CH653693A5 - AMORPHE CHLORALKYLENE ALCOHOLS, METHOD AND CATALYST SYSTEM FOR THE PRODUCTION AND USE THEREOF. - Google Patents

Description

The invention relates to compounds of the formula I which are optically clear and colorless, i.e. have the same visual clarity as distilled water. Their color size (defined below) is less than 10. In addition, they are usually extremely heat and light stable, i.e. they are not degraded under such conditions. In addition, as polyols, they have excellent chemical reactivity towards isocyanates.

The compounds of the formula I according to the invention are hereinafter referred to briefly as "polyols", by which compounds of the following formula I are understood, but which can also have only one terminal OH group.

The virtually colorless poly (chloroalkylene ether) polyols of the invention with a color size <10 have the formula

,1

(i

)

in which R1 and R2 represent hydrogen atoms or methyl groups. R3 and R4 represent hydrogen atoms, alkyl radicals having 1 to 10 carbon atoms or chloroalkyl radicals having 1 or 2 carbon atoms and 1 to 5 chlorine atoms, with the proviso that at least one of the radicals R3 and R4 is such a chloroalkyl radical, R5 is hydrogen or an organic radical, b is an integer from 1 to 50 and d 5 is an integer from 1 to 6. The polyols according to the invention preferably contain 20 to 60 percent by weight of chlorine.

The polyols according to the invention are not only colorless but also amorphous, so that they have no melting point. Based on the average hydroxyl functionality of the polyols, they can be low-molecular materials (MG 250) or high-molecular materials (MG 5000)

be.

The colorless polyols according to the invention are particularly suitable for areas of application in which the color of the end product is important, for. B. the true color of the product is a critical factor. For example, they are suitable for the production of urethane casting systems that can be used as floor coverings, coatings and adhesives. Urethanes made from the polyols of the present invention are superior to conventional urethanes in several ways. For example, they have excellent fat and oil resistance.

The invention further relates to a process for the preparation of the polyols according to the invention and a catalyst system for carrying out the process. These subjects of the invention are defined in independent claims 5 and 6.

The molar ratio of the multivalent tin compound to 30 of the fluorinated compound depends on the compound used in each case. For example, the ratio of the tin compound to the compound of the formula II is preferably in the range from 0.2: 1 to 2: 1, in particular 0.4: 1 to 1.5: 1.

The ratio of the tin compound to the fluorinated 35 compounds of the formula:

HmXFn + m is expediently in the range from 1.13: 1 to 3: 1, preferably 1.2: 1 to 2: 1.

The polyols according to the invention are prepared by bringing together a hydroxyl-containing organic material or water, an alkylene oxide which contains at least one chloroalkyl radical R3 or R4, and the catalyst system according to the invention and polymerizing the mixture obtained. The polymerization can be carried out at a temperature of 0 to 110 ° C, preferably 40 to 80 ° C.

Solvents can be used in the polymerization system, in particular when one or more constituents of the mixture are solids. Suitable solvents solvate the constituents of the mixture, but are otherwise inert. Specific examples are benzene, toluene, methylene chloride, carbon tetrachloride and 1,2-dichloroethane.

ss Although the polymerization is generally smooth to completion, some non-polymerized chloroalkylene oxide can sometimes remain. This material can be separated from the polyols obtained according to the invention by heating the polymerization mixture to 60 80 C and keeping it under reduced pressure (0.01 Torr) for a short time (1 to 2 hours).

A wide variety of hydroxyl-containing materials can be used. Suitable examples are water and liquid and solid organic materials that have a Hy-65 d'roxyl functionality of at least 1. The organic materials can be monomeric or polymeric, mono- and polyhydric alkanols, haloalkanols and polymeric polyols being preferred.

653 693

4th

The hydroxyl groups of the organic materials can be terminal and / or pendant. The molecular weight of the organic hydroxyl-containing materials can vary within wide limits and z. B. are in the range of about 10 to 2500.

Preferably the organic hydroxyl containing material is an aliphatic material containing at least one primary or secondary aliphatic hydroxyl group, i.e. a hydroxyl group attached directly to a non-aromatic carbon atom. Particularly preferred organic materials are alkane polyols.

Suitable mono- and polyhydric alkanols for the purposes of the invention are e.g. B. 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, glycerin and sorbitol.

