CH654221A5 - 2-COMPONENT CATALYST SYSTEM AND METHOD FOR THE PRODUCTION OF ETHERS ENDING WITH HYDROXYL. - Google Patents

Description

The present invention relates to a 2-component catalyst system and to a process for the preparation of hydroxyl-terminated ethers in which haloalkylene radicals are bound to ether oxygen with one of their two free valences and also to ether oxygen or to hydroxyl with the other are. Of the halogen atoms, bromine or chlorine are preferred.

As stated, the invention also relates to new catalyst systems which are used in the process mentioned. In the case of poly (chloroalkylene ether) terminated with hydroxyl groups, the products are essentially colorless.

Hydroxyl group-terminated poly (haloalkylene ethers) and processes for their preparation are known and the cationic polymerization techniques are frequently used, in which oxirane monomers (for example alkylene oxides), alcohols and acid catalysts are used, to synthesize hydroxyl functionalized prepolymers. Compare e.g. U.S. Patents 3,850,856;

3,910,878; 3,910,879 and 3,980,579.

The products described in these patents have not been entirely satisfactory because the temperature of the polymerization has been difficult to control and the products obtained have a dark color. These compounds also tend to react very slowly with various materials, such as isocyanates, unless substantial quantities of catalysts are used. It has also been shown that these products are unstable when exposed to light (e.g. sunlight) and heat (e.g. temperatures above 50X), and that their color tends to darken, their acidity increases and their water content also increases, if they are exposed to such conditions. Furthermore, the materials terminated with hydroxyl groups, which are described in US Pat. No. 3,980,579, adversely affect the catalytic action of the amine catalysts used in the production of polyurethane foams.

Other techniques for the preparation of hydroxyl-terminated poly (chloroalkylene ethers) are disclosed in US Pat. No. 3,450,774, in which the production of hydroxyl-terminated polymers by the cleavage of crystalline poly- (epihalohydrin) a high molecular weight in the presence of certain alkali compounds is described. The resulting polymers are crystalline, have a low molecular weight and are only partially functionalized with hydroxyl groups. Therefore, they can have carbonyl and ethynyl end groups instead of hydroxyl end groups.

Other poly (haloalkylene ethers) are described in U.S. Patents 30,363,663 and 3,850,857. The first patent describes the reaction between epibromohydrin and a phosphorus compound in the presence of a Friedel-Crafts catalyst. The second patent describes the polymerization of epihalohydrin in the presence of a catalyst from a trialkyl-onium salt of HMF6, where M is a group V element.

The present invention describes a process for the preparation of new hydroxyl-terminated ethers of the type mentioned above, and catalyst systems which are used for this.

The hydroxyl group-terminated poly (chloroalkylene ether) which have been prepared in accordance with the present invention are preferred and particularly advantageous because they are generally optically clear and colorless 45 (e.g. they have the same visual clarity as distilled water). So they exercise a color expansion (described in more detail below) of less than about 10 and they are stable to the effects of heat and light (e.g. they resist degradation under such conditions). They also have excellent chemical reactivity with isocyanate materials.

These preferred poly (chloroalkylene ether) materials are particularly useful where the color of the finished product is important (e.g. where the true color is critical 55). For example, they are useful in the manufacture of cast urethane systems that can be used for such things as covering materials, coatings, and adhesives. Furthermore, it has been shown that the urethanes which have been produced with the materials of the present invention have improved fat and oil resistance than urethanes which have hitherto been known.

Because of the simplicity, poly (haloalkyl ethers) terminated with hydroxyl groups, prepared according to the present invention here, are sometimes simply referred to below as “polyols”. The term “polyols” encompasses materials which have at least one terminal hydroxyl group.

654221

According to the present invention, new amorphous hydroxyl-terminated poly (haloalkylene ethers) are made available which consist of the mixture of a hydroxyl group-containing material which contains from 1 to 6 hydroxyl groups, a haloalkylene oxide and a defined 2-component catalyst system can be obtained. The polyol preferably has the formula f

C R3

wherein R1 and R2 each represent hydrogen and methyl; R3 and R4 each represent hydrogen, lower alkyl groups which contain from about 1 to 10 carbon atoms, and lower haloalkyl groups which contain from 1 to 2 carbon atoms and from 1 to 5 halogen atoms, with the proviso that at least one of the radicals R3 and R4 is said lower haloalkyl group; R5 is the remainder of an organic hydroxyl material, this hydroxyl material containing from 1 to 6 hydroxyl groups; b is an integer from 1 to 50; and d is an integer from 1 to 6. Most preferably, the polyols are poly (bromoalkylene ether) or poly (chloroalkylene ether). The poly (chloroalkylene ether) preferably contain from about 20 to 60 wt .-% chlorine.

