GB2104403A

GB2104403A - Polymerisation catalyst system

Info

Publication number: GB2104403A
Application number: GB08133787A
Authority: GB
Inventors: Loren Lewis Barber; Chung I Young
Original assignee: Minnesota Mining and Manufacturing Co
Current assignee: 3M Co
Priority date: 1978-05-17
Filing date: 1981-11-09
Publication date: 1983-03-09
Also published as: CH653693A5; JPS54150497A; AU4710079A; IT7949061A0; DE2919834C2; CA1187107A; AU534485B2; FR2426060A1; DE2919834A1; BR7903018A; GB2021606A; JPS6332813B2; FR2426060B1; GB2021606B; IT1116819B; GB2104403B

Abstract

A catalyst system comprises: (i) a bis(fluorinated aliphatic sulphonyl) alkane or an acid HmXFn+m in which X is B, P, As or Sb; m is 0 or 1, n is 3 when X is B and n is 5 when X is P, As and Sb; and (ii) a tin compound: <IMAGE> in which g is 0 or 1; R<5> and R<6> are saturated or unsaturated aliphatic or aromatic hydrocarbyl groups containing 1 to 10 carbon atoms; R<7> represents = O or a saturated or unsaturated aliphatic or aromatic hydrocarbyl group containing 1 to 10 carbon atoms, provided that when R<7> is = O, g is 0, and when R<7> is not = O, g is 1; and R<8> represents F, an acyloxy group containing less than 10 carbon atoms, a saturated aliphatic hydrocarbyl group containing 1 to 10 carbon atoms, or <IMAGE> provided that R<5>, R<6>, R<7> and R<8> are not all saturated aliphatic hydrocarbyl groups. The catalyst system is useful in the preparation of substantially colourless hydroxyl-terminated chloroalkylene ethers.

Description

1 GB 2 104 403A 1

SPECIFICATION

Catalyst system This invention relates to a catalyst system which is particularly useful in the preparation of 5 substantially colour-less hydroxyi-terminated chloroalkylene ethers.

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 oxides, 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; 10 and 3,980,579.

The products and processes described in these patents have not proven entirely satisfactory. For example, it has been found very difficult 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; 15 and have been found to be unstable upon exposure to sunlight and temperatures above WC. 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 Patent 3,980,579 adversely affect the catalytic activity of amine catalysts utilized in the preparation of polyurethane foam.

Other techniques for the preparation of hydroxyl-terminated poly(chloroalkylene) ethers are also known. Thus, United States Patent Specification No. 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.

Our copending British Patent Application No. 7 91706 7 (Serial No. 2 021 606) describes and claims an amorphous hydroxyi-terminated chloroalkylene ether having a colour magnitude of less than 10 and the formula:

R 1 R 2 5_ 1 1 R (0 - C - C -±bOH 13 14 cl in which R' and R 2 independently represent a hydrogen atom or methyl group; R 3 and R 4 independently represent a hydrogen atom, a lower alkyl group containing from 1 to 40 carbon atoms, a lower chloroalkyl group containing 1 or 2 carbon atoms and from 1 to 5 chlorine atoms, provided that in one of the units R' R 2 1 1 O-C -C- l i R 3 R 4 at least one of R 3 and R 4 is a lower chloroalkyl group; R' is the residue of a hydroxyl material which hydroxyl material contained from 1 to 6 hydroxyl groups; b is an integer of from 1 to 50; and d is an integer of from 1 to 6.

Preferably the ethers of the invention contain from 20 to 60% by weight of chlorine. A preferred ether of has the formula:

H H R 5 (0 1 1 3 d n which R' is a lower chloroalkyl group.

2 GB 2 104 403A 2 The hydroxyl-terminated chloroalkylene ethers are optically clear and colourless, that is they appear to have the same optical clarity as distilled water. Moreover, they are stable to the effects of heat and fight. That is, they resist degradation due to such conditions. Moreover, they possess excellent chemical reactivity towards isocyanate materials.

The colourless materials of that application are particularly useful where the colour of the 5 finished product is important (e.g. where the true colour 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. Moreover, the urethanes produced with the materials of the invention have been found to exhibit improved properties over prior art urethanes. Thus, for example, such urethanes exhibit excellent resistance to grease and oil.

For the purposes of convenience, the hydroxyl-terminted chloroalkylene ethers are sometimes referred to hereinafter simply as ethers.