Mono- and polyvalent haloalkanols which can be used according to the invention are e.g. 2-chloroethanol, 3-chloropropanol, 2,3-dichloropropanol, 3,4-dibromo-l, 2-butanediol, 2,3-dibromo-l, 4-butanediol and l, 2,5,6-tetrabromohexane 3,4-diol.

Polymeric hydroxyl-containing materials that can be used are e.g. Polyoxyethylene and polyoxypropylene glycols and triols with molecular weights from about 200 to 2000 (corresponding to hydroxyl equivalent weights from 100 to 1000 for the diols or 70 to 630 for the triols), polyalkadienes with hydroxyl end groups and polytetramethylene glycols with different molecular weights, e.g. the glycols sold by the Quaker Oats Company under the name "Polymeg" 650, 1000 and 2000. However, various other hydroxyl-containing materials can also be used. The choice of the respective hydroxyl-containing material depends on the desired terminal hydroxyl functionality of the polyol. It was found,

that the polyols according to the invention have the same hydroxyl functionality as the hydroxyl-containing starting material and that the hydroxyl functionality is present in the form of a terminal hydroxyl group. If you use e.g. B. a monofunctional hydroxyl-containing material, a monohydroxyl polyether is formed. On the other hand, when using difunctional hydroxyl-containing materials, divalent polyether polyols etc. are obtained.

According to the invention, a wide variety of chloroalkylene oxides can be used, e.g. B.

Epichlorohydrin, 1-chloro-2-methyl-2,3-epoxypropane,

1,4-dichloro-2,3-epoxybutane and l-chloro-2,3-dimethyl-2,3-epoxybutane.

Higher chlorinated monoalkylene oxides, such as

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

1,1,1-T richlor-2,3-epoxypropane,

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

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

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

Further usable chloroalkylene oxides are e.g. B.

1,1-dichloro-2-methyl-2,3-epoxypropane,

1,1,1-richlor-3,4-epoxybutane,

1,1-dichloro-3,4-epoxybutane,

1,1,1,2,2-pentachloro-3,4-epoxybutane,

1,1,1,4,4-pentachloro-2,3-epoxybutane,

1,1,1,2,2-mixed-pentahalogen-3,4-epoxybutane and

1,1,1,2,2-pentachloro-2-methyl-2,3-epoxybutane.

Tetrachlororepoxybutanes can also be used,

e.g.

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.

The degree of addition and thus the molecular weight of the polyols according to the invention can be regulated by a suitable choice of the proportions of alkylene oxide to hydroxyl-containing material. The molar ratio of alkylene oxide to the hydroxyl groups of the hydroxyl-containing material is, for. B. in the range of 1: 1 to 1:50, preferably 1: 1 to 1:20.

Catalyst systems which can be used according to the invention comprise a) one of the abovementioned fluorinated compounds of the formula II or the formula HmXFn + m or the compound tris (trifluoromethylsulfonyl) methane, and b) one of the abovementioned tin compounds. Already about 0.05 percent by weight of the catalyst system, based on the total weight of hydroxyl-containing material and alkylene oxide, enables the production of optically clear and practically colorless polyols according to the invention.

As mentioned above, the molar ratio of the tin compound to the fluorinated compound suitably depends on the fluorinated compound used in the catalyst system. Regardless of the ratio used in each case, however, the catalyst system can usually be easily prepared by adding the individual components to the polymerization mixture.

Compounds of the formula are suitable as fluorinated compounds

RfS02- C - S02Rf (II)

V

H

in which R9 is hydrogen, halogen, C 1 -C 7 -alkyl, alkenyl with up to 3 C atoms, aryl or alkaryl with up to 10 C atoms, the alkyl, aryl and alkaryl radicals being halogen, highly fluorinated alkylsulfonyl, Carboxyl, alkoxycarbonyl, nitro, alkoxy, acetoxy may have one or more substituents, and Rf is the same or different fluorine-containing monovalent aliphatic or cycloaliphatic radicals, or the compound tris (trifluoromethylsulfonyl) methane, and / or acids of the formula

HmXFn + ra.

The fluorinated compounds are preferably those which have the RfS02 radical twice on the same terminal C atom, and are in particular highly fluorinated alkanes with 1 to 18 carbon atoms. Compounds can also be used which release such alkanes under the action of heat or moisture.

