of heat or moisture.
Fnr example, bis(highly fluorinated alkylsulfonyl) alkenes, upon hydrolysis, will yield bis(highly fluorinated alkyl-sulfonyl) alkanes.
~s it is used herein, the term highly fluorinated aliphatic radical encompasses fluorinated, saturated, mono-valent~ aliphatic radicals having 1 to 10 carbon atoms. The skeletal chain of the radical may be straight, branched or, if sufficiently large (e.g., at least 3 or 4 carbon atoms), cycloaliphatic. Moreover, the skeletal chain may be inter-- rupted by divalent oxygen atoms or trivalent nitrogen atoms bonded only to carbon atoms. Preferably, 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 fluorina-ted group is preferred, but hydrogen or chlorine atoms may be present as substituents in the fluorinated aliphatic radical provided that not more than one atom of either is present in the radical for each carbon atom. Preferably, the fluoroaliphatic radical is a saturated perfluoroalkyl radical having a skeletal chain that is straight or branched and has the formula CxF2x+l- wherein x has a value of from 1 to 18.
The preferred bis(fluorinated aliphatic sulfonyl) 5 alkanes are those compounds having the formula RfS02-1 S02Rf wherein each Rf ~roup is the same or different and is a fluorinated (preferably a highly fluorinated or perfluor-inated) alkyl group containing from 1 to 10 carbon atoms and R is selected from hydrogen, halogen, alkyl groups having from 1 to 10 (preferably 1 to 4) carbon atoms, alkenyl groups con-taining from 1 to 3 carbon atoms, aryl groups (e.g., phenyl, naphthyl) and alkaryl groups of up to 10 carbon atoms. The alkyl5 aryl and alkaryl may, if desired, be substituted by one or more constituents selected from halogen7 highly fluorinated alkyl sulfonyl groups, carboxyl groups 7 al koxycarbonyl groups 7 nitro groups, alkoxy groups and acetoxy groups.
Fully fluorinated groups are preferred, but hydrogen or chlorine atoms may be present as substituents in the ~roup 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. Most preferably they contain up to ~ carbon a~oms.
Represen~ative examples of useful bis(perfluoro-alkylsulfonyl)alkanes are: bis(trifluoromethylsulfonyl)methane, bis(difluorochloromethylsulfonyl) methane, tris(tri-fluoromethylsulfonyl) methane, bis(trifluoromethylsulfonyl)-

4-bromophenylmethane, bis(trifluoromethylsulfonyl)-2-thienylmethane, bis(trifluoromethylsulfonyl)chloromethane, bis(trifluoromethylsulfonyl)benzylmethane~ bis(trifluoro-methylsulfonyl)phenylmethane9 bis(trifluoromethylsulfonyl~-l-naphthylmeth~ne, bis(perfluorobutylsulfonyl)me~han~, bis (2,2,3,3,4,4,4-heptafluorobutylsulfonyl)me~hane, perfluoro-butylsulfonyltrifluoromethylsulfonylmethane~ 1,2,2,3,3,4,4,4-heptafluorobutyltrifluoromethylsulfonylmethane, ethyl-6,6-bis (perfluorornethylsulfonyl)-4-bromohexanoate, n~ethyl-4,4-bis (perfluoromethylsulfonyl)-2-carbomethoxy-2-bromobutanoate, ethyl-4,4-bis(perfluoromethylsulfonyl)-2-carboethoxy-2-nitrobutanoate, 1,1,3,3-tetra(trifluoromethylsulfOnYll propane, and l,l-bis(trifluoromethylsulfonyl)octadecane.
Representative examples of useful bis(fluorinated aliphatic sulfonyl)alkanes are also described in U.S. Patents 3,63298~3; 3,7~4,311i 3,701,~08; 3,776,960 and 3,794~687.
The other class of flu~rinated acids useful in the present invention are substantially fully fluorinated and have the formula H XFm+n wherein X is selected from boron, phosphorous, arsenic and antimony; m is 0 or 1 and n is 3 when X is boron and n is 5 when X is phosphorous, arsenic and antimony. Specific examples of useful fluorinated acids of this type are BF3, HBF4, SbF5, HSbF6, PF5, HPF67 AsF5 and HAsF6 The polyvalent tin compounds useful in the catalyst system of the present invention have the formula R5-~n-R7 (~8) i wherein R5, R6, R7, R8 and g are each as described above.
Specific examples of polyvalent tin compounds of this type include diphenyl dibutyl tin, divinyl dibutyl tin, diallyl dibutyl tin, tributyl tin fluoride, triphenyl tin acetate, dibutyl tin oxide, and bis(tributyl tin oxide).