In addition to being substantially colourless, the chloroalkylene ethers 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 15 upon the average hydroxyl functionality.

Claims

The ethers of that invention may be prepared in the presence of a particular catalyst system, which is claimed herein. According to the present invention there is provided a catalyst system comprising: (i) a fluorinated material selected from bis-ffluorinated aliphatic sulphonyl) alkanes and acids of 20 the formula H-XFn,, in which X is boron, phosphorous, arsenic or 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: R 6 25 1 R'-Sn-Rl (R1)g 30 in which g is 0 or 1; R' and R 6 are independently selected from saturated and unsaturated aliphatic and aromatic hydrocarbyl groups containing from 1 to 10 carbon atoms; R' represents an oxygen atom or a saturated or unsaturated aliphatic or aromatic hydrocarbyl group containing from 1 to 10 carbon atoms, provided that when R' is oxygen g is 0, and when 35 R' is other than oxygen g is 1; and W represents a fluorine atom, an acyloxy group containing less than 10 carbon atoms, a saturated aliphatic hydrocarbyl group containing from 1 to 10 carbon atoms or R5 1 1 R 7 in which R' to R 7 are as defind above, provided that when R, R 6 and R 7 are each saturated aliphatic hydrocarbyl groups then W is not a saturated aliphatic hydrocarbyl group. Generally the molar ratio of the polyvalent tin compound to the bis(fluorinated aliphatic sulphonyl) alkane is in the range of 0.2A to 2A, preferably 0.4A to 1.5A, and the molar ratio of the polyvalent tin compound to said H,XH,,, acid is in the range of 1.13:1 to 3A, preferably 1.2A to 2A. 50 The above described ethers may be prepared by a method in which a hydroxyl material of the formula R5(01-1), in which R5 is as defined above and n is an integer of from 1 to 6, is reacted with an organic oxide material in which at least 50% by weight of said oxide material has the formula: 2 3 55 R 1 f 1 - c - c - R4 \ 0 60 in which R' to R 4 are as defined above, provided that at least one of R' and R4 is a lower chloroalkyl group, in the presence of the above-described catayst system. The ethers are prepared by combining an hydroxyi-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 polymerising the resultant mixture. Polymerisation may be carried out at a 65 I- i 1 4 3 GB 2 104 403A 3 temperature in the range of 0 to 11 WC. Preferably polymerisation is carried out at a temperature in the range of 40 to WC. Solvents may be employed in the polymerisation mixture. They are especially useful when one or more of the ingredients of the mixture is a solid. Suitable solvents solvate (but are otherwise inert to) the materials in the mixture and include benzene,toluene, methylene chloride, carbon 5 tetrachloride and 1,2-dichloroethane. Although the polymerisation proceeds smoothly to completion, there may be some unpolymer ised cloroalkylene oxide left. This material may be separated from the chloroalkylene ethers of the invention by warming the polymerisation mixture to WC and subjecting the heated mixture to reduced pressure (0.01 Torr) for a short period of time (1 to 2 hours). A wide variety of hydroxyi-containing materials are useful. They include, for example, 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 materials include alkanols, haloalkanols and polymeric polyols. The hydroxyl groups of the organic materials may be terminal or pendant (i.e., other than 15 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 about 10 to about 2,500. Preferably, the organic hydroxyl-containing material is an aliphatic material which contains at 20 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 materials useful in the present invention include methanol, ethanol, isopropanol, 2-butanol, 1-octanol, octadecanol, 3-methyl-2-butanol, 5- propyl-3-hexanol, cyclo- 25 hexanol, ethylene glycol, propylene glycol, 1,3-butanediol, 1,4- butanediol, 1,6-hexanediol, 1,4 cyclohexaned i methanol, glycerol and sorbitol. Suitable halogenated hydroxyl-containing materials include 2chloroethanol, 3-chloropropanol, 2,3-dichloropropanol, 3,4-dibromo-1,2-butanediol, 2,3-dibromo-1,4- butanediol, 1,2,5,6-tetra bromohexane-3,4-diol. Suitable