The poly (haloalkylene ether) polyols made in accordance with the present invention are amorphous materials (e.g., they have no melting point). They can be either low molecular weight (e.g., about 250) materials or high molecular weight (e.g., about 5,000) materials based on the average hydroxyl group functionality of the polyols. Furthermore, they are essentially colorless, i.e. they have a color expansion of less than about 10.

New catalyst systems that can be used in the production of the polyols are also presented here. They contain the components defined in claim 1.

The molar ratio between the polyvalent tin compound and the fluorine-containing acid depends on the acid used in each case. 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. The ratio is preferably in the range from 0.4: 1 to 1.5: 1.

The ratio between the tin compound and either the HF or the HmXFn + m fluorinated acids is in the range of 1.13: 1 to 3: 1. The ratio is preferably in the range from 1.2: 1 to 2: 1.

A process for the preparation of the new polyols is also presented, the new catalyst system being used, in which a hydroxyl group-containing material which has from 1 to 6 hydroxyl groups is mixed with an alkyl oxide and in which The presence of the catalyst system described above is polymerized.

The polyols are prepared by mixing a material containing hydroxyl groups, an alkylene oxide (at least 50% by weight of which is a haloalkylene oxide) and the catalyst system according to the invention, and then the resulting mixture is polymerized. The polymerization can be carried out at a temperature in the range of 0 C-110 C. The polymerization is preferably carried out at a temperature in the range of 40 C-80 C.

Solvents can also be used in the polymerization mixture. They are particularly useful when one or more of the components of the mixture is a solid. Suitable solvents dissolve the materials in the mixture, but are otherwise inert. Representative examples of suitable solvents are benzene, toluene, methylene chloride, carbon tetrachloride and 1,2-dichloroethane.

Although the polymerization proceeds smoothly to completion, some unpolymerized haloalkylene-lo oxide may remain. This can be removed from the poly (haloalkylene ether) by heating the polymerized mixture (e.g. to about 80 ° C.) and exposing the heated mixture to a reduced pressure (eg 1.33 Pa [0 , 01 Torr]) for a short period of time (e.g. 1 15 to 2 hours).

A wide variety of hydroxyl group-containing materials can be used in the present invention. These materials include, for example, water and liquid and solid organic materials, which have at least one hydroxyl group functionality. The organic materials can be monomeric or polymeric and are preferably selected from mono- and poly-alkanols, haloalkanols and polymeric polyols.

The hydroxyl groups of the organic materials 25 can be terminal or non-terminal groups. Materials containing hydroxyl groups that contain both terminal and non-terminal hydroxyl groups can also be used. The molecular weight of the organic hydroxyl group-containing material can vary over a wide range. For example, it can range from about 10 to 2500.

Preferably, the organic hydroxyl group-containing material is an aliphatic material that contains at least one primary or secondary aliphatic hydroxyl group (e.g., the hydroxyl group is attached directly to a non-aromatic carbon atom). Most preferably, said organic material is an alkane polyol.

Mono- and polyalkanols which can be used in the present invention are methanol, ethanol, isopropanol, 2-butanol, 1-octanol, octadecanol, 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 45 and sorbitol.

Mono- and poly-haloalkanols which can be used in the present invention are 2-chloroethanol, 3-chloropropanol, 2,3-dichloropropanol, 3,4-di-bromo-l, 2-butanediol, 2, 3-dibromo-l, 4-butanediol, 1,2,5,6-Te-50 trabromohexane-3,4-diol.

Polymeric hydroxyl group-containing materials that can be used in the present invention include polyoxyethylene glycols and polyoxypropylene glycols and triols with molecular weights from about 55 200 to 2000 (corresponding to hydroxyl group equivalent weights from 100 to 1000 for the diols and 70 to 630 for tripoles); hydroxyl group terminated polyalkadienes; and polytetramethylene glycols with a varying molecular weight, such as the Polymegs series of glycols, available from Quaker Oats Company under the names Polymeg "650, 1000 and 2000.

The previous list, in which the hydroxyl group-containing materials have been shown, is to be considered as illustrative only. Other materials containing hydroxyl groups 65 can also be used, as a result of this disclosure.

The exact hydroxyl group containing material suitable for use in the present invention

5

654 221

The choice has been made depends on the hydroxyl group functionality that is desired in the poly (chloroalkylene ether) polyol. It was found,

that the final polyols have the same hydroxyl group functionality as the hydroxyl group containing starting material and that the hydroxyl group functionality is present as a terminal functionality. If, for example, a mono-functionalized hydroxyl group-containing material is used, a mono-polyether is obtained; if di-functionalized hydroxyl group-containing materials are used, divalent polyether polyols are obtained; Etc.

Mixtures of hydroxyl group-containing compounds can be used if desired, for example mixtures of 2 or more poly-functionalized hydroxyl compounds, one or more mono-functionalized hydroxyl compounds with one or more poly-functionalized ones Use hydroxyl compounds etc.

