CH650764A5 - ALKYL-polyoxyalkylene CARBOXYLATE. - Google Patents

Description

650 764

2nd

PATENT CLAIMS 1. The compounds, or mixtures of compounds, of the formula (I)

R-O- £ CHoCH "-03 (CHo-CH-0} - £ CKoCH" -0} -Ro-C00A

22 m 2, p 2 2 n 2

R,

(I),

bliss

R n-C6_22-alkyl,

Ri C ^ alkyl,

R2 C1_3 alkylene,

m 0 or a number from 0.1 to 30, p a number from 0.5 to 20,

n 0 or a number from 0.1 to 30 and

A is hydrogen or a cation from the series alkali metal, alkaline earth metal, ammonium, mono-, di- or tri-C2_4-lo alkanolammonium, mono-, di-, tri- or tetra-C] _4-alkylammonium, pyridinium and morpholinium, where m + n + p is 1 to 50 and at least one of m and n is different from zero.

2. The compounds according to claim 1, of the formula i5 (Ia)

R, -0-6CH9CHo-0} -T-eCH_-CH-0} -r- (CH „CHo-0 ^ 7-RI-COOA '(Ia),

z / m z, p z 2 n 2 -

wherein

R'n-Cg_lg-alkyl, especially C1 (M6-alkyl, R'i Cj_2-alkyl, especially methyl,

R-2 C1-2-alkylene, in particular methylene, m '0 or 0.7 to 20, in particular 0 or 1.0 to 15,

p '0.7 to 15, in particular 2 to 10,

n '0 or 0.7 to 20, in particular 0 or 1.0 to 15, A' hydrogen or a cation from the series alkali metal, alkaline earth metal, ammonium, mono-, di- or tric-C2-4-alkanolammonium, mono- , Di-, tri- or tetra-Ci_4-alkylammonium, in particular hydrogen, lithium, sodium, potassium, a magnesium, calcium, stronzium or barium equivalent or ammonium,

where m '+ n'-l-p' is 1.5 to 35, in particular 3 to 20 and at least one of m 'and n' is different from zero.

3. A process for the preparation of the compounds of the formula (I) according to claim 1, in which A is the radical Aj with the meaning given below, characterized in that a compound or a mixture of compounds of the formula (II)

R-0— (CHoCH “-0) —6CH -CH-O} - £ CHoCH_-0} —H z z m z, p z z m

25 \ (II)

with a compound of formula (III)

30th

Hal-R2-COO A1 (III),

wherein

Shark is chlorine or bromine and 35 A1 is hydrogen or an alkali metal, condensed in the presence of an alkali metal or an alkali metal hydroxide.

4. Use of the compounds of formula (I) according to claim 1 as an active substance for the preparation of surfactant

40 products.

5. surfactant preparations containing 2 to 50 percent by weight of one or more compounds of formula (I) according to claim 1.

The subject of the invention are new alkyl polyoxyalkylene carboxylates, their preparation and their use as surface-active substances, in particular as active substances in surfactant products, e.g. Detergents.

It has been found that the compounds or mixtures of compounds of the formula (I)

R-0- <CH9CHo-03 (CH - CR-0) - (CHoCH „-03-R.-COOA

z z m z, p z z n Z

R,

Oó,

bliss

R n-C.ji alkyl,

Rx C ^ alkyl,

R2 C] _3-alkylene,

m 0 or a number from 0.1 to 30,

p is a number from 0.5 to 20,

n is 0 or a number from 0.1 to 30 and A is hydrogen or a cation from the series alkali metal, alkaline earth metal, ammonium, mono-, di- or tri-C2-4-alkanolammonium, mono-, di-, tri- or tetra-C [_4-alkyl

are ammonium, pyridinium and morpholinium, 60 where m + n 4- p is 1 to 50 and at least one of m and n is different from zero, have an excellent surface activity and are therefore very suitable as active substances in detergents.