polymeric hydroxyl-containing materials include polyoxyethylene and polyoxypropy lene glycols and triols of molecular weights from about 200 to about 2000 (corresponding to hydroxyl equivalent weights of 100 to 1000 for the diols and 70 to 6 30 for triols); hydroxy terminated polyalkadienes; and polytetra methylene glycols of varying molecular weight such as the Polymeg@ series of glycols available from Quaker Oats Company as Poiymeg@ 650, 1000 35 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 is dependent upon the terminal hydroxyl-functionality desired in the alkylene ether. It has been found that the ethers of the invention have the same hydroxyl functionality as that of the 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 difunctional hydroxyl-containing materials are used a dihydric polyether polyol 45 is obtained; and so forth. A wide variety of chloroalkylene oxides are useful. They include, for exampib, epichlorohydrin, 1-chloro-2-methyl-2,3epoxypropane, 1,4-di chloro-2,3-epoxybutane, and 1-chloro-2,3-dimethyi-2,3-epoxy-butane. More highly chlorinated monoalkylene oxides are also useful in the present invention. Representative examples of these 50 materials include 1,1-dichloro-2,3-epoxypropane, 1,1,1-trichloro-2,3- epoxypropane, 1-bromo 1,1-dichloro-2,3-epoxy-propane, 1,1-dichloro-l-fluoro-2,3-epoxypropane, 1, 1-difluoro-l-chloro 2,3-epoxypropane, etc. Still other useful chloroalkylene oxides include 1, 1-dichloro-2-methyi 2,3-epoxypropane, 1,1,1-trichloro-3,4-epoxybutane, 1,1-dichloro-3,4-epoxy- butane, 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-methy]-2,3-epoxybutane. Tetra ch 1 oroepoxy butanes such as 1,1,4,-tetrachloro-2,3-epoxybutane, 1,1,2,2-tetrachloro-3, 4-epoxybutane and 1,1,1,2-tetrachloro-3,4-epoxybutane may also be used. Mixtures of any of the 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 60 alkylene oxides. Exemplary of useful non-halogenated alkylene oxides are propylene oxide, 1 hexylene oxide, cyclohexane oxide, styrene oxide, methyl glycidyl ether and phenyl glycidyl ether. By controlling the proportions of alkylene oxide to hydroxyi-containing material, it is possible to limit the degree of addition and, consequently, the molecular weight of the ethers of the 65 4 GB 2 104 403A 4 invention. Thus the molar ratio of oxide material to hydroxyl group in said hydroxyi-containing material may be in the range of 1: 1 to 50A, preferably the molar ratio is in the range of 1: 1 to 20A. The catalyst systems of the present invention comprising (i) a fluorinated material as is described above and (ii) a polyvalent tin compound as described above, may be used in amounts as little as about 0. 05% by weight of the catalyst system based on the combined weight of the hydroxyl-containing material and oxide is effective in providing the optically clear and substantially coloufles ethers. As discussed above the molar ratio of the polyvalent tin compound to the fluorinated material is dependent upon which fluorinated material is employed in the catalyst system. However, 10 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 stated, the fluorinated material present in the catalyst system of the invention is selected from the group consisting of bis(fluorinated aliphatic sulphonyl) alkanes and acides of the formula H,XF,,,,. The term ---alkane- used herein extends to substituted alkanes. The bis(fluorinated aliphatic sulphonyl) alkanes are preferably highly fluorinated alkanes contain ing from 1 to 15 substantially fully fluorinated carbon atoms. Additionally they include compounds which liberate such alkanes in the presence of heat or moisture. For example, bis(highly fluorinated alkylsulfonyl) alkenes, upon hydrolysis, will yield bis(highly fluorinated alkyl-sulfonyl) alkanes. As it is used herein, the term highly fluorinated aliphatic radical encompasses fluorinated, saturated, monovalent, 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, ihe skeletal chain may be interrupted by divalent oxygen atoms or trivalent nitrogen atoms bonded only to carbon atoms. Preferably, the chain of the fluorinated 25 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 fluorinated 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 