As has been stated, polyols of the present in-vention are optically clear and substantially colorless as is demonstrated by their color magnitude (i,e., they have a color magnitude of less than about 10). Color magnitude represents the deviation of the color of a given material from the color of 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 Dif-ference Meter available from Hunder-Associates Laboratory, 952g Lee Highway, Fairfax, Virginia. The meter measures three parameters which characterize the color of a sample.
These parameters are (i) the gray component "L" of the sample; (ii) the red-green component "a" of the sample (a plus value indicating redness and a minus value indicating greenness); and ~iii) the yellow-blue component "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 = ~ ( r(Z
wherein ~L, ~a and ~b respectively represent the difference between the L, a and b values of distilled water and the sample being tested. Distilled water has a color magnitude of 0 at 25~C.
Color magnitude values of less than about 10 represent optically clear and substantially colorless materials. The color of a material having a color ma3nitude of 10 is very light yellow and a thin film of such a material remains optically clear. As the color 37~

magnitude increases the color and the optical clarity of the sample decreases. Thus, at a color magnitude of 20 the material has light brown color and a thin film thereof has a hazy optical clarity. At a color magnitude of 50 the material has a very dark brown color and a thin film thereof is diFficult to see through.
The invention is further illustrated by means of the following examples wherein the term "parts" refers to 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 within the flask during the reaction.
In each preparation the hydroxyl-containing material (ethylene glycol, 62.0 9, 1 mole) and the catalyst system were charged to the flask and stirred and heated to 60C. The composition and quantity of the catalyst system ~0 was varied in each reactior.. The chloroalkylene oxide (epichlorohydrin) was then slowly charged to the stirred mixture over a period of 3 hours. The reaction was allowed to proceed until it was substantially complete. The temperature of the reaction mixture was maintained be-tween 60 and 85C. The amount of epichlorohydrin employedwas varied so as to control the hydroxyl-equivalent weight of the product. Thus, for example, 93~ g ~10.1 moles) of epichlorohydrin were employed in order to , -16~
provide a prod~ct having a theoretical hydroxyl equivalent weight of 500. On the other hand~ 1938 g (21 moles) of epichlorohydrin were employed in order to provide a product having a theoretical hydroxyl equivalent weight of lOOO.
Examples 1-25 represent a number of poly(chloro-alkylene ether) polyols prepared according to the above-described general procedure utilizing both prior art catalyst systems and catalyst systems of the invention.
The exact nature of the catalyst system utilized and the results obtained are given in Table l.
The catalyst system utilized in Examples 1-3 was BF3; that in Example 4 was HSbF6 H20, that in Example 5 was (C2H5)30 PF6 and that in Example 6 was SbF5. As can be seen the poly(chloroalkylene ether) polyols prepared from these catalyst systems were darkly colored as is demonstra-ted by their high ~E values (i.e., between 30 and 52).
Examples 7-9 demonstrate the effect of the individual components o~ the catalyst system of the present invention upon the poly(chloroalkylene ether) polyols 2Q produced. Thus, in Example 7 the catalyst system was a poly-valent tin compound of the formula R -Sn-R
(18) (i-e-, (C6H5)2Sn~C4Hg)2)~ As can be seen from Example 7 there was no reaction even after 5 hours of mixing when the diphenyl dibutyl tin alone was used as the catalyst system. ~Ihen 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 mag-nitude.
Examples 10-12 demonstrate the criticality of the molar ratio of the fluorinated acid of the formula HmXFm n to the tin compound in the catalyst composition of the invention. Thus in Examples 10 and ll the ratio was l:l and l.l:l. In each case the resulting product was very dark brown (i.e., ~E of 53.1 and 52.g respectively). How-ever, in Example 12 the molar ratio was l.l3:l and theresulting product was optically clear and substantially colorless (i.e., a color magnitude of 2.1).
Examples l3-24 demonstrate the present invention.
In each of these examples an optically clear and substan-tially colorless poly(chloroalkylene ether) polyol was obtained. This is demonstrated by the low ~E values ob-tained (i.e., ~E less than about 5). Examples l3-l6 show the effect of varying the molar ratio of ~he HmXFm+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 halogena~ed alkylene-oxides (e.g., l,l~l-trichlorobutylene oxide) can also be used in the present invention.