The values m, n and p are 65 mean values in most mixtures, i.e. the mixtures differ in the (whole) numbers for m, n and p. In formula (I), independently of one another, R preferably R 'and this n-C8_18-alkyl, in particular C10_15-alkyl, R! preferably R \

3rd

650 764

and this C1_2-alkyl, especially methyl, R2 preferably R'z and this C ^ -alkylene, especially methylene,

m preferably m 'and this 0 or 0.7 to 20, in particular 0 or 1 to 15,

p preferably p 'and this 0.7 to 15, in particular 2 to 10,

n preferably n 'and this 0 or 0.7 to 20, in particular 0 or 1 to 15 and

A preferably A 'and this hydrogen or èin cation from the series alkali metal, alkaline earth metal, ammonium, mono-, di- or tri-C2_4-alkanolammonium and mono-, di-, tri- or tetra-C ^ -alkylammonium, in particular hydrogen , Lithium, sodium, potassium, a magnesium, calcium, stronzium or barium equivalent or ammonium.

If a molecule of formula (I) contains more than one Rj group, these groups can be the same or different, preferably they are the same.

R2 can be straight or branched, e.g. -CH-, -CH-, -CH0CH- or -CHCH--.

T t '»Z

CH,

C2H5

CH,

CH,

When A represents an alkanolammonium residue, the carbon atom bound to the nitrogen does not carry the hydroxyl group. If a nitrogen atom bears several alkanol or alkyl radicals, these can be the same or different, but are preferably the same radicals. A preferably carries no more than two tert-butyl radicals.

In particularly preferred compounds of the formula (I), m = m "and this is 0 or 1.0 to 7, especially 1 to 3, p = p" and this is 2.0 to 5, especially 3 to 5, n = n "and this 0 or 1.0 to 7, especially 1 to 3, and A = A" and 5 this hydrogen, sodium, potassium or ammonium, where m "+ n" + p "= 3.0 to 15 and at least one of m and n is different from 0. Particularly preferred mixtures of compounds of the formula (I) mainly contain those compounds in which the symbols m, n io or p correspond to the values indicated as being particularly preferred %, especially at least 80% of these compounds.

For biodegradability, it is essential that the group labeled R is primarily a linear alkyl.

Suitable alcohols (R-OH) as precursors are generally primary linear alcohols with 6 to 22 carbon-20 atoms, which are usually commercially available in the form of mixtures of such compounds. Accordingly, the statement R = C ^ alkyl is an indication of the mean. Examples of such suitable alcohols are: n-hexyl, n-octyl, n-nonyl, n-decyl, n-undecyl and n-dodecyl alcohol and the linear primary alcohols which are used in the hydrogenation of natural (vegetable or animal) fatty acids from e.g. B. coconut fat, palm oil, tall oil etc. can be obtained.

The process for the preparation of the compounds of formula (I) is characterized in that a compound of formula II

R-O— (CHoCHo-0} - £ CH -CH-03— (CHoCH “-0) —H

2 »Z m ^ | p * m Za Q

CH)

R,

with a compound of formula (III) Hal-R2-COOAi

(HI),

wherein

Shark chlorine or bromine and

Aj mean hydrogen or an alkali metal cation, condensed in the presence of an alkali metal or alkali metal hydroxide. Aj is preferably a sodium ion and the reaction is carried out in the presence of metallic sodium or sodium hydroxide. The reaction conditions correspond to the generally known Williamson carboxyalkylation reaction. If another cation (according to the definition of A) is to be present instead of Ax, this other cation can be introduced by means of a well-known exchange reaction. The intermediates of formula (II) are known in a known manner, e.g. by two- or three-stage reaction of the alcohol R-OH with ethylene oxide and a higher alkylene oxide, preferably propylene oxide. These reactions are preferably carried out in the presence of a catalytic amount of an alkaline compound, e.g. As sodium or potassium hydroxide, under pressure and at higher temperatures. It can be advantageous to carry out these reactions in the presence of a small amount of a reducing agent in order to prevent discoloration of the reaction products as far as possible. Suitable reducing agents are e.g. Sodium borohydride, lithium aluminum hydride, and diborane, preferably sodium borohydride. For example, a mixture of compounds of the formula (II), in which the polyoxyalkylene chain contains ethylene oxide and higher alkylene oxide