perfluoroaikyl radical having a skeletal chain that is straight 30 or branched and has the formula C.F,, wherein x has a value of from 1 to 18. The preferred bisffluorinated aliphatic sulfonyl) alkanes are those compounds having the formula R9 RfSiO,-C-SO,Rf H wherein each Rf group is the same or different and is a fluorinated (preferably a highly fluorinated or perfluorinated) 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 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 alkary! may, if desired, be substituted by one or more constituents selected from halogen, highly fluorinated alkyl sulfonyl groups, carboxyl groups, alkoxycarbonyl groups, nitro groups, alkoxy groups and acetoxy groups. Fully fluorinated groups are preferred, but hydrogen or chlorine atoms may be present as subsituents in the group provided that not more than one atom of either is present in the radical 50 for every two carbon atoms. The alkyl groups generally contain not more than 10 carbon atoms. Most preferably they contain up to 4 carbon atoms. Representative examples of useful bis(perfluoroalkyisuifonyl)alkanes are: bis(trifluoromethyisui fonyl) methane, bis(difluorochloromethyisuifonyi) methane, tris(trifluoromethyisuifonyi) methane, bis(trif 1 uoromethyisu Ifonyl)-4-bromophenyl methane, bis(trifluoromethyisuifonyl)-2-thienyimeth55 ane, bis(trif luoromethyisu Ifonyl)ch loro methane, bis(trif luoromethyIsu Ifonyl)benzyl methane, bis (trif luoromethyisu If onyl)phenyl methane, bis(trif 1 uoromethyisu If onyi)- 1 -naphthyl methane, bis(perfl uorobutylsuifonyi)methane, bis(2,2,3,3,4,4,4heptafluorobutyisuifonyi)methane, perfluorobuty] suifonyitrifluoromethyisuifonyimethane, 2,2,3,3,4,4,4heptafluorobutyitrifluoromethyisulfonyi- methane, ethyl-6,6-bis(perfluoromethyisuifonyi)-4-bromohexanoate, methyl4,4-bis(perfluorome- 60 thyfsuifonyl)-2-carbomethoxy-2-bromobutanoate, ethyi-4,4- bis(perfluoromethyisulfonyi)-2-carboe- thoxy-2-nitrobutanoate, 1,1,3,3-tetra(trifluoromethyisuifonyi) propane, and 1,1-bis(trifluorome thyisuifonyi)octadecane. Representative examples of useful bis(fluorinated aliphatic sulfonyl)alkanes are also described in U.S. Patents 3,632.843; 3,704,311; 3,701,408; 3,776,960 and 3,794,687. GB 2 104 403A 5 The other class of fluorinated materials useful in the present invention are substantially fully fluorinated and have the formula H,XF,,,, 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 fluorinted acids of this type are 13F3, H13F, SbF, HSbF6, PF, HPF, AsF, and HAsF, The polyvalent tin compounds useful in the catalyst system of the present invention have the formula R6 10 1 Rs-Sn-R 7 1 (R")9 wherein R5, R 6, R 7, R8 and g are each as described above. Specific examples of polyvalent tin 15 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, the ethers are optically clear and substantially colorless as is demonstrated by their color magnitdue (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 20 water when both colors are measured at about 25'C. The color of the water and of the samples is measured by a Hunterlab Model D25-4 Color Difference Meter available from Hunder Associates Laboratory, 9529 Lee Highway, Fairfax, Virginia. The meter measures three para meters 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 (AL) 2 + (Aa) 2 + (Ab) 2 wherein AL, Aa and Ab respectively represent the difference between the L, and b values of distilled water and the sample being tested. Distilled water has a color magnitude of 0 at 25C. Color magnitude values of less than about 10 represent optically clear and substantially colorless materials. The color of a material having a color magnitude of 10 is very light yellow and a thin film of such a material remains optically clear. As the color magnitude increases the color and the optical clarity of the sample decreases. Thus, at 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 40 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 ethers were prepared according to the following general procedure. The ethers 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 g, 1 mole) and the catalyst system were charged to the flask and stirred and heated to WC. The composition and quantity of the catalyst system was varied in each reaction. The chloroalkulene oxide (epichio- 50 rohydrin) 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 between 60' and WC. The amount of epichlorohydrin employed was varied so as to control the hydroxyl-equivalent weight of the product. Thus, for example, 938 g (10. 