Highly fluorinated aliphatic radicals are preferably understood to mean fluorinated saturated monovalent aliphatic radicals having 1 to 10 carbon atoms. The basic chain of these radicals can be straight, branched or, if they are of sufficient length (for example at least 3 or 4 carbon atoms), cycloaliphatic. In addition, the basic chain can be interrupted by divalent oxygen atoms or trivalent nitrogen atoms which are only bonded to carbon atoms. Preferably the chain of the fluorinated aliphatic radical contains no more than one heteroatom (i.e. nitrogen or oxygen) per two carbon atoms in the base chain. Although perfluorinated radicals are preferred, hydrogen or chlorine atoms can also be present as substituents in the fluorinated aliphatic radical.

5

10th

15

20th

25th

30th

35

40

45

50

55

60

65

5

653 693

provided that there is no more than one of these atoms for each carbon atom in the remainder. The fluoroaliphatic radical is preferably a saturated perfluoroalkyl radical with a branched or unbranched basic chain, which has the formula CxF2x + [-, in which x has a value from 1 to 18.

Perfluorinated groups Rf are preferred, but hydrogen or chlorine atoms can also be present as substituents in the group; however, there should not be more than one of these atoms per two carbon atoms in the remainder. The alkyl radicals usually contain no more than 10 carbon atoms, preferably they contain up to 4 carbon atoms.

Specific examples of suitable compounds of formula II are

Bis (trifluoromethylsulfonyl) methane, bis (difluorochloromethylsulfonyl) methane, bis (trifluoromethylsulfonyl) -4-bromophenylmethane, bis (trifluoromethylsulfonyl) -2-thienylmethane, bis (trifluoromethylsulfonyl) bis (chloromethanyl) benzylmethane, bis (trifluoromethylsulfonyl) phenylmethane, bis (trifluoromethylsulfonyl) -1-naphthylmethane, bis (perfluorobutylsulfonyl) methane, bis (2,2,3,3,4,4,4-heptafluorobutylsulfonyl) methane, Perfluorobutylsulfonyltrifluoromethylsulfonylmethane, 1,2,2,3,3,4,4,4-heptafluorobutylsulfonyltrifluoromethylsulfonylmethane,

6,6-bis (perfluoromethylsulfonyl) -4-bromcaproic acid ethyl ester,

4,4-bis (perfluoromethylsulfonyl) -2-carbomethoxy-2-bromo-

methyl butyrate, 4,4-bis- (perfluoromethylsulfonyl) -2-carboethoxy-2-nitrobut-

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

Specific examples of compounds of formula II which can be used are described in US Pat. Nos. 3,632,843, 3,704,311, 3,701,408, 3,776,960 and 3,794,687.

The other class of fluorinated compounds which can be used according to the invention are essentially completely fluorinated acids of the formula: Hm XFm + n, in which X denotes boron, phosphorus, arsenic or antimony, m has the value 0 or 1 and n has the value 3 if X Is boron, or n has the value 5 if X is phosphorus, arsenic or antimony. These fluorinated acids are BF3, HBF4, SbF5, HSbF6, PF5, HPF6, AsF5 and HAsF6.

The tin compounds which can be used in the catalyst system according to the invention have the formula:

lf ° -Sn-R7

.1".

in which R10, R6 and R7, R8 and g have the meaning defined in claim 5. Specific examples of these tin compounds are diphenyldibutyltin, divinyldibutyltin, dial-lyldibutyltin, tributyltin fluoride, triphenyltin acetate, di-butyltin oxide and bis (tributyltin oxide).

The polyols according to the invention are optically clear and essentially colorless, as is evident from their color size of less than 10. The color size reflects the deviation of the color of a certain material from the color of distilled water when both colors are measured at around 25 ° C. The color of the water and samples are measured using a Hunterlab Model D25-4 color differential sold by Hunter-Associates Laboratory, 9529 Lee Highway, Fairfax, Virginia. The device measures three parameters that 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 positive value means red, a negative value green) and (3) the yellow-blue component «b» of the sample (a positive value means yellow, a negative value blue). The color size AE io is calculated using the following formula

Ae = / v / (al) 2 + (Aa) 2 + (Ab) 2

15

in the AL, Aa and Ab mean the respective difference between the L, a and b values of distilled water and those of the sample examined. Distilled water has a color size of 0 at 25 ° C.