A wide variety of haloalkylene oxides can be used in the present invention. They include, for example, epichlorohydrin, epibromohydrin, 1-chloro-2-methyl-2,3-epoxypropane, 1-bromo-2-methyl-2,3-epoxypropan, l, 4-dichloro-2,3-epoxybutane, l , 4-dibromo-2,3-epoxybu-tan and 1 chloro-2,3-dimethyl-2,3-epoxybutane. Higher halo-monoalkylene oxides can also be used in the present invention. Representative examples of these materials include 1,1-dichloro-2,3-epoxypropane, 1,1,1-trichloro-2,3-epoxypropane,

1-bromo-l, l-dichloro-2,3-epoxypropane,

1,1-dichloro-1-fluoro-2,3-epoxypropane,

1,1-difluoro-1-chloro-2,3-epoxypropane, etc.

Other haloalkylene oxides that can be used include 1,1-dichloro-2-methyl-2,3-epoxypropane, 1,1,1-richloro-3,4-epoxybutane,

1,1-dichloro-3,4-epoxybutane, 1,1,1,2,2-pentachlor-2-methyl-2,3-epoxybutane. Tetrachloro epoxybutanes 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,

can also be used.

Mixtures between the haloalkylene oxides mentioned above can also be used, as can mixtures between at least one haloalkylene oxide with up to 50% by weight of one or more non-halogenated alkylene oxides. Examples of usable non-halogenated alkylene oxides are propylene oxide, 1-hexylene oxide, cyclohexane oxide, styrene oxide, methyl glycidyl ether and phenyl glycidyl ether.

By checking the ratios between alkylene oxide and material containing hydroxyl groups, it is possible to limit the degree of addition and consequently the molecular weight of the polyols which can be prepared according to the invention. Thus the molar ratio between alkylene oxide material and the hydroxyl groups in said hydroxyl group-containing material can be in the range from 1: 1 to 50: 1, preferably the molar ratio is in the range from 1: 1 to 20: 1.

Catalyst systems which can be used in the present invention include (1) a fluorine-containing acid selected from the group described above and (2) a polyvalent tin compound as described above. A small amount of 0.05% by weight of the catalyst system based on the combined weight of the hydroxyl group-containing material

riales and the alkylene oxide, is effective to provide the polyols that can be produced according to the invention.

As discussed above, the molar ratio of the polyvalent tin compound to the fluorine-containing acid is dependent on which fluorine-containing acid is used in the catalyst system. However, whichever ratio is used, the catalyst system can be easily made by simply adding each component to the polymerization mixture.

As stated above, the fluorine-containing acid which is used in the catalyst system is selected from the group consisting of compounds having the group of the formula h

15.

r-so -c-so -r z l of the radicals R, which are identical or different, each 20 is a fluorinated aliphatic or fluorinated cycloaliphatic organyl radical, HF and acids of the formula HmXFn + m. Highly fluorinated alkanes which contain 1 to about 15 carbon atoms are preferred. Also included are those compounds which release such alkanes in the presence of heat or moisture. For example, bis (highly fluorinated alkyl sulfonyl) alkanes on hydrolysis yield bis (highly fluorinated alkyl sulfonyl) alkanes.

The term "highly fluorinated-aliphatic residues" used here includes fluorinated, saturated, monovalent, aliphatic residues with 1 to 10 carbon atoms. The carbon skeleton of the residue can be straight or branched or, if it is long enough (e.g. at least 3 or 4 atoms) cycloaliphatic. Furthermore, the carbon skeleton can be interrupted by divalent oxygen atoms 35 or trivalent nitrogen atoms which are bonded to the carbon atoms. Preferably, the backbone of the fluorinated aliphatic residue contains no more than one hetero-atom (e.g., stock or oxygen) per 2 carbon atoms present in the backbone. A fully fluorinated group is preferred, however, hydrogen or chlorine atoms may be present as substituents in the fluorinated aliphatic group, provided that there is no more than 1 atom in the group for each carbon atom. Preferably, the fluoroaliphatic radical is a saturated perfluoroalkyl radical which has a carbon skeleton which is straight or branched and has the formula CxF2x + al, where x is from 1 to 18.

The preferred bis (fluorinated-aliphatic sulfonyl) -so alkanes are those compounds which have the formula

R9

RfS02-Ç ~ S02Rf h

wherein each Rf group is the same or different and is a fluorinated (preferably a highly fluorinated or 60 per-fluorinated) alkyl group containing from about 1 to 10 carbon atoms and R9 is selected from hydrogen, halogen, alkyl Groups which have from 1 to 10 (preferably 1 to 4) carbon atoms, alkenyl groups which contain from about 1 to 3 carbon atoms, aryl groups (for example phenyl, naphthyl) and alkaryl groups with up to 10 Carbon atoms. The alkyl, aryl and alkaryl radical may, if desired, be substituted by one or more groups selected from Ha

654 221

logen, highly fluorinated alkyl sulfonyl groups, carboxyl groups, alkoxy carbonyl groups, nitro groups, alk oxy groups and acetoxy groups.