Blocks (e.g. propylene oxide blocks) contains, prepared by using a linear, primary C ^ alcohol first with the desired amount of ethylene oxide (if all ethylene oxide has reacted, the pressure in the reaction vessel drops) then with propylene oxide or another higher alkyl oxide and finally reacted again with ethylene oxide. The product of formula (II) thus obtained can then be mixed with a weak acid, e.g. Glacial acetic acid are treated in order to neutralize, if desired, any residues of the basic catalyst. The reaction of the compounds of formula (II) with those of formula (III) is generally carried out with a stoichiometric excess of compounds of formula (II). However, it is then not necessary to remove the small amounts of unreacted compounds from the end product, they do not impair the action of the compounds of the formula (I) and can even be advantageous in some cases. 55 The compounds of formula (I) are extremely surface-active. Thanks to this property, they are suitable for a wide variety of purposes, e.g. as detergents, surfactants, in a wide variety of uses and for a wide variety of materials. They are also suitable as emulsifiers, dispersants, lubricants, wetting agents and fabric softeners in the textile, leather, paper, dyeing, coating and cosmetic industries and as cleaning agents. The compounds of formula (I) can include also as intermediates for the production of organic esters, which are used in the field of textile finishing or thermoplastic plastics. The surfactant preparations with the compounds of formula (I) can be the usual additives (detergency builders), e.g. B. water soluble

650 764

Salts of pyrophosphates, orthophosphates, polyphosphates, phosphonates, carbonates, bicarbonates and silicates, or the generally known organic compounds used for this purpose, e.g. Alkali metal and optionally substituted ammonium salts of polyacetates (ethylenediaminetetraacetic acid sodium and sodium nitrile triacetate), carboxylates, polycarboxylates and polyhydroxysulfoxylates, but also the usual detergent additives (bleach, defoamers), dirt distributors or additives that modify the viscosity . They can be used in a wide pH range. Because of the excellent qualities of the compounds according to the invention, the phosphate content can be largely reduced in surfactant preparations, and it is even possible in many cases to completely omit these additives (builders).

The surfactant preparations contain from 2 to 50 percent by weight, preferably from 10 to 40, in particular 15 to 30 percent by weight of one or more compounds of the formula (I), these compounds) being the only surface-active substances. However, these preparations can also contain one or more nonionic, anionic, ampholytic or zwitterionic surface-active substances. The preparations can be in liquid or solid form. If the surfactant preparations contain defoamers, these are present in amounts between 0.005 and 5%, preferably between 0.01 and 3%, in particular between 0.1 and 1%. The viscosity regulating substances are generally used in amounts between 0.5 and 5%. As additional additives such. B. still dirt distributors (between 0.25 and 5 percent by weight) and enzymes (proteolytic enzymes, in amounts up to 1,

preferably from 0.25 to 0.75 percent by weight).

The new compounds of the formula (I) have an anionic character in aqueous solution and also have the low tendency to foam which is customary for anionic, surface-active substances. However, they also have some properties that are customary only with nonionic surface-active substances, e.g. excellent stability in hard water and good compatibility with ionic compounds.

In the following examples, the temperature information means Celsius degrees.

example 1

15 a) a 5-liter round-bottomed flask, which is provided with a stirrer, a dropping funnel, nitrogen supply, a cooler and a gas inlet tube, is charged with 436.4 g (4.28 mol) of n-hexanol and 10 , 1 g of potassium hydroxide granules. A vacuum 20 of 5 mm Hg is applied over 30 minutes, broken with nitrogen, flushed with a stream of nitrogen, heated to 148 ° and at the same time begins to add 424.0 g (9.64 mol) of ethylene oxide. The temperature of the reaction mixture is kept between 148 and 166 ° with constant stirring. After all ethylene oxide 25 has been added and reacted, the mixture is cooled, evacuated to 5 mm Hg and flushed again with a stream of nitrogen. Then, as described above (at temperatures between 148 and 166 °), 1116.0 g (19.24 mol) of propylene oxide and finally, after cooling, evacuating and flushing 30 with nitrogen, a further 424.0 g (9.64 Mol) ethylene oxide implemented. The intermediate product of the formula nC6H13- ° ^ C2V0 ^ C3H6- °% 7ir <C2V0 ^ H is thus obtained

with a hydroxyl number of 103.1.

b) 1000.0 g (1.78 mol) of the mixture of compounds of the formula (II) obtained according to a) are in small portions at 25 to 50 °, alternately, with 71.2 g (1.78 mol) of sodium hydroxide and 207, 7 g (1.78 mol) of sodium monochloroacetic acid were added. The temperature is held at 50 ° for 30 minutes, raised to 75 ° in a further 30 minutes and. Held for 90 minutes. It is then cooled to 50 ° and acidified 40 with 175.0 g of sulfuric acid (50 percent) in 600 g of water. After a short time, two layers form, of which the oily the desired product (mixture) of the formula

, l-C6H13- ° - <C2H4-C>% ^ C3H6-0% XfC2H4-0% ^ rCH290H '

which has an acid number of 53.2.