20 A color size of less than about 10 indicates an optically clear and essentially colorless material. Materials with a color size of 10 are colored slightly yellow and a thin film made of such a material can be described as optically clear. At higher values of the 25 color size, the color increases, while the optical clarity of the sample decreases. A material with a color size of 20 is colored light brown and a thin film made from it is cloudy. With a color size of 50, the material is colored dark brown and the thin film is hardly 3o more transparent.

The examples illustrate the invention. All parts are by weight unless otherwise stated. In the examples, the polyols are prepared by the following general procedure:

35 Production takes place in a glass flask, which is aligned with a stirrer, thermometer and dropping funnel. A dry atmosphere is maintained in the flask during the reaction.

In each batch, the hydroxyl-containing material 40 (ethylene glycol, 62.0 g, 1 mol) and the catalyst system are introduced into the flask and heated to 60 ° C. with stirring. The composition and amount of the catalyst system are changed with each approach. Then the stirred mixture is slowly added with the chloroalkylene oxide (epichlorohydrin) within 3 hours. The reaction is continued until it is substantially complete. The temperature of the reaction mixture is kept at 60 to 85 ° C. The amount of epichlorohydrin used is chosen so that the desired hydroxyl equivalent weight of the product is obtained. For example, 938 g (10.1 mol) of epichlorohydrin is used to obtain a product with a theoretical hydroxyl equivalent weight of 500. On the other hand, 1938 g (21 mol) of epichlorohydrin are required to obtain a product with a theo-55 retic hydroxyl equivalent weight of 1000.

In Examples 1 to 25, a number of poly (chloroalkylene ether) polyols are prepared by the general process described above using both known and inventive catalyst systems 60. The exact composition of the catalyst systems and the results obtained are shown in Table I.

The catalyst systems used in Examples 1 to 3 are BF3, in Example 4 HSbF6 • H20, in Example 5 65 (C2H5) 30 * PF6 ~ and in Example 6 SbFs. The poly (chloroalkylene ether) polyols obtained with these catalyst systems are dark in color, as can be seen from their high AE values between 30 and 52.

653 693

Examples 7 to 9 explain the influence of the individual components of the catalyst system according to the invention on the properties of the poly (chloroalkylene ether) polyols obtained. In Example 7, the catalyst system consists of a polyvalent tin compound of the formula if-Sn-R7

<R8),

namely (C6H5) 2Sn (C4H9) 2. As can be seen from Example 7, when using diphenyldibutyltin alone as a catalyst, there is no reaction even after 5 hours of mixing. If, on the other hand, a sulfonylalkane is used as the catalyst system (Examples 8 and 9), products are obtained which are darker than the products according to the invention, as can be seen from their color size.

Examples 10 to 12 explain the great importance of the molar ratio of the fluorinated acid of the formula HmXFm + n to the tin compound in the catalyst system according to the invention. In Examples 10 and 11, the ratio is 1: 1 and 1.1: 1. In any case, the product obtained is deep dark brown (AE 53.1 and 52.9, respectively). On the other hand, in Example 12, when using a molar ratio of 1.13: 1, an optically clear and essentially colorless product (color size 2.1) is obtained.

Examples 13 to 24 illustrate the invention. In each of these examples, an optically clear and essentially colorless poly (chloroalkylene ether) polyol is obtained, as can be seen from the low AE values of less than about 5. Examples 13 to 16 show the influence of different molar ratios of the fluorinated acid HmXFm + n to the polyvalent tin compound. Examples 17 to 20 illustrate the use of compounds of formula II and the use of various ratios of these acids to the tin compound in the catalyst system. In the Bei-2o play 21 to 24 different tin compounds are used for the catalyst system. Example 25 shows that, according to the invention, highly halogenated alkylene oxides (e.g. 1,1,1-trichlorobutylene oxide) can also be used.