1 moles) of epichlorohydrin were employed in order to provide a product 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 1000. Examples 1 -25 represent a number of chloroalkylene ethers prepared according to the above described general procedure utilizing both prior art catalyst systems and catalyst systems of the 60 invention. The exact nature of the catalyst system utilized and the results obtained are given in Table 1. The catalyst system utilized in Examples 1 -3 was 13F,; that in Example 4 was I-ISbF6-H20; that in Example 5 was (C2H1)30'PF6- and that in Example 6 was SbF, As can be seen the chloroalkylene ethers prepared from these catalyst systems were darkly colored as is demon- 65 6 GB 2 104403A 6 strated by their high AE values (i.e., between 30 and 52). Examples 7-9 demonstrate the effect of the individual components of the catalyst system of the present invention upon the chloroalkylene ethers produced. Thus, in Example 7 the catalyst system was a polyvalent tin compound of the formula R 6 1 R'-Sn-R' 1 (R 8), (i.e., (C6H1)2Sn(C,H1)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. When the catalyst system was the sulfonyl alkane compund (Examples 8 and 9) darker products than those of the invention were obtained as is shown by their color magnitude. Examples 10- 12 demonstrate the criticality of the molar ratio of the fluorinated acid of the formula H,XF,-, 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 was very dark brown (i.e., AE 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 an substantially colorless (i.e., a color 20 magnitude of 2.1). Examples 13-24 demonstrate the present invention. In each of these examples an optically clear and substantially colorless chloroalkylene ethers was obtained. This is demonstrated by the low AE values obtained (i.e., AE less than about 5). Examples 13-16 show the effect of varying the molar ratio of the HXF,,n fluorinated acid to the polyvalent tin compound. Examples 1720 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 alkyleneoxides (e.g., 1, 1, 1 -trichlorobutylene oxide) can also be used in the present invention. K T A B L E 1 CATALYST SYSTEM MOLECULAR COLOR W -----WL-A-R (a) CON- yr. TIME RATIO QUANTITY VERSION HO EQ. WT.. EX. A B B/A %A %B (%) FOUND mn Rw E Hours 1 B F 3 0.30 99 500 496 863 1040 52.6 6 2 8F3 0.10 99 1020 930 1420 1040 50.4 6 3 B F 3 0.10 99 275 252 542 589 43.5 6 4 NSbF66H 2 0 0.10 99 491 450 854 1050 51.6 6 C 2 H 5)3 0 + P F 6_ 0.20 99 500 426 882 1180 36.8 6 6 SbF5 0.10 99 1020 950 1210 2060 31.7 6 7 ( C 6 H 5)Sn(C 4 H 9)2 0.0 0.224 0 No reaction 5 8 (CF 3 so 2)2CH6H5 0.50 0.0 81 810 665 1070 1570 12.6 24 9 (CF3SO 2)2CHC6 H 5 0.50 0.0 93.7 470 410 815 958 10.5 24 HW 6 6N 2 0 (C6H 02 S n (C' 4H02 1:1 0.10 0.118 99 490 420 884 1070 53.1 5 11 HW 6 6H 2 0 (C6H,)2Sn(C4H9)2 1.1:1 0.10 0.124 99 490 425 921 1050 52.9 5 12 HW 6 6H 2 0 (C6N 5)2Sn(C4R9)2 1.13:1 0.10 0.127 99 490 437 896 1000 2. 1 5 13 HSbF 6' 6H2 0 (C 6H02 Sn( C4 H9)2 1.16:1 0.10 0.130 99 490 437 894 1000 1.5 5 14 HW6 6H 20 (C6N 02 Sn (C002 1.51: 1 0.10 0.1.7 99 490 450 883 7070 2.2 5 (a) Percentages are percentages by weight of the combined weight of the ethylene glycol and the epichlorohydrin. 00 T A B L E 1 (Continued) MOLECULAR COLOR RXN MOLAR CON - WT. TIME RATIO QUANTITY(') VERSION HO EQ. WT EX. A B B/A %A %B (%) CALC FOUND Mn 9w A E Hours H5bF 6 6H 2 0 (C 6 H 5)2 Sn (C4 Hq)2 2.0:1 0.10 0.224 99 490 470 860 993 0.8 5 16 H5bF 6 6H 2 0 (C 6 H 5)2 Sn (C4 Hg)2 2.65:1 0.10 0.298 99 490 433 827 967 1.8 5 17 (CF 3 so 2)2 CHC6H5 (C6 H 02 Sn (C4 Hg)2 0. 19 5: 1 0.30 0.064 93 465 452 883 1020 3.6 10 18 (CF 3 so 2)2 CHCOS (C6 H 02 Sn (C4 H9)2 0. 3 9 2:l 0,30 0.128 99. 5 496 470 939 1 025 2, 1 5 19 (CF 3 so 2)2 CK 6 H 5 (C6 H 5)2 Sn (C4 H9) 2 0. 7 8 5: 1 0.30 0. 256 99 491 478 924 1046 2. 5 3 (CF 3 so 2)2 CK.H, (C6H5)2 Sn (C4 H9)2 1. 96: 1 0.30 0.64 95. 2 476 450 923 1 025 2. 2 5 21 (CF 3 so 2)2 CHC6 '5 (C6 H 03 SnAc 1:

1 0.30 0.34 95 476 450 839 978 2. 5 3 22 (CF 3 so 2)2 CHC6 H 5 (C4 H9)3 SnF 1:l 0.30 0.25 99 496 470 887 1023 3. 5 4 23 (CF 3 so 2)2 CHC6 H 5 (C4 H9)2 Sn (C2 H 3)2 1:l 0.30 0.241 99 491 468 870 995 1. 6 6 24 HBF 4 ( c 6 H 5)2 Sn(C 4 H 9)2 2. 0:l 0.15 1.3 99 490 472 865 998 2. 1 10 ( b)HSbF 6 6H 2 0 (C 6 H 5)2 Sn(C 4 H 9)2 2. 0: 1 0.10 0.224 99 322 318 622 645 5.1 24 (a) Percentages are percentages by weight of the combined weight of the the epichlorohydrin.

(b) 1.1, 1-trichlorobutylene oxide was substituted for epichlorohydrin 11 t, ethylene glycol and in this example.

co 9 GB 2 104 403A 9 EXAMPLES 26-27 A series of hydroxyl-terminated aloalkylene ethers were prepared as described in the general procedure. The resultant polyethers were tested for initial color magnitude then subjected to heat (80'C) for 14 hours after which time the polyethers were tested for final color magnitude. Example 26 was performed using a sample from the polyol prepared in Example 13 of Table 1. 5 Example 27 was performed using a 490 hydroxyl equivalent weight polyether prepared according to the general procedure but employing (C21- 1J,0 + PFj (0.2% by weight of the combined weight of the ethylene glycol and the epichlorohydrin) as the catalyst system.

Table 2 EXAMPLE AE1 AE, 26 1.51 1.56 27 18.55 30.41 15 AE, is the initial color of the ether in the test. AE, is the color of the ether after heat aging at WC for a 14 hour period. The behavior of Example 26 is characteristic of all the ethers of the invention. As can be seen, ethers of the invention exhibit essentially no change in color magnitude while prior art ethers darken dramatically in color.

EXAMPLES 28-34 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. 25 The poiyfunctional isocyanate was---MondurMRS- (a registered Trade Mark for a polymethy lene polyphenyl isocyanate having an average of 2.6 isocyanate groups per molecule and 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 25'C. A moisture free atmosphere was 30 maintained in the reaction vessel. There was no catalyst added to promote the reaction.

Examples 28 and 29 utilized poly(chloroaikylene 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-equivalent weight of 325 while the polyether employed in Exampe 29 had a theoretical hydroxyl equivalent 35 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. The polyols employed in Examples 31 and 32 had theoretical hydroxyl equivalent weights of 500 and 325 respectively and were prepared utilizing (C^),0 + PF, - (0. 2% by weight 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 I-ISbF,.6H20 (0.1 % by weight of the combined weight of the epichlorohydrin and the ethylene 45 glycol) as the catalyst system.

The results of the preparations are given 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 while those of 50 Examples 30-34 did not cure even after 3 days.

GB 2 104 403A 10 Table 3 POLYURETHANE VISCOSITY (cps) INITIAL FINAL EXAMPLE NCO/OH (Time = 0 hours) (Time = 24 hours) 28 1.2:1 4800 Gelled within minutes 29 1.2:1 2200 Gelled within 10 2.5 hours 1.2:1 5900 24000 31 1.2:1 5900 16000 32 1.2:1 2300 5400 33 1.2:1 4800 15000 15 34 1.2:1 2200 27000 Gellation occurs when the viscosity > 1,000,000 cps.

EXAMPLES 35-40 A series of hydroxyi-terminated chloroalkylene 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 % I-ISbF,.6H20 and 0.224% diphenyl dibutyl tin (both percentages being percentages by weight of the combined weight of the hydroxyl material and the epichlorohydrin). The resulting ethers were then tested for percent conversion, hydroxyl equivalent weight and color magnitude. The exact ingredients used to prepare the ethers, the amounts of each and the results obtained are reported in Table 4.