Fully fluorinated groups are preferred, but hydrogen or chlorine atoms can be present as substituents in the group, provided that no more than 1 atom is present in the balance per 1 carbon atom. The alkyl groups generally contain no more than 10 carbon atoms and preferably contain less than 8 carbon atoms. Most preferably they contain up to 4 carbon atoms.

Representative examples of bis (perfluoro-alkylsulfonyl) alkanes that can be used are: bis (trifluoromethylsulfonyl) methane, bis (difluorochloromethylsulfonyl) methane, tris (trifluoromethylsulfonyl) methane, bis (trifluoromethylsulfonyl) -4-bromphenylifluoromethyl thienylmethane, bis (trifluoromethylsulfonyl) chloromethane, bis (trifluoromethylsulfonyl) benzylmethane, 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 (perfluoromethylsulfonyl) -2-carbomethoxy-2-

bromobutanoate, ethyl 4,4-bis (perfluoromethylsulfonyl) -2-carboethoxy-2-

nitrobutanoate, 1,1,3,3-tetra (trifluoromethylsulfonyl) propane and 1,1-bis (trifluoromethylsulfonyl) octadecane.

Representative examples of bis (fluorinated-aliphatic-sulfonyl) alkanes that can be used are also described in U.S. Patents 3,632,843; 3,704,311; 3,701,408; 3,776,960 and 3,794,687, which are also incorporated herein by reference.

Another class of fluorinated acids that can be used in the present invention are essentially completely fluorinated and conform to the formula HnXFm + n, where X, m and n have been described above. Specific examples which can be used as the fluorinated acid of this type are BF3, HBF ^, SbF5, HSbF6, PF5, HPFe, AsFs and HAsFe.

The polyvalent tin compounds used in the catalyst system of the present invention have the formula

R5-Sn R7 (R8) g wherein, R5, R6, R7, R8 and g have each been 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 demonstrated, the chloralkylene polyols made and preferred according to the present invention are generally optically clear and essentially colorless, as shown by their color expansion (e.g., they have a color expansion of less than 10). The color expansion represents the deviation of the color of a given material from the color of distilled water when both colors are measured at a temperature of around 25 ° C. The color of the water and samples are measured using a Hunterlab Model D25-4 Color Difference Meter, available from Hunder-Associates Laboratory, 9529 5 Lee Highway, Fairfax, Virginia. This device measures 3 parameters which characterize the color of a sample. These parameters are (1) the gray component «L» of the sample; (2) the red-green component «a» of the sample (a plus value indicates red and a minus value indicates green); and 10 (3) the yellow-blue component «b» of the sample (a plus value indicates yellow and a minus value indicates blue). The color

Expansion (AE) is calculated from the formula

/

15 AU = {L) 2 + (a) 2 + {b) 2

where L, a and b represent the difference between the L, a and b values of distilled water and the sample to be tested. Distilled water has a color expansion 20 of 0 at a temperature of 25 C.

The color expansion values of less than about 10 indicate optically clear and essentially colorless materials. The color of a material with a color expansion of 10 is slightly yellow and a thin film of such a material remains optically clear. As the color expansion increases (e.g., when AE increases), the color and optical clarity of the sample decrease. With a color expansion of 20, the material has a light brown color and a thin film of it has an indistinct optical clarity. With a color expansion of 50, the material has a strong dark brown color and it is difficult to see through a thin film of it.

The invention is further illustrated with the aid of the following examples, in which the term “parts” refers to 35 parts by weight, unless stated otherwise. In the examples, the poly (alkylene ether) polyols were made according to the following general procedure.

The polyethers were produced in a glass reaction vessel which was equipped with a stirring motor, a thermometer 40 and a dropping funnel. A dry atmosphere was maintained in the reaction vessel during the reaction.

In each preparation, the hydroxyl group-containing material (ethylene glycol, 62.0 g, 1 mol) and the catalyst system were added to the reaction vessel with stirring and heated to a temperature of about 40 ° C to 60 ° C . The composition and quantity of the catalyst system was varied with each reaction. The haloalkylene oxide (epichlorohydrin or epibromohydrin), 50 was then slowly added to the stirred mixture over a period of approximately 3 hours. The reaction was continued until it was essentially complete. The temperature of the reaction mixture was maintained between 40 ° C and 85 ° C. The 55 amount of halohydrin used was varied to control the hydroxyl group equivalent weight of the product. For example, 938 g (10.1 mole) epichlorohydrin was used to to produce a product with a theoretical hydroxyl group equivalent weight 60 of about 500. On the other hand, 1938 g (21 moles) of epichlorohydrin was used to produce a product with a theoretical hydroxyl group equivalent weight of about 1000.