10th

15

Table 1

Catalyst system

Molver amount (a) ratio

B / A

% A% B

Um- hydroxyl- molecular- color reac-

set equivalent weight time weight

(%) calc. Mn Mw AE hours

1 bf3

0.30

99

500

496

863

1040

52.6

6

2 BFj

0.10

99

1020

930

1420

1040

50.4

6

3 BF3

0.10

99

275

252

542

589

43.5

6

4 HSbF6-6H20

0.10

99

491

450

854

1050

51.6

6

5 (C2H5) 30 + PF6-

0.20

99

500

426

882

1180

36.8

6

6 SbFs

0.10

99

1020

950

1210

2060

31.7

6

7

(C6Hs) Sn (C4H9) 2

0.0

0.224

0

no reaction

5

8 (CF3S02) 2CHC6Hs

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

10 HSbF6-6H20

(C6H5) 2Sn (C4H9) 2

1

1 0.10

0.118

99

490

420

884

1070

53.1

5

11 HSbFe-6H20

(C6H5) 2Sn (C4H9) 2

1.1

1 0.10

0.124

99

490

425

921

1050

52.9

5

12 HSbFe-6H20

(C6H5) 2Sn (C4H9) 2

1.13

1 0.10

0.127

99

490

437

896

1000

2.1

5

13 HSbF6-6H20

(C6Hs) 2Sn (C4H9) 2

1.16

1 0.10

0.130

99

490

437

894

1000

1.5

5

14 HSbF6-6H20

(C6H5) 2Sn (C4H9) 2

1.51

1 0.10

0.17

99

490

450

883

1010

2.2

5

15 HSbF6-6H20

(C6H5) 2Sn (C4H9) 2

2.0

1 0.10

0.224

99

490

470

860

993

0.8

5

16 HSbF6-6H20

(C6H5) 2Sn (C4H9) 2

2.65

1 0.10

0.298

99

490

433

827

967

1.8

5

17 (CF3S02) 2CHC6H5

(CeHs) 2Sn (C4H9) 2

0.195

1 0.30

0.064

93

465

452

883

1020

3.6

10th

18 (CF3S02) 2CHC6H5

(C6H5) 2Sn (C4H9) 2

0.392

1 0.30

0.128

99.5

496

470

939

1025

2.1

5

19 (CF3S02) 2CHC6H5

(C6H5) 2Sn (C4H9) 2

0.785

1 0.30

0.256

99

491

478

924

1046

2.5

3rd

20 (CF3S02) 2CHC6H5

(C6H5) 2Sn (C4H9) 2

1.96

1 0.30

0.64

95.2

476

450

923

1025

2.2

5

21 (CF3S02) 2CHC6H5

(C6Hs) 3SnAc

1

1 0.30

0.34

95

476

450

839

978

2.5

3rd

22 (CF3S02) 2CHC6Hs

(C4H9) 3SnF

1

1 0.30

0.25

99

496

470

887

1023

3.5

4th

23 (CF3S02) 2CHC6H5

(C4H9) 2Sn (C2H3) 2

1

1 0.30

0.241

99

491

468

870

995

1.6

6

24 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) percent by weight based on the total weight of ethylene glycol and epichlorohydrin;

(b) In this example, 1,1,1-trichlorobutylene oxide is used instead of epichlorohydrin.

Examples 26 and 27 A series of poly (haloalkylene ether) polyols are prepared according to the general procedure described above. The products obtained are examined for their initial color size, then heated to 80 ° C. for 14 hours and then examined again for their color size. In Example 26, a sample of the one in Example 13

Polyols obtained from Table I used. In Example 27, a polyol having a hydroxyl equivalent weight of 490 is used, which is prepared according to the general method, but 65 using 0.2 weight percent, based on the total weight of ethylene glycol and epichlorohydrin, (C2H5) 30 + PFe- as the catalyst system has been.

653 693

Table II

example

AE,

AE "

26

27th

1.51 18.55

1.56 30.41

AE] means the initial color of the polyol and AEF the color of the polyol after aging for 14 hours at 80 ° C. The results of Example 26 are characteristic of all polyols according to the invention. It can be seen that the polyols according to the invention experience practically no change in color size, while known polyols darken considerably.

Examples 28-34

A number of polyurethanes are produced using various poly (chloroalkylene ether) polyols and a polyvalent polyisocyanate. The polyols were made by the general procedure. “Mondur MRS”, a polymethylene polyphenyl isocyanate with an average of 2.6 isocyanate groups per molecule, which is sold by the Mobay Company, is used as the polyfunctional isocyanate.

The polyurethanes are produced by stirring the components in a suitable reaction vessel at 25 ° C. for 1 to 2 minutes. A moisture-free atmosphere is maintained in the reaction vessel. No catalyst is added to accelerate the reaction.