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~ o a~ ~ w ~n W Ol 0 ~ ~ r. 3 2 A series of hydroxyl-terminated poly(haloalkylene ethers) were prepared as described in the general procedure.
The resultant polyethers were tested for initial color magni-tude then subjected to heat (80C) for 14 hours after which time the polyethers were tested for final color magnitude.
Example 26 was performed using a sample from the polyol pre-pared in Example 13 of Table 1. Example 27 was performed using a 490 hydroxyl equivalent weight polyether prepared according to the general procedure but employing (C2H5)30 PF6 ~0.2% by weight of the combined weight of the ethylenc glycol and the epichlorohydrin) as the catalyst system.

EXAMPLE e~EI ~EF

15 26 1.51 1.56 27 18.55 30.41 EI is the initial color of the polyol in the test~ ~EF is the color of the polyoi after heat aging at 80C for a 14 hour period. The behavior of Example 26 is characteristic of all the polyols of the invention. As can be seen, polyols of the invention exhibit essentially no change in color magnitude while prior art polyols darken dramatically in color.

~7~7 EXAMPLES 2~-34 A series of polyurethanes were made using various poly(chloroalkylene ether) polyols, and a polyfunctional polyisocyanate. The polyols were prepared as described in the general procedure. The polyfunctional isocyanate was "Mondur1 MRS" (a polymethylene polyphenyl isocyanate having an average of 2 . 6 isocyanate groups per molecule and being available from Mobay Company).
The polyurethanes were prepared by combining the ingredients in a suitable reaction vessel and stirring them for 1-2 minutes at a temperature of 25C. A moisture free atmosphere was maintained in the reaction vessel.
There was no catalyst added to promote the reaction, Examples 28 and 29 utili7ed poly(chloroalkylene ether)polyols according to the invention. These polyols were prepared using the same catalyst system and amounts thereof as are set forth in Example 15. The polyol employed in Example 28 had a theoretical hydroxyl-equiva-lent weight of 325 while the polyether employed in Example 29 had a theoretical hydroxyl equivalent weight oF 500.
Examples 30W34 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 comb;ned weight oF the epichloro-hydrin and the ethylene glycol) as the catalyst system.
The polyols employed in Examples 31 and 32 had theoretical hydroxyl equivalent weights of 500 and 325 respectively 87~

and were prepared utilizing (C2H5)30 PF6 (0-2% by weiyht of the epichlorohydrin and the ethylene glycol) as the catalyst system. The polyols employed in Examples 33 and 34 had theoretical hydroxyl equivalent weights of 500 and 325 respectively and were prepared with HSbF6 6H20 (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 ~iven in Table 3. As can be seen the polyurethanes of Examples 28 and 29 (prepared with the polyols of the invention) gelled quickly while the polyurethanes of Examples 30-34 (prepared with prior art polyols, did not gel even after 24 hours. Moreover the polyurethanes of Examples 28-29 cured within 24 hours w~ile those of Examples 30-34 did not cure e~en after 3 days.

-POLYURETHANE VISCOSITY (cps) EXAMPLE NCO/OH INITIAL FINAL
(Time = O hours) (Time = 24 hours) 28 1.2:1 4800Gelled within*
15 minutes 29 1.2:1 2200Gelled within*
2.5 hours 1.2:1 5900 24000 31 1.2:1 5900 1~000 32 1.2:1 2300 5400 33 1.2:1 4800 15000 34 1.2:1 2200 2~000 *Gellation occurs when the viscosity >l,OOOtOOO cps.

~7~

A series of hydroxyl-terminated poly(chloroalkyl-ene ethers) according to the invention were prepared according to the general procedure except that various hydroxyl-containing materials were substituted for ethylene glycol. In each of these examples the catalyst system comprised 0.1% HSbF6 6H20 and 0.224% diphenyl dibutyl tin (both percentages being ~ercentages by weight o-f the combined weight of the hydroxyl material and the epichloro-hydrin). The resulting polyols were then tested for percentconversion, hydroxyl equivalent weight and color magnitude.
The exact ingredients used to prepare the polyols, the amounts of each and the results obtained are reported in Table 4.