K T A B L E 4 HYDROXYL-CONTAINING MATERIAL PARTS EPICHLOROHYDRIN % CONHYDROXYL EQ. WT EXAMPLE TYPE BY WGT PARTS BY WGT VERSION THEORETICAL FOUND E CH3CH20H 46 954 98.5 1000 894 2.9 36 HO(CH2)60H 118 882 99.7 500 427 2.2 37 HOCII-2-.(:-CH20H 144 855 99.5 500 445 1.01 38 C2H5C(CH2OH)3 134 1366 98.7 500 439 2 S 39 HOCH 2 CH-,e-OCH2 CH 2 OH 198 802 99.5 500 424 3.1 Brl-lc = C B r 246 758 99.4 500 446 5.2 HOCH 21.1 c H 2 OH 12 GB 2 104 403A 12 CLAIMS 1. A catalyst system which comprises:

(i) a fluorinated material selected from bis(fluorinated aliphatic sulphonyl) alkanes and acids of the formula 1-1,XF_ m in which X is boron, phosphorous, arsenic or antimony; m is 0 or 1, n is 3 5 when X is boron and n is 5 when X is phosphorous, arsenic and antimony; and (ii) a polyvalent tin compound having the formula:

R 6 1 R'-Sn-Rl 1 (R'), in which g is 0 or 1; R' and R' are independently selected from saturated and unsaturated aliphatic and aromatic hydrocarbyl groups containing from 1 to 10 carbon atoms; R' represents an oxygen atom or a saturated or unsaturated aliphatic or aromatic hydrocarbyl group containing from 1 to 10 carbon atoms, provided than when R' is oxygen, g is 0, and 20 when R' is other than oxygen, g is 1; and W' represents a fluorine atom, an acyloxy group containing less than 10 carbon atoms, a saturated aliphatic hydrocarbyl group containing from 1 to 10 carbon atoms, or R5 25 1 O-Sn-W i R 7 in which R' to R' are as defined above, provided that when R', R' and R' are each saturated 30 aliphatic hydrocarbyl groups then R8 is not a saturated aliphatic hydrocarbyl group.

2. A catalyst system as claimed in Claim 1, which comprises said polyvalent tin compound and said bis(fluorinated aliphatic sulphonyl) alkane in a molar ratio in the range 0.2A to 2:1 respectively.

3. A catalyst system as claimed in Claim 2, which comprises said polyvalent tin compound 35 and said bis(fluorinated aliphatic sulphonyl) alkane in a molar ratio in the range 0.4A to 1.5A respectively.

4. A catalyst system as claimed in Claim 1, which comprises said polyvalent tin compound and said H.XF,,. acid in a molar ratio in the range 1. 13:1 to 3:1 respectively.

5. A catalyst system as claimed in Claim 4, which comprises said polyvalent tin compound and said acid in a molar ratio in the range 1.2:1 to 2:1 respectively.

Printed for Her Majesty's Stationery Office by Burgess Et Son (Abingdon) Ltd-1983. Published at The Patent Office, 25 Southampton Buildings, London, WC2A 1 AY, from which copies may be obtained.

5. A catalyst system as claimed in Claim 4, which comprises said polyvalent tin compound 40 and said 1-1,XFn,acid in a molar ratio in therange 1.2A to 2:1 respectively.

6. A catalyst system as claimed in Claim 1 substantially as herein described with reference to any one of the Examples.

CLAIMS (1 Jul 1982) 1. A catalyst system which comprises:

(i) a fluorinated material which is a bis(fluorinated aliphatic sulphonyl)alkane or an acid of the formula HAsF, or AsF, and (ii) a polyvalent tin compound having the formula:

R6 1 W-Sn-R 7 REI)9 in which g is 0 or 1; R' and R6 are independently selected from saturated and unsaturated aliphatic and aromatic hydrocarbyl groups containing from 1 to 10 carbon atoms; R 7 represents an oxygen atom or a saturated or unsaturated aliphatic or aromatic hydrocarbyl 60 group containing from 1 to 10 carbon atoms, provided than when R 7 is oxygen, 9 is 0, and when R' is other than oxygen, 9 is 1; and R' represents a fluorine atom, an acyloxy group containing less than 10 carbon atoms, a saturated aliphatic hydrocarbyl group containing from 1 to 10 carbon atoms, or 1 13 GB 2 104 403A 13 R5 1 O-Sn-R6 1 R 7 in which R5 to R 7 are as defined above, provided than when R 5, R6 and R 7 are each saturated aliphatic hydrocarbyl groups then W' is not a saturated aliphatic hydrocarbyl group.

4. A catalyst system as claimed in Claim 1, which comprises said polyvalent tin compound 10 and said acid in a molar ratio in the range 1. 13:1 to 3:1 respectively.