65 Examples 1 to 25

Examples 1 to 25 describe a number of poly (chloroalkylene ether) polyols which are prepared according to the general procedure described above.

Table 1

Catalyst system

example

A

B

Molares

Quantity (a)

sales

HO equivalent weight

Molecular weight

Reaction

relationship

colour

time

% A

% B

(%)

calculated found

Mn

Mw

AE

1

bf3

0.30

99

500

496

863

1040

52.6

6

2nd

bf3

0.10

99

1020

930

1420 '

1040

50.4

6

3rd

bf3

0.10

99

275

252

542

589

43.5

6

4th

hsbf0 ■ 6h20

0.10

99

491

450

854

1050

51.6

6

5

(C2h5) 3o + pf6-

0.20

99

500

426

882

1180

36.8

6

6

SbFs

0.10

99

1020

950

1210

2060

31.7

6

7

(C6H5) 2Sn (C4H9) 2

0.0

0.224

0

no reaction

5

8th

(cf3s02) 2chcöh5

0.50

0.0

81

810

665

1070

1570

12.6

24th

9

(cf3s02) 2CHC6hs

0.50

0.0

93.7

470

410

815

958

10.5

24th

10th

HSbF6 • 6H20

(C6H5) 2Sn (C4H9) 2

1

1

0.10

0.118

99

490

420

884

1070

53.1

5

11

HSbF6 • 6H20

(C6H5) 2Sn (C4H9) 2

1.1

1

0.10

0.124

99

490

425

921

1050

52.9

5

12

HSbF6 • 6H, 0

(C6H5) 2Sn (C4H9) 2

1.13

1

0.10

0.127

99

490

437

896

1000

2.1

5

13

HSbFtì • 6H20

(C6H5) 2Sn (C4H9) 2

1.16

1

0.10

0.130

99

490

437

894

1000

1.5

5

14

HSbF6 • 6H, 0

(C6H5) 2Sn (C4H9) 2

1.51

1

0.10

0.17

99

490

450

883

1010

2.2

5

15

HSbF6 • 6H, 0

(C6H5) 2Sn (C4H9) 2

2.0

1

0.10

0.224

99

490

470

860

993

0.8

5

16

HSbF6 • 6H, 0

(C6H5) 2Sn (C4H9) 2

2.65

1

0.10

0.298

99

490

433

827

967

1.8

5

17th

(cf3s02) 2CHC # hs

(c6Hs) 2Sn (c4H9) 2

0.195

1

0.30

0.064

93

465

452

883

1020

3.6

10th

18th

(cf3s02) 2chc6h5

(C6H5) 2Sn (C4H9) 2

0.392

1

0.30

0.128

99.5

496

470

939

1025

2.1

5

19th

(cf3s02) 2chc6h5

(C6H5) 2Sn (C4H9) 2

0.785

1

0.30

0.256

99

491

478

924

1046

2.5

3rd

20th

(cf3SO,), CHC6hs

(C6H5) 2Sn (C4H9) 2

1.96

1

0.30

0.64

95.2

476

450

923

1025

2.2

5

21st

(cf3s02) 2CHC6hs

(C6H5) 3SnAc

1

1

0.30

0.34

95

476

450

839

978

2.5

3rd

22

(cf3SO,) 2CHC6hs

(C4H9) 3SnF

1

1

0.30

0.25

99

496

470

887

1023

3.5

4th

23

(cf3s02) 2CHC6hs

(C4H9) 2Sn (C2H3) 2

1

1

0.30

0.241

99

491

468

870

995

1.6

6

24th

hbf4

(C6H5) 2Sn (C4H9) 2

2.0

1

0.15

1.3

99

490

472

865

998

2.1

10th

25 (b)

HSbF6 • 6H20

(C6H5) 2Sn (C4H9) 2

2.0

1

0.10

0.224

99

322

318

622

645

5.1

24th

(a) The percentages are% by weight of the combined weight of ethylene glycol and epichlorohydrin.

(b) Instead of epichlorohydrin, 1,1,1-trichlorobutylene oxide was used in this example.

654 221

ren have been produced, both using known, conventional catalyst systems and with the catalyst systems according to the invention. The exact name of the catalyst system used and the results obtained are given in Table 1.

The catalyst system used in Examples 1-3 is BF3; in Example 4

HSbFe • H20 used; in Example 5

(C2Hs) 30 + PF6-used and in Example 6 SbFs was used. As can be seen, the poly (chloroalkylene ether) polyols made with these catalyst systems were dark in color, as evidenced by their high AE values (e.g. between 30 and 52).