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\ / I 01 ---- ~ X0 O 1~ I r~ o O ~ I 2 ~_ O ~ 2~
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.p~ ~ iC~ _I
07 CO-P P Oo cn s_~ rll ~0 D
rr r~ _l ~ ~ 9 ~ ~ W
--I I
oOo ~o to ~ r ~1 CJ~ .Jl O
CC ~ ~ ~ ~ ~ w ~ r~
o ~ ~ ~

~:
CO ~
.p ~1 ~I ~1 ~J ~Jl 0 2 2~

I Cl o x ~7 o o o o o o rrl O
o o o o o O I X
D r-. r r ~ 'P ~ ~ ~ 00 C _ -P r~ ~ ~ ~ ~ c rn ~~ocn l -P c ~ _ ~ o1~7 ~D r~

Claims

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. An amorphous hydroxyl-terminated poly(chloro-alkylene ether) having the formula wherein R1 and R2 are each selected from hydrogen and methyl; R3 and R4 each selected from hydrogen, lower alkyl groups containing from 1 to about 10 carbon atoms, and lower chloroalkyl groups containing from 1 to about 2 carbon atoms and from 1 to about 5 chlorine atoms, provided that at least one of R3 and R4 is said lower chloroalkyl group; R5 is the residue of an organic hydroxyl material which hydroxyl material contained from 1 to about 6 hydroxyl groups; b is an integer of from 1 to about 50; and d is an integer of from 1 to about 6 characterized by the feature that said poly(chloroalkylene ether) has a color magnitude of less than 10.

2. An amorphous hydroxyl-terminated poly(chloro-alkylene ether) according to claim 1 further characterized by the feature that said ether has the formula wherein R3 is a lower chloroalkyl group containing from 1 to 2 carbon atoms and from 1 to 5 chlorine atoms.

3. An amorphous hydroxyl-terminated poly(chloroalkylene ether) according to claim 2 further characterized by the feature that said ether has the formula

4. An amorphous hydroxyl-terminated poly(chloroalkylene ether) according to claim 1 further characterized by the feature that R5 is the residue of a hydroxyl material selected from ethylene glycol and 1,4-cyclohexanedimethanol.

5. A method for the preparation of hydroxyl-terminated poly(chloro-alkylene ethers) according to claim 1 characterized by the feature that said preparation comprises reacting a hydroxyl material containing from 1 to 6 hydroxyl groups and a chloroalkylene oxide in the presence of a catalytic amount of a catalyst system comprising (i) a fluorinated acid selected from the group consisting of bis-(fluorinated aliphatic sulfonyl protonic) alkanes and acids of the formula HmXFn+m wherein X is selected from the group consisting of boron) phosphorous arsenic and antimony;
m is 0 or 1; n is 3 when X is boron and n is 5 when X is phos-phorous, arsenic and antimony; and 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 contain-ing from 1 to 10 carbon atoms, provided that when R7 is oxygen then g is 0; and R8 is selected from the group consisting 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 provided that the molar ratio of said polyvalent tin compound to said bis(fluorinated aliphatic sulfonyl) alkane in said catalyst system of 0.2:1 to 2:1 and provided the molar ratio of said polyvalent tin compound to said HmXFm+n acid in said catalyst system is in the range of 1.13:1 to 3:1.

6. A method according to claim 5 further characterized by the feature that said catalyst system comprises (i) said bis(fluorinated aliphatic sulfonyl) alkane and (ii) said polyvalent tin compound.

7. A method according to claim 5 further characterized by the feature that said catalyst system comprises (i) said acid of the formula HmXFn+m and (ii) said polyvalent tin compound.

8. A catalyst system for producing an amorphous hydroxyl-terminated poly(chloroalkylene ether) according to claim 1 characterized by the feature that said catalyst system comprises (i) a fluorinated acid selected from the group consisting of bis-(fluorinated aliphatic sulfonyl) alkanes and acids of the formula HmXFn+m wherein X is selected from the group consisting of boron, phosphorous, arsenic and antimony; m is 0 or 1; n is 3 when X is boron and n is 5 when X is phosphorous, arsenic and antimony; 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 consisting 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 provided that the molar ratio of said polyvalent tin compound to said bis(fluorinated aliphatic sulfonyl) alkane in said catalyst system is in the range of 0.2:1 to 2:1 and provided that the molar ratio of said polyvalent tin compound to said HmXFm+n acid in said catalyst system is in the range of 1.13:1 to 3:1.

9. A catalyst system according to claim 8 further characterized by the feature that said catalyst system comprises (i) said acid of the formula HmXFn+m and (ii) said polyvalent tin compound.

10. A catalyst system according to claim 9 further characterized by the feature that said catalyst system comprises (i) said bis(fluorinated aliphatic sulfonyl) alkane and (ii) said polyvalent tin compound.