Examples 28 and 29 use poly (chloroalkylene ether) polyols according to the invention. These polyols were made using the same catalyst system. Their amounts are given in Example 15. The polyol used in Example 28 has a theoretical hydroxyl equivalent weight of 325, while the polyether used in Example 29 has a theoretical hydroxyl equivalent weight of 500.

Examples 30 to 34 use poly (chloroalkylene ether) polyols which have been obtained using known catalyst systems. The polyol used in Example 30 has a theoretical hydroxyl equivalent weight of 1000 and was prepared using 0.3 weight percent based on the total weight of epichlorohydrin and ethylene glycol BF3 as a catalyst. The polyols used in Examples 31 and 32 have a theoretical hydroxyl equivalent weight of 500 and 325, respectively, and were prepared using 0.2% by weight, based on epichlorohydrin and ethylene glycol, of (C2H5) 30 + PF6 ~ as the catalyst. The polyols used in Examples 33 and 34 have a theoretical hydroxyl equivalent weight of 500 and 325, respectively, and were prepared using 0.1% by weight, based on the total weight of epichlorohydrin and ethylene glycol, HSbF6 • 6H20 as catalyst.

The results obtained are shown in Table III. The results show that the polyurethanes from Examples 28 and 29 which have been prepared from the polyols according to the invention gel quickly, while the polyurethanes of Examples 30 to 34 produced using known polyols do not gel even after 24 hours. In addition, the polyurethanes from Examples 28 and 29 cure within 24 hours, while the polyurethanes from Examples 30 to 34 do not cure even after 3 days.

Table III

20th

Example NCO / OH polyurethane viscosity (cP)

Start value End value (0 hours) (24 hours)

25th

30th

28

29

30th

31

32

33

34

1.2: 1

1.2: 1

1.2: 1 1.2: 1 1.2: 1 1.2: 1 1.2: 1

4,800 gels within

15 minutes * 2,200 gels within

2.5 hours *

5 900 24 000 5 900 16 000 2 300 5 400 4 800 15 000 2 200 27 000

35

* Gelation occurs when the viscosity is more than 1,000,000 cP.

Examples 35 to 40 A series of poly (chloroalkylene ether) polyols according to the invention is prepared by the general process, but different hydroxyl-containing materials are used instead of ethylene glycol. In each of these examples, the catalyst system, based on the total weight of hydroxyl-containing material and epichlorohydrin, consists of 0.1% HSbF6 • 6H20 and 0.224% diphenyldibutyltin. The polyols obtained are examined for their percentage conversion, the hydroxyl equivalent weight and the color size. The constituents used to prepare the polyols, their respective amounts and the results obtained are shown in Table IV.

Table IV

material containing hydroxyl

Hydroxyl equivalent weight

At

Art

Weight

Epichlorohydrin

Sales calc.

found

E

game

parts

Parts by weight

(%)

35

CH3CH2OH

46

954

98.5

1000

894

2.9

36

HO (CH2) 6OH

118

882

99.7

500

427

2.2

37

HIGH ^ - £) -CH

2 ° H

144

855

99.5

500

445

1.01

38

C2HsC (CH2OH) 3

134

1366

98.7

500

439

2.5

39

hoch2CH2 ^ 5) -OCH2CH

20H 198

802

99.5

500

424

3.1

Br \

c = c C,

^ Br

40

HIGHg /

0H 246

758

99.4

500

446

5.2

s

Claims (11)