Examples 7 to 9 show the effect of the individual components of the catalyst system according to the invention with respect to the poly (chloroalkylene ether) polyols produced. In example 7, the catalyst system was a polyvalent tin compound of the formula

R6

R5-Sn R7

(a8) g

(For example, (CäHs) 2Sn (C4Hg) 2. As can be seen from Example 7, even after 5 hours of mixing, no reaction took place when the compound diphenyl-dibutyl-tin was used as the catalyst system Sulfonyl-alkane compound (Examples 8 and 9), darker products compared to the products according to the invention were obtained, which is evident from the corresponding color expansions.

Examples 10 to 12 show the relationship between the molar ratio of the fluorinated acid of the formula HmXFm_n and the tin compound in the catalyst composition according to the invention. In Examples 10 and 11, the ratio was 1: 1 and 1.1: 1. In each case, the product obtained was very dark brown (e.g. the AE value was 53.1 and 52.9, respectively). However, in Example 12 the molar ratio was 1.13: 1 and the product obtained was optically clear and essentially colorless (e.g. the color expansion was 2.1).

Examples 13 through 24 demonstrate the present invention. In each of these examples, an optically clear and essentially colorless poly (chloroalkylene ether) polyol was obtained. This is evident from the low AE values obtained (e.g. less than about 5). Example 13 shows the effect of varying the molar ratio between the HmXFra + n-fluorinated acid and the polyvalent tin compound. Examples 17 to 20 show the use of bis (fluorinated aliphatic sulfonyl) alkanes and the use of varying ratios of this acid and the tin compound in the catalyst system. Examples 21 to 24 show the use of various tin compounds in the catalyst system. Example 25 shows that highly halogenated alkylene oxides (e.g. 1,1,1-trichlorobutylene oxide) can also be used in the present invention.

Examples 26 and 27

A series of hydroxyl-terminated poly (haloalkylene ethers) was made according to the general procedure described above. The initial color expansion was determined from the polyethers obtained. Thereafter, the polyethers were subjected to a heat treatment at a temperature of 80 ° C. for 14 hours, and subsequent to this treatment, the final color expansion of these polyethers was determined. Example 26 was carried out using a sample of the polyol, the preparation of which is described in Example 13 of Table 1. Example 27 was carried out using a polyether with a hydroxyl group equivalent weight of 490, prepared according to the general procedure described above, but using (C2H5) 30 + PF6 "(0.2% by weight of the combined weight of ethylene glycol and epichlorohydrin) as a catalyst system.

Table 2

Example Et EF

26 1.51 1.56

27 18.55 30.41

20 E [indicates the initial color of the polyol in the test procedure. EF is the color of the polyol after heat aging at a temperature of 80 ° C for a period of 14 hours. The results described in Example 26 are characteristic of all polyols according to the invention. As can be seen, there is essentially no change in the color expansion in the poly (chloroalkylene ether) polyols according to the invention, while the color of the conventional poly (chloroalkylene ether) polyols becomes much darker.

30th

Examples 28 to 34 A series of polyurethanes was made using various poly (chloroalkylene ether) polyols and a poly-functionalized polyisocyanate. 3S The polyols were prepared as described in the general procedure further above. The poly-functionalized isocyanate used was "Mondur MRS" (a poly-methyl-polyphenyl isocyanate, which has an average of about 2.6 isocyanate groups per molecule and was available from the Mobay 40 Company).

The polyurethanes were produced by combining the constituents in a suitable reaction vessel and then stirring for 1 to 2 minutes at a temperature of about 25 ° C. Care was taken 45 that a moisture-free atmosphere was present in the reaction vessel. No catalyst was added to accelerate the reaction.

Examples 28 and 29 used poly (chloroalkylene ether) polyols, corresponding to the present invention. These polyols were made using the same catalyst system and the respective amounts are given in Example 15. The one in example

28 polyol used had a theoretical hydroxyl group equivalent weight of 325, while the polyether used in Example 29 had a theoretical hydroxyl group equivalent weight of 500.

In Examples 30 to 34, poly (chloroalkylene ether) polyols were used, which had been prepared using conventional catalyst systems. The polyol used in Example 60-30 had a theoretical hydroxyl group equivalent weight of 1000 and was made using BF3 (0.3% by weight of the combined weight of epichlorohydrin and ethylene glycol) as the catalyst system. The 65 polyols used in Examples 31 and 32 had theoretical hydroxyl group equivalent weights of 500 and 325, respectively, and were prepared using (C2H5) 30 * "PFÖ (0.2% by weight of epichlorohydrin and ethylene glycol) as a catalyst

System. The polyols used in Examples 33 and 34 had a theoretical hydroxyl group equivalent weight of 500 and 325, respectively, and were made with HSbFfl • 6H20 (0.1% by weight of the combined weight of epichlorohydrin and ethylene glycol) as Catalyst system.

The results of the preparations are given in Table 3 below. As can be seen, the polyurethanes from Examples 28 and 29 (produced with the poly (chloroalkylene ether) polyols according to the invention) gelatinized rapidly, while the polyurethanes of Examples 30 to 34 (produced with conventional poly (chloroalkylene ether)) Polyols) not gelatinized even after 24 hours. Furthermore, the polyurethanes from Examples 28 and 29 cured within 24 hours, while the polyurethanes from Examples 30 to 34 were not cured even after 3 days.