The following Table 1 shows further compounds (mixtures) that can be produced analogously to the above working instructions.

of the formula (I), in which Rj is always methyl, and the hydroxyl number of the intermediate (of the formula (II)) and the acid number of the end product.

Table 1

Example No. R m p n hydroxyl number of the acid number of the final

Intermediate product

2nd

n-Ci0H2i

0.15

2.4

0.45

192.4

88.6

3rd

59

0.45

2.4

0.15

188.0

70.7

4th

99

0.9

14.4

2.7

58.4

24.7

5

99

0.6

0.6

1.8

186.7

108.0

6

99

1.8

0.6

0.6

186.9

110.8

7

9)

3.6

3.6

10.8

60.0

42.6

8th

55

10.8

3.6

3.6

61.3

33.3

9

n-C14.H29

0.25

0.5

0.25

211.0

98.0

10th

99

2.25

4.5

2.25

89.3

51.2

11

n-Ci8H37

0.15

2.4

0.45

130.3

45.2

12

99

0.45

2.4

0.15

132.9

44.9

5

Table 1 (continued)

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Example No. R m p n hydroxyl number of the acid number of the final

Intermediate product

13

5?

0.6

0.6

1.8

134.2

83.4

14

55

1.8

0.6

0.6

132.4

81.3

15

55

2.7

14.4

0.9

61.6

31.4

16

55

3.6

3.6

10.8

55.3

38.0

17th

5 »

10.8

3.6

3.6

55.7

36.2

18th

55

0.9

7.2

0.9

83.8

18.2

19th

n-C22H4.s

2.25

4.5

2.25

79.3

42.5

Table 2 below shows further compounds of the formula (I) which can be prepared analogously to the working procedure of Example 1, in which R.! always methyl and one of m and n im-

i5 mer 0, and the hydroxyl and acid number of the intermediate or End product.

Table 2

Example No. R m p n hydroxyl number acid number final

Intermediate product

20th

n-C14H29

0

4.5

4.5

89.7

55

21st

n-Ci8H37

0

0.8

0.2

174.8

69.7

22

n-Ci0H2i

0

0.2

0.8

275.8

88.8

23

55

0

7.2

1.8

95.5

35.0

24th

55

0

0.8

0.2

268.7

99.4

25th

n-C14H29

4.5

4.5

0

90.75

21.3

26

n-Ci8H37

14.4

3.6

0

57.7

14.1

27th

n-C18H37

0.5

0.5

0

172.5

60.8

trium silicate (Na20: Si02 = 1: 2.5), 2 parts toluene sulfonic acid-35 rem sodium, 0.3 part sodium carboxymethyl cellulose, 13 parts sodium sulfate, 0.16 part water-soluble fluorescent dye and 8 parts water.

Example 29

40 A liquid surfactant preparation is mixed by mixing 12 parts by weight of the compound according to (a) Example 1, (b) Example 20 or (c) Example 25, with 19 parts of tetrapotassium pyrophosphate, 3.8 parts of sodium silicate (Na20: Si02 = 1: 1.6), 8.5 parts of toluenesulfonic acid potassium, 0.3 part of Na-45 trium-carboxymethyl cellulose, 0.2 part of fragrance and 56.2 parts of water.

If the procedure in the examples is as given in Example 1, but the final acidification is dispensed with, the sodium salt of the compounds given in the examples is obtained in any case.

Example 28

In order to produce a surfactant preparation typical of the invention and in solid form, a) 17 parts by weight of the compound according to Example 1 are mixed,

b) 17 parts by weight of the compound according to Example 20 or c) 17 parts by weight of the compound according to Example 25 with 50 parts by weight of sodium tripolyphosphate, 6 parts of Naso

55

60

65

S