653 693 1.13: 1 to 3: 1. 1 o 20 (R) wherein g has the value zero or 1, R10 and R6 are identical or different and mean aliphatic or aromatic hydrocarbon radicals with 1 to 10 C atoms, R7 represents oxygen or an aliphatic or aromatic hydrocarbon radical with 1 to 10 C atoms, with the proviso that g has the value zero when R7 is oxygen, and R8 is fluorine, an acyloxy radical with less than 10 C atoms, a saturated aliphatic hydrocarbon radical with 1 to 10 C atoms or the rest 25th 30th in which R3 is a chloroalkyl radical having 1 to 2 carbon atoms and 1 to 5 chlorine atoms. -1 - I I K C-M> H H or can have more than one substituent, and Rf is identical or different fluorine-containing monovalent aliphatic or cycloaliphatic radicals; or the compound tris (trifluoromethylsulfonyl) methane; or an inorganic fluorine compound of the formula Hm XFn + m where X is boron, phosphorus, arsenic or antimony, m io is zero or 1 and n is 3 if X is boron or 5 if X is phosphorus, arsenic or antimony; and b) a tin compound of the formula 2. Alcohols according to claim 1 of the general formula H - (- 0 2nd PATENT CLAIMS 1. Amorphous chloroalkylene alcohols of the general formula I i - {- o - c - 3rd 653 693 3. Alcohols according to claim 2 of the general formula .3 t 4k-oh U R c *) in which R1 and R2 represent hydrogen atoms or methyl groups, R3 and R4 represent hydrogen atoms, alkyl radicals having 1 to 10 carbon atoms or chloroalkyl radicals having 1 or 2 carbon atoms and 1 to 5 chlorine atoms, with the proviso that at least one of the radicals R3 and R4 is such a chloroalkyl radical R5 is hydrogen or an organic radical, b is an integer from 1 to 50 and d is an integer from 1 to 6, which have a color size of less than 10. 4. Alcohols according to claim 1, characterized in that R5 is ethylene or 1,4-cyclohexylene-bis-methylene. 4-0 - H I. C. I. H ch2ci c 4t ^ H Jt R - O - Sn-R with the proviso that R8 is fluorine, an acyloxy radical having less than 10 carbon atoms or the rest 5. A process for the preparation of the compounds of formula I according to claim 1, characterized in that an organic substance which has 1 to 6 hydroxyl groups, or water with a corresponding chloroalkylene oxide in the presence of a catalytic amount of a catalyst system, the following components contains: a) a fluorinated compound of the formula 45 50 R J RfS02-C-S02Rf H (II) wherein R9 is hydrogen, halogen, C 1 -C 7 -alkyl, alkenyl with up to 3 C atoms, 2-thienyl, benzyl, aryl or alkaryl with up to 10 C atoms, the alkyl, aryl, and alkaryl residues halogen, highly fluorinated alkylsulfonyl, carboxyl, alkoxycarbonyl, nitro, alkoxy, acetoxy as one R10 I. - 0 - Sn - R ( I7 55 means when R10, R6 and R7 are each saturated aliphatic hydrocarbon radicals. 6. A catalyst system for carrying out the process according to claim 5, comprising the components a) and b) defined in claim 5. 60 7. A catalyst system according to claim 6, characterized in that it contains as component a) a compound of formula II. 8. A catalyst system according to claim 7, characterized in that the molar ratio of component (b) to 65 component (a) of the formula II is 0.2: 1 to 2: 1. 9. A catalyst system according to claim 6, characterized in that it contains as component a) a compound of the formula HmXFn + m. 10. A catalyst system according to claim 9, characterized in that the molar ratio of component (b) to component (a) of the formula HmXFn + m 10th 35 10 1 7 R -Sn-R 11. Use of chloroalkylene alcohols according to claim 1 for the production of polyurethanes, characterized in that the chloroalkylene alcohols are reacted with polyhydric polyisocyanates. Poly (chloroalkylene ether) polyols and processes for their preparation are known. In most cases oxirane monomers, e.g. Alkylene oxides, alcohols and acidic catalysts converted into hydroxyl-functional prepolymers by cationic polymerization; see. e.g. U.S. Patent Nos. 3 850 856.3 910 878.3 910 879 and 3 980 579. However, the products and processes described in these patents are unsatisfactory. For example, it has proven extremely difficult to control the polymerization temperature. In addition, the products are colored dark, react very slowly with different materials, e.g. B. isocyanates, if not considerable amounts of catalyst are used, and are unstable when exposed to sunlight and at temperatures above 50 ° C. When exposed to light and heat, these materials turn even darker and their acidity and water content increase. The products described in US Pat. No. 3,980,579 also adversely affect the catalytic activity of amine catalysts used in the manufacture of polyurethane foam. Another process for the preparation of polymers having hydroxyl end groups is described in US Pat. No. 3,450,774, in which high molecular weight, crystalline poly (epihalohydrin) is cleaved in the presence of certain alkali compounds. The polymers obtained are crystalline and have a low molecular weight. In addition, they have only partial hydroxyl functionality. Instead of hydroxyl end groups, they can have carbonyl and ethynyl end groups.