Table 3

Example NCO / OH polyurethane viscosity in Pa.s at the beginning at the end

(Time = 0 hours) (time = 24 hours)

28

1.2: 1

480 (4800 cps)

Gelatinized inside

half of 15 minutes *

29

1.2: 1

220 (2200 cps)

Gelatinized inside

half of 2.5 hours *

30th

1.2: 1

590 (5900 cps)

2400 (24 000 cps)

31

1.2: 1

590 (5900 cps)

1600 (16,000 cps)

32

1.2: 1

230 (2300 cps)

540 (5400 cps)

33

1.2: 1

480 (4800 cps)

1500 (15,000 cps)

34

1.2: 1

220 (2200 cps)

2700 (27,000 cps)

* Gel binding occurred when the viscosity was greater than 100,000 Pa.s (1,000,000 cps).

Examples 35 to 40 A series of hydroxyl-terminated poly (chloroalkylene ethers) according to the present invention were prepared according to the general procedure described above, except that various hydroxyl group-containing materials were used instead of ethylene glycol. In each of these examples, the catalyst system contained 0.1%

HSbFg • 6H20 and 0.224% diphenyldibutyl tin (both percentages are% by weight of the combined weight of the hydroxyl group material and epichlorohydrin). The percentage conversion, the hydroxyl group equivalent weight and the color expansion of the polyols obtained were then determined. The used

9 654 221

The constituents used for the preparation of the polyols, the amounts thereof and the results obtained are given in Table 4 below.

s Example 41

A poly (bromoalkylene ether) according to the present invention was made. A mixture of cyclohexanedimethanol (72 g, molecular weight 144, 0.5 mol) and methylene chloride (500 ml) was heated to a temperature

10 heated to 40 ° C and the catalyst system (48% aqueous fluoroboric acid and 1.8 g diphenyldibutyl tin) (3.8 g) was added. Epibromohydrin (purified by distillation; 528 g) was then slowly reacted over a period of one hour.

15 mixture was added, and the reaction temperature was kept at 40 to 45 ° C. The mixture was further stirred at a temperature of 40 ° C for 16 hours. 58% ammonium hydroxide was then added, and the mixture was stirred until the mixture had reached a pH of 2o of 7. Anhydrous magnesium sulfate and Ce-lite were added slowly, stirring was continued and the mixture was then filtered. The solvent and the remaining epibromohydrin were removed in vacuo. A yield of 96% of yellowish polyepibromo-25 hydrine was obtained (hydroxyl group equivalent weight = 358, molecular weight = 1023; Mn = 817, Br% = 46.7%).

Example 42

30 A poly (chloroalkylene ether) was made in accordance with the present invention. A mixture of cyclohexanedimethanol (36 g, molecular weight = 144, 0.25 mol) and the catalyst system (0.31 g 48% aqueous hydrofluoric acid and 0.17 g diphenyl-dibutyl-35 tin) was brought to a temperature of 60 heated to 65 ° C. Epichlorohydrin (214 g, 2.31 mol) was slowly added to the reaction mixture while maintaining the same temperature. The reaction mixture was stirred for an additional 16 hours. After vacuum distillation, a colorless and slightly cloudy poly (chloroalkylene ether) according to the present invention was obtained in 72% yield. The product had a hydroxyl group equivalent weight of 332, an average molecular weight of 838 and a color expansion of 45 1.69. The yield of the chloroalkylene ether can be increased to 97.3% if a catalyst system consisting of 0.75 g of 48% aqueous hydrofluoric acid and 0.5 g of diphenyldibutyl-tin is used. The product obtained from this reaction had a hydroxyl group equivalent weight 50 of 407.

Table 4

Material containing hydroxyl groups

Example type

Parts by weight epichlor hydrin

Parts by weight

% Hydroxyl group equivalent

Sales theoretically found AE

35 CH3CH2OH 46

36 HO (CH2) 6OH 118

37 HIGH, CH, OH 144

38 C2H5C (CH, OH) 3 134

39 HOCH2CH, OCH, CH, OH 198 Br Br

40 C = C HIGH, CH.OH

954

98.5

1000

894

2.9

882

99.7

500

427

2.2

855

99.5

500

445

1.01

1366

98.7

500

439

2.5

802

99.5

500

424

3.1

Claims (9)

654 221 2. Process for the preparation of hydroxyl-terminated ethers in which haloalkylene radicals are bound to ether oxygen with one of their two free valences and likewise to ether oxygen or to hydroxyl with the other R Sn R7 - R where oxygen is excluded as meaning of R7. 2 I 2 io of their radicals R, which are identical or different, each is a fluorinated aliphatic or fluorinated cycloaliphatic organyl radical, HF and acids of the formula HmXFn + m, in which X is boron, phosphorus, arsenic or antimony and m is the number 0 or 1 and n is 3 in the case that X is boron and 5 in the case that X is phosphorus, arsenic or antimony, and (b) a tin compound of the formula as the second component R6 RS-Sn R7 (RS) g where g is 0 or 1; R5 and R6, which are the same or different, are selected from saturated and unsaturated aliphatic and aromatic hydrocarbon groups which contain 1 to 10 carbon atoms, R7 is selected from oxygen and saturated and unsaturated aliphatic and aromatic hydrocarbon groups containing 1 to 10 carbon atoms with the proviso that g if R7 is oxygen is 0 and otherwise 1 and R8 from fluorine, acyloxy groups containing less than 10 carbon atoms, saturated aliphatic hydrocarbon groups containing 1 to 10 carbon atoms, and - O - R Sn R7 - R wherein oxygen is excluded as the meaning of R7 is selected with the proviso that when R5, R6 and R7 are each saturated aliphatic hydrocarbon groups with 1 to 10 carbon atoms, R8 is selected from fluorine, acyloxy groups which are less than 10 Contain carbon atoms, and - O - R Sn * 7 - r are characterized in that hydroxyl group-containing material which contains 1 to 6 hydroxyl groups and haloalkylene oxide are reacted in the presence of a catalytic amount of a 2-component catalyst system, and that this 2-component catalyst System includes: (a) the first component is a fluorine-containing acid from the group consisting of compounds having the group of the formula H r-so2-c-so2-r 15 of whose radicals R, which are the same or different, each is a fluorinated aliphatic or fluorinated cycloaliphatic organyl radical, HF and acids of the formula HmXFn + m, where X is boron, phosphorus, arsenic or antimony and m is 0 or 1 stands for n in the case that X is boron, the number 3 and in the case that X is phosphorus, arsenic or antimony, the number 5, and (b) as a second component a tin compound of the formula 20th 25th 30th R R5-Sn R7 (rv wherein g is 0 or 1; R5 and R6, which are the same or different, are selected from saturated and unsaturated aliphatic and aromatic hydrocarbon groups which contain 1 to 10 carbon atoms 35, R7 is selected from oxygen and saturated and unsaturated aliphatic and aromatic hydrocarbon groups containing 1 to 10 carbon atoms with the proviso that g if R7 is oxygen is 0 and 40 is otherwise 1, and R8 from fluorine, acyloxy groups containing less than 10 carbon atoms, saturated aliphatic hydrocarbon groups containing 1 to 10 carbon atoms, and 45 50 - O - R Sn 17 - R wherein oxygen is excluded as the meaning of R7 is selected with the proviso that when Rs, R6 and R7 are each saturated aliphatic hydrocarbon groups with 1 to 10 carbon atoms, R8 is selected from fluorine, acyloxy groups which are less than 10 Contain carbon atoms, and 60 - O - where oxygen is excluded as meaning of R7. 2nd PATENT CLAIMS 1.2-component catalyst system, characterized in that it contains: (a) the first component is a fluorine-containing acid from the group consisting of compounds having the group of the formula H 1 r -; -; o -c-so ^ -r 3. The method according to claim 2, characterized in that the hydroxyl-terminated ether has the formula 654 221 where R1 and R2 are each hydrogen or methyl; R3 and R4 each represent hydrogen, lower alkyl which contains 1 to 2 carbon atoms, or lower haloalkyl which contains 1 to 2 carbon atoms and 1 to 5 halogen atoms, with the proviso that at least one of the radicals R3 and R4 is a lower haloalkyl of the aforementioned type ; Rs is the residue of an organic hydroxyl group-containing material containing 1 to 6 hydroxyl groups, b is a number from 1 to 50, and d is a number from 1 to 6. 4. The method according to claim 2, characterized in that the fluorine-containing acid (a) said compound having the group of the formula h i r-s02-c-s02-r, each of whose radicals R, which are the same or different, is a fluorinated aliphatic or fluorinated cycloaliphatic organyl radical. 5. The method according to claim 4, characterized in that the molar ratio of the tin compound (b) to the fluorine-containing acid (a) is in the range from 0.2: 1 to 2: 1. 6. The method according to claim 2, characterized in that the fluorine-containing acid (a) is selected from HF and acids of the formula HmXFn + m. 7. The method according to claim 6, characterized in that the molar ratio of the tin compound (b) to the fluorine-containing acid (a) is in the range from 1.13: 1 to 3: 1. 8. The method according to claim 6, characterized in that the fluorine-containing acid (a) is selected from the group consisting of BF3, HBF4, SbFs, HSbF6, PF5, HPF6, AsF5 and HAsFö. 9. The method according to claim 6, characterized in that the fluorine-containing acid (a) is HF.